Hydrometallurgy 2009 PDF

The Southern African Institute of Mining and Metallurgy
Founded in 1894
The SAIMM Southern African
Hydrometallurgy Conference 2009

SYMPOSIUM SERIES S54
CONTENTS
2426 February 2009
Misty Hills, Muldersdrift, Gauteng
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THE SOUTHERN AFRICAN INSTITUTE OF MINING AND METALLURGY

JOHANNESBURG 2008
SYMPOSIUM SERIES S54
The SAIMM Southern African
HYDROMETALLURGY CONFERENCE 2009
2426 February 2009
MISTY HILLS, MULDERSDRIFT, GAUTENG
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SAIMM PUBLICATIONS
THE MONOGRAPH SERIES
Ml
Lognormal-De Wijsian Geostatistics for Ore Evaluation

(2nd ed 1981) D.G. Krige
M2
An Introduction to Geostatistical Methods of Mineral Evaluation

(2nd ed 1981) J.-M.M. Rendu
M3
Principles of Flotation
(1982) (3rd imp. 1986) Edited by R.P. King
M4
Increased Underground Extraction of Coal

(1982) Edited by C.J. Fauconnier and R.W.O. Kersten
M5
Rock Mechanics in Mining Practice

(1983) (3rd imp. 1986) Edited by S. Budavari
M6
Assay and Analytical Practice in the South African Mining Industry

(1986) W.C. Lenahan and R. de L. Murray-Smith
M7
The Extractive Metallurgy of Gold in South Africa,

2 volumes (1987) Edited by G.G Stanley
M8
Mineral and Metal Extraction An Overview

(1994) L.C. Woollacott and R.H. Eric
M9
Rock Fracture and Rockburstsan illustrative study

(1997) Edited by W.D. Ortlepp
THE SPECIAL PUBLICATIONS SERIES

SPI
Proceedings, Underground Transport Symposium

(1986) Edited by R.C.R. Edgar
SP2
Backfill in South African Mines (1988)
SP3
Treatment and Re-use of Water in the Minerals Industry (1989)
SP4
COREX Symposium 1990

(1990) Edited by H.M.W. Delport and P.J. Holaschke
SP5
Measurement, Control, and Optimization in Mineral Processing

(1994) Edited by H.W. Glen
SP6
Handbook on Hard-rock Strata Control

(1994) A.J.S. Spearing
SP7
Rock Engineering for underground coal mining

(2002) J. Nielen van der Merwe and Bernard J. Madden
SUPPLEMENT TO THE SAIMM JOURNAL

The Metals and Minerals Industry in South Africa - Part 1 (1989)
Edited by H.W. Glen
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THE SYMPOSIUM SERIES

S1
S2
S3
S4
S5
S6
S7
S8
Mathematical Statistics and Computer Applications in Ore Valuation (1966)

Planning Open Pit Mines (1970) (4th imp.) Edited by P.W.J. van Rensburg
Application of Computer Methods in the Mineral Industry (APCOM 1973) Edited by M.D.G. Salamon
Infacon 1974 Edited by H.W. Glen
Proceedings of the 12th CMMI Congress 2 volumes (1982) Edited by H.W. Glen
Rockbursts and Seismicity in Mines (1984) Edited by N.C. Gay and E.H. Wainwright
The Planning and Operation of Open Pit and Strip Mines (1986) Edited by J.P. Deetlefs
GOLD 100: Proceedings of the International Conference on Gold (1986)
Volume 1: Gold Mining Technology Edited by H. Wagner and R.P. King
Volume 2: Extractive Metallurgy of Gold Edited by C.E. Fivaz and R.P. King
Volume 3: Industrial Uses of Gold Edited by G. Gafner and R.P. King
S9
APCOM 87: Proceedings of the Twentieth International Symposium on the
Application of Computers and Mathematics in the Mineral Industries (1987)
Volume 1: Mining Edited by L. Wade, R.W.O. Kersten and J.R. Cutland
Volume 2: Metallurgy Edited by R.P. King and I.J. Barker
Volume 3: Geostatistics Edited by I.C. Lemmer, H. Schaum and F.A.G.M. Camisani-Calzolari
S10 International Deep Mining Conference (1990)
Volume 1: Innovations in Metallurgical Plant Edited by G.A. Brown and P. Smith
and
Application of Materials Engineering in the Mining Industry Edited by B. Metcalfe
Volume 2: Technical Challenges in Deep Level Mining Edited by D.A.J. Ross-Watt and P.D.K. Robinson
S11 Infacon 6 ( Incorporating Incsac) (1992) Edited by H.W. Glen
S12 Massmin 92 Edited by H.W. Glen (out of print)
S13 Minefill 93 Edited by H.W. Glen
S14 XVth CMMI Congress Publications (1994)
Volume 1: Mining Edited by H.W. Glen
Volume 2: Metals Technology and Extractive Metallurgy (1994) Edited by H.W. Glen
S15 Surface Mining 1996 Edited by H.W. Glen
S16 Hidden Wealth (1996) Edited by H.W. Glen
S17 Heavy Minerals 1997 Edited by R.E. Robinson
S18 The 8th International Platinum Symposium (1998)
S19 Mining in Africa 98
S20 Extraction Metallurgy Africa 98
S21 Sixth International Symposium for Rock Fragmentation by Blasting (1999)
S22 Metallurgy Africa 99
S23 Heavy Minerals 1999 Edited by R.G. Stimson
S24 Tunnels under Pressure Technical Editor T.R. Stacey
S25 Mine Hoisting 2000
S26 CoalThe Future (2000)
S27 The Fifth International Symposium on Rockburst and Seismicity in Mines (RaSim 5) (2001)
S28 6th International Symposium on Mine Mechanization and Automation (2001)
S29 XIV International Coal Preparation Congress and Exhibition
S30 Surface Mining 2002Modern Developments for the New Millennium
S31 IFSA 2002, Industrial Fluidization South Africa
S31A APCOM 2003Application of Computers and Operations Research in the Minerals Industries
S32 ISSA/Chamber of Mines ConferenceMines and Quarries: Prevention of Occupational Injury and Disease
S33 ISRMTechnology Roadmap for Rock Mechanics
S34 Heavy Minerals Conference 2003
S35 Safety in Mines Research Institutes (2003)
S36 VII International Conference on Molten Slags, Fluxes & Salts (2004)
Tenth International Ferroalloys Congress INFACONX 2004
S37 Deep and high stress mining 2004
S38 Platinum adding value 2004
S39 Base MetalsSouthern Africas response to changing global base metals market dynamics 2005
S40 Strategic versus Tactical approaches in mining 2005
S41 Best practices in rock engineering SARES 2005
S42 IFSA 2005 (Mintek)
S43 Southern African Pyrometallurgy 2006 International Conference
S44 Stability of rock slopes in open pit mining and civil engineering situations
S45 Platinum Surges Ahead 2006
S46 Hydraulic Transport of Solids - Hydrotransport 17 (2007)
S47 Fourth Southern African Base Metals Conference Africas base metals resurgence
S48 Heavy Minerals Conference, 2007
S49 Cave Mining Conference, 2007
S50 International Symposium on Lead and Zinc processing Lead & Zinc 2008
S51 Surface Mining 2008
S52 Hydrometallurgy Conference 2009
S53 IFSA 2008
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Published by The Southern African Institute of Mining and Metallurgy

Fifth Floor, Chamber of Mines Building, 5 Hollard Street, Johannesburg, 2107
Republic of South Africa
The Southern African Institute of Mining and Metallurgy, 2008
ISBN 978-1-920211-22-6
The papers in this volume have been for the most part prepared from files supplied by the authors, with
additional typesetting and formatting by The Southern African Institute of Mining and Metallurgy.
All papers included in this volume were subjected to review.
A technical and critical review of each paper was carried out by one technical reviewer.
Printed by Camera Press, Johannesburg
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FOREWORD
or the first time a conference is being staged that covers the true diversity of the
application of hydrometallurgy in Southern Africa. This conference will bring
together operating hydrometallurgical facilities, research organisations, academic
organisations, project companies, technology and equipment suppliers, and reagent
suppliers, encompassing a wide range of commodities and unit operations.
The SAIMM Southern African Hydrometallurgy conference 2009 will cover an
overview of a significant number of currently operating hydrometallurgical facilities in
Southern Africa. These overviews will encompass a description of the facility, the
technical challenges facing the operation, and any future process improvements,
debottlenecking or expansions envisaged. The conference will highlight
hydrometallurgy research being conducted by Southern African academic institutions
and by mining companies. The conference will also highlight developments being
undertaken by technology suppliers, equipment suppliers and reagent suppliers.
Some of the countries included are South Africa, Namibia, Botswana, Zimbabwe,
Zambia and the Democratic Republic of Congo. Some of the commodities covered will
be copper, nickel, zinc, cobalt, uranium, gold and PGMs. A wide range of unit
processes will be featured, including, atmospheric leaching, pressure leaching,
biological leaching, precipitation, cementation, crystallization, solvent extraction, ion
exchange and electrowinning.
I believe that the papers and presentations submitted for this conference will
provide a valuable future reference for hydrometallurgy, thus making the work of all the
contributors to this conference highly rewarding and worthwhile.
Marek Dworzanowski
Chairman
Organising Committee
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Contents
Page No.
ATMOSPHERIC LEACHING
Leaching of the arsenopyrite/pyrite flotation concentrates using metallic iron in a hydrochloric acid
medium
T. MAHLANGU, F.P. GUDYANGA, and D.J. SIMBI. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Base metals recovery from zinc hydrometallurgical plant residues by digestion method
R.B. NGENDA, L. SEGERS, and P.K. KONGOLO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
17
The progression of metallurgical testwork during heap leach design

S.W. ROBERTSON and P.J. VAN STADEN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
31
PRESSURE LEACHING
Increasing the capacity of existing and new exothermic autoclave circuits
G.M. DUNN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
43
Stress development in refractory due to the rate of temperature change: a pressure vessel refractory
lining design consideration
P. LAUZON, A. KONING, and I. DONOHUE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
57
Mixing system design for the Tati Activox autoclave

M. NICOLLE, G. NEL, T. PLIKAS, U. SHAH, L. ZUNTI, M. BELLINO, and H.J.H. PIETERSE . . . . . . . . .
65
Stabilization of supersonic vent gas from autoclave pressure oxidation

M. FRANCESCHINI and J. WOLOSHYN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
79
BIOLOGICAL LEACHING
Indigenous microorganism strains as bio-extractants of Ca, Fe, and Mg from metallurgical and mine
drainages
A.F. MULABA-BAFUBIANDI, E. FOSSO-KANKEU, and B.B. MAMBA . . . . . . . . . . . . . . . . . . . . . . . . . . .
93
Biosorption of cobalt and copper from hydrometallurgical solutions mediated by Pseudomona spp
A.F. MULABA-BAFUBIANDI, N.P. DLAMINI, and B.B. MAMBA. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
101
An investigation into fungal strains bio-extraction of metal impurities from aqueous effluents
emanating from Ekhuruleni (Gauteng, South Africa) metallurgical and mining operations
M. MWANZA and A.F. MULABA-BAFUBIANDI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
111
Integrated piloting of a thermophilic bioleaching process for the treatment of a low-grade nickelcopper sulphide concentrate
J.W. NEALE, S.W. ROBERTSON, H.H. MULLER, and M. GERICKE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
119
The effect of elemental sulphur and pyrite on the leaching of nickel laterites using chemolithotrophic
bacteria
G.S. SIMATE, S. NDLOVU, and M. GERICKE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
155
Recent advances in BIOX technology

J. VAN NIEKERK . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
167
Systematic characterization of the mixing process for the BIOX reactor

R. VAN DEVENTER, W. KELLER, M. OOSTHUIZEN, and J. STAPELBERG . . . . . . . . . . . . . . . . . . . . . . .
177
Keynote address: Hydrometallurgical process development for complex ores and concentrates
D. DREISINGER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
187
SOLVENT EXTRACTION AND ELECTROWINNING

Copper electrowinning: theoretical and practical design
N.T. BEUKES and J. BADENHORST . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
213
Developments in organic holding tank structure for solvent extraction processes

H.T. LAITALA. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
241
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Contents (Continued)
Page No.
SOLVENT EXTRACTION AND ELECTROWINNING (Continued)

The next generation of permanent cathode and lead anode technology
T. MARSDEN and J. JICKLING . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
249
Solvent extraction design consideration for the Tati Activox plant

E. ROBLES, I. CRONJE, and G. NEL. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
257
The ACORGA OPT series: comparative studies against aldoxime: ketoxime reagents
O. TINKLER, D. SHIELS, and M. SODERSTROM. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
273
Solvent extraction (SX) reagent selection for high temperature, acid, chloride and Cu PLS at Port
Pirie and its impact on electrowinning (EW)
P. CRANE, M. URBANI, K. DUDLEY, A. HORNER, and M. VIRNIG. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
283
Organic degradation in uranium and cobalt solvent extraction: the case for aliphatic diluents and
antioxidants
D.M. VAN RENSBURG, B. MUNYUNGANO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
295
BASE METALS REFINERIES

Development of the Tati Activox BMR ammonia recovery circuit
D.A. VAN DEN BERG, P. MAR, and G.J. NEL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
305
pH advanced process control solution for Impala BMR first stage high pressure acid-oxygen leach
A.F. KHAN, T. SPANDIEL, T. VAN SCHALKWYK, and J.A.M. RADEMAN . . . . . . . . . . . . . . . . . . . . . . . .
313
COPPER, COBALT, NICKEL, ZINC HYDROMETALLURGY

A cobalt solvent extraction investigation in Africas Copper Belt
T. KNIGHOFER, S.J. ARCHER, and L. BRADFORD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
329
Oxidative precipitation of Mn(II) from cobalt leach solutions using dilute SO2/air mixture
N. MULAUDZI and T. MAHLANGU . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
341
Soluble metal recovery improvement using high density thickeners in a CCD circuit: Ruashi II a
case study
M.C. MULLIGAN and L. BRADFORD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
357
Optimizing acid utilization and metal recovery in African Cu/Co flowsheets

M. REOLON, T. GAZIS, and S. AMOS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
365
Processing considerations for cobalt recovery from Congolese copperbelt ores

B. SWARTZ, S. DONEGAN, and S. AMOS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
385
GENERAL HYDROMETALLURGY
Kinetic modelling of chemical processes in acid solution at t 200C i. thermodynamics and speciation
in H2SO4-metal (ii) SO4-H2O system
J.D.T. STEYL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
The evaluation of various oxidants used in acid leaching of uranium
R. VENTER and M. BOYLETT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Application of redox titration techniques for analysis of hydrometallurgical solutions
O. BAZHKO. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
401
445
457
Investigation of granular activated carbon from peach stones for gold adsorption in acidic thiourea
T.T. MASIYA and F.P. GUDYANGA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
465
Elution behaviour of metals from carbon

M. JEFFREY, R. PLEYSIER, and K. BUNNEY. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
475
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The organisers of the conference wish to

thank the following sponsors for their support
-oOo-
Premier
FLSmidth Minerals
Impala Platinum
Protea Mining Chemicals
Exhibitors
Mintek
MIP Process Technologies
Roymec Technologies
Air Liquide
Sponsors
Anglo Operations
ChemQuest Africa
Csiro Minerals
Cytec Industries
Hatch
Purolite International
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Organising Committee
M. Dworzanowski (Chairman)
P. Mar
S. Ndlovu
T. Thulare
B. McGeorge
J. van Huysteen
T. Claasens
K. Manyukwi
L. van Dyk
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MAHLANGU, T., GUDYANGA, F.P., and SIMBI, D.J. Leaching of the arsenopyrite/pyrite flotation
concentrates using metallic iron in a hydrochloric acid medium. Hydrometallurgy Conference 2009, The
Southern African Institute of Mining and Metallurgy, 2009.
Leaching of the arsenopyrite/pyrite flotation

concentrates using metallic iron in a hydrochloric
acid medium
T. MAHLANGU*, F.P. GUDYANGA, and D.J. SIMBI
*Department of Materials Science and Metallurgical Engineering,
University of Pretoria, Pretoria, South Africa
Department of Metallurgical Engineering, University of Zimbabwe, Harare, Zimbabwe
This paper describes experimental investigations into the reductive

decomposition of arsenopyrite/pyrite (FeAsS/FeS2), a gold and silver
bearing iron/arsenic sulphide using metallic iron powder. The main
objective was to establish and experimentally confirm the
thermodynamic and kinetic feasibility of reductively decomposing the
sulphide matrix for precious metals recovery. In this context,
cyanidation leach tests were conducted on the reductive leach
residues. The arsenopyrite/pyrite flotation concentrate, mainly studied
in the hydrochloric acid medium, decomposed through the
nonoxidative chemical dissolution reaction and the reductive
decomposition reaction for the arsenopyrite and pyrite components,
respectively. Desulphurization levels below 65% were achieved at pH
values below 0.15 and iron to concentrate ratios above 1, and the
system was characterized by overall very slow kinetics. The reaction
system had a direct linear relationship with iron to concentrate ratio
and an inverse relationship with pH. An analysis of the pyrite/iron
galvanic system showed that pyrite forms a partially inert cathodic
surface on which the anodic dissolution of iron occurs, supported by
the hydrogen evolution reaction. This phenomenon explained the low
desulphurization levels and the mineral decomposition seemed to be
restricted to the nonoxidative chemical dissolution reaction for the
arsenopyrite component. The cyanide leach of the reductive leach
residues showed very little improvement in gold recovery. The
reductive leach process for arsenopyrite/pyrite has considerable
limitations in terms of both desulphurization and precious metals
liberation.
Keywords: Pyrite, arsenopyrite reductive leaching, hydrogen
sulphide, invisible gold
LEACHING OF THE ARSENOPYRITE/PYRITE FLOTATION CONCENTRATES
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Introduction
A significant fraction of gold in the gold ores that are mined in central and southern parts of
Zimbabwe occurs in submicroscopic form as finely disseminated particles or in solid solution
with the refractory sulphide host minerals, namely, arsenopyrite (FeAsS), pyrite (FeS2) and
stibnite (Sb2S3) (Kadenhe and Makande, 1987; Makande, 1988; Swash, 1988; Casparini,
1983; Husein, 1981). Apart from the conventional roasting pretreatment process prior to
cyanidation, hydrometallurgical pretreatment processes can be used as alternatives. The
hydrogen sulphide route for the decomposition of sulphides has been widely studied in two
main areas of non-oxidative dissolution (NOD) (Cservanyak, 1994; Nicol and Scott, 1979;
Scott and Nicol, 1977; Awakara et al., 1980; Ingraham et al., 1972) and the reductive
decomposition in acidified aqueous medium (House and Kelsall, 1985; Majima et al., 1981;
Majima et al., 1985; Gudyanga et al., 1999a , Chifamba, 1996; Gudyanga et al., 1999b;
House, 1986).
The sulphides decompose to give either the elemental metal or metal sulphide of lower
oxidation state with hydrogen sulphide evolution (Kolodzeij and Adamski, 1990; Cservanyak,
1994; Chifamba, 1996) according to the general reactions [1] and [2]:
[1]
[2]
Iron, the proposed reductant, is a first order transitional element with an [Ar]3d64s2 outer
shell electronic configuration and is able to exhibit multiple oxidation states of 0, +2 and +3
(Mackay and Mackay, 1986). The chemistry and electrochemistry of iron have been widely
investigated and reported in corrosion science and engineering (Wranglen, 1985; Shreir et al.,
1995a; Shreir et al., 1995b). In hydrometallurgical leaching systems, iron and its dissolved
species (Fe(II) and Fe(III) ionic species) have been discussed by correlating thermodynamic
predictions in the form of potentialpH and speciation diagrams, and stability constants for
various complexes (Seon-Hyo et al., 1986). Seon-Hyo et al. (1986), reported two stable
ferrous chlorocomplexes formed according to reaction [3]:
[3]
where n is the stability constant of the ferrous chlorocomplexes and n = 1, 2, 3 and 4; the
number of chloroligands in each complex. When n is equal to unity and two respectively, the
o
stability constants for the two complexes FeCl+ and FeCl2 were determined as 2.2908 and
1.0965 respectively (Seon-Hyo et al., 1986). It was also shown that at chloride ion
concentration less than 2M, the Fe2+ species predominates over both the FeCl+ and FeCl2
complexes while the latter (FeCl2) becomes dominant at concentrations in excess of 2.5M.
Metallic iron is a strong reducing agent as indicated by the redox potential [4]:
[4]
[5]
The conditions under which reductive and chemical decomposition of sulphide minerals
occur are also favourable to the chemical dissolution reaction [5] of iron. The hydrogen
evolution side reaction does not take into consideration the effect of the anions present. The
2
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Gibbs free energy change calculations using data from Bard et al. (1985), clearly shows the
effect of the hydrochloric acid systems [6].
[6]
On the basis of thermodynamic calculations, iron dissolution in chloride systems appears to
be more favourable than in non-chloride systems. This has a negative effect on the leach
system because the iron dissolution side reaction deprives the reductive leach reaction of any
available iron. On the other hand, the Fe(II)/Fe redox system, as a leaching agent in sulphide
concentrate leaching, is not expected to form insoluble compounds with the reaction products
in the chloride medium. Instead, the formed chlorocomplexes expectedly result in more
negative potential conditions that are thermodynamically favourable to the reductive leach
process. These thermodynamic predictions indicate a need for critical control of both acid
concentration and the iron to concentrate ratio during reductive decomposition of sulphide
minerals.
The general reactions governing the reductive decomposition of arsenopyrite, pyrite and
other iron sulphides have been determined by Majima and Awakura (1979). Although the
pyrite decomposition reaction is often classified under the reductive decomposition system,
the reaction exhibits non-oxidative dissolution (NOD) of the mineral when considered in
terms of iron and sulphur oxidation states. This is primarily because neither iron nor sulphur
seems to undergo any change in their original oxidation states. It would be expected that
pyrite decomposition follows reduction to either stoichiometric pyrrhotite [7] or elemental
iron [8] followed by the chemical dissolution of the two products [9] and [10] respectively.
However, strictly speaking, in reaction [8], iron is oxidized by hydrogen ions.
[7]
[8]
[9]
[10]
Reaction [7] has not been experimentally proven to occur in acidic aqueous systems
(Cservanyak, 1994). Also from the potentialpH diagram (Figure 1), pyrite decomposition to
elemental iron and hydrogen sulphide is feasible only at potentials below -0.41V vs SHE. The
ferrous ions are the main products at any reducing potentials above -0.41 V vs SHE depending
on the working pH. Elsewhere (Holdich and Broadbent, 1985; Koch, 1975; Peters and
Majima, 1968), ferrous ions were detected as the principal reaction products instead of
pyrrhotite and elemental iron. Czevanyak (1994) in discussing the work of Peters and Majima
(1968) reported that hydrogen sulphide evolution always occurred after hydrogen evolution
has already started. This scenario clearly indicates that the process efficiency of reductive
decomposition will be adversely affected by any pH reduction.
From the preceding discussion and available thermodynamic data, the application of
elemental iron in the reductive decomposition of pyrite can be inferred. Bourgeois et al.
(1979) as referenced by Czevanyak (1994), were the first to investigate elemental iron driven
dissolution of pyrite. Pyrite and elemental iron, form a galvanic couple with iron being
oxidized to ferrous ions and pyrite reduced to ferrous ions with the evolution of hydrogen
sulphide [11].
[11]
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Figure 1. PotentialpH diagram for the FeSH2O system. Iron activity = 0.001, sulphur = 0.001 (Stabcal software)
The reductive decomposition of arsenopyrite, which occurs together with pyrite in typical
refractory gold ores (Swash, 1988; Yannopoulos, 1990; Chifamba, 1996), can be discussed
under the same principles as that of pyrite. The half reaction, representing the decomposition
of arsenopyrite to elemental arsenic is shown in reactions [12] and [13].
[12]
[13]
The leaching system will also depend on the solution redox potential. The work of Majima
and Peters (1968) gave the following findings:
Polarizing a pyrite electrode in 1M HClO4, they determined a hydrogen overpotential of 0.26V;
In constant potential experiments, monitoring current and the concentration of H2S
evolved, the current efficiency of H2S evolution varied with potential from 34% (at
-0.2 V vs SHE) to 20% (at -0.4 V vs SHE);
Varying the acid concentration from 0.1 to 4M at -0.3 V vs SHE, hydrogen evolution rate
varied linearly with acid concentration and the reaction order for H2S > 1.
The preceeding findings limit not only the working pH range but also the potential.
Gudyanga et al. (1999b), using Cr(II) ionic species as the reductant, measured the solution
redox potential during reductive decomposition of an arsenopyrite/pyrite concentrate and
found a rapid increase in potential with time on reducing pH from 0.43 to 0.2. These results
also agree with the findings of Klein and Sluvey (1978) who concluded that the hydrogen
evolution reaction dominates above pH 0.
The present work extends the reductive decomposition and/or dissolution of a gold bearing
arsenopyrite/pyrite flotation concentrate using metallic iron in a chloride medium. The work
focuses on the factors that enhance desulphurization and the recovery of precious metals,
namely gold and silver from the selected sulphide concentrate. The application of iron in the
reductive decomposition of arsenopyrite/pyrite flotation concentrate is envisaged to provide
an alternative pretreatment method that addresses the technological and environmental
limitations that are characteristic of pyrometallurgical routes while enhancing precious metals
recovery.
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Experimental procedure
Materials
Flotation concentrate samples
The reductive decomposition experiments were conducted on an arsenopyrite/pyrite flotation
concentrate collected as a blend sample from the Kwekwe Roasting Plant, Zimbabwe. The
mineralogical and chemical composition of the material are tabulated in Tables I and II.
A bulk sample of iron shavings was collected, washed, dried, screened to 100% minus
425 m and then stored under dry and oxygen free conditions in order to minimize the
oxidation of the iron particles surfaces. All leaching solutions were prepared using analytical
grade reagents of hydrochloric acid, ferrous sulphate hepta-hydrate and potassium dichromate
diluted with distilled water and where necessary, deoxygenated with high purity nitrogen. The
experimental setup is detailed in Mahlangu et al. (2006).
Reductive leaching
The flotation concentrate was pulped in 500 ml water together with the predetermined mass of
iron shavings and purged with a steady stream of nitrogen gas for a period of 4560 minutes.
Nitrogen gas purging was used for the removal of oxygen prior to the addition of hydrochloric
acid medium. The pH was monitored by periodic withdrawal of 10 ml samples from the
reactor, cooling, recording of pH and then reintroducing the sample back into the reactor.
Effluent hydrogen sulphide was scrubbed through a 1.8 litre hydrostatic column of
hydrochloric (HCl) acidified potassium dichromate solution. The leaching/decomposition
reaction was quantitatively followed by a redox titration of residual dichromate ions in the
column with ferrous ions (Mahlangu et al. 2006). Sodium diphynlamine was used as an
indicator with the colour changing from pale green to purple on reaching the endpoint. The
residues and filtrates were then analysed for Au, Ag, Fe, As, Sb, Pb and S.
Cyanidation leaching
The reductive leach residue was thoroughly washed with distilled water and cyanide leached
in a 0.23% NaCN solution for 48 hours at pH between 11 and 12. The solution pH was
adjusted using technical grade sodium hydroxide. The leach residues and filtrates were then
analysed for Au and Ag.
Table I
Mineralogical composition of the FeAsS/FeS2 flotation concentrate
FeS2 (%)
FeAsS (%)
PbS (%)
CuFeS2 (%)
ZnS (%)
Sb2S3 (%)
Other (%)
27.2
0.1
0.3
1.8
0.8
11.1
58.7
Table II
Chemical composition of the FeAsS/FeS2 flotation concentrate
Fe (%)
36.7
As (%)
Pb (%)
Cu (%)
Zn (%)
Sb (%)
S (%)
Au (g/t)
Ag (g/t)
Other (%)
12.5
0.1
0.1
1.2
0.6
28.7
64.7
43.1
20.2
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Results and discussion

Effect of pH on the decomposition of FeAsS/FeS2
The data in Figure 2 show the variation of arsenopyrite/pyrite decomposition with pH at an
iron to concentrate ratio of 0 and set leaching temperature of 105C. The results exhibit an
inverse near linear relationship between arsenopyrite/pyrite decomposition and pH. In the
absence of iron, arsenopyrite decomposes according to the chemical nonoxidative
dissolution reaction [13]. Under these conditions, pyrite is expected to remain inert as would
be expected from the examination of the FeSH2O potentialpH diagram (Figure 1).
[14]
In this regard, the sulphide mineral nonoxidative dissolution, observed in this work, was
mainly due to the dissolution of the arsenopyrite component. The results also exhibit very low
levels of desulphurization (< 16%) associated with the chemical nonoxidative or direct acid
leaching of the concentrate. This is despite the relatively large negative free energy change
value calculated for the system [13].
The introduction of iron, at an iron to concentrate ratio of 0.16, while working in the same
pH range, gave results shown in Figure 3. An inverse linear relationship between sulphide
minerals decomposition and pH was observed, with very little improvement in the extent of
reaction. The results of further arsenopyrite/pyrite reductive decomposition experiments at
progressively increasing iron to concentrate ratios are graphically presented in Figures 3(b),
(c) and (d). These tests were conducted in the same pH range and temperature. The iron to
concentrate ratio of 0.32 corresponds to the calculated stoichiometric requirement of iron in
the system.
In all the cases, the inverse near linear relationship between arsenopyrite/pyrite
decomposition and pH continue to be exhibited. However, a further pH reduction to values
below 0.25, marginal increases in arsenopyrite/pyrite decomposition are observed. The results
also show a sustained increase in the sulphide minerals decomposition with an increase in the
iron to concentrate ratio. There is a very strong influence of iron to concentrate ratio
demonstrated at pH values equal to or greater than pH 0.25. In order to understand and
explain these phenomena, there is need for the examination of the chemistry and
electrochemistry of the two minerals in acidified chloride systems.
Figure 2. Variation of %sulphur leached arsenopyrite/pyrite with pH at different leaching times (iron/concentrate
ratio = 0; temperature = 105C)
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Figure 3. Variation of %sulphur leached from arsenopyrite/pyrite with pH at different leaching times
(ron/concentrate ratio: (a) = 0.16; (b) = 0.32; (c) = 0.64; (d) = 0.96; temperature = 105C)
In the reductive decomposition of pyrite and arsenopyrite, the reactions governing the leach
systems have been calculated and their thermodynamic feasibility demonstrated in reactions
[11] and [14]. Pyrite decomposes to ferrous ions with the evolution of hydrogen sulphide,
whereas arsenopyrite decomposes both by chemical nonoxidative and reductive dissolution
reactions, giving the same reaction products as in pyrite.
[15]
[16]
[17]
The resultant elemental iron from the arsenopyrite decomposition reaction [17] subsequently
dissolves either by supporting the sulphide mineral decomposition reactions [15 or 16] or by
the hydrogen evolution side reaction [18].
[18]
The involvement of the resultant iron in the reductive leach reaction has a complementary
effect on the leach process, whereas the latter negatively affects the process efficiency.
Thermodynamic calculations, as indicated by the free energy changes for arsenopyrite and
pyrite decomposition reactions, predict a much more feasible process than illustrated by the
results in Figures 2 to 3. This is in spite of the fact that the FeClSH2O potentialpH
diagram (Figure 4) shows that in the presence of the chloride ions, ferrous ions and hydrogen,
sulphide become more stable relative to pyrite. The differences are more evident when
compared to the FeSH2O system (Figure 1).
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Figure 4. The FeClSH2O Eh pH diagram ([Fe] = 0.001M; [S] = 0.01M; [Cl] = 0.01M) (Stabcal, Software)
Table III
Redox reactions and Eo values arsenopyrite, pyrite and iron systems in acidic conditions [Standard temperature =
25C and pressure]
o
Redox reaction
FeS2 + 4H+ + 2e- = Fe2+ + H2S
E/V vs SHE = -0.108 0.118pH 0.0296 log (Fe2+)(H2S)2
o
G kJ/mol
E /V vs SHE
+20.91
-0.108
+16.44
-0.085
+78.87
-0.409
FeAsS + 2H+ + 2e- = Fe + As + H2S

E/V vs SHE = -0.085 0.0591pH 0.0296 log (H2S)
Fe2+
+ 2e- = Fe
E/V vs SHE = -0.409 0.0296 log (Fe2+)
Consideration of the galvanic interactions or the galvanic cell formed by arsenopyrite and/or
pyrite with iron could possibly explain these low levels of desulphurization. In the galvanic
cell, the anodic dissolution of iron can be supported by either the cathodic dissolution of the
mineral sulphide or an inert sulphide mineral surface, which promote the iron dissolution
reaction with the evolution of gaseous hydrogen. The standard electrode potential values of
the pyrite, arsenopyrite and iron are shown in Table III. The relative potential difference
between the FeS2/Fe2+, H2S and Fe/Fe2+ (301 mV) systems hugely favours the galvanic
reaction since galvanic reactions are known to proceed at potential differences of 200 mV
(Jackson, 1986). However, pyrite has been known to remain inert even at potential differences
of more than 400 mV in the case of pyrite/sphalerite galvanic interactions.
[19]
[20]
In the above system sphalerite dissolution is cathodically supported by the oxygen reduction
reaction [21] on the pyrite mineral particles surface.
[21]
8
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Drawing parallels with the pyrite/iron system and the pyrite/sphalerite system, it can be
concluded that iron dissolution is supported by the hydrogen evolution reaction on the inert
pyrite mineral particle surface.
The arsenopyrite/iron redox system has a similar potential difference (324 mV) to that
discussed for the pyrite/iron system (301 mV). In this regard, arsenopyrite is likely to remain
partly or total inert while iron anodically dissolves on its surface supported by the hydrogen
evolution reaction. It has also been demonstrated elsewhere (Peters and Majima, 1968; Klein
and Shuey, 1978; Dreisinger and Abed, 2002) that the hydrogen evolution reaction will occur
at same potentials at which pyrite reduction takes place. They also found out that hydrogen
sulphide evolution commenced only after hydrogen evolution had begun. This possibly
explains the low levels of arsenopyrite/pyrite decomposition. While thermodynamics could
predict the feasibility of any reaction system, kinetic feasibility can be only experimentally
confirmed.
Effect of iron to concentrate ratio on the decomposition of arsenopyrite/pyrite.
Figure 5 shows the variation of arsenopyrite/pyrite decomposition with iron to concentrate
ratio at pH 0.25 and set working temperature of 105C. The data exhibit a direct linear
relationship between arsenopyrite/pyrite decomposition and iron to concentrate ratio. These
results are typical of a reaction system directly controlled by the concentration of a single
reactant (Weis, 1985). As indicated in the earlier results (Figures 2 to 3), iron to concentrate
ratio seems to have a very strong influence on the arsenopyrite/pyrite decomposition relative
to pH in the pH range studied. Although decomposition increases with an increase in iron to
concentrate ratio, the effective desulphurization levels are significantly low (<50%). Further
arsenopyrite/pyriteiron to concentrate ratio plots of the experimental results at progressively
increasing pH values (Figures 6(a) to 6(d)) show similar trends to those observed in Figure 5.
However, the effective dissolution levels progressively decrease in each subsequent figure.
The progressive increase in the levels of mineral sulphide decomposition at increasing iron
to concentrate ratio and decreasing pH was further investigated at pH values 0.1 and 0.15 and
also iron to concentrate ratios of 1.28 and 1.60. The results of these tests are plotted in Figures
7 to 8 and at pH values 0.1 and 0.15, increasing the iron to concentrate ratio from 0.96 to 1.28
improves total sulphur leached. Any further increase in iron to concentrate ratio beyond 1.28
is accompanied by marginal increases in sulphur leached. At longer leaching times of
Figure 5. Variation of %sulphur leached from arsenopyrite/pyrite with iron to concentrate ratio at different leaching
times (pH = 0.25; temperature = 105C)
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times ((a) pH = 0.34; (b) pH = 0.44; (c) pH = 0.54; (d) pH = 0.62; temperature = 105C)
300 minutes, a slight decrease in total arsenopyrite/pyrite decomposition is also observed.

While the marginal increases in the sulphide mineral decomposition can be appreciable,
further pH reductions coupled with the high temperature (105C) provide a highly corrosive
environment that will increase both capital and operational costs of the system.
Influence of arsenopyrite/pyrite decomposition on the precious metals recovery
The arsenopyrite/pyrite ores generally contain significantly large fractions of gold occurring
in submicroscopic form as finely disseminated particles or in solid solution (Iglesias, 1994,
Swash, 1988). In these ores and concentrates of arsenopyrite/pyrite, gold often deposits along
10
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Table IV
Sieve analysis of arsenopyrite/pyrite flotation concentrate and gold distribution (where dist = distribution)
Size range
(m)
Weight
(%)
Au dist
(%)
Au assay
(g/t)
Size
(m)
Cumulative
oversize (%)
Cumulative
Au dist (%)
+212
0.4
212
0.4
-212+150
6.4
3.4
35.2
150
6.8
3.4
-150+106
11.0
10.4
62.56
106
17.8
13.8
-106+75
9.6
6.1
41.84
75
27.4
19.9
-75+53
14.0
14.7
69.92
53
41.4
34.6
-53
58.6
65.4
121.76
Total
100
100
66.80
the arsenic rich grain boundaries and usually form irregular inclusions. These characteristics
define the refractoriness of many arsenopyrite/pyrite ores. The study (Chifamba, 1996;
Gudyanga et al., 1998; Mbewe, 1990; Gudyanga et al., 1999b) of flotation concentrates
utilized in the present work, proved to be refractory to direct cyanide leach. Chifamba (1996)
and Gudyanga et al. (1999b) further demonstrated that reductive decomposition of the same
flotation concentrates with desulphurization values in excess of 95% achieved very low gold
recovery. The reductive leach process dissolved iron and released sulphur as hydrogen
sulphide but elemental or metallic arsenic remained in the residue. The residues were very
refractory giving less than 30% gold extractions into the solution. In this regard, the sulphide
matrix is not solely responsible for the refractory nature of the arsenopyrite/pyrite flotation
concentrates. In fact, subsequent oxidation of the reductive leach residues realized 95% gold
extraction values. These findings concurred with the earlier mineralogical results (Jha, 1987;
Cook and Chryssoulis, 1990; Cabri et al., 1989). It is therefore clear that most of the gold, in
the arsenopyrite/pyrite flotation concentrate exists as invisible or locked gold. In this form,
total decomposition of the host mineral is required for the complete liberation and recovery of
precious metals. Reductive pretreatment does not achieve the complete decomposition of the
host sulphide mineral and therefore presents serious limitations as a pretreatment process. The
results presented in this present work focus on gold and silver deportment in the various sieve
fractions and also the response of gold extraction to desulphurization.
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Sieve analysis and precious metal deportment in the flotation concentrate

The results of the sieve analysis of the arsenopyrite/pyrite flotation concentrate and gold
distribution in various size fractions are tabulated in Table IV. The results show that over 50%
of the material is below 53 m and this size fraction contains more than 60% gold. Silver
distribution is tabulated in Table V and over 90% silver occurs in the minus 53 m fraction. In
this regard, fine grinding is inevitable to liberate both gold and silver from the flotation
concentrate. Fine to ultrafine grinding has been used to treat some refractory ores but presents
two problems, namely (i) high operational costs and (ii) does not necessarily liberate
invisible or locked gold.
In this context, chemical pretreatment methods have often taken precedence over fine to
unltrafine grinding (Wills, 1997; Yannopoulos, 1990). The failure by reductive decomposition
(Chifamba, 1996; Gudyanga et al., 1999b) to liberate the invisible or locked gold
necessitated a subsequent oxidative pretreatment process on the residue. Also, the work of
Dunn and Chamberlain (1997) revealed that the sulphide matrix is not entirely responsible of
the refractory nature of the arsenopyrite/pyrite host mineral. In fact, they realized only around
33% gold recovery after the complete removal of sulphur during pyrolysis. It therefore
follows that cyanidation of the reductive leach residues gives only a measure of the
refractoriness caused by the sulphide matrix.
Table V
Sieve analysis of arsenopyrite/pyrite flotation concentrate and silver distribution (where dist = distribution)
Size range
(m)
Weight
(%)
Ag dist
(%)
Ag assay
(g/t)
Size
(m)
Cumulative
oversize (%)
Cumulative
Ag dist (%)
+212
0.4
212
0.4
-212+150
6.4
150
6.8
-150+106
11.0
106
17.8
-106+75
9.6
1.1
5.12
75
27.4
1.1
-75+53
14.0
7.5
24.40
53
41.4
8.6
-53
58.6
91.4
71.30
Total
100
100
45.67
Figure 9. Effect of desulphurization on gold extraction during cyanidation of the arsenopyrite/pyrite reductive leach
residues
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Effect of desulphurization on gold and silver extraction

Figure 9 shows the variation of gold recovery from the arsenopyrite/pyrite reductive leach
residue during cyanide leaching. The data at zero per cent sulphur removal represents direct
cyanidation of the flotation concentrate. The desulphurization levels range between 14% and
63%. Gold extraction is limited to around 15% maximum at around 63% sulphur removal. It
is evident that the reductive decomposition does not liberate significant amounts of gold.
These results seem to concur with earlier work of Gudyanga et al. (1999b) and Chifamba
(1996), working on similar flotation concentrates, achieved in excess of 90% desulphurization
but the gold extraction was limited to around 27%. The recovery data for silver is presented in
Figure 10. Similar patterns to those obtained in Figure 9 were observed. From the particle size
analysis and precious metals deportment data (Tables IV and V), it was shown that over half
of both gold and silver occur in the fine fraction, that is, minus 53 m. When this data is
considered together with the extraction data (Figures 9 and 10), qualitative conclusions can be
made to the effect that gold exists as invisible or locked gold and as such will require the
total decomposition of the arsenopyrite/pyrite host mineral.
Conclusions
The feasibility of the reductive decomposition of the arsenopyrite/pyrite flotation
concentrate using elemental iron has been demonstrated in the hydrochloric acid medium
with the reactions governing the leach process were:
Chemical non-oxidative dissolution reaction for arsenopyrite;
Reductive dissolution for pyrite.
The reductive leach process followed an inverse relationship with pH and also a direct
relationship with iron to concentrate ratio. Desulphurization levels remained relatively
low (< 65%) at very low pH (< 0.15) and high iron to concentrate ratios (> 1.5). The
analysis of the pyrite/iron galvanic system revealed that pyrite acts as an inert cathode on
which iron oxidation is supported by the hydrogen evolution reaction. This phenomenon
satisfactorily explained the low levels of the mineral sulphide decomposition.
Cyanide leaching of the reductive leach residues showed that there was very little
improvement in both gold and silver extraction. Prior to reductive decomposition, gold
extraction was around 5% and after 63.5% desulphurization, only 15% gold extraction
was realized. In this context, the sulphide matrix was not solely responsible for the
refractoriness of the host mineral.
Figure 10. Effect of desulphurization on silver extraction during cyanidation of the arsenopyrite/pyrite reductive
leach residues
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Gold and silver exist as invisible or locked gold and as such total dissolution of the
arsenopyrite/pyrite flotation concentrate was necessary in order to access the precious
metals.
The limitations of the reductive leach process both in terms of desulphurization and
precious metals recovery makes the whole process less attractive. There is need for
coupling it with subsequent processes that will totally dissolve the host mineral and
increase the precious metals recovery.
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Int. Min. Proc. Congress, Warsaw. J. Laskowski (ed.), 1979. pp. 936956.
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PETERS, E. and MAJIMA, H. Electrochemical reactions of pyrite in acid perchlorite

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SEON-HYO, K., HENEIN, H., and WARREN, G.W. An investigation of the thermodynamics
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Reactions. vol. 1. Butterworth Heinemann. 1995a
SHREIR, L.L., JARMAN, R.A., and BURSTEIN, G.T. Corrosion 2; Corrosion control.
vol. 2. Butterworth Heinemann. 1995b.
SWASH, P.M. A mineralogical investigation of refractory gold ores and their beneficiation,
with special reference to arsenical ores. J. S. Afri. Inst. Min. Metall. vol. 88, no. 5. 1988.
pp. 173180.
WEISS, N.L. SME Mineral Processing Handbook; vol. 2. Society of Mining Engineers of the
Americal Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., New York.
1985. pp. 1324.
WILLS, B.A. 1997. Mineral Processing Technology: An introduction to the practical aspects
of ore treatment and mineral recovery. Sixth Edition. Butterworth Heinemann. 1997.
pp. 1113.
Wranglen, G. An Introduction to Corrosion and Protection of Metals. Chapman and Hall
1985. 260 pp.
YANNOPOULOS, J.C. The Extractive Metallurgy of Ggold, Van Nostrand Reinhold, New
York, 1990. pp. 79110.
Thamsanqa Mahlangu
Senior Lecturer, University of Pretoria, South Africa
Thamsanqa is a Member of the Southern Africa Institute of Mining
and Metallurgy (SAIMM), he is also registered as a Professional
Engineering (Pr Eng) with the Engineering Council of South Africa
(ECSA).
August 2004 to dateSenior Lecturer, Department of Materials
Science and Metallurgical Engineering, University of Pretoria.
June 2003 to May 2004)Post Doctoral Fellow, Mineral Processing Research Unit,
Department of Chemical Engineering, University of Cape Town
March 1995 to May 2003Research Fellow/Lecturer, Department of Metallurgical
Engineering, University of Zimbabwe
March 1994 to February 1995Minerals Process Research Engineer, Institute of
Mining Research, University of Zimbabwe.
My research focus is on the solution purification by both solvent extraction and
precipitation techniques. I have also been involved in the leaching of refractory gold ores as
well as the general hydrometallurgical processes of leaching and metals recovery.
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NGENDA, R.B., SEGERS, L., and KONGOLO, P.K. Base metals recovery from zinc hydrometallurgical plant
residues by digestion method. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and
Metallurgy, 2009.
Base metals recovery from zinc

hydrometallurgical plant residues by
digestion method
R.B. NGENDA*, L. SEGERS, and P.K. KONGOLO*
*University of Lubumbashi, Lubumbashi, Democratic Republic of Congo (DRC)
The Free University of Brussels, Brussels, Belgium
The Kolwezi Zinc Plant, in French Usines Zinc de Kolwezi
(UZK), has produced about 910 000 dry metric tons of residues
during the hydrometallurgical treatment of calcines from sulphide
zinc concentrates. The zinc hydro plant residues contain on average
19.47% Zn, 2.7% Cu, 2.1% Pb, 26.6% Fe, 0.12% Cd, 0.39% As, 157
ppm Ag, 447.8 ppm Ga, 475.4 ppm Ge, etc. This material was
dumped in five ponds in the vicinity of the plant.
The high Fe content in the ore concentrates induced important
conversion of some of zinc and copper into ferrites during the roasting
process. Those ferrites are very stable compounds, which are difficult
to leach with dilute sulphuric acid solution. Therefore, they mainly
report to the leaching residues. Hot leaching has been successfully
applied to the treatment of zinc hydro plant residues. The method,
however, presents the disadvantage of simultaneously dissolving iron
(Fe). It is then necessary to remove an important iron quantity from
solution prior to zinc and other metals recovery.
The digestion method, which has been recently developed for the
treatment of copper smelter slags, has been successfully applied to
zinc hydro plant residues. It has been found in this research work to
be most efficient to recover metal values from such materials. The
method mainly consists of 24 h digestion with half concentrated
sulphuric acid solution (48%) leading to the formation of metal
sulphates. The digested material is subsequently roasted for 2 h at
around 750C to selectively convert iron sulphate into the water
nonsoluble form Fe2O3 (hematite). After leaching with water at 40C,
nearly 98.7% Zn, 99.9% Cu, 100% Cd and only 6.4% Fe have been
recovered into solution. Most of the Fe, Ag, Pb, Ge and Ga were
concentrated in the leaching residues. Zn, Cu and Cd could be
recovered from solution by the usual techniques such as solvent
extraction with subsequent metal electrowinning or salts precipitation.
Moreover, investigations are underway with the aim of developing an
efficient method for the recovery of other metals that remain in the
digestion leaching residues.
Keywords: hydro plant residues, zinc, copper, cadmium, iron,
digestion, sulphuric acid, roasting, water, leaching.
BASE METALS RECOVERY FROM ZINC HYDROMETALLURGICAL PLANT RESIDUES
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Introduction
The Kolwezi Zinc Plant, in French Usines Zinc de Kolwezi (UZK), is located near the
town of Kolwezi in the Katanga Province of the Democratic Republic of Congo (DRC). The
plant belongs to GECAMINES, a state owned mining company operating in South Katanga
which belongs with Zambia to the African Copper Belt. Traditionally, GECAMINES is
known as one of the major copper and cobalt producers in the world. Other metal
commodities such as zinc and cadmium are also produced by the company.
The main source of zinc is the Kipushi underground mine, which is situated some 20 km
west from Lubumbashi, the capital of the Katanga Province. Polymetalic sulphide ores are
extracted from this mine, which contains important quantities of copper, germanium, gallium,
silver, etc. Differential flotation is applied in Kipushi for the production of two kinds of
concentrates: a copper concentrate, which is treated in the copper smelter of Lubumbashi for
blister copper, and a zinc concentrate, which is processed for electrolytic zinc production. The
zinc concentrate is first sent to Likasi, about 120 km north of Lubumbashi, to undergo a
fluidized bed roasting in the Shituru acid plant of the Shituru hydrometallurgical plant. While
the obtained SO2 gas is used for sulphuric acid production, the zinc calcines are sent to
Kolwezi for further processing. The town of Kolwezi is about 380 km north west from
Lubumbashi.
The chain of zinc production at GECAMINES is represented in Figure 1. In the same figure,
the UZK process is briefly described as essentially consisting of sulphuric acid leaching of
zinc calcines, solution purification and zinc electrolysis. Solution purification is performed by
Figure 1. Simplified flowsheet of zinc production at GECAMINES, RDC
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cementation of copper, cadmium and cobalt on zinc powder, with copper and cadmium being
recovered as by-products. Due to the difficult situation in the country since the nineties, the
collapse of the mining industry was the main reason why zinc production in Kolwezi went
down. The plant, which started production in 1953, has stopped since the early nineties. UZK
has been producing up to 65 000 metric tons of zinc per year, along with important quantities
of leaching residues. Approximately 910 000 dry metric tons of leaching residues were
produced and dumped in five ponds near the plant. The materials inside the ponds are about
5.2 m thick layers, 1.46 of density and 36.2% humidity.
Some of the photographs of residues ponds are shown in Figure 2. Environmental issues are
well illustrated. The residues ponds have not been stabilized, therefore crevasses have built up
and the rain has done the rest by washing these materials away to the nearby Musonoie River.
Figure 3 shows disastrous dusts that even invade offices.
Chemical analyses of UZK residues have been carried out at the Research Department of
GECAMINES in Likasi, DRC and at the Industrial Chemistry Laboratory of the Free
University of Brussels in Brussels, Belgium. The results have confirmed the presence of zinc
and iron, as well as valuable associated metals, namely copper, germanium, gallium,
cadmium, silver, lead, etc. From XRF analyses performed on pellets, the chemical
composition of UZK residues was determined as shown in Table I. This result concerns
especially the so-called old residues which were produced before the installation of the
flotation unit inside the plant for the recovery of unroasted sulphide materials. These materials
were recycled to the roasting plant.
Figure 2. Aerial view of the Kolwezi Plant and residues ponds (August 1962)
Table I
Chemical composition of UZK residues (old residues)
Elements
Assay
Ag, ppm
Ga, ppm
Ge, ppm
Cu, %
Cd, %
Fe, %
Pb, %
Zn, %
S, %
80
1100
490
2.86
0.16
32.79
2.43
16.78
4.05
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Because of the presence of heavy metals, these materials are environmentally hazardous.
Figure 3(a) shows a crevasse in pond no. 4. Part of the residues has been washed away by rain
to the neighbouring Musonoie River, which is dangerously polluted. This is clearly visible by
damage to vegetation around the ponds and the river. Furthermore, wind erosion generally
occurs in the dry season, as shown in Figure 3(b) where a storm of residues dust invades the
plants offices. This also happens to inhabited areas and especially to the plant, causing
irritation of lung and eye to local people and workers.
Table II has been calculated taking into account the average composition of UZK residues
(old and new residues) and the market value of contained metal commodities on 4 September
2008. The market value of 1 metric ton of UZK residues is therefore about US$1133.8.
From the foregoing it is clear that processing of UZK residues is both economically and
environmentally necessary. This research work therefore aims to develop an environmentally
friendly process to economically recover zinc and the associated metals. The process is
essentially hydrometallurgical in combination with some useful pyrometallurgical and
chemical operations which render it more competitive from a different point of view. It has
been initially developed for the retreatment of copper smelter slags and is now successfully
adapted to reprocessing residues from zinc hydrometallurgical plant.
(a)
(b)
Figure 3. Some views of the residues ponds: (a) Crevasse in pond no. 4, (b) Storm of residues dust to the plants
offices (August 2008)
Table II
Contained metal value of one metric ton of UZK residues (September 2008)
Assay, (average)
Quantity in 1 t residues, kg
Price, US$/kg
Recovery rate, %
Value, US$
Value, %
Economic classification
20
Zn, %
Cu, %
Cd, ppm
Ge, ppm
Ga, ppm
Ag, ppm
19.5
195
1.73
100
337.35
29.7
2
2.7
27
7.221
100
194.967
17.2
4
1 199.3
1.1993
6.393
100
7.667
0.7
6
475.4
0.4754
1500
50
356.55
31.4
1
447.8
0.4478
450
100
201.51
17.8
3
157.1
0.1571
455.2
50
35.756
3.2
5
Total
1 133.8
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Experimental
Generalities
The experimental method used in this work essentially consists of sulphatation of oxide
compounds which are present in residues followed by selective thermal decomposition of the
sulphates. Sulphatation is performed by digestion of the materials with sulphuric acid. The
products are roasted to selectively convert some sulphate compounds into water nonsoluble
oxide forms. Thereafter, leaching in water is conducted in order to dissolve metals from the
remaining sulphates.
Unlike previous studies where sulphatation of different kind of materials was performed in a
large temperature range 13, 5, 6, in this work sulphatation has been conducted at room
temperature in accordance with the conditions used by Banza for the recycling of copper
smelter slag 4. While the digestion product from copper slag was dry porous material,
digestion of UZK residues lead to a wet and pasty one, which necessitates drying at 100C
24 h. After roasting of the digested materials, most of base metals could be leached in water,
while iron preferentially went as Fe2O3 into leaching residues.
In this first phase, the research work aims to develop a process for the recovery of base
metals, especially zinc and copper, by a selective method towards iron. Purification of the
obtained metal solutions and recovery of associated metal values will be addressed later on.
Nevertheless, the behavior of these metals has also been investigated.
Equipment and reagents
Roastingthe roasting equipment essentially consists of a vertical resistance electric
furnace. It has two half shells in series with a cylindrical alumina crucible in between. A
stainless steel rod ended with four arms has helped stirring the material to roast. Roast gas
was allowed to escape into a water container prior to going to the atmosphere. The
temperatures in the material and inside the furnace were measured by thermocouples and
continuously recorded. Temperature control was performed with a PID regulator.
Leachingleaching experiments were conducted in a vessel that was externally heated by
thermostatically controlled water circulating from a water-bath. An alcohol thermometer
and an electronic pH-meter have been used to measure both temperature and pH of the
leaching pulp.
Analyticin addition to different measurements that were taken during the experiments,
numerous analyses have been performed for Zn, Fe, Cu, Ge, Ga, Cd, Pb, Ag, etc. with the
following appropriate equipment:
Crystalline phase identification on solid by X-ray diffraction (XRD) with a SIEMENS
D 500 apparatus
Semi quantitative determination of different elements in solid by X-ray fluorescence
(XRF) with a SIEMENS SRS 300 Analyzer
Chemical elemental analysis of liquid by optical emission spectrometryinductively
coupled plasma (OES-ICP) using a VISTA MPX Varian type apparatus
Grain morphology determination by JEOL JMS-6100 scanning electron microscope
(SEM)
Granulometric analysis by laser diffraction on solid using an instrument of
SCIROCCO MASTER SIZER 2000 type.
Reagentssulphuric, hydrochloric and nitric acids were used in the experiments along
with distilled water. All reagents were of analytical quality. Half concentrated sulphuric
acid solution has been identified from preliminary tests as the best digestion agent.
Therefore 48% H2SO4 solutions were used all over the test series.
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Experimental procedure
Digestion experiments were conducted by adding a given volume of 48% H2SO4 solution to a
given quantity of UZK residues, without any agitation, allowing the digestion reaction to take
place for some hours. The resulting dough was then dried overnight in an oven prior to
grinding. This product was then roasted and thereafter leached in water under agitation. After
leaching, the leach pulp was filtered and the solid cake washed until a colourless filtrate was
obtained. The filtrate was adjusted to 1 000 ml while the solid was dried overnight and
weighted thereafter. Sulphuric acid consumptions are expressed in metric ton (t) of acid per
dry metric ton of treated residues. The solids and liquids from different process operations
were analysed using the appropriate methods and apparatus.
Results
Sample characterization
Granulometric analysis of the UZK residues has shown that nearly 100% of this material is
under 106 m and about 80% of particles are smaller than 38 m. A semi quantitative
mineralogical analysis by XRD has identified the following crystalline phases that are present
in UZK residues. The proportions are expressed in % by weight.
Zinc is present as franklinite ZnFe2O4 (80.4%), willemite Zn2SiO4 (3.9%) and sphalerite
(Zn, Fe)S (1.3%)
Lead occurs as beudantite Pb(Fe2,54Al0,46)(As1,07 O4)(S0,9304)(OH)6 at 10.2%
Quartz SiO2 is also present at about 1.6%
Gypsum CaSO4.2H2O is present at about 2.6%.
The SEM-EDX studies confirmed the important presence of zinc ferrite together with small
quantities of zinc silicate, sphalerite and quartz. The presence of large quantities of
precipitated iron hydroxide or iron oxide-hydroxide phases in intimate association with SiO2
is significant. This phase is not detected by XRD analysis; it is assumed to be an amorphous
iron-silica gel. An estimate by XRD, with 5% TiO2, shows that the amorphous phase occurs at
approximately 42% in UZK residues. Due to their very small quantities, cadmium,
germanium, gallium and silver phases could not be identified by XRD analysis, the detection
limit of the used analyzer being 1%, and also because they are probably blocked in the
hydroxide phase.
Sulphatation of zinc ferrites by sulphuric acid digestion
Generalities
Metallic oxides that are present in UZK residues are essentially ferrites with the general
formula MeFe2O4 where Me represents the metallic cation Zn, Cu, Cd, etc. Digestion with
sulphuric acid is conducted by allowing the mixture of acid with the material to stand for a
long time, without agitation. The acid enters the matrix of ferrite to transform its structure by
liberating the metals in the form of soluble sulphates according to the general Reaction [1].
[1]
Iron is also converted to the soluble sulphates during this process.
Digestion products that have been dried for 24 h at 100C in oven became hard.
Microscopic images of grain morphology for the raw material and the dried and ground
digested can be seen in Figure 4. Grain attack by acid is clearly visible in the figures. The
white areas are dominated by acid presence. Iron sulphate precipitate7 is also present.
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(a)
(b)
(c)
Figure 4. Morphology of UZK residues grains before (a) and after digestion (b), (c) a white zone of high sulfuric acid
quantity. Digestion conditions: 1 t H2SO4/t residues, S/L = 0.9 [g/ml], 24 h
Figure 5. Solubilization of base metals from UZK residues in function of the digestion time. Test conditions: digestion
(1 t H2SO4/t residues, S/L = 0.9 (g/ml)), if dry sample (100C, 24 h), leaching (water, 2 h, 40C)
Impact of the digestion time

In this series of experiments, digestion time has been varied from 2 to 72 hours, while acid
consumption remained constant at 1 t H2SO4/t residues, which is theoretical quantity for
complete sulphatation of all the contained metals. The ratio solid/liquid remained at 1/1.1 or
0.9 g/ml unchanged in all test series.
XRD analyses performed on materials from different digestion times have confirmed
sulphatation of zinc and iron into compounds such as gunningite ZnSO4.H2O, rhomboclase
FeH(SO4)2.4H2O and hohmannite Fe(H2(H2O)4((SO4)2O).4H2O. These investigations also
revealed that after 2 to 4 h digestion the treated material contained rhomboclase to 30% and
gunningite to 40%. These proportions changed to 60% and 25% respectively when the
digestion time was increased beyond 4 h.
Leaching in water of digestion cake at different times could solubilize zinc, copper and iron
to approximately 70% irrespective of the digestion time. Metal solubilization, which is the
proportion of the dissolved metal, generally increased with digestion time, as shown in
Figure 5. The digested materials were analysed before drying on wet samples and after drying
at 100C for 24 h.
From 2 to 4 h a sharp increase in the yield of leaching was observed for all metals, except
for lead. This tendency slowed after 4 h. It was observed that metal leaching was less on wet
samples compared to the same samples after they have been dried, suggesting that the
sulphatation process still continues during sample drying in an oven. Therefore, drying of the
digested material renders the subsequent leaching operation more effective.
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From the above, it has also been observed that zinc and iron sulphatation has not been
completed, due to the presence of some quantities of zinc ferrite and sulphide which could not
react with the acid. Franklinite ZnFe2O4 and sphalerite (Zn,Fe)S have been identified by XRD
analysis in all samples which were obtained as leaching tests residues. Leaching of lead
remained relatively very low at about 5%, due to its low solubility limit in sulphuric acid
solutions. Thus, anglesite PbSO4 was also present in the new leaching residues.
Semi quantitative XRD analysis unambiguously identified franklinite as the main compound
of the leaching residues (75%), followed by anglesite (15%), quartz (7%) and sphalerite (4%).
Jarosite (K,H 3O)Fe 3(SO 4) 2(OH) 6 has been rarely identified in leaching residues from
materials which have been digested for more than 4 h.
Impact of sulphuric acid consumption
The impact of change in sulphuric acid consumption during the digestion process has been
investigated in the range 0.6 to 2.0 t H2SO4 / t UZK residues (Figure 6). Increase of acid
consumption generally induced an increase in leaching efficiency.
At high acid consumption from 1.7 to 2.0 t /t, a pasty product was obtained, which was in
turn difficult to dry. This product was probably silica gel, which covered the solid material
particles with the effect of slowing down the sulphatation kinetics.
From both metallurgical and economic reasons, a specific consumption of 1 t H2SO4/t UZK
residues seemed to be a good compromise for the practice. Sulphatation efficiency was high
and the resulting product easy to manipulate. In these conditions, metal leaching was
performed to 79.5% Zn, 87.4% Cu and 82.8% Fe. Similar phases as those observed in the first
series of experiments have been identified, but the proportion of soluble zinc and iron
increased with increasing acid consumption.
Investigation into thermal decomposition
Thermogravimetric, differential thermal analyses and mass spectrometry
Iron conversion from the soluble sulphate compound to the nonsoluble oxide one occurs at
high temperature according to Reaction [2]7, 8:
Figure 6. Solubilization of base metals from UZK residues in function of sulphuric acid consumption. Test conditions:
Digestion (1 t H2SO4/t residues, S/L = 0.9 (g/ml), if dry sample (100C, 24 h), leaching (water, 2 h, 40C)
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[2]
Sulphates of other metals also undergo thermal conversion in a similar way.
Thermogravimetric and differential thermal analyses have been conducted in previous works
together with mass spectrometry in order to determine the optimum temperature range where
selective iron sulphate decomposition is most effective7, 8. The selected range of roast
temperature was between 650C and 850C. Although different from the results in some other
works1014, this temperature interval corresponds to that given elsewhere9. In fact, UZK
residues contain a number of complex sulphates which have been determined by XRD7, 8,
while the literature deals with pure sulphates.
Roasting experiments
The dried and ground digested materials were roasted under smooth agitation in the roasting
installation described above. The impact of roasting temperature and time has been
investigated in this series of experiments.
a) Influence of roasting timethis test series has been conducted at 750C on UZK residues
after digestion (1 t H2SO4/t residues, 24 h), drying in oven (100C, 24 h) and grinding.
The roasting time was varied in the range 1 to 4 h. The influence of the roasting time on
metal leaching in water is shown in Figure 7. It has been observed that within 1 h roasting
iron dissolution was still important. This was essentially due to insufficient conversion of
iron sulphate into oxide compound. After 1 h roasting, iron leaching continuously
decreased, as result of increasing formation of the nonsoluble hematite, while copper,
cadmium and zinc solubilization increased.
XRD analyses have revealed that the proportion of mikasaite (Fe2(SO4)3), which is
about 57% of crystalline phase in the digested materials, continuously decrease to 37%
after 1 h roasting, 14% after 2 h to reach about 2% after 4 h, in favour of hematite
(Fe2O3) increasing formation.
According to literature6, there are two main phenomena which occur during the roast
process. In the first place, dehydration is happening thus creating micropores in the
Figure 7. Leaching recovery of base metals as function of the roast time. Operating conditions: digestion (1 t H2SO4/t
UZK residues, S/L = 0.9 (g/ml), 24 h), drying (100C, 24 h), grinding, roasting (750C), leaching (water, 40C, 2 h)
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material. The other is a sulphatation by SO3 which could come into contact with the
rest of the minerals through the micropores created by dehydration. This phenomenon
is observed at a temperature of about 600C.
b) Influence of roasting temperaturethis test series has been conducted for 2 h in similar
way to the previous one by varying the roast temperature from 650 to 850C. The roasted
materials have then been used in leaching tests.
The influence of the roasting temperature on leaching efficiency is shown in Figure 8.
Leaching recovery of copper, zinc and cadmium remained constant until 770C for
copper and zinc and until 800C for cadmium. This result clearly indicated that copper
and zinc were stable until the temperature of 770C was reached. Thereafter, their
sulphates are progressively converted nonsoluble oxide compounds.
On the other hand, leaching recovery of iron sharply decreased from 79% at 650C to
reach 34% at 700C, 6% at 770C and became zero at 800C, which clearly indicated
that iron sulphates were completely converted. The best conditions for selective iron
conversion were reached between 750C and 770C. Beyond this range, some stable
iron compounds of ferrite type were formed with zinc and copper, as confirmed by
XRD analysis.
Summary and conclusions
The method used to investigate the treatment of residues from the Zinc Hydro Plant of
Kolwezi essentially consists of digestion of the materials with a 48% H2SO4 solution without
agitation or heating. The test material has been used as received (100% de 106 m). After
digestion, drying and grinding of the obtained compact product, roasting was performed prior
to leaching with water. Zinc, copper and cadmium were leached into solution, while iron
preferentially remained in the leach residues. The process is summarized in the simplified
flow sheet shown in Figure 9. It is clear that the SO2 roast gas can be used for the manufacture
of sulphuric acid.
Digestion of UZK residues gave a wet product, unlike the result obtained in previous works
on copper smelter slags from Lubumbashi4, where dry porous products have been obtained. In
Figure 8. Leaching recovery of base metals as a function of the roast temperature. Operating conditions: digestion (1
t H2SO4/t UZK residues, S/L = 0.9 (g/ml), 24 h), drying (100C, 24 h), grinding, roasting (750C), leaching (water,
40C, 2 h)
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Figure 9. Proposed flowsheet for the retreatment of UZK residues by digestion method
the present study, it was therefore necessary to dry and grind the material after digestion.
Furthermore, an increase in sulphatation occurs during the drying process. Thus, sulphatation
is a thermally activated reaction13, 56.
Total sulphatation by digestion with sulphuric acid was difficult to achieve in the prevailing
test conditions. Fortunately, it was discovered that sulphatation continues under the direct
action of SO3 during the drying operation. Complete sulphatation is therefore possible.
Fluidized bed roasting can hardly be conducted with such fine materials like those obtained
after digestion which have been previously subject to drying and grinding. Roasting in a fixed
bed with smooth agitation of the material might be the best industrial practice. In this case,
using a Wedge type roaster along with careful handling of fine materials would be
recommended.
Following the above described outline, leaching in water could be performed to 98.7% Zn,
99.9% Cu, almost 100% Cd and only 6.4% Fe under the best test conditions as given in the
flowsheet.
Iron preferentially remained as hematite (Fe2O3) in leaching residues, which assayed in
average 0.4% Zn, 17 ppm Cu, 0% Cd, 3.8% Pb and 49.3% Fe. These materials may be
considered as Ge (800 ppm) and Ga (1 660 ppm) concentrates containing most of the silver.
Subsequent studies will enable the development of a process for the recovery of these
valuable metals.
The leach solutions on average contained 15 g/l Zn, 2.5 g/l Cu, 1.7 g/l Fe and 134 mg/l Cd.
After solutions purification and concentration by appropriate methods, the contained valuable
metals could be recovered by salt precipitation or metal electrowinning.
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From the above, it can be concluded that the described digestion method has a significant
advantage, since elaborate iron precipitation from solution was no longer necessary, this metal
being selectively discarded into residues before leaching. Compared to the hot leaching
method, this technique has the additional advantage of the opportunity to recycle the SO2
roast gas for sulphuric acid production. Recycling of the generated acid would substantially
reduce fresh acid consumption, thereby improving the process viability.
Acknowledgements
The authors appreciate the support from the Gecamines Research Centre in Likasi, DRC. The
fruitful cooperation between the Free University of Brussels, Belgium, and The University of
Lubumbashi, DRC, is gratefully acknowledged.
References
1. SULKA, L.B., PANDA, S.C., and JENA, P.K. Recovery of cobalt, nickel and copper
from converter slag trough roasting with ammonium sulphate and sulphuric acid,
Hydrometallurgy, vol. 16, no. 2, June 1986, pp. 153165.
2. FREEMAN, G.M. and NIGHTINGALE, D.E. Treatment of zinc plant leach residues for
recovery of contained metals values, European Patent Application, 25 09 1979.
3. STEVEN, J.A. Extraction method for non ferrous metals, United States Patent, May 25,
1976.
4. BANZA, A.N. Processes for the recycling of copper smelter slag from Lubumbashi/D.R.
Congo, (Doctorale Thesis in German), Cuvillier Verlag Goettingen, Goettingen 2001
(ISBN 3 89873 151 0)
5. CUNEY, A. and FATMA, A. Recovery copper, cobalt and zinc from copper smelter and
converter slags, Hydrometallurgy, vol. 67, 2002, pp. 17.
6. TURAN, M.D., ALTUNDOGAN, H.S., and TUMEN, F. Recovery of zinc and lead from
zinc plant residue, Hydrometallurgy, vol. 75, 2004, pp. 169176.
7. NGENDA, R.B. Etude de mise en solution slective du zinc et du cuivre contenus dans
les rejets des Usines Zinc de Kolwezi par la technique de digestion acide, Mmoire de
spcialisation, Services Matires et Matriaux, Facults des Sciences Appliques,
Universit Libre de Bruxelles, Janvier 2006.
8. NGENDA, R.B., SEGERS, L., and P. KONGOLO K, Dcomposition thermique slective
des sulfates forms lors de la digestion acide des rejets des Usines Zinc de Kolwezi,
Annales du ple Mines-Gologie-Universit de Lubumbahi 1, 2007. pp. 97104.
9. SIRIWARDANE, R.V., POSTON JR., J.A., FISHER, E.P., SHEN, M.S., and MILTZ,
A.L. Decomposition of sulphates of copper, iron (II), iron (III), nickel and zinc: XPS,
SEM, DRIFTS, XRD and TGA study, Applied Surface Science, vol. 159, 1999,
pp. 219236.
10. KOLTA, G.A. and ASKAR, M.H. Thermal decomposition of some sulphate,
Thermochimica Acta, vol. 11, 1975, pp. 6572.
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11. HILDENBRAND, D.L., LAU, K.H., and BRITTAN L.D. Mechanistic aspects of metal
sulphate decomposition process, High Temperature Science, vol. 26, 1990, pp. 427440.
12. NARAYAN, R.N., TABATABAIE-RAISSI, A., and ANTAL, M.J. A study of zinc
sulphate decomposition at low heating rates, Ind. Eng. Chem. Res., vol. 27, 1988,
pp. 10501058.
13. MU, JJ. and PERIMUTTER, D.D. Thermal decomposition of inorganic sulphates and
their hydrates, Ind. Eng. Chem. Process, Des. 20, 1981, pp. 640646.
14. TAGAWA, H.H. and SAIJO, H. Kinetics of thermal decomposition of some transition
metals sulphates, Thermochimica Acta, vol. 91, 1985, pp. 6567.
Kitala Pierre Kongolo
University of Lubumbashi, Polytechnic Faculty, Lubumbashi,
Democratic Republic of Congo (DRC)
Doctoral Research, 19831989
Technical University of Clausthal, Germany, Institute for Mineral Processing,
Department Flotation and Chemical Processes, Research in Hydrometallurgy.
Research cooperation with the Technical University of Munich, Physic
Department (Laboratory of Mossbauer Spectroscopy).
1989Qualification as Doctor of Engineering (Hydrometallurgy) at the Technical University of
Clausthal, Germany.
Mining industry, since 1990
Gecamines (19902006):
Research Centre in Likasi, DRC, Senior Research Engineer (19902000, Mineral Processing), Research
Director (20012006, Hydrometallurgy).
Plant manager of Kambove and Kakanda Concentrators (20002001).
Chemaf: Director of Operations (20062007).
Groupe Bazano: Consulting Engineer (since April 2008).
Academic positions, since 1993
University of Lubumbashi, Polytechnic Faculty, Department of Metallurgy
Associate Professor (19952001)
Professor (20012007)
Ordinary Professor (2007to date)
Deputy Faculty Dean for Research (since 1997).
International activities, since 1995
Cooperative research with the Technical University of Clausthal, Germany (since 1995), the Free
University of Brussels, Belgium (since 2003).
External examiner at the University of Dar Es Salaam, Tanzania (20042007).
Invited lecturer at International Symposium on the Industrial Application of the Mossbauer Effect,
ISIAME 96, November 1996, Johannesburg, South Africa, The extractive metallurgy of gold.
Chairman of session on solvent extraction/electrowinning at XX. International Mineral Processing
Congress, September 1997, Aachen, Germany.
Reviewer (2006), journal Hydrometallurgy, Elsevier Publisher.
Publications
Numerous publications in international journals (Metallurgical Transactions, Hyperfine Interactions,
Hydrometallurgy, Minerals Engineering, etc.) in the fields of mineral processing, hydrometallurgy,
Mossbauer spectroscopy and surface chemistry.
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ROBERTSON, S.W. and VAN STADEN, P.J. The progression of metallurgical testwork during heap leach
design. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and Metallurgy, 2009.
The progression of metallurgical testwork during

heap leach design
S.W. ROBERTSON and P.J. VAN STADEN
Mintek, Randburg, South Africa
The depletion of favourably located and higher-grade mineral

deposits, combined with more favourable metal prices and higher
capital costs, has stimulated research into heap leaching of lower
grade ores and wastes. This has resulted in renewed interest in heap
leaching of uranium ores, and in the development of processes for the
bacterial heap leaching of low-grade chalcopyrite ores and the acid
heap leaching of nickel laterites. A complete programme of heap
leach testwork typically involves a sequence of bottle roll tests and
column tests, followed by piloting on test heaps. The initial testwork
is aimed at determining the amenability of the ore to heap leaching,
which depends on the characteristic of the ore with respect to porosity
and permeability to leach liquor, acid consumption, metal recovery
and percolation. Subsequent phases of the testwork focus on the
development of the process design criteria for the treatment of the ore.
Basic techno-economic models have also been developed as a tool for
the initial estimation of heap leach viability. Mintek has also
developed in-heap monitoring probes, coupled to an operator
guidance system, in order to assist the operator in achieving optimal
conditions for bacterial growth and heat preservation during pilotplant operation.
Introduction
Heap leaching is used extensively for the processing of copper and gold ores. Low capital and
operating costs and simple atmospheric leach processes make heap leaching suitable for lowgrade ores and small deposits. Disadvantages include low recoveries, long ramp-up times,
large footprint and acid-mine drainage of wastes3. Factors that may make ores unsuitable for
heap leaching are poor percolation due to the presence of swelling clays, and high gangue
acid consumptions. Percolation may be improved by agglomerating with acid or binder, and
by minimizing ore compaction during stacking, for example by using conveyors instead of
trucks.
For ores that contain silicate gangue minerals, it may be possible to reduce gangue acid
consumption by introducing the lixiviant more slowly, for example, by using higher irrigation
rates at lower lixiviant acid strengths. However, it is usually not possible to achieve an
THE PROGRESSION OF METALLURGICAL TESTWORK DURING HEAP LEACH DESIGN
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economically viable optimum between metal extraction and acid consumption if the ore
contains highly reactive gangue such as carbonates. For high acid-consuming uranium ores, it
is more economical to use sodium carbonate as lixiviant.
Nickel sulphide and laterite ores usually have high acid consumptions compared with
copper ores, but this is offset by the higher nickel value. The cost of acid typically comprises
about 40% of the total operating cost for nickel laterite ores, so acid needs to be produced on
site and heaps need to be operated counter-currently to optimize acid utilization.
Bacterially assisted heap leaching has been applied extensively for secondary copper
sulphide ores, where the bacteria assist in the oxidation of ferrous iron and sulphur species. If
the ore contains pyrite, bacterial oxidation can be utilized to generate acid and exothermic
heat, which may be preserved within the heap through the appropriate manipulation of
aeration and irrigation rates9. Higher temperatures will improve kinetics for more refractory
species such as chalcopyrite, which do not give economic leach rates at ambient temperatures.
This paper discusses the metallurgical testwork sequence for heap leach design, with
specific reference to chalcopyrite, uranium and nickel laterite heap leaching.
Progression of metallurgical testwork
Figure 1 shows the typical progression of metallurgical heap leach testwork through
subsequent phases of roll bottles, column tests and pilot heaps. Since the duration and cost of
testwork increases progressively, it is beneficial to optimize as many parameters as possible
earlier on in the testwork programme.
Table I gives a summary of outputs for various testwork stages. Roll bottle or shake-flask
tests are normally performed first, to obtain an initial indication of maximum achievable
extraction and acid consumptions. However, acid consumptions are normally overestimated in
rolling bottles, hence the acid consumption results must be treated as semi-quantitative. The 1
metre columns provide more accurate extraction and acid consumption data under trickle bed
Figure 1. Staged approach to heap leach testwork and design
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Table I
Metallurgical testwork programme
Stage
Outputs
Approximate duration days
Roll bottle,
shake-flask or
stirred tank
benchmark recoveries and reagent consumptions

effect of mineralogy (laterites)
effect of crush size, lixiviant strength, redox and temperature
Cu oxides 7 D
Cu sec. sulphides 14
Cu prim. sulphides 30
Ni laterites 14
1 m columns
identify severe percolation problems

maximum extraction and reagent consumptions under
percolation-contact mode
optimal agglomerate moisture content
isothermal or temperature adjustment with heat model
aeration, inoculation and bacterial activity
Cu oxides 50 d
Ni laterites 80150
6 m columns
extraction kinetics, reagent consumptions under typical lift

height of heap
impurity build-up in recycled solutions
more reliable simulation of compaction and percolation
neutralizing potential of ore for counter-current operation (laterites)
effect of bacterial activity on temperature behaviour predicted
by heat model
Cu oxides 150200
Cu sec. sulphides 250-300
Ni laterites 250500
Test heaps
best judgement on heap permeability in the absence of column

side support
dynamic temperature variation as a result of bacterial activity
demonstrated
net reagent consumption and impurity build-up in closed circuit
with recovery step
counter-current operation to maximize copper recovery and
minimize gangue reaction
Cu oxides 150-200
Ni laterites 250500
conditions, as well as an initial indication of possible severe percolation problems. But for a
given irrigation rate (in terms of l/h/m2), the extraction kinetics from the column of ore (in
terms of % extraction per day) are accelerated compared to the extraction kinetics that will be
obtained from a taller heap of ore.
Since the kinetics and pregnant leach solution composition vary with lift height in
commercial size heaps, a more realistic indication of leach kinetics and impurity build-up is
obtained in taller columns, at a lift height equivalent of an actual heap (typically 6 metres).
Although the taller columns provide an indication of slumping and permeability, the side
support from the column may result in less compaction than will be observed on an actual
pilot or commercial heap. Therefore, whereas solution build-up in columns provide a definite
indication that percolation problems will be experienced at larger scale, trouble-free
percolation in columns unfortunately does not guarantee successful percolation for the given
irrigation rate on the commercial heaps.
As shown in Table I, the leach cycle increases from 150200 days for oxides to 250300
days for secondary sulphides and 300365 days for primary copper sulphides (chalcopyrite).
In order to demonstrate the effect of leach cycle on the pad area and mining rate, a production
calculation is shown in Table II for a heap leach plant producing 20000 tonnes per annum
copper, with a head grade of 0.6% copper. The chalcopyrite material has a longer leach cycle
and lower recovery, resulting in bigger pad area and ore processing rate. This will result in
larger capital costs for the mining, crushing and leaching sections.
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Table II
Effect of leach cycle on pad area and mining rate
Cu production
Cu grade
Leach cycle
Cu recovery
Mining/stacking rate
Ore mass under leach
Stacked bulk density
Ore volume under leach
Lift height
Surface area under leach
Oxide
Sec. sulphide
Prim. sulphide
Units
20 000
0.60
200
80.0
4 166 667
2 283 105
1.8
1 268 392
6.0
211 399
20 000
0.60
280
80.0
4 166 667
3 196 347
1.8
1 775 748
6.0
295 958
20 000
0.60
365
60.0
5 555 556
5 555 556
1.8
3 086 420
6.0
514 403
tpa Cu
% Cu
days
% Cu leached
tpa ore
tonnes
t/m3
m3
m
m2
Table III
Operating stages during heap leach cycle
Stage
Conditions
Purpose
High irrigation rate, moderate acid strength

(ILS), GL: GA ~ 10
Create suitable pH gradient for

bacterial activity
Early leach
Moderate irrigation rate, moderate acid strength

(ILS), GL: GA ~ 5
Maximize copper recovery, limit gangue reaction,

promote bacterial activity, preserve heat
Late leach
Low irrigation rate, strong acid (raffinate)
Maintain the copper tenor while the leach rate is slowing
High irrigation rate, low copper tenor (raffinate)
Recover entrained copper prior to heap closure
pH reduction
Rinse
Low grade chalcopyrite heap bioleaching

Chalcopyrite is the most abundant copper mineral, comprising about 70% of the worlds
known copper reserves. Many low-grade reserves are untreatable with conventional heap
leaching due to the slow heap leach kinetics at ambient temperatures. Since the leach kinetics
improve with temperature, it is possible to improve kinetics by generating exothermic heat
through the bacterial-assisted conversion of sulphide species (most importantly pyrite), and to
preserve the heat within the heap through the appropriate manipulation of aeration and
irrigation rates. The following approach is followed during metallurgical testwork for
chalcopyrite ores:
Column tests are performed in conjunction with a heat balance, which simulates the axial
temperature profile in the core of a heap in the absence of side effects. Daily measured
oxygen consumption data are input into the heat balance, and the temperatures in each
jacketed column section is adjusted to simulate dynamic heap temperature behaviour.
Columns are inoculated and aerated to promote bacterial activity
The process is demonstrated on test heaps, typically 25000 tonnes, 40 m x 60 m x 6 m.
Crushed ore is mixed with acid and inoculum in an agglomeration drum. The base of the
pile is fitted with aeration pipes connected to a low pressure blower. The pilot heap is
operated in closed circuit with a solvent extraction/electrowinning plant
The heap life cycle is divided into distinct stages, in order to meet the combined
objectives of maximizing copper recovery, minimizing gangue reaction and creating
conditions for bacterial growth and heat preservation. Each stage has its own set of
criteria for the control of the irrigation rate (GL, kg/m2/h), aeration rate (GA, kg/m2/h) and
lixiviant acid strength as described in the Table III. New heaps are irrigated with
intermediate leach solution (ILS) whereas old heaps are irrigated with return raffinate
from the solvent extraction plant.
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Mintek has developed in-heap probes (lysimeters), which allow solution and gas-phase
samples to be taken for daily analysis at various depths in the heap. The lysimeters are placed
in augured holes, and are also fitted with thermocouples. An example of the development of
pH, redox and temperature profiles in the core of the heap as measured by the in-heap probes
is shown in Figure 2. The reduction in pH gradient in the heap creates suitable conditions for
bacterial growth. The increase in bacterial activity is evidenced by a corresponding increase in
redox potential and temperature. Temperatures of about 40C were maintained in the bottom
half of the heap.
The lysimeter measurements assist the site engineer in making decisions concerning
changes in irrigation and aeration rates, and changeover between subsequent stages in the
leach cycle. Mintek has developed software for logging the daily measurements and assay
results for multiple heaps. Each day, the software produces a report of the valve and flow
adjustments required on the plant, as well as a log sheet for the measurements and assays
required for the day. This operates in conjunction with a particluar irrigation manifold and
valve arrangement, which simplifies the task of visualizing the daily irrigation valve
adjustments required, which is illustrated on the daily report. The heap software can also be
applied to oxide and secondary sulphide ores.
Uranium ore
The rise in uranium prices has resulted in renewed exploration, expansion and construction of
new projects such as Langer Heinrich (Namibia), Keyelekera (Malawi), Ezulwini (South
Africa), and Buffelsfontein (South Africa). There is also renewed focus on exploitation of
previously uneconomical ores and wastes such as Rossing (heap leaching of low grade ore)
and Buffelsfontein (treatment of pyrite-gold tailings). Expansion through heap leaching is
being investigated at Ranger (Australia) and construction of a heap leach plant at Arlit
(Niger)4, amongst others.
Figure 2. Progression of Eh, pH and temperature in bioheap core
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Figure 3. Heap leach control software
Table IV
Common uranium minerals
Leachable oxides
Mineral
Formula
Operation
UraniniteTL
PitchblendeTL
+4
+6
U 1-xU xO2+x
Rossing, Dominion Reefs, Ezulwini

Narbalek, Kintyre
UO2 to UO2.25
Leachable silicates
CoffiniteTL
U(SiO4)1-x(OH)4x
Rystkuil
Refractory complex oxides
BranneriteTr
DaviditeTr
(U,Ca,Fe,Th,Y)(Ti,Fe)2O6
3+
(La, Ce, Ca)(Y, U)(Ti, Fe )20O38
Elliot Lake
Radium Hill
Hydrated oxides
BecquereliteHL
GummiteHL
7UO2.11H2O
UO3.nH2O
Silicates
UranophaneHL
UranothoriteHL
SklodowskiteHL
Ca(UO2)2Si2O7.6H2O
(UTh)SiO4
(H3O2)Mg(UO2)2(SiO4)22H2O
Rossing
Dominion Reefs
Vanadates
CarnotiteHL
TyuyamuniteHL
K2(UO2)2(VO4)2.3H2O
Ca(UO2)2(VO4)2.8H2O
Langer Heinrich
Phosphates
TorberniteHL
AutuniteHL
Cu(UO2)2(PO4)2.10H2O
Ca(UO2)2(PO4)2.11H2O
Rum Jungle
Rum Jungle
Carbonates
SchroekingeriteHL
NaCa3(UO)2(CO3)3(SO4)F.10H2O
Arsenates
ZeunariteHL
Cu(UO2)2(AsO4)2.10-12H2O
Hydrocarbons
ThucholiteTL
HLhexavalent readily acid leachable without oxidation

TLtetravalent readily acid leachable with oxidation
TRtetravalent refractory
Uranium occurs in primary (tetravalent) and secondary (hexavalent) forms. Primary

minerals require oxidation during hydrometallurgical extraction. The Table IV provides a
summary of common uranium minerals. Uranium ores are usually processed by atmospheric
tank leaching, pressure leaching, in situ leaching or heap leaching. Pressure leaching and
bacterial heap leaching are applied where oxidation of pyrite is required, such as the
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Buffelsfontein pyritic gold tailings project or Urgeirica heap leach (Portugal). Whereas tank
leaching requires crushing and milling steps, heap leaching is performed on crushed or run of
mine ore.
The most common leaching medium is sulphuric acid with ferric sulphate as oxidant (e.g.
Rossing). Ferric sulphate is regenerated by addition of an oxidizing agent such as MnO2,
H2O2, or NaClO3. Where the ore has high gangue acid consumption (>90 kg/t), leaching is
performed in carbonate medium (e.g. Langer Heinrich tank leach, Trekkopje heap leach).
Uranium recovery from the leach solution is usually performed by solvent extraction, ion
exhange, a combination of solvent extraction and ion exhange (Eluex/Bufflex), or direct
precipitation. Uranium is precipitated from the eluate or strip liquor and calcined to produce
U3O8. Figure 4 shows the normal sequence for hydrometallurgical processing of uranium ore.
Most uranium heap leach plants have been satellites to existing operations, for example for
treatment of low-grade waste with acidified ferric iron bleed streams (e.g. Rossing, Narbalek),
and have been applied to ores with grades of below 0.1% U3O83. However, current high
uranium prices and plant capital costs makes uranium heap leaching attractive as a primary
(greenfield) process (e.g. Trekkoppje, Arlit, Chirundu), provided reagent costs can be kept
low.
For a standalone operation, ferric sulphate may be added as reagent (typically 0. g/L Fe,
ORP 475425 mV), or sufficient iron may be leached from the gangue minerals or by
leaching pyrite acid plant calcine. A suitable oxidizing agent such as hydrogen peroxide,
sodium chlorate, pyrolusite, or caros acid is added to regenerate the ferric iron.
Bacterial heap leaching requires minimal additional capital cost, namely the installation of
aeration piping and low pressure blowers. If the ore already contains pyrite, it may be possible
to reduce the overall acid consumption by bacterial oxidation of the pyrite, which also results
in exothermic temperature increase in the heap which may improve kinetics. At the same time
ferric iron is regenerated by bacterial oxidation in the pile, resulting in reduced cost of
oxidizing agent. The bacterial action throughout the heap maintains the iron in the ferric form,
and since ferric iron precipitates above pH 2 (effectively yielding acid during precipitation),
the pH throughout the heap is more rapidly buffered at a lower pH value when there is
Figure 4. Uranium processing sequence
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bacterial activity in the heap. Minerals indicated in Table IV as readily leachable are acid
leached at pH 1.52.0 and 3560C, which are suitable conditions for bioleaching. Minerals
indicated in Table IV as refractory require higher temperature (6080C) and stronger acid
(up to 50g/L).
Figure 5 illustrates the effect of bacterial leaching versus chemical leaching for a
uraninite/uranophane ore. Tests were performed in 1 metre columns, irrigated with 0.5 g/L Fe
at pH 1.6. For the chemical leach column, the redox potential in the feed was maintained at
470 mV with hydrogen peroxide. For the bacterial leach, 2% pyrite was mixed into the ore,
and the column was aerated and inoculated. The redox potential of the feed solution was
initially adjusted to 450 mV, whereafter the redox in the recirculating solution was allowed to
increase. Whereas the leach kinetics and uranium recoveries were similar, the acid
consumption (measured as the acid in the feed solution minus the acid in the drainage) was
about 35% lower for the bacterial column.
Nickel laterite ores
Laterites are usually processed with ammonia or high pressure acid leaching (suitable for
limonites with high Fe, low Mg, low Si), or with smelting for ferronickel production (suitable
for saprolites with high Mg, high Si). Whereas laterites were previously thought to be
unsuitable for heap leaching due to the high clay content and acid consumption, the
demonstration of a nickel laterite heap leach pilot plant in Caldag, Turkey, has resulted in a
number of subsequent projects, e.g. Jump-Up dam, Canegrass and Murrin-Murrin. However,
to date only one brownfield project is operational at Murrin Murrin. Laterites normally have
very high acid consumptions (typically 500 kg/t), so a low-cost acid source or on-site acid
plant is required. The leach solution also contains high levels of impurities such as iron that
need to be precipitated prior to nickel recovery. The limonite fraction normally has poorer
leach kinetics, so heap leaching may be suitable as an add-on to an existing PAL process, for
example heap leaching of a saprolite fraction to neutralize the pressure acid leach liquor.
Figure 6 shows the linear behaviour that was observed between nickel recovery and acid
consumption in column tests performed on nickel laterite ore. This means that faster nickel
recoveries can be achieved by increasing the rate at which acid is added, which may be
achieved by speeding up the irrigation rate, or by increasing the acid strength in the lixiviant,
or by admixing a large acid dosage to the ore before stacking of the heaps.
Figure 5. Bacterial versus chemical leaching of uranium ore
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Figure 6. Acid consumption vs. nickel recovery
Figure 7. Proposed heap leach plant schematic
Figure 7 shows a proposed nickel laterite heap leach arrangement. The plant is divided into
a series of old heaps and fresh heaps. In order to maximize leach kinetics, a high acid
strength (75120 g/L) is used over the old heaps. New heaps coming into production are
irrigated with intermediate leach solution draining from the old heaps and the acid is
neutralized over the fresh heaps. Any residual acid remaining in the drainage from the fresh
heaps has to be neutralized prior to nickel hydroxide precipitation, resulting in increased
neutralizing agent and acid costs. An important part of column testwork is therefore to
determine the neutralizing potential of the fresh heaps, so that the acid strength can be
maximized, while at the same time ensuring complete neutralization of residual acid over the
fresh heaps.
Figure 8 shows the experimental determination of the acid neutralizing potential of the
laterite material in 6 metre columns. In order to simulate the arrangement in Figure 7, the
column testwork was divided into fresh heap and old heap stages. Initially the heap was
irrigated at 50 g/L acid, to simulate neutralization of intermediate leach solution (ILS) over
fresh heaps. As indicated, this acid concentration was completely neutralized over the fresh
ore. After 80 days, the feed acid concentration was increased to 75g/L, and later to 100 g/L
and 150 g/L, to optimize the acid concentration for the old heaps. The aim was to produce
drainage with an average acid content of 50 g/L over the entire old-heap part of the leach
cycle of the ore.
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Figure 8. Determination of neutralizing potential of ore in 6 metre columns
From the date in Figure 8, it appears that an average of 50 g/L acid in the drainage of old
nontronite and saprolite ores is obtained by irrigating it with 100 g/L acid solution, and to
obtain the same on composite material (consisting of limonite, nontronite and saprolites)
irrigant acid strength of 100 to 150 g/L is required. These figures provided the first iterations
of the liquor and acid balances over the process.
In addition to chemical acid leaching, there are also two potential routes for bioleaching of
laterites:
In order to save on the capital cost of an acid plant, elemental sulphur may be mixed in
with the ore during agglomeration, and sulphuric acid may be generated bacterially
within the heaps. Evidence from past heap leaching testwork has shown that bacteria can
generate and tolerate up to around 70 g/Ll acid produced from commercial-grade
peletized sulphur added to the heap. This approach has, however, not been demonstrated
or optimized in large-scale piloting or commercial-scale applications. There may be a
capital cost saving from not building an acid plant; on the other hand, the cost of sulphur
could be the same or even higher if the sulphur utilization is poor.
Fungi have been used to generate organic acids (citric, oxalic) from a carbon source such
as molasses, and nickel recovery from laterites of up to 60% has been reported7. There
are, however, serious disadvantages associated with the use of fungal organisms on
industrial scale. The cost of the organic carbon used as energy source makes their
application very expensive and unless it can be replaced by inexpensive waste organic
products, it would not be a viable process. Selective growth of the fungi would also be
impossible under commercial conditions due to contamination with other undesirable
microorganisms.
Longer leach cycles and lower recoveries associated with chalcopyrite heap leaching will
typically result in larger pad capital costs and larger ore processing rates for a given copper
recovery. Chalcopyrite heap leaching may therefore be more suitable to brownfield
applications, for example where existing solvent extraction and electrowinning infrastructure
on brownfield installations is used. It is also necessary that the ore contains sufficient pyrite,
in order to generate exothermic heat through bacterial oxidation.
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The application of bio-heap leaching to copper ores provides flexibility to treat a blend of
secondary copper sulphides and oxides with minimal additional capital cost, and an existing
operation could also be adapted to process primary copper sulphides once the oxides and
secondary sulphides become depleted. However, not all oxide/secondary sulphide copper ores
are suitable to heap leaching, especially if the ore contains highly reactive gangue minerals.
Most uranium heap leach plants have been satellites to existing operations, for example for
treatment of low-grade waste with ferric iron bleed streams. However, current high uranium
prices and plant capital costs has resulted in standalone uranium heap leaching processes
being developed (e.g. Trekkopje, Arlit), provided reagent costs can be kept low. Bioleaching
offers a possible route with little additional capital expenditure for reducing oxidizing agent
costs and also acid addition if the ore contains pyrite.
Due to the high costs of sulphuric acid and poor leaching characteristics of the limonitic
fraction of the laterite mineralogy, laterite heap leaching may also find application as an addon process, for example neutralizing acid liquor from a pressure leach plant over saprolite ore.
Since the capital cost of the leaching section may be a small percentage of the overall capital
cost of a greenfield project with large infrastructure requirements, the overall savings on
capital cost may not be significant. As a result, laterite heap leaching will be more suitable to
small projects with low infrastructure requirements, producing an intermediate product (e.g.
Caldag), or where existing infrastructure is used, such as Murrin Murrin.
References
1. LONGWORTH, M. Jump-up dam nickel laterite heap leach project, ALTA Nickel/Cobalt
Conference, Perth, 2007.
2. TAN, I. Canegrass Nickel-Cobalt Heap Leaching project, ALTA Nickel/Cobalt
3. TAYLOR, A. Heap leaching and its application to copper, uranium and nickel ores, short
course, ALTA, Perth, 2008.
4. TAYLOR, A. Review of Uranium industry developments in 20072008, ALTA Uranium
5. PEACY, J., XIAN-JIAN, G., and ROBLES, E. Copper hydrometallurgy: current status,
preliminary economics, future direction and positioning versus smelting, Trans.
Nonferrous Met. Soc. China, vol. 14, no. 3, June 2004, pp. 560568.
6. VAN STADEN, P.J. May 2007. Progress at Mintek in Heap Bioleaching. Presented at
IV International Copper Hydrometallurgy Workshop, 1618 May 2007. Department of
Mining Engineering, University of Chile.
7. ALIBHAI, K.A.K., DUDENEY, A.W.L., LEAK, D.J., AGATZINI, S., and TZEFENIS, P.
Bioleaching and bioprecipitation of nickel and iron from laterites, FEMS microbiology
reviews 11, 1993. pp. 8796.
8. VALIX, et al., Fungal bioleaching of low-grade laterite ores, Minerals engineering,
vol. 14, no. 2, 2001.
9. VAN STADEN, P.J. Heap leach research at Mintek, ALTA Copper Conference, Perth,
2008
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Stefan Walters Robertson

Chemical Engineering, Mintek, Randburg, South Africa
Stefan obtained a research-based MSc at UCT in chemical engineering
in catalysis (1997). He joined Minteks hydrometallurgy division
(1997) and biotechnology divisionsion (2003), working in the fields of
hydrometallurgical process development, pilot plants, development of
engineering and costing models for tank and heap leach processes,
design of heap leach pilot plants and prefeasibility studies.
Publications include: (1) A bacterial Heap Leaching Approach for
Primary Copper Sulphide Ore, presented at the 3rd Southern African Conference on Base
Metals, hosted by the South African Institute of Mining and Metallurgy, Kitwe, Zambia,
2629 June 2005,
(2) Heap bioleaching of a low-grade chalcopyrite ore from the Darehzare deposit,
presented at ALTA Copper Conference, 2007, Perth, Australia
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DUNN, G.M. Increasing the capacity of existing and new exothermic autoclave circuits. Hydrometallurgy
Conference 2009, The Southern African Institute of Mining and Metallurgy, 2009.
Increasing the capacity of existing and new

exothermic autoclave circuits
G.M. DUNN
Hydromet (Pty) Ltd, South Africa
Pressure leach autoclave circuits are employed in the leaching of ores,

concentrates, mattes, alloys and intermediates for the recovery of
metals into solution. Once the metals are extracted into solution, the
value metals can be recovered by hydrometallurgical means such as
by purification followed by electrowinning, hydrogen reduction,
pyrohydrolysis, crystallization and other unit operations. In many of
these integrated flowsheets the pressure leach step is pivotal to the
recovery of the value metals from the host material.
Furthermore, the autoclave circuit invariably is a high capital cost
component of the plant and an area that is carefully scrutinized when
debottlenecking and capacity increases are being considered. This
paper identifies a unique proven way of increasing the capacity of
existing or new exothermic pressure oxidative leach autoclave circuits
by as much as two or three times.
Introduction
Pressure leach autoclave circuits are employed in the leaching of ores, concentrates, mattes,
alloys and intermediates for the recovery of metals into solution. Once the metals are
extracted into solution, the value metals can be recovered by hydrometallurgical means such
as by purification followed by electrowinning, hydrogen reduction, pyrohydrolysis,
crystallization and other unit operations. In many of these integrated flowsheets (refer
Figure 1) the pressure leach step is pivotal to the recovery of the value metals from the host
material.
The exothermic leaching process
The leaching of sulphide concentrates and intermediates as well as alloys is often
accompanied by the release of energy, which has to be removed from the autoclave slurries in
order to avoid the slurry temperatures within the vessel exceeding the design operating values.
For example, in the pressure leach of chalcopyrite the reaction could be represented by the
following relationship:
The energy release, as calculated from heats of formation (25C), is approximately 1 690
kilojoules per gram mole. This exothermic heat release can limit the capacity of an autoclave
INCREASING THE CAPACITY OF EXISTING AND NEW EXOTHERMIC AUTOCLAVE CIRCUITS
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Figure 1. Example of hydrometallurgical flowsheet for the recovery of copper from a flotation concentrate
to 1.1 to 1.3 tonnes of concentrate per active cubic metre per day where a retention time of
approximately 1.2 hours has been prescribed. There are chalcopyrite concentrate autoclave
circuits that have been subjected to feasibility studies and designed to operate in this capacity
range (approximately 812% (w/w) feed solids).
At higher feed concentrations the energy release is such that the autoclave temperature will
exceed the 210230C typical operating range being considered for POX autoclaves treating
chalcopyrite. This condition triggers the need to remove energy from the autoclave in order to
maintain temperature control and the desired oxygen partial pressure in the vessel.
There are a variety of heat removal processes that are available to the autoclave designer,
and these will be examined individually.
Quenching
The quenching processes appear to be favoured by most engineers involved in autoclave
design. The general concept is captured in Figure 2. It is simple to configure and has relatively
simple control features. Quench liquor, in the leaching of copper concentrates, can be a
solvent extraction raffinate or spent electrolyte. The CCD 2 liquor can be considered for the
quench in cases where there is a counter current decantation solid-liquid separation circuit.
The cool aqueous liquor is normally fed to the autoclave compartments on temperature
control. In cases where there are little solids present in the quench fluid, multistage centrifugal
pumps can be employed and, where this is not the case, an appropriate positive displacement
pump may be suitable.
The quench circuit of Figure 2 is also employed in the leaching of nickel and nickeliferous
sulphides and mixed nickel and copper sulphides.
The use of a quench liquor does require an increase in the autoclave active volume and can
result in dilution of the pregnant leach solution (PLS) if water or some diluted liquor is
employed in this duty.
Internal cooling coils
In some autoclaves, internal cooling coils have been fitted into the compartments to abstract
heat. These cooling coils are often fixed to the dividing walls of the autoclave and are
serviced by cooling water or other process fluids. There are numerous limitations associated
with the use of coils, which include:
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Figure 2. Flowsheet of autoclave with quench cooling
Figure 3. Flowsheet of autoclave with internal cooling coils
Difficulties in fixing the coils to the vessels internals

Designing the coils and their supports for the thermal stresses
Deprivation of reactor volume by the coils
A low degree of flexibility in being able to accommodate an increase in reaction extent
and its concommitant impact on where the heat is generated within the autoclave, and
Scaling of heat transfer surfaces by precipitates or gangue from the feed materials.
Cooling coils are employed in the mixed mineral millerite, chalcocite and covelite leach
autoclaves of Southern Africa and the USA1. They are also used extensively in the Norilsk
pyrrhotite-pentlandite leach autoclaves2. Figure 3 provides the cooling system concept
employed in some Southern African autoclaves.
External coolers
An enhancement of the internal cooling coil concept is to be found in the use of external
coolers. The slurry is removed from the autoclave and pumped through a heat exchanger
before being returned to the same compartment of the autoclave.
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Figure 4. Flowsheet of autoclave with external coolers
Some of the disadvantages of the internal cooling coils are addressed in the use of these
external heat exchangers, however:
Scaling of the heat transfer surfaces can still occur, albeit to a lesser extent. This reduced
scale propensity is as a consequence of the higher tube side velocities that can be
achieved within the heat exchanger
The pumps required to circulate the autoclave contents through the external heat
exchangers have certain temperature and pressure limitations, resulting in this concept
being limited to low and medium pressure autoclave circuits, and
Significant wear to isolation valves can be experienced on the pump suction and heat
exchanger discharge lines.
One acceptable feature of external pumped coolers is that additional cooling surface can be
added, thereby improving their flexibility with respect to varying or unpredictable reaction
extents during the operation phase.
Figure 4 provides a simple flowsheet of the external cooler employed in a copper-cobalt
leach autoclave in Zambia3.
Flash-recycle
In most exothermic autoclave circuits a majority of the energy is liberated in the first
compartment, with only smaller quantities being generated in the downstream compartments.
An alternate approach to the removal of heat from exothermic autoclaves was introduced in
South Africa in the mid 1980s in a pressure leach step for a blend of chalcocite, covelite and
small quantities of millerite. Since then it has been installed in two other operations in South
Africa1, one in Zimbabwe4, the USA6 and Australia. The flowsheet for some Southern
African operations is given in Figure 5.
Any energy release in the first compartment that will result in the slurry exceeding the
design temperature is abstracted by removing slurry from the first compartment to the feed
tank via a flashing process and returning it to the autoclave. The feed tank becomes an
extension to the first compartment in this circuit and while a recycle loop is established
between this tank and the autoclave, the overall retention time of the autoclave is related to
the net new feed rate entering the circuit from the concentrate tank and is not influenced by
the recycle loop flow rates.
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Figure 5. Flash-recycle flowsheet
There are several control methods available to the autoclave engineer for the flash-recycle
circuit and these serve, in a well designed system, to maintain the temperature in the first
compartment at the set point with a tolerance of +3C. This temperature control is normally
acceptable for most brick lined, alloy or alloy clad autoclaves.
Some of the advantages of this system compared to the three options above are that it
provides:
For optimal utilization of the installed reactor volume
For enhanced water balance control
The ability to concentrate the reactor contents, if required, through the evaporation of
water flashed as steam
The potential to use the flashed steam as an energy source elsewhere in the operation,
and
For an opportunity to introduce first compartment reagent addition into the feed tank.
The flashed slurry recycle loop can provide a lower cost vehicle for reagent additions to
the first compartment of an autoclave.
The flash recycle (FR) circuit can be retrofitted to autoclaves employing any of the alternate
heat removal systems listed above. Invariably, any exothermic heat carried over into the
second and ensuing compartments can be removed, for example, by the use of coils as this
normally constitutes a small portion of the overall exothermic heat load.
When the above heat removal interventions are considered holistically only the FR circuit
provides the autoclave designer with the maximum degrees of freedom.
A disadvantage, for example, of the quench process is that the fluid introduced into the first
compartment for temperature control can often contain the products of the autoclave
discharge, which may disturb the desired equilibrium conditions in that first compartment. It
could also, for example, as in some matte leach circuits, be a spent electrolyte, which
introduces an acidic liquor into the first compartment. The acid concentration in this and
ensuing compartments is therefore influenced by the thermal quench and may result in a
condition where the operator is not able to control this parameter. He may in fact require a
different acid concentration for the optimal leach conditions over that which is delivered by
the quench temperature control.
A further disadvantage in the case of the internal and external cooler system is that any feed
density fluctuations above the set point may result in the introduction of a larger feed mass,
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for example, of the slurry to the autoclave. The temperature rise in the autoclave first
compartment may be excessive and the energy release greater than what the coolers can
handle. In continuous operations the reaction extent in the first compartment could be reduced
and consequently the second and ensuing compartments heat removal circuits may not be
able to abstract the extra heat load thrust on them by the feed density fluctuation in this case.
Unless design flexibility is provided, the temperatures can run away and an incomplete
leached product can be discharged from the autoclave.
However, in the flash-recycle circuit:
Temperature control is achieved without disturbing or changing the process variables
within the first compartment by the return of another process fluid
The leachate can be concentrated, if required, by not replacing all the water that is
flashed as steam in the flash step
If the feed mass is higher to the autoclave as a consequence, for example, of poor density
control then the automatic level adjustment of the feed tank can be invoked to ensure the
design reaction extent is achieved in the first compartment, thereby preventing
conditions developing in which unreacted product is discharged from the autoclave, and
The mean autoclave retention time is the highest of all the known methods of abstracting
heat from the autoclave, thereby increasing the autoclave productivity (tonnes per day
per cubic metre of autoclave volume).
Autoclaves in matte leach circuits today have been increased in capacity by in excess of
45 per cent employing the flash recycle system whereas others have been derated in pressure
and temperature without impacting the original treatment rate.
In autoclaves operating at temperatures close to the atmospheric boiling point of the
aqueous fraction, Norilsk have proposed their patented vacuum flash. This circuit was in
operation at its Tati Nickel demonstration plant in Botswana6. The first compartment flash
vessel is operating at partial vacuum, which allows the flash underflow slurry to be reduced in
temperature below the atmospheric boiling point. This generates a higher sensible heat loss
than would otherwise occur in an flash-down to an atmospheric boiling condition. Additional
mechanical equipment in the form of condensers, vacuum pumps and sealing fluid cooling
circuits, etc. are required in this variant of the flash-recycle circuit.
Flash-thickener-recycle (FTR) circuit
An extension of the flash-recycle circuit is to be found in the incorporation of a solid-liquid
separation step after the flash. This solid-liquid separation step can be on the first
compartment flash but it can also be on the flash from any compartment of the autoclave.
This solid-liquid separation is often best achieved with a thickener but it can be effected with
other equipment such as a classifier or a filtration step. This flow sheet modification will be
referred to as the flash-thickener-recycle or FTR circuit.
The FTR circuit provides a means of increasing the retention time of the solids fraction
within the autoclave over that of the liquid fraction.
A further embellishment of the flowsheet concept of Figure 5 incorporates a thickener in the
flash-recycle loop. In circumstances where there is a mass reduction of the feed concentrate in
the leach, the incorporation of a thickener in the flash cooling circuit permits the removal of a
fraction of the leachate. The partially leached solids are returned from the thickener to the
autoclave via the feed tank. The thickener thus provides a means of increasing the solids
retention time in the autoclave over that of the liquid phase. Alternately, for a fixed retention
time, the capacity of an autoclave can be increased subject to the impellers delivering
sufficient oxygen mass transfer.
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Figure 6. Flashthickenerrecycle flow sheet
Figure 6 depicts this concept of the FTR circuit.

The FTR circuit not only permits the abstraction of leachate from the first compartment, but
also provides a means of restoring some water to the feed tank to drive the equilibrium in
favour of the leach extraction. Alternately, in the absence of water addition, salt hydrolysis
can occur if this is desired.
In the design of or a modification of an existing autoclave, the first compartment is sized to
achieve in excess of 50 per cent but typically 85 to 95 per cent of the overall reaction extent.
This can and often results in the thickener overflow being very similar in composition to the
autoclave discharge stream after flash.
The mean mass flow rate in the first and ensuing compartments of the autoclave is:
In the FTR circuit the net feed rate5 through the autoclave can be adjusted to suit the
required mass flow and extraction simply by adjusting the volumetric flow at stream4 subject
to thickener underflow viscosity and density constraints. By diverting the thickener overflow
to the discharge tank it has been possible to increase the retention time by as much as 200 per
cent before the autoclave slurry density increases to a point where it is not economical to
increase it any further. Other factors such as oxygen mass transfer at the autoclave impellers
may become rate limiting.
The flash-thickener-recycle (FTR) concept has been patented by Hydromet7.
Applications
Covellite-chalcocite pox leach
The flowsheet of Figure 7 has been considered and tested by an operation processing nickelcopper sulphide mattes. The autoclave was operated as a bulk leach to provide an
approximately 90% mass reduction in the feed. It was followed by a polishing leach autoclave
circuit. This modification was made to an existing three compartment autoclave and:
Increased the retention time of the solids fraction from 3.0 hours to an excess of
7.5 hours, and
Increased the capacity of the autoclave from 0.71 to 1.32 tonnes of feed per cubic metre
(active volume) per day at an operating temperature of 150C.
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Figure 7. Covellite-chalcocite POX leach
Figure 8. Extraction of copper in the FTR circuit for a covellite-chalcocite leach
The impellers in the autoclave were not upsized for the FTR duty. These agitators became
rate limiting in their oxygen transfer rate and were responsible for a capacity increase
significantly below what would have been expected for the additional retention time that was
achieved with this modification.
The extraction of copper and oxidation of sulphide sulphur at the higher capacity in the FTR
circuit is given in Figure 8 and Figure 9. It needs to be noted that this was a three
compartment autoclave possessing the normal deficiencies of such a vessel.
In this case the overall reaction extent in the first compartment was in excess of 80%.
When the circuit was operated as a standard flash recycle cooling circuit (without the
thickener in service) and with a mean solids retention time of 3 hours, the copper extraction
profile was typically that shown in Figure 10 with a first compartment copper extraction of
97%.
The lower copper extraction in the FTR circuit is attributed to the rate limiting features of
the agitation systems, which was unchanged in both cases.
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Figure 9. Oxidation of sulphide sulphur in the FTR circuit for a covellite-chalcocite leach
Figure 10. Kansanshi Minings chalcopyrite POX circuit with quench cooling
Chalcopyrite leach
The pressure oxidative leach of chalcopyrite is a strongly exothermic process. The classical
approach with quench cooling can result in the feed density being reduced to between 8 and
12% feed solids equivalent on a weight basis. In Zambia, Kansanshi Mining plc (a company
80% owned by First Quantum Minerals Limited) installed a chalcopyrite pressure oxidation
(POX) process to the flowsheet in Figure 10. An atmospheric leach of oxidized copper ore is
being undertaken on the present site and the plan is to integrate the sulphide POX leach into
the atmospheric leach circuit to provide sulphuric acid, energy and some ferric iron as a
lixiviant for some secondary sulphides in the oxide ore. The PLS from the atmospheric leach
CCD circuit is fed to a copper SX circuit. The raffinate from this SX circuit is returned, in
part, to the POX circuit for the repulp of concentrate and the quench.
The POX circuit has been designed to operate:
At 210C and approximately 3.0 MPa(g)
With a first compartment mean solids residence time of just under one hour and an
overall residence time of approximately 1.7 hours, and
With two autoclaves for a concentrate treatment rate of 105 kt/annum.
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Figure 11. Kansanshi Minings chalcopyrite POX Circuit with FTR
Table I
Process factors of the circuit
Specific autoclave feedrate at 1.7 hours

Overall retention time
Sulphuric acid requirements
First compartment mean solids retention time
First compartment slurry feed rate
First compartment dilution feed rate
First compartment oxygen transfer rate
m3)
(t.concentrate/day
(t.Cu/day m3)
(t.S=/day m3)
(t/tonne concentrate)
(h)
(m3/h)
(m3/h)
(kg/m3h)
Quench concept
FTR concept
1.14
0.33
0.37
0.43
0.94
7.2
65
62
3.04
0.89
0.97
~nil
0.94
78
110140
147
Kansanshi Mining are considering the FTR circuit on a single POX autoclave employing the
flowsheet of Figure 11. The FTR circuit will:
Operate at 210C and approximately 3.0 MPa(g), i.e. at identical conditions as those in
the quench concept
With the same mean solids retention time distribution as the quench circuit, and
With one autoclave designed to treat approximately 130150 kt/annum.
The specific process factors of the circuit are summarized in Table I.
In the FTR circuit, in excess 75% of the leached copper in the autoclave will be removed in
the thickener overflow and diverted directly to the discharge tank. This is approximately 80%
of the total copper leached in the first compartment. The remaining leached copper is in the
slurry overflowing from the first compartment to the second and ensuing compartments of the
autoclave.
The leaching of nickel sulphides
Nickel sulphides mattes have been leached in Southern African matte POX circuits for over
35 years8,9.
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Figure 12. Pressure oxidation of nickeliferous sulphides with FTR
Figure 13. FTR circuit for minerals displaying different leach kinetics
The leaching of nickeliferous sulphide concentrates has been practiSed at Outokumpu using
the Hitura concentrate10 and is currently practiSed at Norilsk on pyrhhotite rich concentrates.
Inco are considering a pressure leach circuit for its Voisey Bay concentrate.
The flow sheet in Figure 12 has merits where there is a significant mass loss from the feed
concentrate in the leach. It is, for example, suited to the acid pressure oxidative leaching of
mixed nickel and cobalt sulphides generated from a hydrogen sulphide precipitation process
of a laterite leachate. The autoclave capacity can be reduced by over 200% of that employed
in the classical quench cooling process.
Kinetically different leach systems
The platinum group metals are known to respond slower than the base metals in the acid
leach of a mix of base metal sulphides and PGM sulphides, selenides, tellurides, arsenides,
bismuthides, etc.
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Where it is the intent to dissolve both the base metals and the precious metals, it may be
appropriate to separate a majority of the base metal leachate in a first compartment FTR
circuit. The extraction of the precious metals can then be made in the downstream
compartments of the autoclave in a considerably smaller autoclave.
The circuit of the type shown in Figure 13 has some merits in that:
A large part of the base metals are removed in the leachate overflow from the FTR
thickener
Any PGE that do dissolve in the first compartment are precipitated on the concentrate,
which is blended with the first compartment leach slurry prior to thickening. The
thickener overflow will therefore be low in precious metals concentration
The lixiviant that is employed for PGE dissolution e.g. chloride ions in the Platsol
process may need to be only added into the second compartment of the autoclave. This
could reduce the material and maintenance costs of the autoclave significantly, and
The volume of leachate containing PGE is much smaller as is the autoclave itself.
Conclusions
The introduction of the thickener in the flash front end cooling circuit increases the retention
time of the solids fraction over that of the aqueous stream.
The FTR circuit can be retrofitted to existing POX circuits to increase the capacity of these
circuits at minimal capital and operating cost.
The FTR concept can be designed into new POX circuits to reduce the size of the autoclave
or reduce the operating complement of autoclaves where parallel units are being considered
for a plant.
References
1. STEENEKAMP, N. and DUNN, G.M. Operations of and Improvements to the Lonrho
Platinum Base Metal Refinery, EPD Congress, 1999, pp. 356390.
2. BORBAT, V.F. and VORONOV, A.B. Autoclave Technology for Processing of NickelPyrrhotite Concentrates, Metallurgy, Moscow, 1980, 185.
3. MUNNIK, E. SINGH, H. UYS, T. BELLINO, M. DU PLESSIS, J. FRASER, K., and
HARRIS, G.B. Development and Implementation of a Novel Pressure Leach Process for
the Recovery of Cobalt and Copper at Chambishi, Zambia, The Journal of the South
African Institute of Mining and Metallurgy, Jan.Feb. 2003.
4. MONTGOMERY, G.W.G. and HOLOHAN, T.N. Development and Design of the
Hartley Platinum Base Metal Refinery Flow sheet, South African Institute of Mining and
Metallurgy, April. 1997.
5. NEWMAN, L. and WYRICK, R. Modification of the Stillwater Base Metal Refinery
Process Pressure, Hydrometallurgy, 2004, pp. 499525.
6. SWARTS, A. HOLLIDAY, H. DONEGAN, S., and NEL, G.J.G. The Tati Activox
Demonstration Plant: Changing the Future of Nickel Production in Southern Africa, Cape
Conference, South Africa, 2005.
7. DUNN, G.M. Exothermic Pressure Leach Autoclave Circuits, PCT/ZA 2005/000002.
8. PLASKET, R.P. and ROMANCHUK, S. Recovery of Nickel and Copper from HighGrade Matte at Impala Platinum by the Sherritt Process, Hydrometallurgy, 1978,
pp. 135151.
9. PLASKET, R.P. and DUNN, G.M. Commissioning Experiences in the Cobalt plant at
Impala Platinum Ltd, Minerals and Metallurgical Processing, 1986, Feb Issue.
10. NYMAN, B., AALTONEN, A., HULTHHOLM, S.E., and KARPALE, K. Application of
new hydrometallurgical developments in the Outokumpu HIKO process,
Hydrometallurgy, 1992, pp. 471478.
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G.M. Dunn
Director, Hydromet (Pty) Ltd, South Africa
Mr Dunn has held various positions over 22 years at Impala Platinum
Refineries in pressure hydrometallurgical operations from shift
operator to plant manager to general manager. He then spent brief
periods at SRK and Hatch in consulting roles. In 2000 he established
his own consulting company in South Africa, Hydromet (Pty) Limited,
working in nickel, cobalt, manganese, uranium and PGE.
He has spent 18 years in pressure hydrometallurgical operations and base metal and PGM
recovery. He has spent 20 years in project engineering and project management.
Mr. Dunn is a Chartered Engineer (UK) and Professional Engineer (South Africa) having
graduated at the University of Cape Town in 1970 with an honours degree in Chemical
Engineering. He is a Fellow of the Institute of Chemical Engineers in the UK, a member of
the SA Institute of Mining and Metallurgy and the SA Institute of Chemical Engineers. He is
a member of American Institute of Mining, Metallurgical and Petroleum Engineers
(AIME,TMS).
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LAUZON, P., KONING, A., and DONOHUE, I. Stress development in refractory due to the rate of temperature
change: a pressure vessel refractory lining design consideration. Hydrometallurgy Conference 2009, The
Stress development in refractory due to the rate of

temperature change: a pressure vessel refractory
lining design consideration
P. LAUZON*, A. KONING*, and I. DONOHUE*
*Hatch, Ontario, Canada
Vessels that are used for pressure hydrometallurgical operations

require an impermeable membrane that provides corrosion protection
and one or more courses of refractory lining or ceramic brick. A
significant amount of work goes into the design of a refractory lining
to ensure that it is mechanically stable at steady state process
conditions. Steady state analysis techniques are covered in detail in
the paper Design fundamentals for hydrometallurgy pressure vessel
refractory linings by A. Koning and P. Lauzon. Since new
hydrometallurgical processes are pushing the pressure and
temperature envelope with each new generation of plants it becomes
equally important to perform transient analysis.
The purpose of this paper is to build on the design fundamentals of
refractory linings by demonstrating the importance of transient
thermal and stress analysis. A transient analysis is necessary because
heating or cooling a vessel too quickly can result in lining failure as a
result of exceeding the stress limits of the refractory. To demonstrate
the effects that the rate of temperature change has on the stresses in a
refractory lining, a transient thermal and stress analysis was
conducted on a typical refractory lining design for an autoclave.
The results obtained from the analysis shows a significant increase
in peak stress when the rate of heating or cooling is increased by
5C/h. Peak stresses were increased by approximately 2 MPa. A stress
increase of this magnitude is significant because tensile failure of
refractory brick occurs in a range of 6 to 10 MPa. The magnitude of
stress development is highly dependent on geometry, materials, and
the thermal boundary conditions. Since stress development is affected
by multiple factors it is important to analyse the transient effects of
heating or cooling a vessel.
STRESS DEVELOPMENT IN REFRACTORY DUE TO THE RATE OF TEMPERATURE CHANGE
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Introduction
Pressure hydrometallurgy operations require vessels to be lined with an impermeable
membrane for corrosion protection and one or more courses of refractory or ceramic brick.
Examples of unit operations that utilize composite lining systems include pressure oxidation
autoclaves, sulphide precipitation autoclaves, chloride leach reactors, flash vessels, cyclone
separators, and direct contact condensers (heater vessels and quench vessels). The refractory
lining must satisfy multiple requirements: it must thermally insulate the membrane from
process fluid, be structurally stable, provide erosion resistance, be chemically compatible with
process fluid, and provide an economic service life.
Refractory lining design begins with selecting lining materials based on chemical stability in
the process environment. The thickness of the different refractory layers is initially
determined using 1D heat transfer calculations. If the membrane or shell temperature is
greater than what is permitted then the refractory thickness is increased. Following the
thermal analysis is a 1D mechanical stability analysis, which is used to examine various
loading conditions and the effects of material properties. Mechanical stability is determined
by ensuring that the hot face refractory layer is in compression through all operating
conditions and that the stresses do not exceed the materials failure strength. An equally
important consideration is the calculated overlap between the brick lining and the membrane.
This stability factor requires that the overlap should be positive, that is, that the steel shell
should be in contact with the refractory lining throughout all operating conditions.
The main drawback of 1D calculations, is the assumption of an infinitely long cylindrical
vessel that does not take into account the effects of additional attachments: supports, nozzles
and hemi-heads. A designer must resort to the use of finite element analysis (FEA) because
the various attachments require complex mathematical analysis for which exact formulae are
difficult or impossible to obtain. With the use of 2D axisymmetric and full 3D models the
designer will perform thermal and stress analysis for various load conditions. FEA will
highlight hot spots in the vessel or stress concentrations, which would lead to failure. The
designer can then concentrate on the hot spots or stress concentrations and modify parameters
such as gaps, geometry, and material selection in order to eliminate these hot spots or stress
concentrations.
Once a refractory lining design passes the mechanical stability and thermal requirements at
steady state process conditions it becomes necessary to examine the effects of start-up and
shutdown procedures. Steady state analysis techniques are covered in detail in the paper
Design fundamentals for hydrometallurgy pressure vessel refractory linings by A. Koning
and P. Lauzon. Analysis of start-up and shutdown procedures for a vessel is required because
a refractory lining is dramatically affected by the rate of temperature change. The purpose of
this paper is to demonstrate the effect that the rate of temperature change has on refractory
stresses during start-up and shutdown.
If the vessel is heated or cooled too quickly stresses can be generated that exceed the stress
limits of the refractory, leading to failure of the lining. It is the hot face of the process brick
that will experience the greatest effects of thermal shock and will crack or spall if the rate of
temperature change is too high. To assist in prolonging the life of the refractory lining it is
important that appropriate heating and cooling rates be determined and followed. The
damaging effects of a large rate of temperature change will be discussed and examined using
FEA.
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Transient thermal stresses

Refractory material is selected for its excellent insulating material properties: low
conductivity, high density, and high specific heat capacity. The insulating ability of the
refractory is required for the thermal protection of the vessel membrane. The downside is the
length of time required to heat or cool the refractory lined vessel.
When the refractory in a pressure vessel is being heated it resists the transfer of heat from
the hot face to the cold face, generating steep thermal gradients through the material. Stresses
are generated within the refractory as a result of uneven thermal expansion due to the nonuniform temperature distribution. If the refractory is heated quickly, large enough compressive
stresses can be generated, which cause the lining to fail due to thermal shock. The same type
of failure can also occur when the vessel is cooled too quickly. In this case the hot face
becomes cooler than the remainder of the refractory and develops a tensile stress. The results
of a transient thermal and stress analysis, using FEA, effectively shows the magnitude of
stresses generated as a result of rapid temperature change.
Transient analysis using FEA
The effects of rapid temperature change on refractory will be shown using the results from a
two-dimensional FEA model. Figure 1(a) shows the general arrangement of the model used
for the analysis, which approximates a cross-section of a quarter of the pressure vessels
cylindrical body. It is assumed that this geometry represents an infinitely long cylinder into
the page. In the model, plane strain applies. This model geometry will behave identically to a
complete annulus and reduces the computational time because the model is smaller.
The model is made up of 8 different layers as shown in Figure 1(b): steel shell, lead
membrane, 3 mortar layers, and 3 brick layers. The brick layers are modelled as monolithic
layers that do not account for the mortar that is between the bricks circumferentially or
axially. These mortar joints could be modelled but are not necessary to show the effects of the
rate of temperature change.
Figure 1. (a) General arrangement of the model used for the transient analysis and (b) the different material layers
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The model geometry is a representation of the cylindrical portion of an autoclave.

Thicknesses used for each layer in the model are from the design of an existing autoclave. The
autoclave is being used for the processing of an orebody that contains gold. Transient thermal
and stress analysis was conducted using the 210C process design temperature for this
particular autoclave. Autoclaves used to process an orebody containing gold can have process
temperatures that range from about 200C to 250C. Process conditions will vary depending
on the orebody being processed, the chemical reaction taking place, and the type of vessel
being used.
The effect of heating rate on refractory
The refractory used to line a vessel is selected for its excellent insulating properties to keep
the membrane below a particular temperature at process conditions. At steady state operating
conditions the thermal gradient through the refractory generates compressive hot face stress
and tensile cold face stress. Larger stresses will be developed in the refractory as the vessel is
being heated, as shown in Figure 2. The peak stress occurs when the vessel reaches the 210C
process temperature and then stabilizes to a steady state position. For the given analysis a
5C/h increase in the heating rate increased the peak stress by approximately 3 MPa. A peak
stress is formed due to the thermal gradient through the refractory.
The steepest thermal gradient occurs when the vessel reaches the desired process
temperature. This is illustrated by the thermal gradient at the time of 19 h for Case 2 in
Figure 3. This occurs because the hot face has achieved its steady state temperature but the
remainder of the refractory is still being heated. The faster a vessel is heated the steeper the
thermal gradient through the refractory when the vessel reaches the process temperature, as
shown in Figure 4 for Case 1 and Case 2. This accounts for the largest peak stress for Case 2.
The slope of the thermal gradient through the refractory and stresses are reduced over time as
the refractory reaches steady state.
The 12 h hold shown for Case 3 and 4 in Figure 2 is an example of a temperature hold
typically included in a vessel heating schedule during commissioning or after prolonged shutdown. The hold period allows the lining to settle into place and helps prevent damage to the
Figure 2. Hot face stress of the process brick
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lining. It provides time for the acid to completely soak through the refractory to prevent
flashing. A hold period allows the vessel to reach an equilibrium state so the operator has an
opportunity to check that nothing is out of the ordinary (i.e. hot spots) before continuing the
heating process.
Figure 3. Process brick thermal gradient for Case 2
Figure 4. Process brick thermal gradient
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The effect of cooling rate on refractory

The tensile strength of refractory typically falls within a 610 MPa range. When a vessel is
cooled there is greater potential for lining failure due to the possibility of exceeding the low
tensile strength of the refractory. Looking at Cases 2, 3, and 4 in Figure 5 it can be seen that
the peak stress is approaching the tensile strength of refractory as the cooling rate is increased.
The stress on the hot face has become tensile because it is now cooler than the cold face. For
the given analysis a 5C/h increase in the cooling rate increased the peak stress by
approximately 2 MPa. A peak stress is formed due to the thermal gradient through the
refractory.
For Cases 2, 3, and 4 the steepest thermal gradient occurs when the vessel temperature
reaches 60C and cooling by means of natural convection is initiated. This is illustrated by the
thermal gradient at a time of 6 h for Case 4 in Figure 6. It can be seen that at the 7 h mark the
hot face increased in temperature and the remainder of the refractory continued cooling. This
occurred because the rate of heat removal due to convection is slower than the rate of heating
by the latent heat remaining in the hotter portion of the refractory.
The faster a vessel is cooled the steeper the thermal gradient through the refractory when the
vessel temperature reached 60C, as shown in Figure 7 for Cases 2, 3, and 4. This accounts
for the largest peak stress for Case 4. The slope of the thermal gradient through the refractory
and stresses are reduced over time as the refractory reaches steady state.
The effect of cooling the vessel interior from 60C to 20C using convection can be seen
looking at Case 1 and 5 in Figure 5. These two cases do not have a stress peak because the
vessel is cooled to 60C using a slow enough rate that the convective air passing though the
vessel has a larger influence on the tensile stress development. The tensile stress is caused by
the 40C temperature difference between the convective air and the hot face of the process
brick. Case 5 has a larger tensile stress because forced convection has a larger effect on the
thermal gradient through the brick because it removes more heat than natural convection. The
forced convection rapidly decreased the hot face temperature of the process brick causing the
generation of the larger tensile stress on the hot face.
Figure 5. Hot face stress of the process brick
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Figure 6. Process brick thermal gradient for Case 4
Figure 7. Process brick thermal gradient
Conclusions
The rate of temperature change has a noteworthy effect on the stresses that are developed in a
refractory lining. The stress observed, during heating or cooling, is significantly higher than
steady state stress, which demonstrates the need for transient thermal and stress analysis when
designing a lining system. The stresses are highly dependent on geometry considerations,
material properties, and thermal boundary conditions. So there are many variables that can be
changed to reduce the stresses within the refractory. Performing a transient thermal and stress
analysis during the design phase will result in a better engineered refractory lining with an
improved life expectancy.
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Al Koning
Mechanical Engineer, Hatch, Ontario, Canada
Mechanical engineer for the design and construction of chemical and
metallurgical processing plants, encompassing detailed mechanical
design and project engineering for the extraction of non-ferrous metals
such as gold, nickel, cobalt and copper. Extensive experience using
finite element analysis (FEA) and other analytical methods in the
design, diagnoses and retrofitting of pressure vessels and piping
components.
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NICOLLE, M., NEL, G., PLIKAS, T., SHAH, U., ZUNTI, L., BELLINO, M., and PIETERSE, H.J.H. Mixing
system design for the Tati Activox autoclave. Hydrometallurgy Conference 2009, The Southern African
Institute of Mining and Metallurgy, 2009.
Mixing system design for the Tati

Activox autoclave
M. NICOLLE*, G. NEL, T. PLIKAS, U. SHAH, L. ZUNTI,
M. BELLINO*, and H.J.H. PIETERSE
*Hatch Africa (Pty) Ltd, South Africa, Norilsk Nickel Africa (Pty) Ltd, South Africa
Hatch (Pty) Ltd, Ontario, Canada, Pieterse Consulting Inc., Arizona, USA
The Tati Activox Project will be the first full-scale implementation
of the patented Activox process. The process was developed by
Norilsk Process Technology and has been tested on Tati mine
sulphide concentrates in laboratory, pilot and demonstration plant
scales and demonstrated its viability. There are inherent risks to the
final scale-up of the process from the demo plant and one of them will
be investigated in this paper.
Compartment 1 is designed to leach approximately 77% of the total
nickel leached. For this reason agitation requirements in the first
compartment of the autoclave are reviewed. An attempt is made to
minimize the process and mechanical risks associated in achieving
oxygen mass transfer into the slurry solution. The agitator powers for
oxygen mass transfer are calculated using empirical correlations and
compared to demonstration plant testwork. The resulting gassed
power per unit volume (P/V) is higher than most commercial
autoclaves and raises uncertainty on the viability of using such high
unit power inputs. Additionally, there is concern about the ability of
the autoclave shell to withstand and support the higher loading of
large agitators. An alternative solution to designing for the increased
P/V is assessed in which the number of compartments within the
autoclave is reduced from 5 to 4 by removing the compartment wall
separating compartments 1 and 2. This results in an enlarged first
compartment containing 3 agitators instead of 2. Therefore the
compartment 1 oxygen demand is supplied through 3 agitators, which
lowers the P/V per agitator.
The reduction in the number of autoclave compartments raises the
potential for short-circuiting the mean flow pattern by slurry particles.
Short-circuiting and low velocity zones could result in a lower
recovery of metal and localized hot spots, respectively. A
computational fluid dynamic (CFD) analysis was conducted to
quantify these concerns and also to evaluate further design
considerations. The results indicate that the proposed design change
to 4 compartments affects short-circuiting. The impact of increased
short-circuiting on the overall autoclave recoveries is not quantified,
however; it is expected to be negligible based on testwork done in the
Tati Demonstration Plant and similar modifications made to another
operating autoclave. The CFD analysis also suggests that there will be
no low velocity zones within the compartment.
MIXING SYSTEM DESIGN FOR THE TATI ACTIVOX AUTOCLAVE
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Introduction
Tati Nickel base metals refinery makes use of the patented Activox process and will be the
first full-scale commercial implementation. The ultra fine grinding (UFG) and autoclave
pressure leach process conditions are the heart of the Activox patent. The hydrometallurgical
process has environmental and financial benefits over a pyrometallurigcal process in that it
does not produce sulphur dioxide or acid as a by-product. The hydrometallurgical base metal
refinery is designed to produce 25000 tpa nickel, 22000 tpa copper and 639 tpa cobalt as
cobalt carbonate.
In the first phase of project implementation, process verification was completed during
which the bankable feasibility study (BFS) design was assessed. Compartment one is
designed to leach approximately 77% of the total nickel mass leached across the autoclave, as
determined by the Tati Demonstration Plant campaigns. As a high portion of the leach
reaction occurs in compartment one, significant attention was given to the compartment
design. One particular area of review was the BFS basis for the oxygen mass transfer and
dispersion within the autoclaves first compartment. The following sections of the paper
outline the testwork completed and methods used to evaluate the mixer design in
compartment 1 of the autoclave. This resulted in a design that was subjected to CFD
modelling and analysis. The results of this analysis are used to validate aspects of the final
autoclave design.
PROCESS OVERVIEW
The concentrate is repulped with copper raffinate and fed via attrition scrubbers to a UFG mill
circuit. The mill circuit consists of primary and secondary mills in series, which produce a
finely ground concentrate. The size reduction significantly increases the surface area for the
oxidation reactions to occur in the Activox autoclave. Milled slurry is fed into 2 parallel
Activox autoclaves where the sulphide concentrate is oxidized. The autoclave operating
temperature, pressure and chloride catalyst concentration result in the formation of favourable
chemical species for handling downstream. Copper, cobalt and nickel are leached from the
concentrate as sulphates in solution while elemental sulphur is formed as a by product.
Elemental sulphur, a solid, allows more cost-effective processing than sulphate ions, which
would require neutralization before removal from the circuit. The oxidation of concentrate is
exothermic and requires careful temperature control. Temperature is maintained by direct
quenching and a flash recycle. Due to the moderate operating temperatures in the leach
vessels, the flash cooling and flash discharge systems are operated at a vacuum to increase the
heat removal. The flash vent gases report to a condenser where cooled water condenses
vapour from the vent gases. Non-condensables and the remaining water vapour is drawn by a
vacuum pump and discharged into a venturi scrubber, which removes residual solids and
entrained droplets, prior to discharge to the atmosphere.
The leach discharge slurry is cooled in slurry cooling towers after which it reports to the
solid-liquid separation area where the leach residue solids are washed with recycled process
water. The washed leach solids are then pumped to the platinum group elements (PGE)
flotation circuit. The solution is clarified prior to solvent extraction, electrowinning and
precipitation to produce nickel cathode, copper cathode and cobalt carbonate.
Basis for mixing system design
The Activox autoclave mixing system design is based on the process conditions outlined in
Table I:
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Table I
Process conditions in autoclave compartment one
Parameter
Value
Unit
Normal operating temperature

Normal operating pressure
Oxygen (O2) partial pressure
Compartment 1 nickel mass recovery
Stoichiometric O2 required in the first compartment
O2 gassing ratetotal required in first compartment
O2 utilization
Solids weight percent
Solids specific gravity
Liquor specific gravity
Solids volume percent
Slurry volume C1A (BFS compartment 1,autoclave agitator 1)
Slurry volume C1B (BFS compartment 1, autoclave agitator 2)
Slurry volume C2C (BFS compartment 2, autoclave agitator 3)
105
11
9.8
77
11181
12423
90
35
2859
1304
19.7
51.8
44.7
42.7
C
bar (a)
bar (a)
%
kg/h
kg/h
%
% wt/wt
kg/m3
kg/m3
%
m3
m3
m3
Design development
The autoclave mixing system serves two purposes: firstly it creates an homogenous
environment for the leach reactions to occur in by suspending the solids in the slurry, and
secondly to replenish oxygen in solution as it reacts and oxidizes the ore. Gaseous oxygen is
fed to each autoclave compartment through nozzles located under the agitator shafts and as
such at the localized point in the autoclave with the highest shear. This maximizes oxygen
mass transfer into the slurry solution whereafter it reacts with the sulphide ore according to
the leach reactions.
Empirical correlation for the P/V
The agitation duty requirement in the first compartment is the greatest as the reactions in this
compartment have the greatest oxygen demand. The stoichiometric mass of oxygen
transferred into solution in compartment 1 is therefore critical to the leaching efficiency of the
process. The transfer rate of oxygen to solution is known as the oxygen mass transfer rate
(OTR) and is given in kg/m3/h. The OTR is a function of the mass transfer coefficient (kL), the
interfacial area (a), oxygen solubility in the slurry solution (CO2-solution) and the actual
concentration of dissolved oxygen in solution (C). This relationship is shown in Equation [1].
[1]
The dissolved oxygen concentration C cannot be negative and the leach reaction extents are
not controlled (the leach reactions are mass transfer limited when C = 0). Therefore, C must
be greater than zero (C > 0) to achieve the required mass transfer. As the actual concentration
of oxygen in the slurry solution cannot be greater than (CO2-solution), C is expressed as a
percentage of (CO2-solution) in Equation [2].
[2]
From test work (which gives values for O2 gassing rate and O2 utilization) it is possible to
determine the OTR per agitator using Equation [3]:
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[3]
where O2-gassing rate = 12 423/number of agitators in compartment 1 [kg/h]
O2-utlization = 0.90
Liquid volume = Slurry volume (1 volume fraction of solids in slurry)
In order to calculate the mass transfer coefficient using Equation [1] the solubility of oxygen
in slurry solution (C O2-solution) must first be determined. (C O2-solution) is lower than the
solubility of oxygen in pure water (CO2-water) due to the presence of dissolved salts. The
relationship for (CO2-water) is shown in Equation [4] (Tromans 1998).
[4]
where H
= Henrys coefficient [kg.atm.mol-1]
= Partial pressure of oxygen gas [atm]
po
CO2-water = Molal concentration of dissolved oxygen in water [mol O2. kg water-1]
Henrys coefficient is calculated from the relationship given in Equation [5].
[5]
Where T = temperature in K.
At the process temperature of 105C (378K)
g
To convert to units of Latm the formula must be multiplied by the density of water and the
molecular weight of oxygen:
The oxygen solubility is lowered due to the presence of dissolved salts (mainly nickel,
copper and cobalt sulfate) by a derating factor, (Tromans 1998). The relationship between
solution oxygen solubility and water oxygen solubility is shown in Equation [6].
[6]
The value of from Equation [6] is determined (using Figure 6 in Tromans 1998) with the
expected molal concentration of nickel, copper and cobalt sulphate in the solution (2.047
mol/kg). is approximately 0.70 to 0.75. It is now possible to calculate C from Equation [2]
as varies between 0.2 and 0.3 according to industry norms. A value of 0.3 was used in this
case and this assumption was validated at a later stage through testwork. It is anticipated that
high actual concentrations of oxygen in solution (C) are unlikely due to the high sulphide
concentration in the Tati concentrate slurry. With C known it is possible to calculate kLa from
Equation [1], and so from Equation [7] below the gassed power per unit volume (P/V). The
P/V required is calculated using the empirical Equation [7] (based on a recommendation made
by Pieterse 2004) and adjusted using data the authors subsequently obtained from several
commercial sized autoclaves.
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[7]
where
P/V
= gassed power per unit volume in kW.m-3
And kLa = the mass transfer coefficient in h-1
P/V calculation for two agitators in compartment 1

The resulting power demand (3.89 kW/m3 4.73 kW/m3) on the agitators is very high in
comparison to commercial autoclaves. This high power demand results in a very large agitator
and raises concerns about the ability for the autoclave shell design to support the large weight
and forces without the need for significant localized strengthening.
By removing the weir wall separating compartment 1 from 2 the new compartment 1 will
have 3 agitators under which the required oxygen can be added. This configuration is assessed
in the same way as the scenario with 2 agitators in compartment 1. (Table II.)
P/V calculation for three agitators in compartment 1
Table III summarizes the empirical calculation outlined in the section Empirical correlation
for the P/V of this paper. The same conditions as Table II were used with the exception that
the oxygen demand was split over 3 agitators and not 2.
The reduction in oxygen demand per agitator and subsequent reduced P/V (from between
3.89 kW/m34.73 kW/m3 to between 2.28 kW/m3 to 2.94 kW/m3) reduces concern about the
agitator support on the autoclave shell as there are a limited number of commercial autoclaves
operating under similar agitator duties and supports to those proposed for this application.
Testwork in Tati demonstration plant
Testwork was carried out on the Tati demonstration plant in Botswana in order to further
clarify the agitation requirements of the autoclave. These test results were compared to the
Table II
A summary of the empirical calculation as applied to 2 agitators in compartment 1
O2 gassing rate per agitator
Weight percent solids
Specific gravity solids
Specific gravity liquor
Volume percent solids
Slurry volumeC1A
Slurry volumeC1B
Oxygen solubility in waterEquation [4]
Derating factorEquation [6]
O2 solubility in solutionEquation [6]
Dissolved O2 as % of soluble O2 in solution
Dissolved O2 concentration in solutionEquation [2]
Oxygen transfer rate in C1AEquation [3]
Oxygen transfer rate in C1BEquation [3]
kLa in C1AEquation [1]
kLa in C1BEquation [1]
P/V required in C1A [7]
P/V required in C1B [7]
6212 kg/h
35% wt/wt
2859 kg/m3
1304 kg/m3
19.7% vol./vol.
51.82 m3
44.65 m3
0.2430 kg/m3
0.735
0.1786 kg/m3
30%
0.0536 kg/m3
134 kg/h.m3
155 kg/h.m3
1069 h-1
1241 h-1
3.89 kW/m3
4.73 kW/m3
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Table III
A summary of the empirical calculation as applied to 3 agitators in compartment 1
Oxygen transfer rate in C1CEquation [3]
kLa in C1Aequation [1]
kLa in C1Bequation [1]
kLa in C1Cequation [1]
P/V required in C1C [7]
4141 kg/h
0.2430 kg/m3
0.1786 kg/m3
0.0536 kg/m3
89 kg/h.m3
103 kg/h.m3
108 kg/h.m3
713 h-1
827 h-1
865 h-1
2.28 kW/m3
2.77 kW/m3
2.94 kW/m3
Table IV
A summary of the empirical calculation as applied to 8th March 2007 testwork results
Weight percent solids
Specific gravity solids
Specific gravity liquor
Volume percent solids
Slurry volumeC1A
Slurry volumeC1B
Average P/V measured in C1A
Average P/V measured in C1B
36 kg/h
35% wt/wt
2859 kg/m3
1200 kg/m3
18.4% vol./vol.
0.64 m3
0.58 m3
0.2430 kg/m3
0.1786 kg/m3
0.0536 kg/m3
62 kg/h.m3
69 kg/h.m3
497 h-1
552 h-1
1.42 kW/m3
1.63 kW/m3
2.64 kW/m3
2.93 kW/m3
empirical results to develop confidence in the proposed commercial design. The results of the
testwork are summarized in Table IV. The same conditions as Table II were used with the
exceptions listed below. Most importantly the oxygen demand is lower than the commercial
plant.
By comparing the average measured P/V from the testwork and that calculated using
Equation [7] in Table IV it is possible that during the testwork either the agitator power was
higher than the power required for oxygen mass transfer or that too low a value for (from
Equation [2], = 0.3) had been assumed. It was suspected that the agitator power was higher
than the power required for oxygen mass transfer. This suspicion was confirmed by additional
tests (summarized in Figure 1 in which the P/V was reduced but no appreciable change in Ni
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metal recovery was recorded until the P/V dropped below well 1.4 kW/m3. The P/V for
compartment 1A, as calculated in Table IV and based on the assumption that = 0.3, is
1.42 kW/m3. Hence the original assumption that = 0.3 is validated.
The demo plant OTR is 6269 kg/m 3h while the commercial plants design OTR is
89108 kg/m3h. The commercial design takes into account the potential for an ore with a high
sulphur content that will require additional oxygen per unit mass of feed solids to leach. In
order to compare the same oxygen inputs the Tati demonstration plant conditions are
recalculated in Table V to indicate what the P/V would be if the OTR were in the region of
89108 kg/m3h. The resulting P/V is between 2.392.74kW/m3, which is similar to the
commercial plant requirements in Table III. The same conditions as Table IV were used with
the exception that the OTR was increased to what the commercial plants design will be.
It should be noted that the Tati demonstration plant oxygen transfer rates (OTR) are only a
guideline and cannot be scaled up linearly.
Design considerations
Agitator design
Table VI shows the proposed design of the agitator to meet the mass transfer requirements
outlined in Table III.
A custom 8-bladed Rushton turbine with increased blade height connected to a 186 kW
variable speed drive motor was selected. Increasing the blade height is a common means of
increasing the power number of a Rushton turbine. The recommended design shaft speed is
92 RPM, which produces a gassed power input of 129 kW (69% of motor load) per agitator
and a volume averaged P/V of 2.8 kW/m3 in the compartment. The design shaft speed results
Table V
Demo plant P/V with OTR in the region of 89108 kg/m3h
53.3 kg/h
0.2430 kg/m3
0.1786 kg/m3
0.0536 kg/m3
92 kg/h.m3
102 kg/h.m3
739 h-1
819 h-1
2.39 kW/m3
2.74 kW/m3
i% Recovery

Figure 1. Effects of P/V on nickel recovery recorded in the Tati demonstration plant
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Table VI
P/V from the proposed design
Agitator
P/V required
Equation [7]
P/V measured during

8 March 2007 testwork
P/V at 69% of
motor capacity
P/V at 85% of
motor capacity
Unit
2.28
2.77
2.94
2.64
2.93
2.49
2.89
3.02
3.05
3.54
3.70
kW/m3
kW/m3
kW/m3
Compartment 1 A
Compartment 1 B
Compartment 2 C
Table VII
P/V sensitivity analysis on assumed values
CO2-solution
( )
kg
m3
( )
kg
kLa (h-1)
m3
Required
P
V
( )
0.1822
C1A: 49
C1B: 579
C2C: 605
C1A: 1.43
C1B: 1.73
C2C: 1.84
0.1
0.1822
0.0179
C1A: 554
C1B: 643
C2C: 673
C1A: 1.64
C1B: 1.99
C2C: 2.11
0.2
0.1822
0.0357
C1A: 624
C1B: 724
C2C: 757
C1A: 1.91
C1B: 2.33
C2C: 2.47
0.3
0.1822
0.0536
C1A: 713
C1B: 827
C2C: 865
C1A: 2.28
C1B: 2.77
C2C: 2.94
0.4
0.1822
0.0714
C1A: 831
C1B: 965
C2C: 1009
C1A: 2.79
C1B: 3.40
C2C: 3.60
0.5
0.1822
0.0893
C1A: 998
C1B: 1158
C2C: 1211
C1A: 3.55
C1B: 4.32
C2C: 4.58
kW
m3
in an impeller tip speed of 6.5 m/s, which is below the design maximum of 7 m/s, reducing
impeller blade erosion. At the maximum motor load (~85%) the volume averaged power per
unit volume is 3.4 kW/m3.
From Table VI the comparative P/Vs indicate that the proposed 3 agitator first compartment
arrangement adequately provides the required P/V range obtained from empirical calculations.
Agitator design sensitivity
The sensitivity of the power per unit volume to the assumed value of for the proposed
commercial autoclave is summarized in Table VII.
Table VII indicates the high sensitivity that the required P/V has to the assumed value of .
For this reason the additional flexibility offered by the proposed agitators is important.
Calculations indicate that at the maximum motor load (~85%) = 0.42 and provides an
additional design margin on agitator power.
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Short-circuiting
By reducing the number of compartments from 5 to 4 the potential for slurry particles to
short-circuit in the autoclave and exit unreacted is increased. This would lead to lower metal
recoveries. A factor that will help minimize the affect of short-circuiting on overall recovery is
the small contribution of compartment 5 to the overall recovery. This is supported by data
collected during test runs on the pilot plant in which compartment 5 increased the overall
recovery of nickel, copper and cobalt by an average of 0.3%, 0.9% and 0.2% respectively.
Short circuiting was analysed by performing a CFD analysis and is outlined in the next
section. This analysis provided insight into the 3 agitator configuration in sufficient detail to
determine if the proposed arrangement will experience short-circuiting.
Objectives of CFD modelling
A CFD model was used to evaluate the following design objectives:
Determine overall mixing and flow patterns in compartment 1 to determine the effect on
process performance
Determine the optimum impeller and baffle configuration that maximizes back mixing in
compartment 1 while minimizing swirling flows beneath the impeller that lead to vessel
lining wear
Determine impeller rotation direction
Determine if the required slurry particle residence time in compartment 1 is achieved
given the large recirculation flow of slurry through the flash cooling and autoclave feed
system.
CFD simulation results
A three dimensional CFD model of the first compartment in the autoclave was constructed to
its actual dimensions. Figure 2 shows the model. The model was set up with the following
boundary conditions (see Figure 2 for location of each):
Slurry feed inletvelocity inlet boundary
The overflow from the weirpressure outlet boundary
The slurry free surfacezero shear (slip boundary)
Vessel wallsno slip boundary.
Agitator rotation direction
The mixing was analysed with each of the agitators operating at a 92 rpm. Two different cases
were studied.
1.
All three agitators rotating in the same direction
2.
Middle agitator rotating in the opposite direction.
Figure 3 shows the velocity profile of the slurry on a horizontal plane 1.863 m from the
slurry free surface. The following observations were made:
There is weak interaction between the flow from adjacent agitators and the overall flow
pattern was found to be similar for both cases.
The dotted lines represent the net slurry flow from the feed end to the discharge end. It
indicates a different flow pattern for the net slurry given the agitator rotation direction.
However, it was observed that the net slurry flow path length was approximately the
same for both cases. The residence time distribution (RTD) of the slurry explains this
quantitatively in a later section.
Figure 4 shows that this agitator and baffle configuration produces two distinct flow loops
one the upper half of the vessel and one in the lower half. This is required for suspension of
solids and effective top to bottom blending of solids with dissolved oxygen.
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Figure 2. Geometric model of autoclave first compartment illustrating major operating conditions
Figure 3. Slurry velocity profile, coloured by velocity magnitude (m/s) on a horizontal plane across impellers. Lines
represent the net slurry flow direction
Figure 4. Slurry velocity profile, colored by velocity magnitude (m/s) on a vertical plane across impellers. Lines
represent the net slurry flow direction
Figure 5 and Figure 6 show the velocity profile on a vertical plane. Similar flow patterns
were observed for both cases (same rotation and middle agitatorreverse rotation). It was
also observed that the slurry flow to the discharge dip-pipes is predominantly from the middle
agitator. The flash discharge pipes are positioned at the location shown to allow a
compartment wall to be inserted between the second and third agitator. A previous CFD
analysis showed this as the optimum location for the dip-pipes for an autoclave with two
agitators in C1 and therefore provides the option to revert back to a two agitator compartment
if desired.
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Figure 5. Velocity profile, on a vertical plane cutting through the left-side (looking downstream) feed and discharge
pipes illustrating the slurry flow pattern
Figure 6. Velocity profile, coloured by velocity magnitude (m/s), on a vertical plane cutting through the right-side
(looking downstream) feed and discharge pipes illustrating the slurry flow pattern
Swirling flow beneath the impeller is unavoidable as angular momentum is imparted to the
slurry by the rotating impeller. Larger solids caught up in this swirling vortex can cause
erosion of the vessel lining underneath the impeller. Therefore, it is important to minimize the
magnitude of such swirling velocities. Extending the baffles closer to the bottom can
minimize the swirling velocity significantly. The final baffle configuration is shown in
Figure 2. Note that extending the baffles right to the bottom of the vessel, breaks the single
swirling vortex into 2 or more smaller vortices on either side of the baffle. These smaller
vortices can actually rotate at a higher velocity than the single swirling vortex beneath the
impeller accelerating the erosion rate of the vessel lining over a smaller, localized region.
Figure 7 shows the velocity profile on a horizontal plane at an off-bottom distance of 0.3 m
illustrating swirling velocity magnitudes on a plane underneath the impellers. A maximum
velocity magnitude of 2 m/s was observed for both cases. It must be noted that the velocities
should not be minimized to an extent that can allow solids settling, and therefore movement of
solids along the vessel bottom is required to avoid solids packing. For the Tati Activox
process, solids suspension does not appear to be a concern due to the very small particle sizes
of solids in the slurry feed (P80=10 m).
The general flow field results indicate that the slurry flow inside the first compartment is
well mixed and no low velocity regions are observed that could otherwise allow the formation
of hot spots. The mixing is quantitatively described by the turnover rate of slurry volume for
the agitator discharge flow. Turnover rates greater than 3 are required for medium to violent
agitation (Bowen 1985). The CFD model predicts a flow rate of 20000 m3/h is generated by a
single impeller corresponding to 7.2 turnovers per minute.
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Mass fraction
Figure 7. Velocity profile, coloured by velocity magnitude (m/s), on a horizontal plane at 0.3 m off-bottom distance
and cutting along the compartment illustrating the swirl velocity magnitudes
Time (min)
Figure 8. Residence time distribution comparison
Residence time distribution (RTD)

The residence time distribution of the slurry in the compartment can also be used to evaluate
the mixing performance and its subsequent effect on recovery. A tracer analysis was
performed to determine the residence time distribution. Mass-less tracers, which follow the
slurry flow closely, were injected into the compartment through the feed inlets and tracked to
determine their residence time. The slurry exiting through the discharge pipe is recycled back
to the front of the compartment after flash cooling. Thus, fresh slurry fed to the first
compartment will flow through a number of recycles before it overflows to the second
compartment.
Figure 8 shows the RTD results for the tracer analysis, single continuous stirred reactor
(CSTR) and for 2 CSTRs in series (calculated from Davis 2002). The RTD for two CSTRs in
series represents the autoclave with the additional weir wall in place. The CFD model predicts
an RTD similar to what would be expected from a single CSTR. When comparing the CFD
model and the 2 CSTRs RTD the potential for short circuiting is likely.
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The impact of the increased material short circuiting on the overall autoclave recoveries still
needs to be quantified; however, it is expected to be negligible based on testwork done in the
Tati demonstration plant and similar modifications done on other operating autoclaves.
Conclusion
Based on all of the calculations and CFD analysis, the following conclusions were reached:
The general flow field results indicate that the flow inside compartment 1 is well mixed
and no distinct low velocity regions are seen that may form hot spots.
The impact of increased short circuiting on the overall autoclave recoveries still needs to
be quantified, however; it is expected to be negligible based on testwork done in the Tati
demonstration plant and similar modifications made on other operating autoclaves.
Due to the small particle sizes of the solids in the incoming slurry feed (P80=10 m),
solids suspension is not a concern, and it is expected that solids will be uniformly
suspended to the full liquid height of the autoclave.
Very good mixing between solids and dissolved oxygen is expected, leading to a uniform
leach reaction extent and process temperature throughout the vessel volume.
A baffle off-bottom clearance of 0.14 D was found to be optimum to minimize the
swirling velocity near the tank bottom.
There is weak interaction between the discharge flow from adjacent agitators for the
given operating condition and the overall flow patterns are uninfluenced by the relative
rotational direction of adjacent agitators.
Different flow patterns for the net slurry flow from the feed end to the discharge end was
observed for the two cases: (1) all agitatorssame rotation direction and, (2) middle
agitatorreverse rotation. However, it was observed that the net slurry flow path length
is approximately the same for both the cases.
Acknowledgements
The authors acknowledge that this paper was originally published as part of the proceedings
of Hydrometallurgy 20086th International Symposium honoring Robert Shoemaker, August
1720, 2008, Phoenix, AZ.
The authors would like to thank the management of Norilsk Nickel Africa, Norilsk Process
Technology and Hatch for their encouragement and permission to publish this paper.
References
TROMANS, D. Temperature and Pressure Dependant Solubility of Oxygen in Water: A
Thermodynamic Analysis. Hydrometallurgy, vol. 48, 1998. pp. 324342.
TROMANS, D. Oxygen Solubility Modeling in Inorganic Solutions: Concentration,
Temperature and Pressure Effects. Hydrometallurgy, vol. 50, 1998. pp. 279296.
PIETERSE, H. Oxidation Autoclave Agitation Review. Pressure Hydrometallurgy 2004, 34th
Annual Hydrometallurgy Meeting, Banff, Alberta, Canada. 2004.
BOWEN, R.L. Agitation Intensity: Key to Scaling Up Flow-Sensitive Liquid Systems.
Chemical Engineering, March 18, 1985.
DAVIS, M.E. and DAVIS, R.J. Fundamentals of Chemical Reaction Engineering. McgrawHill Chemical Engineering Series, International Edition, July 2002.
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Marc Nicolle
Process Engineer, Hatch Africa (Pty) Ltd, South Africa
Marc is a process engineer with over 3 years experience in the design,
engineering and construction of mineral processing and
hydrometallurgical processes. He is developing specialist technical
expertise in ultra-fine grinding, countercurrent decantation, highpressure acid leach, slurry cooling towers and PGM flotation.
In recent years Marc has been part of the process design and project
development for various hydrometallurgical plants around the world.
These include the Norilsk Nickels Tati Activox Project, Phelps Dodges Tenke Fungurume
feasibility study, First Quantum Minerals Kolwezi tailings project, Teal Mining and
Explorations Kalumines project, African Rainbow Minerals and Norilsk Nickels Nkomati
site options study and Anglo Platinums DC/DA acid plant at Waterval Smelter.
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FRANCESCHINI, M and WOLOSHYN, J. Stabilization of supersonic vent gas from autoclave pressure
oxidation. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and Metallurgy, 2009.
Stabilization of supersonic vent gas from

autoclave pressure oxidation
M. FRANCESCHINI* and J. WOLOSHYN*
*Hatch (Pty) Ltd, Ontario, Canada
The ability to control the velocity distribution of a fluid flow is a
fundamental problem in many industrial applications of fluid
engineering. This problem is compounded in hydrometallurgy
because the process fluid is typically two phase, as well as corrosive
and abrasive in nature. This paper investigates the use of a perforated
plate to achieve a stable and uniform flow field downstream of a
shock wave in a blast shroud entering a quench vessel from pressure
oxidation autoclave. Fluid mechanics analysis has been used to
provide insight into the proper diffuser geometry in order to produce
an adequate flow field both downstream and upstream of the plate.
The addition of a perforated plate is found to reduce the maximum
velocity entering the quench vessel to one-fifth of the original
velocity, mitigating the risk of wear on the vessel bottom and
excessive splashing of the water pool. The analysis also indicates that
both the open area and the number of holes in the plate are important
parameters in stabilizing upstream gas flow and minimizing flow
separation downstream of the shock.
The mechanical design of the shroud and perforated plate addresses
concerns around thermal expansion, natural vibration frequency,
strength limitations of nitride-bonded silicon carbide, and the erosive
environment created by supersonic flow with entrained particulate.
Prudent mechanical design is required to ensure a durable long lasting
perforated plate, which will reduce wear on pressure letdown
equipment. Placing the perforated plate in a metal spacer ring allows
it to float between top and bottom supporting flanges. Strict control of
fabrication tolerance is required to maintain clearance between the
plate, spacer ring, and other ceramic components, limiting stresses
induced by thermal expansion to 0.5 MPa. Soft packing and gasket
materials, which are susceptible to erosion, are isolated from the flow
by a tongue-and-groove joint between the ceramic shroud liner and
perforated plate.
Introduction
This paper presents the results of computational fluid dynamics (CFD) and finite element
analyses (FEA) in the design of a novel blast shroud configuration using a perforated plate, as
it applies to pressure letdown of vent gas from a pressure oxidation process. The blast shroud
STABILIZATION OF SUPERSONIC VENT GAS FROM AUTOCLAVE PRESSURE OXIDATION
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is designed to let down the pressure of a vent gas discharging from an autoclave at
4100 kPa(g) into a quench vessel at 14.7 kPa(g). Figure 1 shows an example of a typical
autoclave circuit, where slurry is processed in the autoclave at elevated temperature and
pressure using steam and oxygen gas.
High-pressure vent gas composed mainly of steam and oxygen, but also containing slurry
particles, is vented from the autoclave. The quench vessel condenses the steam and removes
slurry carryover from the vent gas before final cleaning in a cyclonic separator, which then
vents to the atmosphere.
A shock wave is expected within the blast shroud because of the large pressure drop.
Therefore, the design must ensure that the shock wave is stable in order to prevent the risk of
flow-induced vibrations on the blast shroud structure. Moreover, the design must also ensure
that the velocities entering the quench vessel are minimized to prevent wear on the bottom of
the vessel or excessive splashing of the water pool. The addition of the perforated plate is
proposed to address both the shock stability and improve flow uniformity entering the quench
vessel.
CFD analysis result and discussion
The geometry of the blast shroud is shown in Figure 2.
The gas, which is primarily composed of steam, passes through a conical upper section
before reaching the perforated plate. The geometry of the conical section is defined based on
an internal angle of and a length of L1. The second part of the blast shroud, downstream of
the cone and perforated plate, is a cylinder with a diameter of D and a length of L2.
The boundary conditions used for the CFD model of the blast shroud are shown in Figure 2.
The boundary conditions are set as the mass flow at the inlet and a specified gauge pressure at
the outlet. The model inlet represents the throat of the diffuser and the flow at this location is
STACK
TO
ATM
SAFETY RELIEF
CYCLONE
SEPARATOR
AUTOCLAVE
FEED SLURRY
VENT
QUENCH
VESSEL
FLASH
TANK
AUTOCLAVE
FEED TANK
TO THICKENING
AUTOCLAVE
OXYGEN
OXYGEN
BLOWBACK VESSEL
HP STEAM
FLASH DISCHARGE
PUMP BOX
STEAM
BLOWBACK VESSEL
Figure 1. Example of an autoclave circuit
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Figure 2. Geometry of the blast shroud and boundary conditions for the CFD model
Figure 3. Velocity distribution inside the blast shroud without perforated plate
choked (i.e. Ma = 1). Due to model limitations phase change has been neglected. Phase
change is an important phenomenon near the shock wave where the temperature decreases
dramatically. Although the temperature is expected to drop below 0C in a small region just
prior to the shock wave, the impact of neglecting phase change is considered minimal because
the flow has an extremely low residence time within the cold zone. The overall flow field
and trends predicted by the CFD model are expected to be valid.
To understand the effect of adding a perforated plate to the blast shroud, the flow field is
first modelled without a plate present. Figure 3 shows contours of gas velocity inside the blast
shroud without a perforated plate.
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Figure 4. Initial perforated plate geometry investigated using CFD analysis. The geometry is based on a 50% open
area and 1 diameter holes
The supersonic flow accelerates with increasing cross-sectional area. As the gas velocity
increases, the pressure decreases until a shock wave occurs. As expected1, the flow separates
immediately downstream of the shock wave and a central jet of high speed flow persists. The
result is a complex pattern of shocks within a jet of mixed supersonic and subsonic flow.
Furthermore, the position of this jet was found to be unstable. The flow separation
downstream of the initial shock causes the jet to move toward the wall of the shroud. This
behaviour sets up an unstable separation bubble, causing the jet to oscillate with time. The
instability in the flow field is a concern because it may pose a risk of flow-induced vibrations
in the structure of the shroud. This would occur if the frequency of the oscillations were to
coincide with any of the natural frequencies of the structure.
Figure 4 shows the initial perforated plate geometry that was investigated. The use of a
perforated plate for this application is novel, so no standard practices are available for
selection of hole size or open area.
A 50% open area and 1 holes were selected as a starting point based on Hatch experience in
other fields.
Figure 5 shows pressure contours and a plot of the pressure and velocity along the centerline
of the shroud both with and without the perforated plate.
The presence of the plate dramatically affects the upstream and downstream flow fields. A
pressure drop of approximately 13.5 in-H2O (3360 Pa) across the plate, which is very low
relative to the total pressure let down, effectively creates a higher and more uniform pressure
field upstream. The shock wave is stabilized and the flow separation and secondary shocks are
prevented.
The velocity distribution and flow field inside the shroud are shown in Figure 6.
Comparing this result to that of Figure 5, a significant improvement in the uniformity of the
velocity field across the shroud is seen. The two key improvements observed are: (1) the
elimination of the unstable, high speed jet observed in the previous case, and (2) a uniform or
plug flow profile exiting the shroud. Based on these improvements, the risk of flow induced
vibrations and of wear and pool disturbance in the quench vessel are mitigated.
Figure 7 shows the effect of the perforated plate on the exit velocity distribution from the
blast shroud and entering the quench vessel.
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Figure 5. Pressure and velocity variation through the blast shroud (a) without the perforated plate, and (b) with the
perforated plate
Figure 6. Velocity distribution and flow field inside the blast shroud with a perforated plate
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Velocity (m/s)
Distance from shroud centreline (m)
Figure 7. Velocity distribution across the shroud exit plane (i.e. entering the quench vessel)
Without a perforated plate, the separated flow upstream affects the exit velocity profile,
which is non-uniform and unstable. The maximum velocity entering the quench vessel is in
the range of 110 m/s to 285 m/s. By contrast, with the perforated plate in use, the velocity
profile is uniform and the maximum velocity entering the quench vessel is reduced to 62 m/s.
This velocity is considered acceptable for the current application.
Effect of perforated plate geometry
The geometry of the perforated plate has a significant effect on the flow stabilization inside
the shroud. CFD modelling was used to test another design for the perforated plate to
determine the effect of the opening density (as defined by Equation [1]).
[1]
With the open area maintained at 50%, the hole diameter was increased from 1 to 2, i.e.
the hole density was decreased from 987 m-2 to 247 m-2. Figure 8 compares the velocity
distribution inside the blast shroud with this new perforated plate geometry to the previous
two cases.
With the reduced hole density the pressure drop across the plate is reduced from 13.5 in-H20
(3360 Pa) to 11.5 in-H20 (2870 Pa) and a mix of sub and supersonic flow exists upstream of
the perforated plate. Comparing this result to the velocity distributions without any plate, the
downstream flow has been somewhat stabilized; however, the upstream jet still exists. This
penetrating jet creates normal shocks upstream of the plate. Further work is underway to
determine the critical pressure drop at which the upstream flow field is fully stabilized and the
best combination of percent open area and hole density to achieve this pressure drop.
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Figure 8. The velocity distribution inside the blast shroud with (a) no perforated plate, (b) a perforated plate with a
hole density of 987 m-2, (c) a perforated plate with a hole density of 247 m-2
FEA analysis result and discussion

Geometry
The perforated plate geometry is driven by the process opening of the blast shroud and the
requirement for 50% open area, as defined by the CFD analysis. For practical reasons the
geometry is modified slightly from that shown in Figure 4; however, the hole diameter and
open area are maintained. The outside diameter of the perforated plate is oversized to allow
for a clamping annulus, as depicted in Figure 9.
To obtain the required flow characteristics, the disk has 187 holes arranged in triangular
pitch pattern, as depicted in Figure 10.
Figure 9. Mechanical assembly of ceramic blast shroud and perforated plate. Gaskets and PTFE are shown in their
hot, compressed form
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Figure 10. Plan view of perforated plate showing hole pattern and pitch details. A total of 187 holes combine to create
91,793 mm2 of open area. Radii on the circumferential slot and leading/trailing edges of holes are visible
Table I
Physical properties of nitride bonded silicon carbide (NBSC) provided by Blasch Precision Ceramics, Albany,
NY, USA
Youngs modulus
Poissons ration
Density
Thermal expansion
Thermal conductivity
Specific heat
Tensile strength
80
0.15
2800
4.68E-06
14
940
3033
GPa
kg/m3
/C
W/m2K
J/KgC
MPa
The layout is critical to provide sufficient webbing between holes to ensure structural
integrity. Stress concentrations are minimized by smoothing sharp junctions with 6 mm radii
on concave corners and 1 mm on convex edges, specifically at the leading and trailing edges
of holes. The outer annulus has been slotted circumferentially to accommodate overlapping of
the ceramic blast shroud and perforated plate to protect the PTFE packing and gasket. This is
required to prevent the abrasive process fluid from eroding the soft packing and gasket
material, thus compromising the pressure barrier. The diverging ceramic shroud and
perforated plate are constructed from nitride bonded silicon carbide (NBSC). This material
was chosen for its hardness and resistance to erosion. Physical properties of NBSC required
for FEA analysis are listed in Table I.
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Figure 11. Thermal profile through the perforated plate
Table II
Summary of FEA results. Three cases are considered with different boundary constraints. Case 1 is free to expand
radially and axially, case 2 is constrained in the radial direction, and case 3 is constrained axially
Case
Radially
Free
Fixed
Free
Axially
Free
Free
Fixed
Front
232C, 500 W/m2C
232C, 500 W/m2C
232C, 500 W/m2C
Back
230C, 500 W/m2C
230C, 500 W/m2C
230C, 500 W/m2C
Boundary conditions
Heat load
Rim
150C, 2
W/m2C
150C, 2
W/m2C
150C, 2 W/m2C
Stress intensity
0.521 MPa
Hole edgetop surface
224 MPa
Hole edgeinside
308 MPa
Outside edge of lap joint
Max principal
0.358 MPa
Outer rim
264 MPa
Lap joint fillet
139 MPa
Outside edge of lap joint
Min principal
-0.518 MPa
-223 MPa
-347 MPa
Bottom of lap joint valley
0.64
0.05
nonefixed
0.31
0.68
nonefixed
Deflection/growth
Radial (mm)
Axial (mm)
Mechanical design
It is critical that thermal expansion of the blast shroud and perforated plate be managed to
mitigate the risk of overstressing the NBSC resulting in cracking, and ultimately failure. To
simulate operating conditions the temperature profile in Figure 11 is generated by applying
temperature and convection coefficients to the top, bottom and outer plate surfaces.
Temperatures for the top and bottom faces are from the CFD analysis. The temperature and
convection coefficient applied to the outer edge of the plate is approximated from past FEA
experience.
Thermal growth in the axial and radial directions is reported in Table II, along with
maximum stresses due to the temperature gradient through the perforated plate. As expected,
the stresses in the unconstrained case are orders of magnitude lower. Generally, stresses are
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developed in the plate when the hot centre portion expands and is constrained by the cooler
outer clamping annulus. As shown in Figures 12 through 14, this generates compressive
stresses in the centre portion and tensile stresses in the outer portion of the plate.
These stresses are intensified in the thin wall sections between holes and the slotted
circumferential groove. There is also a variation in stress between the hot and cold faces due
to the 2C temperature difference between them. Ceramic materials tend to fail in a brittle
manner, which occurs abruptly with no yielding as the rupture strength is exceeded. The
tensile strength of NBSC is given by the manufacturer as 3033 MPa2. In the unconstrained
state (case 1), peak stress levels in the plate are 0.36 MPa in tension and -0.52 MPa in
compression. These values are less than 2% of the rupture strength. However, if growth of the
perforated plate is restrained as seen in cases 2 and 3, stress levels rise dramatically and will
certainly exceed the tensile limit causing failure.
It is of absolute importance that the perforated plate be allowed unrestrained thermal
growth, while being held in place to minimize vibration. Radial expansion is permitted by
centring the ceramic perforated plate within the metal spacer ring. All mechanical loads from
piping, bolting and pressure will be transferred through the spacer ring instead of the fragile
ceramic plate. The spacer ring inside diameter is slightly larger than the perforated plate
Figure 12. Stress intensity plots in true scale from Ansys Workbench
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Figure 13. Maximum principal stress plots in true scale from Ansys Workbench
outside diameter, thus allowing ample space for radial thermal expansion. Axial thermal
growth is taken up by compressing the PTFE packing on the top and bottom surfaces of the
clamping annulus. In the cold state, the PTFE will be uncompressed, but not loose. As the
assembly is heated, the metal and ceramic components will expand compressing the PTFE up
to 20%, while holding the perforated plate in position. Also, the PTFE will cushion the
perforated plate from impacting other metal or ceramic components.
Natural frequency
There is potential for vibration to cause cracking and failure of the ceramic plate. The first and
second natural frequencies are calculated by axially restraining the plate around the outside
top edge. The first and second natural frequencies occur at 442 and 1129 Hz respectively. The
undamped deformation pattern is shown in Figure 15. The first natural frequency is quite high
(442 Hz or 26520 RPM) making it unlikely for process equipment such as pumps to vibrate at
this frequency. However, it is difficult to predict all sources of vibration and it is possible for
process valves to create excitation frequencies at this level. If vibration causes the failure of
the perforated plate it is possible to increase or decrease the natural frequency by reducing or
increasing the thickness of the perforated plate.
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Figure 14. Minimum principal stress plots in true scale from Ansys Workbench
Design benefits and conclusions

The CFD analysis has shown that the use of a perforated plate in the blast shroud improves
the flow field by eliminating the unstable, high-speed jet downstream of the shockwave and
by creating a uniform flow profile exiting the shroud into the quench vessel. The reduced
entry velocity eliminates the need for replaceable wear components such as impingement
blocks and ceramic tiles. The absence of a high-speed jet eliminates the need for a large liquid
pool for energy dissipation, while protecting the vessel lining and shell from erosion. As a
result, pressure let down vessels can be made more compact and cost-effective without
sacrificing availability or performance. The stability of the shockwave will mitigate the risk of
flow-inducted vibration and fatigue in metallic the blast shroud, nozzle and vessels
components. The ability to control large pressure drops has further economic potential in that
multistage letdown might be achieved in fewer stages, reducing the required number of
vessels and capital cost.
The analysis shows that the performance of the perforated plate is related to the pressure
drop across it. The hole density and percent open area are two key design parameters that can
influence the pressure drop. Two bounding cases were studied, but further investigation is
required to determine the optimal design case.
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Figure 15. Deformation pattern at first and second natural frequencies
Thermal stresses can be minimized through generous filleting and contouring of corners,
and most importantly, by allowing unrestricted thermal growth in both radial and axial
directions. The spacer ring is designed to carry all mechanical loads and provide enough
support to prevent chatter, thus ensuring the longevity of the ceramic perforated plate.
Acknowledgements
The authors would like to acknowledge Dave Warnica, Hatch Ltd., for suggesting the use of a
perforated plate flow diffuser for this application.
References
1. PAPAMOSCHOU, D. and JOHNSON, A. Unsteady Phenomena in Supersonic Nozzle
Flow Separation, 36th AIAA Fluid Dynamics Conference and Exhibit, June 2006, San
Francisco, CA.
2. CONNORS, T. Blasch Precision Ceramics, September 2007, Albany, NY, USA.
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Michael Franceschini
Mechanical Engineering Autoclave Technology Non-Ferrous,
Hatch (Pty) Ltd, Ontario, Canada
Michael is experienced in mechanical engineering in the development of
high pressure acid/oxygen leach process plants and in pressure vessel design
and knowledge of the ASME Boiler and Pressure Vessel Code Section VIII
Division I & II and the associated ASME/ANSI/ASTM Standards. He is
proficient in the use of calculation spreadsheets to perform detailed
mechanical equipment design. He has worked with exotic metals such as
titanium, duplex and super duplex stainless steels, tantalum, and nickel
alloys. His expertise in various other computer programs including Codeware Compress, AFT Arrow
and Fathom.
Michael has the ability to conduct finite element analysis (FEA) using Ansys Workbench, Design
Modeller and ICEM. He has completed Div II thermal, structural, modal and bucking analysis of
refractory lined pressure vessels, large bore ducting and various vessel internals.
Barrick Gold Corporation, Pueblo Viejo, Dominican Republic Detailed Engineering
responsibilities to date include pump sizing and the preparation of a pump specification for
budget quotation, as well as finite element analysis of pressure equipment, ducting and vessel
internals.
Barrick Gold U.S. INC., Donlin Creek, Alaska, USA, Bankable Feasibility Study
responsibilities included sizing of mechanical equipment for pressure oxidation circuit using
Codeware Compress. He assembled specifications and drawing for tender packages, and
completed vendor bid evaluations. He completed bankable capital cost estimate for autoclave
area.
Metals Enterprise, Moa Bay, Cuba, 16K Expansionsmodelled mechanical equipment using
Codeware Compress and checked vendor calculation to ensure code compliance.
Sargold Resource Corporation, Sardinia, Italy, Class Four Estimatecarried out equipment
sizing for a pressure oxidation autoclave circuit and generated factored capital cost and
operating cost estimates
Jennifer Woloshyn
Specialist in the application of computational fluid dynamics,
Hatch (Pty) Ltd, Ontario, Canada
Jennifer received her MA Sc in the area of fluid in 2004 from the University
of Waterloo in Canada. She has been working at Hatch since 2004,
specializing in the application of computational/fluid dynamics (CFD)
modelling techniques to solve problems for which traditional analysis trials
are not sufficient.
Jennifer contributed to the design of a variety of purposes vessels as well as
capture hoods and ventilation systems.
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MULABA-BAFUBIANDI, FOSSO-KANKEU, E., and MAMBA, B.B. Indigenous microorganism strains as

bio-extractants of Ca, Fe, and Mg from metallurgical and mine drainages. Hydrometallurgy Conference 2009,
The Southern African Institute of Mining and Metallurgy, 2009.
Indigenous microorganism strains as

bio-extractants of Ca, Fe, and Mg from
metallurgical and mine drainages
A.F. MULABA-BAFUBIANDI*, E. FOSSO-KANKEU*, and B.B. MAMBA
*Department of Extraction Metallurgy, Faculty of Engineering and the Built Environment,
University of Johannesburg, South Africa
Department of Chemical Technology, Faculty of Science,
Attempts to remediate the high concentration of calcium, iron and
magnesium in surface waters from metallurgical areas by
experimenting at laboratory scale on the removal of these metals in
synthetic solutions (30 and 50 ppm), using indigenous strains of
Shewanella sp, Bacillus subtilis sp and Brevundimonas sp, revealed
variable abilities of these microorganisms in the removal process.
Bacillus subtilis sp and Shewanella sp absorbed the higher amount of
each of the three metals from solution, and calcium was the metal
most easily removed. Metals removal from solution decreased when
their concentrations were at 50 ppm. It was found that when metals
were combined in the same solution they contribute to inhibit
microorganisms, change the microbial affinity for metal and affect the
removal efficiency. Depending on the metal, there was a tendency for
microorganisms to release the absorbed metal into the solution after a
certain time, likely due to an efflux transport system previously
demonstrated by some authors. Use of non-living biomass did not
improve the removal efficiency.
Keywords: indigenous strains, biosorption, bioaccumulation, living
biomass, non-living biomass, metal removal
Introduction
For decades concerned companies and local authorities have demonstrated interest in
managing water from metallurgical and mining areas. A general tendency is to shift from the
ineffective and costly physico-chemical techniques to the biological techniques found to be
cheap and eco-friendly (Alluri et al., 2007; Cohen, 2006; Kefala et al., 1999). Although some
of the bench-scale experiments have been successful, the challenge remains to implement the
technique at industrial level. This results from the fact that the concept is not entirely
understood and therefore requires more effort in improving the removal process on
operational level (Wang and Chen, 2006).
INDIGENOUS MICROORGANISM STRAINS AS BIO-EXTRACTANTS
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The presence of residual metals in effluent water represents primarily a substantial loss in
revenue for metallurgical companies. Secondly, it could be the cause of legal liability vis a vis
environmental safety as these metals are potential pollutants of the water system. According
to the South African National Standard (2005) an excess of calcium and iron in water could
cause aesthetic or operational problems while excess of magnesium in water could cause
esthetic and health problems.
Microorganisms possess inherent abilities suitable for the removal of metals from solutions
(Nies, 1999; Langley and Beveridge, 1999; Beveridge and Murray, 1976). These abilities have
been identified as passive or active for accumulation and biosorption respectively (Brandl and
Faramarzi, 2006). However, there are always challenges that contribute to undermine the
benefit of this process: the high concentration of metals could be toxic for microorganisms
and acidic conditions are unfavourable for the development of most of microorganisms which
are neutrophiles (Kim et al., 2006; Sandrin and Maier, 2003). To overcome these challenges,
one needs to use indigenous microorganisms adapted to conditions in situ, or alternatively use
either genetically modified microorganisms or non-living biomass that could cope with
existing conditions. Bacillus strains have been widely reported in literature to be effective in
the removal of metals (Pb, Cd, Cu, Ni, Co, Mn, Cr, Zn) from waste waters (Kim et al., 2007;
Srinath et al., 2003; Philip and Venkobachr, 2001), but other strains (Brevundimonas and
Shewanella) also identified during this study at mining sites, have not been tested for the
treatment of metallurgical and mine drainages. In this study, living and non-living biomass of
all these strains will be tested for their effectiveness to clean out Ca, Mg and Fe predominant
in surface water around mining areas in Nigel.
Methodology
Isolation and identification of microorganisms
Water and soil samples collected in sterile glass bottles around mining areas in Nigel were
preserved at 4C during transportation to the laboratory. Soil samples were suspended in
sterile distilled water vortexed, and the supernatant as well as the water samples diluted in
sterile phosphate buffer prior to inoculation in chromogenic media for coliforms and
Escherichia coli, and in nutrient agar. After overnight incubation of cultured media, colonies
of microorganisms were isolated from the plate and subcultured in fresh media. Unknown
microorganisms were subsequently identified by gene sequencing at Inqaba Biotechnical
Industries (Pty) LtdSouth Africa.
Preparation of synthetic solutions
Synthetic metal sulphates obtained in powder or crystal form were weighed and diluted in
sterile distilled water to make a stock solution of 1 000 ppm. From the stock solution various
volumes were removed into the final solution to obtain concentrations between 30 and
50 ppm.
Microorganisms growth and biomass preparation
Microorganisms were inoculated into the nutrient broth (Lab-Lemco powder 0.1%, yeast
extract 0.2% and NaCl 0.5%), incubated at 37C in the incubator with shaker (150 rpm) for
twenty-four hours. The culture was centrifuged for 15 minutes at a speed of 8 000 rpm, the
supernatant was discarded and the pellet washed several times with sterile distilled water then
suspended in a sterile flask. Concentrated cells were lyophilized and autoclaved at 121C for
15 minutes to prepare non-living biomass.
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Metal removal
The ability of microorganisms to remove metal from solution depends on two mechanisms
called biosorption and bioaccumulation, which are passive or active respectively:
Biosorption is described as a chemical interaction between an anionic group (amino acids,
hydroxyl, phosphate, etc.) on the bacterial cell membrane and the positively charged metal in
solution. There is no net energy required during this process. (Figure 1.)
Bioaccumulation is a reaction whereby the metal is sequestered through the bacterial
membrane into the cytoplasm of the cell; during this process microorganisms use energy (ATP
hydrolysis) to catalyse the reaction. This process could also contribute to the supply of
cofactor for enzymatic reactions; however, an excess of metal could be excreted from the cell
by an efflux transport system (Nies, 1999). (Figure 2.)
For the experimentation of metal removal in this study, synthetic metal solution was mixed
with microorganisms (100 mg wet cell) in a 250 ml Erlenmeyer flask, and sterile distilled
water added up to a final volume of 100 ml. Microorganisms were exposed to 30 ppm and 50
Figure 1. Adsorption of copper on the cell surface of bacteria (from Kim et al., 2007)
Figure 2. Active transport of arsenate into bacterial cytoplasm (from Nies, 1999)
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ppm concentrations of each metal separately as well as with a mixture of metal ions. The
mixture was then incubated at 37C in the incubator with shaker (150 rpm) and 5 ml of sample
solution was taken after one, two and twenty-four hours, as previous authors obtained
maximum metal removal at these times (Kefala et al., 1999; Kim et al., 2007). The solution
was then centrifuged at 8 000 rpm for five minutes and the supernatant collected for
quantification of the amount of metal.
Metal quantification and experimental procedure
Determination of the amount of metal in solution was done using inductively coupled plasma
optical emission spectrometry (ICP-OES). All the experiments were done in triplicate with a
control; the difference between the replicate was less than 10%. The average value of the
triplicate was considered when drawing the graph.
Strains of Bacillus subtilis, Shewanella sp and Brevundimonas sp were identified in soil and
water samples from mining areas by gene sequencing. These strains were tested for their
abilities to remove Fe, Ca and Mg from synthetic solution containing 30 and 50 ppm of the
above metal.
Metal tolerance
To determine whether microorganisms were alive during the whole removal experiment, at
each time sample was collected for analysis; one ml was simultaneously inoculated in
phosphate buffer, diluted five times (10-1, 10-2, 10-3, 10-4 and 10-5) then plated on agar media
(chromogenic media for coliforms and Escherichia coli) and incubated at 37C overnight.
Microorganism survival was then assessed as the occurrence and number of typical colonies
in the agar media.
Results and discussions
Removal of individual metal
% metal removed
The ability of Bacillus subtilis to remove metal ions varied depending on the metal specie;
there was a greater affinity for calcium than for other metals (Figure 3). In fact calcium
removal was around 14% while iron and magnesium removal was less than 10%. It was also
noticed that the removal efficiency was lower at 50 ppm concentration of metal after 24 hours.
Figure 3. Separate removal of Fe, Ca and Mg by Bacillus subtilis sp
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% metal removed
Shewanella sp also showed greater affinity for Ca but there was a tendency to release the
metal into solution from the second hour of the experiment (Figure 4). A higher removal rate
was recorded at 30 ppm concentration of metal.
Among all the bacteria, Brevundimonas sp has the lower performance as far as metal
removal is concerned. However, it also has greater affinity for calcium and the highest
removal was approximately 9% of Ca at 50 ppm concentration (Figure 5).
It is observed that metal removal in this experiment is greatly influenced by the affinity of
the microorganism for the metal, as during the first hour (contact time) metal binding rate to
the microbial cell wall differed from one metal to the other. According to work done by
Kefala et al. (1999) the composition of the cell wall (reactive groups) of microorganism play
an important role in determining the attraction of the metal. However, other factors such as
surface availability on the cell wall could affect the removal efficiency, knowing that
saturation of the cell is quickly reached in solution containing high concentration of metal,
decreasing the ratio of metal removed to total metal in solution. This explains why generally
after the first hour the percentage of metal removed is higher in solution with 30 ppm of
metal.
% metal removed
Figure 4. Separate removal of Fe, Ca and Mg by Shewanella sp
Figure 5. Separate removal of Fe, Ca and Mg by Brevundimonas sp
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During the second and twenty-fourth hours it is likely that a bioaccumulation mechanism
dominates over biosorption, since the second mechanism reaches the maximum after
5 minutes contact time (Sadowski et al., 1991). The removal rate could therefore increase,
meaning that the metal is progressively transported into the cell or decrease when there is
efflux transport or rupture of bounds between metal and reactive groups on the microorganism
cell wall.
The low rate of metal removed during this study is partly due to the fact that a smaller mass
of cells was used compared to other studies. It is reported (Schiewer and Volesky, 1995a;
Kefala et al., 1999; Wang, 2002a) that higher cell concentration could increase metal removal.
Removal of mixed metals
To simulate the conditions in mine areas, living biomass was exposed to solution containing
all three metals, each present at concentration of 30 or 50 ppm, depending on the set of
experiment. Results (not shown) revealed that the removal efficiency of the microorganisms
decreased by almost half and the affinity shifted to iron.
To enhance the removal efficiency by overcoming the limitations associated with living
cells such as metal toxicity and inefficiency under adverse operating conditions (Tobin et al.,
1994), it was decided to use non-living cells, which are reported to have higher metal uptake
capacities (Gadd, 1990).
No difference was found (results not shown) in the removal efficiency of mixed metal as
compared to the use of living cells but the specificity of metal binding was affected as the
heating process could contribute to destabilize reactive groups.
Metal tolerance
Evaluation of the survival of microorganisms after one, two and twenty-four hours of metal
exposure showed little decrease of microbial number in solution of 50 ppm of nickel. In
solution containing mixed metals, cells of Shewanella sp were all dead after the first hour
while Brevundimonas sp biomass was seriously affected. However, Bacillus subtilis is not
affected by the presence of metal, showing no significant change in the growth rate. This
implies that in the presence of high concentrations of metals, microbial biomass can be
reduced, therefore reducing the removal efficiency of metal from solution.
Conclusion
Attempts to remove metal from solution using indigenous microorganism isolated around
mine areas, showed that this process is largely dependent on the affinity between the
microbial cell wall and the metal. It was found that when using living cells, removal
efficiency could be affected by factors such as inhibition and efflux transport system.
However, use of non-living biomass did not bring any change in removal efficiency but has
the advantage that it is simple. Further studies to determine optimal biomass efficiency
through a maximum metal removal rate in the shortest possible time (the kinetics of the
reaction), coupled with analysis of cost involved, will improve the understanding of the
approach to the recovery of excess residual metals in process water discharged from
metallurgical activities.
Acknowledgements
Dr Barnard of the Water and Health Research Unit (UJ) has opened the doors to their research
facilities and the South African National Research Foundation (NRF) and the University of
Johannesburg provided the research funds and the scholarship.
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References
ALLURI, H.K. et al. 2007. Biosorption: An eco-friendly alternative for heavy metal removal.
African Journal of Biotechnology, vol. 6, no. 25, 2007. pp. 29242931.
BEVERIDGE, T. and MURRAY, R.G.E. 1976. Uptake and retention of metals by cell walls of
Bacillus subtilis. Journal of Bacteriology, vol. 127, no. 3, 1976. pp. 15021518.
BRANDL, H. and FARAMARZI, M.A. Microbe-metal-interactions for the biotechnological
treatment of metal-containing solid waste. China Particuology, vol. 4, no. 2, 2006.
pp. 9397.
COHEN, R.R.H. 2004. Use of microbes for cost reduction of metal removal from metals and
mining industry waste streams. Journal of Cleaner Production. vol. 14, no. 1213, 2004.
pp. 11461157.
GADD, G.M. Biosorption. Chemistry and Industry, vol. 2, 1990, pp. 421426.
KEFALA, M.I., ZOUBOULIS, A.I., and MATIS, KA. Biosorption of cadmium ions by
Actinomycetes and separation by flotation. Environmental Pollution, vol. 104, no. 2,
1999. pp. 283293.
KIM, S.U., CHEONG, Y.H., and SEO, D.C. et al. 2007. Characterisation of heavy metal
tolerance and biosorption capacity of bacterium strain CPB4 (Bacillus spp). Water
Science and Technology, vol. 55, no. 3, 2007. pp. 105111.
LANGLEY, S. and BEVERIDGE, T.J. Effect of O-side-chain-Lipopolysaccharide chemistry
on metal binding. Applied and Environmental Microbiology, vol. 65, no. 2, 1999.
pp. 489498.
NIES, D.H. Microbial heavy metal resistance: Molecular biology and utilisation for
biotechnological processes, 1999. pp. 145.
PHILIP, L. and VENKOBACHR, C. An insight into mechanism of biosorption of Cu by
B. Polymyxa. Indian Journal of Environmental Pollution, vol. 15, 2001. pp. 448460.
SADOWSKI, Z., GOLAB, Z., and SMITH, R.W. Flotation of Streptomyces pilosus after lead
accumulation. Biotechnology and Bioengineering, vol. 37, 1991. pp. 955959.
SANDRIN, T.R. and MAIER, R.M. Impact of metals on the biodegradation of organic
pollutants. Environmental Health Perspectives, vol. 111, no. 8, 2003. pp. 10931101.
SCHIEWER, S. and VOLESKY, B. Mathematical evaluation of the experimental and
modeling errors in biosorption. Biotechnology Technology, vol. 9, 1995a. pp. 843848.
SOUTH AFRICAN NATIONAL STANDARD. 2005. Drinking Water. SANS 241, edition 6;
ISBN 0-626-17752-9.
SRINATH, T., GARG, S.K., and RAMTEKE, P.W. Biosorption and elusion of Cr from
immobilized Bacillus coagulens biomass. Indian J Exp. Biol. vol. 41, 2003. pp. 986990.
TOBIN, J.M., WHITE, E., and GADD, G.M. Metal accumulation by fungi: applications in
environmental biotechnology. Journal of Industrial Microbiology, vol. 13 1994.
pp 126-130;
WANG, J. and CHEN, C. Biosorption of heavy metals by Saccharomyces cereviceae: A
review. Biotechnology Advances, vol. 24, 2006. pp. 427451;
WANG, J.L. Immobilization techniques for biocatalysts and water pollution control. Beijing:
Science Press. 2002a.
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Elvis Fosso-Kankeu
Master in Biotechnology completed in 2006 at the University of
Johannesburg; Research Associate at the University of Johannesburg
(2005-2008); Assistant consultant in the monitoring and improvement
of plant water treatments (2007). One full article published in 2008
and two manuscripts submitted for publication in 2008. Registered for
a doctorate in bioprocessing at the University of Johannesburg
(Department of Extraction Metallurgy).
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MULABA-BAFUBIANDI, A.F., DLAMINI, N.P., AND MAMBA, B.B. Biosorption of cobalt and copper from
hydrometallurgical solutions mediated by Pseudomona spp. Hydrometallurgy Conference 2009, The Southern
African Institute of Mining and Metallurgy, 2009.
Biosorption of cobalt and copper from

hydrometallurgical solutions mediated by
Pseudomona spp
A.F. MULABA-BAFUBIANDI*, N.P. DLAMINI*, and B.B. MAMBA
*Department of Extraction Metallurgy, Faculty of Engineering and the Built Environment,
Department of Chemical Technology, Faculty of Science,
Pseudomonas spp was isolated from mine water and tailings samples
collected from mining effluents and mine dumps in the Gauteng and
Northern provinces of South Africa respectively. Adsorption
properties of Pseudomonas spp were then tested for the removal of Cu
and Co initially from their synthetic sulphate solutions, subsequently
from effluents derived from metallurgical operations. The effects of
experimental conditions such as pH, temperature, time, volume and
metal concentration on the efficiency of the biosorption process were
studied. Absorption of 45% Cu (pH 6, 37C, 24 hours) and 40% Co
(pH 6, 37C, 24 hours) was observed from solutions with low
concentrations (0.07 M). A maximum of 73% and 65% of Cu and Co
respectively were recovered from the mine water samples derived
from effluents.
Introduction
Metal accumulation in the environment as a result of mining and metallurgical activities is
arising as a matter of serious concern. The removal and recovery of metals from
hydrometallurgical solutions and waste water prior to their release to the environment are
important in preserving the ecosystem as well as from an economical perspective. There are
several technologies used to recover metals such as Cu, Co, Zn, Hg and many others. These
include among others, ion exchange, precipitation, filtration, electrochemical treatment,
electrowinning, reverse osmosis and reduction. These technologies, however, tend to be
excessively expensive when the metal concentrations are less than 100 mg/l (Bueno et al.,
2008). Since microorganisms have developed survival strategies in metal polluted habitats,
their different microbial detoxifying mechanisms such as bioaccumulation, biotransformation,
biomineralization or biosorption can be applied either in situ or ex situ. Bacteria also make
excellent biosorbents because of their high surface to volume ratios and a high content of
potentially active chermosorption sites such as teichoic acid in their cell walls (Beveridge,
1989).
BIOSORPTION OF COBALT AND COPPER FROM HYDROMETALLURGICAL SOLUTIONS
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Biosorption of metals is one of the most promising technologies involved in the removal of
toxic substances from industrial wastes and has been receiving a great deal of attention in
recent years, not only because of its scientific novelty but also because of its potential
application in industry (Wase and Forster, 1997; Bailey et al., 1999; Kumar et al., 2006). It is
also a cost-effective technology since it does not require high starting costs.
Metal ions uptake by biosorption is complex and may involve the contribution of diffusion,
adsorption, chelation, complexaton, coordination or microprecipitation mechanisms,
depending on the specific biomass or substrate (Veglio and Beolchini, 1997). Therefore this
biological phenomenon can be affected by many chemical and physical variables such as pH,
ionic strength, biomass concentration and presence of different heavy metals in solution. All
these factors have to be investigated in order to understand how this phenomenon takes place
and to optimize operating conditions.
Pseudomonas spp, on the other hand, is a widespread bacteria and was observed in the early
history of microbiology. The name Pseudomonas meaning false unit was derived from
Greek pseudo ( 'false') and monas ( / 'a single unit'). The term monad
was used in the early history of microbiology to denote single-celled organisms. This genus
was first defined in 1894 as a genus of Gram negative, rod-shaped and polar-flagellated
bacteria ( Wikipedia, 2008-09-06) It has been used in bioremediation processes because of its
ability to bind to metal ions. The extent of binding is dependent on the nature of binding,
metal chemistry and metal affinity of binding sites (Brady and Tobin 1994).Copper and cobalt
were chosen for biosorption studies to their wide use in industry and potential pollution
impact. Mining companies have become increasingly aware of the potential of
microbiological approaches for recovering base and precious metals from low-grade ores, and
for bioremediating acid mine drainage and mine tailings. There are two strategies: biomining
and bosorption where microorganisms are used to recover metals in solution (e.g. acid mine
drainage) by precipitation of the metal, or complexing or absorption with cellular molecules.
Biopyrometallurgy then enables recovery of these metals with the microbial biomass
contributing as fuel.
Materials and methods
Isolation of microorganisms
Samples of water and soil were collected from mining effluents and mine dumps in the
Gauteng and Northern provinces of South Africa respectively. These samples were kept in
cool conditions for about 12 hours before isolation could be done.
Media preparation
Pseudomonas agar base powder (24.20g) was weighed and suspended in 500 ml of distilled
water. 5 ml of glycerol was added and the mixture was boiled for about 2 minutes in a
microwave to dissolve the mixture completely. The media was sterilized by autoclaving using
the HUXLEY HL 341 speedy autoclave at 121C for 15 minutes. The medium was allowed to
cool to about 50C and a vial of Pseudomonas supplement (SR 103) was aseptically added.
The mixture was mixed well and poured into Petri dishes and then allowed to cool for 3
hours.
Dilutions (sample preparation)
Each sample was mixed thoroughly using a vortex mixer and diluted with a phosphate buffer
to 10-1(9 ml of phosphate buffer to 1 ml sample) and 10-2 (9 ml of phosphate buffer to 1 ml of
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10-1 sample). These were then spread on the media and incubated in the Scientific Series
incubator. After 24 hours, some colonies were observed in the media and the number of
colony forming units in each sample was calculated using the formula below.
After notable growth was observed, the microorganisms were transferred into nutrient broth
and incubated for 24 hours then concentrated by centrifugation and the obtained solid material
was washed with deionized water. From this a glycerol stock culture was made for further
experiments.
Test solutions
The metal solutions were divided into three categories i.e. single metal system (Co or Cu),
binary metal (Co and Cu mixed system and multi element system (Co and/ Cu plus impurities
in varying ratios). The concentrations of Cu (II) and Co (II) were 0.07 M, 0.33 M and 0.66 M
and their ratios were varied depending on the category in testing.
Batch biosorption experiments
The factors that affect the adsorption rate were examined in a batch system. All experiments
were carried out with microorganism suspention in Erlenmeyer flasks in an incubator at
370.5C with constant shaking to elucidate optimum conditions (contact time, pH, initial
metal concentration and bacterial dose). The contents of the flasks were filtered and the
filtrates were diluted (10 ml was pipetted into 100 ml volumetric flask and filled to the mark
with distilled water.) This was done in order to get lower concentrations, which could be
analysed by flame absorption spectrometry to obtain residual metal concentrations. The metal
adsorbed by biomass was calculated as:
where Ci is the initial metal concentration, Cf is the final metal concentration and MAS is the
total amount of metal adsorbed by other co-existing possible biomass contaminants or metal
precipitated from the solution.
Bacterial interaction with metal species
Interaction of the bacteria with the different categories of metal species was studied using the
scanning electron microscope (SEM), model SEM Joel JSM 5600.
Recovery from mine water samples
Mine water samples were collected from mining effluents and mine dumps in the Gauteng
province of South Africa. These samples were assayed to determine the presence of copper
and cobalt ions. Pseudomonas spp isolated from metallurgical operation effluents was then
used to recover these metals from their solutions. This was done by spiking 100 ml of the
water with 20 ml of Pseudomonas spp.
Isolation of bacteria
The isolation of bacteria using Pseudomonas agar base yielded positive results meaning that
there blue-green colonies of Pseudomonas spp were observed.
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Effect of biomass (bacteria) and metal ion concentration

In the first stage of batch biosorption experiments on Pseudomonas spp., the combined effects
of the amount of biomass (bacteria) and metal ion concentration were examined. Three
different amounts were used (50 104 CFU/ml , 100 104 CFU/ml and 150 104 CFU/ml)
i.e. 1:1, 1: 3 and 3:1 ratios and 0.07, 0.33 and 0.66 M solutions of both Cu and Co sulphate
solutions. These results are illustrated in Figure 1.
Low concentrations of both copper and cobalt sulphate solutions are absorbed more than
higher concentrations and the 3:1 (bacteria: metal ion) ratio absorbs more than 1:1 and
1:3 ratios.
The effect of the initial concentration of Co (II) and Cu (II)
The effect of the initial concentration of Co (II) and Cu (II) ions is illustrated in Figure 1, i.e.
metallic uptake as a function of the equilibrium concentration. The results demonstrate a
decrease in metallic uptake with an increase in the equilibrium concentration. This
observation is linked to the metallic concentration gradient with respect to the active and
available sites of the Pseudomonas sp, which means that metal uptake decreases with an
increase in initial ion concentration. For example, the highest removal percentages are
observed in the 0.07 M concentration solutions for both Cu2+ and Co2+ i.e. 45% and 40%
respectively. This could be attributed to the microbial tolerance of the bacterial species. For
example, the bacteria thrive better in the case of low concentration levels of cobalt than in
high concentrations. As time progresses the die off is not as bad as in the highly concentrated
solutions. Different biosorbents used on the uptaking of various heavy metals yielded similar
observations (Kumar et al., 2006; Fiol et al., 2006; Abu Al-Rub et al., 2006, Pan et al., 2006).
The effect of biomass concentration
As illustrated in Table I and Figure 1, an increase in the amount of adsorbent, which in this
case are bacteria (biomass), results in the increase in metal absorption efficiency (removal
efficiency). This behaviour is due to an increase in binding sites as the bacterial species
increase (surface area), (Brady and Tobin 1994).
Table I
The effect of biomass (bacteria) and metal ion concentration on metal extraction
Solution concentration Amount of bacteria ( 104 CFU/ ml) Amount of solution (ml)
Ratio
Removal efficiency (%)

Cu
Co
0.07 M
50
100
150
150
100
50
1:3
1:1
3:1
26
38
45
21
31
40
0.33 M
50
100
150
150
100
50
1:3
1:1
3:1
22
33
38
19
22
29
0.66M
50
100
150
150
100
50
1:3
1:1
3:1
19
24
31
18
21
25
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Figure 1. The combined effect of biomass (bacteria) and metal ion concentration on metal extraction
Table II
Showing the effect of co-cations on metal extraction (3:1 biomass:solution ratio)
Solution
Cu/Co SO4
Cu/Co SO4
Co/CuSO4
Cu/Co SO4
Co/CuSO4
Concentration of solution (M)
0.07:0.07
0.07:0.33
0.33:0.07
0.07:0.66
0.66: 0.07
Ratio CO:CU
1:1
1:5
5:1
1:9
9:1
% Metal extracted
CU
CO
43
41
36
44
32
31
26
38
21
40
The effect of co-cations on metal extraction

Many researchers have explored the feasibility of this approach (Tsezos, 1983). However, the
majority of published work on biosorption is concerned with one metal. Very little
information is available for binary and multimetal biosorption systems (Gonzalez Davila,
1990). Since biosorption is foreseen to be implemented in the fields of water treatment and
hydrometallurgy where complex multicomponent metal systems are common, more work is
required. The copper and cobalt sulphate solutions were further mixed to try and mimic or be
as close to reality as possible and to see the effect each cation has on the other. This was done
by varying the concentrations of the two cation solutions and the observations were as
follows:
Mixing of the two cations does affect the rate at which biosorption occurs. Table II depicts
the effect the two cations have on each other. It is notable especially when comparing the
single element matrices in Table I with binary element system in Table II that mixing of the
two cations results in an enhancement in the amount of copper absorbed by the bacteria. The
more dilute combinations showed better absorption than concentrated solutions. These results
are illustrated graphically in Figure 2.
The 5:1 and 9:1 copper: cobalt ratio (0.33:0.07 and 0.66: 0.07 respectively) in Table II and
Figure 2 illustrates an almost comparable recovery of copper and cobalt, with cobalt being
favoured. This could be due to the fact that the cobalt is more dilute than the copper and thus
binds easily to the surfaces of the bacteria.
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Figure 2. The effect of co-cations on metal extraction
Figure 3. Langmuir isotherm
The data fitted well on both Langmuir and Fruendlich equations but the correlation was
much higher on the Fruendlich as expected, since Freundlich approach gives an equation that
includes the heterogeneity of the surface of the ion exchanger and the exponential distribution
of active sites and their energies.
As seen from Figure 3, when 1/ (x/m) is plotted against 1/c, the Langmuir model fits the
data quite well; (1/ab) is the intersection of the line with the y-axis.
As observed in Figure 3 and 4 both models fit the data well. The Freundlich equation gave a
plot with higher correlation as compared to the Langmuir equation. The Freundlich gave an
R 2 value of 0.9622 whereas the Langmuir had an R 2 value of 0.8615. Therefore the
Fruendlich plot is favoured over the Langmuir.
The effect of contamination on metal extraction (for a 3:1 biomass: solution ratio)
The 3: 1 bacteria: solution ratio was further examined for contaminant tolerance abilities. The
contaminants used were silicon dioxide and iron chloride.
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Figure 4. Freundlich Plot
It is observed that the presence of any contaminant decreases the copper and cobalt
biosorption by Pseudomonas spp. From the results in Table III it is observed that
contamination in single element species does not result in major decreases in extraction of
metal ions. SiO2, however, decreases ion extraction more when compared to FeCl2. The same
trend is observed in the binary element category. When both contaminants exist further
reduction in the extracted metal ions is observed, especially in the case where the ratio of the
contaminants to solution is higher (2:1). This is the same case in both single metal and binary
metal categories.
It is observed that in all conditions that there is better adsorption of Cu (II) than that of Co
(II). This may be accounted for by the nature of the two metal ions. The charges on both Cu
(II) and Co(II) ions are the same, but they have different hydrated radii; Cu(II) has a lower
hydrated radius than Co(II). Adsorption of an ion by an ion exchanger largely depends on the
hydrated radius. Similar observations on an adsorbent called clinoptilolite were observed by
Erdem, who concluded that the larger the diameter, the slower its mobility and thus the less
likely its exchange will be (Erdem et al; 2004). It appears that for ease in adsorption the water
molecules surrounding the cation should be fewer.
Interaction of bacteria with metal ions
Interactions of the micro-organisms with the metal species were examined using scanning
electron microscopy (SEM), model SEM Joel JSM 5600) and transmission electron
microscopy, as illustrated in Figure 5 and 6. The SEM micrograph revealed attachment of
metal ions on the cell wall of the Pseudomonad and the same observation is confirmed by the
darkish accumulations observed in the cell wall of the bacterium in the TEM image.
The interaction of the Pseudomonas rods with the multi-element matrix is illustrated in
Figures 5 and 6. Figure 6 shows the bioaccumulation of the metal ions on the cell walls of the
bacteria.
Recovery from mine water
The metal removal concept was then applied on mine water sampled from Nigel town and
Table IV shows the recovery of copper and cobalt from the mine water.
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Table III
The effect of contamination using silicon dioxide and iron chloride on metal extraction (for a 3:1 biomass: solution
ratio)
Solution
Cu : Si
Co : Si
Cu : Fe
Co : Fe
Cu : (Si : Fe)
Co : (Si : Fe)
(Cu/Co) : Si
(Cu/Co) : Fe
(Cu/Co) : (Fe: Si)
Solution: contaminants ratios

Cu
SiO2 contaminant only, on single element species
1:1
29
1:2
22
2:1
35
1:1
1:2
N/A
2:1
FeCl2 contaminant only, on single element species
1:1
33
1:2
26
2:1
37
1:1
1:2
N/A
2:1
FeCl2 and SiO2 contaminants on single element species
1:1
23
1:2
19
2:1
26
1:1
1:2
N/A
2:1
SiO2 contaminant only, on binary element speices
1:1
28
1:2
24
2:1
36
FeCl3 contaminant only, on binary element species
1:1
33
1:2
28
2:1
40
FeCl3 and SiO2 contaminant on binary element species
1:1
26
1:2
19
2:1
31
% Metal extracted
Co
N/A
22
19
28
N/A
24
20
28
N/A
19
14
22
23
16
28
24
19
34
18
12
24
Metallic species
Bacterium with metal ions

accumulated on the cell wall
Figure 5. SEM micrograph showing bacterial interaction with metallic species (1:3 ratio)
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Possible accumulation
of metal ions on the cell
Pseudomonas spp
Figure 6. TEM image of metal ion accumulation on the cell wall of Pseudomonas spp.
Table IV
Metal recovery from mine water
Sampled site
1. Big dam Nigel
2. River Nigel A
3. River Nigel B
4. Stream Nigel
5. Nigel 169 (Artisanal)
6. Small dam (HVH)
7. Stream (HVH)
8. Shaft C
9. Piet Farm A
10.Piet Farm B
11. Piet Farm C
12. Piet Farm D
Copper % recovery
Cobalt % recovery
50
42
37
73
61
29
24
36
37
67
38
40
45
35
65
46
11
22
40
20
52
30
0
0
The results in Table IV illustrate an increased recovery efficiency of copper and cobalt. A
maximum of 73% and 65% of copper and cobalt respectively was recovered. This could be
attributed to the fact that the mine water samples were very dilute with concentrations ranging
from 220 ppm of copper and from 18 ppm of cobalt . Other possible minor contaminants
(whose effects were not considered in this study) include Fe, Ca and Mg.
Conclusion
From the results obtained thus far, it can be concluded that Pseudomonas spp reclaims both
copper and cobalt from their sulphate synthetic solutions. It tends to remove or extract more
metal ions at low concentrations and the ratio of bacteria population to solution volume being
3:1 works best. The bacteria have successfully removed up to 45% of copper from 0.07 M and
up 40% from 0.07 M cobalt from cobalt sulphate solutions and 73% and 65% of copper and
cobalt respectively from mine water samples. The absorption favours the removal of copper
over that of cobalt, which may be accounted for by the structural differences of the two
cations.
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References
ABU AL-RUB, F.A., EL-NAAS, M.H., ASHOUR, I., and AL-MARZOUQI, M. Biosorption
of copper on Chlorella vulgaris from single binary and ternary metal aqueous solutions,
Process Biochem. vol. 41, 2006. pp. 457464.
BAILEY, S.E., OLIN, T.J., BRICKA, R.M., and ADRIAN, D.D. A review of potentially lowcost sorbents for heavy metals, Water Res. vol. 33, 1999. pp. 24692479.
BEVERIDGE, I., PULLMAN, A.L., MARTIN, R.R., and BARELDS, A. Effects of
temperature and relative humidity on development and survival of the free-living stages
of Trichostrongylus colubriformis, T. Rugatus and T. Vitrinus ). Veterinary Parasitology,
vol. 33, no. 2, 1989. pp. 143153.
BRADY, J.M., and TOBIN, J.M. Adsorption of metal ions by Rhizopus arrhizus biomass:
Characterization studies. Enzyme and Microbial Technology, vol. 16, no. 8, 1994.
pp. 671675.
BUENO, B.Y.M., TOREM, M.L., MOLINA, F., and DE MESQUITA, L.M.S. Biosorption of
lead(II), chromium(III) and copper(II) by R. Opacus. Equilibrium and kinetic studies,
Minerals Engineering, vol. 21, 2008, pp. 6575
ERDEM, E. KARAPINAR, N., and DONAT, R. The removal of heavy metal cations by
natural zeolites, Journal of Colloid and Interface Science, vol. 280, no. 2, 2004.
pp. 309314.
FIOL, N., VILLAESCUSA, I., and MARTINEZ, M. Sorption of Pb(II), Ni(II), Cu(II) and
Cd(II) from aqueous solution by olive stone waste, Sep. Purif. Technol. vol. 50, 2006.
pp. 132140.
GONZALEZ, D.M., SANTANA-CASIANO, J.M., and MILLERO, F.J. The adsorption of Cd
(II) and Pb (II) to chitin in seawater. J. Coll. Interf. Sci. vol. 137, 1990. p. 102.
KUMAR, Y.P., KING, P., and PRASAD, V.S. Equilibrium and kinetic studies for the
biosorption system of copper(II) ion from aqueous solution using Tectona grandis L.f.
leaves powder, J. Hazardous Mater. B137, 2006. pp. 12111217.
PAN, J., GE, X., LIU, R., and TANG, G.H. Characteristic features of Bacillus cereus cell
surfaces with biosorption of Pb(II) ions by AFM and FT-IR, Colloids Surfaces B:
Biointerfaces, vol. 52, 2006. pp. 8990.
TSEZOS, M. The role of chitin in uranium adsorption by R. Arrhizus. Biotech. Bioeng.
vol. 25, 1983. p. 2025.
VEGLIO, F. and BEOLCHINI, F. Removal of metals by biosorptiona review,
Hydrometallurgy, vol. 44, 1997. pp. 301316.
WASE, J. and FORSTER, C. Biosorbents for Metal Ions, Taylor and Francis Ltd, 1997.
http://en.wikipedia.org/wiki/Pseudomonas_aeruginosa , accessed , 2008-09-06
Nonjabulo Prudence Dlamini

Student, University of Johannesburg
Nonjabulo Prudence Dlamini received a Bachelor of Science degree
from the University of Swaziland in 2006 where she has majored in
Chemistry and Biological Sciences. She has just completed her MSc
(chemistry) on the use of micro-organisms in removing metals from
hydrometallurgical solutions. She will be graduating in May and is
looking forward to pursuing a PhD in mineral processing.
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MWANZA, M. and MULABA-BAFUBIANDI, A.F. An investigation into fungal strains bio-extraction of metal
impurities from aqueous effluents emanating from Ekhuruleni (Gauteng, South Africa) metallurgical and mining
operations. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and Metallurgy, 2009.
An investigation into fungal strains bio-extraction

of metal impurities from aqueous effluents
emanating from Ekhuruleni (Gauteng, South
Africa) metallurgical and mining operations
M. MWANZA* and A.F. MULABA-BAFUBIANDI*
Mineral Processing and Technology Research Group, Faculty of Engineering and the
Built Environment, Wits, South Africa
This paper discusses an attempt to use indigenous fungal strains for

the fixation and immobilization of identified metal impurities from
aqueous effluents collected in Nigel, Gauteng (South Africa). Ca, Fe
and Mg were predominantly found in aqueous effluents in Nigel
areas. Fungal species obtained by culturing soil samples from Nigel
areas on agar medium and identified by gene sequencing were tested
for their abilities to absorb (biosorption/bioaccumulation). The
dominant metals in situ were exposed to known concentrations of
fungal cultures and assed for fungal absorption. Fungal cultures
(Aspergillus niger and Aspergillus fumigatus) were washed from their
home medium and cultured in sterile water for 24 hours. Two
different concentrations (30 and 50 ppm) of Ca, Fe, and Mg were
spiked separately in triplicate. Concentration of metals measurements
were taken after 1, 2, and 24 hours. The results obtained thus far show
that Ca, Fe and Mg absorption by Aspergillus niger and Aspergillus
fumigatus is reduced with time of exposure. Additionally, it was
observed that both metal concentrations did not affect the fungi as
these were still alive even after 24 hours exposure, suggesting that
probably higher concentrations of metals could be absorbed without
destroying the surrounding fungal ecosystem.
Introduction
Environmental constraints have become an important issue and most mining industries are
asked to get involved in the reduction of waste as it is known that mining wastes and drainage
are the major contributors in polluting the surroundings. Several techniques as well as
microorganisms such as bacteria are also being used in this regard. Barros et al. (2003) and
Bhainsa and DSouza (1999) used Aspergillus niger and Aspergillus fumigatus strains for
uranium and cadminium absorption. In addition, Blanquez, 2008, Blaudezi et al., 2000,
AN INVESTIGATION INTO FUNGAL STRAINS BIO-EXTRACTION OF METAL IMPURITIES
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Satofuka et al., 1999, and Dupre de Boulois et al., 2007 found that some fungal species such
as white fungi could be used in water detoxification and also some other fungi such as
micorrhiza can be used in soil detoxification from minerals and discharging the environment
from heavy metals. In addition, the presence of these fungi is a good as they may play an
important role in soil by precipitating of carbonates, phosphates, and hydroxides, which
increases soil aggregation and also in stimulating the precipitation of compounds that act as
bonding agents for soil particles (Arnott, 1995; Burford et al., 2006; Gorbushina, et al., 2002).
This study looked at the possible use of fungal strains (Aspergillus niger and Aspergillus
fumigatus) capacity to reduce selected metal concentration in water and their possible use in
the detoxification of the environment. The results obtained thus far show that Ca, Fe and Mg
absorption by Aspergillus niger and Aspergillus fumigatus increased with time of exposure.
Methodology
Soil samples (21) from Nigel gold mines were collected in sterile caped bottles and were
transported to the laboratory in a cooler box.
In the laboratory samples were stored in a fridge, samples were thoroughly mixed, and 1 g
was transferred into a McCartney bottle containing 9 ml of sterile ringer solution (1 ringer
tablet in 500 ml of purified water). One milliliter was then transferred to a further 9 ml of
ringer solution and then diluted five times using the same dilution method under aseptic
conditions. One milliliter from each McCartney bottle was added to a petri dish containing 20
ml of Ohio Agricultural Experimental Station agar (OAESA) (Kaufman et al., 1963) or potato
dextrose agar (PDA) and mixed. After solidification, the plates were incubated for 47 days at
28C. On the fourth to the seventh day, plates were screened for different types of fungal
colonies. These isolated fungal colonies were sub-cultured on PDA, Czapek 20 (CY20S),
Czapek (CZ) and malt extract agar (MEA) (Klich, 2002) under aseptic conditions and
incubated at 28C for 3 to 4 days. On the fourth day, pure fungal colonies were stained with
Lactophenol blue solution on microscope slides for identification. The macro scopic and
microscopic identifications of fungi were determined according to Pitt and Hocking (1997)
and Klich (2002) for Aspergillus and Penicillium spp. and Nelson et al. (1983) for Fusarium
spp. The isolates were sent to Inqaba Biotechnology in Pretoria for DNA sequencing. From
selected cultures, 200 mg of fungal cultures were inoculated in sterile medium composed of
97 ml of distilled water and 30 ppm of metal or 95 ml of distilled water and 50 ppm of metal.
All samples and controls were run in triplicate. The mixture was incubated in a shaker
incubator at 25C and a speed of 150200 rpm. Five ml of the solution were collected every 1
hour, 2 hours and 24 hours for analysis. The collected samples were filtered using filter paper
and analysed for metal quantification using the ICP-MS.
The macroscopical and sequenced results, shown in Figure 1, revealed the presence of fungi
in these samples with a predominance of Aspergillus fumigatus (100%), Aspergillus niger
(100) both seen in Figure 2, Trichoderma harzianum (37%), Hypocrea lixii (6%),
Mucoromycote spp (3%). Penicillium janthinellum (4%), Cochliobolus lunatus (7%),
Trichoderma koningiopsis (7%), Gibberella moniliformis figure (5%), Bipolaris spicifera
(7%) and Cochliobolus spicifer (1%) of analysed soil samples. In addition it was recorded that
the samples were contaminated with several fungal species at one.
The growth of fungi in these areas might also be explained by their biological ability to
resist in lower pH environments (28) as compared to other bacteria (Pitt and Hocking, 1997)
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tus niger anum a lixii

pp ellum natus iopsis igure icifer
ifer
f
iga
i
pic
p
e
u
te s
in
g
s
fum rgillu a harz ypocr myco janth olus l konin ormis laris s olus s
s
b
o
H
a
ilif Bipo
illu Aspe erm
m
iob
cor
lliu ochlio derm mon
erg
chl
Mu enici
hod
o
C
Co
Asp
lla
h
e
c
P
i
r
Tric
Tr ibbe
G
Figure 1. Graph illustrating fungal contamination from Nigel soil samples
Figure 2. Aspergillus niger (left) and Aspersgillus fumigatus (right)
but also by the presence of these minerals, valuable nutrients for the growth and survival of
fungi (Pitt and Hocking, 1997). Aspergillus niger, characterized by its black spherical conidia,
can grow down at pH 2 at high aw (Pitt and Hocking, 1997) while Aspergillus fumigatus is
characterized by overgrowth white to greenish mycelium, it is has a thermophilic nature and
can grow at optimum temperature 1242C and required up to o.90 aw (Pitt and Hocking,
1997).
The results obtained from the ICP-MS on the two major fungi found present in soil,
Aspergillus niger (Figure 3) and Aspergillus fumigatus (Figure 4) show progressive increased
absorption of metal over the time of exposure. It was observed that Ca and Fe were highly
absorbed as compared to Mg. This might be explained by the fact that Ca and Fe are required
for many vital processes in plants and animals (Moreau, 1987, and Pitt and Hocking, 1997).
There was not much significant statistical difference in absorption between the three metals
and between the two fungi although Aspergillus fumigatus showed a slightly higher abortion
of metals as compared to Aspergillus niger.
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Figure 3. 30 ppm of percentage of absorption vs. exposure time of metal by Aspergillus niger
Figure 4. 30 ppm of percentage of absorption vs. exposure time of metal by Aspergillus fumigatus
Table I
Percentage means concentrations of metal absorption by fungal exposure on ICP-MS
Conc. ppm
Exposure time
Aspergillus niger
Aspergillus fumigatus
Metal
Fe
Ca
Mg
Fe
% absorption
Ca
Mg
30
1 hour
2 hours
24 hours
21.50
27.3.9
81.80
21.05
29.50
85.50
06.33
17.63
46.60
22.21
33.50
85.23
27.98
35.29
88.65
26.36
30.25
42.26
50
1 hour
2 hours
24 hours
5.50
16.56
65.34
7.45
15.36
75.24
05.89
13.52
57.97
06.91
21.06
70.50
07.31
29.05
84.06
07.02
40.25
61.13
The results obtained and summarized in Table I revealed that the metal absorption capacity
of Aspergillus niger and Aspergillus fumigatus showed no significant difference. However,
Aspergillus fumigatus revealed a slightly higher absorption capacity as compared to
Aspergillus niger. It was observed that calcium was highly absorbed by both fungi as
compared to iron and magnesium sulphate with high absorption level with Aspergillus
fumigatus with 84% absorption and only 76% absorption for Aspergillus niger. This might be
explained by the fact that calcium is required for many vital processes in plants and animals
(Moreau, 1987, and Pitt and Hocking, 1997). In addition, it was found that at the end of the
experiment all fungal cultures were alive. This confirms that the absorption process is
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biological and does not lead to the death of the fungal ecosystem (Moreau, 1987, and Pitt and
Hocking, 1997). These findings agree with those of Strandberg et al., 1981, who demonstrated
the rapid uptake of uranium and postulated that polyphosphate groups and carboxyl groups in
Sarcomyces. cerevisiae cell walls are active in metal complexation. The results obtained in
this study also agree with Barros et al. (2003) and Bhainsa and DSouza (1999) who used
Aspergillus niger and Aspergillus fumigatus strains for uranium and cadminium absorption.
This also confirms the findings of Blanquez (2008), Kefala et al., (1999), Blaudezi et al.,
(2000), Satofuka et al., (1999) and Dupre de Boulois et al., (2007), who found that fungal
species such as white fungi can be used in water detoxification and also some other fungi such
as micorrhiza can be used in soil detoxification from minerals by discharging the environment
from heavy metals. In addition, the presence of these fungi is good as they may play an
important role in soil by precipitating of carbonates, phosphates, and hydroxides which
increase soil aggregation and also in stimulating the precipitation of compounds that act as
bonding agents for soil particles (Arnott 1995; Burford et al., 2006, Gorbushina, et al., 2002).
Conclusion
The current global environmental challenges are mainly due to pollution are caused, to a large
extend, by modern industries and mines. It is thus important to look at environment friendly
methods to reduce water and soil pollution. There is a need for metal detoxification of soil and
probably of water from mines. The use of fungal strains such Aspergillus niger and
Aspergillus fumigatus commonly found surviving in these soils would be of importance as
they contribute to environmental detoxification by absorbing these metals as nutrient sources.
Acknowledgments
This work was supported by Professor Mike Dutton: Food Environmental and Health
Research Group, Faculty of Health Sciences, University of Johannesburg and Dr Herman Van
Niekerk: RAUSPECTRA, University of Johannesburg. This work was funded by The
University of Johannesburg Research Council and National Research Foundation for financial
assistance.
References
ALLURI, H.K., et al. Biosorption: An eco-friendly alternative for heavy metal removal.
African Journal of Biotechnology. vol. 6, no. 25, 2007. pp. 29242931.
ARNOTT, H.J. Calcium oxalate in fungi. Khan S.R. (ed.), Calcium Oxalate in Biological
Systems. CRC Press, Boca Raton, 1995. pp. 73111.
BHAINSA, K.C., and D'SOUZA, S.F. Biosorption of uranium (VI) by Aspergillus fumigatus.
Biotechnol. Tech. vol. 13, 1999. pp. 695699.
BARROS, L.M., MACEDO, G.R., DUARTE, M.L., SILVA, E.P., and LOBATO, A.K.C.L.
Biosorption of Cd using the fungus A. niger. Braz J. Chem. Eng. vol. 20, 2003.
pp. 229239.
BLANQUEZ, P., SARRA, MM., and VICENT, T. Development of a continuous process to
adapt the textile wastewater treatment by fungi to industrial conditions. Process
Biochemistry, vol. 43, 2008. pp. 17.
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BLAUDEZI, D., JACOBI, C., TURNAU, K., COLPEART, J., AHONEN, V., FINLAY, U.,
BOTTONI, B., and CHALOTTI., M. Differential responses of ectomycorrhizal fungi to
heavy metals in vitro. Mycol. Res. vol. 104, no. 11, 2000. pp. 13661371.
BURFORD, E.P., HILLIER, S., and GADD, G.M. Biomineralization of fungal hyphae with
calcite (CaCO3) and calcium oxalate mono- and dihydrate in Carboniferous limestone
microcosms. Geomicrobiology Journal, vol. 23, 2006. pp. 599611.
DUPRE DE BOULOIS, H., JONER, H.J., LEYVAL, C., JAKOBSEN, L., CHEN, B.D.,
ROOS, P., THIRY, Y., RUFYIKIRI, P., DELVAUX, B., and DECLERCK, S. Impact of
arbuscular mycorrhizal fungi accumulation by plants. Journal of Environmental
Radioactivity, vol. xx: 2007. pp. 110.
IBEANUSI and WILDE. Bioremediation of coal Pile off waters using an integrated microbial
ecosystem. Biotechnology letters, vol. 20, no. 11, 1998. pp. 10771079.
GORBUSHINA, A.A, KRUMBEIN, W.E., and VOLKMANN, M. Rock surfaces as life
indicators: new ways to demonstrate life and traces of former life. Astrobiology, vol. 2,
2002. pp. 203213.
KAUFMAN, D.D., WILLIAMS, L.E., and SUMNER, C.B. Effect of plating medium and
incubation temperature on growth of fungi in soil-dilution plates. Canadian Journal of
Microbiology, vol. 9, 1963. pp. 741751.
KEFALA, M.I., ZOUBOULIS, A.I., and MATIS, K.A. Biosorption of cadmium ions by
Actinomycetes and separation by flotation. Environmental pollution, vol. 104, no. 2,
1999. pp. 283293.
KLICH, M.A. Identification of common Aspergillus species. Ponson and Looijen,
Wageningen. The Netherlands, 2002. 1-107.
MOREAU, R.A. Calcium-building proteins in Fungi and Higher Plants. J. Dairy Sci., vol. 70,
1987. pp. 15041512.
NELSON, P.E., TOUSSIN, T.A., and MARASSAS, W.F.O. Fusarium Species. An illustrated
Manual for Identification. University Park Pennsylvania: Pennsylvania State University
Press. 1983.
PITT, J.I. and HOCKING, A.D. Primary keys and miscellaneous fungi. Fungi and Food
Spoilage. 2nd Edition. Blackie Academic and Professional. London, Weinheim, New
York, Tokyo, Melbourne, Madras, 1997. pp. 59171.
SATOFUKA, H., SATOSHI, A., ATOMI, H., TAGAGI, M., KAZAMUSA, H., KAZUHISA,
M., and TADAYUKI, I. Rapid Method for Detection and Detoxification of Heavy Metal.
1999.
Ions in Water Environments Using Phytochelatin. J. of Bioscience Engineering, vol. 88, no. 3,
pp. 287292.
STRANDBERG, G.W., SHUMATE II, S.E., and PARROT, J.R. Microbial cells as biosorbents
of heavy metals: Accumulation of uranium by Saccharomyces cerevisiae and
Pseudomonas aeruginosa. Appl Environ Microbiol, vol. 41, 1981. pp. 237245.
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Mulunda Mwanza
PhD Fellow, University of Johannesburg, South Africa
Qualified Vet from the University of Lubumbashi/DRC, I joined the
University of Johannesburg for a master degree in Biotechnology
(obtained 2007). I am Actually working on a PhD project at the
University of Johannesburg on fungal and their mycotoxin
contamination in animal feed, animal products and tissues with
particular reference to synergistic effects of mycotoxins on animal and
human system. In addition, I am interested on environmental questions such as soil and water
contamination and their detoxifications.
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NEALE, J.W., ROBERTSON, S.W., MULLER, H.H. and GERICKE, M. Integrated piloting of a thermophilic
bioleaching process for the treatment of a low-grade nickel-copper sulphide concentrate. Hydrometallurgy
Integrated piloting of a thermophilic bioleaching

process for the treatment of a low-grade nickelcopper sulphide concentrate
J.W. NEALE, S.W. ROBERTSON, H.H. MULLER and M. GERICKE
Mintek Biotechnology Division, South Africa
Mintek was a leading participant in the BioMinE project between

2004 and 2008. This project, which was funded in part by the
European Commission, was aimed at the development of
biotechnology for the minerals industry in Europe. Minteks research
programme focused mainly on the development of integrated
bioleach-based processes for the recovery of base metals from
complex, low-grade sulphide concentrates. Specific European mineral
resources were targeted and used in integrated piloting campaigns
involving bioleaching, solution purification, and metals recovery.
This paper describes the use of thermophilic bioleaching for the
recovery of nickel and copper from a low-grade nickel-copper
concentrate produced at the Aguablanca Mine in southern Spain.
Currently, the Aguablanca Mine produces a bulk nickel-copper
concentrate for sale to a smelter, and the proposition is to increase the
profitability of the operation by the on-site production of metal or
metal intermediate.
Initially, bench-scale bioleach tests were conducted to determine the
bioleach operating conditions. These tests included an evaluation of
mesophilic, moderately thermophilic and thermophilic
microorganisms. In order to achieve sufficiently high levels of both
copper and nickel extraction, a thermophilic process was selected
this was necessary for leaching of the refractory chalcopyrite that
occurs in this concentrate. Additional bench-scale test work was
carried out to derive a conceptual process flowsheet for the solution
purification and metals recovery circuit.
The results of the bench-scale tests were used to design, construct
and commission an integrated pilot plant, which was subsequently
operated at Mintek for over seven months. During this time, the
solution purification and metals recovery processes were optimized,
and all recycle loops were closed. The final process flowsheet
included the following unit operations: concentrate regrinding,
thermophilic bioleaching at 70C, primary iron removal using
limestone, copper solvent extraction and electrowinning, secondary
INTEGRATED PILOTING OF A THERMOPHILIC BIOLEACHING PROCESS
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iron removal, nickel hydroxide precipitation using magnesia, and

final solution purification using lime. Where applicable, process
solutions were recycled to preserve water.
The process design data derived from this pilot-plant campaign
formed the basis for a conceptual engineering study for the developed
process. In the study, mass and energy balances were derived, and a
process flowsheet was developed and used as the basis for estimating
the capital and operating costs of the process. This enabled a
preliminary economic analysis of the process to be undertaken. The
findings of this study are discussed.
Introduction
The BioMinE project
The BioMinE project1,2 was a four-year-long integrated project under the Sixth Framework
Programme of research supported by the European Commission, which ran from November
2004 to October 2008. The project was aimed at the evaluation of biohydrometallurgy to
improve the exploitation of the European non-ferrous metal resources in a sustainable way. At
the time of its completion, the project had 37 participating partners covering a diversity of
interests: research organisations, academic institutions, and industrial and mining companies.
South Africa was well represented: besides Mintek, two academic institutions and one mining
company from South Africa were members of the BioMinE consortium.
Minteks role in BioMinE
Minteks Biotechnology Division played a leading role in the project, both as coordinator of
the bioleaching Work Package and by active participation in key aspects of the research and
technology development (RTD). One of the main focuses of Minteks research programme
was the development of integrated bioleach-based processes for the recovery of base metals
from complex, low-grade sulphide concentrates. Specific European mineral resource types
were targeted and used in integrated piloting campaigns involving bioleaching, solution
purification, and metals recovery. One such resource is copper polymetallic concentrates, and
a nickel-copper concentrate, which is currently produced at the Aguablanca Mine in southern
Spain, was selected as one of the target resources in this project. Mintek conducted extensive
bench-scale bioleach testing on this material, the results of which formed the basis for an
integrated bioleaching pilot-plant campaign that was conducted at Mintek.
Bioleaching of base metal concentrates
The bioleaching of concentrates of base metal sulphides has been the subject of extensive
research and development over several decades3. The use of mesophilic bacteria to oxidize
sulphide minerals such as cobaltiferous pyrite, pentlandite and millerite (nickel), sphalerite
(zinc), galena (lead), chalcocite, covellite, cubanite and bornite (all copper) has been
demonstrated, and in some cases the bioleaching process has successfully been integrated
with downstream metals recovery processes4,5,6.
In the early 1990s, BHP Billiton demonstrated the bioleaching of a pentlandite concentrate
using mesophiles and moderate thermophiles, in a demonstration plant with a design capacity
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of 300 kg/d of concentrate. This plant produced more than 700 kg of Class 1 nickel in a sixmonth-long campaign. Subsequently, an integrated pilot plant situated at the Yabula Nickel
Refinery in Queensland, Australia, was successfully operated as part of a feasibility study4.
In the late 1990s, the worlds first commercial bioleaching plant treating a base metal
concentrate was established at the site of the defunct Kilembe Copper Mine in Uganda. The
plant, owned an operated by the Kasese Cobalt Company, was designed to produce about
1000 t/a of cobalt cathode from a cobaltiferous pyrite concentrate. The technology for this
plant was supplied by the French company, BRGM5.
Bioleaching of the primary copper sulphide, chalcopyrite, has presented more of a
challenge, since the surface of the chalcopyrite tends to passivate at the temperatures and
redox potentials found in typical mesophilic bioleach processes, effectively stopping the
leaching of the mineral. This behaviour can be overcome by a variety of approaches, often
applied in combination, which include increasing the operating temperature (requiring the use
of thermophilic micro-organisms), finer grinding of the concentrate, the addition of catalysts
(such as silver), and control of the redox potential3,6,7,8,9.
In 2001, Mintek and its partners, Industrias Peoles S.A. de C.V. of Mexico and BacTech,
successfully demonstrated the bioleaching of chalcopyrite using moderate thermophiles at an
operating temperature of 45C, in an integrated demonstration plant that was commissioned
and operated in Monterrey, Mexico. The plant, with a design capacity of 1 t/d of copper,
produced more than 40 t of LME A-grade cathode copper from a complex polymetallic
concentrate in which the main copper mineral was chalcopyrite6.
In 2003, Alliance Copper, a joint venture between BHP Billiton and Codelco, demonstrated
the thermophilic bioleaching of chalcopyrite concentrate, at an operating temperature of 78 C
in a prototype plant situated at Chuquicamata in Chile, which was designed to produce 20 000
t/a of copper cathode9. A unique feature of this prototype plant is that the air supply is
supplemented with pure oxygen, which necessitates the use of an automated system to control
the dissolved oxygen concentration in the process.
In the past 20 years, the bioleaching of a wide variety of base metal concentrates has been
demonstrated. In the past decade, the development has focused mainly on the bioleaching of
chalcopyrite, and the investigations have been aimed either at complex polymetallic
concentrates containing several sulphide minerals (the Mintek/BacTech/Peoles project), or
copper concentrates that contain impurities such as arsenic (the Alliance Copper operation).
The Aguablanca Mine
The Aguablanca Mine is an open-pit nickel-copper sulphide mine, located in the province of
Badajoz, about 80 km north of Seville in southern Spain (Figure 1a). The mine currently
produces a bulk, low-grade copper-nickel concentrate for sale to a smelter. Aguablanca was
the first nickel sulphide mine in production in Western Europe. Construction of the on-site
treatment plant (Figure 1b) was completed in December 2004, commissioning and production
commenced early in 2005, and production parameters were reached in early 2006. The project
has an initial projected mine life of 10 years.
The on-site flotation plant was designed to treat 1.5 million tonnes of ore per year, with an
additional milling capacity of 0.3 million tonnes per year. The plant produces a bulk coppernickel-PGM concentrate, but also has the flexibility to produce separate copper and nickel
concentrates. The process flowsheet comprises primary jaw crushing, primary semiautogenous grinding, secondary ball milling, gangue pre-flotation, flotation, concentrate
thickening and filtration. Production data for the first two full years of operation are
summarized in Table I.
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Figure 1a. Location of the Aguablanca Mine in southern Spain
Figure 1b. The Aguablanca treatment plant

Table I
Aguablanca Mine production data
Ore mined (tonnes)

Ore milled (tonnes)
Ore grade
Nickel (%)
Copper (%)
Flotation recovery
Nickel (%)
Copper (%)
Concentrate grade
Nickel (%)
Copper (%)
Production (metal contained)
Nickel (tonnes)
Copper (tonnes)
122
2006
1 550 437
1 486 800
2007
1 707 330
1 668 959
0.6
0.5
0.5
0.4
72
90
76
92
6.6
6.8
7.3
6.9
6 398
6 616
6 630
6 281
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The concentrate is transported either to Glencores Huelva smelter, located 140 km away on
the Spanish coast, or to other smelters, for treatment. Cash costs (including by-product
credits) in 2007 amounted to US$7.23 per pound of nickel sold10.
The mineralization of the Aguablanca deposit is similar in type to both the Voiseys Bay
deposit in eastern Canada and the Norilsk deposit in Russia. Nickel, copper, platinum and
palladium mineralization occurs within magmatic breccia bodies that form gossans at the
surface. Pyrrhotite, pentlandite and chalcopyrite comprise the dominant sulphide
mineralization.
Following the acquisition of the operation by Lundin Mining Corporation (Lundin) in 2007,
encouraging exploration results were announced, indicating the existence of a deep orebody
below the existing one. The most recent exploration results have confirmed the potential for a
significant increase in the mines resource base and for an expansion of the current open pit
production to include underground reserves. In March 2008, Lundin announced that a
feasibility study was being conducted on undertaking underground mining, which was
expected to be completed towards the end of 2008. If approved, a plant expansion project will
be finalized to cater for the processing of underground ore.
Objectives and scope of work
The proposition underpinning this work is to extend the Aguablanca treatment plant by the
addition of a bioleaching and metals-refining facility, allowing the on-site production of metal
or metal intermediate products, and thus substantially increasing the realized metal value.
The selection of bioleaching for treatment of Aguablanca concentrate may have certain
advantages over alternative hydrometallurgical processes such as pressure leaching:
The Aguablanca operation is relatively small, and bioleaching may be more suitable for
this scale of operation than pressure leaching, which has relatively high capital and
operating costs and has been shown to be more cost-effective at larger scales11.
Bioleaching is also readily able to treat low-grade concentrates, and one option that could
be considered if bioleaching was to be implemented is to produce an even lower-grade
concentrate than is presently the case, in order to improve the overall recovery of metal
(particularly nickel) in the concentrate.
If plant expansions were implemented at Aguablanca in the future, the modular nature of
bioleach tanks would make it possible to expand the plant with relative ease.
Extensive bench-scale amenability and pilot-plant testing of the Aguablanca concentrate
was performed at Mintek. Three phases of testing were completed.
In phase one, the concentrate sample used in the test work was subjected to chemical,
physical and mineralogical characterization. Amenability testing comprised open-circuit
bioleach testing in small-scale, continuously operated bioleach reactors, with process volumes
of a few litres. The results of these tests were used to define the bioleach operating parameters
for the next two phases of test work.
In the second phase, a continuous bioleach miniplant was operated in open circuit, using the
bioleach operating parameters defined in phase one. The product from this miniplant was used
to carry out bench-scale tests aimed at assessing the operating parameters for solution
purification and metals recovery. The results of these tests were used to define the initial
operating parameters for the final phase of test work.
In the third and final phase, an integrated pilot plant comprising bioleaching, solution
purification and metals recovery was operated for a period of over seven months. During this
integrated piloting campaign, seven cycles of downstream processing were completed, and
integration was achieved by recycling of the purified process solution. The primary aims of
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the integrated piloting campaign were to assess the impact, if any, of recycling of the purified
process solution on the bioleach process performance, to optimize the operating parameters
for the purification and metals recovery circuit, and to define the process design criteria to be
used as the basis for a conceptual engineering study and preliminary economic evaluation of
the process. In this phase, additional optimization test work was also conducted to assess the
effect of bioleach process parameters such as redox potential, concentrate grind size and feed
solids concentration on copper and nickel extractions and leach kinetics. The results of these
additional optimization tests were included in the engineering and economic study.
The outcomes of this comprehensive bench-scale and pilot-plant test work programme are
discussed here, together with the results of the engineering and economic study.
Conceptual flowsheet development
At the outset, a conceptual process flowsheet for bioleaching and the recovery of metals from
the Aguablanca concentrate was envisaged. The conceptual flowsheet aimed to address the
following key issues:
Solid-liquid separation and washing of the bioresidue, wastes and metal products
Removal of iron from the leach liquor
Purification of the leach liquor
Recovery of copper from the leach liquor
Recovery of nickel from the leach liquor
Waste products and their disposal
Re-use of water
The acid balance.
Solid-liquid separation and washing of the residues, wastes and products is usually achieved
either by countercurrent decantation (CCD) using a series of thickeners, or by filtration. The
choice depends on many factors, including the settling and filtration characteristics of the
solid materials, the required washing efficiency, and the availability of water.
The removal of iron from leach liquors such as these is usually achieved by precipitation
using limestone, at a pH level of around 3.0. The aim of this process step is to remove iron
prior to copper solvent extraction, without coprecipitating or entraining the valuable metals
(nickel and especially copper), and in so doing to produce a waste product which has good
filtration or settling characteristics. The factors that govern this process include the operating
temperature, the overall residence time, the number of precipitation stages and the rate at
which the pH level is raised, and the final pH level.
The recovery of copper from bioleach liquors is usually achieved by the well-established
method of solvent extraction (SX) using a copper-selective organic reagent. The SX process
selectively removes copper from the pregnant solution, and produces a purified copper
solution from which copper can be extracted as a cathode using electrowinning (EW).
Important factors that govern this process are the number of extraction and stripping stages,
the organic reagent that is applied, and the pH level and copper tenor of the pregnant solution.
A few variations for the residue washing, iron removal and copper SX-EW operations were
considered, including:
Precipitation of the iron directly after bioleaching, without first separating the pregnant
leach liquor from the bioresidue. This would remove one solid-liquid separation and
washing step from the process, but it would have to be established that the resultant solids,
comprising the bioleach residue, iron precipitates and gypsum, could be thickened or
filtered easily.
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Performing the copper SX step prior to removing the iron from the leach liquor. This
would eliminate the possibility of encapsulation or coprecipitation of copper in the iron
precipitate, but it would have to be established that the iron in the SX feed did not affect
the extraction of copper.
Purification of the SX raffinate is usually required prior to nickel recovery. The SX process
reduces the pH level of the liquor, and this purification is usually achieved by further
neutralization of the liquor by limestone, to a pH level of about 5.0. The objective is to
remove all impurities that may contaminate the nickel product.
There are several options that could be considered for the recovery of nickel from the leach
liquor. In the nickel laterite industry, which has seen the implementation of hydrometallurgical
nickel extraction and recovery processes in a number of projects in the past decade, several
different approaches have been followed. These include precipitation to form a metal salt,
precipitation to produce a metal sulphide, and SX-EW, usually after the formation and
redissolution of an intermediate product (either a salt or a sulphide), to produce metal.
After a careful evaluation of the various alternatives, it was decided that the integrated pilot
plant would incorporate the metal salt precipitation route, for the following reasons:
It is conceptually the simplest route to follow.
Nickel SX-EW is not as well established as copper SX, and the process circuits are
complex, difficult to operate, with high capital and operating costs.
The production of an intermediate metal salt does not preclude the option of producing
metal by SX-EW. The metal salt could be redissolved and the solution used as a feed to a
refinery including nickel SX-EW. Such a refinery could be added at a later stage; this
would reduce the initial technical risk associated with the project.
Figure 2. Conceptual flowsheet for the Aguablanca nickel-copper concentrate
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One of the objectives of the bench-scale test work programme conducted prior to the
integrated piloting campaign was to evaluate which metal salt should be produced as a nickel
intermediate.
The final step in this process (in which a nickel salt is produced) would involve a partial or
total neutralization of the barren liquor to remove any residual impurities that remain or that
may have been added during the nickel precipitation process, prior to recycling of the liquor
to the front end of the circuit.
This conceptual flowsheet is shown in Figure 2. In this case, magnesia is used as the alkali
in the nickel precipitation process, and the product is nickel hydroxide.
For this process flowsheet, the soluble magnesium sulphate produced in the nickel
hydroxide precipitation process would need to be removed by the addition of lime in the final
neutralization step.
Concentrate characterization and bioleach amenability testing
Characterization of the Aguablanca concentrate
The Aguablanca concentrate was characterized both physically and chemically.
The dry density of the Aguablanca concentrate was determined to be 3 292 kg/m3.
In all of the test work, the concentrate was reground prior to bioleach testing, and a particlesize distribution with a d90 of 1012 m was targeted. The size distributions of the as-received
and reground concentrates are illustrated in Figure 3.
The typical chemical analysis of the Aguablanca concentrate is summarized in Table II.
A scanning electron microscope was used to perform a quantitative modal analysis of the
Aguablanca concentrate, and the results are summarized in Table III. This analysis shows that
the bulk of the concentrate comprises the sulphide minerals pyrite, pyrrhotite, chalcopyrite
and pentlandite, with a variety of silicates such as amphibole, feldspar, talc and chlorite being
the predominant gangue minerals.
Figure 3. Typical particle-size distributions for the as-received and reground Aguablanca concentrates
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Table II
Typical chemical analysis of the Aguablanca concentrate
Constituent
Concentration
(%)
6.29
5.24
24.4
24.36
28.9
6.28
2.74
1.16
1.00
0.18
Cu
Ni
STOT
S2Fe
Si
Mg
Al
Ca
Co
Table III
Typical modal analysis of the Aguablanca concentrate
Mineral
groups
Mineral name
Chemical formula
Sulphides
Pyrite
FeS2
23.7
Fe1-x(Ni)S
20.7
Chalcopyrite
CuFeS2
18.5
Pentlandite
(Fe,Ni)9S8
14.5
NiAsS
0.04
CuS
0.03
Sphalerite
Cu2S
0.02
Galena
ZnS
0.02
Amphibole
NaCa2(Mg,Fe)4Al(Si6Al2)O22(OH)2
9.8
Feldspar
CaAl2Si2O8; KAlSi3O8
4.2
Talc
Mg3Si4O10(OH)2
3.2
Chlorite
(Mg,Fe,Al)6(Si,Al)4O10(OH)8
2.2
Ni-bearing silicates
Fe(K,Al,Mg,Ni)-silicate
1.8
Quartz
SiO2
0.3
Fe-oxides
Fe2O3; -FeOOH; Fe3O4
0.6
Ilmenite
FeTiO3
0.04
Cu-bearing sulphate
Ca(Fe,Cu)-sulphate
0.2
Gypsum
CaSO4.2H2O
0.1
Phosphate
Apatite
Ca5(PO4)3(OH,F,Cl)
0.02
<0.5
PGM species
PtPd-BiTe and PtRh-S
<0.01
<0.5
Pyrrhotite
Gersdorffite
Cu-sulphides
Silicates
Oxides
Sulphates
Mass % *
77.4
21.6
0.6
0.4
Including pyrrhotite with and without detectable nickel

Mostly covellite but includes chalcocite
* Where relevant, two decimal figures are given merely to demonstrate proportional differences between trace minerals
1
2
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Bioleach amenability test work

The results obtained from amenability test work performed in continuously operated benchscale reactors using mesophile, moderate thermophile and thermophile cultures indicated that
nickel extractions of over 98% could be obtained using moderately thermophilic and
thermophilic cultures operating at 45 and 70C, respectively. For copper, which occurs as
chalcopyrite, extractions of over 95% could only be achieved using the thermophile culture at
70C (Table IV). Based on these results, the thermophile culture was selected for further
optimization test work.
Further optimization of the process focused on determining the effects of key process
parameters such as grind size, residence time and feed solids concentrations on the leach
kinetics, metal extractions and performance of the thermophile culture.
It was shown that the performance of the thermophile culture was negatively affected when
operating at feed solids concentrations above 12%, and so a conservative feed solids
concentration of 10% was selected.
Bioleach tests performed at 70C at grind sizes ranging between 10 and 35 m indicated
that a nickel extraction of over 97% could be obtained over the range of grind sizes. There
was, however, a reduction in copper extraction with increasing grind size, and copper
extractions of 95% could only be achieved at a particle size of d90 = 10 m and an overall sixday residence time (Table V).
Based on the results of the amenability test work, a set of bioleach operating parameters was
set for the integrated piloting campaign. These are summarized in Table VI.
Bench-scale purification and metals recovery test work
Phase two of the overall metallurgical test work programme comprised bench-scale testing
that evaluated the downstream unit operations: iron removal, copper SX, nickel precipitation,
and solution purification. The results of these tests were used to set the initial operating
conditions for the third phase of testingthe integrated pilot plant run.
Table IV
Metal extractions achieved in three-stage continuously operated reactor
systems, 6-day residence time, 10 % feed solids concentration, particle size of
d90 = 10 m
Mesophiles (35 C)*

Moderate thermophiles (45 C)
Thermophiles (70 C)
* Single-stage reactor at 3-day residence time
Metal extraction (%)

Cu
Ni
30
76
65
99
95
99
Table V
Summary of bioleach results showing the effect of grind size on metal
extractions
Operating conditions
3-stage, 70C, 10 m, 6 days
Batch, 70C, 35 m, 6 days
R1/2/3 = Reactor 1/2/3
128
Cu extraction (%)
R1
R2
R3
83.5 92.0 95.1
72.4 82.0 90.7
52.9
72.8
Ni extraction (%)
R1
R2
R3
98.7 99.3 99.4
96.3 97.4 97.4
87.7
98.1
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Table VI
Bioleach operating parameters for Aguablanca nickel-copper concentrate
Operating conditions
Microbial culture
Operating temperature (C)
Feed solids concentration (%)
Feed grind size (d90) (m)
Overall residence time (d)
Operating Eh level (mV vs. Ag|AgCl)
Operating pH level
Oxidation level and metal extractions
Sulphide oxidation (%)
Copper extraction (%)
Nickel extraction (%)
Solution metal tenors
Iron concentration (g/l)
Copper concentration (g/l)
Nickel concentration (g/l)
Thermophiles
70.0
10.0
10
6.0
600
1.31.1
99.0
95.1
99.4
26.0
8.0
6.5
In order to provide sufficient samples for the bench-scale test work, a continuous bioleach
miniplant was operated in open circuit treating a sample of Aguablanca concentrate. The
product from this plant was used to undertake a series of batch bench-scale tests. These tests
aimed to assess each of the proposed unit operations, and in particular to evaluate various
options for the precipitation of iron and nickel, and to carry out an initial assessment of the
solid-liquid separation characteristics of the products from each process.
It was recognized that optimization of the precipitation processes can only be undertaken
during continuous testing, where the impact of steady process operating conditions, and the
use of recycle streams for seeding of the precipitation reactions, can be assessed. These
factors are likely to have a direct and beneficial impact on the rate and extent of metal
precipitation that can be achieved in practice, and on the settling and/or filtration
characteristics of the resulting precipitates. The aim of these tests, therefore, was merely to
provide the initial operating parameters for the integrated piloting campaign.
Table VII contains a summary of the initial operating parameters that were selected for each
unit operation.
Integrated piloting test work
Integrated pilot plant
The pilot plant that was used for the integrated piloting tests is comprised of three main units:
a bioleach plant, a precipitation plant, and a solvent extraction plant. The bioleach plant was
operated continuously for the duration of the campaign. However, it was not possible to
operate the precipitation and solvent extraction plants continuously throughout the campaign,
because of the wide disparity between the retention time in the bioleach plant and in the
subsequent purification and metals recovery processes. To overcome this, the product from
the bioleach plant was collected over a period of several weeks, and then used to feed the
precipitation and solvent extraction unitswhich were then operated continuously, but for
short periods. The same precipitation plant, comprising five equal-volume reactors arranged
in series, was used for each of the successive precipitation processes.
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Table VII
Initial operating parameters for integrated piloting of Aguablanca concentrate
Primary iron precipitation
Temperature (C)
Final pH level
60.0
3.0
Final iron tenor (g/l)
0.45
Iron removal (%)
99.4
Limestone consumption (kg/t liquor)

Precipitate settling rate (m/h)
25.0
0.0382
Precipitate underflow density (%)
27.6
Calculated thickener area (m2/(t/h))
69.1
Copper solvent extraction

Organic extractant
LIX984N-C
Diluent
ShellSol 2325
Extractant concentration (%)
25
Organic-to-aqueous ratio
0.8:1
Final copper tenor (g/l)
0.163
97.5
Secondary iron precipitation

Temperature (C)
Final pH level
60.0
5.0
0.05
Iron removal (%)
98.3
Limestone consumption (kg/t liquor)

13.7
6.0-7.8
20-24
2.0-4.3
Nickel precipitation
Temperature (C)
Final pH level
Final nickel tenor (g/l)
Nickel removal (%)
60.0
7.8
~0.2
~97.1
Product nickel grade (%)
24.2
Magnesia consumption (kg/t liquor)
18.4

9.3
12.8
4.6
Final (magnesium) precipitation

Temperature (C)
Final pH level
Final magnesium tenor (g/l)
60.0
10.0
0.0062
Magnesium removal (%)
99.5
Product magnesium grade (%)
12.7
Lime consumption (kg/t liquor)
4.65

130
3.0
7.0
22.7
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The integrated pilot plant is illustrated in Figures 4 and 5.

The integrated pilot plant was operated for a period of 220 days, during which seven
downstream solution purification and metals recovery cycles were completed. Each
downstream cycle consisted of five additional unit operations, carried out in sequence. The
product from each unit operation was stored, and used as the feed for the next unit operation
in the sequence. The five unit operations were:
Primary iron precipitation, in which the bioleach pulp was neutralized with limestone
Copper SX, treating the pregnant leach solution after primary iron removal
Secondary iron precipitation, in which the SX raffinate was neutralized with limestone
Figure 4. The integrated pilot plant: the solvent extraction plant is on the left, the bioleach pilot plant is in the centre,
and the precipitation plant is on the right
Figure 5a. The integrated plants bioleach reactors,

with the solvent extraction plant in the background: on
the right is the feed tank, the dark grey vessel is the 60litre primary reactor, with three 20-litre reactors
arranged in series to the left of that
Figure 5b. The integrated plants neutralization

reactors, comprising a feed tank (hidden) and five 20litre reactors arranged in series; in the foreground are
various settlers that were used during the operation of
this plant
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Nickel precipitation, in which nickel hydroxide was precipitated from the purified solution
Magnesium precipitation, to remove excess magnesium from the circuit.
At the completion of each cycle, the barren solution was recycled to the bioleach plant, by
using it as the make-up water in the bioleach feed tank. In this way, full integration of the
process was achieved. The use of recycled barren process solution for bioleach feed dilution
was the only connection between the bioleach process and the downstream solution
purification and metals recovery cycles.
Bioleach plant performance
The operation of the bioleach pilot plant is illustrated in Figures 6 to 12, which contain graphs
of the routine data for several of the measured operating parameters.
In the early stages of the pilot-plant campaign, it was observed that the measured feed solids
concentration was below the target value of 10%, as shown in Figure 6. This was despite the
fact that the feed constituents (concentrate, nutrients and dilution water) were carefully
metered to target this feed solids concentration. At first, it was suspected that this may be due
to inadequate agitation in the feed tank, but even after this was addressed (by installing a
larger impeller in the feed tank), the measured feed solids concentration remained below the
Figure 5c. The integrated pilot plants solvent extraction units; this versatile plant has eight mixer-settlers that can
easily be configured to provide the required number of extraction, washing and stripping stages
Figure 6. Bioleach feed solids concentrations during the integrated piloting campaign
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target value. Inspection of the feed material revealed that, during the drying process after
regrinding, the concentrate had formed persistent agglomerates that that did not break up in
the feed tank. It is possible that residual flotation chemicals associated with the concentrate
may have caused this. These large particles remained in the lower region of the feed tank, and
were preferentially pumped into the primary bioleach reactor. Thus, when the solids
concentration in the feed tank was measured just before refilling the tank, the measured value
was below the target value. To overcome this, the concentrate was given a light regrind prior
to use, in order to break up the coarse agglomerates.
Figure 7. Measured pH levels during the integrated piloting campaign
Figure 8. Measured Eh levels during the integrated piloting campaign
Figure 9. Measured oxygen uptake rates levels during the integrated piloting campaign
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The rate of evaporation from the bioleach reactors was high, since they were being operated
at a temperature of 70C. At this scale of operation, the ratios of surface area to tank volume
and of aeration rate to tank volume are very high. This results in much higher rates of
evaporation than would be experienced in a production-scale process. To counter this, dilution
water was pumped into each reactor to replace the water lost through evaporation. The rate of
evaporation was not constant, and was affected by seasonal variations in the ambient
humidity. Consequently, step changes were occasionally made to the rate of dilution water
addition, which explains why the soluble metal concentrations shown in Figures 10 to 12
Figure 10. Measured soluble iron concentrations during the integrated piloting campaign
Figure 11. Measured soluble copper concentrations during the integrated piloting campaign
Figure 12. Measured soluble nickel concentrations during the integrated piloting campaign
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display several sudden changes during the course of the campaign. This had no material
impact on the process performance, as evidenced by the stable redox potential levels
(Figure 8) and oxygen uptake rates (Figure 9) for most of the campaign.
The bioleach plant operation was found to be stable and robust, and capable of withstanding
upsets in plant operation. At various times, power, heater and compressed air failures were
experienced, but the process recovered swiftly from these disturbances.
Four mass balance sampling campaigns were performed over the bioleach section of the
plant during the integrated pilot plant trial, allowing a detailed set of performance parameters
to be calculated. The results of these mass balances were broadly similar. The results of one of
these, performed on day 92, are summarised in Table VIII.
The results of the mass balances indicated that the target nickel and copper extractions of
99.4% and 95.1% were consistently achieved or exceeded. The target sulphide oxidation level
of 99.0% was also consistently achieved.
Microbial identification
The microbial populations present in the bioleach reactors were identified and quantified
using Q-PCR and T-RFLP techniques, respectively (Tables IX and X). Acidianus sp. was
identified as the most abundant organism in all four stages, with Metallosphaera sp. and
Sulfolobus sp. present in much lower numbers.
Additional bioleach optimization test work
Additional bench-scale bioleach test work was conducted to study the effect of redox
potential, grind size and feed solids concentration on copper and nickel extractions and
bioleach kinetics.
Table VIII
Results of bioleach mass balance conducted on day 92
Reactor number
Solids concentration %
Feed flow rate (l/d)
Product flow rate (l/d)
Residence time (d)
Temperature (C)
pH level
Redox (mV, Ag/AgCl)
[Fe] (g/l)
[Ni] (g/l)
[Cu] (g/l)
Fe extraction (%)
Fe precipitation (%)
Ni extraction (%)
Ni precipitation (%)
Cu extraction (%)
Cu precipitation (%)
S2- extraction (%)
[S] (%)
1
8.6
20.2
19.8
3.03
70
1.35
599
19.4
6.2
5.2
65.6
Soluble analysis
2
3
4.04
70
1.33
667
19.8
6.3
5.6
64.7
5.06
70
1.34
685
19.3
6.2
5.8
66.7
6.07
70
1.35
687
17.9
5.8
5.6
65.9
97.0
97.7
99.6
99.3
78.4
86.7
92.7
95.0
93.8
0.2
98.2
0.3
98.9
0.26
99.4
0.23
Total (HCI-washed) analysis

2
3
92.5
29.1
97.5
0.46
81.7
3.94
92.6
30.1
99.4
1.69
87.8
1.24
94.3
29.3
99.7
0.17
93.0
0.31
95.8
30.4
99.8
0.21
96.5
3.92
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Although the most common means of overcoming the slow and incomplete extraction of
copper from chalcopyrite is to operate the process at high temperature using thermophiles, an
alternative approach is to operate at controlled redox potential levels. Previous test work has
indicated that faster copper leach kinetics can be achieved by maintaining the redox potential
at levels between 410 and 440 mV vs. Ag|AgCl, although a reduction in the rate of nickel
extraction was observed at redox potential levels below 460 mV vs Ag|AgCl.
Based on these results, a three-stage continuously operated reactor system was operated at
70C and an overall 6-day residence time, using Aguablanca concentrate milled to a particle
size of d90 = 10 m. The redox potential in the first-stage reactor was maintained at 430 mV
vs. Ag|AgCl, while the redox levels in the secondary stages were not controlled. Redox
potentials of 550 and 580 mV vs. Ag|AgCl were measured in the second- and third-stage
reactors, respectively.
The results of this test are summarized in Table XI. This test confirms that, by controlling
the redox potential in the first-stage reactor, considerably faster copper leach kinetics can be
achieved. Around 96% of the copper was extracted in the first-stage reactor, compared to an
extraction of 78% without redox control. The overall copper extraction improved from 95 to
98%. Furthermore, the high redox potential levels maintained in the secondary reactors
ensured that a nickel extraction of over 98% was achieved in the second-stage reactor. This
result indicates that operating the first-stage reactor at a low redox potential level allows a
reduction in the overall bioleach residence time from six to four days.
In a second test, the effect of concentrate grind size on the copper and nickel extractions was
evaluated using concentrate milled to a d90 of 20 m. As before, the redox potential in the
first-stage reactor was maintained at a level of 430 mV vs. Ag|AgCl, while the redox potential
levels in the secondary reactors were not controlled. As before, redox potential levels of 550
and 570 mV vs. Ag|AgCl were measured in the second- and third-stage reactors, respectively.
The results of the second test are summarized in Table XII. Despite the coarser feed
material, a copper extraction of around 92% was achieved in the first-stage reactor, and an
overall copper extraction of 96% was achieved. The high redox potential levels in the
Table IX
Quantification of the microorganisms using Q-PCR
Microorganism
Acidianus sp.
Metallosphaera sp.
Sulfolobus sp.
ND: Not detected
Reactor 1
2.7 x 109
5.4 x 107
7.6 x 104
Cell concentrations (cells/ml)

Reactor 2
Reactor 3
6.1 x 109
4.5 x 109
8
1.3 x 10
8.4 x 107
4
9.9 x 10
6.4 x 104
Reactor 4
3.2 x 109
5.4 x 107
ND
Table X
Relative abundance of the microbial populations occurring in the bioleach reactors
Sample
Reactor 1
Reactor 2
Reactor 3
Reactor 4
*ND: not detected
136
Acidianus sp. (%)

Q-PCR
T-RFLP
98.0
78
97.9
85
98.2
89
98.3
92
Metallosphaera sp. (%)

Q-PCR
T-RFLP
1.9
22
2.0
15
1.8
11
1.7
8
Sulfolobus sp. (%)

Q-PCR
T-RFLP
0.003
ND
0.002
ND
0.001
ND
0
ND
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secondary reactors ensured that a nickel extraction of almost 98% was achieved. This result
suggests that, with a coarser feed material and by controlling the redox potential in the firststage reactor, the overall bioleach residence time can be reduced from six to five days.
Subsequent testing was conducted in which the feed solids concentration was raised to 12%,
and it was found that stable operation could be maintained at this solids concentration.
Integrated purification and metals recovery tests
As mentioned previously, seven cycles of operation of the integrated purification and metals
recovery circuit were completed during the integrated pilot plant campaign.
Table XI
Effect of controlled low redox potential on bioleach process performance
Microbial culture
Temperature (C)
pH level
Redox (mV, Ag|AgCl))
Cumulative residence time (d)
Grindd90 (m)
Feed
Thermophiles
Reactor 1
Reactor 2
Reactor 3
70
1.6
430
3
70
1.3
550
4.5
70
1.25
580
6
14.5
7.1
6.7
48.4
96.2
93.8
67.3
17.4
7.0
6.9
68.6
97.8
98.4
94.2
18.0
7.0
7.0
75.6
98.1
98.7
98.8
9.8
10
[Fe] (g/l)
[Cu] (g/l)
[Ni] (g/l)
Fe extraction (%)
Cu extraction (%)
Ni extraction (%)
S2- extraction (%)
Table XII
Effect of grind size and controlled low redox potential on bioleach process performance
Microbial culture
Temperature (C)
pH level
Redox (mV, Ag|AgCl))
Cumulative residence time (d)
Grindd90 (m)
[Fe] (g/l)
[Cu] (g/l)
[Ni] (g/l)
Fe extraction (%)
Cu extraction (%)
Ni extraction (%)
S2- extraction (%)
Feed
Thermophiles
Reactor 1
Reactor 2
Reactor 3
70
1.7
430
3
70
1.4
550
4.5
70
1.3
570
6
13.6
7.3
6.7
40.7
92.7
85.1
63.7
16.0
7.4
7.0
63.1
95.8
96.9
84.7
19.2
7.6
7.5
70.1
96.0
97.9
94.2
9.4
20
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During the commissioning of the plant, it was established that it was possible to conduct the
primary iron precipitation on the bioleach product pulp, without first having to separate and
wash the bioresidue. Since this removed a solid-liquid separation and washing operation from
the flowsheet, it was decided to proceed on this basis for the remainder of the integrated
piloting campaign.
The primary iron precipitation process was operated at a variety of temperatures between 45
and 70C. The pH level in the first-stage reactor was maintained at a level of between 1.8 and
2.9, and the final pH was maintained at a level of between 3.0 and 3.5. The neutralizing agent
was limestone. Recycling of the product was used to promote seeding in the first reactor.
Various recycle ratios were used.
It was found that the product pulp from the primary iron precipitation process was very
difficult to settle, irrespective of the operating temperature and the recycle ratio. It was also
found that, as the operating temperature varied, the settling characteristics changed to such an
extent that different flocculants were required to achieve the best result. Although some
flocculants achieved good settling rates, it was observed that the product liquor was turbid and
unsuitable as a feed to the copper solvent extraction plant. The clarity of the settler overflow
was improved considerably by the addition of a coagulant. It was shown that the coagulant
could be used on its own or in conjunction with a neutrally-charged flocculant. However,
large coagulant doses of over 1 kg/t were required, compared with around 330 g/t for
flocculants.
The best set of results resulted in a batch settling rate of 282 mm/h. In this run, the settler
overflow was clear and relatively small doses of coagulant and flocculant were required.
The copper SX plant was a mixer-settler unit operated using a mixture of 25% LIX984N-C
in ShellSol 2325 as the organic extractant. LIX984N-C, which is manufactured by Cognis,
is a reagent that has been developed especially for use with pregnant liquors containing high
copper concentrations, and ShellSol (made by Shell Chemicals) is a paraffin-based
hydrocarbon solvent. The sulphuric acid concentration in the strip liquor was maintained at
180 g/l.
The flow rate through the SX plant is determined by a required minimum residence time of
three minutes in the mixer, taking account of both the organic and aqueous phases. The
second parameter is the loading capacity of the organic, specified by the manufacturer as
being 0.3 g/% or 7.5 g/l copper for a 25% solution of LIX984N-C. This, together with the
copper concentration in the pregnant leach solution (PLS) determines the organic-to-aqueous
(O:A) ratio. The strip liquor flow rate is determined by the electrowinning section, where a
reduction of 15 g/l copper is required. In the stripping section of the SX plant, this quantity of
copper must be replaced, thus setting the organic-to-strip (O:S) ratio. In this instance an O:S
ratio of two is typical.
Provided that the O:A ratio was maintained above about 0.7:1, copper extractions between
98.2 and 98.9% were achieved using three extraction stages.
Copper electrowinning
At the completion of the pilot plant campaign, a sample of the strip liquor (which had built up
to a copper concentration of around 50 g/l) was used to perform an electrowinning test, using
a standard set of operating conditions. Two small copper cathodes (each with an area of
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0.0315 m2) were produced in this test. They were characterized as being smooth, compact and
bright. One cathode was drilled and submitted for chemical analysis, to determine whether the
copper cathode meets the requirements for LMA A-grade copper. Table XIII summarizes the
results.
The detection limits for the analyses of the elements P and S are higher than the threshold
values. The measured values of the other elements were all well below the LME A-grade
threshold values, and the sum (excluding P and S) of 16.07 ppm for these elements is well
below the threshold value of 65 ppm. The LME A-grade specification also provides upper
limits for several elements in combination, and once again the measured values (excluding P)
are well below the threshold limits.
These results indicate that, unless the cathode contains over 15 ppm of either S or P, it will
easily satisfy the requirements for LME A-grade classification.
The purpose of the secondary iron precipitation process was to reduce the concentration of
iron and other metals in the pregnant liquor as far as possible prior to the precipitation of
nickel hydroxide, in order to reduce the level of contamination of the nickel hydroxide
precipitate by these elements. This was achieved by raising the pH of the liquor to a level of
around 5.0 using limestone, at a temperature of 60C. Recycling of the product was used to
promote seeding in the first reactor. Various recycle ratios were used.
Table XIII
Aguablanca copper cathode analysis
Element(s)
Ag
As
Bi
Cd
Co
Cr
Fe
Mn
Ni
P
Pb
S
Sb
Se
Si
Sn
Te
Zn
Sum
As+Cd+Cr+Mn+P+Sb
Bi+Se+Te
Se+Te
Co+Fe+Ni+Si+Sn+Zn
LME A grade
threshold (ppm)
25
5
2
10
5
15
4
2
2
65
15
3
3
20
Measured
value (ppm)
0.17
0.00
0.53
0.00
0.00
0.00
0.00
0.50
0.00
<20
0.00
<100
0.00
1.17
12.67
0.50
nd
0.53
16.07
0.50
1.70
1.17
13.70
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The product from this process was mostly gypsum, and the product pulp had a very low
solids concentration (of between about 2 and 4 %). The gypsum particles in the product solids
were large, and were easily settled.
Copper and nickel scavenging
There was some loss of both copper and nickel to the precipitated solids in the secondary iron
removal process. Gravity separation of the product was investigated as a means of upgrading
the copper and nickel. Three options were evaluated: a shaking table, a Falcon concentrator,
and a cyclone.
The shaking table was ineffectual, with around 90% of the copper and nickel reporting to
the slimes, which comprised over 60% of the mass. The same was true of the Falcon
concentrator, where over 99% of the copper and nickel reported to the tailings, which
comprised over 90% of the mass.
The cyclone proved effective in upgrading the copper and nickel. Over 75% of the copper
and over 80% of the nickel could be recovered in the cyclone overflow, at a mass recovery of
18.4%. It is likely that further optimisation of this process, with a slightly coarser cut and with
underflow recycle to scavenge the tails, would further improve this result.
The cyclone overflow would be recycled back to the bioleach process to redissolve the
copper and nickel.
Nickel precipitation to produce nickel hydroxide was achieved by raising the pH of the liquor
to a level of around 7.8 using magnesia, at a temperature of 60C. Recycling of the product
was used to promote seeding in the first reactor. Various recycle ratios were used.
The objective of this process was to produce a nickel hydroxide product of the highest
possible purity, with reasonable filtration characteristics, and to ensure a high recovery of
nickel. This presents a challenge: a good nickel recovery is obtained at pH levels in the region
of 7.7 to 8.0, but as the pH increases above a level of about 7.5, the product becomes
increasingly contaminated with magnesiumeither in the form of unreacted magnesia or
precipitated magnesium hydroxide.
One approach that has been adopted is to conduct a two-stage nickel hydroxide
precipitation. The first-stage process is operated at a target pH level of around 7.2, and aims to
recover around 90% of the nickel and produce a high-grade nickel hydroxide product. The
second-stage process is operated at a pH level of between 7.5 and 8.0, and aims to recover the
remainder of the nickel in a lower-grade nickel hydroxide precipitate. This product can either
be recycled to the leach process or sold at a lower cost.
A second approach is to conduct the precipitation in multiple stages with careful control of
the pH level throughout the process, to ensure that both targetsrecovery and product purity
are met. This approach, if achievable, has the advantage of reducing the number of unit
operations required, and producing a single high-grade nickel hydroxide product. It was
therefore decided to aim for a single-stage nickel hydroxide precipitation process.
In the piloting campaign, the solids were settled in order to provide a recycle stream for
seeding purposes. In practice, the nickel hydroxide product will be filtered to minimise the
water content. It was observed that nickel hydroxide precipitation required a considerable
amount of seeding to initiate the precipitation processmore so than the iron removal steps.
The product was observed to flocculate well, although the overflow remained slightly turbid
due to the presence of very small particles in suspension. When part of the settler underflow
was recycled for seeding, nickel recoveries of well over 99% were achieved.
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It was also noted that a fresh magnesia slurry was required for the best performanceit was
found that when an older magnesia slurry was used, the product nickel grade was lower.
The nickel content of the nickel hydroxide precipitate varied between 31.6 and 47.5%. This
variance reflects the fact that the operating conditions in the nickel recovery process were
changed in an effort to understand the impact of the operating conditions on the process.
Based on the results, it is considered that a target nickel grade of between 40 and 45% can be
achieved using a single-stage precipitation process.
Magnesium precipitation
The final step in the process flowsheet is magnesium precipitation, which was achieved by
raising the pH of the liquor to a level of around 9.5 using slaked lime, at a temperature of
60C. Recycling of the product was used to promote seeding in the first reactor. Various
recycle ratios were used. In some cases, the product was settled prior to recycling, whereas in
others the recycle stream comprised the product pulp.
The objective of this process step was to remove magnesium and most other contaminants
from the stream, to enable it to be recycled to the front of the process. The treatment of a
bleed stream could be considered, provided that the presence of some magnesium could be
tolerated in the bioleach process. Bioleach amenability tests had shown that up to 10 g/l of
magnesium could be tolerated, but there were concerns that the presence of high
concentrations of magnesium in the iron removal, copper solvent-extraction and nickel
hydroxide processes would be undesirable. Therefore, it was decided to process the entire
stream through the magnesium precipitation process.
It was observed that the magnesium product flocculated relatively easily, but that the
overflow contained some fine particles that did not settle.
Upgrading of magnesium precipitate
An attempt was made to upgrade the magnesium precipitate using a cyclone, in order to assess
whether the upgraded product might be used in the nickel hydroxide precipitation process.
This test was only partially successful, in that around 40% of the magnesium was recovered in
the cyclone overflow, which had a mass recovery of 11.5%. The upgraded product had a
magnesium grade of 22.2%, but also contained 12.5% calcium, indicating that gypsum had
also reported to the overflow. If this was to be used in the nickel precipitation process, the
gypsum would contaminate the nickel hydroxide product, and it is therefore not proposed to
utilize this upgraded product in the nickel precipitation process.
Summary of integrated piloting tests
The results of the integrated piloting tests were used to establish the basic process design
criteria for the proposed bioleaching and metals recovery plant for the treatment of the
Aguablanca concentrate. The design criteria are summarized in Table XIV.
The piloting programme demonstrated that integration of the bioleaching process with the
downstream purification and metals recovery processes had no impact on the bioleach process
performance. Therefore, the design criteria for the bioleaching process remained unchanged
from those obtained in the amenability tests.
These basic process design criteria were used as the basis for the process design and costing
of the commercial-scale plant.
Process design and costing
The flowsheet and data derived from the integrated piloting of the Aguablanca nickel-copper
concentrate were used to develop a process design and costing model for a hydrometallurgical
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Table XIV
Basic process design criteria based on integrated piloting results
Bioleaching
Bacterial culture
Operating temperature (C)
Feed grind size (d90) (m)
Overall residence time (d)
Operating Eh level (mV vs. Ag|AgCl)
Operating pH level
Sulphide oxidation (%)
Nickel extraction (%)
Temperature (C)
Number of stages
Residence time per stage (h)
Final pH level
Iron removal (%)
Limestone consumption (kg/m3 slurry)
Thickener underflow density (%)
Temperature (C)
Organic extractant
Diluent
Extractant concentration (%)
Organic-to-aqueous ratio
Number of extraction stages
Number of scrubbing stages
Number of stripping stages
Final pH level
Final copper tenor (g/l)
Temperature (C)
Number of stages
Final pH level
Iron removal (%)
Limestone consumption (kg/m3 slurry)
Filter cake moisture (%)
Filtration rate (m2/(t/h))
Temperature (C)
Number of stages
Final pH level
142
Thermophiles
70.0
10.0
12
6.0
650
1.4-1.2
99.0
95.1
99.4
60.0
5
1
3.0
0.09
99.5
60
30-40
10-20
35
LIX984N-C
ShellSol 2325
25
1:1
3
2
3
1.1-1.2
0.1
97.0
60.0
5
1
5.0
0.00
95.0
12.5
46.5
62.4
60.0
5
1
7.8
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Table XIV (continued)

Basic process design criteria based on integrated piloting results
Final nickel tenor (g/l)
Nickel removal (%)
Product nickel grade (%)
Magnesia consumption (kg/m3 slurry)
Thickener underflow density (%)
Final (magnesium) precipitation
Temperature (C)
Number of stages
Final pH level
Final magnesium tenor (g/l)
Magnesium removal (%)
Product magnesium grade (%)
Lime consumption (kg/m3 slurry)
0.02
99.5
40.045.0
4.0
2025
2.03.0
55.2
126
60.0
5
1
9.5
0.00
98.8
10.2
10.0
64.0
166
plant consisting of bioleaching and associated purification unit operations. The data from the
integrated piloting test work were used as inputs for the model. In some instances, most
notably in sizing the settling and filtration equipment, in-house database information was used
to obtain realistic settling and filtration rates. The settling and filtration tests that were
performed during the integrated pilot plant campaign were limited in scope and extent, and
were not optimized. It is therefore considered that the in-house database information is more
reliable than the test work data.
Process description
The proposed hydrometallurgical plant will be situated at the site of the existing Aguablanca
concentrator in southern Spain. The plant will be designed to treat 96 000 t/a of Aguablanca
concentrate, producing 4 857 t/a of nickel in an intermediate precipitate and 5 400 t/a of
copper cathode. The design criteria for the plant are summarized in Table XV.
Milling
The concentrate is repulped to between 50 and 60% solids, and fed to a vertical bead mill,
where it is reground to achieve a particle size distribution with a d90 of 10 m. Regrinding of
the concentrate to this extent is required to achieve suitable copper recoveries in the
bioleaching process. For the design capacity, it is considered that the regrinding will be
achieved in a mill similar to a Deswik 1000 vertical bead mill. The Deswik 1000 is fitted with
up to 24 polyurethane impellers on a vertical shaft. The milling medium comprises 1 mm
zirconia beads. This mill is similar in concept to the IsaMill, with the principal difference
being the orientation of the mill: the IsaMill is a horizontal bead mill, whereas the Deswik has
a vertical orientation. Bead mills have been found to be more energy efficient than stirredINTEGRATED PILOTING OF A THERMOPHILIC BIOLEACHING PROCESS
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Table XV
Design criteria used in the costing model
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media mills such as the Svedala VertiMill and the Metso Minerals Stirred Media Detritor
(SMD), particularly for ultra-fine grinding to particle sizes below a d90 of around 20 m.
Based on information obtained from the Deswik mill supplier in South Africa, it is estimated
that the power consumption required to achieve the target particle-size distribution in a
Deswik 1000 vertical bead mill is about 14.3 kWh/t.
The reground pulp is delivered to a pulp storage tank, with a sufficient capacity to allow the
bioleach plant to be fed for two days.
Bioleaching
The bioleach feed pulp is diluted to the required solids concentration of 10% (m/m), using
fresh water or water recycled from the downstream process. Appropriate control systems are
utilized to maintain the desired pulp feed rate and solids concentration.
The bioleach reactors are operated at a temperature of 70C, and will consist of two
modules, each comprising six reactors. Each module comprises three primary reactors
operated in parallel, and three secondary reactors operated in series. The feed pulp is evenly
distributed to the primary reactors to ensure a uniform feed to each primary reactor.
The overall residence time of the bioleaching process is maintained at six days, and each
individual reactor has a volume of approximately 1 620 m3. The bioleach reactors are
mechanically-agitated, aerated vessels, made from an appropriate materialeither a duplex
stainless steel or a ceramic-lined concreteto enable them to withstand the corrosive, acidic
process conditions. The reactors are agitated using specialized impellers that promote the
dispersion of large volumes of air and maintain the solids in suspension. Aeration is via
specially-designed aerators that are positioned in the proximity of the impellers. The oxidation
reactions taking place in the reactors are exothermic, and the temperature of the reactors are
controlled at 70C using cooling water that is circulated through a cooling tower. In some of
the secondary reactors, where the reaction rates may be lower, some heating may be required,
which is achieved by live steam injection.
The product from the two bioleaching modules, comprising a pulp with a pH level of around
1.6, containing unleached gangue minerals, some iron precipitates, and a liquor containing
sulphuric acid, ferric sulphate, copper sulphate and nickel sulphate, is combined and delivered
to the primary iron removal plant.
Primary iron removal
The primary iron precipitation takes place in a series of five neutralization reactors, in which
the temperature is maintained at 60C. Limestone slurry is used as the neutralizing agent. The
pH is raised to a level of 3.0, and the overall residence time is 5 hours. The main products
from the neutralization reaction are gypsum (from acid neutralization) and ferric hydroxide
(from iron precipitation).
The product pulp from the primary iron removal reactors is fed to a continuous countercurrent decantation (CCD) circuit, comprising 4 thickeners. In this circuit, wash water is used
to wash the product solids. The liquor from the CCD circuit, containing copper sulphate and
nickel sulphate, is fed to the copper SX plant.
Copper solvent extraction and electrowinning
The SX plant receives the pregnant leach solution (PLS) from the primary iron removal
circuit, and produces a rich electrolyte that is sent to the electrowinning plant. Copper SX is
performed in two extraction, one scrubbing, and two stripping stages. In the extraction stages,
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copper is extracted into the organic phase. The organic phase comprises a mixture of 11%
LIX984N-C in ShellSol 2325 as the organic extractant (based on a specification of 0.29 g/l
per volume % in the organic phase). Although a concentration of 25% organic was used in the
pilot plant test work, the process model takes into account dilution from the CCD wash, which
results in a lower copper tenor and organic concentration. An organic-to-aqueous ratio of 1:1
is maintained in the extraction stages. The tailing (raffinate) from the extraction stages, which
contains nickel sulphate, forms the feed to the secondary iron removal circuit.
The loaded organic is fed to the stripping section, where it is contacted with spent
electrolyte from the electrowinning section, typically containing around 180 g/l of sulphuric
acid. The copper is stripped from the organic phase into the electrolyte, which forms the feed
to the electrowinning plant. The barren organic phase is returned to the extraction stages.
In the electrowinning section, the rich electrolyte from the copper solvent extraction plant is
fed to a series of conventional electrowinning cells, where the copper is plated out on stainless
steel cathodes to produce LME A-grade copper. The electrowinning plant comprises a series
of cells, with non-soluble lead anodes and 316L stainless steel cathodes, a rectifier, an
overhead crane to handle the cathodes, an automatic cathode stripping machine and accessory
equipment. The spent electrolyte is returned to the stripping section of the copper SX plant.
Secondary iron removal
The copper SX raffinate is fed to the secondary iron removal circuit, where the pH is raised to
a level of 5.0 using a limestone slurry in order to purify the leach solution prior to nickel
recovery. The plant comprises five reactors in series, operated at a temperature of 60C. In
this process, the acid produced in the copper SX process is neutralized, and any residual iron
is precipitated. Additional elements that are removed in this process are aluminium and
chromium, with partial removal of silicon and zinc. Any copper remaining in the raffinate is
also precipitated, and there may be a small loss of nickel sulphate. The main products from
the neutralization reaction are gypsum (from acid neutralization) and ferric hydroxide (from
iron precipitation).
The product pulp from the secondary iron removal reactors is fed to a continuous filter,
where wash water is added. The filtrate, containing nickel sulphate, is fed to the nickel
precipitation plant. The filter cake is repulped and fed to a cyclone, with the objective of
concentrating and recovering most of the precipitated copper and nickel. The cyclone
overflow, containing 20% of the mass and about 7580 % of the copper and nickel, is
recycled to the bioleach circuit. The cyclone underflow is disposed of.
Three downstream nickel recovery options were investigated.
Hydroxide precipitation. This is the base case, and is the one that was piloted. Nickel is
precipitated as an hydroxide by the addition of magnesia. This the least sophisticated
option, as it generates a lower-quality product, which is difficult to dewater and therefore
more expensive to transport. It is environmentally more benign than the other routes,
provided inexpensive supplies of lime and magnesia can be obtained.
Sulphide precipitation through the addition of hydrogen sulphide. This process involves a
higher degree of complexity, requiring pressurised reactors and a low cost-source of
hydrocarbon or H2S. This route also has environmental concerns, owing to the use of
pressurized reactors and the production of toxic and flammable gases, and it requires a
more sophisticated workforce. However, the product has a lower moisture content than the
hydroxide product, and is therefore less expensive to transport.
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Solvent extraction and electrowinning of nickel cathode is the most sophisticated and
complex route, requiring a skilled workforce. A reliable power supply is required. This
route is suitable if refining charges are high and the additional capital expenditure can be
justified.
Nickel hydroxide precipitation
In this route, the filtrate from the secondary iron removal circuit is fed to the nickel
precipitation plant, which comprises five reactors operated in series, each at a temperature of
60C. The pH is raised to a level of 7.8 using a magnesia slurry, and the overall residence time
is five hours. The nickel precipitates as nickel hydroxide, and some unreacted magnesia and
magnesium hydroxide also reports to the solids. The aim is to produce a nickel hydroxide
product containing at least 45% nickel and less than 10% magnesium (measured on a dry
basis). The product pulp is fed to a settler, and the settler underflow is further dewatered with
a continuous Larox-type filter, where the aim is to reduce the moisture content of the nickel
hydroxide product to below 80%.
The barren filtrate, containing magnesium hydroxide that was formed in the nickel
precipitation process, is fed to the magnesium removal circuit in order to purify the process
solution prior to recycling. Magnesium precipitation is performed in a plant comprising five
reactors operated in series, each at a temperature of 60C. The pH is raised to a level of about
9.5 using a slaked lime slurry, and the overall residence time is five hours. The product pulp
from the magnesium removal reactors is filtered, and the barren filtrate is recycled, and the
filter cake, containing mainly magnesium hydroxide and gypsum, is disposed of.
Nickel sulphide precipitation
Nickel sulphide precipitation is carried out in two autoclaves operated in parallel, with a 30minute residence time each. The feed solution is heated to 90C, and H2S gas is introduced at
a pressure of 600 kPa. The product is fed to a settler, and the underflow is filtered to produce a
dewatered nickel sulphide product. The settler overflow is fed to a neutralization plant,
consisting of five reactors in series, with a total residence time of five hours. The solution is
neutralised with slaked lime to a pH level of 9.5 in order to neutralize the free acid and
precipitate impurities. The gypsum product is fed to a settler, and the settler overflow is
recycled to the bioleach process.
Nickel solvent extraction and electrowinning
Nickel SX consists of four extraction, three scrubbing, and three stripping stages. The organic
extractant is 7% Versatic acid in a paraffin diluent. The O:A ratio is 1.25:1 for extraction,
5.5:1 for scrubbing and 5.5:1 for stripping. Extraction is carried out at a pH level of 6.5, using
sodium hydroxide (NaOH) as the neutralizing agent. For the purposes of this study, it was
assumed that nickel SX is performed in closed circuit with the leaching circuit. However, this
approach may not be technically feasible, owing to the build-up of the SX neutralizing agent
(NaOH or NH4OH). It may be necessary to precipitate and redissolve the nickel, followed by
SX in a separate purification circuit, as is done in most laterite pressure leaching circuits.
Such an option would add significantly to the capital and operating costs, and was not
considered in this study.
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Process costing and financial analyses

Mass and energy balances were developed for the overall hydrometallurgical circuit, followed
by the design, sizing and costing of major equipment items, using in-house equipment cost
indices. The equipment costs were factored to estimate the installed capital costs. Capital
costs were calculated from installed equipment costs and factored indirect costs. Operating
costs were calculated from stoichiometric reagent consumptions, estimated labour rates, and
calculated power consumptions.
Capital cost estimate
Capital costs (basis: 2007/2008) were calculated for the three proposed process flowsheets,
covering the three different nickel recovery options. Based on the mass balance and design
specifications, major equipment items such as tanks, thickeners, filters and compressors were
sized and costed using an in-house Mintek equipment cost database. Installation and auxiliary
items were estimated by multiplying the equipment costs by the appropriate factors.
Indirect capital costs were calculated by multiplying the total installed capital cost by
appropriate factors. The total project cost is the sum of the total installed capital cost and the
indirect costs, plus a contingency. The breakdown of capital costs is given in Table XVI for
the three purification options. Capital costs were approximately US$5.7/lb annual nickel for
the hydroxide and sulphide precipitation options, and approximately US$6.1/lb annual nickel
for the SX-EW option.
Operating cost estimate
Operating costs were calculated from the stoichiometric reagent consumptions, estimated
reagent costs, calculated power consumption and labour rates. The cost for maintenance is
included in the labour element, and an additional 6% of the total installed capital cost was
provided for maintenance materials and consumables. The breakdown of operating costs for
the various components is shown in Figure 13.
Figure 14 expresses the operating cost elements for four different refining options:
concentrate sale, nickel hydroxide production, nickel sulphide production and nickel cathode
production. In each case, the value of refining charges and by-product credits was included in
the operating cost breakdown. The cost of mining and concentrate production of US$3.8/lb
nickel was obtained from the most recent published data for the Aguablanca operation (2007
data).
Financial analysis
For the base case financial analysis, it is assumed that capital is spent in the first two years. A
mining rate of 1.5 million tonnes per annum is assumed, and a concentrate production rate of
96,000 t/a. Depreciation of 33% per annum and a taxation rate of 35% is assumed. No
provision is made for loan financing. The project is assumed to be fully equity funded. The
capital and operating costs of the mine and concentrator are included, and these costs were
taken from the published Aguablanca prefeasibility study12 and other published costs, with
appropriate escalation. The economic analysis therefore comprises the costs of mining,
concentrate production, bioleaching and purification.
In Table XVII, the major outputs from the economic calculations, including a comparison of
the IRR for each option, are summarized. In this analysis, metal prices prevailing in June/July
2008 were used: these were US$10.00/lb nickel and US$3.50/lb copper. It is noted that these
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Table XVI
Capital cost breakdown
Item
Fine grinding
Bioleach utilities
Bioleach
CCD/residue filter
Fe removal I
Fe removal II
Ni-OH precipitation
Mg precipitation
Ni-S2- precipitation
Neutralsn - S2- ppt
NiSX
NiEW
CuSX
Cu EW
Reagents and services
Tailings neutralization
Infrastructure
Total directs (TIC)
EPCM
Site temp facilities
Technology fees
First Fill
Owners cost
Total Indirects
Contingency
Total project cost
OH ppt
$ 000
1 920
1 937
11 497
4 702
620
2 238
3 231
2 368
S2- ppt Ni SXEW

$ 000
$ 000
1 920
1 920
1 937
1 937
11 497
11 497
4 702
4 702
620
620
2 238
2 238
OH ppt
$/a lb Ni
0.18
0.18
1.07
0.44
0.06
0.21
0.30
0.22
4,029
1 515
1 778
5 903
960
960
4 235
42 349
6 352
847
423
1 133
4 235
12 991
5 534
60 874
1 778
5 903
960
960
4 235
42 287
6 343
846
423
1 133
4 229
12 974
5 526
60 787
3 005
5 666
1 778
5 903
960
960
4 235
45 761
6 864
915
458
1 133
4 576
13 946
5 971
65 678
0.17
0.55
0.09
0.09
0.40
3.95
0.59
0.08
0.04
0.11
0.40
1.21
0.52
5.68
S2- ppt Ni SXEW OH ppt

$/a lb Ni $/a lb Ni $/tpa conc.
0.18
0.18
20
0.18
0.18
20
1.07
1.07
120
0.44
0.44
49
0.06
0.06
6
0.21
0.21
23
34
25
0.38
0.14
0.28
0.53
0.17
0.17
19
0.55
0.55
61
0.09
0.09
10
0.09
0.09
10
0.40
0.40
44
3.95
4.27
441
0.59
0.64
66
0/08
0.09
9
0.04
0.04
4
0.11
0.11
12
0.39
0.43
44
1.21
1.30
135
0.52
0.56
58
5.68
6.13
634
S2- ppt
$/tpa conc.
20
20
120
49
6
23
42
16
19
61
10
10
44
440
66
9
4
12
44
135
58
633
Figure 13. Operating cost breakdown (expressed in USc/lb Ni)
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Figure 14. Operating cost breakdown
Table XVII
Capital and operating cost summaries and financial calculations
Concentrate
production
Mass of ore mined (t/a)
Concentrate production (t/a)
Nickel price (US$/lb)
Copper price (US$/lb)
Capital cost (US$ million)
Operating cost (US$ million/a)
Metal value paid out (%)
NPV, @ 8 % (US$ million)
IRR (%)
1 500 000
96 000
10
3.5
119
42.0
65
145.7
31
Bioleach +
hydroxide
precipitate
1 500 000
96 000
10
3.5
61
10.3
90
203.5
30
Bioleach +
sulphide
precipitate
1 500 000
96 000
10
3.5
61
12.4
90
196.4
29
Bioleach
+ SX-EW
1 500 000
96 000
10
3.5
66
11.2
100
239.7
33
prices have fallen substantially since then. Based on nickel refining charges reported by
Lundin in a fourth quarter 2007 press release, an average nickel refining charge of 35% of
nickel value was used in this model for direct concentrate sale. Nickel refining charges of
between 5 and 15% of value have been quoted13,14. An average refining charge of 10% of
metal value was used in this model.
An internal rate of return (IRR) over 10 years of 31% was calculated for concentrate sale,
30% for nickel hydroxide production, 29% for nickel sulphide production, and 33% for nickel
cathode production. At a discount rate of 8%, the NPV is US$145.7 million for concentrate
sale, US$203.5 million for hydroxide production, US$196.4 million for nickel sulphide
production, and US$239.7 million for nickel cathode production.
The effect of the low redox bioleach option on the process economics was calculated for the
hydroxide precipitation route, and a comparison is summarized in Table XVIII.
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Table XVIII
Effect of low-redox bioleach operation on project economics
Solids concentration in leach

Leach residence time days
Tank sizes
Capex bioleach
Capex bioleach + purification plant
Opex bioleach + purification plant
Opex bioleach
Opex bioleach utilities
Aeration rate
IRR, % 10 years
High redox case

10.0%
6.0
1.625
11.5
60.9
10.3
1.6
0.8
51 916
29.9%
%
M3
M$
M$
M$
M$
M$
Nm3/h
%
Low redox case

12.0%
4.0
922
6.9
53.3
9.9
1.3
0.7
52 004
31.7%
Oxidation levelslow redox

Redox potential
Pentlandite
Chalcopyrite
Pyrite
Pyrrhotite
mV
%
%
%
%
Stage 1
430
93.0
96.0
50.0
90.2
Stage 2
550
98.0
97.0
70.0
95.1
Stage 3
560
98.0
98.0
80.0
99.0
Stage 4
570
99.5
98.0
87.0
99.5
Oxidation levelshigh redox

Redox potential
Pentlandite
Chalcopyrite
Pyrite
Pyrrhotite
mV
%
%
%
%
Stage 1
580
97.0
78.0
78.5
90.2
Stage 2
600
97.7
87.0
82.7
95.1
Stage 3
640
99.5
93.0
86.1
99.0
Stage 4
700
99.5
95.0
87.0
99.5
As indicated in Table XVIII, the low redox case yielded a higher overall copper extraction
of 98% with a 4-day residence time, compared with 95% with a 6-day residence time for the
high redox case. The low redox case also tolerated a higher feed solids concentration of 12%
(against 10% for the high redox case). The decrease in residence time and the increase in
solids concentration resulted in a decrease in the bioleach tank volume from about 1 600 m3 to
920 m3. This reduced the capital cost of the bioleach unit operation by 40%, and the overall
hydrometallurgical plant capital cost by 12%. The impact on the overall operating cost for the
hydrometallurgical plant was smaller; it decreased by about 4% for the low redox case. The
net effect was that the IRR of the project increased from 29.9% to 31.7%.
Discussion and conclusion
Despite extensive research and development work spanning a period of at least 20 years, the
uptake by industry of bioleaching technology to treat base metal sulphide concentrates has
been slow. This is despite the fact that several projects have proceeded to an advanced
commercial demonstration level, and despite a sustained boom in commodity prices. The
main reason for this slow uptake is that smelting and refining charges have been on a longterm downward trend for over a decade, since peaking in 1998. There was a brief period
(between 2004 and 2006) where these charges rose steeply, but they subsequently fell back to
even lower levels. New hydrometallurgical technologies find it difficult to compete with the
existing smelting industry, where the capital investment has already been made.
Nevertheless, the indications early in 2009 are that smelting and refining charges are rising
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steeply (by between 60 and 70% for long-term contracts), and a sustained increase in these
charges could result in hydrometallurgical technologies, including bioleaching, being
considered for new projects in the future. Further impetus for selecting hydrometallurgical
processes such as bioleaching will be gained as environmental considerations become
increasingly important, and as the technologies themselves are improved, reducing costs and
improving efficiencies.
The present study, using Aguablanca nickel-copper concentrate as an example, has achieved
several objectives:
It has demonstrated the technical feasibility of the technology. The use of thermophilic
microorganisms to oxidize chalcopyrite has been demonstrated in an integrated pilot plant
over an extended period of time.
A feature which distinguishes this technology with a previously developed thermophilic
bioleach technology for chalcopyrite oxidation is that it is based on the use of air, as
opposed to oxygen-enriched air. This obviates the need for sophisticated process control
systems to regulate the dissolved-oxygen concentration in the bioleach reactors.
It has been shown that the economics of this technology is comparable with that of
concentrate production and sale.
Significant advances have been made in applying a redox control strategy to improve
chalcopyrite oxidation rates, thereby reducing the capital cost of the bioleach process and
improving the overall process economics.
This study has demonstrated that thermophilic bioleach technology is ready for commercial
implementation. In Europe, where environmental factors and clean production are strong
commercial drivers, and where sulphide deposits often have complex mineralogies and low
grades, it could well become the technology of choice. In Africa and the rest of the resourcerich developing world, where large, higher-grade resources are still to be found in abundance,
the timeline for acceptance may be longer. However, the first world is consuming most of
these resources, and it can be expected that clean production practices will in future be
dictated by the consumers and not the producers of raw materialsand then the same drivers
currently at play in places like Europe will begin to determine technology choices in the
producing countries. Bioleaching stands ready to meet this challenge.
Acknowledgements
This paper is a contribution to the research activities of the BioMinE project (BioMinE
NMP2-CT-2005-500329 Contract Number 500329), which was co-financed by the
European Commission (EC). Mintek received additional financial support for its research
activities from the South African Department of Science and Technology (DST). The authors
gratefully acknowledge the EC and the DST for their support which made this work possible,
and thank all the BioMinE partners who contributed to the joint research effort. In particular,
the contributions made by Bioclear and the University of Bangor to the microbial
identification and quantification work are noted.
References
1. MORIN, D., LIPS, A., PINCHES, T., HUISMAN, J., FRIAS, C., NORBERG, A., and
FORSSBERG, E. BioMinE Integrated project for the development of biotechnology for
metal-bearing materials in Europe. Hydrometallurgy, vol. 83, 2006. pp. 6976.
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2. MORIN, D., PINCHES, T., HUISMAN, J., FRIAS, C., NORBERG, A., and
FORSSBERG, E. Progress after three years of BioMinEResearch and Technological
Development project for a global assessment of biohydrometallurgical processes applied
to European non-ferrous metal resources. Hydrometallurgy, vol. 94, 2008. pp. 5868.
3. WATLING, H.R. The bioleaching of sulphide minerals with emphasis on copper
sulphidesA review. Hydrometallurgy, vol. 84, 2006. pp. 81108.
4. WATLING, H.R. The bioleaching of nickel-copper sulfides. Hydrometallurgy, vol. 91,
2008. pp. 7088.
5. PAVLIDES, A.G. and FISHER, K.G. The Kasese cobalt project. Extraction Metallurgy
Africa 98. Johannesburg, The South African Institute of Mining and Metallurgy, 1998.
20 pp.
6. VAN STADEN, P.J. The Mintek/Bactech copper bioleach process. ALTA Copper
Hydrometallurgy Forum. Brisbane, 1921 Oct., 1998.
7. CLARK, M.E., BATTY, J., VAN BUUREN, C.B., DEW, D.W., and EAMON, M.A.
Biotechnology in minerals processing: Technological breakthroughs creating value.
8. PINCHES, A., MYBURGH, P.J., and VAN DER MERWE, C. Process for the rapid
leaching of chalcopyrite in the absence of catalysts. US Patent 6,277,341: Appl.: 3 March
1997: Acc. 21 August 2001.
9. BATTY, J.D. and RORKE, G.V. Development and commercial demonstration of the
BioCOP thermophile process. Hydrometallurgy, vol. 83, 2006. pp. 8389.
10. ANONYMOUS. Lundin Mining Corporation Annual Report 2007. Lundin Mining
Corporation, 2008. 78 pp.
11. CARTER, A.J. Economic comparison of the alternative methods for the recovery of gold
from refractory ores. Colloquium: Bacterial Oxidation. Johannesburg, South African
Institute of Mining and Metallurgy, June 1991.
12. ANONYMOUS. Aguablanca nickel-copper feasibility report. vol. 1, Metallurgical
Design and Management (Pty) Limited.
13. ANONYMOUS. Fenix hydrometallurgical expansion preliminary assessment report.
Rev. 1, Hatch Limited, 2006. 176 pp.
14. TAYLOR, A., FAIRLEY, H., and WINBY, R. Re-opening of the Radio Hill Nickel
project, Western Australia using bacterial leaching of nickel sulphide concentrates. ALTA
1997 Nickel/Cobalt Pressure Leaching and Hydrometallurgy Forum, Perth. ALTA
Metallurgical Services, Melbourne, 1997. 34 pp.
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John William Neale

Specialist Engineer, Biotechnology Division, Mintek, South Africa
Metallurgical and biohydrometallurgical assessment of refractory
gold ores and concentrates.
Mathematical modelling and computer-based simulation of bacterialoxidation processes.
Design, construction, commissioning, and operation of 1 t/d
bacterial-oxidation pilot plant.
Project engineer for 1 t/d pilot-plant campaigns.
Mintek project engineer during commissioning and operation of 20 t/d bacterial-oxidation
demonstration plant at Vaal Reefs gold mine.
Development, optimisation, and scale-up of agitation, aeration, and heat transfer systems for
bacterial-oxidation reactors.
Development of downstream processes for solid-liquid separation, gold recovery, and ironarsenic precipitation.
Waste treatment and environmental management of bacterial-oxidation waste streams.
Feasibility studies involving commercial-scale bacterial-oxidation process design and
costing for refractory gold and base metal ores and concentrates.
Project engineer for the development of bacterial-oxidation processes for copper and
copper-nickel sulphide concentrates, including integrated flowsheets involving solid-liquid
separation, solvent extraction, electrowinning, and iron precipitation.
Heap leaching of copper-sulphide ores.
Bacterial oxidation of copper, nickel, and PGM-bearing concentrate.
Bacterial oxidation of gold-copper concentrates.
Mintek process engineer responsible for process design of the Beaconsfield and Laizhou
bacterial-oxidation plants.
Commissioning and trouble-shooting of the Beaconsfield bacterial-oxidation plant in
Tasmania, Australia.
Project leader responsible for R4-million BioPAD-funded research project.
Development of thermophilic bioleaching processes.
Deliverable coordinator in the European Commission-funded BioMinE project, responsible
for integrated piloting and techno-economic evaluation of two bioleach process flowsheets.
Co-author of numerous papers in the field of bacterial oxidation.
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SIMATE, G.S. and NDLOVU, S., and GERICKE, M. The effect of elemental sulphur and pyrite on the leaching
of nickel laterites using chemolithotrophic bacteria. Hydrometallurgy Conference 2009, The Southern African
The effect of elemental sulphur and pyrite on the

leaching of nickel laterites using
chemolithotrophic bacteria
G.S. SIMATE* and S. NDLOVU* and M. GERICKE
*School of Chemical and Metallurgical Engineering,
University of the Witwatersrand, South Africa
Biotechnology Division, Mintek, Randburg, South Africa
In this study the efficiency of using either elemental sulphur or pyrite
in the bacterial leaching of nickel laterites was investigated. Mixed
cultures of Acidithiobacillus ferrooxidans, Acidithiobacillus caldus
and Leptospirillum ferrooxidans were used. By measuring released
nickel and pH changes, it was found that elemental sulphur yielded
considerably better results than pyrite over a duration of one month.
In the initial leaching the nickel recovered in the presence of the
pyrite substrate was somewhat higher than that produced in the
presence of the sulphur substrate. It should be noted, however, that
although there was a definite observed trend for all the pHs studied,
the difference was not that very significant in terms of statistically
quantification. These observed results are attributed to the fact that
bacteria are not very active in the initial leaching stages. At this stage
of the process, abiotic oxidation of the substrates is the dominating
factor. Ferrous ions in the leach media solution abiotically oxidize to
ferric ions in the presence of oxygen. At acidic pH levels, elemental
sulphur is inert to abiotic oxidation although other species such as
thiosulphate and tetrathionate are oxidized abiotical to sulphate. Pyrite
is oxidized by ferric ions via the thiosulphate route, producing
sulphuric acid. It is thus expected that pyrite will result in slightly
higher pH drops and thus the observed slight differences in nickel
recoveries.
Keywords: nickel laterites; chemolithotrophic microorganisms;
leaching
Introduction
With an ever increasing demand for nickel and daily depletion of high grade nickel sulphide
ore reserves, research on how to process the more abundant nickel laterite ore reserves is
necessary. Nickel laterite ores have complex mineralogy, low nickel content, and are difficult
to treat by conventional methods. However, new processes such as biotechnological leaching
THE EFFECT OF ELEMENTAL SULPHUR AND PYRITE ON THE LEACHING OF NICKEL
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play an ever increasingly important role in the extraction of metals from low grade ores
(Nemati et al., 2000). These processes offer potential economic, environmental and technical
advantages over conventional methods (Nemati and Harrison, 2000; Acevedo, 2000).
Although bacterial leaching has found widespread application in the minerals industry, the
use of chemolithotrophic bacteria in recovery of nickel from lateritic ores is relatively
unexplored. The chemolithotrophs, which use sulphur and sulphide minerals such as pyrite as
their energy sources in the bioleaching, ultimately produce sulphuric acid, which is
subsequently used for the leaching of the metal values. Although nickel laterite contains metal
values, it is not capable of participating in the primary chemolithotrophic bacterial oxidation
process, probably because of the lack of the sulphidic content of the ore needed to produce the
required sulphuric acid. Previous studies have shown that the metal value in the nickel
laterites can be recovered by allowing the primary bio-oxidation of substrates such as pyrite
or elemental sulphur to provide sulphuric acid solutions, which solubilize the metal content
(Simate and Ndlovu, 2007; Simate and Ndlovu, 2008). These substrates are biogenically
oxidized by acidophilic chemolithotrophic microorganisms for their energy supply, producing
sulphuric acid (Ross, 1990), as shown in Equations [1] and [2]. The rate of recovery of nickel
laterites by bacterial leaching is, however, affected by the type of substrate used to generate
the acidic leaching reagent.
[1]
[2]
[3]
The sulphuric acid produced lowers the pH of the reaction media (Equations [1] and [2]).
The pH or hydrogen ion concentration, [H+], is an important parameter that can be utilized to
determine the extent to which nickel laterites dissolve (Equation [3]). It also determines the
diversity of the microorganisms in a colony, e.g., obligate acidophiles such as those used in
this study require low pH for growth since their membranes dissolve and cells lyse at
neutrality (Todar, 2000). The solution pH in a given bioleaching operation is determined by
the balance between the acid-producing and acid-consuming reactions. In the construction and
use of culture media, one must always consider the optimum pH for growth. Therefore, the
primary objective of this particular work was to investigate the pH requirements for the
bacterial leaching of nickel laterites using a mixed culture of chemolithotrophic
microorganisms in the presence of externally added substrates of elemental sulphur and
pyrite.
Materials and methods
Ore samples and preparation
The nickel ore was crushed and was classified into -75+63 m size fractions using standard
sieve plates. This size range was used because it was the size class in which most of the nickel
laterite material fell in terms of mass. In addition, previous studies have shown that this
particular size range gave higher nickel recoveries (Valix et al., 2001; Tang and Valix, 2006)
not only due to the large percentage of nickel in the ore but also due to the higher survival of
the microorganisms during the bioleaching process at this particular size range. The chemical
composition of nickel was determined prior to chemical leaching experiments. The typical
chemical composition of various oxides in the laterite ore used is given in Table I.
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Table I
Chemical composition of nickel laterite ore sample
Mineral
SiO2
Fe2O3
Cr2O3
Al2O3
MgO
NiO
CoO
CaO
MnO
CuO
Mass %
52.79
21.86
0.99
2.5
7.46
1.87
0.25
0.68
1.28
0.01
0.119
0.034 0.064
Microbes
A mixed culture of chemolithotrophic microorganisms (Acidithiobacillus Ferrooxidans,
Acidithiobacillus caldus and Leptospirillum Ferrooxidans) used in the experiments was
provided by Mintek, South Africa. The bacteria were cultured in standard 9K nutrient medium
(Silverman and Lundgren, 1959).
Experimentation
Bioleaching experiments were carried out in 250 ml Erlenmeyer flasks with 100 m l of slurry.
The slurry comprised a mixture of 5 g nickel laterite ore and 100 m l of medium together with
an appropriate amount of sterilized energy sources (30% w/w elemental sulphur and 56% w/w
pyrite to that of nickel laterite). These quantities of energy sources were chosen so as to have
the same sulphur content in both elemental sulphur and pyrite. The slurries were inoculated
with 10% (v/v) mixed bacterial culture. The pH of the mixtures was adjusted to 1.0, 1.5, 2.0
and 2.5, respectively. These pH ranges (i.e. pH <3) were chosen because they are known to
optimize the growth of acidophilic microorganisms (Norris and Johnson, 1998). Some
experiments were also run at initial pH of 1.5 using fresh liquid medium with an appropriate
amount of sterilized energy source but without the inoculation of bacteria for comparison with
inoculated experiments. Uninoculated distilled water and nutrient media were run as sterile at
an initial pH of 1.5.
The flasks were covered with pieces of aluminium foil to reduce evaporation and prevent
contamination, but allow free supply of air, and then incubated in a platform shaking
incubator at 30C and 190 rpm. The pH profiles and redox potentials of the leach solution
were measured but not controlled throughout the leach period using 744 pH meter Metrohm.
The redox potentials readings were obtained using the Ag/AgCl, 3M KCl reference electrode
and subsequently converted to the standard hydrogen electrode (SHE) (Friis et al., 1998).
Samples (1.5-m l ) were drawn from flasks every three days to determine the concentration of
nickel dissolved using the Varian SpectrAA-55B atomic absorption spectrophotometer.
Solution loss through sampling was compensated by the addition of distilled water or 9K
medium. The nickel recovery during the leaching of nickel laterites at any sampling time was
calculated as a percentage of nickel in the liquid phase (concentration) to that in the original
nickel laterite ore.
The bacterial population was determined by measuring turbidity or optical density of the
bacterial suspension using a UV-Visible double beam spectrophotometer (Model 4802). Since
turbidity is directly proportional to the number of cells, this property was used as an indicator
for bacterial concentration. The cells suspended in the suspension interrupt the passage of
light, allowing less light to reach the photoelectric cell, and the amount of light transmitted
through the suspension was measured as percentage transmission (or %T). The turbidity for
cell suspension was measured at 550 nm (Plumb et al., 2008) against sterile 9K media as a
reference. The wavelength of 550 nm is chosen because at this wavelength changes in both
size of the cells as well as changes in the total nucleotide concentrations are reflected
(Alupoaei and Garca-Rubio, 2004).
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Note that the relationships among absorbance (A), transmittance (T) and optical density
I
(OD) are as follows: T = I0, where I is the light passing through the sample and I0 is the light
hitting the sample. A = log10T. Optical density is a measure of absorbance and is related to
transmittance by the following expression; OD = 2 log (%T).
Other available methods based upon measurement of nitrogen or protein content or
ammonia consumption, and that of using the phase contrast microscope were less convenient
and slower than the UV-Visible double beam spectrophotometer. On the other hand, the UVVisible spectrophotometer is a versatile, quantitative, rapid, and reliable analytical tool
(Alupoaei and Garca-Rubio, 2004). It must be noted, however, that this method measures
both the dead and active bacteria as it does not differentiate between the two states. However,
the results obtained used in conjunction with pH and redox potential changes would
reasonably outweigh the disadvantages of counting the dead bacteria. Prior to reading, the
samples were filtered through Whatman filter number 1 to remove any solid particles.
Effect of substrate type on nickel recovery
In the first two weeks there were no significant differences in nickel recoveries, though
slightly higher recoveries of nickel were observed in the presence of the pyrite substrate than
sulphur substrate (Figure 1a). Initially ferrous ions in the 9K media oxidize to ferric ions
according to reaction [4] below.
[4]
The ferric ions in turn attack pyrite producing ferrous ions and sulphuric acid through the
thiosulphate mechanism (Schippers et al., 1996; Schippers and Sand, 1999). In the case of
elemental sulphur under acidic conditions, oxidation is exclusively carried out by bacteria
(Friedrich et al., 2001; Rohwerder et al., 2003; Rohwerder and Sand, 2007) although other
sulphur species such as thiosulphate and tetrathionate are oxidized abiotically to sulphate
(Schippers and Sand, 1999; Rohwerder et al., 2003). It is also expected, in the initial stages,
that the bacteria are not very active; so abiotic oxidation of the substrates is supposedly
dominant. However, higher recoveries were observed for the sulphur substrate than for the
pyrite substrate at all pH levels after two weeks of leaching (Figure 1b). This showed that
there was more acid produced by the leaching bacteria from the sulphur substrate than from
pyrite substrate after two weeks.
Effect of initial pH on nickel recovery
Figures 2 and 3 show that the dissolution of nickel laterites is largely dependent on the initial
solution pH. Although there was a general increase in the rate of nickel dissolution with time
for all pH levels, higher recoveries of nickel were observed at lower pH with about 50%
nickel being extracted within the first two weeks at initial pH level of 1.0. The higher
recoveries at lower pHs indicate the possible dominance of abiotic leaching during this
dissolution stage due to the high levels of acid in solution.
Figures 2 and 3 also show that a rise in the nickel recovery was more for the pH of 2.5 after
two weeks. This was attributed to the higher rate of acidification at this pH level (Figure 4
and 5). Previous studies have shown that higher rates of acidification imply that there were
higher microbial activities (Rossi 1990; Hanford and Vargas, 2001; Schippers and Sand,
1999). Acidification in this context means production of H+ ions. The production of H+ ions is
depicted by the pH drop, and that pH is a measure of concentration of H+ ions (i.e. pH =
-log10[H+]).
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(a)
(b)
Figure 1. Dissolution rates of nickel laterites as a function of substrate type at different pH. (a) is recoveries within
two weeks; (b) is recoveries in a month
Figure 2. Effect of pH on the leachability of nickel laterite with sulphur substrate
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Figure 3. Effect of pH on the leachability of nickel laterites with pyrite substrate
Figure 4. pH drop for sulphur and pyrite substrates within two weeks
Figure 5. pH drop for sulphur and pyrite substrates in a month
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Effect of substrate on pH drop

The pH rise for all the pH levels tested (i.e. pH 1.0, 1.5, 2.0, 2.5) was initially higher for
sulphur than for pyrite within two weeks (Figure 4). Bacteria are expected not to be very
active in the early stages of leaching. Initially, the pH rise was due to the consumption of the
added acid since there was low production of acid through either abiotic oxidation or biotic
oxidation of the substrates. However, in the case of the pyrite substrate, the abiotic oxidation
of ferrous ions in the 9K medium to ferric ions leads to the subsequent oxidation of pyrite to
produce ferrous ions and sulphuric acid. As a result there is a slight balance between the acid
consuming and producing reactions and thus the pH rise is less than that for the sulphur
substrate. In the subsequent leaching period pH drop was higher for the sulphur substrate than
for pyrite at the same initial pH, implying that there was higher rate of acidification with the
sulphur substrate as a result of bacterial activity (Figure 5). The results in Figures 4 and 5 also
show that the pH decreased rapidly at higher initial pH, 2.5>2.0>1.5>1.0. This can be
attributed to either; (1) the bacteria were naturally inactive at the low pH level or, (2) metal
toxicity due to higher metal recoveries (due to initial rapid chemical leaching) at low pH.
Furthermore, at higher pH both elemental sulphur and ferrous iron are oxidized abiotically at
significant rates (Rohwerder et al., 2003). The trend in pH changes, arising from the
substrates, was also observed during the identification of influential factors in the previous
studies (Simate and Ndlovu, 2008). The results of the differences in pH changes can also be
seen in the recoveries, being slightly higher in the presence of the pyrite substrate in the early
stages, and subsequently higher with the sulphur substrates (Figures 1).
Effect of substrate on bacterial growth
Figure 6 shows the bacterial growth curve that was taken during the leaching period. The
figure shows that bacterial concentration was higher for sulphur substrate than pyrite
throughout the leaching period. The higher microbial growth with sulphur is as result of more
energy gained from the oxidation of sulphur compared to the oxidation of ferrous ions
(Rawlings et al., 1999; Yu et al., 2001). At the solution pH of 2, the Gibbs free energy
released from the oxidation of ferrous iron is -9.49 kcal/mol, and that released from elemental
sulphur is -185.9 kcal/mol (Yu et al., 2001).
The trends in the nickel recoveries (Figure 1a) and pH drops (Figures 4) compared to
bacterial concentration in the first two weeks (Figure 6) indicate that the rate of abiotic
oxidation of pyrite was higher than the biotic oxidation of sulphur in the beginning. The
higher amount of nickel recovered in the presence of the sulphur substrate after the two weeks
tally with the peak of bacteria population as seen in Figure 6. These observations, therefore,
show that a period of more than two weeks is an effective duration for the bacterial leaching
of nickel laterites. After two weeks the high acid levels from the biotic oxidation of the
sulphur substrates result in the higher nickel recoveries in the presence of the sulphur
substrate than pyrite substrate. It seems, therefore, that the effect of bacteria on the nickel
laterite dissolution depends mostly on the relationship between the bacteria and the substrate
added to the media.
Effect of media composition on pH and oxidation reduction potential
Figures 7 and 8 show the effects of different media composition on pH and oxidation
reduction potential (ORP), respectively. It is observed in Figure 7 that for inoculated
experiments, there was a slight increase of pH initially and a subsequent decrease of pH
thereafter. This was most likely due to the predominance of abiotic oxidation process initially.
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Figure 6. Optical density at 550 nm as a function of time at pH of 1.5
Figure 7. Evolution of pH with time at initial pH of 1.5 for different media compositions
Figure 8. Evolution of ORP with time at initial pH of 1.5 for different media composition
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Even though acid production took place in the long-term through the subsequent bioxidation
of sulphur or pyrite, the initial net leaching process was likely acid consuming and hence the
initially pH rise. In summary, the overall decrease in pH observed in the inoculated media is
attributed to the oxidation of elemental or reduced sulphur to sulphuric acid by the leaching
bacteria (see Equations [1] and [2]).
In sterile controls (acidified distilled water, and sterilized media with no cells), the pH
decrease was not observed. An initial rise and final decrease in pH was observed in
experiments where uninoculated sulphur and pyrite media were used (results not shown here).
However, the pH decrease for these uninoculated media was still lower than the inoculated
media. This shows the efficacy of the presence of bacteria in the production of acid leading to
pH reduction. The pH drop observed with uninoculated pyrite media can be attributed to the
slow pyrite oxidation by oxygen in the presence of water forming ferrous iron and sulphate
(Larsson et al., 1990) according to Equation [5] below. Sulphur was assumed to be slowly
oxidized by oxygen in the presence of water according to Reaction [6] below (Hanford and
Vargas, 2001).
[5]
[6]
Figure 8 shows that higher ORPs were obtained with inoculated media than sterile media.
The metal ion recoveries are higher with inoculated media than sterile media, thus implying
higher ionic activities in the inoculated media. The ORP, which in the framework of this
study, is a measure of the activities or strength of metal ions in relation to their concentration,
is thus higher in the inoculated media.
Conclusions
This study investigated the bacterial leaching of nickel laterites using a mixed culture of
chemolithotrophic microorganisms in the presence of externally added sulphur containing
material (elemental sulphur and pyrite). The bacterial oxidation of sulphur and pyrite
produces sulphuric acid, which dissolves nickel laterite to yield the required nickel metal.
The results presented showed that the dissolution rates of nickel laterite were high in low pH
media and high ORP, and in the presence of bacteria. However, the study showed that
microbial activities, depicted by acidification, were lower at lower initial pH levels. Although
uninoculated media with energy sources appeared to induce acidification, this was less than
that in active bacterial cultures. This shows that under similar conditions, an inoculated media
is more effective than an uninoculated media.
This study has also shown the relationships between bacterial activities, depicted by
acidification and the type of substrate. The recoveries were slightly higher for pyrite in the
early stages of leaching and subsequently significantly higher for sulphur at all the initial pH
levels studied. The test results and the high nickel recovery yield demonstrated that sulphur
was more effective as a substrate than pyrite. It seems, therefore, that the effect of bacteria on
the dissolution of minerals that are not capable of taking part in the primary chemolithotrophic
bacterial oxidation process depends mostly on the relationship between the bacteria and the
substrate energy source added to the media.
Previous studies have shown that mixed cultures tend to be superior to those containing only
iron- or sulphur oxidizing bacteria. However, little is known about how microorganisms
interacted in this study, and how such interactions may have benefited or detracted the mineral
dissolution process. It is, therefore, recommended that further studies should detect and
differentiate the various species used during the bioleaching experiments.
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Overall, this study has opened up a new era for the potential application of
chemolithotrophic microorganisms for the commercial processing of the difficult-to-process
low grade nickel laterite ores. In regions where the nickel laterite orebody exists the
sustainability of the process will depend on the supply of sulphur-containing material
(commercial sulphur or metal sulphide) for energy requirements of the bacteria. This is likely
to form the dominant operating cost component of the bacterial leaching of nickel laterite ores
using chemolithotrophic microorganisms. In addition, this process is promising because
sulphuric acid is produced in situ whereas in processes such as high pressure acid leaching,
sulphuric acid is produced in external facilities. With the addition of sulphur-containing
material, the use of chemolithotrophic bacteria can be extended to the leaching of other low
grade non-sulphide containing ores. Some examples where this process may be applied
include silicate ores, oxidic converter furnace slags and refractory oxides.
Acknowledgements
The authors wish to thank The Council of Mineral Technology (Mintek), South Africa for the
supply of the nickel laterite sample and microorganisms used in the study. Financial support
to Geoffrey S. Simate by Mintek, and by the NRF South Africa through THRIP and the
African Scholarships Flagship programmes is also gratefully acknowledged. The work is part
of the MSc (Eng) dissertation submitted by Geoffrey S. Simate in 2008 to the University of
the Witwatersrand, Johannesburg.
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SCHIPPERS, A. and SAND, W. Bacterial leaching of metal sulphides proceeds by two
indirect mechanism via thiosulphate or via polysulphides and sulphur. Applied and
Environmental Microbiology, vol. 65, 1999. pp. 319321.
SILVERMAN, M.P. and LUNDGREN, D.G. Studies on the chemoautotrophic iron bacterium
Ferrobacillus ferrooxidans: I. An improved medium and a harvesting procedure for
securing high cell yields. Journal of Bacteriology, vol. 77, no. 5, 1959. pp. 642647.
SIMATE, G.S. and NDLOVU, S. Characterisation of factors in the bacterial leaching of nickel
laterites using statistical design of experiments. Advanced Materials Research 2021,
2007. pp. 6669.
SIMATE, G.S. and NDLOVU, S. Bacterial leaching of nickel laterites using
chemolithotrophic microorganisms: Identifying influential factors using statistical design
of experiments. International Journal of Mineral Processing, vol. 88, 2008. pp. 3136.
VALIX, M., TANG, J.Y., and CHEUNG, W.H. The effects of mineralogy on the biological
leaching of nickel laterite ores. Minerals Engineering, vol. 14, no. 12, 2001.
pp. 16291635.
TANG, J.A. and VALIX, M. Leaching of low grade limonite and nontronite ore by fungi
metabolic acids. Minerals Engineering, vol. 19, 2006. pp. 12741279.
TODAR, K. Physical and Environmental Requirements for Microbial Growth. Website:
http://lecturer.ukdw.ac.id/dhira/NutritionGrowth/physicalandenv.html. Accessed
September 2008. 2000.
YU, J.-Y., MCGENITY, T.J., and COLEMAN, M.L. Solution chemistry during the lag phase
and exponential phase of pyrite oxidation by Thiobacillus ferrooxidans. Chemical
Geology, vol. 175, 2001. pp. 307317.
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Geoffrey S. Simate
Masters Student, University of Witwatersrand, South Africa
Three years experience in metallurgical operations for Zambias major
mining conglomerate (Zambia Consolidated Copper Mines Ltd).
Worked for one year with Konkola Copper Mines Plc after
privatisation of Zambia Consolidated Copper Mines Ltd. Worked for
one year with Anglovaal Mining Zambia Ltd Research Laboratory as a
Process Engineer. Worked for four years with Chambishi Metals Plc as
a Process Controller. Worked for one year with Maamba Collieries Ltd
as a Plants Manager with the responsibility for ensuring efficient, safe and cost effective
operations of the entire metallurgical operations. In my career I have been involved with
plant commissioning, trouble shooting, pilot plant tests, plant efficiency tests and have
provided technical expertise to the plant processes in order to achieve maximum efficiency.
Have experience with leaching, solvent extraction, ion exchange, thickening, and
electrowinning commercial plant operations. Fully qualified Quality Assurance Internal
Auditor (BSI and RT&A). Scheduled to graduate with an MSc (Eng) in Metallurgy and
Materials Engineering from the University of Witwatersrand in May, 2009.
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VAN NIEKERK, J. Recent advances in BIOX technology. Hydrometallurgy Conference 2009, The Southern
African Institute of Mining and Metallurgy, 2009.
Recent advances in BIOX technology

J. VAN NIEKERK
Gold Fields Ltd, South Africa
The past number of years has seen a sharp rise in the gold price. This
has led to renewed activity in the gold sector and especially in
refractory orebodies that are not economically feasible at lower gold
prices.
There have, historically, been a total of eleven BIOX plants
commissioned worldwide, with eight currently in operation. The most
recent plants to be commissioned were Bogoso and Jinfeng in 2007
and Kokpatas in Uzbekistan in 2008.
Design of the Bogoso BIOX plant was started by Minproc in 2005.
The design throughput of the sulphide BIOX circuit is 820 tpd
concentrate at a feed sulphide sulphur grade of 20%. The Bogoso
BIOX plant has the largest biooxidation reactors with a live capacity
of 1 500 m3 each.
Plant design on the Jinfeng project started in 2005 and the
engineering was performed jointly by Ausenco and Nerin. The
BIOX plant has a design capacity of 790 tpd concentrate at 9.4%
sulphide sulphur.
The Kokpatas plant will be the largest BIOX plant in the world
with a phase 1 design concentrate treatment capacity of 1 069 tpd at
20% sulphide sulphur. The throughput will be doubled during
phase 2. Interestingly, unlike other BIOX plants, this plant will use a
resin-in-pulp circuit for gold recovery, but the design will allow the
plant to be converted to carbon-in-pulp if required.
The future growth of the technology is certainly also very good,
with two new projects currently in the engineering phase, the
Amantaytau project in Uzbekistan and the Mayskoye project in
Russia.
There are a number of major R&D projects currently under
investigation with some very positive results. Most R&D is focused
on the main capital and operating cost items in the process, but there
are also projects focused purely on process optimization and
improvement.
Introduction
The BIOX process for the pretreatment of refractory gold concentrates has been in
commercial operation for the last 20 years. It has grown from a small-scale start at the
Fairview Gold Mine to a mature, worldwide recognized technology with a total installed
concentrate treatment capacity of 4 507 tons per day of concentrate. At current production
rates a total of 1.5 million ounces of gold will be produced in 2009 using the BIOX process.
RECENT ADVANCES IN BIOX TECHNOLOGY
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Growth of the technology

The BIOX technology started off as a 10 ton per day pilot plant operating in parallel with old
Edwards roasters at the Fairview plant in South Africa. The process proved to be robust and
the capacity of the BIOX section was increased in 1991 to treat the full 35 tpd concentrate.
The capacity of the plant was again increased in 1994 and 1999 to the current design capacity
of 62 tpd.
The second BIOX plant was the Sao Bento plant in Brazil in 1990. The first BIOX
licence was sold in 1991 for the application of the technology at the Harbour Lights project in
Western Australia. This was quickly followed by Wiluna in 1993 and Ashanti in 1994/1995.
Ashanti was a major breakthrough for the technology, confirming the ability of the process to
be scaled up to any throughput rate using the modular design. Ashanti also proved the
robustness of the technology and the suitability of the technology to remote locations.
A total of eleven BIOX plants was commissioned over the last 20 years with five new
plants commissioned in the last three years. Table I gives a summary of the current and
historical BIOX plants and the concentrate treatment capacities.
Figure 1 shows the installed concentrate treatment capacity, in ton per day concentrate, for
all the BIOX plants worldwide. After commercialization of the technology in 1991 the
installed concentrate treatment capacity increased quickly with the commissioning of the five
plants in quick succession. However, with the drop in the gold price in the middle 1990s,
there was a marked slowdown in the interest in the BIOX technology with only one low
capacity plant commissioned between 1995 and 2005.
Interest in the technology started to increase again from ~ 2003 with the increase in the gold
price. This led to the commissioning of five new BIOX plants between 2005 and 2008.
During 2009 there will be a total of eight BIOX plants in operation with a combined
installed concentrate treatment capacity of 4 500 tpd. The total estimated gold production
from BIOX operations for 2009 will be over 1.5 million ounces (> 47 tons of gold).
Table I
A summary of the commercial BIOX operations
Mine
Fairview
Sa Bentob
Harbour Lightsc
Wiluna
Ashanti
Coricanchad
Fosterville
Suzdal
Bogoso
Jinfeng
Kokpatas
Country
Concentrate treatment
capacity (tpd)
Reactor size
(m)
Date of
commissioning
Current
status
S.Africa
Brazil
Australia
Australia
Ghana
Peru
Australia
Kazakhstan
Ghana
China
Uzbekistan
62
150
40
158
960
60
211
196
820
790
1069
340a
550
160
480
900
262
900
650
1 500
1 000
900
1986
1990
1991
1993
1994
1998
2005
2005
2007
2007
2008
Operating
C&Me
Decommissioned
Operating
Operating
C&Me
Operating
Operating
Operating
Operating
Operating
aThe
volume of the two primary reactors at Fairview

Mine is under care and maintenance
cMining operations were completed and 1994 and the plant decommissioned
dOperations were temporarily stopped in 2008
eCare and maintenance
bThe
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Figure 1. Installed BIOX concentrate treatment capacity
There are also currently four projects under engineering and construction, two expansions to
existing facilities and two new projects that will increase the installed BIOX treatment
capacity to over 6 500 tons per day concentrate by 2012. The capacity can potentially
continue to grow to over 8 500 tons per day concentrate by 2015 based on projects currently
in the various stages of testwork and development.
Detailed description of the new BIOX plants
This section will give a brief introduction to the three new BIOX plants, Bogoso, Jinfeng
and Kokpatas.
The Bogoso BIOX plant
The Bogoso Gold Mine, owned by Golden Star Resources, is located in south-west Ghana
approximately 200 km west of the capital city Accra. The first set of batch amenability tests
on Bogoso concentrate was performed at Gencor Process Research in 1996. The results from
the initial batch tests were very encouraging and continuous BIOX pilot-plant testwork was
performed in 1998 at SGSLakefield Research Africa on two bulk concentrate samples from
the Bogoso deposit.
The Bogoso BIOX plant has a design capacity of 820 tons per day of concentrate at a
sulphide sulphur grade of 20%. The BIOX plant consists of two modules, each module
consisting of seven BIOX reactors, followed by the CCD washing circuit, solution
neutralisation and the carbon-in-leach circuit for gold recovery. Construction of the Bogoso
Sulphide Expansion Project (BSEP) began on 13 June 2005 with GRD Minproc awarded the
contract for the design and construction of the plant. The inoculum build-up and
commissioning of the BIOX plant started late in 2006 and was completed mid 2007 with the
production of the first BIOX treated gold.
The BIOX technology achieved a new milestone at Bogoso with the successful
commissioning of the largest BIOX reactors. The plant also uses a closed circuit evaporative
cooling system. Although the capital cost of this option is higher than the conventional open
circuit system, it is expected that the operating cost (including maintenance) will be lower for
the closed circuit due to better control of the water quality flowing through the cooling coils.
Inoculum build-up at Bogoso was expedited by receiving 24 m3 of active inoculum from
AngloGold Ashantis Sansu BIOX plant, enabling the inoculum build-up process to start
directly in a 100 m3 reactor.
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The Jinfeng BIOX Plant

The Jinfeng gold deposit, owned by Sino Gold Limited, is located in the Guizhou Province,
approximately 240 km south-west of the provincial capital Guiyang, in the Peoples Republic
of China.
Batch BIOX testwork on Jinfeng concentrate samples started in 2002 at SGS Lakefield
Research Africa. The concentrate samples proved to be amenable to biooxidation pretreatment, achieving high sulphide oxidation and gold recovery results. The batch testwork
was followed up by a continuous BIOX pilot-plant test programme in 2003.
The first process design package was delivered to Sino Gold Limited in 2003 following the
successful completion of a BIOX licence agreement for the use of the BIOX technology for
the Jinfeng deposit. The plant was designed to treat up to 790 tons per day of concentrate at a
sulphide sulphur grade of 9.37% in two BIOX modules, each module comprising eight
1 000 m3 reactors. The retention time across the BIOX reactors is four days at the design
feed rate. The biooxidation section is followed by a standard CCD washing circuit, solution
neutralization and a carbon-in-leach circuit for gold recovery.
The Jinfeng Bankable Feasibility Study was completed in March 2004 and construction of
the plant began in February 2005. Inoculum build-up started in April 2006 with the first gold
poured in March 2007.
Jinfeng is currently one of the largest gold mines in China. Optimization of the Jinfeng mine
is ongoing to increase gold production to optimal levels. Jinfeng mine is also faced with major
logistical challenges, especially during the wet season with an average rainfall of 1.2 m
annually, accompanied by landslides and wind storms.
Currently the Jinfeng project is consistently achieving operational performance at or above
design parameters. The Jinfeng BIOX plant is performing exceptionally well with sulphide
sulphur oxidation well above design as well as BIOX/CIL gold recovery above design
parameters.
The Kokpatas BIOX plant
The Kokpatas Mine is located in the Kyzylkum desert, 32 km north-east of the town of
Uchkuduk in Central Uzbekistan. The deposit is owned and operated by the Navoi Mining
and Metallurgical Combinat, the largest gold producer in Uzbekistan. Ore will be supplied
from various open pits, including the Daugystau deposit some 140 km from Kokpatas.
Laboratory test work conducted by GENCOR Process Research (GPR), on samples from the
Daugystau and Kokpatas pits, indicated that the sulphide ore is amenable to upgrading by
sulphide flotation. Pretreatment of the flotation concentrate by the BIOX Process liberated
the gold sufficiently to improve gold dissolution during cyanidation to over 90%.
Pilot-scale flotation and BIOX test work conducted in South Africa in 1994 confirmed the
positive results of the laboratory test work and provided sufficient data for the design of a full
scale sulphide treatment plant. In 1997, similar test work was performed at GPRs facilities in
South Africa on a 15 ton ROM ore sample from the Kokpatas sulphide deposit, and excellent
results were achieved.
Following the conclusion of a licence agreement between NMMC and Biomin Technologies
S.A. for the supply of the BIOX technology, a BIOX plant was designed to treat flotation
concentrate from the Kokpatas deposit during phase 1 of the project. The design concentrate
treatment capacity of phase 1 of the project is 1 069 tpd. During phase 2 the plant capacity
will be increased to 2 137 tpd to incorporate flotation concentrate from the Daugystau deposit.
This is made possible by the modular design of the biooxidation section of the BIOX plant.
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The phase 1 BIOX plant consists of four modules. Each module has three primary reactors
and three secondary reactors. The counter current decantation thickeners (CCDs) were sized
to accommodate the Phase 2 capacity of the plant. During Phase 2, four additional BIOX
modules will be added and the neutralization plant capacity increased. The supply capacity of
cooling water and air will also be increased accordingly.
The detailed design of the phase 1 BIOX section was performed by Institute OzGeotexliti
in Uzbekistan with equipment fabrication, construction and the electrical installation
performed by local contractors. Civil works on the BIOX reactor foundations for phase 1
started during July 2005. Commissioning of phase 1 began mid-2008 and is expected to be
completed early 2009 after the delivery of the final equipment.
New BIOX projects under development
There are currently four BIOX projects in various stages of design or construction. Two of
these are expansions to existing BIOX plants while the other two are new BIOX projects.
The Suzdal BIOX plant in Kazakhstan is expanding the capacity of the treatment plant
from 196 tpd concentrate to over 520 tpd concentrate. This will be achieved by duplicating the
existing BIOX circuit and adding additional cooling and blower air capacity. The solids
concentration in the feed will also be increased slightly to ensure that sufficient residence time
is maintained in the BIOX reactors. A new CCD circuit will be constructed and the number
of neutralization reactors will be increased to cater for the higher concentrate throughput.
The Kokpatas plant in Uzbekistan has started with the planning for phase 2 of the project, to
double the treatment capacity of the plant to 2 163 tpd concentrate. This will be achieved by
duplicating the phase 1 BIOX circuit. The CCD circuit was sized for phase 2 during phase 1
while additional neutralization reactors will be added. The blower and cooling tower capacity
will also be increased as required to cater for the increased aeration and heat loads.
The Amantaytau project is also located in central Uzbekistan near the town of Zarafshan.
The project will also be implemented in two phases. The phase 1 BIOX plant will have a
design capacity of 376 tpd concentrate, increasing to 564 tpd in phase 2. The sulphide sulphur
grade in the concentrate can be as high as 36% due to the high in situ ore sulphide grades.
The Mayskoye project is located in the Chukotka region in Russia. The BIOX plant will
have a design capacity of 350 tpd concentrate. The extreme climatic conditions in this region
will pose a number of engineering challenges, starting with a relatively short shipping window
in the summer months. The ambient temperature also only exceeds freezing point for two
months of the year.
BIOX at sub-zero temperatures
The Suzdal BIOX plant is located near the town of Semey in Kazakhstan. The BIOX plant
has a design capacity of 196 tpd concentrate at a sulphide sulphur grade of 12%. The BIOX
section consists of 6 x 650 m reactors, configured in the standard three primary and three
secondary reactor configuration.
The extreme climatic conditions experienced at Suzdal made the design of the plant very
interesting. The design had to take hot, humid conditions during summer into consideration
and ensure that the cooling towers can deliver the required duty under these conditions.
The bigger problem, however, was to design for the winter conditions when the
temperatures could go as low as45C, without taking any wind chill into consideration. For
this reason the bulk of the plant is located inside a building with only the BIOX reactors and
the cooling towers outside the building. The walkways on top of the BIOX reactors were
covered to protect the operators from the extreme conditions when taking samples.
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The BIOX process is exothermic and extensive modelling was performed to ensure that
sufficient heat is produced by the process to maintain the temperatures in the BIOX reactors
even at the coldest conditions. The modelling indicated that the BIOX reactors would still
have to be cooled even at the coldest conditions. Significant planning also went into planning
for power failures and unplanned stoppages to ensure that the reactors do not freeze if
standing for too long.
The Suzdal BIOX plant has now operated through three winters and has performed very
well. So far no problems were experienced with maintaining the temperature in the primary
reactors even at reduced sulphur feed rates in the first year than initially anticipated. Suzdal
has certainly proven that BIOX is not only a viable technology to consider for sub-zero
temperature applications, but that it holds certain advantages over other processes. The
advantage lies in the modular design of the plant and the number of reactor stages. Even if
one or more of the reactors is off-line the rest of the process plant does not have to be stopped
and can continue to operate as normal. For other refractory processes, if the treatment process
is stopped for any length of time, the rest of the processing plant must also stop, a situation
that can be catastrophic at sub-zero conditions.
The performance of the Suzdal BIOX plant has certainly proven beyond a doubt that the
BIOX technology can be used successfully at sub-zero conditions.
Research and development
The BIOX process has been commercially in operation for nearly 20 years. Throughout this
period Gold Fields has maintained a strong focus on research to improve the efficiency of the
process and the design of the commercial reactors. Maintaining an active research and
development program is critical to ensure the long-term viability of the technology. For this
reason Gold Fields has developed a strategic research and development programme to address
the main capital and operating cost items in the BIOX process. The programme is being
implemented in stages, focusing on the highest priority items first.
Figure 2 shows a breakdown of the capital cost for a typical BIOX plant. The graph
indicates that the stainless steel for the BIOX and neutralization reactors will make up
approximately 35% of the installed equipment cost, followed by the agitators at
approximately 27% and the blowers at 13%.
The operating cost breakdown for four operating BIOX plants is shown in Figure 3 and the
reagent cost breakdown in Figure 4. It can be seen that between 40% and 50% of the opex
cost is for power and between 30% and 45% for reagents.
The reagent cost breakdown for the same four plants is shown in Figure 4. It can be seen the
bulk of the cost is for pH control, accounting for ~ 70% of the reagent cost, but can vary from
as low as 40% to as high as 85% depending on the relative reagent cost and consumption
rates. This includes both BIOX pH control and neutralization of the acid solution.
Nutrient cost is usually fairly low at less than 20% and can be as low as 4% after a dedicated
nutrient optimization programme is completed. The exception is plant B where the nutrient
cost is exceptionally high, but this is a factor of low neutralization cost and the fact that the
plant was fairly recently commissioned and must still undergo nutrient optimization. The
remainder of the reagents is usually less than 10% of the overall reagent cost.
The cost for cyanide leaching of the BIOX product is not included in the operating cost
given above. Analyses of the CIL operating cost for the same four BIOX plants indicate that
reagents make up between 70% and 90% of the operating cost, with cyanide accounting for
65% of the reagent cost.
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Figure 2. Breakdown of the installed equipment cost for a BIOX plant
Figure 3. Operating cost breakdown for four BIOX plants
Figure 4. Reagent cost breakdown for four BIOX plants
Four research and development areas were identified based on the capital and operating cost
structures described above:
Development of an improved agitation system
BIOX process optimization, focused on BIOX retention time reduction and reagent
cost savings
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Evaluation of alternative materials of construction

Cyanidation optimization.
A number of projects were identified based on these main R&D areas and are progressively
being implemented. The main projects currently underway are described in more detail below.
Development of an improved agitation system
Axial flow impeller technology in biooxidation reactors is conventionally based on the
concept of down pumping. The impeller circulates the slurry in a downward motion with the
objective of increasing the gas retention time in the reactor. Alternative agitation systems are
being developed in an effort to reduce the overall power input required for aeration and air
dispersion. One of the options under investigation is the use of an up-pumping axial flow
impeller in biooxidation reactors.
An extensive laboratory-scale test programme was conducted where a range of different
impeller combinations was tested in a 500 l reactor using the Lightnin A310, A315 and A340
impellers. Different combinations of these impellers were compared with each other and the
A315 was used as a bench mark with the main objective to reduce the power per unit volume
and reducing the air demand while still maintaining high levels of oxygen mass transfer.
The configuration that performed the best in the laboratory test programme was scaled up to
a 20 m3 test reactor at Fairview BIOX plant. The selected configuration was tested under the
same conditions as in the laboratory determining the power numbers, oxygen mass transfer
and power per unit volume, using the A315 as a benchmark. The final stage was to test the
impeller under BIOX conditions by operating the test reactor as a primary BIOX reactor.
The Fairview BIOX plant personnel have been a tower of strength in making this test work
possible. Results to date are looking very promising in achieving the main objectives.
BIOX process optimization
There are a number of factors that determines the rate of sulphide oxidation. These include
both BIOX operating parameters and concentrate characteristics. The BIOX process has
been in operation for 20 years and the operating conditions are well defined. However, we
have seen from results of the operating BIOX plants that the BIOX bacteria are capable of
handling conditions outside the standard operating parameters. It was decided to start a
project to investigate the effect of changing certain operating conditions or concentrate
characteristics on the performance of the process. The objectives of the programme were to
reduce the BIOX retention time, and thereby capital cost and to reduce the reagent
consumption rates.
Due to the number of potential parameters to investigate, a structured programme was set
up. The initial set of tests focused on the effect of following parameters:
BIOX feed density variation
Effect of fine grinding of the concentrate
Effect of BIOX liquor removal to control the ferric iron concentration in the primary
reactors and
Effect of pH in the final biooxidation stages.
The test work was performed in a 120 l continuous pilot plant located at the Fairview
BIOX plant. The pilot plant was operated for a total of 6 months using a bulk Fairview
concentrate sample collected over a seven-day period as feed. Batch amenability tests were
also performed on the concentrate samples using similar conditions as in the pilot plant. In
future the test programme will be expanded to include other parameters.
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Materials of construction
Stainless steel for the BIOX reactors is one of the main capital cost items for any new
BIOX plant. For this reason Gold Fields is continually evaluating the performance of various
and potentially cheaper stainless steel grades under BIOX conditions. Various coatings for
mild steel are also tested as a coated mild steel reactor may have cost benefits, provided the
coating can withstand the operating conditions in a BIOX reactor. The testwork includes
both anaerobic conditions, typically found in the CCD thickeners, as well as aerobic
conditions found in the BIOX reactors.
Three sets of test racks were prepared and installed at the Fosterville BIOX plant in
Australia. Test samples from a number of steel grades were included in the racks, including
304, 316, 317, 2205 and LDX2101. A number of mild steel samples, coated with different
coatings were also installed. Samples will be removed after 6, 12 and 24 months for
evaluation. Fosterville was selected as the test site due to the relatively high chloride content
of the water, averaging approximately 600 ppm.
Combination mesophile and thermophile biooxidation process
Test work has shown that the use of high temperature or thermophillic micro-organisms can
allow almost complete oxidation of all the intermediate sulphur species, thereby significantly
reducing thiocyanate formation during the cyanidation of the biooxidation product. This will
result in significantly lower cyanide consumption during leaching with potentially no loss in
gold recovery. The use of thermophillic micro-organisms does, however, come at a price.
Increased capital costthe micro-organisms (thermo-acidophillic archaea) operate in a
temperature range of 6580C, and this increases the corrosive nature of the acidic bioleaching slurry. Standard austenitic stainless steel grades cannot be used for this
application and more exotic materials of construction such as duplex stainless steels or
acid lined concrete tanks are required for the manufacturing of the reactors. The process
operates at reduced solids concentrations, but this is traded off with faster reaction
kinetics.
Increased operating costthe equilibrium solubility of oxygen in water is very low at
these high temperatures and oxygen enrichment of the air introduced into the slurry is
required to achieve the required mass transfer rates in the reactors. Water consumption is
also increased due to increased evaporation rates at the higher operating temperatures,
and oxygen enrichment may be required to reduce the volume of air flowing through the
reactors.
A combination mesophile and thermophile process was proposed to make the best use of the
advantages of the different microbial strains. In this process the mesophilic BIOX bacteria
are used for the primary oxidation stage to achieve approximately 70% sulphide oxidation.
This is then followed by a thermophile oxidation stage to complete the oxidation, targeting the
intermediate sulphur species. A number of batch and continuous test work programmes using
this process were completed over the last five years.
A large-scale thermophile pilot-plant test work program was completed at the Fairview
BIOX plant to test the process under conditions expected to be encountered during full-scale
operation and to generate data for the design of a commercial scale thermophile plant at
Fairview. This included using daily overflow samples from the primary reactors at Fairview as
feed to the thermophile plant. The pilot plant was operated for 6 months testing various
parameters to optimize the process. Daily oxidation values were monitored as well as
subsequent gold recovery and cyanide consumption during leaching of the oxidized product.
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The results from the test programme were very encouraging, indicating that a very short
retention time is required in the thermophile stage to maintain bacterial activity and achieve
the required sulphide oxidation. The plant was able to operate at higher solids concentrations
than initially expected, and it was found that no solution removal stage is required between
the BIOX and thermophile stages. Sulphide oxidations similar or better than the BIOX
plant were maintained and similar gold recoveries were achieved at substantially lower
cyanide consumption rates.
Conclusions
The BIOX technology has been commercially in operation for more than 20 years. The
technology has proven itself to be robust and ideally suited for remote locations. The recent
interest in the technology, as evidenced by the number of BIOX projects recently
commissioned or in development, confirms that the technology offers significant advantages
over other refractory processes.
The combined installed treatment capacity of the eight operating BIOX plants across the
world is currently 4 500 tpd with an expected 1.5 million ounces of gold to be produced using
the BIOX technology in 2009.
Recent operating experience at the Suzdal plant has confirmed the applicability of the
BIOX technology to projects located in cold climates. BIOX again offers certain
advantages over other treatment processes, including high plant availabilities and the ability to
operate continuously even with a number of reactors offline.
Gold Fields also manages a structured research and development programme to ensure
continuous development of the technology. The programme is focused on the main capital and
operating cost items, namely power for aeration and agitation, BIOX retention time and
cyanide consumption.
Jan van Niekerk

Senior Consultant: Metallurgy (Refractory Gold),
Gold Fields Ltd, South Afirca
Jan van Niekerk started his career in 1995 at Gencor Process Research.
He spent the early part of his career on various BIOX projects,
including a number of BIOX continuous pilot plant tests. He spent a
short period of time at Beatrix Gold Mine to gain operational
experience until the forming of Gold Fields Ltd from the gold assets of
Gencor and Gold Fields of South Africa. He then returned to the BIOX department at Gold
Fieldss corporate office.
There he was still involved in testwork, but also started to get involved in the design of
BIOX plants and giving assistance to operating plants. He was involved in the
commissioning of the Tamboraque plant in Peru and was the BIOX representative for the
testing, design and commissioning of the Fosterville BIOX plant in Australia. In 2006 he
was promoted to the head of the BIOX department within Gold Fields overlooking all
aspects of managing thetechnology.
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VAN DEVENTER, R., KELLER, W., OOSTHUIZEN, M., and STAPELBERG, J. Systematic characterization
of the mixing process for the BIOX reactor. Hydrometallurgy Conference 2009, The Southern African Institute
of Mining and Metallurgy, 2009.
Systematic characterization of the mixing process

for the BIOX reactor
R. VAN DEVENTER*, W. KELLER, M. OOSTHUIZEN, and
J. STAPELBERG
*Gold Fields Mining Services, Johannesburg, South Africa,
Ekato RMT GmbH, Schopfheim, Germany, Ekato Corporation, Oakland, NJ USA,
Ekato Africa, Johannesburg, South Africa
The BIOX process was developed for the biological pre-treatment of

refractory gold ores and concentrates ahead of conventional cyanide leach
gold recovery. Rights to the process are currently with BIOMIN Technologies
SA, a subsidiary of Gold Fields Limited. There are currently eight operating
installations worldwide employing the process on a commercial scale.
EKATO is a company specializing in developing new or optimizing existing
mixing applications. EKATO has acquired a vast amount of expertise in
agitation over its 75 year history.
In a joint research project the reactors of the BIOX process were
characterized from the aspect of their mixing performance. BIOMIN is
constantly testing new mixing solutions and reviewing potential vendors to
increase the efficiency of the BIOX process. EKATOs intention was to
qualify as an approved vendor for supplying agitation equipment to the
BIOX process. A two step approach was planned: In phase one of the
project EKATO would develop an alternative agitation solution to the
established option, exhibiting at least similar performance levels. In phase
two potential possibilities to improve the overall design would be developed.
This paper focuses on phase one and addresses the systematic approach
applied by EKATO in characterizing the mixing processes. Mixing tasks were
assessed individually applying basic theory and scale-up and -down rules to
the individual tasks. Testing with model systems was done at the EKATO
technology center in Schopfheim, Germany, on scales of 50 liters and 1 m.
The results showed that the ISOJET-B impeller design showed promising
performance under BIOX reactor conditions. Scale-up with the ISOJET-B
was done in order to apply it in the 21 m live volume test reactor at Fairview
mine in South Africa. At Fairview tests were performed using model systems
and eventually under real plant conditions with BIOX slurries. The results
were a success and confirmed that the scale-up factors determined during the
testing at EKATOs technology center could be substantiated in the model
scale 25 m reactor. Testing under the actual process conditions showed that
all design parameters were within the desired range to be considered an
excellent leaching performance.
This successful joint development shows the importance of a close
cooperation of technology licensors or end-users and equipment suppliers. It
is vital for understanding all factors influencing the mixing performance of
processes. Exercises such as this will provide equipment suppliers and plant
operators more confidence in managing further scale ups at ever larger
engineered plants.
SYSTEMATIC CHARACTERIZATION OF THE MIXING PROCESS FOR THE BIOX REACTOR
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Introduction
The BIOX process was developed for the biological pretreatment of refractory gold ores and
concentrates ahead of conventional cyanide leach gold recovery. Rights to the process are
currently with BIOMIN Technologies SA, a subsidiary of Gold Fields Limited. There are
currently eight operating installations worldwide employing the process on a commercial
scale. EKATO is a company specializing in developing new or optimizing existing mixing
applications. EKATO has acquired a vast amount of expertise in agitation over its 75 year
history.
In a joint research project the reactors of the BIOX process were characterized from the
aspect of their mixing performance. BIOMIN is constantly testing new mixing solutions and
reviewing potential vendors to increase the efficiency of the BIOX process. EKATOs
intention was to qualify as an approved vendor for supplying agitation equipment to the
BIOX process. A two-step approach was planned: in phase one of the project EKATO would
develop an alternative agitation solution to the established option, exhibiting at least similar
performance levels. In phase two potential possibilities to improve the overall reactor design
would be developed.
This paper focuses on phase one and addresses the systematic approach applied by EKATO
in characterizing the mixing processes.
The BIOX process
The BIOX plant typically consists of six equidimensional reactors configured as three
primary reactors operating in parallel followed by three secondary reactors operating in series.
The feed concentrate from the stock tank is diluted to 20% solids by mass before being fed to
the primary BIOX reactors. The operating slurry solids content is determined primarily by
the sulfide content of the concentrate feed and the rate of oxygen transfer necessary to
maintain the required rate of oxidation. The slurry solids content is also determined by the
amount of toxic elements present in the slurry fed to the BIOX reactors.
The pulp residence time in the bio-oxidation reactors is typically four to six days depending
on the oxidation rates achieved, which is a function of the sulphide/sulphur content and
mineralogical composition of the concentrate. Generally, half of the retention time is spent in
the primary reactors to allow a stable bacterial population to be established and to prevent
bacterial washout. Once a stable bacterial population has been established, a shorter retention
time can be tolerated in the secondary reactors where sulphide sulphur oxidation is completed.
Nutrients in the form of nitrogen, phosphorous and potassium salts are also added to the
primary reactors to promote bacterial growth. The mixed culture of mesophilic bacteria used
in the BIOX process can operate at temperatures ranging from 30C to 45C. The pulp
temperature in commercial reactors is controlled between 40C and 45C. This temperature
allows maximum sulphide oxidation rates to be achieved while minimizing cooling
requirements. The oxidation of sulphide minerals is an exothermic process and the reactors
must be cooled continuously by circulating cold water through a series of cooling coils
installed inside the reactors.
Low-pressure air is injected into the BIOX reactors to supply oxygen for the oxidation
reactions. It is extremely important that a dissolved oxygen concentration of > 2 ppm be
maintained at all times in the slurry. Axial flow fluid foil impellers are used in the BIOX
reactors they offer improved efficiency over radial-flow turbines. Figure 1 shows the typical
BIOX process flowsheet.
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Concentrate from flotation/regrind
Stock tank
Water
Nutrients
Nutrient
make-up
tank
Feed splitter
Blower
Secondary BIOX reactors
Cooling
tower
CCD Thickeners
Primary BIOX reactors

Wash water
To leach
Neutralization
To tails
Figure 1. Typical BIOX process flowsheet
Objectives and developments

A systematic approach was applied by EKATO in characterizing the mixing processes.
Mixing tasks were assessed individually applying basic theory and scale-up and -down rules
to the individual tasks. Testing with model systems was done at the EKATO technology centre
in Schopfheim, Germany, on scales of 50 litres and 1 000 litres. Different types of impellers
which were an option for the applied process conditions were tested and their performance
compared. The results showed that the ISOJET-B impeller (Figure 2) design yielded the best
performance at BIOX reactor conditions. Scale-up with the ISOJET-B was done in order to
apply it in the 21 m live volume test reactor at Fairview mine in South Africa. At Fairview
tests were performed using model systems and eventually under real plant conditions with
BIOX slurries.
Mixing: characterization of the BIOX process
The basic mixing tasks encountered in practice can be classified into four main categories:
Blending
- mixing miscible liquids; eliminating differences in concentration, temperature, etc.
Suspension
- uniform distribution of solids
- off-bottom suspension of solids
Dispersion gas/liquid and liquid/liquid
- mass transfer between the gas/liquid phases and liquid/liquid phases
- stable emulsions
Heat transfer
Every mixing task is governed by natural laws, which must be known for the scientific
design of the agitator. Complex mixing tasks involve two or more of these mixing tasks
simultaneously. In these cases, special attention must be given to the dominant mixing
category. (Figure 3.)
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Figure 2. The EKATO ISOJET-B impeller
Figure 3. Basic mixing tasks
For the continuous BIOX process all of these mixing tasks have to be fulfilled.
Homogeneous process conditions, i.e. of oxygen, pH, temperature, nutrients, are very
important to be able to establish and keep a stable bacterial population. All of these
parameters are related to blending. High pumping rates and therefore short mixing times will
ensure a high degree of homogeneity.
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Since ore slurries are processed solids, these have to be suspended. A high degree of
homogeneity for all particle sizes has to be achieved to prevent an accumulation of particles
with time. The physical properties of the treated solids and the pure liquid have to be taken
into account when designing the agitator. These properties will affect the hindered settling
velocity of the particles which release a settling power. In order to maintain a defined degree
of uniformity the agitator must provide a power input to the liquid to counteract this settling
power.
Air has to be dispersed so that enough surface is created between the air and the slurry. This
will ensure that enough oxygen is transferred to the bacteria. The specific power input by
agitation is one of the main parameters to ensure high mass transfer rates. Therefore it is
necessary to have sufficient knowledge of the power number Ne of an impeller at gassed
conditions. With gas being added to an impeller the friction between the impeller and the fluid
will be reduced, so that the ungassed power number Ne0 is greatly diminished, as shown in
Figure 4. The amount of gas being added to an impeller is described by the dimensionless
gassing number Q,
where q is the gas feed rate, n the shaft speed and d2 the impeller diameter.
Besides the air dispersion duty of the impeller it has to be confirmed that the impeller will
not flood, meaning running completely in a gas cavity.
The oxidation of sulphide minerals is an exothermic process and the reactors must be cooled
continuously, meaning heat transfer is of importance as well. Cooling is done by circulating
cold water through a series of cooling coils installed inside the reactors.
Using the experience of an agitator manufacturer, the required power inputs to solve the
separate mixing tasks can be evaluated. Calculations showed that the gas/liquid dispersion
duty requires the highest level of power input and therefore is the dominant mixing task.
Figure 4. Reduced power input due to gassing
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Test work
EKATO laboratory
As described earlier, the gas dispersion duty is the main mixing task and therefore the decisive
design parameter. Therefore tests were mainly focused on the gas dispersion duty. Since the
power input is of utmost importance, power number measurements have been done for
different impeller types and gassing conditions.
Measurements at the EKATO laboratory were carried out at two different test scales, 50
litres (Figure 5) and 1 000 litres. Air was, as in the production scale the BIOX reactors,
added via a sparge ring located below the impeller. Tests were run at different gas feed rates
and shaft speeds and the torque measured. From the torque measurements the power number
could be derived. Figure 6 shows the comparison of two impeller types for BIOX conditions.
Figure 5. Test set-up 50 litres
Figure 6. Bioleachingpower input due to gassing
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As can be seen, the power did not drop at the very low Q numbers as described before but
increased. Two curves for different impeller types are given. This increase of the power
number is a known characteristic of impellers at very low gassing rates, although so far no
explanation can be found in literature. Anyhow, this increase in power number has to be
known and considered to properly design the agitator. By choosing the appropriate test
conditions in the 50 litre and 1000 litre scale a wide set of dimensionless data was obtained.
This enables the design of the agitator for a required gassed power input for any production
scale and therefore to fulfil the mass transfer mixing task.
To compare different impeller types regarding their suspending performance, model
particles were added to the test vessel while measuring the gassed power numbers. This
allowed EKATO to compare different impeller types easily. Not surprisingly when tested, the
radial flow types of impellers showed a poor solids suspension performance. Although these
types of impellers in general are able to handle more gas than axial flow types, this
disqualifies them for the BIOX process. The EKATO ISOJET-B impeller showed the best
suspending performance at gassed conditions.
To compare the mass transfer performance of the different tested impeller types, a model
reaction was applied at the 50 l scale. At comparable test conditions, i.e. the agitator power
input, all impeller set-ups showed more or less the same mass transfer capability.
All tests at the EKATO lab so far were carried out using model systems. To get additional
information how the different impeller types perform in original slurry, a 50 l BIOX sample
was shipped from the Fairview mine site to EKATO. Slurry samples were taken from the
vessel bottom and liquid surface and the particle concentrations compared. The ISOJET-B
showed a very homogeneous distribution of the solids over the filling height; no differences in
solids contents were measurable. The main advantage of the ISOJET-B was its fast
resuspending capability for complete settled out conditions (after 16 h), see Figure 7.
Figure 7. Testing with original slurryrestart after 16 h
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Fairview test reactor

After the successful tests with the ISOJET-B at the EKATO technology centre a test reactor of
21 m live volume was installed at the Fairview BIOX plant in South Africa. The test reactor
is shown in Figure 8. A scale-up for the ISOJET-B was done using the data derived from
model testing. An impeller with a diameter of 1 250 mm was machined and sent to the mine
site. Again model tests were performed before finally testing the impeller at real BIOX
conditions.
First the power number was measured for different gassing rates in water. Test results from
the EKATO laboratory could be confirmed. After these tests mass transfer measurements were
carried out to be able to predict the mass transfer performance for bigger production reactors.
After these tests with model liquids, the ISOJET-B was tested at real plant conditions. Ore
slurry was added from the production plant and the same data derived/analysed as for the
production-scale reactors.
Mass transfer/chemical resultscontinuous testing over several weeks was carried out.
Achieved oxidation rates and process specific parameters such as pH, dissolved oxygen,
Fe2+ to Fe3+ conversion values, OUR etc., were measured during a daily routine sampling
procedure. All measured data were within specifications and constant. The average
amount of oxidized sulphur was higher than achieved in the adjacent production plant.
Solids suspensionTwo litre slurry samples were taken at four sample nozzles at
different filling heights. Solids homogeneity over the filling height was excellent. No
difference in solids concentration from vessel bottom to filling level was observed.
Extensive water testing and continuous slurry testing was performed at lab and pilot scale.
Based on the favorable results generated from these test, the EKATO ISOJET-B impeller was
classified as suitable impeller to be used in commercial BIOX installations. Additional
Figure 8. Fairview test reactor 21 m
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information on the mixing characteristics in this specific process could be derived and helped
to even better understand the process. Design values were confirmed by testing, and will be
applied to design the production scale reactors for upcoming projects. General design
parameters were agreed upon between BIOMIN and EKATO.
This successful joint development shows the importance of close cooperation between
technology licensors or end-users and equipment suppliers. It is vital for understanding all the
factors influencing the mixing performance of processes. Exercises such as this will provide
equipment suppliers and plant operators more with confidence in managing further scale-ups
at ever larger engineered plants.
Wolfgang Keller
Senior Process Engineer, EKATO RMT GmbH, Schopfheim, Germany
Education:
MSc Process Engineering University of Karlsruhe, Germany.
Professional Memberships: VDI
Current position:
Senior Process Engineer working for EKATO Mixing Technology
since 9 years.
Previous affiliations:
Assistant production manager and research and development at LONZA, Germany.
Experience:
polymer plant operation
engineering / construction
process development
R&D mixing technology
EKATO expert for minerals processing.
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DREISINGER, D. Keynote address: Hydrometallurgical process development for complex ores and
concentrates. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and Metallurgy,
2009.
Keynote address: Hydrometallurgical process

development for complex ores and concentrates
D. DREISINGER
University of British Columbia, Department of Materials Engineering, Canada
Hydrometallurgical processing of complex ores and concentrates is

becoming increasingly important as the mining and metallurgical
industry seeks to exploit mineral deposits that are difficult to treat
using conventional mineral processing and pyrometallurgical
technologies. Mineral processing is often challenged by the difficulty
or inability to separate valuable minerals into marketable
concentrates. Hydrometallurgical processing, using selective leaching
technology, can often chemically beneficiate such difficult deposits.
Pyrometallurgical treatment of base metal concentrates is capital
intensive and subject to ever more stringent environmental control.
Hydrometallurgical processing is generally lower in capital cost for an
equivalent metal production rate and avoids the gas and dust issues
associated with pyrometallurgical processing. The possibility of byproduct recovery may also increase with hydrometallurgical
treatment. Two examples of new technology or flowsheet
development for treatment of complex ores and concentrates are used
as illustration. These include the El Boleo process of Baja Mining for
recovery of copper, cobalt, zinc and manganese from a complex
clayey ore and the PLATSOL process for recovery of copper,
nickel, cobalt, platinum, palladium and gold from a bulk sulphide
concentrate.
Introduction
The treatment of base and precious metal deposits has as a final goal the recovery of final
metal products of sufficient purity and in a suitable commercial form to meet customer
specifications. Historically for metals like copper, nickel, zinc and lead recovery from
sulphide deposits, processing has included mining, flotation of concentrates and finally
smelting/refining of the concentrates through to final products (generally high purity metals).
However, a number of factors are causing a gradual but steady shift away from the traditional
processing routes. Mineral processing technologies may be constrained in the processing of
complex ores (fine grained) or ores that contain multiple valuable metals. Hydrometallurgical
leaching technology may actually benefit from the fine grained character of the raw material
and offers the possibility of recovery of multiple metals from a single feed source. Similarly,
pyrometallurgical processing of sulphide concentrates is becoming increasingly expensive,
KEYNOTE ADDRESS: HYDROMETALLURGICAL PROCESS DEVELOPMENT
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environmental constraints due to emission of gases and production of dusts are increasing and
pyrometallurgical processing often results in the losses of valuable metal byproducts into
slags and residues. Hydrometallurgical technologies have lower unit capital costs, avoid
production of gaseous or dust emissions, and can manage recovery of multiple metals from a
single feed source. In this way, hydrometallurgical processing is growing in importance to the
global metal industry as shown in Figure 1.
The success of hydrometallurgy as a technological field lies in the ability to extract valuable
metals into solution, purify the metal containing solutions to concentrate valuable metals and
reject impurities, and finally to recover a pure metal product by electrolysis, metal
precipitation or other means. Advances in hydrometallurgy are rooted in improvements in the
science and technology of leaching, solid-liquid separation, solution purification (solvent
extraction, ion exchange, cementation) and metal recovery.
The following sections illustrate two new process developments that highlight the potential
of hydrometallurgical treatment to solve difficult metallurgy and extract base and precious
metals into marketable form.
The Boleo process1 is applied to the recovery of copper, cobalt, zinc and manganese from a
mixed sulphide/oxide deposit hosted in clay. The keys to process development for Boleo were
to incorporate novel seawater based leaching, high rate thickening for solid/liquid separation,
the CSIRO DSX technology2 for cobalt and zinc recovery away from manganese, and finally
the use of manganese precipitation for recovery of a manganese carbonate by-product.
The PLATSOL process 3 was developed to process mixed base and precious metal
sulphide concentrates containing copper, nickel, cobalt, platinum, palladium, gold and silver
where the grade and nature of the concentrates produced by flotation were not amenable to
toll smelting. The PLATSOL process uses chloride assisted total pressure oxidation of bulk
sulphide concentrates to extract base and precious metals into an autoclave solution. The
ability to directly extract precious metals as chloro-complexes is the key to the PLATSOL
process development.
The Boleo process
The Boleo Copper-Cobalt-Zinc-Manganese Project of Baja Mining Corp. is situated adjacent
to Santa Rosalia on the Baja Peninsula of Mexico (Figure 2). The Boleo deposit has a large
geological resource with 277 million tonnes @1.77% Cu. Eq grade of measured and indicated
and 253 million tonnes @ 1.29% Cu Eq. grade of inferred material (www.bajamining.com).
Figure 1. Growing importance of hydrometallurgy
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Figure 2. The Boleo mine site close to Santa Rosalia, Baja California
The ore will be treated by a hydrometallurgical process involving acidseawater leaching

with recovery of copper and cobalt metal cathode, zinc sulphate crystal and eventually
manganese carbonate precipitate.
Process development of the metallurgical flowsheet for Boleo has gone through bench and
integrated pilot-plant testing.
An initial proof of principle pilot plant was executed at SGS Lakefield Research in Canada
in November 2004. The major focus of the proof of principle pilot plant was to confirm that
the clayey Boleo mineralization could be thickened and washed in a conventional CCD train
using high rate thickeners and that the CSIRO DSX solvent extraction system could be used
to recover cobalt and zinc. The DSX system involves mixing LIX 63 with Versatic 10
extractant to improve selectivity for (Co+Zn)/Mn.
Since the initial proof of principle pilot plant in 2004, further work has been undertaken
with CSIRO (Australia) to optimize the DSX solvent extractant composition and to add a
manganese recovery process to the Boleo flowsheet. The simple addition of sodium carbonate
(soda ash) to the DSX raffinate was found to precipitate a manganese carbonate product of
high purity. This manganese carbonate material may form a feedstock to the production of
manganese chemicals, manganese metal or electrolytic manganese dioxide.
The improved metallurgical flowsheet for Boleo has now been evaluated in a fully
integrated demonstration pilot plant at SGS Lakefield Research in Canada.
Metallurgical treatment of Boleo ore
After a quick review of the major elements of the process, the focus will be on the
demonstration pilot plant results. Figures 35 show the overall flowsheet in simplified format.
Milling and leaching circuit
The Boleo ores are clayey and generally fine grained and easily broken. The milling circuit
design takes material from the ROM pad into a static grizzly with the oversize to a primary
crusher. The combined product is then scrubbed in copper solvent extraction raffinate. The
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Figure 3. Flowsheet for Boleo processPart 1: feed preparation, leach, CCD, copper SX/EW, iron removal,
acid/power plant
scrubber product is screened with the oversize sent to a secondary crusher. The combined
product goes to the ball mill sump before cycloning. The coarse cyclone product is directed to
the ball mill. Milling is conducted in raffinate. (Figure 3.)
The milled product is heated to a target temperature of 80C for atmospheric leaching.
Leaching proceeds in two steps: acid, oxidative leaching with manganese dioxide oxidation
for leaching of Cu, Zn and Co sulphides and: acid reductive leaching with addition of sulphur
dioxide gas to reduce residual manganese dioxides. The reductive leaching of surplus
manganese dioxide is essential for maximizing the extraction of cobalt.
Oxidation leaching (acid leaching with manganese dioxide in the ore)
Cu2S + 2MnO2 + 4H2SO4 = 2CuSO4 + 2MnSO4 + S + 4H2O
ZnS + MnO2 + 2H2SO4 = ZnSO4 + MnSO4 + S + 2H2O
CoS + MnO2 + 2H2SO4 = CoSO4 + MnSO4 + S + 2H2O
Reduction leaching (addition of sulphur dioxide to the ore slurry)
MnO2 + SO2 = MnSO4
The slurry from oxidation and reduction leaching is then partially neutralized using local
limestone that is available on the Boleo mine lease. The purity of the limestone is about
6570% and it is highly reactive for acid neutralization. A small amount of air is added during
partial neutralization to ensure that there is no residual cuprous ion (that may form if reductive
leaching goes to too low a redox value) in solution. Cuprous ion is not extracted by
conventional oxime solvent extraction reagents.
Solid-liquid separation and CCD washing
The first proof of principle pilot plant confirmed that the Boleo leach pulp could be thickened
and washed using high rate thickening. High rate thickening involves the dilution of the
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incoming slurry (by recycle of overflow from the same thickener) so as to create a dilute
slurry (35% solids) for flocculation and settling into the thickener bed. This approach was
verified by testing performed by Pocock Industrial and by Outokumpu in lab and pilot-scale
testing at SGSLakefield. The wash solution to be used at Boleo consists of a combination of
barren solution (after cobalt, zinc and manganese removal) and fresh brine solution.
The recovery of copper from complex chloride containing solutions is feasible using modern
selective copper solvent extractants combined with a wash stage during SX recovery of
copper to prevent transfer of chloride from leaching through to electrowinning. This approach
has been widely reported at plants in Chile with saline PLS solutions and has been adopted for
Boleo as well. High levels of copper extraction are expected due to the low free acid level in
solution (after partial neutralization) and the use of a strong oxime formulation. (Figure 4.)
Copper extraction
CuSO4 + 2HR(org) = CuR2(org) + H2SO4
Copper stripping
CuR2(org) + H2SO4 = CuSO4 + 2HR(org)
CuSO4 + H2O = Cu + O2(gas) + H2SO4
Figure 4. Flowsheet for Boleo process Part 2: cobalt and zinc SX using DSX, zinc sulphate evaporation, manganese
carbonate precipitation and limestone milling
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Copper is electrowon conventionally using permanent cathode blank technology. LME

Grade A cathode quality was produced in the proof of principle pilot plant and is also
expected to be produced in the commercial plant.
The copper solvent extraction raffinate contains free acid (from copper solvent extraction)
and so it is advantageous to return a portion of the raffinate to the milling and leaching circuit,
to reduce overall use of fresh acid and to concentrate Co, Zn and Mn in solution. The balance
of the raffinate is directed to the Co, Zn, Mn recovery circuit.
Iron removal
The removal of iron from the raffinate advancing to Co, Zn, Mn recovery is accomplished
with pH adjustment and aeration. The bulk of the iron in solution will be present as ferrous.
Ferrous is oxidized and precipitated as ferric hydroxide precipitates. Aluminum will coprecipitate with iron in this step.
Two stages of iron removal were allowed in the pilot plant design. The first stage is used to
precipitate more than 95% of the iron with the second stage precipitation reducing iron to less
than 10 ppm residual. The second stage precipitate is returned to oxidative leaching to ensure
that any co-precipitated pay-metals are recovered. The first stage cake is filtered, washed
and then repulped and sent to tailings. The iron removal solution is then advanced to cobalt
and zinc solvent extraction.
Cobalt and zinc solvent extraction
CSIRO (Australia) has developed a range of synergistic extractants, tailored to specific metal
separations. In the case of Boleo, the major challenge is the extraction of cobalt and zinc
without extraction of manganese. The particular synergistic system selected for Boleo is the
Versatic 10 LIX 63 mixture. Cobalt is loaded in preference to zinc, which in turn is loaded
in preference to manganese with this system.
Figure 5. Flowsheet for Boleo process Part 3: zinc and cobalt solvent extraction and cobalt electrowinning
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The cobalt and zinc circuit is designed for bulk extraction and bulk stripping of zinc and
cobalt. Some of the zinc strip solution is also employed as a manganese scrub solution makeup. Zinc and cobalt loading must be done with pH control. The most convenient alkali for this
duty is sodium carbonate. Bulk stripping of zinc and cobalt is performed using sulphuric acid
and pH control.
Cobalt and zinc solvent extraction (with small amount of Mn co-extraction)
CoSO4 + 2HR(org) + Na2CO3 = CoR2(org) + Na2SO4 + CO2(g) + H2O
ZnSO4 + 2HR(org) + Na2CO3 = ZnR2(org) + Na2SO4 + CO2(g) + H2O
MnSO4 + 2HR(org) + Na2CO3 = MnR2(org) + Na2SO4 + CO2(g) + H2O
Manganese scrubbing
MnR2(org) + ZnSO4 = ZnR2(org) + MnSO4
Zinc and cobalt stripping
ZnR2(org) + H2SO4 = ZnSO4 + 2HR(org)
CoR2(org) + H2SO4 = CoSO4 + 2HR(org)
The fully stripped organic is then recycled back to loading. The DSX raffinate advances to
manganese recovery.
Cadmium control
Cadmium is a minor impurity in the Boleo ore and must be removed from both the zinc/cobalt
strip solution prior to zinc sulphate extraction and crystallization and cobalt solvent extraction
and electrowinning. The method chosen for cadmium control is zinc dust cementation. Zinc
dust is widely used for cadmium control in conventional roast-leach-electrowin (RLE) plants
for zinc recovery from concentrates.
In this application, it is important to cement only cadmium and not cobalt. This can be
accomplished using lower temperature and not activating the cementation. Activation with
Cu/As or Cu/Sb is the method used in the removal of cobalt by cementation in conventional
RLE plants.
Cadmium cementation
CdSO4 + Zn = Cd + ZnSO4
Cobalt metal electrowinning
The zinc/cobalt (bulk) strip solution from DSX will be treated sequentially by zinc solvent
extraction and stripping and then cobalt solvent extraction, stripping and electrowinning. The
zinc and cobalt solvent extraction circuits will both use Cyanex 272 extractant. The zinc
sulphate strip solution will be sent to zinc sulphate crystallization. The cobalt strip solution is
purified and electrowon.
There is provision in the cobalt electrolysis circuit for ion exchange polishing of minor
elements prior to sulphate electrolysis. The cobalt cathode deposit is harvested, crushed and
marketed.
Zinc extraction (Cyanex 272)
ZnSO4 + 2HR(org) + Na2CO3 = ZnR2(org) + Na2SO4 + CO2(g) + H2O
Zinc stripping
ZnR2(org) + H2SO4 = ZnSO4 + 2HR(org)
Cobalt extraction (Cyanex 272)
CoSO4 + 2HR(org) + Na2CO3 = CoR2(org) + Na2SO4 + CO2(g) + H2O
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Cobalt stripping
CoR2(org) + H2SO4 = CoSO4 + 2HR(org)
Cobalt electrowinning
CoSO4 + H2O = Co + O2(gas) + H2SO4
Zinc sulphate crystallization
The recovery of zinc as a metal product by electrolysis is technically challenging and
probably not cost-effective at a low production rate (notwithstanding the current prices of zinc
metal). Hence, the zinc product selected for the Boleo process is zinc sulphate crystals. Zinc
sulphate is used in a variety of agricultural formulations (fertilizers and feeds).
Zinc sulphate crystallization
ZnSO4 (aqueous) + H2O = ZnSO4.H2O (crystals)
Manganese carbonate recovery
The raffinate from the DSX circuit has been subjected to iron/aluminum removal and the use
of DSX to recover cobalt and zinc. The DSX is also effective at removing other heavy metals
from solution. The remaining cations in solution are largely manganese, magnesium, calcium
and sodium. The manganese rich nature of the Boleo ore provides a perfect opportunity for
recovery of a manganese by-product from this solution.
The simplest and most cost-effective method to precipitate manganese from solution
involves addition of sub-stoichiometric amounts of sodium carbonate to the DSX raffinate.
The reason for sub-stoichiometric addition is to prevent co-precipitation of impurities such as
calcium and magnesium and various minor elements.
Manganese precipitation
MnSO4 + Na2CO3 = MnCO3 + Na2SO4
Manganese carbonate is not hydrated and hence is lower in weight (relative to hydroxide
precipitates) for shipping off site. Initial proof-of-principle testing indicated that the
precipitate graded 4648% Mn after washing and drying of free moisture.
Demonstration pilot-plant results
Feed preparation
The blended feed material was sampled during each milling campaign. The average assay was
2.18% Cu, 0.135% Co, 0.49% Zn, 5.01% Mn, 8.26% Fe, 1.08% Ca, 2.85% Mg, 5.18% Al,
0.014% Ni and 19.7% Si. The average particle size for the milled feed was 80% passing 38
microns. The feed rate to leaching was set at 14 kg/h. Over the 16 day pilot plant,
approximately 5 tonnes of Boleo feed material were processed.
Leaching, partial neutralization and counter-current decantation
The leaching conditions were varied during the 16-day pilot run. Specifically the pH in
oxidative leaching was varied from around 1.2 to 1.7. The extractions of Cu, Co, Zn were
generally increased when the pH was lowered. However, the addition of acid to maintain a
low pH leach environment can be excessive. The partial neutralization was performed with
Boleo limestone addition. This worked well and produced a pH 2 product slurry to CCD. The
CCD itself generally performed very well. The use of high rate thickeners with overflow
recycle for dilution of the feed to ~ 3% solids worked well. The solids settled rapidly,
producing a well clarified, low-solids overflow as feed to copper SX. (Table I.)
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Table I
Summary of metal extraction and reagent addition as a function of leach pH
Oxid Leach pH
Red. Leach ORP

(mV vs Ag/AgCl)
H2SO4
(kg/t)
SO2
(kg/t)
Limestone
(kg/t)
Cu
Co
399
397
399
427
225
235
315
513
80
73
124
152
68
75
113
368
90.9
90.9
92.7
94.4
82.6
81.4
83.8
90.3
53.9
55.4
61.0
72.3
97.1
96.4
98.0
96.7
Ni
Sn
Ag
<1
<1
<1
<1
<1
<1
<25
<25
<25
<15
17.4
<15
1.7
1.5
1.4
1.2
Extraction (%)
Zn
Mn
Table II
Analysis of three copper cathode samples
Sample
Cathode 1
Cathode 2
Cathode 3
Se
Te
Bi
Sb
Pb
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1.2
<1
Analysis (g/t)
As
Fe
<1
<1
<1
2.4
1.4
1.3

The CCD overflow solution advanced to a conventional solvent extraction and electrowinning
circuit utilizing 2E 1Sc 2S configuration. An organic solution of 20% LIX 664N (Cognis)
in ORFOM SX80 CT (Chevron Phillips) was used for copper recovery. Copper was
electrolysed on stainless steel blanks at ~ 250 A/m2 current density.
The copper concentration in the feed to copper SX was typically between 2 000 and
3 000 mg/l (23 g/l) with raffinates ranging between 10 and 50 mg/l. This represents 9599%
copper extraction through most of the pilot-plant run. The raffinate was largely recycled to
leach during the pilot plant allowing for secondary recovery of a significant portion of the
copper remaining in the first raffinate.
A total of 47.4 kg of copper was plated in 4 cycles during the pilot plant at a current
efficiency of 97%. Table II shows the assays for three cathode samples from the pilot plant.
With the exception of Cathode 2 with a slightly high level of sulphur in cathode, the copper
quality was excellent. It is expected that copper produced commercially at Boleo would
exceed requirements for LME Grade A or COMEX Grade 1 cathode. The cathode product
was smooth, except for slight nodulation at the edges.
Iron and aluminum removal
The iron and aluminum removal circuit operated successfully, typically producing less than
10 mg/l of residual iron in the feed to the DSX circuit. The circuit was started as a two-stage
circuit but after commissioning was changed to one-stage as the second stage circuit was
deemed to be superfluous. For the purpose of the pilot plant, supplemental oxidation with
hydrogen peroxide addition was required to ensure complete iron oxidation and removal. The
iron precipitate thickened well but demonstrated variable filterability, depending on the
operating temperature of the circuit (T > 45C produced a more easily filtered product).
Cobalt and zinc recovery using the DSX circuit
Cobalt and zinc were recovered using the CSIRO DSX system. The extractant used was
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13.2% LIX 63 and 6.25% Versatic 10 in Orfom SX80CT. The DSX circuit consisted of 3
extract stages (pH ~ 4.5), 2 scrub stages (with zinc sulphate solution), 2 zinc strip stages at pH
3.2 and 2 bulk strip stages at pH 1. The results were excellent with > 99% recovery of both
cobalt and zinc with near perfect rejection of manganese. Selective stripping was trialed in the
i.e. too much cobalt was stripped in the zinc selective strip. A single bulk strip to zinc
and cobalt recovery circuits has been selected for the commercial plant.
Zinc solvent extraction
The zinc solvent extraction circuit used 30% Cyanex 272 in Orfom SX 80CT. The circuit
consisted of 4 extraction stages at pH 2.62.9, 2 scrub stages (using zinc strip solution) and
2 strip stages at pH 1. The zinc concentration in the raffinate was controlled to around
100 mg/l Zn. The zinc strip solution was gradually increased to nearly 80 g/l (80 000 mg/l Zn).
The cobalt concentration of the zinc strip solution was less than 20 mg/l Co (Zn:Co ratio of 4
000:1), confirming an excellent separation of zinc and cobalt.
Cobalt solvent extraction and electrowinning
The raffinate from zinc solvent extraction was processed via cobalt solvent extraction and
electrowinning. Cobalt was extracted in 4 stages at pH 5.2 to 5.5 using 30% Cyanex 272 in
Orfom SX 80CT followed by 2 stages of scrubbing, 3 stages of stripping (with spent
electrolyte) and 1 stage of conditioning before organic recycle. The cobalt strip solution was
polished by using DOWEX M4195 and PUROLITE S-950 resins for minor element capture
prior to cobalt electrowinning in a divided cell. Cobalt was deposited at 250 A/m2 at 70C.
The residual zinc entering the cobalt circuit is extracted and stripped in the conditioning
step. The conditioning solution is recycled back to zinc solvent extraction, permitting
recovery of this zinc.
The average feed solution concentration was about 6 000 mg/l of Co with raffinates of less
than 1 mg/l indicating nearly 100% cobalt recovery in this process. The cobalt strip solutions
rose to nearly 90 g/l (again due to optimization) allowing effective cobalt electrolysis.
Table III shows the analysis of two cobalt samples from the production. The cobalt is of
very high purity with respect to key elements. There may be opportunity to further reduce the
lead levels in cathode by strontium carbonate treatment of Co EW cell feed. Similarly, even
lower levels of Cd in cathode may be achieved by more efficient Cd cementation ahead of the
zinc and cobalt solvent extraction circuits.
Manganese carbonate precipitation
The DSX raffinate was treated with sodium carbonate solution to selectively precipitate
manganese carbonate as a potential by-product from the Boleo process. The manganese
Table III
Analysis of two cobalt cathode samples
Sample
Cathode 1
Cathode 2
196
Analysis (ppm)
Cd
Cu
Fe
Mn
Ni
Pb
Zn
66
43
<2
<2
<4
<4
<0.3
<0.3
55
56
40
41
<10
<10
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carbonate formed as a fine pinkish precipitate that settled, filtered and washed very well. The
typical composition of the manganese carbonate is shown below. Nearly 200 kg of wet
MnCO3 was recovered. (Table IV.)
The Boleo project of Baja Mining Corp continues to move forward to production. The
process selected for Boleo involves oxidative and reductive leaching of the milled ore,
conventional countercurrent decantation (CCD) washing of the leached ore in high rate
thickeners, copper solvent extraction and electrowinning, cobalt and zinc solvent extraction
and recovery as zinc sulphate crystals and cobalt metal and finally manganese carbonate
production as a by-product.
The demonstration pilot plant for the Boleo project was built and operated at SGS Lakefield
Research in Canada in June and July of 2006. A total of about 5 tonnes of blended feed were
processed. The optimized extraction of metals yielded 91% Cu, 82% Co, 55% Zn and 97%
Mn extraction. These values represent the overall extraction after oxidation and reduction
leaching, partial neutralization and CCD 6 washing. The oxidation leach condition was set at
pH 1.5 to 1.7 to control the addition of acid. The leach residue was effectively settled and
washed in a 6 stage countercurrent decantation circuit using highrate thickener design.
Copper was very efficiently recovered by SX/EW and electrowon as smooth, high purity
copper cathode. A portion of the copper raffinate was treated to remove iron and aluminum by
oxidation and pH adjustment followed by DSX recovery of cobalt and zinc. The CSIRO DSX
system performed extremely well with >99% recovery of cobalt and zinc from the DSX feed
with nearly complete manganese rejection. Zinc was recovered as high purity zinc sulphate
solution and cobalt was recovered as cathode metal of high purity. Finally, manganese
carbonate grading up to 47% Mn was recovered by precipitation with sodium carbonate.
The Platsol process
PolyMet Mining Corp. (PolyMet) is advancing the development of the NorthMet Project. The
NorthMet deposit is located in northern Minnesota, adjacent to the historic Iron Range. The
deposit was discovered in the 1960s and consists of a large, magmatic, disseminated sulphide,
polymetallic deposit with values in Cu, Ni, Co, Zn, Au, Ag and platinum group metals
(PGM). The shallow, tabular orebody may be mined by open-pit methods with minimal prestrip and a low waste:ore strip ratio.
The NorthMet deposit is large with measured and indicated resources of 638.2 million
tonnes and an inferred mineral resource of a further 251.6 million tonnes. Within this
resource, there is a proven and probably reserve of 274.7 million tonnes and the operating
plan is to mine 224 million tonnes of this reserve over the 20 year life of the operation
(32 000 tpd).
A definitive feasibility study (DFS) has been completed by Bateman Engineering (Australia)
in 2006. The project is currently in the environmental permitting phase of the project.
The heart of the processing strategy revolves around the acquisition of the Erie Plant from
Table IV
Typical analyses of MnCO3 precipitate
Analysis (%)
Analysis (g/t)
Species
Mn
Ca
Mg
Na
Al
CO3
SO4
Ni
Zn
Fe
Cu
Co
Cd
Cl
Precipitate
47
0.3
0.6
0.5
45
350
300
200
<5
50
<5
100
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Cleveland Cliffs. The Erie plant acquisition allows for PolyMet to proceed with a
brownfields processing strategy with an existing 100 000 tpd crushing and grinding plant
and associated infrastructure (roads, power, railway, water supply) including waste disposal.
The Erie plant was built in the 1950s for approximately $355 million USD and operated until
2001 processing taconite ore. The acquisition of this plant and related infrastructure has
provided most of the heavy equipment needed for production. Initial plans are to use
approximately one-third of the existing plant capacity.
Figure 6 below shows the NorthMet site in northern Minnesota, adjacent to the Mesabi Iron
Range. Figure 7 provides an overview of the Erie plant site with the tailings area in the
background. Figure 8 shows the (existing) indoor view of the Erie plant milling circuit with
parallel rod and ball mill lines.
Figure 6. Location of the NorthMet property in northern Minnesota
Figure 7. The Erie plant site
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Figure 8. The Erie plant milling circuit with parallel rod and ball mill lines
The current development strategy for NorthMet is to produce a saleable concentrate product
upon plant start-up and then move to implementation of a hydrometallurgical process plant for
recovery of the valuable metals. The PLATSOL process has been selected.
The DFS programme has included several pilot-scale test programmes at SGS Lakefield
Research Limited in Ontario, Canada. Pilot-plant tests have been performed on ore flotation to
produce bulk concentrate samples and on hydrometallurgical treatment of the bulk concentrate
materials. The base case flowsheet involves high temperature chloride-assisted leaching
(PLATSOL), solid-liquid separation and washing, PGM/Au precipitation, neutralization
and Cu SX/EW to produce copper cathode. A portion of the Cu SX raffinate is treated for
nickel and cobalt recovery (the remainder is recycled to the autoclave) sequentially by
neutralization, first and second stage iron/aluminum removal, residual copper removal by
precipitation as a sulphide, first stage Ni/Co/Zn precipitation with magnesia, second stage
Ni/Co/Zn precipitation with lime, and then magnesium removal with lime. The product from
this treatment is a mixed hydroxide of nickel, cobalt and zinc.
NorthMet process flowsheet and pilot-plant studies
The overall NorthMet process flowsheet involves two distinct circuits: a classical mineral
processing flowsheet to produce a bulk concentrate and a hydrometallurgy flowsheet for
extracting Cu-Ni-Co-Zn-Au-PGM from the bulk concentrate. The further separation of the
bulk concentrate into copper and nickel concentrates for sale is a further refinement of the
basic flowsheet. The hydrometallurgy flowsheet involves chloride-assisted leaching of base
and precious metals followed by a series of metal recovery steps for the base and precious
metals.
Figures 9, 10 show the process flowsheets in pictorial form. Figure 9 is the mineral
processing flowsheet (to produce a bulk concentrate) with Figure 10 showing the
hydrometallurgy circuit.The pilot-scale tests for the DFS at SGS-Lakefield were performed in
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Figure 9. NorthMet process flowsheet: crushing, grinding and flotation of a bulk Cu-Ni-Co-Zn-Au-PGM concentrate
Figure 10. NorthMet process flowsheet: hydrometallurgical treatment of bulk Cu-Ni-Co-Zn-Au-PGM concentrate
with production of copper cathode, Au/PGM precipitate and mixed Ni/Co hydroxide
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2005 and 2006. The ore samples sent to SGS-Lakefield comprised four composites and a
sample of assay reject material that was used as start-up material for the flotation pilot plant.
The ore samples were processed through crushing, grinding and flotation to produce a series
of bulk concentrates for hydrometallurgical pilot-plant testing. Table V below summarizes the
pilot plant feed assays and weights processed.
The following is a general description of each part of the proposed plant along with selected
results from the 2005 and 2006 continuous pilot testing of the process at SGS Lakefield. The
pilot-scale tests at SGS Lakefield form the test work basis for the final feasibility study design
for the NorthMet plant.
Crushing, grinding and flotation
The crushing, grinding and flotation circuit (Figure 9) receives ore from the mine into a coarse
crusher dump pocket. The ore then proceeds through primary, secondary, tertiary and
quaternary crushing followed by rod and ball milling to a size of 100125 m P80. The
crushing and grinding circuits are existing circuits within the Cliffs Erie plant and will
utilize only a third of the available capacity.
The flotation circuit is designed to produce a bulk concentrate carrying pay metals and a
tailing with low residual sulphur content. The float circuit has the following elements:
Rougher conditioning with potassium amyl xanthate (PAX)
Rougher flotation with MIBC/DF250 addition
Scavenger flotation conditioning with copper sulphate (to activate sulphides)
Scavenger flotation with application of PAX, MIBC and DF250
The rougher float concentrate (and the first scavenger float concentratenot shown on
Figure 9) is sent to conditioning followed by three stages of cleaning to produce a final
concentrate
The scavenger flotation concentrate and the first cleaner flotation tailings are reground to
2530 m particle size (P80) and directed back to the rougher flotation circuit
The third cleaner concentrate is thickened and reground to approximately 15 m particle
size (P80) and sent to the autoclave feed tanks.
A series of batch and continuous pilot-plant crushing/grinding/flotation tests was performed
at SGS-Lakefield as part of the metallurgical development programme. The results of a series
of six test periods are summarized in Table VI. The first two sample periods were treating
assay reject start-up material followed by treatment of a composite (C4). The C4 composite
sample was obtained from NorthMet deposit in the area of the first five years of the NorthMet
mine life. On average for the four periods in which C4 sample was processed, the results
indicate:
Table V
Pilot plant ore samples processed at SGS-Lakefield Research in 2005 and 2006
Sample*
Composite 1
Composite 2
Composite 3
Start-up material
Composite 4
Weight (t)
9.5
19.2
9.6
3.6
4.4
Assay (% or g/t)
Cu
Ni
Pt
Pd
Au
0.31
0.35
0.40
0.31
0.31
0.095
0.10
0.11
0.09
0.10
0.73
0.77
0.87
0.87
0.91
0.06
0.07
0.09
0.04
0.05
0.23
0.33
0.30
0.31
0.28
0.03
0.05
0.05
0.05
0.08
*Composites 13 were processed in 2005 and the start-up material and composite 4 were processed in 2006
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Table VI
Selected flotation pilot-plant test results obtained at SGS Lakefield in 2006
Test Comp Product
Wt
No.
Start-up
Start-up
C4
C4
C4
C4
0.05
Au
Pt
Pd
96.8 0.036 0.035 0.13 0.007 0.008 0.006 0.044
9.9
Conc
3.17
10.1
2.20 20.8 0.110
1.28
1.46
6.71
90.1 67.6 83.8 34.0 84.0 88.8 83.3
Feed
100.0 0.38
0.11 0.85 0.008
0.05
0.05
0.25 100.0 100.0 100.0 100.0 100.0 100.0 100.0
0.26 100.0 100.0 100.0 100.0 100.0 100.0 100.0

32.4 16.2 66.0 16.0 11.2 16.7
96.2 0.032 0.030 0.12 0.005 0.009 0.009 0.043
8.1
Conc
3.80
9.22
2.04 19.3 0.095
1.17
1.17
6.47
91.9 73.0 85.9 42.8 83.7 83.7 85.6
Feed
100.0 0.34
27.0 14.1 57.2 16.3 16.3 3.4
0.10 0.87 0.008
0.04
0.06
0.29 100.0 100.0 100.0 100.0 100.0 100.0 100.0
96.4 0.034 0.030 0.12 0.005 0.014 0.008 0.053
9.6
Conc
3.58
8.57
1.97 21.1 0.095
0.83
1.41
6.63
90.4 71.3 86.4 41.4 68.8 86.7 82.3
Feed
100.0 0.34
0.10 0.93 0.008
0.04
0.07
0.29 100.0 100.0 100.0 100.0 100.0 100.0 100.0
28.7 13.6 58.6 31.2 13.3 17.7
95.8 0.037 0.029 0.11 0.005 0.006 0.005 0.051 10.5 28.7 11.0 62.7 13.6 6.7 16.8
Conc
4.20
7.16
1.66 19.8 0.068
0.87
1.59
5.76
Feed
100.0 0.33
0.10 0.85 0.009
0.04
0.06
0.28 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Tailing
0.05
Co
Tail
Tailing
0.10 0.79 0.010
100.0 0.35
Tailing
Distribution, %
Ni
Feed
Tailing
Grade
Cu, % Ni, % S, % Co, % Au, g/t Pt, g/t Pd, g/t Cu
89.5 71.3 89.0 37.3 86.4 93.3 83.2
96.3 0.032 0.028 0.10 0.006 0.010 0.008 0.044
9.3
Conc
3.74
8.05
1.91 20.0 0.088
0.74
1.30
6.25
90.7 72.7 88.5 36.3 74.2 86.3 84.7
Feed
100.0 0.32
0.10 0.86 0.010
0.03
0.06
0.26 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Tailing
Conc
27.3 11.5 63.7 25.8 13.7 15.3
96.6 0.039 0.034 0.13 0.007 0.013 0.018 0.052 11.6 33.1 15.1 70.2 36.2 27.6 19.4
3.41
8.4
1.97 21.5 0.084
0.65
1.34
6.12
88.4 66.9 84.9 29.8 63.8 72.4 80.6
3.73% mass pull and float recoveries of 89.8% for Cu, 70.5% for Ni, 87.2% for S, 36.2%
for Co, 73.3% for Au, 84.7% for Pt and 82.7% for Pd.
A recent series of flotation tests has been performed using two further samples of PolyMet
ore at 0.30 and 0.25% Cu head grade with the goal of producing a higher grade bulk
concentrate product.
The results of the recent series of tests are encouraging. The mass pull was reduced by
cleaning more aggressively and use of a gangue depressant in the cleaning stages. The higher
grade bulk concentrate will be separated into copper and nickel rich concentrates using
conventional separation methods.
Autoclave leaching
The autoclave leaching process for NorthMet utilizes a small amount of chloride
(approximately 710 g/l) in solution under total pressure oxidation conditions to extract Cu,
Ni, Co, Zn, Au, Pt, Pd from the bulk concentrate. The principles of the PLATSOL process
for NorthMet ore processing have been described elsewhere 3 and will be only briefly
reviewed here. The process is regarded as a nominal step-out from commercial practice in
total pressure oxidation for base and precious metal ore/concentrate treatment.
The autoclave oxidation process converts metal sulphide minerals into metal sulphates and
iron hydrolysis products (primarily hematite but some basic ferric sulphate may also form
under high acid conditions), while the precious metals are converted to chloro-complexes.
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The chemical reactions believed to occur in the autoclave are shown below. (Note that the
mineralogy of the PGMs may be very complex, but for simplicity only the metallic species are
considered.)
Chalcopyrite oxidation/iron hydrolysis
CuFeS2 + 4.25O2 + H2O = CuSO4 + 0.5Fe2O3 + H2SO4
Pyrite oxidation
FeS2 + 3.75O2 + 2H2O = 0.5Fe2O3 + 2H2SO4
Pyrrhotite oxidation
Fe7S8 + 16.25O2 + 8H2O = 3.5Fe2O3 + 8H2SO4
Nickel sulphide oxidation
NiS + 2O2 = NiSO4
Basic ferric sulphate formation
Fe2O3 + 2H2SO4 = 2Fe(OH)SO4 + H2O
Gold oxidation/chlorocomplex formation
Au + 0.75O2 + 4HCl = HAuCl4 + 1.5H2O
Platinum oxidation/chlorocomplex formation
Pt + O2 + 6HCl = H2PtCl6 + 2H2O
Palladium oxidation/chlorocomplex formation
Pd + 0.5O2 + 4HCl = H2PdCl4 + H2O
The temperature range for total pressure oxidation is typically 220 to 230C. The autoclave
discharge from the leach process contains dissolved Cu, Ni, Co, Zn, Au, Pt and Pd. The solids
are relatively barren of value, consisting of iron precipitates, unreacted gangue, and minor
amounts of residual base and precious metal minerals.
The original PLATSOL pilot plant utilized a straight through design in which fresh
concentrate was introduced into the first compartment of a six-compartment pilot autoclave
with raffinate (for controlled cooling of the autoclave slurry) and oxygen (for oxidation). The
results of the straight through pilot plant indicated that virtually all the copper and nickel
were extracted in the first compartment of the autoclave due to the rapidity of the sulphide
oxidation process. However, the platinum and palladium minerals continued to react through
the entire autoclave volume, reaching ultimate extractions of about 95%. This situation was
revisited in the more recent bench and pilot-scale testing. It was concluded that a recycle
design would be more efficient with respect to autoclave design. The recycle design involves
thickening the autoclave discharge and recycling a portion of the underflow to the autoclave
feed. This recycle allows for any unreacted mineral to have a chance at second-pass
extraction. The greater the recycle, the longer the average residence time of solids in the
autoclave. The limit of the recycle will be when the solids density in the autoclave becomes
unmanageable.
Figures 11 and 12 show the impact of solids recycle on base and precious metal extraction.
While there is some noise in the results, there is a strong indication of improvement in both
base and precious metal extraction in applying the recycle system. Nickel extraction improved
from 97% extraction to over 98%, whereas platinum and palladium extraction improved from
less than 90% to between 90% and 95% overall extraction. Regardless of the recycle ratio, the
copper extraction was excellent at over 99%. Gold extraction was highly variable, probably
due to the small amount of gold in the feed sample (0.8 to 1.3 g/t), but always around 90%.
The method of reporting recycle is mass of recycle solids per mass of feed solids (t/t),
expressed as a per cent.
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Figure 11. Copper and nickel extraction as a function of recycle of autoclave discharge solids. Standard conditions:
225C, 1.1 hour single pass residence time, 100 psig of oxygen overpressure, 10 g/l Cl, six-compartment autoclave
Figure 12. Au, Pt and Pd extraction as a function of recycle of autoclave discharge solids. Standard conditions:
225C, 1.1 hour single pass residence time, 100 psig of oxygen overpressure, 10 g/l Cl, six-compartment autoclave
Inspection of the graphs indicates that at least 100% recycle ratio will improve overall metal
extractions.
Further insight into the kinetics of the pressure oxidation process can be obtained by taking
compartment samples from the autoclave at steady-state. Figure 13 shows the precious metal
solution and solids assays in the compartment samples obtained at 74% recycle ratio.
Figure 14 gives the comparable information for the base metals. Note that the feed grades in
each case have been diluted with the barren solids recycled from the autoclave discharge.
The results show clearly that even with recycle and a relatively short autoclave residence
time of 1.1 hours, the oxidation and extraction of the bulk of the base and precious metals is
largely complete within the first two compartments of the autoclave (approximately 22
minutes of the 66 minute residence time). This result is consistent with all other reported
information on total pressure oxidation of sulphide concentrates including the developments
of Placer Dome and Phelps Dodge on copper concentrate total oxidation4,5.
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Figure 12. Compartment sample assays for 74% recycle ratio for Au, Pt, Pd at steady state. (a) solution assays and
(b) solid assays
Figure 14. Compartment sample assays for 74% recycle ratio for Ni, Cu, Fe at steady state. (a) solution assays and
(b) solid assays
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Au and PGM precipitation

The autoclave discharge slurry is partly recycled (after thickening) and partly filtered to
advance the metal bearing solution to the downstream recovery steps in the process. The gold
and platinum group metals in solution are the first target for recovery using reductive
precipitation.
In the first PLATSOL pilot plant reported in 2001, a combination of sulphur dioxide
reduction of ferric ion followed by sulphide precipitation was used to recover the precious
metals from the pregnant solution.
In the recent pilot campaign an improved method of precious metal recovery was tested.
Copper sulphides produced by precipitation of copper from the bleed stream advancing to
nickel and cobalt recovery were utilized for precious metal recovery. The copper sulphides
cement the precious metals onto the solid surface, resulting in an enriched product to
advance to further processing. The improved process was proven to be robust and flexible. It
is still advantageous to reduce the ferric species in the advancing solution using sulphur
dioxide gas to minimize the CuS demand for Au and PGM precipitation.
Ferric reduction
Fe2(SO4)3 + SO2 + 2H2O = 2FeSO4 + 2H2SO4
Gold precipitation
2HAuCl4 + 3CuS + 3H2SO4 = 2Au + 3CuSO4 + 8HCl + 3S
Platinum precipitation
H2PtCl6 + 2CuS + 2H2SO4 = Pt + 2CuSO4 + 6HCl + 2S
Palladium precipitation
H2PdCl4 + CuS + H2SO4 = Pd + CuSO4 + 4HCl + S
The recovery of gold, platinum and palladium from the autoclave solution (after filtering
and washing the solids) was accomplished by precipitation with CuS in the pilot plant. The
precipitate solids are collected in a thickener/clarifier arrangement and then filtered.
Recoveries of gold, platinum and palladium into this precipitate concentrate were excellent, in
excess of 99.5% in each case. Base metal losses from solution into the PGM and gold residue
were negligible.
Approximately 4 kg of precipitate were collected during the 2005 pilot plant analysing
56 g/t Au, 211 g/t Pt and 907 g/t Pd. Most of the precipitate mass was copper (35.7%) and
sulphur (49%). Batch releaching of the precipitate to remove copper and sulphur was tested
and resulted in an upgraded material analysing approximately 1.6% or 16 000 g/t total
contained gold, platinum and palladium. The solution after gold, platinum and palladium
recovery advances to base metal recovery. The solution is still acidic and must be neutralized
prior to copper solvent extraction.
Solution neutralization
The extraction of copper by solvent extraction is inhibited by acid in solution. It is therefore
important to neutralize the excess acid from the autoclave process prior to advancing to
copper recovery.
The neutralization process was piloted in a three-stage neutralization circuit with limestone
slurry for neutralization. The gypsum product is thickened. A 300% recycle of gypsum as
seed for precipitation was used to grow coarse, clean, crystals of gypsum.
The chemistry of neutralization is shown below.
Gypsum precipitation
H2SO4 + CaCO3 + 2H2O = CaSO4.2H2O
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The utilization of carbonate exceeded 99% in the pilot tests due to the use of the 300%
recycle. The gypsum product assay is shown below. The chemical quality, physical nature and
colour of this synthetic gypsum produced in the pilot plant appear to be suitable for entry into
the gypsum wallboard market in the US. If an off-take for synthetic gypsum can be finalized,
the gypsum residue will not fill space in the lined tailings facility planned for hydromet
tailings. The value of the gypsum will partially offset the cost of oxygen for oxidation of
sulphur in the concentrate to sulphate and the cost of purchasing limestone for neutralization.
(Table VII.)
Copper SX/EW
The recovery of copper by SX/EW is conventional technology. The presence of chloride in the
feed solution to copper solvent extraction necessitates the application of a wash or scrub step
to displace any entrained chloride from the loaded organic solution.
Copper extraction
CuSO4 + 2HR(org) = CuR2(org) + H2SO4
Copper stripping
CuR2(org) + H2SO4 = CuSO4 + 2HR(org)
CuSO4 + H2O = Cu + O2(gas) + H2SO4
In the pilot plant, copper was extracted in three countercurrent stages, scrubbed in one and
stripped in two stages with spent electrolyte from the electrowinning cell. Two extractants
were evaluated, 35% Acorga M5640 from Cytec in Orfom SX 80CT and 35% LIX 973NS LV
from Cognis in the same diluent. Both extractants performed well in the pilot-plant operation.
Extractions averaged about 95% from a starting solution concentration of 17.4 g/l of Cu
(average). A total of 68 kg of copper were extracted and electrolyzed during the 2005 pilot
plant run at a current density of +270 A/m2. The copper metal cathode was analysed and
found to meet LME grade A copper purity specifications. This product can be sold directly to
copper consumers. Table VIII summarizes the assay for copper for two samples taken from
the second strip cycle in the pilot plant.
Raffinate neutralization
The purpose of raffinate neutralization is to trim the acid level in the copper raffinate prior to
splitting the raffinate flow between the nickel and cobalt recovery circuit and returning the
raffinate to the autoclave circuit as a cooling solution. Acid must be neutralized prior to the
Table VII
Gypsum solids assay from neutralization of autoclave acid
Ni %
0.005
Co %
<0.02
Cu %
0.005
Fe %
<0.05
Zn %
0.003
SiO2 %
0.19
Al2O3 %
<0.01
Fe2O3 %
0.06
MgO %
0.2
CaO %
31.7
Na2O %
<0.05
K 2O %
<0.01
TiO2 %
<0.01
P2O5 %
<0.01
MnO %
<0.01
Cr2O3 %
<0.01
V2O5 %
<0.01
LOI %
21.3
SO4 %
51
CO3 %
0.07
Cl g/t
24
Dry product P80 ~105 microns, wet PSD determinations using Malvern Mastersizer 2000.
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Table VIII
Copper assays for samples taken from the second pilot plant strip cycle*
Analysis (g/t)
Sample
Cathode 1
Cathode 2
LME Grade A
Fe
1.02
1.31
10
S
10.50
6.00
15
Pb
0.52
3.63
5
Ag
<1
<1
25
nickel and cobalt recovery process steps and excess acid is undesirable in the feed to the
autoclave as excess acid will increase the formation of basic ferric sulphate in the autoclave
solids.
The chemistry of raffinate neutralization is the same as the primary neutralization discussed
above.
Fe and Al removal
The removal of iron and aluminum prior to recovery of nickel and cobalt is necessary to
prevent product contamination.
The process of iron oxy-hydrolysis is well known. Iron is oxidized from the ferrous to the
ferric state with oxygen or air with limestone addition for neutralization and pH control. The
temperature for iron removal was set to 60C and the pH to 3.0. The iron was removed to less
than 5 mg/l by this process with negligible losses of Ni/Co to the iron precipitate residue.
Similar results were obtained in the pilot plant using limestone to pH 4.64.7 and 65C.
Terminal aluminum levels were 38 mg/l on average.
The iron precipitate is washed and disposed to tailings. The aluminum precipitate is
thickened and recycled to the iron removal step.
Copper removal
Residual copper is removed before nickel, cobalt and zinc recovery using NaSH precipitation.
The copper sulphide product (synthetic covellite) is then recycled internally to precipitate
gold and PGM from the autoclave discharge solution.
The chemistry is straightforward
CuSO4 + NaSH = CuS + 0.5Na2SO4 + 0.5H2SO4
In the 2005 pilot plant, the copper level in solution advancing to copper removal was
reduced to less than 50 mg/l.
Nickel, cobalt and zinc recovery
There were two options for nickel, cobalt and zinc recovery that were continuously piloted at
SGSLakefield in 2005. The first option utilized a classic mixed hydroxide precipitation
*The
first strip cathode had higher levels of contaminants. This was attributed to the start-up conditions used and the fact
that the lead anodes in electrowinning were not conditioned prior to commencement of the pilot plant. The purity of the
second strip cathodes is believed to be representative of the full-scale chemistry of the copper cathodes to be produced at
NorthMet.
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route for recovery of the pay metals in a single product. The second option was to separate
cobalt and zinc away from nickel using solvent extraction, followed by selective stripping of
cobalt and zinc. The purified nickel, cobalt and zinc streams can then all be treated with
magnesia to recover purified hydroxides (or in the case of zinc, be sold directly into the zinc
chemicals industry).
Mixed hydroxide results
The mixed hydroxide process uses two-stage precipitation for nickel and cobalt recovery. In
the first stage, approximately 85% of the nickel and cobalt are precipitated with magnesia
(MgO). This precipitate is then thickened, filtered and washed and sent to a nickel off-take
party. The balance of the nickel and cobalt are then precipitated with lime to form mixed
gypsum metal hydroxide precipitate. This precipitate is recycled to solution neutralization to
redissolve the precipitated nickel and cobalt.
Zinc in solution will report quantitatively to the final mixed hydroxide precipitate.
Nickel precipitation with magnesia
NiSO4 + MgO + H2O = Ni(OH)2 + MgSO4
Cobalt precipitation with magnesia
CoSO4 + MgO + H2O = Co(OH)2 + MgSO4
Zinc precipitation with magnesia
ZnSO4 + MgO + H2O = Zn(OH)2 + MgSO4
Residual nickel precipitation with lime
NiSO4 + CaO + 3H2O = Ni(OH)2 + CaSO4.2H2O
Residual cobalt precipitation with lime
CoSO4 + CaO + 3H2O = Co(OH)2 + CaSO4.2H2O
Residual nickel precipitation with lime
ZnSO4 + CaO + 3H2O = Zn(OH)2 + CaSO4.2H2O
The mixed hydroxide material is high quality and may be placed with an off-take/refinery
partner for final separation into pure nickel and cobalt and by-products. (Table IX.)
Magnesium removal
The NorthMet ore and concentrate contains some magnesium silicate mineralization. During
high temperature autoclave leaching of the concentrate, some magnesium is leached. In
addition, magnesia is used around the circuit for nickel and cobalt precipitation, which also
results in an increase in the magnesium content of recirculating solutions. In order to control
the build-up of magnesium in solution, a magnesium removal step (with lime) was introduced
into the circuit. Magnesium sulphate reacts to form magnesium hydroxide and gypsum with
lime.
Table IX
Analysis of the mixed hydroxide product from the pilot plant
Sample
Moist. %
Ni %
Co %
Cu %
Fe %
Zn %
Al %
Mg %
Ca %
Si %
Mn %
51.2
36.3
1.92
0.37
0.59
4.84
0.07
1.04
0.02
0.05
0.03
41.2
31.5
31.3
1.67
1.67
0.31
0.32
0.51
0.54
4.31
4.27
0.04
0.04
0.62
0.62
0.04
0.04
0.03
0.03
0.02
0.02
56.3
40.6
2.17
0.41
0.68
0.56
0.05
0.76
<0.08
0.04
0.03
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Magnesium precipitation with lime

MgSO4 + CaO + 3H2O = Mg(OH)2 + CaSO4.2H2O
The removal of magnesium is a control for the build-up of magnesium across the circuit. In
the pilot plant approximately 50% of the magnesium was precipitated per pass with the
balance of the magnesium allowed to recirculate in the overall circuit.
The NorthMet project of PolyMet Mining is well advanced and ready to proceed to
construction upon receipt of key permits. The NorthMet project will begin with an initial
phase of separate copper and nickel concentrate production for sale followed by
commissioning of the hydrometallurgical circuit for bulk concentrate leaching.
The PLATSOL process will be used for the treatment of the concentrate. The
PLATSOL process will dissolve all the metals of value to high levels of extraction in an
autoclave, followed by a series of precipitation and SX/EW processes for recovery of final
metal products. The final products from the commercial plant will include:
Copper cathode of LME Grade A quality
Au and PGM precipitate for toll processing
Mixed hydroxide product containing Ni-Co-Zn
Synthetic gypsum.
The current design basis is for 32,000 short tons of ore per day to be processed through the
refurbished Erie plant and a new hydrometallurgical refinery for metal extraction. Figure 14
shows how the hydrometallurgical plant will be integrated with the existing Erie facility.
The existing Erie plant has capacity to operate at approximately three times the planned
production rate. Expanded production could be supported by existing resources at NorthMet,
exploration success or treatment of other known deposits in the area. Expansion beyond the
current permit application would involve additional environmental review and permitting.
Figure 14. Plant layout for NorthMet plant with hydrometallurgical concentrate treatment
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Conclusions
Hydrometallurgical processing of complex ores and concentrates offers the possibility of
unlocking new and valuable mineral deposits for production of metals. Two such
developments have been reviewed as examples of what is possible by developing or
integrating new science and technology into a process flowsheet. The Boleo process offers the
promise of being able to unlock the value in a complex, clayey ore containing significant
amounts of copper, cobalt, zinc and manganese. The use of high rate thickener technology
permits the separation and washing of a clayey leach residue. The integration of the CSIRO
DSX technology for cobalt and zinc separation away from manganese permits recovery of
these important by-product metals, vastly improving the economics of the metallurgical
treatment of the Boleo ore. The PLATSOL process has opened the way to treat the
NorthMet ore of PolyMet mining. Small additions of chloride to total pressure oxidation
leaching conditions allows for direct extraction of small concentrations (but economically
significant) of platinum, palladium and gold. This novel leaching process, when combined
with known methods of copper, nickel/cobalt and precious metal recovery have permitted the
development of a hydrometallurgical process for treatment of the NorthMet ore.
Acknowledgements
The authors education in metallurgical process development began many years ago with W.
Charles Cooper (PhD supervisor) and E. Peters (PDF supervisor). In the case of the Boleo and
PLATSOL developments, extensive collaborative work has occurred with colleagues at
SGS Lakefield Research, Bateman Engineering, CSIRO and others. The technical work
presented in this paper is a reflection of the combined efforts of many people in various roles
moving from early testing and concepts through to final feasibility for each of the process
developments.
References
1. DREISINGER, D., MURRAY, W., BAXTER, K., HOLMES, M., JACOBS, H., and
MOLNAR R. The metallurgical development of the El Boleo copper-cobalt-zinc project.
Proceedings of ALTA Copper 2005, Perth, ALTA Metallurgical Services, Melbourne,
Australia, 2005.
2. CHENG, C.Y. and URBANI, M.D. Solvent extraction process for separation cobalt
and/or manganese from impurities in leach solutions. Patent Publication No. WO
2005/073415 A1.
3. FERRON, C.J., FLEMING, C.A., OKANE, P.T., and DREISINGER, D. Pilot plant
demonstration of the PLATSOL process for the treatment of the NorthMet coppernickel-PGM deposit, Mining Engineering. Littleton, CO, United States, 2002, vol. 54,
no. 12, pp. 3339.
4. MARSDEN, J.O., BREWER, R.E., and HAZEN, N. Copper Concentrate Leaching
Developments by Phelps Dodge Corporation, Hydrometallurgy 2003, C.A. Young, A.M.
Alfantazi, C.G. Anderson, D.B. Dreisinger, B. Harris and A. James (eds.), TMS,
Warrendale, USA, 2003, pp. 14291446.
5. BREWER, R.E. Copper Concentrate Pressure Leaching Plant Scale-Up from
Continuous Laboratory Testing, Minerals and Metallurgical Processing, November,
2004, vol. 21, no. 4, pp. 202208.
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David Dreisinger
Professor, University of British Columbia Canada and
Chairholder, Industrial Research Chair in Hydrometallurgy
David Dreisinger holds the position of Professor and Chairholder of
the Industrial Research Chair in Hydrometallurgy at the University of
British Columbia (UBC). Dr Dreisinger received BSc and PhD
degrees in Metallurgical Engineering from Queens University in
Kingston before beginning his career at UBC in 1984.
At UBC, Dr Dreisinger supervises a wide ranging programme of
research and development in atmospheric and pressure leaching of ores and concentrates,
solution purification and the use of electrochemical methods for metal recovery.
Dr Dreisinger (with co-workers) has been actively involved in commercializing the
Mt. Gordon and Sepon copper processes in Australia and Laos as well as a number of novel
ion exchange technologies. Through the Industrial Research Chair in Hydrometallurgy,
Dr Dreisinger is engaged in teaching technical short courses to the global metallurgical
industry. Within the METSOC of CIM, David has participated in the organizing or coorganizing of a number of technical conferences. Dr Dreisinger has received awards
including the Sherritt Hydrometallurgy Award (1993), the Extraction and Processing Division
Science Award from the TMS (2005) and the Alcan Award from the METSOC of CIM
(2005). Recently, David has been named a Fellow of the Canadian Academy of Engineering
and has received a Meritorious Achievement Award from the Professional Engineers and
Geoscientists of BC. Dr Dreisinger serves as a director or officer of a number of TSX listed
mining companies.
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BEUKES, N.T. and BADENHORST, J. Copper electrowinning: theoretical and practical design.
Hydrometallurgy Conference 2009, The Southern African Institute of Mining and Metallurgy, 2009.
Copper electrowinning: theoretical and practical

design
N.T. BEUKES* and J. BADENHORST*
*TWP Matomo Process Plant, South Africa
An engineering houses perspective of required inputs in designing a

copper electrowinning tank house and ancillary equipment calls for
both understanding of the key fundamental controlling mechanisms
and the practical requirements to optimize cost, schedule and product
quality. For direct or post solvent extraction copper electrowinning
design, key theoretical considerations include current density and
efficiency, electrolyte ion concentrations, cell voltages and electrode
overpotentials, physical cell dimensions, cell flow rates and electrode
face velocities, and electrolyte temperature. Practical considerations
for optimal project goals are location of plant, layout of tank house
and ancillary equipment, elevations, type of cell furniture, required
cathode quality, number and type of cells, material of construction of
cells, structure and interconnecting equipment, production cycles,
anode and cathode material of construction and dimensions, cathode
stripping philosophy, plating aids, acid mist management, piping
layouts, standard electrical equipment sizes, electrolyte filtration,
impurity concentrations, bus bar and rectifier/transformer design,
electrical isolation protection, crane management, sampling and
quality control management, staffing skills and client expectations,.
All of the above are required to produce an engineered product that
can be designed easily, constructed quickly and operated with
flexibility.
Introduction
The electrowinning of copper ions derived from leaching, or solvent extraction is a significant
contributor to the global copper commodity supply. The process of electrolysis for copper was
first developed in the late 19th century and despite numerous advancements in technology the
principles and basic equipment remain the same. The first part of this paper deals with the
theoretical requirements and fundamental equations and principles that govern copper
electrowinning. The second part discusses the practical requirements for designing a copper
electrowinning plant.
COPPER ELECTROWINNING: THEORETICAL AND PRACTICAL DESIGN
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The hardware used is simple in nature; for electrowinning an acid resistant bath with
anodes and cathodes submersed in solution with current passing through the electrodes is the
fundamental process unit. The fundamental concepts lie in reaction kinetics, mass transfer
phenomenon, thermodynamics and other electrochemical specific models, the application of
which leads us to a deeper and more appreciative knowledge of the simple electrowinning
reactor.
The first part of the paper goes through the fundamentals and culminates in an example
reactor being developed. Note that not all design procedures are named as this would
compromise TMPs intellectual property. However the reader will be able to get a very good
understanding of what is required to design and build a copper electrowinning plant.
Part 1: Copper electrolysis theoretical considerations
Faradays law
For the winning of copper by the addition of electrons
[1]
Cations go towards the cathode, and anions go to the anode. The working electrode is where
reduction takes place and the counter electrode is where oxidation occurs. The working
electrode is the cathode and the counter electrode the anode. For the general
oxidation/reduction reaction:
[2]
Faradays Law gives the total amount of charge spent to reduce M mols of Ox (Q) is:
[3]
The charge spent per unit time is defined as the current (I):
[4]
Normalizing with unit area gives Faradays Law expressed in Current Density (i) :
[5]
Faradays law then is: the current flowing in an external circuit is proportional to the rate of
the reaction at the electrode.
Nernst equation
The standard electrode potential is the potential difference between energy states of product
and reactant and is a manipulation of the Gibbs free energy reaction (G)
Reaction thermodynamics gives the following relationship for Gibbs Free energy:
[6]
For a single electrode
[7]
Since the electrode potential regulates the energy of electron exchange, it also controls the
current and thus the rate of exchange. Current and Potential (E) are dependant variables of one
another. Where the work done (W) is related to the Potential difference by:
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[8]
Substituting for (Q) and work (W) for (G), where (W) and (G) are in joules then Gibbs Free
Energy can be re-written as:
[9]
Substituting (7) and (8) with (9) gives the Nernst Equation for an electrode (or half cell):
[10]
Mechanism of electron transfer
For elementary reactions at an electrode the following two mechanisms are primarily
responsible for electron transfer.
Mass transfer controlled
1) Diffusion of copper cations from the bulk phase to where the reaction occurs at the
surface.
[11]
Reaction kinetics controlled
2) Heterogeneous transfer of electrons from the solid electrode to the copper cation at the
surface of the electrode.
[12]
Further phenomena, coupled chemical reactions, adsorption and formation of phases are
reported to also have a role in the electron transfer mechanism. The formation of phases is
relevant to the plating of copper on the cathode and involves nucleation and crystal growth
steps. Copper atoms diffuse through the solid phase to a location in an appropriate site of the
crystal lattice. Adsorption and nucleation steps are considered to be included in the
Heterogeneous Electron Transfer reaction rate mechanism.
The overall rate is controlled by the slowest step which can be either mass transfer or
reaction kinetics. For the purposes of copper electrowinning reactor design it is necessary to
determine the rate limiting step to optimize conditions so that capital costs and operating
ability is optimized.
Heterogeneous electron transfer
By analogy with chemical kinetics for a simple first order reaction:
[13]
[14]
Using (5) the current for the forward reaction is given by:
[15]
And for the reverse reaction:
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[16]
The total current density for the electrode is:
[17]
Using Arrhenius and the Activated Complex Theory it can be shown that rate of reaction kf
and krev takes the forms:
[18a]
and
[18b]
E is the applied potential to the electrode and E the formal electrode potential that differs
from the standard electrode potential by the activity coefficients. Recalling the Nernst
Equation:
[10]
The activity is equal to activity coefficient multiplied by the concentration in the bulk phase.
Therefore:
[19]
It then follows that:
[20]
Equation [17] can be written as:
[21]
Substituting for kf and krev from equation [18] gives the Bulter-Volmer Equation (B-V):
[22]
This current-potential relationship governs all fast and single step heterogeneous electron
transfer reactions.
At equilibrium the exchange current density is:
[23]
The overvoltage () can be defined as:
[24]
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where Eeq is the equilibrium voltage, Eeq=E when Cox(bulk) = Cred(bulk) and E =E when
activity coefficients are equal to one, see Equation [20]. An expression for the equilibrium
potential is derived and shows Eeq to be close to the standard electrode potential and to vary
according to changes in temperature and bulk concentrations.
[25]
The Butler-Volmer equation can then be written as follows:
[26]
This relationship shows that exponential changes to the current can result from changes to
the potential. Furthermore current is constrained by the surface to bulk concentration ratios of
oxidant and reductant species. The reaction rates do not grow indefinitely as potential is
increased and are thus limited by the transport of species to the electrode. A system that is
moved from equilibrium for Ox species to be reduced and Red species to be oxidized is
described by the B-V equation. This is achieved by setting the potential different to the
equilibrium potential, increasing the voltage thus increases the equilibrium difference which
increases the current hence speeding up the Faradaic process.
The maximum current that can be applied to maintain a reaction is known as the Diffusion
Limited Current. No matter what the standard rate constant is if the applied potential is
sufficiently large the maximum current will be reached. Assuming and adequate supply of
reactants to the reaction surface (the electrode) the rate of reaction is described by the ButlerVolmer Equation. If the applied potential is adequate to maximize the Heterogeneous Electron
Transfer reactions the rate of reaction is then limited by the supply of reactants to the
electrode surface and is said to be mass transfer limiting (or controlled).
Assuming that the surface and bulk concentrations are equal (condition of non mass transfer
limited), for only large negative or positive overpotentials (only forward or reverse reaction
dominant) the B-V equation can be manipulated by taking a Log of both sides of the equation
then resolving for overvoltage gives:
[27]
And has the general form:
[28]
Recognized as the well know Tafel Equation and is derived from the B-V equation for
specific condition of non mass transfer limiting, equal surface to bulk concentrations and
dominant forward or reverse reactions. The procedure provides a means of linearizing the
relationship between overpotential and current or rate of reaction.
Mass transport
The movement of species from the bulk solution to the electrode surface occurs via three
possible mechanisms:
Convection (or conveyance), forced or natural described by hydrodynamics or
density/temperature differences
Diffusion described by a gradient in concentrations
Migration described by a gradient in electrical potential.
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Experimental conditions of the electrode reactions are generally chosen to minimize the
effects of migration. This is done by providing a large quantity of inert electrolyte that does
not interfere with the electrode reaction, leaving only diffusion and convection mechanisms
for consideration.
Ficks First Law for one-dimensional diffusion
[29]
Expanded to include convection (conveyance) and migration is the Nernst-Planck Equation8:
[30]
Minimizing the potential gradient using an inert electrolyte reduces the equation to:
[31]
This equation describes the one dimensional flux of species across the bulk solution to the
electrode interface due to the mechanism of conveyance and diffusion.
For a three dimensional volume it can be extended to:
[32]
Assuming that at steady state there is no change in concentration with time and that the
conveyance inside the diffusion layer is significantly smaller than the diffusion component,
Equation [32] becomes:
[33]
and by definition of rate of consumption
[34]
[35]
The rate of consumption (or generation) is equal to the rate change of concentration
difference across the diffusion layer. Using a circulation tank to minimize the change in
concentration over two of the three spatial axes we find that.
[36]
and
[37]
The use of the circulation tank to minimize the change in concentration over the two axes
parallel to the electrode surface significantly simplifies the mathematical mass transfer
relationship. Also sufficient concentration of ions across the face of the electrode is provided
to ensure that the mass transfer and supply of species to the surface of the electrode remains
sufficient. If the concentration gradients across the two parallel axes were not minimized a
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varying current over the electrode surface would be required to maintain the rate of reaction.
The mathematical and practical difficulties of this are self evident. The resulting mass transfer
relationships are the following, and are relevant to one dimension normal to the electrode
surface.
[38]
And:
[39]
Faradays law:
[5]
Where:
[40]
Gives:
[41]
Substituting Equation [39] into equation [41] gives:
[42]
Defining the mass transfer coefficient (kd) as:
[43]
then
[44]
Equation [44] is different to Equation [42] in that using the mass transfer coefficient forces
an adequate hydrodynamic treatment of the flow reactor. Equation [42] is widely regarded in
the technical literature as the only mass-transfer equation for electrochemical systems. While
the difference may be trivial to the diffusion layer mechanism advocate not so from the
perspective of good chemical engineering practice, the universal application of heat and mass
transfer coefficients provides a more rigorous means of solving a hydrodynamic problem.
Mass transfer coefficients and diffusion limited current
Two equations that represent the same thing, namely, the reaction rate have been derived. The
B-V equation which describes Heterogeneous Electron Transfer and Ficks Law substituted
into Faradys Law that describes Mass Transfer. Increasing the overpotential up to a point
increases the reaction rate. When all species that reach the electrode are oxidized or reduced
the rate of mass transfer of the species to the electrode surface is the rate limiting step for the
production of copper. The diffusion limited current is the current above which an increase in
potential will not increase the rate of reaction. For that reason the Diffusion Limited Current
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(DLC) should be determined to optimize the reactor design. In the field, operating reactors are
normally run at levels well below the DLC to achieve a good adherent product. This should be
considered when determining the actual applied current to the cell.
At the Diffusion Limited Current the surface concentration of species is zero meaning that
all surface species are consumed as quickly as they are supplied to the electrode. The DLC
equation then becomes:
[45]
Two important observations can be made at this point:
1) Increasing the concentration of the bulk reactant increases the DLC. This is a function
of the extraction process that was used to remove the copper from the host body and
other upgrade processes used before the electrowinning of the copper
2) Increasing the mass transfer coefficient increases the DLC. This is a function of the
hydrodynamics of the reactor cell and physical properties of the solution in which the
electrolyte is present such as temp, viscosity and other competing ions. The most
efficient supply of fresh solution is provided by enhancing the bulk motion. This is
easily achieved by stirring or by flowing the solution past the electrode or using other
methods to enhance the mass transfer coefficient.
Mass transfer coefficients are usually determined using empirical correlations that are based
on test work and made up of dimensionless parameters such as:
Reynolds Number:
[46]
Schmidt number:
[47]
Sherwood number:
[48]
Grashof number:
[49]
Prandtl number:
[50]
Rayleigh number:
[51]
A number of correlations appear in the literature and for convective mass transfer have the
general form:
[52]
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For parallel plate electrodes of finite width and fully developed laminar flow. (Only
applicable if the maximum electrode length is less than 35 times the equivalent diameter. Re
<2000)3:
[53]
For parallel plate electrodes of infinite width and fully developed laminar flow. (Only
applicable if the maximum electrode length is less than 35 times the equivalent diameter. Re
<2000)3, 15:
[54]
Natural convection nearly always occurs at an electrode even when forced convection takes
place. Natural convection dominates forced convection at very low flow cell flow rates. The
upward flow component of natural convection may oppose forced convection and results in
very low mass transfer coefficients. The following correlations are concerned with comparing
natural convection to forced convection. In stationary solutions the effects of natural
convection will be the dominant mode of mass transport.
By analogy with Heat transfer4:
[55]
[56]
[57]
[58]
For mass transfer by natural convection1:
[59]
Equations [53] [54] [55] and [59] are solved for the mass transfer coefficient (kd). Using
data from the world EW copper survey16 values for kd and the DLC were calculated for 22
operating plants. The plants chosen represent a wide variety of plant operating conditions.
Table I compares the four different correlations mass transfer coefficients for copper
electrowinning plants.
An unveiled warning to all chemical engineers is that any mass transfer coefficient
correlation must be used with caution as the accuracies could easily be 50% off, as practical as
possible mass transfer coefficients should try to be determined by test work.
The mass transfer coefficients compare well with each other for the different calculation
methods over a wide variety of plant operating conditions.
Table II compares the DLCs calculated using the four different methods to each other and
to the Faradaic current requirement.
The table shows that the DLCs calculated by the four different methods compare well with
the Faradaic current density. The Faradaic Current Density includes the current efficiencies
reported for the process plants.
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Table I
Calculated kd (m/s) for 22 operating Cu EW plants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Nullabar M
Pasimco M
Girilambone Cu
CM Cerro Colorado
CM Quetrada Blanca
Minera El Abra
Codelco Chile Div
Empresa Minera
CM Zaldivar
Mantos Blancos
CM Carmen Andacolla
Hellenic Copper Mines
Nicico sarchesh
Mexicana de corbe
Miccl main plant
Southern Peru limited
Silver Bell Mining LLC
BHPB Copper San Manuel
Phelps Dodge Morenci S-side
Phelps Dodge Morenci Central
Phelps Dodge Morenci Stargo
First Quantum Bwana Mkubwa
kd3 m/s
kd15,3 m/s
kd4 m/s
kd1 m/s
2.09E-06
1.73E-06
2.08E-06
2.31E-06
2.03E-06
2.20E-06
2.12E-06
2.05E-06
2.18E-06
2.36E-06
2.24E-06
2.13E-06
2.02E-06
2.10E-06
2.05E-06
2.22E-06
2.12E-06
1.95E-06
1.79E-06
1.67E-06
1.85E-06
1.94E-06
2.04E-06
1.68E-06
2.04E-06
2.28E-06
1.98E-06
2.16E-06
2.09E-06
2.02E-06
2.17E-06
2.36E-06
2.21E-06
2.11E-06
1.98E-06
2.07E-06
2.01E-06
2.19E-06
2.08E-06
1.90E-06
1.74E-06
1.61E-06
1.80E-06
1.88E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.76E-06
1.75E-06
1.75E-06
1.75E-06
1.75E-06
2.18E-06
2.11E-06
2.19E-06
2.18E-06
2.27E-06
2.20E-06
2.18E-06
2.18E-06
2.20E-06
2.11E-06
2.21E-06
2.18E-06
2.12E-06
2.05E-06
2.17E-06
2.16E-06
2.22E-06
2.26E-06
2.14E-06
2.16E-06
2.14E-06
2.13E-06
Table II
Calculated DLC (A/m2) for 22 operating Cu EW plants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
222
Nullabar M
Pasimco M
Girilambone Cu
CM Cerro Colorado
CM Quetrada Blanca
Minera El Abra
Codelco Chile Div
Empresa Minera
CM Zaldivar
Mantos Blancos
CM Carmen Andacolla
Hellenic Copper Mines
Nicico Sarchesh
Mexicana de corbe
Miccl main plant
Southern Peru limited
Silver Bell Mining LLC
BHPB Copper San Manuel
Phelps Dodge Morenci S-side
Phelps Dodge Morenci Central
Phelps Dodge Morenci Stargo
First Quantum Bwana Mkubwa
i3 A/m2
i15,3 A/m2
i4 A/m2
i1 A/m2
i Faradaic A/m2
240
193
246
266
278
263
260
246
285
254
275
260
213
207
236
253
268
258
205
197
210
205
235
188
241
263
271
259
257
242
283
253
271
256
209
204
232
250
264
251
199
190
205
199
203
197
209
203
241
211
216
211
230
189
215
214
185
173
202
201
223
233
201
208
200
186
250
236
260
251
312
264
267
261
287
227
271
265
224
202
249
247
281
299
245
255
243
226
226
239
321
256
246
233
234
236
244
262
286
272
231
246
240
266
316
231
234
251
239
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The DLC should always be greater than the Faradaic current for a plant to ensure that a
good adherent copper cathode is produced and that the hydrodynamics of the system are
sufficient to ensure production is not limited by inadequate flow conditions.
It is important to note that the DLCs reported here are based entirely on the correlations
used and not on any test work done by the authors. This method is used to demonstrate the
phenomenon of determining the DLC with common literature information, as well as the
reasonably comparative results obtained from the different correlations. It can be seen that
some Faradaic currents are greater than the DLCs calculated this does not mean that the plant
is incapable of adequate production but only means that the correlation may not be
representative of the exact conditions in that plant.
The correlations do not take into account gas evolving electrodes of which all copper
electrowining anodes are, this omission in the correlations may underestimate the DLC
significantly. This gas evolution can have a strong influence on the mass transfer of ions due
to the forced convection effects inside the parallel plate arrangement.
Overall electrode process
The earlier sections dealt with the two mechanisms of electron transfer for an electrode. This
section deals with an overall process of both heterogeneous electron transfer and mass transfer
that is relevant to copper electrowinning in practice.
The B-V equation that describes the Heterogeneous Electron transfer in terms of current and
overpotential is:
[26]
The current density is described by Ficks and Faradays law for mass transfer is:
[44]
And
[45]
Substituting and resolving for concentrations gives:
[60]
For copper reduction on an electrode the last term of the B-V equation can be neglected to
give:
[61]
Taking the log of both sides of the equation and separating for overpotential gives:
[62]
Substituting for the concentration ratio gives:

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Table III
Operating conditions for the four scenarios compared
Fictional cell design

Number of cathodes
Number of anodes
Cell spacing A-C
Cell inlet concentration
Cell outlet concentration
Cell volumetric flow rate
Copper production rate
Temperature
Density
Diffusion coefficient
Current efficiency
iL3
iL15,3
iL4
iL1
Faradaic current density
units
no off
no off
m
g/l Cu2+
g/l Cu2+
m3/h
kg/h
C
kg/m3
m2/s
%
A/m2
A/m2
A/m2
A/m2
A/m2
Cell 1
Cell 2
Cell 3
Cell 4
Lo MT
48
49
0.045
40.00
35
2.50
12.5
65
1216
1.95E-09
85
191
182
273
272
129
Hi MT
48
49
0.045
35.77
35
16.25
12.5
65
1216
1.95E-09
85
300
301
244
237
129
Lo MT Hi Cu
48
49
0.045
38.75
35
5.00
18.75
65
1216
1.95E-09
85
228
221
264
262
194
Hi MT Hi Cu
48
49
0.045
36.07
35
17.50
18.75
65
1216
1.95E-09
85
309
311
246
239
194
[63]
This equation describes overpotential, applied current and DLC in a single equation.
Example of fictional cell reactor
A fictional cell reactor is developed to show the relationship of overpotential to current for
varying conditions of concentration and flow in the cell. High level differences between the
scenarios are:
Cell 1, low flow rate
Cell 2, high flow rate
Cell 3, low flow rate high copper concentration
Cell 4, high flow rate high copper concentration.
Each cell has the same physical characteristics and features a cathode plating area of 1 m x 1
m. The physical properties of the electrolyte are kept constant except for the concentrations
and flow rates in the cells. Table 3 also gives the DLC results for various correlations.
The Forced Convection correlation of Equation [53] and Equations [54] described by the
hydrodynamic characteristics of the cell are strongly influenced by the change in flow
rate. Compared to the Natural convection correlations of Equations [55] and Equations
[59] that, as expected, are not influenced by the changing flow rate as these correlations
do not take into account the flow system but only density difference along the plate
surface
The graph of overpotential versus current is called a Voltammogram. For the
development of the Voltammogram the correlation from Equations [53] is used as this
DLC changes with concentration and flow rate which is phenomenologically correct.
Although it may not fully account for all mass transfer driving forces such as the gas
evolution at the anode this correlation demonstrates that reactor design is strongly
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Figure 1. Voltammograms for fictional cells
influenced by flow rate and concentrations.

The DLC3 for each cell is used to plot the voltammogram on overpotential versus current
density graph. The exchange current density io is taken from17 as
[64]
Figure 1 compares the Voltammograms for the four fictional cells:
This graph shows the following conclusions to be drawn:
Increasing the flow rate at the same copper production rate results in an increase of DLC
from 190 A/m2 to 300 A/m2, Cu Lo MT to Cu Hi MT
Increasing the copper concentration and flow rate slightly results in increasing the DLC
from 190 A/m2 to 230 A/m2, Cu Lo MT to Cu Lo MT Hi Conc
Increasing the copper concentration and flow rate significantly has the largest effect of
increasing the DLC, from 190 A/m2 to 310 A/m2, Cu Lo MT to Cu Hi MT Hi Conc.
Although the DLC equations used to determine this voltammogram are based on literature
work, the functionality remains correct. In order to optimize the cell design in terms of capital
cost for the same production rate, the DLC must be as high as possible so that the Faradaic
current density is as high as possible (limited to producing a good product). These conditions
will allow for the same transformer/rectifier arrangement to:
Minimize installed electrowinning total plating area
Minimize installed electrowinning cell size
Minimize installed electrowinning cell house structure and civil footprint.
Methods to increase current density
Increased DLCs can be achieved by a number of different methods described in an excellent
paper on the subject10. Three main ways to increase the current density are suggested:
Optimizing the cell design
- EMEW Cell13
- Continental copper and steel (CCS) cell11
- Increased flow rate pattern and distribution in standard cell
Employing various types of forced convection
- Air sparging
- Ultrasonic agitation
Periodic current reversal.
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Table IV
Comparison of current density (A/m2) operating conditions of different cell types
Reported current densities A/m2
Type
Low
High
Traditional cell3,6,10,15,16
EMEW cell12,13
CSS cell11
Air sparging10
Ultrasonic agitation10
Periodic current reversal10
110
250
430
1000
3300
430
350
600
1000
3000
10500
---
The EMEW cell is a recent design used to produce copper powder and circular plate at high
flow rates and high current densities. The CCS cell is a redundant design that used nozzles
placed at the cathode face to improve flow patterns.
The present paper does not discuss the various types of improvements that can be made but
does note that significant increases in current density can be obtained by using the methods
listed above. Table III compares operating conditions that produce a stable adherent pure
copper product at vastly increased current densities. The table is based on information from
reference10 as well as other sources.
The reported figures for the various techniques are significantly greater than standard
practice and design currently allows for. There are negative effects at these current densities
such as:
Increased anode wear
Acid mist control
Corrosion of suspension bars
Cell potential
The total voltage across the cell can be divided into three components:
The reversible decomposition potentials (Vmin)
The activation and concentration overpotentials of the electrodes (a) (c).
The Potential drop due to Ohmic resistance of the electrolyte and the electrical contacts
(Vohm).
[65]
The reversible decomposition potential is:
[66]
This is the difference between the two standard reduction potentials for the species being
oxidized and reduced and is the minimum voltage required at standard conditions
The overpotential due to potential and concentration has been discussed previously and are
represented by the modified B-V equation as:
[63]
And for no concentration overpotential influences then
[28]
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The ohmic resistance due to the solution and the contacts are:
[67]
By Ohms law for a current flowing between the solution and an electrode. The relationship
between current drop and potential drop in an electrical conductor is5:
[68]
For current density in one direction only (parallel plates), Ohms law reduces to:
[69]
where the specific conductivity is a function of concentration and ionic mobility of the form5
[70]
The solution resistance and required potential difference is then a function of the
interelectrode gap, the ionic mobility, the concentration of the species in solution and the
current density applied to the solution.
Then for the electrowinning of copper from acid sulphate matrix:
[1]
[71]
[72]
Operated at a DLC of 300 A/m2 and an applied current density of 200 A/m2 (Cell 4
Conditions) the cathodic overpotential is:
[73]
For the production of oxygen at the anode, excluding the acid concentration overpotential,
the Tafel equation is3
[74]
This gives:
[75]
The solution and contact resistance can be taken as <0.6 V combined6.
Then the required cell voltage to obtain a current flow to produce copper cathode from
solution is
[76]
Copper electrowinning cell voltages are well standardized at ~2-2.3 V per cell.
Current efficiencies
The current efficiency is the ratio of the current producing the copper to the total current
applied to the cell. It is normally quoted in percentages. Practically it is determined by the
amount of copper produced divided by the amount of current applied to the system for a
theoretical amount of copper.
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[77]
The efficiency is strongly dependant on additional side reactions that occur, for the
electrowinning of copper the decomposition of water lowers the current efficiency. However
the single greatest effect is the presence of Iron in the solution. The cyclic oxidation and
reduction of dissolved iron can significantly reduce the efficiency of an operation. Iron can be
removed by a number of methods that include.
Solution precipitation
Prior reduction of iron (III) by SO2 or copper metal
Increasing the bleed stream volume
Use of a diaphragm cell.
Current efficiencies for direct electrowinning operations can be as low as 65% while
efficiencies for post SX electrowinning can be as high as 95%.
Part 2: Practical considerations
The following is based on a case study of the Ruashi BMR designed by TWP Matomo
Process Plant
Production rates
Production rates are usually specified by the client, depending on the mass balance and the
environment in which the electrowinning is to be designed for. Design conditions will
normally be in the region of specified rate plus 10%, this excludes availability.
Availability
Mechanical availability depends on the following factors:
Site conditions and location. The Ruashi BMR is located in Lubumbashi, DRC, and as
such, consideration was given to have stand-by units for all key mechanical equipment.
Operation within South Africa would not necessarily require the same design. Dual
availability design was included for cellhouse circulation pumps, feed to and return from
pumps servicing the cellhouse, overhead cranes, stripping machines (for which an
additional allowance was made to allow manual stripping of cathodes in a specifically
designated area in case of equipment breakdown). Both the loaded electrolyte pond
feeding the cellhouse as well as the spent electrolyte pond returning spent electrolyte
solution to the solvent extraction circuit is of split design, providing for maintenance on
the pond linings without having to shut down the plant
Maintenance programmes proposed or in place at the operation depend on site
management in terms of pro-active maintenance, service schedules, etc. This cannot
always be quantified, especially for new operations; however, in general, larger
established companies normally have a better maintenance system in place than small
companies
Education and experience level of both maintenance and operational personnel. Consider
geographic location of the area, whether there are existing operations from where
personnel could be sourced, language barriers, culture of work, political stability.
Current density
Depending on the type of operation, current densities can vary between 200 and up to about
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375 A/m2. Operations where Solvent Extraction precedes Electrowinning normally produce
cathodes with a good surface quality at higher current densities than direct electrowinning
operations. Furthermore, the clarity of the feed solution needs to be taken into account. The
Ruashi design includes multimedia coalescing filters for the removal of both solids as well as
organics from the Cu Feed solution before the solution reports to the Cellhouse. Process
Engineers are in general quite comfortable operating in the region of 250 to 300 A/m2 when
SX and multimedia filters are employed.
It is also advisable to consult the vendors of the rectiformers. There are standard designs for
the transformer-rectifier pairs, ranging in size from small up to 30 kA. For the Ruashi design,
two sets of 30 kA were purchased to satisfy the design requirement of 60 kA total DC supply
to the electrowinning cells. Depending on the rectiformer supply, the cell design can be
modified to suit.
Cathode centre to centre spacing
Design current density is also dependant on electrode spacing. The minimum spacing
recommended for Cu Electrowinning operations for cathode centre to cathode centre is 95
mm. Below this the risk of shorts due to electrode alignment and nodular growths is
considered to be unacceptably high.
Cathode quality
This is normally specified by the client. Within the Cellhouse, there are very few variables
that influence cathode quality; it is normally a function of the preceding purification steps.
Sampling specification and procedure
Sampling on site is normally done on site for in-house quality control purposes only. The
client usually sells his product through a third party, who will be responsible for sample
analysis. Some mining houses have accredited laboratories, in this case, the laboratory
analyze samples received from the plant. Two commonly used methods to obtain a sample are
to either drill holes in randomly selected samples on randomly selected locations of the
cathode. The drillings are then sent for analysis in the accredited laboratory. The second
method follows the same procedure, however instead of drillings; a manually operated
punching machine is used. It has to be taken into consideration that normal drill bits are not
used for the drilling of samples, since iron contamination of the samples frequently occurs.
Regarding the selection of cathodes in a group to be analyzed and the location on each
cathode, a standard procedure was published by the ISO organization. The standard title is
ISO 7156 Refined Nickel Sampling. No procedure for Copper sampling could be found
for Copper Sampling, however the same principles for Cu sampling as for Ni sampling is
assumed to be applicable.
Number of cells
This is dependant on a number of factors, including cell dimensions, real estate available for
the Cellhouse building, applied current density, production rate, DLC, current efficiency.
There is normally an equal amount of cells, making the busbar arrangement practical. Cells in
a Leach-Solvent Extraction-Electrowinning design should be split into scavenger and
production cells to limit organic contamination of cathodes in case of organic carry-overs
occurring at the Solvent Extraction Purification Plant. Scavenger Cells are then designed to
maintain the same cathode face velocity as for the Production/Commercial Cells of
approximately 0.08m3/hr/m2 cathode surface, the difference being that there is a once-off pass
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of electrolyte through these cells. The scavenger cells then produce the potentially poor
surface quality cathode by burning off any organic substances, before the bulk production of
cathodes in the commercial cells. For Ruashi, the design accommodated 24 scavenger cells,
which constituted exactly one bank of cells. This design facilitated easy piping arrangement
of feed and overflow to the cells.
Cellhouse layout
Practical considerations to be considered include optimizing availability and maintaining
flexibility inside the Cellhouse. For Ruashi, the Cellhouse was split into two sides, each
containing two banks of 24 cells. This configuration allowed the two stripping machines to be
placed in the middle of the Cellhouse, minimizing travel time for the cranes harvesting the
cathodes and returning blank cathodes to the cells. Furthermore, it allows one half of the cells
to be shorted out with relatively little effort, which came in handy during the commissioning
of the Cellhouse. The connecting busbar from the end of the Cellhouse was connected to the
centre of the Cellhouse, allowing a ramp-up stage of electrowinning on the one side, while
construction was still ongoing on the other side of the Cellhouse.
The distance between the end of the cell and the supporting structure of the Cellhouse has to
be taken into consideration in order to minimize the possibility of electrical accidents. A
distance of at least 2 to 3 metres is recommended. The same applies to the distance between
the cells comprising one bank and the opposite bank of cells (the middle of the Cellhouse
walkway).
Feed valves to the individual cells should be practically located in order to allow easy
operation of these valves, without interfering too much with the harvesting procedure. For
Ruashi, the feed valves were located on top of the cells in the middle of the Cellhouse
walkway.
Walkways need to be constructed from non-conductive material. Two options are available,
the one being wooden walkways, of which a high grade knot-free pine is considered the most
feasible option. Wood is then also treated with CCA (Copper/Chrome/Arsenic). The second
option is the use of FRP grating. This is much more expensive, but operating cost is much
lower. Certainly, for the areas close to the liquid, FRP will have to take preference, since the
timber will not last in this environment. For Ruashi, the majority of the walkways consist of
CCA treated timber, with some FRP inserts at the two ends of the cell to allow for visual
inspection of overflows.
Figure 2. Cell house layouts showing access platform, feed pipes
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Figure 3. Showing Intercell busbar and lead anode
Figure 4. Showing internal feed pipe arrangement
Figure 5. Showing Cathode bail removing four cathodes
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For practicality, the Cell Feed inlet pipes all run along the centre of the Cellhouse, allowing
for only two feed manifolds to feed the entire Cellhouse, that is, both the East and the West
Banks. The feed manifolds enter the Cellhouse at the electrical neutral point in case of the
production cells, and enters in the middle of the Cellhouse for the scavenger cells. This was to
accommodate piping where limited space was available between the two banks of cells.
Ideally, the scavenger cells feed manifold would also have entered the Cellhouse at the
electrical neutral point to minimize stray currents. Cell drain points were also located in the
centre of the building, thus allowing the civil slope of the floor to act as a run-off trench for
spillages. Spillages are thus mainly confined to only the centre of the Cellhouse, minimizing
acidic attack of the civil structures to only the centre of the building.
Piping layout
For practicality, the cell feed inlet pipes all run along the centre of the Cellhouse, allowing for
only two feed manifolds to feed the entire Cellhouse, that is, both the East and the West
Banks. The feed manifolds enter the Cellhouse at the electrical neutral point in case of the
production cells, and enters in the middle of the Cellhouse for the scavenger cells. This was to
accommodate piping where limited space was available between the two banks of cells.
Ideally, the scavenger cells feed manifold would also have entered the Cellhouse at the
electrical neutral point to minimize stray currents. Cell drain points were also located in the
centre of the building, thus allowing the civil slope of the floor to act as a run-off trench for
spillages. Spillages are thus mainly confined to only the centre of the Cellhouse, minimizing
acidic attack of the civil structures to only the centre of the building.
Cell elevation
In order to facilitate the gravity overflow of cells to the Circulation Tank, cells need to be
elevated of the ground. When elevation is already a necessity, it is then useful to elevate the
cells high enough to accommodate access for personnel to inspect the civil structures from
time to time, especially since the Cellhouse is such a corrosive environment. Additionally,
floor space underneath the cells can then also be used as storage space for cell furniture. The
Ruashi Cells were lifted approximately 1,6 m of the ground. Even so, the terrace level of the
Tankfarm had to be lowered to allow overflow into the Circulation Tank. Additionally, the
Circulation Tank was designed low with a high floor space (3,5 m high by 12,5 m diameter) to
further accommodate gravity feed into the tank.
Cell potential and current efficiency
Cell potential is a function of the respective half reaction potentials, losses through
electrolyte, busbars and competing reactions. It is normally in the range of 1,9V to 2,3V,
lower for the purer Leach-SX-EW operations than for the direct electrowinning operations.
Current efficiency for direct electrowinning operations can be as low as 65%, and for LeachSX-EW operations up to about 93%. It depends on the concentration of Fe in the feed
solution, as well as proper housekeeping to ensure good electrical contact between electrode
hanger bars and the triangular busbars.
Cathode face velocity
A number ranging between 0,05 and 0.1m3/hr/m2 of cathode surface area available for plating.
It influences the surface quality of the cathode by breaking down the diffusion layer, but too
high a face velocity can cause flushing of the cathode surface area, creating an area of no
plating where the feed is introduced into the cells. For Cu Electrowinning operations, a face
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Figure 6. Overflow launders between cells
Figure 7. Showing Copper busbars
Figure 8. Showing cathode stripping machine
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velocity of 0.08 is normally employed. The cathode face velocity will then determine the flow
rate per cell, and thus the internal recycle required inside the Cellhouse.
Feed and spent tenors
The Leach and Solvent Extraction processes will determine the copper and acid tenors of the
feed to the Cellhouse. For Leach-SX-EW operations, feed tenors of Cu can go as low as
25 g/l Cu, depending on the applied current density, which will have to be reduced as the Cu
tenor is reduced. The sulphuric acid tenor of the feed solution is a function of the stripping
process inside SX, and that of the spent solution is a function of the rate of copper production,
where a stoichiometric balance exists of 1,98 g of acid produced for every gram of copper
plated.
The Ruashi EW operation was started up with unpurified Primary Leach Solution at a pH of
~1,8 and a Copper tenor of 24 g/l, the resultant cathode had a very good surface quality, albeit
at an applied current density of only 75 A/m2. Raising the current density to 110A/m2 resulted
in the formation of nodules, but this was attributed to no control over the flow rate (cathode
face velocity) to the cells. Since the flow rate was increased, good surface quality cathodes are
achieved at current densities of 100A/m2 and Cu tenors of ~27 g/l. Ruashi design caters for a
Cu Feed tenor of 50 gpL and a Cellhouse bite of 5 g/l Cu, at these operating conditions; the
design applied current density of 275A/m2 is expected to deliver good surface quality
cathodes. This has not yet been achieved at Ruashi, due to the SX section still being
constructed and the front end of the plant still being commissioned.
Cathode harvesting
The cathode harvesting cycle was designed so as to accommodate a deposit thickness of
~5mm. The thickness is dependant on the capability of the stripping machines to separate the
copper from the blanks, for which the stripping machine suppliers have to be consulted.
Furthermore, the longer a cathode is allowed to plate in a cell, the higher the risk of shorting
becomes due to the exponential nature of nodular growths inside the cell. A harvesting cycle
of more than eight days is not recommended, but this is again dependant on the applied
current density (rate of plating).
Busbar design
In order to minimize heat losses through the busbars, the current density through the busbars
have to be limited. Conservative clients prefer not to go above 1A/mm2, while design
companies are normally quite comfortable designing busbars at 1,2A/mm2. Of importance is
to run parallel busbars with a gap between them so as to allow heat reduction through air
cooling. The Ruashi busbar designs for the main busbars were 6 busbars, each of size 450 mm
x 20 mm, separated by a 20 mm gap between each busbar. This fulfilled the 1,2A/mm2
requirement for the total design current of 61kA.
Intercell busbar design
Two options are available for the design of intercell busbars. Conventional dogbone type of
designs was previously employed and is still preferred by some clients. It is however much
more expensive than triangular busbars, due to the larger amount of copper needed. Triangular
busbars are a more viable option, provided that proper consideration is given to the design and
layout of contact points between hanger bar (cathode and anode) and triangular busbar. It
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becomes even more critical when the design had to cater for cathodes that are symmetrical to
cater for the 180o rotation during the stripping operation. Furthermore, due consideration
needs to be given to the different elevations between cathode and anode hanger bars on the
cell to allow for shorting out of the cell with a shorting frame. Although this can be avoided if
a bullhorn anode hanger bar design is employed, it is unnecessary and a straight anode hanger
bar design allows for the maintenance of anodes using the same bailer as is used for cathode
harvesting.
Cathode design to cater for hooking by the bailer can be through either cut-outs from the
cathode surface above the liquid level, or through the attachment of stainless steel fish-eyes to
the hanger bars. Fish eyes are economically more feasible since it comprises less work for the
suppliers. It then implies that cut-outs are made from the anode surfaces to accommodate the
use of one bailer size to both harvest cathodes as well as do anode maintenance.
Dimension and number of electrodes per cell
Cathode size is selected to accommodate industry standards, where shipping of cathodes in
containers as well as furnace openings in the production industry has to be taken into
consideration. Client liaison will normally give a good guideline as to cathode sizing. Anodes
are designed at least 30 mm bigger than cathodes on both the width and the height (wetted
dimensions). This is to ensure that copper plating does not occur around the sides of the
cathode. There will always be one more anode than cathode per cell, and depending on the
harvesting design, either every second or every third cathode is harvested per pull. Using the
standard design of every third cathode, cathodes per cell then have to equal multiples of three.
Anode composition and type
New electrowinning operations at the moment almost exclusively employ cold-rolled lead
anodes, since it yields better dimensional stability. Standard additions to the lead anode
includes a fraction of Calcium (0,05 to 0,08%) and Tin (1,2 to 1,5%). Anode life expectancy
is in the order of 7 to 9 years.
Electrode furniture
Anode buttons from non-conductive PVC material is readily available on the market. Three
to five anode buttons are located to the anode, that being in the two bottom corners of the
anode, one in the centre of the anode, and an optional two at the two top corners of the anode.
The anode buttons prevent shorts between cathode and anode. Edge strips are located to the
edges of the stainless steel cathodes to ensure that the two sides of the cathode are not
intergrown. Various types of edge strips are available. Ruashi and various EW operations in
Zambia employ the Rehau cross-slot configuration of edge strips. It is important to design
the edge strips long enough so that it ends well above the liquid level of the cell, since liquid
between the edge strip and the cathode will cause metal plating and thus damage to the edge
strips.
Electrowinning cells
Continuous improvement to the polymer concrete industry has led to the almost exclusive use
of polymer concrete as material of construction for electrowinning cells. There are two main
suppliers in Southern Africa, they being CSI and PCI. Product quality from both suppliers is
acceptable and the Copper industry in Zambia is split almost equally between the two
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suppliers. The polymer concrete cells contain a fiberglass lining, which is part of the
moulding/casting process. This further protects the concrete from acid attack. Other
operations use lead linings or normal concrete with fiberglass lining moulds to house the
electrowinning process. This is not feasible for new operations.
Cathode stripping
Various suppliers can custom design stripping machines for the electrowinning operation.
Options include fully automatic machines, semi automatic machines and options for water
spray rinsing booths. Design considerations should include simplicity if the machine is used
in remote locations, availability of spares, stripping rate and capital expenditure. Ruashi
employs two semi-automatic Styria stripping machines; this gives flexibility in case of a
breakdown as well as ease of maintenance.
Plating agents
Various smoothing agents are commercially available, ranging from glues to guars to
synthetic products. It is best to test these in research facilities such as at Mintek to determine
the effect of the smoothing agent on current efficiency and surface quality of the cathode.
Dosage rates range from 150 to 400g of smoothing agent per ton of Cu produced. Chloride
levels inside the Cellhouse should be kept below 30ppm to ensure the stainless steel cathodes
are not corroded. Addition points can be at the Circulation Tank for the Commercial Cells and
inline at the Feed manifold for the Scavenger Cells. Care should be taken to design the
Scavenger system so as not to have reverse flow of electrolyte back into the smoothing agent
supply tank, as such a non-return valve is recommended in-line for the scavenger cells
smoothing agent supply.
Acid mist management
Hollow polypropylene balls are commonly employed in Cellhouses. Additionally, synthetic
foaming agents are available, the effect of these on the Solvent Extraction should be
considered. Designing a Cellhouse with open sides helps with natural ventilation, and if
CAPEX considerations are not of primary importance, extraction fans can be employed to
minimize acid mist.
Temperature management
Feed to the Cellhouse could be heated using heat exchangers, the optimum temperature is
considered to be in the range of 45 to 55C for optimum electrolyte conductivity. Due to heat
generation inside the Cellhouse, a cooling heat exchanger is then required for both circulating
electrolyte and spent electrolyte. Solvent Extraction plants which use Spent electrolyte for
stripping need to be maintained below 40C to prevent the degeneration of the organic phase.
Inventories
For optimum plant availability, sufficient storage capacity is required. Ruashi employs split
ponds with double liners and leak detection systems. In designing the storage pond systems,
consideration need to be given to the type of pumps to be used. Options available include selfpriming pumps (Sulzer) or conventional pumps with priming tanks. The self-priming pumps
employed at Ruashi have proved to be difficult to commission, and to date little support from
the supplier was received. Additionally, self-priming pumps are considerably more expensive
than the combination conventional pump and priming tank system.
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Cathode washing
Heated dip tanks are allowed for at the Ruashi BMR, however other systems available include
the use of heated water spray systems or, as previously mentioned, spray systems as part of a
stripping machine.
Electrolyte filtration
Scheibler filters are employed in industry to aid in the filtration of circulating electrolyte,
there-by reducing the need to clean cells. Capital expenditure availability has to be
considered, and if a filter is not part of the initial design, real estate allowance should be made
to later locate the filter when client finances allows.
Conclusions
The above paper has two parts, the first part describes the theoretical requirements for copper
electrowinning and the second part describes the practical requirements based on the Ruashi
case study.
The first part is based on the fundamental equations of reaction rate kinetics and
thermodynamics as well as hydrodynamics to describe the baseline equations that can be used
in designing a copper electrowinning process. The important considerations for the designer
are determination of the Diffusion Limited Current and the appropriate selection of the
operating current. These numbers which are based on numerous variables such as flow rate to
cell, cell bite, plating area, copper, acid and iron concentrations, temperature of electrolyte
and current efficiency will determine the structural size and footprint of the copper
electrowinning process building. They have the largest effect on overall capital cost and
consequently the timeline of building the process plant. It has been discussed that the use of
high current densities requires some modifications to the conventional 100 year old
electrowinning cell design. Conventional cells are operated at maximums of approximately
~350-400A/m2 but most designers will not exceed these values in conventional designs, with
good reason. With adequate hydrodynamics and increase of the Diffusion Limited Current the
capital cost of a copper electrowinning building can be reduced. There are problems
associated with this, particularly acid mist generation. Adequate ventilation systems or
enclosed hoods similar to those used in the nickel industry can be used. Any designer straying
from the path of tried and tested technology should confirm the new design with appropriate
test work before committing the clients project and their career to the annals of technical
success or failure.
The second part of the paper discusses practical requirements around the electrowinning
building and process areas based on the Ruashi case study. A significant number of issues
need to be addressed during the design phase to ensure a successful project and an operable
plant. Key aspects such as plant location and skill set are critical. Physical aspects such as
electrolyte storage, operating temperatures, cell sizes, busbar design, circulation tank and
piping layout are very important. Plating and leveling agents need to be considered. Cathode
product handling and acid mist control are vital.
Acknowledgement
The authors would like to thank Metorex the owners of Ruashi BMR for the opportunity to
present their findings.
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Nonmenclature
Symbol
Q
I
n
F
M
i
A
dQ/dt
dM/dt
G
o
G
R
T
n
aP
m
aR
aRed
aOx
V
W
E
kd
kr
Ox
Red
e
kf
Cox
ic
ia
krev
Cred
ko
o
E
o
E
io
Eeq
Nox
D
(x,t)
238
Definition
Charge
Current
Valance
Faradays constant
Number of Mols
Current density
Area
Charge per time
Mols per time
Gibbs free energy
Standard Gibbs free energy
Universal gas constant
Temperature
Activity of products
Activity of reactants
Activity of oxidized species
Activity of reduced species
Potential
Work
Potential
Mass transfer coefficient
Reaction rate constant
Oxidized species
Reduced species
Electrons
Rate constant of forward reaction
Concentration of oxidized species
Current density of cathodic reaction
Current density of anodic reaction
Rate constant of reverse reaction
Concentration of reduced species
Rate constant at equilibrium
Separation factor
Formal electrode potential
Standard electrode potential
Activity coefficient
Exchange current density
Equilibrium potential
Overpotential (overvoltage)
Mass flux of oxidized species
Diffusion coefficient of species
Species vector at time t and position x
SI Units
Coulombs
Amps, C/s
gEq/gmol
C/gEq
gmol
A/m2
m2
C/s
gmol/s
J/gmol
J/gmol
J/(gmol.K)
Kelvin
Dimensionless
Dimensionless
Dimensionless
Dimensionless
Volts
Joule
Volts
m/s
1/s
Dimensionless
Dimensionless
Dimensionless
1/s
gmol/m3
A/m2
A/m2
1/s
gmol/m3
1/s
Dimensionless
Volts
Volts
Dimensionless
A/m2
Volts
Volts
gmol/(m2.s)
m2/s
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v
d/dx
ra
rox
rred
dx,dy,dz
iL
Re
L
Sc
Sh
de
Gr
g
Ts
T
Pr
Cp
k
Ra
Nu
Le
Va
Vc
Vmin
Vohm
Vir
Vcontacts
ui
10:52 AM
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Velocity of species
Potential gradient across electrolyte
Laplace operator
Reaction rate for species a
Reaction rate for oxidized species
Reaction rate for reduced species
Distance in x,y and z directions
Boundary layer thickness
Diffusion limited current
Reynolds number
Characteristic length
Density
Viscosity
Schmidt number
Sherwood number
Characteristic length/hydraulic diameter
Grashof number
Gravitational acceleration
Thermal expansion coefficient
Temperature at the surface
Temperature at bulk
Prandtl number
Specific heat capacity
Thermal conductivity
Rayleigh number
Nusselt number
Lewis number
Anodic standard electrode potential
Cathodic standard electrode potential
Decomposition potential
Ohmic resistance
Solution potential
Contacts potential
Resistivity
Ionic mobility of species i
Current efficiency
m/s
Volts/m
------gmol/(m3.s)
gmol/(m3.s)
gmol/(m3.s)
m
m
A/m2
Dimensionless
m
kg/m3
kg/(m.s)
Dimensionless
Dimensionless
m
Dimensionless
m/s2
1/K
K
K
Dimensionless
J/(kg.K)
W/(m.K)
Dimensionless
Dimensionless
Dimensionless
Volts
Volts
Volts
Volts
Volts
Volts
S/cm
gmol.cm2/(J.s)
percentage
References
1. HAYES, P.C. Process Principles in Mineral and Materials Production, Hayes Publishing
Co., 1983.
2. PETRUCCI, R.H. AND HARWOOD, W.S. General Chemistry Principles and Modern
Applications, Prentice Hall International, Inc., 1993.
3. LORENZEN, L. Mineral Processing Class Notes, Electrochemical Reactor Design,
University of Stellenbosch, 2000.
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4. INCOPERA, F.P. and DEWITT, D.P. Fundamentals of Heat and Mass Transfer, John
Wiley and Sons, Inc., 1996, (4th Edition), Chap 6, Chap 9.
5. PERRY, R.H. and GREEN, D.W. Perrys Chemical Engineers Handbook, McGraw-Hill,
1997.
6. JACKSON, E. Hydrometallurgical Extraction and Reclamation, Ellis Horwood Limited,
1986, Chap 5.
7. WANG, J. Analytical Electrochemistry, John Wiley and Sons, Inc., 2001, (2nd Edition).
8. ZANELLO, P. Inorganic Electrochemistry: Theory, Practice and Application, The Royal
Society of Chemistry, 2003.
9. BRETT, C.M.A. and BRETT, A.M.O. Electrochemistry Principles, Methods, and
Applications, Oxford University Press, Inc., 1993.
10. MACKINNON, D.J. and LAKSHMANAN, V.I. Recent Advances in Copper
Electrowinning, Mineral Research Program, Mineral Research Laboratories, CANMET
Report 7610, 1976.
11. ANDERSEN, A.K. and BALBERYSZSKI, T. Electrowinning of Copper at High Current
Densities with the CCS Cell, The Metallurgical Society of AIME, TMS Paper Selection,
Paper A68-17, 1968.
12. ESCOBAR, V., TREASURE, T., and DIXON, R.E. High Current Density EMEW
Copper Electrowinning, Electrometals Technologies Ltd. Official Website.
http://www.electrometals.co.au.
13. ROUX, E., GNOINSKI, J., EWART, I., and DREISINGER, D., Cu-Removal From the
Skorpion Circuit Using EMEW Technology, The South African Institute of Mining and
Metallurgy, The Fourth Southern African Conference on Base Metals, 2007.
14. Short course on Electrochemistry, Electrochemical Engineering and Electrometallurgy:
Module on Thermodaynamics and Kinetics, University of the Witwatersrand,
Johannesburg, 2005.
15. SANDENBERGH, R. University of Pretoria Electrochemistry Class Notes, 2007.
16. HOULACHI, G.E., EDWARDS, J.D., ROBINSON, T.G. Cu 2007, vol. V, Copper
Electrowinning and Elecrorefining, Toronto, Metsoc Publication, August 2007.
17. Short course on Electrochemistry, Electrochemical Engineering and Electrometallurgy:
Module on Applications of Fundamentals to Electrowinning and Electrorefining of
Metals. University of the Witwatersrand, Johannesburg, 2005.
Nicholas Terence Beukes

Process Engineer, TWP Matoma Process Plant, South Africa
Nick has worked as a process engineer for seven years since
graduating as a chemical engineer. Experience includes projects
commissioning for Anglo Platinum copper-nickel matte smelting and
converting. Following that he has worked as a process design engineer
involved primarily in mass and energy balance, pipe and
instrumentation, process flow diagrams and equipment selection and
sizing, mechanical layout and functional specification design and development. The above
includes ore beneficiation, hydrometallurgy and pyrometallurgy applications, such as chrome
recovery, gold, uranium and base metal refining.
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LAITALA, H.T. Developments in organic holding tank structure for solvent extraction processes.
Developments in organic holding tank structure

for solvent extraction processes
H.T. LAITALA
Outotec Oyj, Finland
Traditionally every solvent extraction process contains an organic

tank. The purpose of such a tank is to provide constant feed to the
organic pumps and to offer the buffer volume needed for the dynamic
variations in the organic phases inventory. A conventional organic
tank is a large piece of equipment, requiring a large footprint in the
SX process area, and it contains a high inventory of costly organic
phase. The latest development in organic holding tanks is a
combination of the organic tank and a mixer-settler unit, and thus no
separate organic tank is needed in the solvent extraction process. This
new generation organic tank has several additional important process
tasks to perform. These include removal of the aqueous entrainment
coming from the extraction stages, washing of the organic phase
before organic is sent to the stripping stage(s), and the organic
inventory in the whole SX process can be minimized. Organic
inventory reduction can vary from 10 to 40% of the conventional total
organic inventory. The current development in the design of the
organic tank makes the investment in the SX process cheaper, with
the added benefits of higher electrolyte quality and lower operating
cost.
Introduction
A conventional organic holding tank in a solvent extraction process is a tank that provides a
constant feed to the organic pumps. The physical size of the new, innovative organic tank
design is comparable to a settler unit, while a conventional organic tank can contain up to
40% of SX process organic inventory. In this paper different organic tank modifications are
presented. All these organic tank modifications are in use or will be taken into service in the
near future. The aim of these modifications is to reduce the total investment and operating
costs of a solvent extraction-electrowinning (SX-EW) plant, while maintaining product
quality and quantity.
Conventional loaded organic tank
A conventional loaded organic tank is primarily an organic holding tank that provides
DEVELOPMENTS IN ORGANIC HOLDING TANK STRUCTURE
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constant feed to the organic pumps in the solvent extraction process, hence providing buffer
capacity for any organic phase inventory changes. A schematic drawing of a conventional
organic tank is shown in Figure 1 below.
The conventional organic tank can be located after the stripping stages (barren organic tank
= BOT) or after the extraction stages (loaded organic tank = LOT). For copper and zinc
solvent extraction processes, a LOT is usually preferred, but for other metals such as Ni and
Co a barren organic tank can also be installed for process reasons. In Cu and Zn SX processes
LOT can be used to wash out physically and chemically entrained impurities. In Ni and Co
SX processes BOT can be used for organic phase pretreatment purposes before the extraction
stages.
The shape of the conventional organic tank is unimportant and can be round or rectangular.
The effective residence time of a conventional organic tank is usually between 30 and 60
minutes. Construction material for the organic tank generally is concrete with a liner.
Commonly used liners are for example FRP, HDPE or stainless steel. Organic tanks can also
be made from FRP or stainless steel with external supports.
In a conventionally designed organic tank no reduction of physically or chemically entrained impurities can be expected and no specific flow patterns inside the organic tank are
used. For the conventional organic tank arrangement, equipment investment cost is low,
organic inventory cost is high, and operational cost for the SX-EW process is high.
Loaded organic tank with entrainment removal and washing functions
The modern organic tank in a solvent extraction process has multiple tasks including
provision of constant flow to the organic pumps, and to remove and wash out impurities from
the incoming organic phase (Figure 2).
The design of this modern organic tank is usually rectangular and the tanks effective retention time is 15 to 30 minutes, which is significantly shorter when compared to that of a
conventional organic tank. The organic tanks shape is important because a certain flow
profile has to be achieved inside the tank. It is equipped with coalescing zones, where
physically entrained aqueous impurities can be coalesced and separated from the organic
phase. In these zones 5090% of the physical entrainment can be removed. This generation of
organic tank can also be equipped with a washing/scrubbing function, where aqueous phase is
circulated inside the organic tank. Washing is done with pure water and scrubbing is done
with acidic, metal containing aqueous solution (depending on the specific process under
consideration).
Figure 1. Conventional organic tank
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Figure 2. Outotecs organic tank with entrainment removal and washing functions
Figure 3. Loaded organic tank with entrainment removal and washing/scrubbing functions. Total organic flow
2 500 m3/h
Because separate dispersion-creating pumps and mixers are not used in this design, removal of impurities that were chemically transferred to the organic phase during extraction is
limited to 2050%, depending on the impurity type and the washing/scrubbing conditions
being employed. This type of LOT is used, for example, at Escondida, Cobre Las Cruces and
Sepon Copper.
An alternative LOT design includes a washing/scrubbing function (Figure 3) that can be
used in some cases as the primary stage of organic phase washing, generally where a separate
washing stage is not justified, but some impurity removal from the loaded organic is still
needed. A LOT with a washing/scrubbing function can also be installed to assist a separate
washing stage in cases where PLS (pregnant leach solution) impurity levels are very high or
difficult to handle.
The capital investment required cost for a LOT with a washing/scrubbing function is lower,
organic inventory cost is lower, and operational cost for the SX-EW process is lower when
compared to an SX-EW process employing a conventional organic tank.
Combined lot and mixer-settler stage
It is also possible to combine a mixer-settler stage with the organic tank. This is illustrated in
Figure 4.
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Figure 4. Combined mixer-settler and organic tank
Figure 5. Design of the Franke-project combined washing mixer-settler and organic tank
The combination of a mixer-settler unit and an organic tank exhibits all the main features of
individual mixer-settler and LOT/BOT units. This combination can be done to any solvent
extraction stage, but the combination is most suited to the first extraction stage, last stripping
stage or washing stage. This combination can reduce the solvent extraction organic inventory
by 1040% and the total SX process investment cost from 1025%. This SX process upgrade
will be taken into service by Franke-project in Chile in year 2009 (Figure 5). This equipment
and process is proprietary technology of Outotec.
From Figure 6 it can be seen that the combination of a mixer-settler unit and an organic tank
reduces the SX plant area around 1020%.
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(a)
(b)
Figure 6. Mixer-settler units combination with an organic tank and its effect on the SX process layout (a = SX layout
with configuration 3E+1W+1S+LOT, b = same SX layout but with combined washing stage and loaded organic tank)
Figure 7. Process connection of the conventional organic tank and mixer-settler units, and that of the new approach
where the mixer-settler unit and organic tank are combined
Impurity removal in a loaded organic tank

The conventional link between the organic tank and the mixer-settler units and that of the
more modern arrangement where the mixer-settler unit and organic tank are combined are
presented in Figure 7.
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Figure 8. Impurity removal in a Cu SX-EW process
Table I
Effect of impurity removal on Cu EWs bleed stream
Conventional organic tank, no separation, no washing
Income organic
A/O entrainment from SX
CI concentration in aqueous
Electrolyte CI max. conc.
Electrolyte bleed
1 000 m3/h
300 ppm
10 000 ppm
30 ppm
100 m3/h
Outotec organic tank, separation, no washing

Income organic
Electrolyte bleed
1 000 m3/h
300 ppm
10 000 ppm
30 ppm
25 m3/h
Outotec organic tank, separation, and washing

Income organic flow
Electrolyte bleed
1 000 m3/h
300 ppm
10 000 ppm
30 ppm
2.5 m3/h
In Figure 8 and Table I an example is calculated of how the different process connections
affect the EW bleed stream. In this example, the main impurity has been the physically
entrained chloride ion in the copper electrowinning circuit. Similar calculations can be made
for example, to iron, aluminum, manganese and calcium.
Conclusions
In the new generation organic tank designs, several process tasks can be combined. Conventionally the organic tank acts as a dynamic volume for the SX process organic phase, but it
can also be employed to reduce the amount of physically and chemically entrained impurities,
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and provide residence time for the SX reactions to proceed. By combining an organic tank
with a mixer-settler stage, the overall SX process organic inventory will be reduced, thus
reducing the associated fire risk and the first fill cost of the SX process. The total plant size
and the number of main process equipment pieces will also be reduced, thus lowering the
project investment cost while not jeopardizing the cathode quality and quantity.
Hannu Tapani Laitala

Process Manager, SX Technology Manager, Outotec Oyj, Finland
2005
Outotec Oyj, Base Metals, Hydrometallurgy, SX Technology

Manager
20022005 Ashland Specialty Chemicals, Porvoo Polyester Plant, Finland,
Plant Engineer
19992002 JP-Engineering, Process Design Department, Vantaa, Finland,
Senior Process Designer
19971999 Outokumpu Engineering Contractors, Project Implementation
Department, Espoo, Project Engineer
19941997Outokumpu Harjavalta Metals, Ni Refinery, Harjavalta, Finland, Process development
engineer at Harjavalta Nickel plant (leaching, purification, Co SX, hydrogen reduction and EW)
Relevant project experience
20082010 Tia Maria, Peru, SPCC Cu SX-EW Plant, Process Manager, SX technology manager,
(responsible for the technical solutions used in the project).
20082009 Chambishi, Zambia, Chambishi Metals Plc Cu SX Plant, Process Manager, SX
technology manager (responsible for the technical solutions used in the project).
20082009 Harjavalta, Finland, Norilsk Nickel Ca SX Plant, Process Manager, SX technology
manager (responsible for the technical solutions used in the project).
20072009 Franke, Chile, Centenario Copper Cu SX-EW Plant, Process Manager, SX technology
manager (responsible for the technical solutions used in the project).
20072009 Miheevsky, Russia, RCC Cu SX-EW Plant, Process Manager, SX technology manager,
(responsible for the technical solutions used in the project).
20072009 Assarel, Bulgaria, Assarel Medet Cu SX-EW Plant, Process Manager, SX technology
manager, (responsible for the technical solutions used in the project).
2008
EdZ, Spain, Espanola del Zinc Hydrometallurgical Plant, Process Manager, SX
technology manager, (responsible for the technical solutions used in the project and pilot run).
20072008 Pueblo Viejo, Dominican Republic, Barrick Gold Hydrometallurgical Base Metal Plant,
Process Manager, SX technology manager, (responsible for the technical solutions use in
the project and pilot run).
20052006 Outokumpu Technology, Finland, New Generation SX Cell, SX Technology Manager,
design and development of a new generation SX cell.
20052006 Outokumpu Technology, Finland, New Generation SX Mixers and Separation Fences,
SX Technology Manager, Design and development of a new generation SX equipment.
2006
Mopani Copper Mines Plc, Zambia, Co Plant Audit, Project Manager, Technical audit of
the Co plants leaching, solution purification and EW departments.
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19942005 Many implementation projects for different customers mainly in Finland and Europe for
metallurgical and chemical industry, Senior Process Designer, Project Manager and
Engineering Manager.
Extension courses
2005
1999
1999
248
AELCentre for technical training, Examination for pressure equipment supervisors,

2003 TUKES, Safety Technology Authority in Finland, examination for supervisors of
usage and storage of flammable and explosive chemicals.
Helsinki University of Technology, Metallurgy, 48 CEUs.
Helsinki University of Technology, Plant Engineering, 18 CEUs, Patent no 107236:
Method to reduce the SX cells physical size and a SX cell to be used in a SX process.
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MARSDEN, T. and JICKLING, J The next generation of permanent cathode and lead anode technology.
The next generation of permanent cathode and

lead anode technology
T. MARSDEN* and J. JICKLING
*Thuthuka Group Ltd, Johannesburg, South Africa
EPCM Services Ltd, Toronto, Canada
The demand for continuous improvement in the industrial world is an
ongoing process. Some sectors, where the competitive forces are well
established, have led the development of new and reliable
technological innovations. Although the metallurgical industry can
rightfully be proud of its process improvements, there is still work to
be done in materials and in material handling. In some cases, the
improvements will be as simple as adopting technologies that have
been perfected in other processing or manufacturing industries.
This paper discusses the next design generation for copper
tankhouses which will yield:
Improved copper quality
Improved equipment availability
Lower life cycle costs
Safer operations.
These benefits will be realized through new developments and
design improvements in:
Permanent cathodes
Cathode washing
Cathode stripping machines
Anode preparation machines
Improved lead anode design
Recycling of lead anodes and refurbishment of cathodes.
The demand for base metals, and in particular copper, has led to
more research into improving efficiencies in electrowinning and
refinery plants around the world.
One of the areas previously taken as a matter of course was the
production of lead anodes and stainless steel cathodes. In South
America alone there are over 600 000 cathodes and anodes in
circulationa very significant figure.
Lead anodes
Much has changed in the manufacture of lead anodes over the past 50 years.
Alloys
Similar to the automotive battery, antimony was the first metal to be used as an additive to
THE NEXT GENERATION OF PERMANENT CATHODE AND LEAD ANODE TECHNOLOGY
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improve the grain structure and give the anode more mechanical strength. The additional
strength was mainly required to give the anode blade more rigidly and reduce shorting caused
by the anode buckling due to deformation occurring during normal handling in the cleaning or
stripping process. Six% to 8% antimony was added to the refined lead. Antimonial lead was
used in the recovery of copper, cobalt and nickel. One% silver alloy was used for the recovery
of zinc and manganese. The automotive battery manufactures had in the interim reduced the
antimony content in their alloys with the addition of arsenic and selenium, and subsequently
introduced calcium as an alloy, particularly in relation to the maintenance free battery.
Calcium, for the same reason, was first introduced worldwide as an additive to a silver lead
alloy in a patent developed by Michael Thom in South Africa in 1982. The addition of
calcium enabled the end user to reduce the silver content first from 1% to 0.75% and then
eventually to 0.5%. Prior to this the silver lead alloy anode was easily bent, causing shorting
on contact with the cathode. The addition of the calcium gave the blade more rigidity and
increased the life of the anode by more than double.
Calcium, with tin and aluminium, was then introduced into anodes for the recovery of
copper, nickel and cobalt. Whereas lead antimonial and silver lead alloys cast relatively easily,
problems were encountered in casting calcium lead alloys, which necessitated a change in
manufacturing techniques.
Method of manufacture
Casting
Initially the anodes were cast in book-type moulds. Casting was from the top with the copper
hanger bar in position. To get sufficient flow and give sufficient strength the anode, blade was
cast up to 16 mm thick. Casting from the top resulted in air entrapment, dross inclusion and
hot spots in the centre of the anode. The latter items all increased corrosion of the anode,
reduced the life of the anode, and in some cases increased the migration of lead into the
electrolyte.
Another South African first was the introduction of a semi-pressure die casting method by
casting the anode through a valve and runner at the bottom of the mould. The runner (later cut
off from the blade bottom) absorbed the heat and eliminated the hot spot. The lead pushed the
air upwards and escaped through air vents above the copper hanger bar. The moulds are
hydraulically operated and water cooled. It must be emphasized that temperature control is
critical in the process.
Rolled anode
At the time South Africa was a leader in the improvement of casting lead anodes. The same
success was not achieved elsewhere, particularly with calcium lead alloys, and in some cases
this accelerated the introduction of the anode with a rolled blade. The automotive battery
manufactures had moved to a process involving a continuous cast rolling mill producing thin
lead plates.
The electrical flux density (the capacity of a conductor to convey electrical current) is
directly proportional to the grain size and grain structure in the metal conveyer. The smaller
the grain size, the better the electrical current properties. It was found by rolling the blades,
particularly in the case of calcium lead, the size of grain structures decreased. Lead, similar to
copper, also work hardens. The rolling also increased the mechanical strength of the blade.
The anode manufacturers cast the header bar section (encapsulating the copper in position)
and rolled lead plates on a conventional rolling mill. The lead blade was then lead burnt
(welded) to the header bar section.
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In the case of calcium lead, it is extremely difficult and in fact not practical to weld calcium
lead sheet to calcium lead sheet. The calcium lead oxidizes immediately on the introduction of
the welding heat. It is virtually impossible to weld once it is oxidized. As a result it was found
that the hanger bar had to be cast in antimonial lead (normally 6% antimony) and then welded
to the calcium rolled plate using a flux and antimonial rod. It is a well-known fact that even in
steel the weld is more susceptible to corrosion than the rest of the plate. Lead and the other
base metals are not the exception.
Another method of overcoming the above welding problem was slotting the lead blade into
the pre-lead plated copper hanger bar and soldering the blade in place.
In 2005 John Turner and Thomas Meyer developed a patent for the manufacture of a rolled
anode with no weld or joint between the lead and copper hanger bar. This was a seamless
rolled anode and was described by a leading international consultant as the first meaningful
innovation in lead anodes in 20 years. In principle, the patent is held on the process whereby a
complete anode with its busbar cast in position and the blade portion of the anode then put
through a rolling mill and the blade thickness reduced with resulting benefits including the
reduction of grain size, added mechanical strength and weight reduction. The seamless rolled
anode is manufactureds as follows:
Plant and equipment
A casting facility incorporating water cooled hydraulically operated mould.
A patented rolling mill, which enables the cast anode to be rolled with the copper busbar
in position with a minimum of 5 mm lead encapsulated around the copper and
eliminating all soldered or welded joints.
Method of manufacture
After casting the anode is rolled with the copper busbar section in position and reduced by
30% to 40%. This work hardens the metal hence giving the anode more rigidity, and the lead
has a finer grain structure, giving the anode a longer life than a cast anode.
Conventional rolled anodes as described are being supplied to base metal electrowinning
plants around the world. While these conventional rolled anodes are an improvement on a cast
anode, the conventional rolling method has the following disadvantages when compared to
the patented anode.
The conventional rolled anode has a welded or soldered joint. The weld is dependent on
manual welding (lead burning) which is subject to human error. The same applies to a
soldered joint, which could be prone to corrosion from mechanical damage to the plated
lead layer. The corrosion attack on the weld is at times greater than that on the rest of the
anode and as a result the solution level in the cell may have to be kept lower than the
level of the weld of the anode. The weld leads to the common corrosion found in the
liquid gas phase corrosion area, which is often the most severely attacked area in a
reaction vessel. The soldered joint is also subject to splashing and any mechanical
damage to the plated copper busbar will expose the copper to a corrosion attack. The lead
covering on the cast header bar is at least 5mm thick, which will protect the copper
busbar.
The conventional rolled calcium anode has a calcium lead blade but the lead used
covering the header bar is often antimonial lead (As mentioned, the antimonial lead
facilitates the welding of the joint.) When recycling, the two different alloys (antimonial
and calcium) are often not separated before the time, and the alloys are then mixed.
Costly alloy adjustments have to be done to adjust the alloys to the original
compositions. The seamless rolled anode has calcium lead throughout with the distinct
advantage that on recycling, the calcium lead alloy is not contaminated by the antimonial
lead
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The method of manufacture of the new anode eliminates the weld and this makes the
anode more competitively priced in comparison to the conventional rolled anode. It must
be emphasized that the anode in question is not a new anode but an improved anode.
Anodes from this method of manufacture have performed to expectation in the DRC
(Democratic Republic of Congo) for over two years. Resultant samples from these
anodes passed on to Mintek (Mineral technology of South Africa) showed no visible
corrosion. It has been estimated that a service life of at least five years can be achieved,
provided the electrolyte remains constant. In particular chlorides must be kept to a
minimum. Replacement of the anodes will mostly be due to mechanical damage and not
due to catastrophical failure of the anode.
Cathodes
This section describes the cathode blanks available from the vendors, outlines the relative
advantages and disadvantages of these cathodes and provides a qualitative level valuation of
several common parameters of the cathodes.
Cathode design alternatives
Outotec cathode
This cathode blank is manufactured by welding the stainless steel sheet to a stainless steel
hanger bar, which has an internal solid copper core.
We have limited knowledge of the service experience of this Outotec cathode. To the best of
our knowledge the Outotec cathode is in at least five plants that are in commercial operation
or in construction. The plants include Las Cruces SX-EW in Spain, the Milpilas SX-EW plant
in Mexico, the Frambros refinery in China, a small SX-EW plant in Laos, and a refinery in
Finland.
Cobra unsheathed cathode
This cathode blank is manufactured by welding the stainless steel sheet to a copper hanger
bar, using a dissimilar metal weld.
This cathode is based on cathode designs that have been used for over 30 years. The number
in service exceeds five hundred thousand (500 000) cathodes.
EPCM sheathed cathode
This cathode blank is similar in design to the Cobra unsheathed cathode described above,
except that it has a stainless steel sheath covering the hanger bar above the sheet. The sheath
provides protection for the copper and the Cu/SS weld against corrosion attack by acid mist.
The ends of the cathode sheath can be sealed to the hanger bar using either a seal weld or by
installation of a copper sleeve, with a chemical resistant sealant.
Xstrata ISA cathode
This cathode blank is manufactured by welding a stainless steel hanger bar to the stainless
steel sheet. To provide electrical conductivity, a 2.5 mm copper layer is plated over the hanger
bar and 15 mm down the sheet.
This cathode is based on cathode designs that have been used for over 30 years. The number
in service exceeds one million five hundred thousand (1 500 000) cathodes.
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Xstrata Kidd cathode

This cathode blank is similar in construction to the EPCM sheathed cathode described above,
except that the cavity between the sheath and the hanger bar is filled with a chemical resistant
filler to isolate weld from contact with electrolyte.
It is important to note that all of the available cathodes are now supplied with a 90 degree Vgroove along the bottom edge of the sheet. The V-groove aids in separation of the copper
deposit from the cathode blank.
Electrical resistance
The electrical resistance is an important parameter of the cathodes as it affects the cell voltage
drop and the overall power consumption of the tankhouse. For the purpose of this paper, the
resistance is calculated by adding the theoretical resistance in the hanger bar copper from one
end of the bar to the centre, and the calculated resistance in the stainless steel sheet from the
hanger bar attachment point to the electrolyte level. This is an approximation only as several
factors will affect the resistance of the cathode in service. However, it provides a close
approximation to the relative resistance between the different cathode types and is appropriate
for this paper.
The estimate of the cathode resistance also determines the estimated annual power cost per
cathode, for this cathode resistance, based on the nominal current density and operating time
of the refinery.
Another important aspect to the electrical resistance is the increase in resistance over time.
As discussed any exposed copper on the hanger bar is subject to dissolution over time due to
contact with sulphuric acid in the atmosphere above the cells. While dissolution rates as high
as 1 mm per year have been reported in some SX-EW plants, the slow dissolution of the
copper can significantly affect the electrical resistance over time.
Corrosion resistance
Generally, three types of corrosion occur with stainless steel cathodes, as follows:
Chloride pitting of stainless steelcorrosion of the stainless steel sheet can occur,
generally in the form of pitting near the solution line. The cause of this corrosion is
normally high chloride levels in the electrolyte and it generally occurs in SX-EW plants,
and is a rare occurrence in refineries. All of the cathodes being considered would be
similarly affected by chloride pitting, as they all use the specified 316L stainless steel for
the sheets. New materials are being substituted for 316L stainless steel and this will be
discussed further in this paper.
Dissolution of copper on hanger barsdue to the solubility of copper in sulphuric acid
and the presence of acid mist in the air above the cells, some dissolution of any exposed
copper on the hanger bar will occur. This is very prevalent in some SX-EW plants due to
the high levels of acid mist but is generally less prevalent in refineries. Nevertheless,
some copper dissolution will occur and cathodes with exposed areas of copper will
require repair or refurbishment at some point.
Galvanic corrosionany area where dissimilar metals are in contact in the hanger bar or
at the hanger bar/sheet connection will be subject to galvanic corrosion. Again this is
most prevalent in SX-EW plants as condition is aggravated by acid mist, but it does
occur in refineries. Experience has shown that some refineries have inherently more
corrosive environments than others and there is no obvious technical reason for this.
Durability
The durability of a cathode blank relates to how it will withstand the normal operations of a
copper refinery, excluding corrosion that is discussed earlier. Generally, cathodes face
possible damage due to the following:
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Overloading of hanger barcathode hanger bars can sometimes be overloaded by overplating on the cathode, impact loading on the cathode during handling, or excessive force
being applied in the CSM, normally during copper stripping. Over-plating is not
normally an issue as the weight of the copper is well within the load carrying capacity of
the hanger bar. However, impact loading during handling and excessive forces in the
CSM can sometimes lead to large forces being applied to the hanger bars
Abrasion of the hanger barabrasion of the hanger bar occurs during handling of the
cathode, mainly by the CSM. During processing through the CSM the cathode is
necessarily supported by the hanger bar on transfer cars, conveyors and in
flexing/stripping stations. Additionally, abrasive media brushing normally cleans the end
of the hanger bar where it contacts the busbar.
Bending of sheetbending of the sheet may occur due to overflexing of the sheet or
otherwise overstressing the sheet with a compressive force, most frequently in the CSM.
Generally, this affects the verticality of the cathode so that it is not acceptable for use in
the process, but does not lead to structural damage to the cathode.
Maintainability
Maintainability refers to the ease at which minor and major repairs can be performed on a
cathode. Minor repairs include:
Replace edgestrips
Repair minor scratches on sheet
Straighten slightly bent sheet
Straighten slightly bent hanger bar
Repair cathode verticality
Clean sheet.
Major repairs are normally required only as a result of gross damage to the cathodes from
handling or CSM mishaps and include the items listed below. Major repairs include:
Replace entire hanger bar
Replace entire sheet
Recuperation of damaged sheet
Replate stainless steel header bar.
Alternative materials of construction
The sharp increase in nickel and molybdenum during the period of 2004 through 2008, led
both permanent cathode suppliers and customers to look for alternative and substitutes for the
traditional 316L stainless steel cathode sheet.
The substitutes currently being offered are lean duplex stainless steels. Duplex stainless
steels contain approximately 50% ferrite and 50% austenite, which result in a material that has
properties representative of both classes of stainless steels.
Like nickel free ferrite grades, duplex grads are magnetic and more resistant to chloride
stress corrosion cracking than austenitic series grades.
Duplex alloys have a good ductility and toughness, approaching that of the austenitic
grades. Also duplex alloys are stronger than comparable austenitic and ferritic stainless steels.
Lean duplex stainless steels have been designed to have the properties of a duplex material,
but contain less nickel and molybdenum than standard duplex grades such as 2005, which
results in a cost savings.
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Tom Marsden
Marketing Manager, Thutuka Group Limited, South Africa
Tom Marsden joined the family business in 1961 to eventually become
sole owner and Managing Director in 1969. Introduced Lead anodes as
a product line in the latter part of the nineteen sixties and has been
involved in the manufacture of anode plant and manufacture ever
since. With Michale Thom patent. Introduced calcium as a beneficial
addition to the silver lead alloy. This was a worldwide first for lead
anodes as used in the zinc industry. Introduced new casting techniques
for the casting of all lead alloys and in particular calcium and strontium lead alloys. Since
involved in various methods of rolled anodes including plant and equipment for the
manufacture of seamless rolled anodes. Besides the anode industry, has been involved in
development of continuous cast lead sheet programs in Australia, the UK and the USA and
lead radiation shielding with various international companies.
John Jickling
Director, EPCM
John Jickling studied Mechanical Engineering at Queens University
in Canada. After completion of his Bachelors Degree, he joined
EPCM Services Ltd. A consulting and technology company located in
Ontario Canada. Afrter working for two (2) years at EPCM, he was
prompted to start-up Technologies Cobra S.A., an EPCM Technology
Group Company located in Antofagasta, Chile. While at Tecnologias
Cobra, EPCM developed our services to provide after market support to the Permanent
cathode Technology users in the Copper Refining Industry. John has been active in
Permanent Cathode Product development, Manufacturing processes and the development of
Permanent Cathode Refurbishment Technologies.
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ROBLES, E., CRONJE, I., and NEL, G. Solvent extraction design consideration for the Tati Activox plant.
Solvent extraction design consideration for the

Tati Activox plant
E. ROBLES*, I. CRONJE*, and G. NEL
*Hatch Africa (Pty) Ltd, South Africa
Norilsk Nickel Africa (Pty) Ltd, South Africa
The Tati Activox Project (TA P) is the first step towards the
implementation of the Norilsk Nickel Activox process. The ultra
fine grinding (UFG) and autoclave pressure leach process conditions
are the heart of the Activox patent. Low grade base metal sulphide
concentrates are leached in the process to recover the base metals and
to produce LME grade nickel and copper cathodes and cobalt
carbonates. The downstream processing of the metal-containing
liquor produced by this process includes solvent extraction circuits to
extract and concentrate metal-rich solutions, before the various final
products are obtained.
This paper gives an overview of many of the relevant design aspects
taken into consideration in the design of the Tati Activox solvent
extraction circuits. It addresses key design elements related to leach
process conditions such as scaling, materials selection for corrosive
solutions, pH control, crud formation and treatment, multiple SX
trains designed to prevent organic cross-contamination, and design
aspects related to the mitigation of fire risks.
Introduction
The Activox process is a hydrometallurgical process route developed by Norilsk Process
Technology to treat a wide variety of metal sulphide concentrates1. A combination of ultra fine
grinding, which activates the sulphide minerals and oxidation at a relatively low temperature
and pressure, form the core of the patented technology, which is expected to provide a
competitive alternative to the traditional pyrometallurgical process routes. Work on the Tati
Activox Project (TAP) started in 1998 with laboratory testwork. The development towards
commercialization has advanced systematically from laboratory-scale testing in Australia
through various studies to the design, construction and successful operation of a 1:170 scale
demonstration plant on the Phoenix mine site in the North Eastern district of Botswana,
Southern Africa. In 2006 Hatch was awarded the contract for the execution of the Botswana
Metal Refinery (BMR) for TAP. This hydrometallurgical refinery is designed to produce
25000 tpa nickel and 22000 tpa copper as LME grade cathodes and 630 tpa cobalt as a cobalt
carbonate.
SOLVENT EXTRACTION DESIGN CONSIDERATIONS FOR THE TATI ACTIVOX PLANT
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Figure 1. Tati Activox flowsheet
The general flow sheet for the TAP process is shown in Figure 1.
The Tati concentrate is trucked from the Tati Phoenix mine complex to the BMR where the
concentrate is repulped in attritioners to 50% solids with recycled copper raffinate. The repulped concentrate is ground to 80% passing 10 microns using two-stage vertically stirred
detritor ultra fine mills. The mill product is fed to two parallel autoclaves where the slurry
reacts with oxygen at moderate high pressures (10 bar gauge) and moderate temperatures (105
degrees Celsius) to produce copper, cobalt and nickel sulphates in solution for downstream
recovery. The pregnant leach solution (PLS) reports to a solid-liquid separation section, which
includes a multi-stage counter current decantation (CCD) washing circuit where the leach
residue solids are washed with recycled process water. Washed leach residue solids are
pumped to the PGE recovery circuit. The overflow solution from the CCD train is clarified
prior to reporting to a copper PLS pond.
Copper PLS is contacted with an organic solvent in the copper SX circuit that selectively
extracts copper from the copper PLS solution. Copper is stripped from the organic using spent
electrolyte from the copper EW circuit (Cu EW). The rich electrolyte is treated to remove
trace organic before being pumped to the Cu EW circuit. The bulk of the copper SX raffinate
is recirculated back to the concentrate repulp and the remainder is advanced to the cobalt and
nickel recovery circuits. The Cu-rich electrolyte is sent to the Cu EW circuit to produce
copper as LME grade copper cathode. Spent electrolyte is recirculated back to copper SX for
enrichment via stripping of the copper-loaded organic phase.
Iron in the copper SX raffinate is removed to less than 10 ppm in solution using limestone,
in a two-stage iron removal circuit. Cobalt PLS is contacted with an organic solvent that
selectively extracts cobalt from solution. Cobalt is stripped from the loaded organic phase
with an acidic strip solution and the resultant loaded strip liquor (LSL) is filtered and pumped
to the cobalt precipitation circuit. Organic is removed from the Cobalt SX raffinate before
proceeding to the nickel PLS storage tank. Nickel PLS is contacted with an organic solvent
that extracts the nickel (selectively over calcium and magnesium) from solution. Nickel is
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stripped from the loaded organic phase with spent nickel electrolyte recirculated from nickel
electrowinning circuit (Ni EW). The rich electrolyte is treated to remove trace organic before
reporting to the Ni EW cell house. The nickel SX raffinate stream is transferred to the
ammonia recovery circuit.
The Ni EW process is designed to produce LME grade nickel cathode. Recovered spent
electrolyte from Ni EW is treated to remove lead prior to being recirculated to nickel SX for
stripping. Ammonia is recovered from the nickel SX raffinate stream for reuse as an aqueous
ammonia solution for pH control in the cobalt and nickel SX processes. The ammonia is
liberated from the nickel raffinate using the Norilsk patented ammonia recovery process. The
process solution from ammonia recovery is recycled back to the CCD circuit and used as
wash water. The residue from the CCD circuit is treated by flotation to recover the PGEs in
the leach residue. Tails from the rougher circuit are neutralized together with other process
effluent streams before reporting to the tailings dam.
Description of TAP solvent extraction plants
In TAP the process for leach liquor purification and concentration of metals consists of three
SX circuits to remove Cu, Co and Ni in sequential stages by using different selective
extractants.
Description of the SX circuits
Copper solvent extraction circuit (Cu SX)
Copper is selectively transferred from the relative low grade Cu PLS into a high-purity
electrolyte stream using a copper selective extractant. The extractant employed is an oximebased copper-selective chelating reagent that is dissolved in a high flashpoint hydrocarbon
diluent to make up the organic phase.
The copper solvent extraction circuit consists of three main process steps:
Extractioncopper PLS is contacted with the stripped organic phase in two extraction
stages to transfer copper from the aqueous to the organic phase
Scrubbingthe loaded organic is scrubbed with copper electrolyte bleed to remove coextracted iron and aqueous-entrained chloride and manganese. Although highly selective
for copper over most other cationic species under extraction conditions, a small quantity
of Fe3+ is co-extracted. The scrubbing stage minimizes entrainment of aqueous in the
loaded organic phase that otherwise will result in the undesirable build-up of species
such as chloride and manganese in the electrolyte
Strippingthe scrubbed organic phase is contacted with spent electrolyte from EW in
two stages, utilizing the acid generated during the copper deposition process in Cu EW.
Copper is transferred from the organic into an aqueous phase.
Cobalt solvent extraction circuit (Co SX)
Cobalt is recovered from the Co PLS following the iron removal process, using a solvent
extraction circuit. The extractant employed is the phosphinic acid-based Cyanex 272,
dissolved in a high flashpoint hydrocarbon diluent. This provides selective extraction for
cobalt over nickel by controlling the pH in the extraction stages. Co-extraction of iron,
manganese, zinc and copper also occurs.
The cobalt solvent extraction circuit consists of four main process steps:
ExtractionCo PLS is contacted with stripped organic phase and cobalt is transferred
from the aqueous to the organic phase in three stages. The pH is controlled by the
addition of aqueous ammonia
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Scrubbingloaded organic is washed with acidified, filtered water to remove coextracted nickel from the organic phase in a single stage
Strippingscrubbed organic is contacted with acidified cobalt strip liquor and the cobalt
is transferred from the organic to the aqueous phase in two stages
Cyanex recoveryraffinate is washed with fresh diluent to minimize organic cross
contamination to the nickel solvent extraction circuit in a single stage.
Nickel solvent extraction circuit (Ni SX)
Nickel is recovered from Co SX raffinate using solvent extraction. The extractant employed is
the carboxylic-acid based Versatic 10 that is dissolved in a high flashpoint hydrocarbon
diluent. By control of the extraction pH, the solvent-extraction process is selective for nickel
over such species as calcium and magnesium.
The nickel solvent extraction circuit consists of the following four main process steps:
Extractionnickel pregnant leach solution (Ni PLS) is contacted with organic phase and
nickel is transferred from the aqueous to the organic phase in five stages. The pH is
controlled by the addition of aqueous ammonia
Versatic recoveryprior to entering the extraction circuit the stripped organic phase is
contacted with nickel raffinate exiting the extraction circuit in a single stage to recover
aqueous-soluble Versatic 10 from the aqueous into the organic phase. This is achieved by
reducing the pH with diluted sulphuric acid solution in this stage. Recovering the soluble
Versatic 10 minimizes reagent losses and downstream frothing in the ammonia recovery
circuit.
Scrubbingloaded organic is scrubbed with acidified nickel rich electrolyte bleed
solution to remove co-extracted calcium from the organic phase in a single stage.
Strippingscrubbed organic is contacted with spent electrolyte from Ni EW in two
stages and nickel is transferred from the organic to the aqueous phase. Most of the
sulphuric acid utilized in stripping is generated in the electrowinning process.
Contactor equipment
The Tati Activox SX plant design is based on the use of mixer-settlers as contactor
equipment. It makes use of the countercurrent Side-FeedTM mixer-settler concept of Miller
Metallurgical Services (MMS)2. Each mixer-settler consists of a two-stage mixer and a settler.
A dual mixing system provides high overall stage efficiency by minimizing back-mixing,
minimizing short circuiting, and by ensuring sufficient retention time in the mixers. The
primary mixing vessel is fitted with a pump-mix type of impeller, which provides the head for
the inter-stage pumping of solutions as well as mixing of the two phases. The primary mixing
vessel incorporates a false bottom into which the organic, aqueous and recycle streams are
introduced. Mixed phases enter the secondary mixing vessel via a connecting pipe. This
vessel is fitted with a mixing impeller designed for maximum mixing efficiency with
minimum shear. The dispersion overflows into a shallow gravity settler where sufficient area
is provided for disengagement of the aqueous and organic phases. Cross-sectional picket
fences maintain a band of dispersed phase through which finer droplet coalescence is
promoted. A weir arrangement at the discharge end of the settler allows for separate discharge
of the organic and aqueous phases. The aqueous/organic interface level in the settler is set
during commissioning by manual adjustment of the physical height of the aqueous overflow
weir.
The design allows all the mixer-settlers to run with organic or aqueous continuity by
adjusting the internal recycles to the primary mixer from the settler. The general philosophy
followed in all three circuits is that the extraction stages be operated in organic-continuous
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mode. This minimizes the entrained organic loss in the raffinate and assists in the compaction
of crud solids. Organic continuity in the first extraction stage could result in high aqueous
entrainment to the loaded organic phase. The deleterious effects of this are curtailed to some
extent by the inclusion of the loaded-organic scrub stage that is present at all the circuits.
Configuration of the TAP solvent extraction circuits
The Table I below shows a comparison between the three SX circuits for TAP. Parameters
compared are type of extractant and diluent, number of mixer-settlers per process step,
existence of pH control and configuration for organic removal and recovery.
The number of extraction stages differ from circuit to circuit depending on the extraction
time, type of extractant employed and the concentration of the metal present in the PLS. The
propensity for scaling in the circuit may require the addition of an extra extraction stage as in
the case of the nickel circuit. The likelihood of downtime is reduced by the addition of an
extra extraction stage, which allows extraction operations to carry on as planned while
cleaning can be carried out simultaneously.
Stripping in all three circuits comprise two stages where loaded organic is contacted with
spent electrolyte or acidic strip liquor. As for extraction, the aqueous and organic phases flow
countercurrently with loaded organic entering the first stripping stage and spent electrolyte or
strip liquor entering the second stripping stage. The aqueous solution exiting the first stripping
stage is enriched in metal, and after organic removal, becomes the feed to the metal winning
circuit that follows.
Table I
Comparison of the TAP SX circuits
Extractant
Extractant family
Diluent
Total flow rate per settler
Operating temperature
PLS feed storage
Nr of extraction mixer-settlers
Copper SX
Cobalt SX
LIX 984N
Oxime based
Sasol SSX 210
1002 m3/h
3040C
Pond (4 days)
2
Cyanex 272
Phosphinic acid
Sasol SSX 210
309 m3/h
40C
Pond (2 days)
3
Nickel SX
Versatic 10
Carboxylic acid
Sasol SSX 210
383 m3/h
40C
Tank (4 hours)
5 (plus one spare stage for potential
descaling of stage 1 or 2)
Nr of scrub mixer-settlers
1
1
1
Nr of stripping mixer-settlers
2
2
2
Organic recovery stage
No
Yes
Yes
pH control in extraction stages
No
Yes (ammonium hydroxide)
Yes (ammonium hydroxide)
pH control in scrub stage
No
Yes (sulphuric acid)
pH control in stripping stages
No
pH control in organic recovery
No
No
Potential scaling
No
Yes
Yes
Raffinate after-settler
Yes
Yes
Yes
Rich electrolyte/LSL after settler
No
No
Yes
Raffinate coalescing filters
No
Yes
No
Electrolyte/LSL coalescing filters
Yes
Yes
Yes
Electrolyte/LSL carbon columns
No
No
Yes
Crud treatment system
Tri-phase centrifuge
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Sufficient surge capacity is provided upstream of the SX circuits. In the case of copper, fourday surge capacity is provided in the PLS storage pond. This pond features two pre-settlement
compartments to minimize solids ingress to the solvent extraction process. The Co PLS pond
has two days of surge capacity. Cobalt raffinate is stored in a four-hours surge tank with
sufficient capacity to buffer against operational surges upstream of Ni SX. All three SX
circuits can therefore be operated independently without being affected by upstream
bottlenecks. This provides the system with flexibility and continuity avoiding unnecessary
shutdowns and start-ups. The surge capacities between process steps were sized based on a
dynamic model.
In all three circuits loaded organic flows via gravity from the respective extraction stages
into a series of two organic surge tanks. Both tanks are equipped with internal weirs for the
separation of entrained aqueous. Loaded organic is pumped to a single scrub stage where it is
contacted with an acidified aqueous solution. The scrub raffinate flows by gravity into the
raffinate after settler to minimize the entrainment of organic in the aqueous phase.
The other significant difference between these SX circuits is the strategy to remove or
recover entrained organic from the aqueous products (raffinate and rich electrolyte/loaded
strip liquor). The strategy for organic removal or recovery is essentially dictated by the
requirements of the downstream process stage, as explained below.
For TAP it is very important to minimize the loss of extractant from the circuit, to reduce
the impact on the downstream operations. Also, organic extractant entrainment losses must be
minimized from an operating-cost perspective. The Cu raffinate reports to an after settler
followed by the iron removal process, which forms a buffer between Cu SX and Co SX. The
Co raffinate stream first passes through an after settler, then a diluent wash stage and finally
mixed-media coalescing filters before advancing to Ni SX. In the nickel circuit, the aqueous
solubility of Versatic 10 increases significantly with an increase in pH. Acidification of the
raffinate is required to recover the Versatic from the aqueous phase. This is achieved in a
single stage where raffinate is contacted with stripped organic phase at a reduced pH ensuring
that soluble Versatic is recovered into the organic phase. Similarly to Cu SX and Co SX, the
raffinate is then transferred to an after settler.
Similarly to the raffinate, the rich electrolyte or loaded strip liquor needs to be treated to
remove or recover entrained organic. The organic removal strategy for both copper rich
electrolyte and cobalt loaded strip liquor is similar. In these two cases the metal-rich liquor is
advanced to a series of mixed media coalescing filters.
The nickel EW process is particularly sensitive to the presence of SX organic phase
components. Before advancing to the EW circuit the Ni rich electrolyte undergoes two
organic removal steps. The first is a system of mixed media coalescing filters where the bulk
of the entrained organic phase is removed. The solution exiting this stage is passed through
activated carbon absorption columns to further reduce the organic content.
Crud that collects in the settlers is removed on a regular basis by suction with a peristaltic
pump from just ahead of the overflow weir via a manifold collection system into the crud
holding tank. The emulsion is fed into a tri-phase centrifuge that separates the solution phases
(organic and aqueous) for recycle to the process and discharges a solid for disposal.
Removal of degradation products and solids from the organic phase is achieved in a similar
way in the copper, cobalt and nickel SX circuits. An agitated crud treatment tank is provided
where a portion of the organic phase is contacted with diatomaceous earth in the case of
cobalt and nickel, while clay for the copper circuit to help remove solids and degraded organic
products.
On each SX plant a remote emergency pond can receive overflows from all the sumps
located in the bunded areas for the SX process and its associated tank farm.
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Design issues related to TAP process conditions

The conditions of the leaching process that are dictated by the type of ore to be processed, the
nature of the leach reagents, and the type and sequence of processes used to obtain the metal
products, have an important effect in the design of the multiple SX circuits. In TAP the most
important design issues in the SX circuits that are related to the leach process conditions and
operating parameters are scaling, the presence of a highly corrosive environment, and crud
formation and control.
Scaling
The Tati concentrate is primarily a pyrrhotite (iron sulphide) type ore with some calcium,
magnesium and manganese minerals. The dissolved iron is removed in a two-stage
atmospheric precipitation process using limestone. Ground limestone slurry is introduced into
the reaction tanks to increase the pH to precipitate ferric hydroxide. A small amount of nickel
and cobalt will co-precipitate at the operating pH.
The most common cause of scaling in SX is the saturation of CaSO4.2H2O due to the
extraction and loading of calcium in the last few extraction stages and stripping of the calcium
off the organic into the aqueous phase in the first extraction stages. Excessive scaling results
in blocked pipes and reduced processing capacity. This in turn may lead to reduced production
capacity, increased energy requirements (e.g. pumping and mixing) and increased downtime
and maintenance cost.
The approach for the design of the areas most likely to be affected by scaling has been to
make adjustment in the process parameters and to take special care to design details that could
decrease downtime and maintenance cost.
Adjustment of process parameters
The TAP design has catered for the dilution of the Co PLS liquor with 5% filtered raw water
to maintain the calcium concentration in the Co PLS below Ca saturation. Although this
reduces the risk of scaling, the increased flow rate requires larger processing capacity with
incremental capital cost.
Solution temperature is also an important parameter that affects the scaling rate. The
temperature in Co SX is maintained around the range of temperature that allows the maximum
solubility of calcium sulphate. The change of pH of the solutions feeding Co SX and Ni SX,
which is essentially dictated by the needs of the selective extraction of these metals, is
controlled to minimize co-extraction of Ca in the back end of extraction and stripping in the
front end of the extraction stages.
Piping design
Conductive fibre reinforced plastic (FRP) piping materials are selected for the TAP SX
plants to prevent static electricity build-up in the pipes. FRP piping also minimizes the
adhesion of scale to the material surfaces, due to its smoother surface finish compared to
stainless steel piping. The pipe spools were designed for easy removal and descaling. The
plant layout was optimized to improve access to the pipes for periodical de-scaling.
Design for easy cleaning and maintenance
The Ni SX plant, which is particularly prone to scaling, is designed for regular descaling. One
extraction mixer-settler is included as a spare unit with dedicated piping to allow descaling of
any of the first two extraction mixer-settlers without operation interruption. The SX train
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layout is optimized to improve access to mixer tanks, settler and pipes and facilitate the
removal of internal parts and pipe spools. The mixer tanks have removable lids and the
settlers roofs are designed with removable sections that include inspection hatches to monitor
the accumulation of gypsum in the settler internals. Special nozzles were included in the
mixer tanks to facilitate hydro-blasting of scale from tank internals.
Use of synergists
The use of synergists to improve the selectivity of certain metals is a relatively novel idea not
widely implemented in the industry. A study conducted by du Preez et al.3 which evaluates the
use of a synergist system for nickel-calcium separation on Tati Demonstration Plant solutions
shows that selectivity for nickel over calcium can be improved by adding a synergist to the Ni
SX organic. This performance versus the increased operating cost has to be weighed up to
establish the overall added value of the synergist.
Corrosive solutions
The TAP design relies on the addition of chlorides to improve copper extraction in the
autoclave. This creates a corrosive leach solution requiring the use of higher grade metallic
materials for certain specified applications. Based on the experience at the Tati Demonstration
Plant, duplex stainless steel SAF 2205 was selected for metal components in contact with all
process liquors that contain chlorides. For the SX circuits, where the working temperature is
below 45C, the TAP has chosen to use FRP as an alternative to SAF 2205, as the maximum
temperature recommended for the use of FRP is 60C.
Crud formation and control
In SX the formation of crud is generally caused by a variety of substances present in the
solutions being processed. This includes fines from ultra fine milling, entrained
solids/precipitates from leaching; foreign material such as dust, insects; or silica in the TAP
filtered water.
The strategy for crud control and treatment for the TAP includes the following:
PLS clarificationpin bed clarifiers are used in the TAP design to reduce the solids
content of the Cu PLS and Co PLS. The uncontrolled separation of solids from the
process liquor is usually a significant contributor to crud formation
Settling ponds prior to SXsettling ponds provide sufficient surface area and reduce
flow rates so that ultra fine material has an opportunity to settle out prior to SX
Removal of degradation productsdegradation products are produced by reactions on
the organic phase caused by biological, chemical and environmental factors. These
degradation products tend to be surface active and promote crud formation. Degradation
products are continually removed in the Cu SX circuit by clay treatment and in Ni SX by
the use of carbon columns
Isolation of SX mixer-settlers from external environmentroofing of the SX mixersettlers, which provides isolation from the external environment significantly reduced the
collection of dust and insects
Water purificationwater treatment and purification is used in the TAP design to
minimize silica concentration in the plant filtered water that is used as SX dilution water.
Phase continuitythe TAP design utilizes preferably organic phase continuity to
promote compaction of crud solids
pH controlthe TAP design optimizes pH control to prevent saturation of calcium in
Ni SX and subsequent crud formation
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Crud treatmentthe TA P design includes the installation of a permanent crud

collection manifold system, which removes the crud that accumulates in the settlers,
using a peristaltic pump for crud suction. The crud collection manifold consists of short
sections of perforated pipes, located adjacent to the organic weir, that are connected to a
header. The collected crud is treated by means of a tri-phase decanter centrifuge for
organic recovery. Each SX circuit has its own crud treatment system to prevent organic
cross-contamination.
pH control
The TAP design requires very tight pH control in Co SX and Ni SX to prevent co-extraction
of metals. Impurities are scrubbed of the loaded organic using acidified scrub liquor in the
scrubbed organic phase.
The most important challenge for a pH control system is the reliability of the pH
measurement in the solution feeding the settler. Such a measurement could be hampered by
organic coating or scaling of the pH electrode probe. Hence, in theTAP design the electrode
is located in a dedicated pH pot that receives aqueous solution from the feed end of the settler,
through a pipe that connects the lower part of the settlers sidewall with the pot. This location
allows pH measurement in clean aqueous solution and facilitates access for cleaning and
calibration of the electrode.
The TAP design allowed for a cascading control system where the flow rate of neutralizing
or acidification reagent is the primary control measure and the pH of the aqueous solution is
the secondary measure. The reagent flow set point is a calculated ratio of the main incoming
flow (PLS, strip liquor or loaded organic) with a multiplier that is based on the output
provided by the pH controller. The control logic minimizes reagent flowrate fluctuations and
reliability on accurate pH measurements. The control logic allows for timely identification of
pH deviations. Low and high alarms alert the operator to pH measurement faults or dosing
ratios outside the set ranges.
The pH electrodes in the first three extraction stages of Ni SX were duplicated, with the
additional electrodes located in the aqueous launders of these settlers to provide back-up for
the pH control loops.
Design issues related to multiple SX trains
The multiple SX trains in the TAP design present certain challenges in terms of optimizing
plant layout, contactor design and minimizing possible organic cross-contamination. Organic
cross-contamination occurs when organic from one SX circuit is carried over to the next SX
circuit causing process upsets, reduction of efficiency, metal loss, and off spec product.
Plant layout
One of the major challenges that the SX design for the TAP faced was to accommodate the
various SX circuits in an optimal manner. The following had to be taken into account:
minimization of the SX train footprint; location of storage ponds and/or connecting pipelines
with upstream and downstream process facilities; and safe separation distance between SX
circuits to minimize fire risks.
Norilsk selected the side-feed design of MMS for the SX settlers. This allows a smaller
footprint for the SX train of mixer-settlers and better access for operational control, cleaning
and maintenance. All operational and maintenance work can be carried out on one side of the
settler.
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Each SX plant is laid out with all equipment containing large quantities of organic solution
grouped together in the SX area (SX train, organic storage tanks, after-settler(s), crud
collection tank) and associated equipment including organic recovery and crud treatment
systems are grouped into the SX tank farm area. A safe separation distance is allowed between
these two areas to ensure asset protection in the case of a fire. For the same reason, the three
SX trains are separated by a safe distance. These distances were defined after a fire plume
analysis was performed for each SX plant.
Optimization of flow patterns inside the SX settler
The optimal design of the main phase separation equipment in the SX plants is critically
important since excessive turbulence and insufficient coalescence and phase separation result
in increased entrainment that may lead to cross-contamination. Hatch used computational
fluid dynamics (CFD) models for settler optimisation in theTAP. CFD is an important design
tool that allows the designer to visualize and test innovative design concepts quickly and
economically47.
Single and multi-phase CFD models were used for theTAP to predict the flow behaviour
and flow distribution in the entrance and early flow development regions of the side-feed
settler vessels. The crossover launder that connects the secondary mixer tank with the settler
and its guide vanes were modified to provide an optimum low-speed transition into the settler
vessel, which is critical to its overall performance. Multiphase modelling has also provided
significant guidance in the design of the TAP mixer interconnecting pipe, picket fences and
collection launders.
In reality all settlers deviate from an ideal plug-flow distribution and results from visual
inspection or physical modelling can be difficult to interpret and are therefore of limited use
in design. Computation of the integrated volumetric-flow distributions across the width of the
settler, as shown in Figure 2, has been used to evaluate and rank a number of different
designs. The settler internals were modified to achieve a uniformly distributed flow across the
width of the settler.
Figure 2. Post processing is used to evaluate the mass flow across each quarter of the width
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Table II
Distribution of mass flow across the width of the settler for the original design and after using CFD analysis
Integrated mass flow through lateral quarters of the settler cross-section (kg/s)
Inner
Inner-mid
Outer-mid
Outer
106
91
46
92
66
90
105
87
Original design
Optimized design
The computed mass flow rates through each of the lateral quarters of the settler for the
original design and after using CFD analysis are listed in Table II. The optimized design
provided a significantly more uniform flow distribution with a lower overall pressure drop.
Organic removal equipment
The TAP design defined various strategies and equipment for the removal of organic phase
from aqueous streams. These include physical and chemical processes depending on the state
of the organic for recovery (dissolved and/or entrained). Organic recovery processes fall into
four process categories:
Primaryreducing organic entrainment from >200 ppm or more down to <50 ppm and
recovering the organic phase
Secondaryreducing organic entrainment from 100 ppm to <2 ppm and recovering the
organic phase
Dissolved organic recoveryreducing the soluble organic content from >200 ppm to
<10 ppm
Tertiaryreducing the total organic content, both entrained and soluble, from 10 ppm to
<1 ppm.
Primary organic removal equipment
After-settlers are utilized in the three SX circuits as the preferred primary organic removal
equipment in the TAP design. Essentially they provide additional area for phase separation
and are the first barrier to stop organic entrainment peaks should a major upset happen in the
mixer-settlers. The organic collected in the after-settlers is periodically removed and returned
to the extraction stages via the corresponding crud treatment system. The only exception to
this is in the Co loaded strip liquor stream, where this aqueous stream is passed though a tank
with coalescing media before downstream processing. The coalescing media generate large
organic droplets from small entrained droplets by creating random collision opportunities.
Larger droplets are separated more readily. The coalesced organic is periodically removed
from the tank and returned to the extraction stages via the Co SX crud treatment system.
Non-mechanically agitated flotation cells, which are also widely used as primary organic
removal equipment, were not included in the design because of the induction of high volumes
of air (at ratios of about 0.8:1 v/v) may result in evaporative loss of significant proportions of
the valuable organic phase or cause other process problems including oxidation.
Secondary organic removal equipment
As a secondary organic removal equipment downstream of the after-settlers, the TAP design
allowed for pressure filtration using dual-media filters, with a combination of anthracite and
garnet media, to reduce entrained organic level to <2 ppm. Organic removed from the filters is
returned to the extraction stages via the corresponding crud treatment system.
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The only two product streams that do not have downstream processing by pressure filtration
are the raffinate streams in Cu SX and Ni SX. As they are fed into storage ponds, floating
organic is removed from the ponds surfaces using rope mop-type organic skimmers. Organic
removed from the ponds is also returned to the extraction stages via the corresponding crud
treatment system.
Soluble organic recovery
Highly soluble extractants need to be recovered through physicochemical and chemical means
as opposed to simple physical removal. The TAP design has two methods for bulk removal
of soluble organic from the aqueous phase, depending on the nature of the extractant. One is
for removal of phosphinic acid-based extractant solubilized in Co SX raffinate that is simply
washed with diluent in a single stage. On the other hand, carboxylic acid-based extractant
solubilized in Ni SX raffinate has to be recovered through pH adjustment with an acid
solution in a single stage to reduce organic solubility in the aqueous phase8.
Tertiary organic removal equipment
In the TAP design, tertiary recovery equipment is employed to ensure the achievement of
<1 ppm organic in the rich electrolyte going to Ni EW. The equipment selected is a package
of columns filled with granular activated carbon.
The carbon columns package consists of three columns, which are connected as a lead-lag
system. At any given time two of the columns are in service and one is out of service. Feed
electrolyte flows into the lead column, from there to the lag column, and then leaves the
system. When the granular activated carbon media in the lead column is saturated with
organics, that column is taken out of service. The lag column then takes lead status and the
previously out-of service column takes lag status. The process is sequenced so that over a
given period each of the columns will have been in lead status, followed by being out-of
service, followed by being in lag status.
Mitigation of fire risks
Recent fires in SX plants have highlighted the importance of safety in design in order to
eliminate or mitigate the risk of fire and subsequent damage to facilities, injuries and
fatalities. Although SX plants normally operate below the flashpoint of the organic solvent
rendering the environment inherently safe, the creation of aerosols or static build-up create
conditions suitable for ignition by an electrostatic charge9.
The TAP SX plants are designed to reduce the risk of fire initiation with the moderate
operating temperature in SX, the minimization of aerosols formation in all the feeds to tanks
and launders and the prevention of static charge build-up by the use of conductive FRP for all
the piping systems and tanks and appropriate earthing devices along the piping systems and
on tanks. These plants are also designed under an integrated fire management strategy that
allows early and reliable fire detection, effective fire suppression, and fire containment and
isolation.
Fire detection and alarm
The fire detection system is designed to be reliable, robust and fast. This system has detection
in multiple points to prevent false alarms and subsequent damage caused by the unnecessary
release of water and or foam into the processing units. The fire detectors in the TAP SX
plants, which are of the infrared flame type, are placed under the removable settler roofs,
across groups of mixer-settlers and storage tanks and along pipe routes.
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The purpose of the alarm system is to provide an audible warning that enables safe and
timely evacuation of the plant. Manual call points and evacuation speakers are positioned
around the SX areas. Fire alarm panels located in the field centralize monitoring of all the
devices, which form part of the fire detection and alarm system of the area and are connected
to the main fire alarm panel in the central control room.
Fire suppression system
Two options of fire suppression were analysed for the TAP design: a water deluge system
with dumping of the settler content during fire and a fixed foam-water deluge system. The two
options were assessed based on minimum statutory requirements, international recognized
codes and standards, insurance requirements, best industry practice, occupant life safety, asset
protection, potential business interruption, site operational procedures, and capital cost.
The initial design for the fire suppression system was a water deluge with a dump system.
This system was designed to prevent escalation of fire by cooling the equipment and
structures adjacent to a fire to protect them from heat radiation. The system included the
automatic water deluge on tank externals, structures, pipe racks and bunds and manual water
hydrants along plant perimeter. The dump system was designed to allow the dumping of the
contents of the mixer-settler on fire by means of actuated valves, which are activated by the
fire detection and alarm systems. Sumps within the SX areas were also designed in such a
way to drain the area fast and effectively to the remote fire dump pond.
This water deluge system was found to be insufficient after evaluating against the design
requirements. Four main drawbacks were identified in the system. Firstly, the need to
extinguish a fire in the SX mixer settler as quickly as possible was not met by this design
since deluge water does not offer the extinguishing properties that foam does. Secondly, the
location of the TAP is fairly remote and the availability of trained fire crews are limited.
Thirdly, the need to minimize loss of plant production leading to minimizing down time and
minimizing damage to equipment, highlighted the need for a more robust fire suppression
system with lower water demand. The final drawback was the reliability of the dumping
system. Regular testing of the dump valves was required to maintain the integrity of the
system. False alarms would have led to the dumping of the SX inventory.
The water deluge system was then replaced by a fixed automatic foam-water deluge system.
The fixed foam system consists of permanently installed piping and deluge/foam sprays tied
into a fire water supply and dedicated foam concentrate supply and proportioning equipment.
The deluge system provides external protection to vessels, tanks and pumps, located in each
SX plant area and in the diluent storage area. Manual yard hydrants/monitors with foam
making equipment are placed along the plant perimeter. The spray foam/deluge system is
activated with a pilot operated water fusible plugs network. Special dedicated foam lines are
provided for the internal organic tank/vessel protection. These lines are manually operated.
The SX plants are divided into three to five areas with separately activated deluge foam
systems. All deluge-foam nozzles are located outside the mixer settler tanks to prevent
process contamination.
The foam recommended for use on the TAP design is a low viscosity AFFF/A4P 3%. This
conventional foam is suitable for extinguishing hydrocarbon liquid and polar fire.
Fire containment and isolation
A fire plume analysis was used as basis for the layout of the TAP SX areas. The analysis
takes into account the area of the fire, the volume and type of fuel that could burn, climatic
and wind conditions, and the presence of other assets and public access. From the fire plume
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analysis, the physical layout of the assets within each SX plant is arranged in such a way to
reduce impact of fire escalation and increase ease of isolation and containment. This analysis
also provides information to arrange each SX plant in relation to the others.
Each SX area containing all mixer-settlers, after-settlers and crud collection and organic
tanks, is separated into individual fire suppression zones. These zones facilitate fire
containment within the SX area.
On each one of these zones there is a bund with a sump that allows fluids to overflow into a
remote emergency pond to prevent foam/water or process liquor spillage spreading to other
zones during a fire event. Fire retardant, conductive FRP piping were used inside the SX
plants to prevent the spreading of a SX fire through the piping.
Conclusions
The three SX circuits of the TA P were designed with careful consideration to the
characteristics of the leach solution, the operation of multiple SX circuits in sequential mode,
and the mitigation of fire risks.
The TA P design utilizes several process steps (clarifiers, settling ponds, filters) to
minimize solids entrainment into the PLS.
The design allows for a full standby mixer settler, PLS dilution and tight pH control to
minimize scaling during operation.
Primary, secondary and tertiary organic removal steps are utilized to prevent organic cross
contamination and rich electrolyte contamination.
A foam-water deluge system was selected for all three TAP SX plants with emergency
ponds to collect overflow form the SX bunded areas.
Acknowledgements
The authors would like to thank Norilsk Nickel Africa (Pty) Ltd. and Hatch Africa (Pty) Ltd.
for their permission and support in writing this paper. We also like to acknowledge the
consultancy work provided by Graeme Miller and the good work of the multidiscipline SX
design team that worked out of the Hatchs Brisbane office.
References
1. PALMER, C.M. and JOHNSON, G.D. The Activox Process: Growing significance in
the nickel industry. Journal of Minerals, Metals and Materials Society, vol. 57, no. 7,
July 2005, pp. 4047.
2. MILLER, G. Design of Mixer Settlers to Maximise Performance, Proceedings from
ALTA 2006 Copper Conference, 10th Copper Event, ALTA Metallurgical Services,
Melbourne, Australia.
3. DU PREEZ, R., NEL, G., KOTZE, M., DONEGAN, S., and MASSINA, H. Solvent
Extraction test work to evaluate a Versatic 10/NicksynTM Synergistic system for Nickel Calcium separation, Proceedings of The Fourth South African Base Metals Conference,
Africas base metals resurgence. Symposium Series S47, South African Institute of
Mining and Metallurgy, 2007, pp. 193210.
4. GUNNEWIEK, L.H., OSHINOWO, L., PLIKAS, T., and HAYWOOD, R. Using CFD in
the Design and Scale-up of Hydrometallurgical Processes, 3rd International Conference
on CFD in the Minerals and Process Industries, CSIRO, Melbourne, Australia, 2003
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5. SCHWARZ, M.P., LANE, G., NIKOLOV, J., YANG, W., BUJALSKI, J.M.,
SOLNORDAL, C.B., and HOUCHIN, M. Development of a Design Capability for SX
Contactors Using Multi-Phase CFD and Experimental Modelling, Proceedings ALTA
2007 Copper Conference, 11th Copper Event, ALTA Metallurgical Services, Melbourne,
Australia.
6. ROBLES, E., CRONJE, I., POULTER, S., and HAYWOOD, R. Aspects of the Design of
SX Plants for the Modern Hydrometallurgical Refinery, Proceedings of the International
Solvent Extraction Conference ISEC 2008, Tucson, Arizona.
7. GIRALICO, M., GIGAS, B., and PRESTON, M. Advanced Mixer Settler Designs that
will Optimize Tomorrows Large Flow Production Requirements, Proceedings
Hydrometallurgy 2003Fifth International Conference in Honour of Professor Ian
Ritchievol. 1, Leaching and Solution Purification. TMS, 2003.
8. BACON, G. and MIHAYLOV, I. Solvent Extraction as an Enabling Technology in the
Nickel Industry, Proceedings of the International Solvent Extraction Conference ISEC
2002, K.C. Sole, P.M. Cole, J.S. Preston, D.J. Robinson, (eds.), South African Institute of
Mining and Metallurgy, Johannesburg. pp 853863.
9. HAIG, P., KOENEN, T., and MAXWELL, J. Electrostatic Hazards in Solvent Extraction
Plants, ALTA SX/EW World Summit, Perth, ALTA Metallurgical Services, Melbourne,
Australia, 2003
Ilne Cronje
Process Engineer, Hatch, South Africa
Recent experience in the design of hydrometallurgical plants.
Involvement in the area of Solvent Extraction consisted of flowsheet
development, Process and Instrumentation Diagrams, equipment
sizing, completion of Mechanical Data Sheets and hydraulic
calculations for sizing of Mixer Settler units, developing control
philosophies, commissioning and operating manuals.
More recently involved in a project management role as a Study
Manager on a Smelter Pre-Feasiblity Study and a Waste Heat Utilization Concept Study.
Involvement included setting up of the project, project controls, management of the
engineering disciplines and assisting with Process Deliverables.
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TINKLER, O., SHIELS, D., and SODERSTROM, M. The ACORGA OPT series: comparative studies against
aldoxime: ketoxime reagents. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and
Metallurgy, 2009.
The ACORGA OPT series: comparative studies

against aldoxime: ketoxime reagents
O. TINKLER*, D. SHIELS, and M. SODERSTROM
*Cytec Industries Inc., South Africa
Australia Holdings Pty Ltd, Melbourne, Australia
Cytec Industries Inc., Phoenix, United States of America
Cytec
In 2006, Cytec Industries Inc. announced the development of a new

series of solvent extraction reagents that optimize copper transfer
through the use of formulations containing aldoxime and ketoxime as
well as selected modifiers. The patented technology results in
increased copper transfer due to the interaction between the modifier
and oximes within the blend. These new formulations also show a
significant improvement in copper iron selectivity, which can result in
lower bleed and copper reprocessing costs. The name given to the
new series is OPT which falls under the Cytec Industries
ACORGA brand of copper solvent extractants. These new copper
extractant formulations have been successfully commercialized and
show a significant metallurgical advantage over the unmodified
aldoxime: ketoxime formulations that are in common use in Zambia.
This paper discusses results from extended side-by-side testing of
ACORGA OPT5510 against an aldoxime:ketoxime blend, at two
agitated leach operations in Zambia and the full conversion to
ACORGA OPT5510 from an aldoxime:ketoxime blend, at a heapleach operation in Arizona.
Introduction
In 2006 Cytec Industries inc. announced the development of a new series of solvent extraction
reagents that optimize copper transfer through the use of formulations containing aldoxime
and ketoxime as well as selected modifiers. The incorporation of selected modifiers results in
increased copper transfer, due to the interaction between the modifier and oximes within the
blend. These new formulations also show a significant improvement in copper iron selectivity,
which can result in lower bleed and copper reprocessing costs. The name given to the new
series is OPT which falls under the ACORGA brand of extractants. The first part of this
paper discusses results from extended side-by-side testing of ACORGA OPT5510 against LIX
984N* (supplied as LIX984N-C*), an aldoxime:ketoxime blend, at Kansanshi Mining Plc,
*LIX is a registered trademark of Cognis Corporation
THE ACORGA OPT SERIES: COMPARATIVE STUDIES
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Solwezi, Zambia. The objective of the trial was to compare copper transfer, iron transfer,
phase disengagement time, rate of crud formation under the same operating conditionsi.e.
equal reagent concentration, equal flow rates, equal settler rating, equal bed depths and equal
mixer speeds. The second part of the paper reviews results of a high concentration application
as well as the conversion from LIX 984N to ACORGA OPT5510 at a heap-leach operation in
Arizona.
Study 1: Kansanshi Mining Plc, Solwezi, Zambia
Experimental
A side-by-side pilot plant comparison of ACORGA OPT5510 and LIX 984N was conducted
on site at Kansanshi Mining Plc. during September 2007 (total run-time 30 days). Kansanshi
Mining Plc. operates an agitated leach-SX-EW circuit, which produces 120 000 tpa of copper
cathode. The pilot plant circuits were configured with two extract stages and one strip stage,
with separate loaded organic tanks but common PLS and spent electrolyte feeds. The physical
and metallurgical behaviour of the two reagents was evaluated under identical operating
conditions (i.e. equal reagent concentration, equal flow rates, equal settler rating, equal bed
depths and equal mixer speeds). Operating parameters are shown in Table IV.
The evaluation was conducted at three different O/A ratios:
Low recovery conditions
Extract O/A ratio of 1.2
Medium recovery conditions
High recovery conditions
PLS and spent electrolyte ranges are presented in Table I. Temperature profiles were taken
during the trial for record purposes. Table II shows the average daytime mixerbox
temperatures for 28 and 30 September.
The primary consequence of the warm operating temperature was the high level of diluent
evaporation, which resulted in a steady increase in max. loads (Table III) through the course
of the trial.
Table I
PLS min. and max. range during the trial
PLS
Max
Min
Average
Spent electrolyte
Fe3+
Mn
Si
H2SO4
Cu
Fe
Fe2+
(gpl)
(gpl)
(gpl)
(gpl)
(ppm)
(ppm)
(gpl)
7.96
5.27
6.77
2.63
0.59
1.16
0.16
0.33
0.23
2.47
0.26
0.93
614
408
522
360*
8.8
3.4
5.7
pH
1.87
1.18
1.51
TSS
Cu
H2SO4
Fe
Fe3+
Mn
(ppm)
(gpl)
(gpl)
(gpl)
(gpl)
(ppm)
180
36
97
40.8
29.2
35.3
215
174
193
2.03
0.6
1.28
1.33
0.12
0.77
140
190
160
Table II
Mixer box temperature
Data
28/9/2007
30/2/2007
274
ACORGA OPT 5510
LIX 984N
E1
E2
S1
E1
E2
S1
35.2
39.1
37.2
40
39.8
41.5
36.5
39
37.3
40.2
39.7
41.2
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Table III
Organic maximum loads and reagent concentrations
ACORGA OPT 5510
Date
6 September
10 September
13 September
15 September
26 September
1 October
Average
LIX 984N
ML - Cu (gpl)
Vol %
ML - Cu (gpl)
Vol %
11.9
11.0
11.8
12.9
13.8
14.1
12.6
21.8
20.2
21.6
23.7
25.3
25.9
23.1
11.6
10.3
11.2
13.6
13.4
14.3
12.4
22.3
19.8
21.5
26.1
25.8
27.5
23.8
Table IV
Pilot-plant parameters
Working volume of mixer
Mixer retention time
O/A 1.2 extract

O/A 1.2 strip
O/A 1.5 extract
O/A 1.5 strip
O/A 1.8 extract
O/A 1.8 strip
Impellor tip speed
0.029
m3
2.64
3.95
2.32
3.16
2.33
2.96
min
min
min
min
min
min
250300
m/min
Settler rating
O/A 1.2 extract

O/A 1.2 strip
O/A 1.5 extract
O/A 1.5 strip
O/A 1.8 extract
O/A 1.8 strip
3.0
2.0
3.4
2.5
3.4
2.7
m3/m2/hr
m3/m2/hr
m3/m2/hr
m3/m2/hr
m3/m2/hr
m3/m2/hr
Linear velocity
O/A 1.2 extract and strip

0.28
0.35
0.37
cm/s
cm/s
cm/s
Despite the relatively high operating temperature in the pilot plant, neither organic showed
any signs of hydrolytic degradation (aldehyde and ketone levels were <2 g/l).
Throughout the period of the trial, the physical behaviour of the two circuits was closely
monitored and data carefully recorded. Mixer continuity, phase break times and crud build-up
were measured and recorded several times per shift while organic entrainment was monitored
visually throughout.
PLS and spent electrolyte were bled-off from the feed lines to SX2-HG. For the low,
medium and high recovery tests (Ext O/A 1.2, 1.5 and 1.8) the PLS flow was 0.3; 0.3 and
0.267m 3/h, respectively; the organic flow was 0.36, 0.45 and 0.48 m3/h and the spent
electrolyte 0.08, 0.1 and 0.107m3/h. The resulting operating parameters are recorded in
Table IV. The strip O/A was maintained at 4.5:1 throughout the trial. With the exception of the
last three days, all mixers were operated organic continuous and no aqueous recycle was used
in extract or strip at any time during the trial.
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Results
Metallurgical O/A Ratios and Copper Recovery Comparison
The metallurgical O/A ratio is the change in analysed copper in the aqueous phases divided by
the change in analysed copper in the organic phases. It is an important value as it verifies the
accuracy of the aqueous and organic copper analysis. Figure 1 shows the extract and strip
metallurgical O/A ratios for the three target extract O/A ratios.
The average copper recoveries for the two reagents at the three different O/A ratios are
presented in Figure 2.
Although ACORGA OPT5510 outperformed LIX 984N under all three conditions, the
difference was greatest under the low recovery conditions where it was over 10%.
Figure 1. Metallurgical O/A ratios
Figure 2. Average copper recoveries
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Selectivity of copper over iron (III)

In addition to significantly improving copper transfer, the addition of ester-modifier to the
aldoxime-ketoxime blend has a beneficial impact on selectivity of copper over iron.
Maximizing Cu/Fe selectivity will become increasingly important at Kansanshi as the
availability of the pressure leach circuit increases, which will result in a steady increase in the
total Fe concentration in the PLS. Figure 3 shows the average E1 copper loading vs. the
average E1 iron loading for two circuits. As expected, the iron loading increases sharply as
the copper loading decreases. The difference between the two reagents, under the high
recovery condition, is around 2 ppm. Although this might not seem a lot, by reducing the
chemical iron transfer into the electrolyte by just 1 ppm per pass, the annual Co savings would
be in the range of $100 000$150 000 under current conditions.
Rate of crud formation
The rate of crud build-up both at the interface and on the bottom of the settlers was very
similar for the two reagents (Figures 4 and 5).
Figure 3. Comparison of selectivity of copper over iron (III)
Figure 4. Comparison of crud build-up in extract stages
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Figure 5. Comparison of crud build-up in strip stages
Figure 6. E 1 - phase break times
Phase disengagement times

Phase break times were monitored on a bi-hourly basis. The daily averages for the 30 day trial
are shown graphically in Figures 68.
The trend line in Figure 6 shows a gradual trend upwards, relative to the fresh reagents
though from about the 12th of September onwards the phase break times appear to level out
for both reagents. The range of 90150 seconds is normal for this reagent concentration.
The phase break times in the E2 stage (Figure 7) stayed fairly constant through the trial
period.
The S1 phase break decreased slightly as the trial progressed (Figure 8). This is not
particularly significant as there was no aqueous recycle and the O/A was 4.5:1.
Organic in aqueous entrainment was monitored visually throughout the trial. No difference
was seen in behaviour between the two circuits in any of the stages. Visual indications were
that there was no difference in the aqueous or in the organic entrainment either.
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Figure 7. E2 Phase break times
Figure 8. S1 Phase break times
Study 2: Silver Bell Mining LLC

Conversion from LIX 984N to OPT5510
In April 2007, Silver Bell Mining LLC decided to convert from LIX 984N, a blend of
aldoxime and ketoxime to ACORGA OPT5510 extractant. The initial approach was to let the
composition change over time as the new formulation was added during normal monthly
make-up additions. However, after approximately seven months of make-up, only
approximately 2025% of the plant inventory was OPT5510. Although some of the expected
improvements were seen, the full benefits were not being realized because the plant organic
was only partly converted. Additional testwork was completed which highlighted the benefits
of carrying-out a one-step conversion using a booster formulation.
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In December 2007 a programme was initiated to optimize the full plant organic inventory at
one time by the addition of a carefully calculated volume of ACORGA OPT Booster 1.
Detailed physical and metallurgical plant audits were conducted before and after the addition
of ACORGA OPT Booster 1. Approximately 1 200 gallons (4.5 m3) was added into the
loaded organic weir from intermediate bulk containers in less than one hour. Even at this
addition rate, there was no shock to the system or noticeable change in physical performance.
Post-conversion plant performance
After six months of operation after the full conversion, the plant operators and supervisors
report continued strong performance. Phase separation is good and entrainments are low.
There has been no change in the rate of crud formation. Cu recovery performance has
remained high and Cu:Fe selectivity has improved. In addition, copper recovery remains
higher during times when the PLS Cu grade spikes (converted formulation gives better Cu
recovery).
Study 3: high Cu concentration PLS
An isotherm-based metallurgical comparison of ACORGA OPT5540 against a 2.6:1 blend of
aldoxime and ketoxime (LIX 973N) was carried out using 287 g of each extractant made up to
1 000 ml with ORFOM SX-7**. The maximum loads, uptake factors and concentrations are
reported in Table V. Extraction and strip isotherms were prepared at ambient temperature by
mixing the two organic phases with synthetic pregnant leach solutions (PLS) and spent
electrolyte (compositions in Table VI) at different O/A ratios.
Comparative models were generated using Cytecs MINCHEM SX modeling software. In
all cases extract and strip stage efficiencies of 95% were used. The circuit modelled contains
three primary extract stages (O/A 3.4), two secondary extract stages (O/A 1) and two strip
stages (O/A 1.4), with the organic split 86/14 between the primary and secondary extracts.
Results are reported in Table VII.
Table V
Organic phase composition
Reagent
Mass of reagent (g) made up

to 1 000 ml with diluent
Max load
(g/l)
Uptake
(g/l/vol %)
Conc.
(vol %)
287.1
287.1
17.12
17.57
0.545
0.54
31.4
32.5
ACORGA OPT5540
LIX 973N
Table VI
PLS and spent electrolyte composition
Primary PLS
Secondary PLS
Spent electrolyte
Cu (g/l)
pH
Sulphuric acid (g/l)
Total Fe (g/l)
Fe (II) (g/l)
Fe (III) (g/l)
43.3
7.4
34.0
0.80
1.55
-
176.4
45.88
11.7
-
23.6
6.5
-
22.27
5.2
-
**ORFOM is a registered trademark of Chevron Phillips
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Table VII
Modelled recoveries
Reagent
ACORGA OPT5540
LIX 973N
HG raff
(g/l)
LG raff
(g/l)
HG Cu Rec.
(%)
13.1
14.9
0.4
0.6
69.5
65.4
LG Cu rec. Org. Cu loading

(%)
(g/l)
94.4
92.1
93.8
99.1
Strip efficiency Net Cu t/fer

(%)
(g/lvol %)
68.7
55.2
0.32
0.29
The OPT formulation performs better than the unmodified aldoxime-ketoxime blend
because of the addition of Cytecs ester-modifier, which dramatically improves stripability of
the C9-aldoxime component. The result is a shift in the strip isotherm to the left, which results
in the generation of a lower barren organic copper concentration and hence better overall
extraction.
Conclusions
The copper transfer and copper:iron selectivity improvements achieved by optimal
modification of aldoxime:ketoxime blends has been demonstrated over a wide range of
conditions. Although the metallurgical advantages will vary dependent on specific circuit
conditions within individual plants, on-site pilot testing can quickly determine the optimum
ACORGA OPT formulation and quantify production increases and/or cost savings that can be
expected. Conversion of aldoxime:ketoxime circuits to ACORGA OPT can be done over time
with normal make-up or in a single step with the use of an ACORGA OPT Booster
formulation.
References
1. SODERSTROM, M. New Reagent Developments in Cu SX, ALTA 2006 Copper Session,
Perth, Australia. 2006.
2. PHILLIPS, T., MANG, W., SODERSTROM, M., and CRAMER, K. Optimizing
Metallurgical Performance at Silver Bell mining LLC, Hydro 2008, Phoenix, AZ.
Owen Tinkler
Regional Manager, Cytec Industries
15 years experience in copper & Ni/Co solvent extraction
3 years experience in gold processing
Owen graduated from the University of the Witatersrand with a
BSc(Hons) in Applied Chemistry in 1989. After spending 10 years in
Phoenix, AZ in a variety of positions for Cytec Industries, he moved
back to South Africa in 2007 and currently holds the position of Regional Manager for
Cytec's Metal Extraction Group.
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CRANE, P., URBANI, M., DUDLEY, K., HORNER, A., and VIRNIG, M. Solvent extraction (SX) reagent
selection for high temperature, acid, chloride and Cu PLS at Port Pirie and its impact on electrowinning (EW).
Solvent extraction (SX) reagent selection for high

temperature, acid, chloride and Cu PLS at Port
Pirie and its impact on electrowinning (EW)
P. CRANE*, M. URBANI*, K. DUDLEY, A. HORNER, and M. VIRNIG
*Cognis Australia Pty Ltd., Australia
KD Hydromet Consulting Pty, Ltd., Australia
Nyrstar Port Pirie Smelter, Australia
Cognis Corporation, Tucson, USA
Nyrstars Port Pirie Copper Plant produces copper cathode from the
lead smelting process copper/lead matte by-product. More than 98%
Cu is recovered from the matte by a unique mixed chloride-sulphate
leach technology (formerly known as the BHAS process) followed by
conventional copper solvent extraction and electrowinning processes.
The highly effective agitated chloride-sulphate leach process
presents several challenges for the operation of the downstream Cu
SX-EW plant, namely it:
Produces a high temperature PLS with high concentrations of
acid, chloride and copper
Requires effective solids liquid separation and soluble silica
control
Requires high O/A ratios and high concentrations of extractant
Requires careful monitoring of organic health and regular,
effective organic treatment.
The strategy that was undertaken to examine the historical
performance of the Port Pirie Cu SX plant and the development of a
planned approach on implementing effective measures to combat the
high chloride transfer to the EW process is outlined in this paper. This
involved determining the plant organic constituents and understanding
the characteristics that presented the underlying causes to many of the
Cu SX-EW plant problems being encountered. Operational data
collected during the Cu SX plant reagent transition phase is presented.
The data illustrate the changes in organic chemistry and organic
health that ultimately produced a very different EW electrolyte to that
previously experienced in this operation. A key result of this reagent
change and attention to detail in Cu SX was the significant reduction
of the chloride concentration in the Port Pirie EW plant electrolyte.
From historical levels of >200 ppm, which required the use of
titanium cathodes, electrolyte chloride levels were reduced to less
than 30 ppm.
SOLVENT EXTRACTION (SX) REAGENT SELECTION
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Introduction
The Port Pirie smelter is located on the eastern side of the Spencer Gulf in South Australia, a
little over 200 kilometres north of Adelaide. It has a rich history, being the nearest seaport to
Broken Hill, where the rich ore field containing lead and zinc was discovered in 1883. The
smelter received its first load of ore in 1889 and in due course Port Pirie evolved to be the
centre of a lead smelting and refining industry. Over 100 years later what started out as a
minor smelter grew to become one of the worlds largest.
Originally built in 1889 with a capacity of 80 000 tonnes of lead per year the smelter was
progressively expanded in the 1950s and 1960s. The lead refinery itself was largely rebuilt in
1998 and has a demonstrated production capacity of approximately 270 000 tonnes per year
of lead metal and alloys, although the lead blast furnace and sinter plant capacity limits annual
production to approximately 235 000 tonnes. The precious metals refinery in which gold and
refined silver are recovered after extraction in the lead refinery was also largely rebuilt in
1998. The current zinc production facilities were commissioned in 1967 and have a capacity
of 45 000 tonnes per year.
Copper production facilities were commissioned in 1984 and have a capacity of
approximately 4 500 tonnes per year of copper cathode. The copper units enter the site
through numerous concentrates and are largely free. This makes the manufacture of copper
at the smelter very economical at this small scale. In addition to lead, zinc and copper metal,
Port Pirie also produces approximately 80 000 tonnes of sulphuric acid, approximately 11.5
million troy ounces of refined silver and approximately 16 000 troy ounces of gold.
Port Pirie Cu plant process description
The feed material for the Cu plant is primarily a copper-lead matte by-product from the lead
blast furnace typically containing about 35% copper, 38% lead and 12% sulphur with the
balance being minor elements such as arsenic, zinc, tin, silicon, antimony, iron, cobalt,
cadmium and nickel.
In the 1970s the BHAS Research Department developed a process for leaching the copper
matte using an acidic chloride/sulphate solution and oxygen. The successful laboratory work
led to the construction and operation of a pilot plant during 1980 and the BHAS Board
approved a commercial plant in September 1982. This plant was designed to have a nominal
capacity of 4 000 tonnes EW Cu cathode per annum and was commissioned in 1984. The
copper plant consists of five sections: grinding, leaching/solids liquid separation, SX, EW and
residue neutralization. A brief description of each section follows.1,4
Grinding
The grinding mill treats over 12 000 tonnes of crushed matte per year in a conventional ball
mill charged with 90 mm diameter forged steel balls, operating in closed circuit with a spiral
classifier. Thickened matte slurry, at 100%75 micron, is pumped to a 24-hour capacity surge
tank, where it is continuously agitated to prevent settling.
Leaching chemistry2,3
The BHAS leaching process centres on an oxidative chloride/sulphate leach of the matte to
extract copper into solution, leaving a solid lead and silver rich residue. Leaching is
conducted at atmospheric pressure at 85C. The overall chemistry of the process is
summarized by the Equation:
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[1]
The copper dissolution reaction can be described in two stages:
[2]
[3]
Equation [1] implies the dependency of the reaction on the availability of acid and oxygen.
However, what is not shown is the role of the chloride in the system. The conversion of
chalcocite to covellite, Equation [2], is rate-controlled by the amount of oxygen that can be
dissolved into the system and available to the sulphide surfaces. Distribution of oxygen is
manipulated so as to provide maximum possible oxidant in the initial leaching reactors, and
ensures that approximately 50% Cu dissolution and 100% lead sulphate conversion is
achieved within the first few hours of leaching.
The rate limiting parameter for the oxidation of covellite to Cu2+(aq), Equation [3], is the
concentration of chloride in the system. The role of chloride in sulphide copper leaching is
important to minimize the re-precipitation of covellite from Cu+(aq) if contacted with
elemental sulphur:
[4]
High levels of arsenic also promote Cu re-precipitation in the BHAS process to form a
Cu/As compound (2). It is thought that Cu+(aq) is unstable in low chloride concentrations,
therefore chloride concentrations at the Nernst boundary layer must be sufficient to complex
the Cu+(aq) prior to transport into the bulk solution where the oxidation of Cu+(aq) to
Cu2+(aq) occurs, as:
[5]
Thus, the level of chloride in the BHAS leach process is maintained at around 20 gpl in the
leach liquor to enable sufficient Cu+(aq) to be complexed and minimize the contact potential
with S0 and As during leaching3.
Primary leach
Matte slurry is fed at approximately 35 tonnes per day to six first stage leach reactors in
series, each with a nominal residence time of around 40 minutes, with the leached slurry
gravitating through the leach circuit via covered launders. The slurry is diluted with reheated
SX raffinate and concentrated sulphuric acid, to 8% solids. Compressed oxygen is dispersed
through each of the first five reactors. Leaching is maintained at an optimum temperature of
85C with the addition of steam.
The overflow from the final leach reactor containing 7% solids gravitates to the primary
leach thickener where flocculant, Magnafloc E10, is added to assist with solids liquid (S/L)
separation. The hot thickener overflow, pregnant leach solution (PLS), is pumped to a void
cooling tower where it is cooled so that the temperature in the PLS Tank is around 40C. The
cooled PLS solution is clarified to reduce the final level of suspended solids to SX.
Second stage leachhigh acid repulp
The primary leach thickener underflow at 3540% solids is pumped to the acid repulp reactor,
similar to the primary leach reactors, but with a larger residence time of around 45 hours. All
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of the chloride, as salt, and additional acid is added at this point, to ensure a high acid, high
density, high chloride repulp of the leach slurry. Oxygen is also dispersed through this reactor.
The repulped slurry is then washed with all the returning SX raffinate by mixing in a wash
mixing tank (repulp mixer) before gravitating to the repulp thickener where Magnafloc E10 is
again added.
To aid in silica control, Polysil is also added to the repulp mixer along with the returning
SX raffinate and the repulp reactor overflow. The repulp thickener overflow is directed to the
first leach reactor in the primary leach. The underflow is pumped to an agitated neutralization
tank.
Copper SX
The solvent extraction circuit is configured as a conventional 2E x 1W x 2S circuit. The PLS
containing around 40 g/l Cu, 20 g/l acid and 20 g/l chloride is pumped to two extract stages in
series. The loaded organic from E1 is washed with acidified water in order to reduce impurity
transfer (particularly chloride) then stripped in two stages with spent electrolyte returning
from EW.
Due to the high copper content of the PLS, a higher than typical extractant concentration
of approximatley 3035 volume % (in Shellsol 2046 diluent) is employed in conjunction with
a high O/A ratio of 4:1. This provides a nominal Cu recovery of approximately 70%. While
this may be considered low by industry standards, the high PLS acidity makes further copper
recovery very challenging without making significant circuit modifications or without
neutralization.
Copper electrowinning (EW)
The Cu from SX is recovered by EW process employing the ISA process using 30 cells each
containing 40 stainless steel or (later) titanium cathode plates and 41 anodes of 6% antimonial
lead. More recently a Pb/Ca/Sn composition cast anode has been trialled. FC-1100 is added to
control acid mist.
Residue treatment
The repulp thickener underflow contains recoverable lead and silver. To render the thickener
underflow solids suitable for recirculation through the smelter, it is necessary that all of the
free acid and most of the Cu process solution associated with it be removed. It is also
desirable that prior to discharging the solution associated with the thickener underflow most
of the dissolved metals be precipitated out. Neutralization of repulp thickener underflow is
conducted continuously by controlled addition of milk of lime and the neutralized slurry is
filtered on an Andritz belt filter. The residue discharges from the filter at 6070% solids and is
recycled to the lead plant. The metal free filtrate collects in a filtrate tank and is returned to
the Andritz filter with any excess being discharged to on-site waste collection.
Summary of process difficulties
The use of the highly effective chloride/sulphate leach process produced a warm pregnant
leach solution (PLS) high in acid, chloride and copper content, which resulted in several
challenges for the operation of the Cu SX-EW plant requiring, for example, effective solids
liquid separation and soluble silica control; high concentrations of SX extractant and high
organic/aqueous (O/A) ratios in extraction; and careful monitoring of organic health with
regular, effective, organic treatment.
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Following commissioning of the SX ciruit in 1984, the process experienced a gradual

deterioration in the quality of the organic phase, so causing an increase in the transfer of
chloride to the EW circuit. As chloride levels in the EW electrolyte surpassed 100 ppm, the
original 316L cathodes were replaced by titanium cathode mother plates. In 1990 the original
Acorga P5100 extractant was replaced by Acorga M5640. Over the following years, the plant
struggled with low nett copper transfer rates and high EW chloride levels in the range of 200
500 ppm, which resulted in high chlorine gas concentrations in the surrounding environment
causing corrosive damage to the EW infrastructure.
In August 2003 a sample of Port Pirie plant organic was analysed by Cognis in Tucson to
determine reasons for the poor performance by analysing the composition of the circuit
organic. The main findings were as follows:
The organic phase was dark orange in colour. It was extremely viscous and exhibited
very poor organic continuous phase separation behaviour, >15 minutes at 25C. Aqueous
continuous phase separation time was reasonable
16.2% of the total oxime in the circuit was present as the nitro-C9 aldoximea very high
levelcausing the organic phase to exhibit a very high viscosity (and a dark orange
colour)
The TXIB:C9 aldoxime ratio was significantly higher (0.38) in the plant organic
compared to that in Acorga M5640 (0.28) as a result of the differential degradation rate
of C9 aldoxime compared to the TXIB modifier. This had caused the viscosity of the
plant organic to increase with time and assisted in promoting nitration
Despite the reoximation process, the concentration of C9 aldehyde in the circuit was
quite high (2.3%) compared to other circuits elsewhere. The same conditions that favour
nitration also promote hydrolysis of the aldoxime to the aldehyde (warm temperature and
high acid concentrations in the aqueous phase). Given the operating conditions at Port
Pirie higher hydrolysis levels than conventional circuits may be expected, but the
measured levels seemed excessive, especially as Port Pirie practised continuous reoximation of the plant organic
The organic also contained significant amounts of the 2-cyano-4-nonylphenol and 5nonylsalicylamide, which is unusual. They are typically the result of thermal degradation
of the C9 aldoxime at temperatures higher than those said to be experienced in the Port
Pirie operation. They were estimated to be present at about 1015% of the level of the
C9 aldoxime, thus making a significant contribution to the viscosity of the organic phase
Copper strip kinetics were surprisingly slow, 62% @ 30 seconds. Typical circuit organics
would be expected to be in the range of 95% @ 30 seconds
The overall net transfer capability of the organic was low. It did not strip well due to the
presence of the nitro-C9 aldoxime, which is an extremely strong copper extractant. This
resulted in high stripped organic values. The net Cu transfer was further exacerbated by
the low PLS pH, which in conjunction with a highly modified circuit organic provided a
very shallow equilibrium extraction isotherm
The organic did not respond well to clay treatment probably due to the presence of
unfilterable entrained aqueous solution which deactivates clay. The entrained aqueous
may have existed as micro-emulsions formed due to the presence of the degradation
products or contaminants.
Reagent selection and Isocalc TM modelling proposal to optimize the plant operation
Cognis has experience with the effects of nitration at other Cu SX plants and has conducted
laboratory degradation studies using different extractant compositions to determine which
extractants were more resistant to nitration5,6.
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Figure 1. Effects of modifiers on the stability of oximes in the presence of nitrate
Clearly, the modified aldoximes, LIX 622N and Acorga M5640, and the modified
ketoxime, LIX84-I plus TDA, were much more sensitive to degradation/nitration than the
non-modified reagents, LIX984N and LIX84-I.
Thus, Cognis recommended that (a) Port Pirie cease addition of the modified reagent
Acorga M5640 and employ the more stable nonmodified reagent LIX 984, and (b) Port Pirie
cease re-oximation. Cognis have much experience in re-oximation, and attempts to re-oximate
heavily degraded Cu circuit organics typically result in an organic that demonstrates very poor
physical performance.
LIX 984 was selected for several reasons:
LIX 984 is a 50/50 blend of ketoxime and C12 aldoxime, both of which are more stable
than the C9 aldoxime. LIX 984 does not contain a modifier
Acorga M5640 contains both a C9 aldoxime and modifier, TXIB
TXIB (and all modifiers in general) promote nitration where nitrates are present in the
aqueous solution
LIX 984 showed good performance in the screening tests in Tucson.
In order to support the reagent conversion, a technical service package was negotiated.
Port Pirie accepted the Cognis offer and LIX reagent addition began in May 2004.
Pre-conversion plant survey
In April 2004 Cognis visited the Port Pirie smelter to conduct a pre LIX reagent addition plant
survey and to collect a second plant organic sample to provide a baseline for the conversion.7
Analysis of the plant organic revealed that the Acorga M5640 concentration was
approximately 43 vol% (24.3 g/l Cu). However, the concentration of Cu in the E1 organic was
only 9.05g/l, which calculates to a copper loading of only 37%. The Cu net transfer was very
poor, at approximately 0.14 g/l Cu per % oxime due in part to the presence of the nitro-C9
aldoxime and the weak reagent blend (due to excess TXIB modifier). All mixers were
operated aqueous continuous due to the extremely slow phase separation under organic
continuous mixing.
The phase disengagement times (PDTs) of the plant loaded organic with both the plant PLS
and a synthetic PLS were measured in the laboratory under both aqueous and organic
continuous conditions at room temperature (23C). For comparative purposes, fresh samples
of LIX984 and Acorga M5640 were also tested. The results are provided in Table I.
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Table I
Laboratory PDT results pre-LIX reagent addition
PLS/continuity
Plant organic
Plant O/C
Plant A/C
Synthetic O/C
Synthetic A/C
Sample PDT (sec)

Acorga M5640
Did not separate

126
Did not separate
71
103
119
149
49
LIX 984
104
107
139
35
Table II
Organic viscosity results pre-LIX reagent addition
Sample
SG (@ 43 vol%)
Viscosity (cSt)
Plant LO
Acorga M5640
LIX 984
0.93
26.48
0.86
5.01
0.83
3.93
Under aqueous continuous mixing conditions, the PDT was measured at similar rates to that
as experienced in the operating plant, whereas under organic continuous conditions the
emulsion demonstrated very poor phase separation behaviour taking several minutes for the
emulsion to indicate any signs that the phases would separate; and after 24 hours the aqueous
phase contained a considerable amount of rag and an indefinable interface. This indicated
high levels of organic contaminants were interfering with the coalescence of aqueous droplets
within the organic continuous emulsion. Clay treatmenteven at high dosage (10 wt% clay,
typically 25 wt% is sufficient for heavily contaminated organics)failed to improve the
PDT.
Viscosity and specific gravity (SG) measurements were conducted on the plant loaded
organic and compared to fresh samples of LIX 984 and Acorga M5640 at 43 vol%, with all
sample temperatures equilibrated in the laboratory (23C). The resultant viscosities are listed
in Table II.
The viscosity and SG of the plant organic were much higher than that for fresh LIX 984 and
fresh Acorga M5640. Both the high viscosity and SG resulted from an accumulation of
degradation products that no longer participated in the extraction and stripping chemistry but
which had a profound impact on phase separation, aqueous entrainment and plant
performance.
The physical appearance of the plant organic was unusual in that it had a distinct dark
orange/red coloration when in a thin film, and it tended to coat all surfaces with which it came
in contact. This orange/red colouration is consistent with the presence of nitration products. It
had a very syrup-like consistency and a distinct smell. When filtering plant organic, the
samples required extensive time to filter through Whatman 1PS filter paper and there was a
reasonable amount of aqueous remaining in the filter paper. This would tend to indicate that
the aqueous formed a very fine micro-emulsion in the organic phase that was not readily
released. After the initial plant survey it was concluded that the plant organic was in
extremely poor shape.
Reagent changeover period and resultant plant operation
Following the addition of LIX 984 to the circuit in April 2004, plant monitoring and organic
sampling were conducted on a regular basis to track the chemical composition as well as the
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Table III
Reagent concentrations in the Port Pirie plant organic post-LIX reagent addition
Vol% or Wt/Vol%*
Aug 03 (pre-LIX)
Jan 05
Jul 05
Oct 05
Mar 06
Jun 06
Dec 06
Feb 07
Sep 08
LIX 84-I
M5640
LIX 860-I
Nitro Oxime^
TXIB*
7.6
11.0
12.3
14.0
12.8
8.2
7.0
6.9
34.9
10.9
6.5
4.3
3.1
2.6
1.8
1.6
0.2
9.8
11.9
12.4
12.4
12.9
16.4
18.1
20.5
3.1
3.0
2.8
2.2
2.1
2.0
2.4
1.8
1.2
13.12
7.78
5.76
3.88
1.96
1.64
1.75
1.27
0.32
Note. ^ Concentration is calculated as an M5640 equivalent since the majority of the nitrated material is nitro C9 aldoxime.
The LIX reagent addition blend changed from LIX 984 to LIX 973 in April 2006
chemical and physical performance of the plant organic. Plant samples were assayed for
reagent composition, including C9 and C12 aldoxime, ketoxime, TXIB, hydrolysis products
and nitration products using a variety of analytical techniques refined by Cognis Tucson lab.
The organic composition monitoring was compared with the corresponding chemical and
physical performance monitoring. Analytical results are presented in Table III.
The cessation of re-oximation and the conversion to LIX reagent has gradually improved the
health of the plant organic. This is evident by the lower concentrations of Acorga M5640
(C9 aldoxime) and TXIB with time. The TXIB and M5640 concentrations had decreased from
13.12% and 34.9% in August 2003 to 0.32% and 0.2% in September 2008 respectively,
indicating a significant change from modified to unmodified plant organic.
The level of C9 nitro aldoxime decreased at a lesser rate than the Acorga M5640 and TXIB.
This is consistent with the level of residual copper on the stripped organic. Nitration appeared
to occur on an infrequent basis, suggesting that Port Pirie was getting nitrate into the system
via specific events throughout this period.
The chemical performance of the Port Pirie Cu SX plant was monitored regularly and
compared with the health of the plant solvent. Plant surveys and chemical analysis were used
to monitor the important parameters such as Cu recovery, reagent concentration, E1 organic
loading as % of max load and net Cu transfer. Survey data are listed in Table IV. The reagent
net transfer has improved as the LIX reagent conversion has progressed due to the reduction
in the concentration of nitro oxime species present in the plant organic and an increase in the
transfer capacity. The E1 organic loading has also increased from ~60% to above 80%. (The
low Oct 07 levels were due to a dip in PLS Cu.)
Although organic loading is highly dependent on the Cu and acid concentration in the PLS,
by reducing the TXIB content in the organic the E1 organic loading was increased, both of
which reduce the potential for crud formation.
The extraction and stripping kinetics of the Port Pirie plant organic have improved
significantly since the initial addition of the LIX reagent, as shown in Table V. Surface active
impurities crowd and compete with the oximes at the interface, adversely affecting extraction
and stripping kinetics. The reduction in the concentration of these surface active impurities in
the plant organic has improved the extraction and stripping kinetics.
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Table IV
Survey data for the Port Pirie Cu SX plant
Parameter
May 04
Nov 04
Jan 05
Jun 05
Nov 06
Apr 07
Oct 07
Sep 08
PLS flow (m3/h)

PLS Cu (g/l)
Raffinate Cu (g/l)
Cu recovery (%)
Organic flow (m3/h)
Loaded organic Cu (g/l)
Strip organic Cu (g/L)
Reagent conc. (vol%)
Net Transfer (gCu/vol%)
% max load
18.0
41.0
12.9
68.5
78.8
14.94
8.20
45.0
0.150
59.0
19.8
45.8
15.4
66.4
80.4
12.19
4.70
34.0
0.220
66.4
19.2
44.6
13.9
68.8
84.0
10.62
3.60
30.0
0.234
65.5
20.2
42.3
15.0
64.5
83.9
11.37
4.80
25.8
0.255
83.9
20.4
45.0
15.5
65.6
80.4
13.95
6.46
32.6
0.229
81.5
20.0
51.9
14.8
70.7
80.0
15.52
6.34
33.5
0.273
88.2
18.3
32.0
8.1
65.5
77.0
10.59
4.91
33.3
0.174
65.5
13.3
45.2
10.9
75.8
72.0
11.23
4.98
30.0
0.211
69.3
Table V
Extraction and stripping kinetics data for the Port Pirie Cu SX plant organic
Kinetics
Extraction @ 30 sec
Strip @ 30 sec
Aug 03
Jul 05
Mar 06
Jun 06
Dec 06
Feb 07
Sept 08
62%
71%
86%
78%
90%
90%
90%
92%
96%
96%
92.2%
97%
Table VI
Results from Laboratory PDTs for Port Pirie plant organic and plant PLS
Date
Apr 04
Jan 05
July 05
Oct 05
Mar 06
Jun 06
Dec 06
Feb 07
Apr 07
Oct 07 (45C)
Sep 08
PDT (seconds)
OC
AC
No break
No break
No break
>600
>600
600
600
474
114
49
152
126
130
110
90
72
100
93
109
201
26
450
Clay treatment on the Sept 2008 sample increased kinetics to 99.6% and 98.9% respectively.
The plant physical performance was monitored by measuring operating parameters such as
emulsion temperature, mixer continuity, mixer O/A ratio, emulsion PDT under both AC and
OC mixing (before and after clay treatment), and organic viscosity. Laboratory tests were
conducted at room temperature (22 2C).
Plant physical parameters such as temperature, mixer continuity and mixer O/A ratio
remained relatively constant for all sampling dates. The temperature was 40 2C, the mixer
continuity was always aqueous continuous, and the O/A ratio in the mixers was in the range
1.0 to 1.3. The plant PDT trends were consistent with that for the laboratory PDT. (Table VI)
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As the LIX reagent conversion progressed, the PDT of the Port Pirie plant organic decreased
significantly. This reduction in PDT corresponded with the reduction in degradation products
and impurities in the plant organic. The Port Pirie Cu SX plant is now at a stage where it can
convert all mixers to OC, which is the preferred operation for Cu SX, especially operations
that have high levels of silica and solids present in the PLS.
Initial clay treatment tests conducted in August 2003 proved unsuccessful, possibly due to
the presence of micro-emulsions in the plant organic, as witnessed previously with nitrated
oximes. Later clay treatment proved successful as the levels of nitrated oxime and other
impurities declined, as shown in Table VII.
After 2006, the clay treatment process became a part of normal operation at Port Pirie,
which also aided in improving the physical performance of the plant organic. As the LIX
reagent conversion progressed, the concentration of degradation products and contaminants
decreased, resulting in a subsequent reduction in plant organic viscosity, as shown in
Table VIII.
The chloride concentration in the electrolyte is compared against the % LIX reagent in the
organic below (Figure 2).
Table VII
Clay treatment results
Date
Pre-CT
April 04
March 06
June 06
Extraction (OC)
Post-CT
No break
920 sec
627 sec
Strip (AC)
Pre-CT
Post-CT
72
100
20
20
440
22
22
Table VIII
Viscosity of Port Pirie plant organic in cSt at 25C
Apr 04
Sep 04
Jan 05
Jul 05
Oct 05
Mar 06
Jun 06
Dec 06
Feb 07
Sep 08
26.48
19.43
15.06
15.13
13.15
13.90
12.20
9.50
8.93
6.66
Figure 2. Chloride concentration in the electrolyte
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The chloride concentration in the PLS remained consistent throughout the LIX conversion
period in the range 1525 gpl.
It is evident that as the LIX reagent conversion progressed, the chloride concentration in the
electrolyte has decreased significantly from unacceptable levels of ~200 ppm, to
approximately 100 ppm with less than 50% LIX reagent in the circuit, to less than 30 ppm
when operating with more than 90% LIX reagent in the circuit. This reduction in electrolyte
chloride corresponded exceptionally well with the reduction in nitration products, TXIB and
other impurities in the plant organic.
Conclusions
The conversion of the Port Pirie plant organic from a modified C9 aldoxime to a mainly
unmodified blend of C12 aldoxime and ketoxime, plus the decommissioning of the reoximation stage, has directly resulted in significant improvements in the health of the plant
organic. Since the modified Acorga reagent M5640 was replaced by the non-modified LIX
reagent the health of the SX organic and the performance of the circuit have both significantly
improved:
The strip point has decreased as the level of nitrated oxime has declined
Extraction and strip kinetics have improved
Net transfer has increased to greater than 0.2 gpl Cu/vol%
Reagent strength has decreased to less than 35 vol%
Wash stage acid has been reduced from 40 gpl to 15 gpl, resulting in savings on
neutralization and reduced soluble Cu losses
Organic phase viscosity has declined to a quarter of the viscosity of the pre-LIX period
Organic continuous phase separation time has very significantly improved
Clay treatment is now used to maintain organic health
And most importantly, aqueous entrainments through to EW have significantly declined,
so reducing EW chloride from more than 200 ppm to less than 30 ppm, and improving
the EW atmosphere and environment.
References
1. MEADOWS, N.E. and VALENTI, M. The BHAS CopperLead Matte Treatment Plant,
The AusIMM Non Ferrous Smelting Symposium, Port Pirie, September 1989.
2. JOHNSON R.D., MILLER, I.B., MEADOWS, N.E., and RICKETS, N.J. Oxygen
treatment of Sulphuric Materials at Atmospheric Pressure in and Acid Chloride-Sulphate
Lixiviant, The AusIMM Non Ferrous Smelting Symposium, Port Pirie, September 1989.
3. MEADOWS, N.E. and POLLARD, D.M. Oxidative Leaching of Chalcopyrite in a
Chloride-Sulphate Lixiviant, The AusIMM Adelaide Branch, Research and Development
in Extractive Metallurgy, May 1987.
4. TYSON R.K., MEADOWS, N.E., and PAVLICH, A.D. Copper production from matte at
Pasminco MetalsBHAS, Port Pirie, SA, The AusIMM, pp. 732734.
5. VIRNIG, M.J., EYZAGUIRRE, D., JO, M., and CALDERON, J. Effects of Nitrate on
Copper SX Circuits: A Case Study, Copper 2003, Santiago Chile, Hydrometallurgy of
Copper, vol. VI (2), Riveros, P.A., Dixon, D.G, Dreisinger, D.B., and Menacho, J.M.
(eds.). Canadian Institute of Mining, Metallurgy and Petroleum, 2003. pp. 795810.
6. BART, H., MARR, R., BAUER, A., SCHEIN, R., and MARAGETER, E. Copper
Extraction in Nitrate Media, Hydrometallurgy, vol. 23, 1990. pp. 281295.
7. DUDLEY K., HORNER, A., VIRNIG, M., CRANE, P., and URBANI, M. SX-EW
process optimisation at Nyrstar Port Piriethe influence of employing the correct
reagent type, ALTA 2008, Perth.
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Phil Crane
Business Manager, Cognis Australia, Australia
Phil graduated from Birmingham University with BSc Hons in
Minerals Engineering in 1975; with final year studies on copper
solvent extraction. He worked in metallurgical plants and in research
and development in Zambia and Iran; then in the design and supply of
solids-liquid separation and flotation process equipment in both
England and later South Africa. Moved to Cognis, then Henkel in
1988; working in the PGM flotation field and supporting Henkels
copper and uranium solvent extraction business activities in southern Africa. He then
transferred to Australia in 1996 and from 2002 Phil has been responsible for Cognis Mining
Chemical Technologys business and technical support in the Asia-Pacific region, specifically
in business development and customers plant troubleshooting.
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VAN RENSBURG, D.M. MUNYUNGANO, B., HAIG, P., LOUIS, P., and STOLTZ, J. Organic degradation in
uranium and cobalt solvent extraction: the case for aliphatic diluents and antioxidants. Hydrometallurgy
Organic degradation in uranium and cobalt

solvent extraction: the case for aliphatic
diluents and antioxidants
D.M. VAN RENSBURG*, B. MUNYUNGANO
*ChemQuest (Pty) Ltd, South Africa
Rssing Uranium Limited, South Africa
In the solvent extraction of cobalt, nickel, uranium and zinc, various

parties 1,2 have reported over the years that a certain amount of
degradation of the organic phase has taken place, affecting kinetics,
loading and phase separation times.
When the degradation products of the organic phase were detected
at a uranium operation in Namibia3, a cobalt refinery in South Africa,
and a cobalt pilot plant in the DRC4, a number of steps were taken to
combat the problem, including the use of an aliphatic diluent and the
addition of butyl hydroxy toluene as an antioxidant.
Through a combination of laboratory testing and plant observation,
it was concluded that plant management to identify, isolate and
control the source of the oxidant material was sufficient to combat the
problem, and that neither the diluent change nor the use of the
antioxidant was proven to have made any significant difference to the
degree of organic degradation
Introduction
In 2002, Rssing Uranium mine in Namibia reported that organic phase breakdown products
may be the cause of problems in the strip section of the solvent extraction plant, which
seemed to relate to the presence of nitrosamines3. Extensive crud formation, poor stripping
efficiency and excessive organic entrainment were noted. ChemQuest was approached as the
supplier of the isodecanol in use as a phase modifier, and as link to the supplier of the
diluents, which at that time was Shell Chemicals.
At the same time, a small cobalt extraction facility in South Africa reported very poor
performance on the nickel/cobalt separation stage of their process4, which also appeared to be
linked to breakdown products of the organic extractant and diluents.
ORGANIC DEGRADATION IN URANIUM AND COBALT SOLVENT EXTRACTION
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As ChemQuest was extensively involved in the supply of organic reagents, and a number of
projects in the DRC were beginning to develop, we decided to invest some time in
researching the subject of organic degradation in certain solvent extraction operations, and the
measures taken to combat the problem.
Organic degradation in uranium solvent extraction
The organic phase at Rssing is made up as follows:
Alamine 336, a tertiary amine: 7% by volume
Isodecanol phase modifier: 3% by volume
Diluent, initially Shellsol 2325: 90% by volume
The tertiary amine extractant R3N functions as follows:
First it protonates in sulphuric acid 2R3N + H2SO4 (R3NH)2SO4
Then it exchanges/extracts uranyl sulphate: (3(R 3 NH) 2 SO 4 + UO 2 (SO 4 ) 2 2- (R 3 NH)
6UO2(SO4) 4 +SO42This is a process of ion association and differs from copper extraction (chelation, or
complex formation) and systems using acidic extractants such as D2EHPA and Cyanex 272
(solvation). It is neither highly selective nor as pH dependent as the chelation and solvation
processes, and in practice ion exchange with many anionic species takes place, including coextraction of nitrates to form nitrosamines:
The presence of the nitrosamines and other organic degradation products, detected by gas
chromatographic analysis, was correlated directly with the upset conditions on the SX plant.
In turn, the formation of the nitrosamines was initially linked to two factors: the ingress of
nitrates with process water originating from the explosives in the open pit and high redox
potentials from the leach circuit. The presence of Mo as a catalyst was also identified as a
contributor.
Nitrates and nitrosamine formation
Laboratory tests indicated that the presence of nitrous acid at a concentration of 1 g/l and at a
redox potential of 550 mV led to the formation of nitrosamines.
Water is a scarce resource in the Namib Desert and the recycling of water is unavoidable
there simply is not enough water to bleed and top-up to keep species like nitrates under
control cost-effectively. The use of pit water in the elution of the ion exchange resin
(upstream from the SX, to produce the pregnant leach feed solution to the SX) is inevitable
and thus also the ingress and build-up of nitrates. However, the reduction plant managers have
found that controlling the nitrates in the PLS to SX at 0.50.7 g/l and loadings on the organic
to below 1 g/l controls the nitrosamine formation to acceptable levels.
It was found that the nitrosamines were scrubbed from the organic phase during the solvent
regeneration step using sodium carbonate.
Routine monitoring of nitrates in the concentrated eluate (effectively the SX PLS), the
ammonium sulphate, the strip solvent and at other points has been implemented (see Figures 1
and 2). Control of the pH in the strip and scrub sections was integral to the removal of the
nitrosamines, and better management measures were also introduced.
Obviously, the reduction of the amount of nitrates in the incoming water sources, although
nearly impossibly expensive, is an ongoing exercise.
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Conc. chlorides and nitrates

Cl-
NO3-
1.2
3.5
1
0.8
2.5
2
0.6
1.5
Nitrates (g / l )
Chlorides (g / l )
0.4
1
0.2
0.5
2007/01/28
2006/12/31
2007/01/14
2006/12/17
2006/11/19
2006/12/03
2006/11/05
2006/10/08
2006/10/22
2006/09/10
2006/09/24
2006/08/27
2006/07/30
2006/08/13
2006/07/02
2006/07/16
2006/06/18
2006/06/04
2006/05/21
2006/05/07
2006/04/09
2006/04/23
2006/03/12
2006/03/26
2006/02/12
2006/02/26
2006/01/29
2006/01/15
0
2006/01/01
Figure 1. Rssing plant monitoring
Amm. sulph and strip solv nitrates

Amm. sulph
Target
Strip solvent
8
7
6
g/l
5
4
3
2
1
2007/01/28
2007/01/14
2008/12/31
2008/12/17
2008/12/03
2008/11/19
2008/11/01
2008/10/22
2008/10/03
2008/09/24
2008/09/10
2008/08/27
2008/08/13
2008/07/30
2008/07/16
2008/07/02
2008/06/18
2008/06/04
2008/05/21
2008/05/07
2008/04/23
2008/04/09
2008/03/25
2008/03/12
2008/02/25
2008/02/12
2008/01/29
2008/01/01
2008/01/15
Figure 2. Rssing plant monitoring
Redox potential
The link between high redox potential and the degradation of the organic phase was
investigated, both on the plant and by a survey of similar circumstances reported in the
literature.
The acid leaching of the Rssing uranium-bearing ore requires the oxidation of tetravalent
uranium oxide to the acid soluble hexavalent form. This is achieved by indirect oxidation via
ferric ions. The ferric is reduced to ferrous, then re-oxidized to ferric by the addition of
pyrolusite, manganese dioxide. The process is controlled by the maintenance of the ferric to
ferrous ratio. The carry-over of high redox potentials from the leach to the IX and in turn to
the SX is controlled by the addition of iron metal (wire) to the pregnant solution.
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Despite the link found in research and in the laboratory between high redox potentials and
organic degradation/formation of nitrosamines, no significant correlation was found between
the redox potential in the leach and the redox potential in the SX circuit. The poor milling of
pyrolusite and associated carry-over of MnO2 to the IX did not influence the redox potential
in the SX. Varying redox potentials in the leach and in the concentrated eluate from IX did not
reflect in the measured redox potential anywhere in the SX circuit, nor did it correlate with
nitrosamine formation or SX performance upsets.
Other organic degradation factors/products
The literature survey and the experience of some applications (see below) led to Rssing
investigating the possibility of the degradation of the other organic constituents5,6, namely the
isodecanol and the paraffinic diluent. Dr. Gordon Ritcey7 noted from personal experience as
follows:
Isodecanol (CH3(CH2)9OH) was oxidized in the presence of air and high redox potential to
aldehyde, carboxcyclic acid and eventually primary alcohol which will result in poor
coalescence.
Iso-tridecanol (CH3(CH2)12OH) which is inherently more stable and has lower solubility in
both the aqueous phases and in many organics, had been used in applications where
degradation was noted and possible.
Isodecanol is an essential phase modifier in uranium solvent extraction systems as it
improves the solubility of the tertiary amine in the diluent5. Rssing have a standard method
for testing the kinetics, loading and phase separation characteristics of their fresh organic
constituents, and tested a sample of isotridecanol. They found it offered no significant
difference to isodecanol, and as it was considerably more expensive, they did not pursue its
possible use. Furthermore, in the examinations of the both the fresh organic and degraded
organic chromatographic scans, no difference in the peaks of the isodecanol could be detected.
Without further evidence, it was decided that no isodecanol-linked degradation products
could be detected, and that no change would be made to the isodecanol use or regime.
The diluent presented another scenario entirely. Following the reported experience of cobaltcatalysed degradation of diluents (discussed below), and laboratory testing under accelerated
oxidative conditions, it was decided that the aromatic diluent in use, Shellsol 2325 containing
1623% aromatics, would be replaced by Sasol SSX 210, with < 0.1% aromatic fraction.
Initial testing was performed by ChemQuest in the laboratory, using a jacketed glass
reaction vessel, similar to the Acorga apparatus used for testing copper solvent extraction
reagents, together with a variable speed stirrer. A number of extraction and strip tests were
carried out using a synthetic solution containing uranyl sulphate, and in the case of the
degradation tests, some permanganate ions as the oxidizing agent (5 mg/l as KMnO4) and
butyl hydroxy toluene (BHT) as an antioxidant (0.2% m/v). The starting pH was maintained
exactly by adjustment with NH4OH.
The purpose of the test was to determine, inter alia, the effect of organic oxidation on
extraction and phase separation times with the type of diluent and the presence or absence of
BHT as the variables.
The accelerated oxidation was done at an elevated temperature (45C) using the same
synthetic solution used by Rssing to perform their own kinetic tests, but with the addition of
the permanganate ions. Organic to aqueous ratios were kept at exactly 1:1 and mixing times
and stirrer speed kept constant (180 minutes, 220 rpm). Air was bubbled through uniformly
during the oxidation phase using a constant pressure air pump.
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The organic phase was removed after the oxidation and tested for extraction and phase
disengagement using the same synthetic PLS solution but without the permanganate ion, at
ambient temperature, and using the same apparatus. (See Figure 3.)
The complete test methods, solution concentrations, test parameters and all results are
available from the author in a separate document8 which includes work on copper, zinc and
cobalt/nickel solvent extraction systems.
The key results related to uranium were as follows: (Table I)
The most significant indication was that, with or without BHT anti-oxidant, the aliphatic
diluent showed far fewer deleterious effects after oxidation than was seen by the diluent
containing a portion of aromatics.
As there was no funding or incentive available for ChemQuest to continue these tests, they
were limited to single results and the single set of oxidizing conditions. Rssing, however,
accepted the trends indicated and decided to continue with a plant change-over to the aliphatic
diluent and to test the use of the BHT.
B 24 Sockets
Water out
1 cm Baffle
(4 in all)
Thermometer
pocket
1 litre
Beaker
Graduated
scale (mm)
3 cm
Water in
10.2 cm
Figure 3. Apparatus used in accelerated degradation tests phase disengagement and kinetic apparatus
Table I
Results related to uranium
Extraction of uranium, %
Shellsol 2325
Sasol SSX 210
Shellsol 2325 with 0.2% BHT
Sasol SSX 210 with 0.2% BHT
Phase disengagement time, secs
Before oxidation
After oxidation
Before oxidation
After oxidation
73.1
72.9
72.2
72.9
33.8
54.9
63.8
71.8
35
38
35
36
95
78
51
40
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To date, the aliphatic diluent has not been shown to provide any significant changes in the
operation of the solvent extraction facility. A number of factors, such as strip efficiency, crud
formation at low temperature, and bacterial growth may or may not be linked to the diluent
change, especially as other influencing parameters have also changed.
The BHT has not yet been tested on the plant.
As Rossing have simultaneously instituted corrective measures and tests to control the
ingress of nitrates, and therefore the formation of nitrosamines, the influence of the diluent
change cannot be measured or quantified, and no conclusion drawn.
What is clear from this exercise, however, is that it remains better to tackle the source of the
problem, rather than treat the symptoms and effectsi.e. controlling the formation of
nitrosamines is probably far more beneficial and effective than trying to adapt the organic
reagents to handle the oxidative conditions.
Organic degradation in cobalt/nickel separation solvent extraction
ChemQuest was alerted to a problem encountered in a very small solvent extraction facility in
South Africa. Though not much more than a pilot plant, the facility was part of a plant used to
produce a pure cobalt carbonate product, which in turn was calcined to cobalt oxide for sale in
Europe.
The solvent extraction part of the facility used di-ethyl hexyl phosphoric acid (Bayer
D2EHPA) to extract zinc and manganese from cobalt-rich leachate. A cobalt nickel separation
was then performed using bis (2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272).
The D2EHPA circuit showed increased viscosity, poor phase separation, and an increase in
organic entrainment. Although the zinc and manganese extraction was not significantly
different, it was seen that co-extraction of nickel and increased extraction of cobalt was taking
place, both of which are not expected from the extraction curves for D2EHPA at the pH levels
used in the plant. The Cyanex 272 circuit was performing within normal parameters initially,
but started demonstrating poorer extraction kinetics.
Even though the above plant was shut down by Umicore before resolution of the problem,
samples were obtained for laboratory testwork.
At the same time, Kasese Cobalt in Uganda was reporting crud runs that occurred without
obvious reason in both their D2EHPA and Cyanex 272 (later replaced by Ionquest 290)
circuits9, Chambishi Metals in Zambia reported crud problems in their D2EHPA circuit strip
section10 and Namzinc Skorpion in Namibia was experiencing silicaceous gels in the Zincex
D2EHPA SX and downstream coalescers and filters linked to high acidity in the leach
plant11.
As ChemQuest was in the process of introducing the product Chemorex D2EHPA to the
market, and was assisting on a pilot-plant testing Ionquest 290, it was decided to do a study on
organic degradation in these SX circuits as part of the technical service.
Figures 4 and 5 give extraction curves generated with actual leached ore samples from the
Congo Cobalt Corporation (now Boss Mining) Kakanda Cobalt Facility, which produces a
heterogenite based cobalt concentrate in an oxide flotation circuit.
The literature1,2, as well as a study done by Barnard12 indicated that problems could be
generated by aromatic portions of the diluent breaking down. This could not be the case at
either the Umicore circuit or at Kasese Cobalt, as they were both using aliphatic diluents
(Shellsol D70 and Sasol SSX 210 at Umicore, Escaid 110 at Kasese). However, a common
factor observed was the presence of manganese in high oxidation states at both plants. At
Kasese, the manganese was oxidized in the electrowinning plant and returned with spent
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100
90
80
% Extraction
70
60
50
40
30
20
10
0
0
pH
Figure 4. Chemorex D2EHPA extraction curves. 30% v/v in Escaid 100 at 35C. All aqueous solutions soluble metal
salts, pH adjusted by H2SO4. All points generated by changing O: A ratios
CYANEX 272 17.5% in ESCAID

Using actual PLS solutions ex-Congo + NH4CH
120
100
% Extraction
80
60
40
20
0
0
Equilibrium pH
Figure 5. Cyanex 272 extraction curves
electrolyte as the strip solution in the cobalt/nickel SX. At Umicore, the leach section used
strong oxidants, including peroxide, which were probably carried into the PLS entering the
D2EHPA circuit.
At Kasese, however, parallel testing and plant observations linked the crud formation to
biological growth and high levels of acid-soluble silica. No evidence of permanganateinduced degradation was proven.
The Umicore D2EHPA (18% by volume in Shellsol D70/Sasol SSX 210 blend) was sent for
GCMS scansboth fresh solutions and the sample of degraded organic. Initial observation
indicated peaks similar to those found on samples from a Versatic 10 (neo-decanoic acid)
nickel pilot circuit at Tati Nickel (now Norilsk) in Botswana. In the degraded plant organic,
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Table II
The effect of BHT as an antioxidant
Extraction of zinc, %
Shellsol D70
Sasol SSX 210
Shellsol D70 with 0.2% BHT
Sasol SSX 210 with 0.2% BHT
Phase disengagement time, secs
Before oxidation
After oxidation
Before oxidation
After oxidation
88.2
87.0
88.1
87.4
81.3
80.1
88.2
87.9
27
29
28
28
45
49
33
34
carboxylic acid type peaks were detected at a similar wavelength and retention time as
detected by Barnard. These were not present in the freshly prepared organic. We drew an
interim conclusion that the organic breakdown products contained carboxylic acids, which led
to the co-extraction of nickel that had been observed. No accidental cross-contamination of
the D2EHPA by Cyanex 272 was noted.
Unfortunately, the Umicore plant was shut down before the work could be completed, and
as there was no particular financial advantage for ChemQuest to continue the research, the
work was not completed.
However, during the course of the study, a more detailed study was done on the effect of
BHT as an antioxidant, as mentioned above and in reference8, but with a D2EHPA system
instead of the amine, and using only the aliphatic diluents. Using the same methods and
apparatus described above, and similar artificial oxidation conditions to degrade the organic,
on samples without BHT, the major results of the laboratory study were as follows: (Table II)
The above exercise was aimed at proving firstly that there was no significant difference
between the two diluents, and secondly that there was a measurable influence on extent of
possible degradation by using BHT antioxidant. These objectives were partly achieved, but
the project was not completed for the reasons indicated above.
If organic degradation is found or suspected in SX circuits using solvation-type extractants
such as Cyanex 272, Ionquest 290, D2EHPA or Versatic 10, then the use of an antioxidant is
probably indicated. There is some contradictory evidence on whether aromatic diluents should
or should not be used, but this becomes largely irrelevant when the antioxidant is used.
Acknowledgement
We would like to thank P. Haig, P. Louis and J. Stoltz for their contribution to this paper.
References
1. FLETT, D.S. and WEST, D.W. The Cobalt Catalysed Oxidation of Solvent Extraction
Diluents Proceedings ISEC 86, Munich, 1986, vol. II. pp. 310.
2. RICKLETON, W.A., ROBERTSON, A.J., and HILLHOUSE, J.H. The Significance of
Diluent Oxidation in Cobalt-Nickel Separation, Solvent Extraction and Ion Exchange,
vol. 9, no. 1, 1991. pp. 7384.
3. Personal correspondence between the author and Brodrick Munyangano and others,
Rssing Uranium, 20022008.
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4. Personal correspondence between the author and various parties at Umicore, Waste
Products Utilisation, Chambishi Mines, SGS Lakefield and Mintek. All written.
5. MACKENZIE, J.M.W. Uranium Solvent Extraction using Tertiary Amines, Presentation
Uranium Ore Yellowcake Seminar February 1997, Melbourne, Australia
6. MAXWELL, B., RASDELL, S., and CARLIN, P. Oxidative Stability of Diluents in
Co/Ni solvent Extraction Presentation ALTA 1999.
7. Personal correspondence between the author, Peter Haig of Shell Chemicals and Dr.
Gordon Ritcey. All written correspondence on record.
8. VAN RENSBURG, D.M. Accelerated Degradation Tests on Uranium, Copper, Zinc and
Cobalt/Nickel Solvent Extraction Solutions Currently under preparation and refereeing
for presentation.
9. Personal correspondence between the author and Moses Mugabe, Amos Silungwe and
Stanford Saungweme of Kasese Cobalt.
10. Personal correspondence between the author and Hira Singh, Robert Minango and
Kennedy Mwanza of Chambishi Metals.
11. Personal correspondence between the author and Johan van Rooyen (now with TWM),
Herman Fuls and Jurgen Gnoinski of Namzinc and Dr. Kathy Sole of Anglo Research.
12. BARNARD, K.R. (AJ Parker Co-operative Research Centre) Tools for Diagnosis of Crud
and Organic Degradation Problems in SX Circuits ALTA 2001.
Deon van Rensburg

Product Manager, ChemQuest (Pty) Ltd, South Africa
1995 to date: Manager of Solvent Extraction, Ion Exchange and
Adsorbents Division at ChemQuest (Pty) Ltd;
Responsible for the development of Chemorex range of
extractants;
Solvent Extraction plant technical service and design.
19881995: NCP ACIX Division, manager activated carbon division
19831988: Allied Colloids, technical representative
19801982: Student
19751979: Anglo American Research, learner official/student
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VAN DEN BERG, D.A., MAR, P., and NEL, G.J. Development of the Tati Activox BMR ammonia recovery
circuit. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and Metallurgy, 2009.
Development of the Tati Activox BMR ammonia

recovery circuit
D.A. VAN DEN BERG*, P. MAR*, and G.J. NEL
*Hatch, South Africa
Norilsk Nickel, South Africa
The TATI Base Metal Refinery (BMR) was designed to be a

hydrometallurgical processing plant employing Norilsk Nickel
Process Technologys Activox leaching technology, solvent
extraction and electrowinning to annually extract and recover 25 kt of
LME grade nickel, 22 kt of LME grade copper and 640 tonnes of
cobalt as a carbonate. The BMR requires acid neutralization in the
cobalt and nickel solvent extraction (SX) circuits where pH control is
crucial for selective extraction of the base metal sulphides from the
pregnant leach liquors. The choice of neutralizing reagent and
treatment of the resultant neutralization product affect the overall
plant design.
This work discusses the criteria used to select ammonia as the
neutralizing reagent for the BMR design, as well as the development
of an ammonia recovery circuit.
The ammonia forms a soluble ammonium sulphate neutralization
product, which reports to the SX raffinate stream. The BMR ammonia
recovery circuit uses vibrating mills to contact the ammonium
sulphate with calcium oxide (fine quicklime). The ammonium
sulphate is converted to CaSO4 (fine gypsum precipitate) and aqueous
ammonia. A series of seeded reaction tanks are used to further
encourage the gypsum precipitation and crystal growth. Aqueous
ammonia is then stripped from the slurry in steam stripping column,
and condensed to a 10% solution for reuse. The barren gypsum slurry
reports to the tailings dam, where supernatant solution is recovered
for use as process water.
Anhydrous ammonia is used as top-up to account for losses due to
the ammonia recovery circuit.
Introduction
The Tati Base Metal Refinery (BMR) has been designed as a greenfield project close to
Francistown in Botswana. The remote site location in Sub-Saharan Africa introduces several
challenges specific to the BMR design including logistics, as well as water and power
constraints. An ammonia recovery circuit was designed for the BMR specifically to ease these
constraints.
DEVELOPMENT OF THE TATI ACTIVOX BMR AMMONIA RECOVERY CIRCUIT
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The BMR project is a hydrometallurgical processing plant employing Norilsk Nickel

Process Technologys proprietary Activox leaching technology, solvent extraction and
electrowinning to extract and recover annually 25 kt of LME grade nickel, 22 kt of LME
grade copper and 640 tonnes of cobalt as a carbonate from the Tati Nickel Mine concentrates.
The process consisted of ultra fine milling, low pressure and temperature leach, solid liquid
separation, solvent extraction, electrowinning, iron removal, cobalt precipitation and ammonia
recovery. The BMR requires acid neutralization in the cobalt and nickel solvent extraction
(SX) circuits to selectively extract Co and Ni from the pregnant leach liquors into a high
grade, pure loaded liquor for final metal production. Ammonium sulphate is produced during
the SX neutralization process and remains in the SX raffinate solution.
The ammonia recovery circuit is designed to recover aqueous ammonia from the SX
raffinate solution for reuse in the SX as a neutralization agent. Recovering the ammonia
reduces reagent make-up requirements and reduces the plant fresh water consumption by
producing recyclable process water. The process solution from the ammonia recovery circuit
can be reused as wash water in the solid liquid separation step.
This paper will outline the decision to use ammonia as the SX neutralizing agent, the
decision to use an ammonia recovery circuit, and the overall role played by ammonia recovery
in the BMR design.
The Tati Activox plant
Tati Plant process description
The Tati process is outlined in Figure 1, including the ammonia recovery and ammonia
dosing.
Tati mine concentrates are repulped from 90 to 50% solids using copper raffinate from the
CuSX and fed to an ultra-fine grinding mill circuit where the concentrate is ground to 80%
less than 10 microns. Milled slurry is then fed into the Activox autoclaves where it is reacted
in the multi-compartment horizontal autoclave, using oxygen at elevated pressures of 11 bar
(g) and moderate temperatures of 105C to produce copper, cobalt and nickel sulphates in
Figure 1. Tati Activox BMR process flow
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solution for downstream recovery. The leach discharge slurry proceeds to the solid-liquid
separation section that includes a 7-stage CCD washing circuit, where the leach residue solids
are washed with recycled process water. The washed leach solids are then pumped to the PGE
flotation circuit to recover the PGEs from the wash leach residue. The pregnant leach solution
(PLS) from the CCD train is clarified prior to reporting to the copper PLS pond.
The PLS is contacted with an organic solvent that selectively extracts copper from the
aqueous solution in copper solvent extraction. Copper is stripped from the organic using spent
electrolyte from the copper EW circuit. A portion of copper raffinate is recirculated to the
concentrate preparation area for repulping the concentrate and for temperature control inside
the autoclaves. The remainder of the copper raffinate is advanced to the iron removal circuit
where the iron is precipitated using limestone. The thickener overflow is passed through
clarifiers before it reports to the Co PLS pond.
Cobalt PLS is contacted with an organic solvent that selectively extracts cobalt from
solution in cobalt solvent extraction. Cobalt is stripped from the loaded organic phase with an
acidic strip solution and the resultant loaded strip liquor (LSL) is filtered and pumped to the
cobalt precipitation circuit. The pH in the cobalt SX circuit is maintained using aqueous
ammonia. The LSL from the cobalt SX circuit is treated with sodium carbonate (soda ash) to
recover cobalt as a carbonate product.
The cobalt raffinate is then contacted with an organic solvent that selectively extracts nickel
from the process solution in nickel solvent extraction. Nickel is stripped from the loaded
organic phase with spent nickel electrolyte recirculated from nickel EW. The pH in the nickel
SX circuit is maintained using aqueous ammonia addition. The nickel raffinate stream is
transferred to the ammonia recovery circuit.
Ammonia is dosed for pH control in the cobalt and nickel SX circuits. The ammonia forms a
soluble ammonium sulphate neutralization product, which reports to the SX Raffinate stream.
The TATI ammonia recovery circuit uses vibrating mills to contact the ammonium sulphate
with calcium oxide (fine quicklime). The ammonium sulphate is converted to CaSO4 (fine
gypsum precipitate) and aqueous ammonia. A series of seeded reaction tanks is used in the
BMR design to further encourage crystal growth. The slurry stream is then pumped into a
steam stripping column, where aqueous ammonia is stripped to the column overheads and
condensed to a 10% solution for reuse. The recovered aqueous ammonia is topped up with
anhydrous ammonia to account for losses and recycled for pH control in the SX circuits. The
barren gypsum slurry reports to the tailings dam, where supernatant solution is recovered for
use as process water in the solid liquid separation step.
The Tati reagent selection
Reagent types
The acid neutralization in the SX circuits of hydrometallurgical facilities generally utilize
ammonia, sodium hydroxide or sodium carbonate. The choice of pH control reagent is largely
driven by economic factors, logistics and availability.
Ammonium hydroxide
Ammonia is supplied as liquid anhydrous ammonia, which is stored under pressure. The
anhydrous ammonia is diluted in water to form aqueous ammonium hydroxide; the solution is
easier to handle and simplifies dosing and pH control. The ammonium hydroxide neutralizes
the sulphuric acid in the SX circuit and produces a soluble ammonium sulphate product, as
shown in Equation [1].
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[1]
The ammonium sulphate can be crystallized and sold as fertilizer, or reacted with quicklime
to recover the ammonia for reuse while forming a gypsum by-product.
Sodium hydroxide
Sodium hydroxide is generally provided as a 50% solution and stored in stainless steel tanks.
It is similarly diluted to lower concentrations to simplify usage. The sodium hydroxide reacts
with sulphuric acid to produce a soluble sodium sulphate product, as shown in Equation [2].
[2]
The sodium sulphate is typically crystallized, as is the case of Rustenburg Base Metals
Refinery, and sold for use in detergents, Kraft sulphate pulping, and glass manufacturing.
Sodium carbonate
Sodium carbonate is generally delivered as an anhydrous solid and dissolved in tanks to
around 30% solution. These tanks are mild steel, and must be heated above 36C to prevent
heptahydrates and decahydrates from precipitating. The sodium carbonate reacts similarly to
sodium hydroxide to produce a soluble sodium sulphate neutralization product, as shown in
Equation [3].
[3]
The sodium sulphate is similarly sold for use in detergents, Kraft sulphate pulping, and glass
manufacturing.
Ammonia as the reagent of choice for Tati
The remote plant location in Francistown Botswana resulted in high transportation costs for
all reagentsammonia, sodium carbonate and sodium hydroxide.
The use of ammonia provided the lowest cost option, provided that 90% of the ammonium
sulphate product was recovered and reused to reduce the fresh reagent make-up requirements.
The option to produce ammonium sulphate crystals, which could be upgraded to a saleable
product, was not feasible for the BMR project due to the lack of market in Botswana.
Therefore the choice of neutralizing reagent for the Tati plant was selected due to financial
drivers, and largely to reduce logistics costs6.
The ammonia recovery process
The traditional lime boil process
The recovery of ammonia from ammonium sulphate is historically referred to as a lime boil.
The lime boil consists of two operations, preparing the slaked lime and reacting to recover
ammonia, as discussed by Regan (1999)7.
Typically quicklime is reacted with water in a slaker to form milk of lime. The reaction is
exothermic and the solution temperature increases. The milk of lime is then pumped to a
stirred reactor tank containing the ammonium sulphate solution. The ammonium sulphate and
lime mixture reacts and is brought to the boil by direct steam injection. Ammonia has a lower
partial pressure than the solution and will concentrate in the vapour phase. The vapours are
condensed and ammonia recovered.
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The traditional lime boil process equipment is subject to poor operability due to severe
scaling and the risks associated with descaling the reactor tanks. Furthermore, the gypsum
tends to coat any unreacted lime particles leading to reagent utilizations as low as 50%,
resulting in high reagent consumptions and costs (Regan, 1999)7.
The Tati ammonia recovery circuit
The Tati ammonia recovery developments
The ammonia recovery process utilized in the BMR design was developed by Norilsk Process
Technology to overcome the main drawbacks of the traditional lime boil process, particularly
lime utilization and gypsum scaling, while minimizing steam consumption as discussed by
Johnson and Zhuang (1999)4 and later by Harrison (2008)3.
The BMR ammonia recovery circuit is presented in the Figure 2 as a block flow diagram. It
includes the vibrating mills, reaction tanks, stripping columns, vapour condensers and off-gas
scrubbers.
The detailed design of the ammonia recovery circuit called for materials of construction that
could handle the high chloride levels in the nickel raffinate stream. This necessitated the use
of SAF2205 as the primary material of construction for the mill reactors, reaction tanks and
stripping columns in contact with nickel raffinate. The stripping column vapours did not
contain chlorides and therefore the condensing systems were constructed from 304L stainless
steel.
The innovations in the BMR ammonia recovery process are intended to manage gypsum
scaling. The high scaling probability and process risk demanded that the circuit be designed
with 100% redundancy to allow for descaling on line and 95% plant availability.
Vibrating mills
The barren nickel raffinate solution, rich in ammonium sulphate, reports to the ammonia
recovery circuit. The raffinate is preheated to 90C and fed into a vibrating mill with dry
quicklime (CaO) powder. The quicklime reacts exothermically with the aqueous solution to
form soluble calcium hydroxide, as shown in Equation [4].
Figure 2. Block flow diagram of the Tati ammonia recovery circuit
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[4]
This exothermic reaction maintains the mill temperature and reduces the mill steam
requirement. The fine quicklime particles further react with the ammonium sulphate to release
95% of the ammonia into solution while producing gypsum precipitate, as shown in
Equation [5].
[5]
The use of vibrating mills is unique for this process (Western Minerals Technology, 2000)5
and is intended to reduce gypsum scale from forming on the milling media or the vibrating
mill walls. Furthermore, the agitation of the milling media serves to abrade the gypsum
coating off any unreacted quicklime particles, improving the reagent utilization to as high as
91% (Harrison, 2008)3.
The direct addition of quicklime to the ammonium sulphate solution is a second significant
departure from the traditional lime boil process, where the quicklime is first slaked with
water. This reduces the amount of water dilution and utilizes the significant lime hydration
energy. This results in lower steam consumption, smaller equipment requirements, and
improved stripping column ammonia purity.
The mills are maintained at a temperature close to the solution boiling point by the reaction
energy (and steam as required), thus favouring the liberation of an ammonia rich vapour. The
mill off-gas is vacuum extracted to draw any ammonia gas into the ammonia stripping
column.
Reaction tanks
Analysis of the pilot plant stripping column showed scaling on the slurry feed plate during
start-up and upset conditions, suggesting that complete gypsum precipitation had not occurred
in the vibrating mills during upset conditions. A series of two reaction tanks was included in
the design to provide additional gypsum precipitation residence time and to limit scaling to
the vibrating mill and reaction tanks.
The first reaction tank is seeded with recycled gypsum particles. The seeding serves to
discourage gypsum precipitation on the reaction tank walls, agitators, pipes and pumps by
improving crystal growth. The seeding of precipitation tanks is a recommended method for
reducing gypsum scale on equipment as discussed by Cooper and Slabbert (2005)2. The
reaction tank vapours contain some ammonia and are combined with the vibrating mill
vapours before reporting to the stripping column.
Stripping column
The gypsum slurry, containing ammonia in solution, is pumped from the reaction tanks into
the countercurrent steam stripping column. The ammonia in solution is preferentially stripped,
as shown by Equation [6].
[6]
The ammonia and water vapours exit the top of the stripping column and are condensed in a
series of condensers. A portion of the condensed ammonia solution is removed as a 10%
ammonia product while the remainder is refluxed back to the top of the stripping column to
improve the final ammonia concentration. The product ammonia solution is combined with
fresh anhydrous ammonia to account for the 10% ammonia losses in the plant.
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The stripping column, condensers and scrubber were designed by Process Plant Technology
PTY LTD1. The stripping column was designed to achieve a 95% stripping efficiency and
combined with the 95% reaction efficiency in the vibrating mills, results in an overall
ammonia recovery of 90% in the ammonia recovery circuit. The stripping column design also
minimized steam requirements and catered for the highly scaling gypsum slurry.
The Tati BMR stripping column design was optimized to reduce the plant steam
consumption. This was achieved by using a higher liquid to vapour (L/V) ratio than in the Tati
Hydrometallurgical Demonstration Plant (HDP) plant. The BMR design tray efficiency was
higher than the HDP tray efficiency, due to larger tray spacing, column diameter and
improved liquor flows. The final tray efficiency selected for the Tati BMR design was 15%.
The theoretical number of stages was initially predicted using a McCabe Thiele diagram, as
shown in Figure 3, and later confirmed with ASPEN modelling1. The theoretical number of
stages was corrected using the predicted tray efficiency to calculate the actual number of
stages and the design column height.
The BMR column discharged slurry into a vacuum flash cooler. The flash cooler
incorporated a thermo-compressor, which could recover steam from the discharge slurry and
reduce the live steam requirements by almost 30%. The discharged gypsum slurry is
thickened and sent to the tailings pond. The gypsum is settled and the solution recovered for
reuse as gypsum saturated process water in the solid liquid separation step.
Condensers and scrubber
The ammonia vapours are drawn from the top of the stripping column, through a primary
cooler and secondary condenser system. The resultant ammonia rich solution proceeds to a
product tank, with the non-condensable gas and entrained ammonia vapour reporting to a
multi-stage scrubber.
The primary condenser was designed to cool the ammonia vapours and preheat the nickel
raffinate feed to the vibrating mills. The secondary condenser was designed to condense
ammonia vapours while preheating cooling water to provide a hot water utility for use
elsewhere. These design constraints complicated the condenser and scrubber design. The
BMR design utilized a three-stage scrubber, where the first two stages utilized dilute ammonia
Figure 3. McCabe thiele diagram for ammonia-water system with Tati operating parameters
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condensate to improve the overall ammonia recovery while meeting the cooling constraints.
The final scrubbing stage used sulphuric acid to reduce the ammonia concentration in the off
gas to allow venting to atmosphere.
Conclusion
The choice of neutralizing reagent for the SX circuits affects the overall plant design. The
logistic and economic drivers for BMR favoured the use of ammonia integrated with an
ammonia recovery circuit. The ammonia recovery circuit incorporated several new
technologies over the traditional lime boil operations, resulting in higher quicklime
utilizations, improve plant availabilities, smaller equipment, lower energy requirements, and
improved management of gypsum scale.
References
1. BRADBURY, S. Interview by author, Johannesburg, 27 August 2008.
2. COOPER, R.M.G. and SLABBERT, W. Designing for Scale Control in Hydrometallurgy.
CHEMECA 2005, Brisbane, 2528 September, 2005.
3. HARRISON, R. Norilsk Process Technologys ammonia recovery. Alta 2008 NickelCobalt Sessions, Perth, 1618 June, 2008.
4. JOHNSON, G.D. and ZHUANG, Y. Western Minerals Technologys ammonia
regeneration process. Alta 1999 Nickel-Cobalt Pressure Leaching & Hydrometallurgy
Forum, Perth, 1112 May, 1999.
5. JOHNSON, G.D., ZHUANG, Y., and WESTERN MINERALS TECHNOLOGY PTY
LTD. Ammonia Recovery. International publication number WO 00/41967. 2000.
6. NEL, G. Confirmed by e-mail correspondence with author, Johannesburg, 18 August
2008.
7. REGAN, T.A. An investigation into ammonia recovery by lime boiling. M.S. thesis.
Department of Chemical Engineering, Univ. of Queensland. 1999.
Dylan van den Berg

Process Engineer, Hatch, South Africa
Dylan is a process engineer with two years of experience in the design
and engineering of mineral processing, pyrometallurgical and
hydrometallurgical facilities. He has developed specialist technical
expertise in areas that include METSIM process modelling and
managing mass balance tables. Dylan has been involved as a graduate
process engineer on two significant hydrometallurgical execution
projects in Africa, namely the Kamoto Redevelopment Project in the
DRC (Copper and Cobalt) and the TATI Activox Project in Botswana (nickel, copper, cobalt).
Recently Dylan has been involved in several concept level studies for both
pyrometallurgical and hydrometallurgical projects, including the Eastplats furnace expansion
Project in Marikana (PGM smelter/converter) and Akanani Project (PGM and base metal
refinery/roaster/smelter/converter).
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KHAN, A.F., T. SPANDIEL, VAN SCHALKWYK, T., and RADEMAN, J.A.M. pH advanced process control
solution for Impala BMR first stage high pressure acid-oxygen leach. Hydrometallurgy Conference 2009, The
pH advanced process control solution for Impala

BMR first stage high pressure acid-oxygen leach
A.F. KHAN*, T. SPANDIEL*, T. VAN SCHALKWYK, and
J.A.M. RADEMAN
*Impala Platinum Ltd
Nickel Solutions CC
CSence Systems (Pty) Ltd
Blue
The CSense advanced process control (APC) solutions main

objective was to improve the stability of the pH in the first stage leach
process thereby improving nickel and iron extraction efficiencies and
reducing the base metal (BM) content in the platinum group metals
(PGM) concentrate. By improving the stability of the control of the
pH on the first stage leach it had the corresponding effect of
improving the Ni extraction efficiency by 0.5% and the Fe extraction
efficiency by 3.3%. The system relieved the operators of many
decisions that were virtually impossible to make given the complex,
variable and real-time nature of the processes in their charge. On the
operational side, the operators understand the APC system and they
trust it. Another benefit is the reduction in pH peaks in the autoclave,
which can oxidize certain elements whereby they become difficult, if
not impossible, to leach. These elements go right through the process
and end up contaminating the PGM solids, with the result that the
entire batch has to be recycled through a lengthy and costly
processing pipeline.
Introduction
Impala Platinums Base Metals Refinery in Springs gets its raw material from the companys
mining, concentrating, smelting and converting facilities in Rustenburg. The BMR then
removes as much of the base metals as possible and sends the PGM (Platinum Group Metals)
concentrate to the PMR plant for further processing. The base metals are refined and sold
separately to maximize the conversion of raw material into revenue (Figure 1).
A background to first stage leach
The aim of the first stage leach process is to maximize the dissolution of nickel, cobalt and
impurities and to leave copper and PGMs in the solids for treatment in the second stage
processes. The subsections that follow describe the first stage leach process together with
process chemistry and the process challenges.
pH ADVANCED PROCESS CONTROL SOLUTION FOR IMPALA BMR
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Figure 1. A simplified flow diagram of Impalas processes
Figure 2. First stage leach process flow diagram
Process description
Figure 2 shows a flow diagram of the first stage leach process. The matte from the mineral
processing plants is fed with demineralized water to the ball mill to increase the surface area
of the particles for leaching. Tank TK2100 serves as a buffer tank for the milling operation
and the feed tank to the first stage circuit. Pulp density is adjusted in tank TK2102 with spent
electrolyte solution. The spent electrolyte solution is return solution from the copper
electrowinning section.
The slurry from tank TK2102 is pumped to the first compartment of the autoclave.
Currently two autoclaves operate in parallel. Steam is added to the first compartment to
maintain the required temperature and oxygen is added to maintain pressure as well as to
oxidize the sulphides to sulphates in the presence of sulphuric acid from the spent electrolyte.
The spent electrolyte also serves to control pH in the autoclave.
The overall reaction mechanism could roughly be divided into three stages (as determined
by a batch leaching experiments by Rademan, 1995) where the major reactions occurring in
each stage of the leaching process differ, i.e.:
Stage I (1040 minutes)the cementation of copper and the leaching of nickel from the
alloy phase and out of the Ni 3 S 2 phase. Refer to reactions Equations [1][7] as
determined by Rademan (1995) and Rademan, et al. (1999).
[1]
[2]
[3]
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[4]
[5]
[6]
[7]
Stage II (40160 minutes)the selective leaching of nickel to form various Ni-S mineral
phases and the simultaneous leaching and cementation of copper to form the various CuS mineral phases. Refer to reactions Equations [8][13] as determined by Rademan
(1995) and Rademan, et al. (1999).
[8]
[9]
[10]
[11]
[12]
[13]
Stage III (160300 minutes)the simultaneous leaching of nickel (to form NiS and
Ni 3S 4) and copper (to form and CuS). Refer to reactions Equations [14][18] as
determined by Rademan (1995) and Rademan, et al. (1999).
[14]
[15]
[16]
[17]
CuS is oxidized by O2 (Equation [18]) to form Cu2+ and SO42-.
[18]
The principal reactions occurring in the initial stages of the first stage leach are the reactions
of nickel alloy (Ni) and heazlewoodite (Ni3S2) with sulphuric acid (H2SO4) and Cu2+ in
solution in the presence of oxygen (O2) to form copper sulphide and nickel sulphate.
For control purposes the process needs to be controlled as close to the end of Stage II as
possible at all times.
Process challenges
The required iron (Fe), an impurity, in the matte is below 1%. However, matte batches
delivered to the BMR sometimes have more than 1% Fe. The Fe needs to be leached in the
first stage process and is then removed in the jarosite circuit. When this does not happen, the
Fe finds its way to the PGM circuit where it is very difficult to leach out and therefore
constrains the downstream processes.
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The problem experienced in the first stage leach process is that the process controllers are
not always able to cope efficiently with the apparently capricious behaviour of the process.
This could be due to:
a lack of sufficient understanding of the critical control elements of the process
having to cope with plant emergencies and breakdowns and not being able to closely
monitor the process (specifically pH), and
the fact that they have, most of the time, two processes to monitor continuously, i.e. two
autoclaves.
Because most of the process controllers control the process by experience and feeling,
which inherently means that different operators will control the process differently. Therefore,
this causes an unstable process from the one shift to the next.
Nickel (Ni) in the matte is in the region of 47% and is primarily leached in the first stage
process. Therefore it is crucial to have a high Fe and Ni extraction efficiency in the first stage
leach process. It is known that pH in the region of 1.8 and 2.2 serves to offer good extraction
efficiencies. pH was manually controlled by process operators with some shifts performing
better than others. Considering the myriad reactions taking place in the first stage leach
process as well as the other control variables, the challenge was to control pH within the
specification limits in real time.
Samples are taken hourly from compartment nos. 1 and 4 of the autoclave for analysis of the
metals content (Ni, Cu and Fe). pH samples are taken at shorter intervals to determine the pH
of the pulp in these two compartments because it is the primary control variable. Depending
on the pH, the operator will vary the spent electrolyte flow rate to the autoclave or adjust the
pulp flow rate to the autoclave. In certain instances the operator will also increase the pulp
density in the feed to try and make up for lost production to the detriment of the efficiency of
the process.
The performance improvement design
A feasibility study was conducted to define the boundaries of the problem, assess current
status and to present a solution design before starting with the implementation.
Feasibility study
The problem experienced in the first stage leach process is that the process controllers are not
always able to cope efficiently with the apparently capricious behaviour of the process. To
provide the context of the complex behaviour each parameter used as part of the solution and
its effect on the process are briefly discussed below:
Process disturbance variables
Matte compositionthe variation in the composition (amounts of the different elements)
in the feed matte will have an effect on the leaching process to a varying degree,
depending on the actual increase or decrease of a specific element. For example, if the feed
matte contains a higher concentration of iron (Fe) it will result in a higher concentration of
iron, in either the leach discharge solution or in the solids (depending on the control
efficiency of fist stage leach).
Spent electrolyte solution compositionvariations occur in the acid concentration of the
spent electrolyte solution coming from the copper electrowinning section, as well as in the
concentration of other ionic species (Ni, Cu, Fe, Co, etc.). The variation in the acid
concentration will influence the rate of chemical reactions taking place in the autoclave.
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The variation in the ionic species will have the same effect on the leaching process as does
the variation in the matte composition. Furthermore, it is possible that ammonium ions
(NH4+) in the spent electrolyte solution will form jarosite precipitates under high pH
conditions in the first stage leach, making it almost impossible to leach out in the latter
stages of the process, and it will eventually result in high Fe in PGM (platinum group
metals) concentrate product to PMR (platinum metals refinery).
Pulp feed ratethe feed rate to the autoclave should be set at a setting that is believed to
be the optimum for the maximum throughput while obtaining the desired degree of
leaching. Currently the feed rate is sometimes varied by the operator, to help to get the pH
within the required control range more quickly, but mostly when downstream bottleneck
conditions occur.
Process state variables
Pulp densitythe pulp density is a very important factor in the reaction kinetics of the
pulp, because for lower or higher pulp densities the leaching will either be more, or less
efficient. More importantly, this will affect the pH in the autoclave. Ultimately the pulp
density in the first compartment in the autoclave needs to be controlled. The design
requirement was for a pulp density of minimum 1.35 kg/m3 to a maximum of 1.50kg/m3 in
the autoclave. A too high pulp density will result in high pH values and too low pulp
density will result in too low pH values.
Cu in solutionthe Cu in leach solution is necessary for the cementation reaction with
metallic Ni, but an oversupply of Cu in solution negatively affects downstream processes.
The Cu in solution is primarily supplied via the spent electrolyte that can contain high
concentrations of Cu.
Adjustable variable
Spent electrolyte flow ratethe spent electrolyte flow rate to the autoclave is the primary
variable to control the pulp density and indirectly the pH in the autoclave. The spent
electrolyte flow rate is also adjusted by the operator to achieve the desired pH in the first
compartment of the autoclave that ultimately influences the performance of the process.
Target variable
pH in 1st compartment of autoclavethe pH in the first compartment of the autoclave is
controlled by the addition of spent electrolyte solution to the autoclave. Furthermore, it is
assumed that if the pH (and pulp density) in the first compartment is correct and the standard
process conditions exist, the pH in the fourth compartment will be correct.
Therefore, the primary parameters, from the above list, that lead to variation of the pH in the
first stage leach are:
Pulp density
Spent electrolyte flow rate to the autoclave
Pulp feed rate to the autoclave.
PID control loops
Proportional-integral-derivative (PID) control loops are single-input single-output controllers
based on first order Laplace transform calculations. PID loops are the norm for forming the
base layer control of any industrial plant. Therefore, it is important to ensure that PID control
is used as far as possible, and that the current PID control is maintained properly.
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Sampling and measurement

A key requirement for implementation of automated advanced process control (APC) solution
is that the target measurement is available online and timeously. An online pH sampling
system has been developed by Impala in-house, as shown in Figure 3.
pH sampling sequence:
Sample and the drain valves open for 3 seconds
The drain valve closes but the sample valve remains open for a further 4 seconds
Sample valve closes
All valves remain close for 50 seconds giving the solution in the pot time to settle and
the pH transmitter opportunity to read the sample value
The reading from the transmitter is stored into the correct PLC address location for the
time of sample taken. (Each time interval sample for the 10 minute sequence has its own
address allocated and displayed on Scada)
The drain and flush valves open simultaneously for 6 seconds, flushing out the sapling
pot
Drain valve closes but the flush valve remains open for another second before closing
The pot should now be filled with water waiting for the next sample to be taken.
The sampler sequence is triggered from the PLC clock every 10 minutes, starting on the
hour.
Performance benchmark
The average pH and standard deviation values for the autoclaves 2110C and 2110D are shown
in Table I. The average pH in the first compartment of both autoclaves is acceptable, but the
problem is rather the high standard deviations, i.e. > 1. The high standard deviations are also
an indication of the reactive control that operators have to use to bring the pH back to the
target value, which is roughly around 2.0. The average pH in the fourth compartment of
autoclave 2110D poses a problem as this average of 3.4 is excessively high and will lead to
insufficient leaching (Rademan, 2005). This unleached material is then propagated through
the circuit to the final PGM concentrate that is sent to the PMR.
Figure 3. Picture of actual pH sample pot arrangement on the autoclave
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Table I
pH averages and standard deviations for autoclave 2110C and 2110D
Average pH #1
Standard deviation pH #1
Average pH #4
Standard deviation pH #4
2210C
2210D
2.2
1.16
2.3
0.82
2.4
1.23
3.4
1.49
Figure 4. pH in #1 distribution histogram for autoclaves 2110C and 2110D
Figure 4 is an indication of the distribution of the pH values in the first compartment of

autoclave 2110C (top) and 2110D (bottom). The objective of the proposed pH control system
would be to reduce the tailing of the pH to the high side (as marked on graph). The reduced
variation in pH in the first compartment should lead to reduced pH variation in the fourth
compartment. The pH in the fourth compartment of the autoclave is a direct result of the pH in
the first compartment.
If one analyses the average pH values with the daily extraction efficiencies for Ni, Cu and
Fe, certain trends can be recognized:
The lower the average pH value the higher the Ni extraction
A large difference between the pH average on the #1 and #4 compartments result in a
low Fe extraction
A low Fe extraction gives rise to a high Cu cementation rate (high negative value).
The lower the average pH value, the higher the Ni extraction. This confirm the findings by
Rademan (1995) that for higher acid concentrations, the higher the Ni extraction. Therefore,
Ni extraction is purely a function of acid concentration or pH. A negative outcome of too high
acid concentration is that Cu might start leaching, i.e. the kinetics for Cu extraction will
increase.
A large difference between the pH average on the #1 and #4 compartments result in a low Fe
extraction. This is an effect caused by unstable pHs were the operator has to decrease the pH
in the first compartment significantly to quickly get the pH in the fourth compartment under
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control. This leads to an excessive amount of spent electrolyte being added in the first
compartment, where the Cu in solution has to be cemented first before any significant Fe
leaching can occur. The end result is that only Cu cementation occurs with the associated Ni
leaching, but not much Fe is leached in the process. This then results in the phenomenon
where a low Fe extraction gives rise to a high Cu cementation rate (high negative value).
The objective is to improve the pH control on the first stage leach process. The first step is
to stabilize the control as far as possible by trying to avoid significant pH variations. The
second step is to optimize the process to increase throughput and improve quality.
Control philosophy
Based on the results and discussions above, a practical and low risk control solution can be
developed. However, in certain areas it will also require a change in the current operating
philosophy. In principle the philosophy is to automatically manipulate the spent electrolyte
flow rate via the controller, leaving the pulp feed rate to the autoclave as a variable that the
process controller can adjust.
The proposed control philosophy is to vary as few parameters as practically possible.
The temperature and pressure in the autoclave should be set to 145C and 450 kPa,
respectively and should not be changed
The pulp density in tank 2102 should be kept constant as far as possible
For increasing or slowing down production, the pulp feed rate to the autoclave should be
adjusted
The spent electrolyte flow rate should be used as the parameter for primarily controlling
the pH in the autoclave.
In summary, change the feed rate setpoint for increasing or slowing down production and
change spent electrolyte flow rate to control the pH. By varying any of the parameters
unnecessarily it becomes exponentially more difficult for the process controller to maintain a
constant pH in the first stage leach process.
The controller will be able to adapt for variations in the pulp feed rate to the autoclave. The
controller will also be able to adapt for any change in the variables mentioned above, but it
will result in less stable pH control. The control philosophy for the advanced controller is
schematically shown in Figure 5. The controller will consist of two components, i.e. a
feedback control component and a feed forward control component.
The feedback control component will make use of the latest available pH measurement and
implement set point changes on the spent electrolyte flow rate through a fuzzy controller. The
feed forward control component will calculate the required amount of spent electrolyte given
the current pulp density in tank 2102 and the pulp feed rate to the autoclave. A rule based
method will be followed to combine the feed forward and feedback suggested changes to the
spent electrolyte flow rate to achieve optimal pH control in the first compartment of the
autoclave.
Controller design and simulation
Process and instrumentation data were collected from the plant historian. The data were
analysed to establish the following:
Scope and opportunities for process control and automation improvements
Base layer control stability
Equipment health and constraints
Control element operating range
Current operating and control philosophy
Sufficient step test data to perform system identification.
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Figure 5. Proposed advanced pH process control solution for the first stage leach process
Figure 6. CSense simulationstructure layout
Plant data analysis revealed that there was a real need for higher level automation of the
autoclave since regular operator action was required to maintain plant stability. Due to regular
process step changes by the operators, sufficient step test data were available to perform
system identification. System identification was performed (Ogunnaike and Ray, 1994;
Seborg et al. 1989) and dynamic process models for the process were obtained. This was used
to construct a simulation of the process that in turn was used for control system design
(Ogunnaike and Ray, 1994; Juuso, 2007).
The initial modelling and control system design was done in Matlab after which it was
migrated to the implementation platform, CSense, where further simulation testing was
performed before commissioning of the control system. Figure 6 shows the simulation
configuration that was used in CSense. Commissioning of the control system was rapid since
control system architecture and controller parameter optimization was done upfront.
Figure 7 describes the relationship between the pH setpoint, feed flow rate and copper
concentration. For higher copper concentrations a higher pH is preferred with a maximum pH
of 2.5. pH setpoint is adjusted based on autoclave throughput and discharge copper content
according to Figure 7. Figure 7 was formalized based on operator experience.
The control system consists of the following elements:
Feed forward control on spent electrolyte proportional to the autoclave feed rate
Fuzzy controller feedback control (Reznik, et al. 2000) on the pH measurement by
manipulating spent electrolyte flow rate
Feed forward and feedback controller speed adjustment based on the spent electrolyte
acid concentration
pH setpoint selection based on feed rate and Cu concentration
Logic for that caters for exception process conditions.
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Figure 7. pH setpoint as function of feed flow rate and Cu concentration in first compartment
Figure 8. First stage summary page on SCADA
SCADA interface
The SCADA pages were modified to give the process controller feedback from the APC. The
buttons on the top right-hand corner of the page indicate the status of the controller. From the
first stage summary page one can navigate to the APC page by clicking on the header text for
pH values.
Figure 8 shows the first stage summary page from which the APC pages can be accessed.
Figure 9 is an illustration of the SCADA mimics that the operator can view the samples,
stop and start the pH controller and do some basic troubleshooting. On the APC page the
various parameters used by the APC can be viewed. The pH values obtained for the previous
hour can also be seen.
Commissioning of the APC began in mid-August and lasted four days. This reduced
commissioning period was achieved through good simulation and presentation exercises. The
commissioning did not interrupt the daily operation of the process. Minor changes were
required for better performance of the control system. A value for the concentration of acid in
the spent electrolyte (SE) was added as the concentration of the acid in the SE affects the
leaching kinetics.
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Figure 9. SCADA mimic of pH sampler and advanced process control (APC) solution
On these mimics a suggested setpoint value, target pH value, APC communications status,
spent control faceplate, matte feed value and Cu value can be obtained.
SE flow suggested setpointthis setpoint value is fed back from the advanced controller
and will replace the setpoint of the spent flow control should the APC controller be
turned on. The value is determined by calculation in the APC controller
APC Target pH valuethis value is determined by the APC controller taking into
account the feed rate of matte into the autoclave and also the Cu value of solution in first
compartment of the autoclave
SCADA-APC communications statusthis is also called the heartbeat of the APC
controller. Should communication be lost between APC controller and the plant PLC,
this status will indicate an error. If this error or error indication between RUN/STP
buttons (Bad Data) activates, the controller will automatically be turned off and an
audible alarm will activate to inform the process controller of this action. When this
happens, the last known setpoint will remain active in normal auto mode and can be
changed by the process controller if required
Actual SE flow controlthis is the loop faceplate to control the flow rate of spent into
the autoclave. The setpoint will automatically be adjusted if the APC controller is turned
on. The setpoint will then be the same as the suggested setpoint value from the APC
controller. The process controller must enter the setpoint value for flow when the APC
controller is turned off
Matte feed to autoclavethis value is the total matte feed to the autoclave from the air
pump feed settings
Cu value in first compartmentthis value represents the Cu as sampled in the first
compartment of the autoclave. The value must be entered by the process controller to
adjust spent setpoint accordingly. This value is used in the calculation of pH setpoint and
needs to be updated when significant changes occur in copper values
TK0313 FAthis value gives spent electrolyte acid concentration. It is to increase or
decrease the response speed of the APC feedback controller. When spent acid
concentration is high, the APC controller is slowed down and vice a versa
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Figure 10. Typical control infrastructure for leaches domain
Trendstrends are also added to view historical data of APC controller outputs. These
trends can be viewed by selecting the pop-up trend buttons located on the mimic.
Controller limitations are its dependency on accurate measurements and on the operator to
enter Cu assays as they become available.
Server infrastructure layout and OPC connection
A server is located in the process control server room and connected on the process control
network is used as the CSense server. It communicates with the Citect SCADA servers via
OPC to allow control via SCADA mimics (see Figure 10).
The server is supported by a Dell maintenance agreement providing 4 hours turnaround
time and a cold desktop standby is available in the event of failure. A backup copy of the
control blue print is made every time an audit is conducted on the system. Although the
CSense APC server has not failed since installation two years ago, Impala BMR is
considering a hot server standby as more advanced process controllers are being installed in
the plant to control critical process parameters.
Project management
The project was managed using the guidelines of the project management body of knowledge
(PMBOK) by the PMI (Project Management Institute) and managed by a PMP (project
management professional). A well developed capital application backed by a good feasibility
study, choosing the best project team, having regular project meetings, managing change as
the project progressed, involving stakeholders, good communication, and rewarding team
efforts contributed towards a successful project that was completed on time and within
budget.
Informal hands on training were provided for the first stage process operators and the
supervisor during the commissioning period. The functioning and the operation of the APC
were explained. Formal training was provided on CSense Architect for engineers and
instrumentation technicians. Work procedures have been developed for the use of the
advanced controller via the Citect SCADA. The work procedures are a quality document and
registered on the SAP system. The work procedure is used by operational personnel in
conjunction with the leach domain operational work procedures.
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All stakeholders were involved in the project from the onset. The presence of a control
engineer on site during the commissioning period also helped with change management. The
success of the implementation of the controller could be seen immediately with improved pH
values.
The plant managerleach as well as the leach supervisor were kept fully abreast of the
progress of the project and also participated in project progress meetings. Buy-in from the
leach supervisor was instrumental in getting the process controllers to accept the new
controller. The immediate improvements in the pH values in both first stage autoclaves
resulted in happy customers. The extent of the satisfaction of the end user is remarkable as
they would not allow for the controller to be switched off when a request was made to
conduct a before/after analysis.
Performance results
Data gathered during the scope study (termed old data) were used to compare with data
obtained after controller implementation. The analysis focused on proving the following:
Better pH values
Improvement in Ni and Fe extraction efficiency
Reduction of base metal (BM) content in the PGM concentrate.
The control solutions main objective was to improve the stability of the pH in the first stage
leach process thereby improving nickel and iron extraction efficiencies and reducing the base
metal (BM) content in the PGM concentrate.
All data refer to corresponding periods in October-November 2005 and October-November
2006. The standard deviation for pH decreased from 1.16 to 0.82 and 1.23 to 0.74 in
Autoclaves AC2110C and AC2110D respectively. By improving the stability of the control of
the pH on the first stage leach it had the corresponding effect of improving the Ni extraction
efficiency by 0.5% and the Fe extraction efficiency by 3.3%, as shown in Table II (Rademan,
2007).
The BM content in the PGM concentrate was lower for the period examined. Nickel in the
concentrate was reduced from 1.93% to 1.46% and iron from 5.58% to 3.75%. The standard
deviation for BM in the PGM concentrate was lower for the period. A net improvement of
1.4% in the total PGM concentrate despatched to the PMR was achieved by better control of
the pH in the first stage leach autoclaves.
These results indicate conclusively that the CSense pH controllers have improved the
operation of the first stage leach significantly.
Controller performance monitoring
For support and ongoing monitoring an e-mailed report using the CSense platform is made
available to key stakeholders of the first stage process. The report is emailed at 03:00 every
morning and provides the graphical performance of the pH control on both first stage
autoclaves for the previous days 24 hours. The report offers assistance with detection of
deviations and observance of good performance. Figure 11 shows an example of the daily
report.
Table II
Extraction efficiencies for Ni and Fe in corresponding periods in 2005 and 2006
Extraction efficiency
Ni
Fe
2005
2006
Average
Std deviation
Average
Std deviation
91.2%
85.2%
1.70
5.69
91.7%
88.5%
1.35
6.97
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Real-time monitoring of the controller performance is done via SCADA.

The haphazard adjustment of spent electrolyte flow rate has been reduced. In the past,
process controllers used to change the pH setpoint every 20 minutes, provided that they were
present in the control room. Now, the pH setpoint is changed automatically, every 10 minutes,
by the APC. Figure 12 shows an impressive trend of the pH in autoclave AC2110D. The
green line represents the pH in the first compartment and the red line is the pH setpoint. The
yellow line represents the pH in the fourth compartment. The blue line displays the changes
made on the spent electrolyte flow rate.
Change management
The manner in which the project was implemented enhanced personnel confidence in the
control system. A control engineer spent time on site, not only to gain an understanding of the
process but also to explain the new control system to those who were directly involved. Any
questions or uncertainty experienced by the operators were quickly resolved.
Figure 11. Daily controller performance report
Figure 12. pH and spent electrolyte SCADA trend
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Before the controller was implemented, a setpoint for the spent electrolyte flow was
suggested to the process controller. The process controller then manually adjusted the spent
electrolyte flow. In this manner the process controller could assess the performance of the
APC and also indicate it was achieving the correct result. On the success of this process the
APC then assumed automatic control of the spent electrolyte flow rate.
The leach process supervisor and the first stage process controllers have verbally expressed
confidence in the system. The project was also primarily motivated on the basis of improving
the PGM concentrate quality and this was achieved, making the project a resounding success.
For me, the CSense-based APC is like an extra process controller on that section of the
plant. Previously, if a process controller was to leave the plant for any reason, there was no
one left to control the pH. Today the APC takes care of that. From a manual system, this has
evolved to a system where pH samples are evaluated in real time (instead of through a lab)
and you can see the result of these evaluations changing the process as it happens. Arnoldus
(Vossie) Vosloo, Leach Plant Supervisor, Impala Base Metals Refineries (Khan, et al. 2008).
Conclusion
The system relieved the operators of many decisions that were virtually impossible to make
given the complex, variable and real-time nature of the processes in their charge. On the
operational side, the operators understand the process and the APC system. pH is the control
parameter and the CSense-based APC currently in use has resulted in operators trusting it and
using it to their advantage. Another benefit is that the system allows the operator time to look
after the multitude of critical process variables and equipment.
Realized benefits:
Through less iron and nickel content, the PGM concentrate grade is much improved
From the performance analysis:
The pH variation has been reduced from 1.2 to 0.7 (an improvement of 40% in pH
stability)
The nickel extraction efficiency has increased by 0.5%
The iron extraction efficiency has increased by 3.3%
The PGM grade has increased by 1.4%
These numbers may seem small, but they are extremely significant to the financial benefit of
all our refining processes.
Other benefits include:
A reduction in pH peaks in the autoclave, which can oxidize certain elements whereby
they become difficult, if not impossible, to leach. These elements go right through the
process and end up contaminating the PGM solids, with the result that the entire batch
has to be recycled through a lengthy and costly processing pipeline
Acceptance of the system by operating staff who now also trust it to do the right thing
Stable process control in spite of variations caused by disturbance variables
Indirectly limiting environmental emissions
Real savings affecting Impalas business bottom line.
Acknowledgements
We want to acknowledge Dauw Venter and Dennis Lee for the assistance in commissioning
the APC solution as well as for the write up and picture of the sampling system. We would
also like to acknowledge the operational staff that assisted and contributed in making this a
very successful project, i.e. Selilo Semosa and Vossie Vosloo, as well as Impala Platinum Ltd
for allowing the publication.
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References
JUUSO, E.K. Modelling and Simulation in Advanced Process Control, Control Engineering
Laboratory, Department of Environmental and Process Engineering, University of Oulu,
Finland. 2007.
KHAN, A.F., SPANDIEL, T., VOSLOO, A., and SEMOSA, S. Advanced pH controller helps
Impala BMR. MMS Mag, June 2008, pp. 2022.
OGUNNAIKE, B.A. and RAY, W.H. Process Dynamics, Modeling and Control. Oxford
University Press, New York and Oxford. 1994.
RADEMAN, J.A.M. The simulation of a transient leaching circuit. PhD thesis, University of
Stellenbosch, South Africa. 1995. 261 pp.
RADEMAN, J.A.M. Impala BMR First Stage Leach pH control, Scoping Study CSKM05100263-1.1, 15 December 2005 (Internal document), 2005. 49 pp.
RADEMAN, J.A.M. Impala BMR First Stage Leach pH control, Performance Evaluation.
2007.
CSKM0510-0263-3.3, 12 March 2007 (Internal document), 10 pp.
RADEMAN, J.A.M., LORENZEN, L., and VAN DEVENTER, J.S.J. The leaching
characteristics of Ni-Cu matte in the acid-oxygen pressure leach process at Impala
Platinum. Hydrometallurgy, vol. 52, 1999. pp. 231252.
REZNIK, L., GHANAYEM, O., and BOURMISTROV, A. PID plus fuzzy controller
structures as a design base for industrial applications. Engineering Applications of
Artificial Intelligence, vol. 13, 2000. pp. 419430.
SEBORG, D.E., EDGAR, T.F., and MELLICHAMP, D.A. Process Dynamics and Control.
Johnson Wiley & Sons, New York. 1989.
Abdullah F. Khan
Plant Manager - Systems
Abdullah Khan is equipped with a chemical engineering degree from The University of
Natal. He started his career doing chemical engineering research and then moved on to
consulting work in the automation industry. He was thereafter employed by Impala Platinum
to lead the implementation of information and control systems across the Refineries. He has
served Impala Platinum Refineries for almost 7 years and currently holds the Systems
Manager position.
Over the years, Abdullah has successfully managed many information and control systems
projects that provided significant value to stakeholders. He serves to implement and support
these systems as well as to provide strategic direction in the functionalities that are required
from such systems to meet business goals. He has gained insightful experience in the fields
of APC, MES, LIMS, SCADA, project management, business intelligence, IT infrastructure
and systems integration whilst at the same time being exposed to operations management.
Impala Platinum has afforded Abdullah the opportunity to gain experience and exposure to
the wider management functions within the Refineries which ably equips him to deliver on
key performance areas. He is also a project management professional (PMP) and is currently
completing his MBA studies.
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KNIGHOFER, T., ARCHER, S.J., and BRADFORD, L. A cobalt solvent extraction investigation in Africas
Copper Belt. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and Metallurgy,
2009.
A cobalt solvent extraction investigation in

Africas Copper Belt
T. KNIGHOFER*, S.J. ARCHER, and L. BRADFORD
*TWP Matomo Process Plant (Pty) Ltd, South Africa
MDM Technical Africa (Pty) Ltd, South Africa
Metorex Ltd. South Africa
Processing of copper-cobalt orebodies in Africas Copper Belt has

received much recent attention with various flowsheet options being
developed specifically for the refining of cobalt. The upfront leach
and copper refining routes are well understood whereas the refining of
cobalt is more complex, requiring numerous impurity removal steps
to produce high purity metal. This paper describes an investigation
into one of the possible processing steps in the refining of cobalt,
namely, cobalt solvent extraction.
The paper emphasizes the importance of upstream impurity removal
to achieve the required cobalt solvent extraction feed composition.
18% (v/v) Cyanex 272 in an aliphatic diluents is used as the organic
phase. The pH profiles in the various stages are evaluated in order to
obtain a raffinate containing <10mg/l cobalt and with a low
magnesium content reporting to the stripping section. The pH profile
is also used to minimize the impurity deportment to the cobalt
electrolyte. The effect of adding a pre-neutralization stage before
feeding the organic phase to the extraction circuit is investigated. Zinc
build-up in the stripping stages is also looked at.
It is recommended for the purpose of this study that four extraction
stages at an O:A ratio of 1 with a pH profile from 4.9 to 5.7 be
employed. The pH is controlled with 40g/l NaOH. A preneutralization stage is required, where the organic phase is contacted
with 10 M NaOH. Two scrubbing stages are recommended at an O:A
ratio of 40, using the cobalt electrowinning advance electrolyte as the
scrub liquor. Three strip stages are to be employed at an O:A ratio of
0.67.
Introduction
The high commodity prices in recent years have spawned many investment opportunities in
this market. The Sub-Saharan Copper Belt, extending from Zambia to the Democratic
Republic of the Congo, is rich in copper and cobalt. Recovery of copper from these deposits
results in dissolution of cobalt as well as impurities, and in most operations the dissolution of
A COBALT SOLVENT EXTRACTION INVESTIGATION IN AFRICAS COPPER BELT
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cobalt is promoted by altering the copper leach conditions. Producing copper from the leach
liquor is relatively easy and well understood. However, the purification and production of
premium grade cobalt metal from a copper-circuit bleed stream is more complex and a variety
of flowsheet options can be considered.
The interest shown in producing cobalt metal is attributed to the high price that can be
obtained for premium grade cobalt metal, which was $34/lb in August 2008 (audited by
Pricewaterhouse Coopers LLP)1. The composition of premium and standard grade cobalt
metal is shown in Table 1.
The difficulty in producing premium grade cobalt metal is the ability to maintain low levels
of impurities in the cobalt electrowinning electrolyte in order to achieve a metal that contains
>99.83% cobalt. The metal impurities in a cobalt electrowinning process have high upgrade
ratios and as such a solution composition, as shown in Table II, is required to meet the metal
specification.
Table I
Composition of premium and standard grade cobalt metal
Element
Ni
Fe
Cu
Mn
Si, P, Sn, Sb, As, N
Al
Pb, S
Zn
Cd
Ag
Se, H
Mg
Bi
C
O
Premium grade (99.83% Co), mg/kg
Standard grade (99.73% Co), mg/kg
<1000
<50
<30
<20
<10
<10
<30
<50
<50
<5
<5
<10
<1
<100
<200
<1500
<100
<50
<50
<20
<10
<60
<100
<50
<5
<10
<30
<5
<200
<250
Table II
A typical cobalt electrowinning solution composition
Element
Zn
Cu
Fe
Ni
Element
Mn
Mg
Co
Na
330
Concentration, mg/l
<3
<2
0
46
Concentration, g/l
2.5
7
55
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In a copper-processing circuit a bleed stream is required to avoid a build-up of impurities.

This bleed stream is the feed to the cobalt circuit and contains various metals, such as iron,
aluminium, magnesium, zinc, nickel, manganese and trace amounts of copper.
Typical process unit operations to purify the copper bleed in order to achieve the cobalt
electrolyte compositions include precipitation of iron and aluminium, copper ion exchange,
impurity solvent extraction, zinc ion exchange and cobalt solvent extraction. Figure 1 shows a
simplified flowsheet option incorporating cobalt solvent extraction as one of the process steps
in the production of cobalt metal2, 7. Cobalt solvent extraction is used to selectively extract
cobalt from a purified solution, which typically contains less than 15g/l cobalt and transfers it
into a concentrated electrolyte containing 50g/l cobalt.
A typical copper-circuit bleed stream composition feeding the cobalt purification circuit is
compared to the purified cobalt solvent-extraction feed stream in Table III and shows the
extent to which the bleed-stream cation is required. The flowsheet considerations for each
element are indicated.
Figure 1. A flowsheet option for Co metal production
Table III
Typical copper circuit bleed and cobalt solvent extraction feed compositions
Element Copper circuit Cobalt solvent extraction
bleed mg/l
feed mg/l
Co
Zn
Cu
Fe
Ni
Mg
Al
Mn
2000
<50
175
1200
<30
2000
700
1400
8000
<2
<2
<2
<25
1100
10
30
Flowsheet considerations for undivided-cell

cobalt electrowinning
Cobalt upgrade reduces purification equipment size
Preferential plating resulting in a stressed deposit
Preferential plating resulting in a stressed deposit.
Difficulty in stripping from organic phase.
Cobalt metal contamination
Increases electrolyte viscosity
Crystal-lattice inclusion in cobalt cathode
Manganese dioxide formation at anoderequires electrolyte bleed.
At high concentrations permanganate forms in cobalt electrowinning
circuit that oxides the organic phase.
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The focus of the paper is on the testwork programme and considerations for the cobalt
solvent-extraction component of the process flowsheet and uses Ruashi Phase II as a case
study performed at MINTEK research facility.
The objectives of the testwork are to:
Produce a raffinate stream containing <10 mg/l cobalt in order to minimize cobalt losses
Limit the amount of magnesium, reporting to the cobalt electrowinning to less than 5%
of that contained in the feed to the cobalt solvent-extraction circuit
Test pre-neutralization with 10 M NaOH3
Determine the zinc build-up within the cobalt solvent extraction strip circuit.
Theory
In the cobalt solvent-extraction circuit Cyanex 272 in an aliphatic diluent is primarily
employed to recover cobalt from solution. Cyanex 272 is a phosphinic acid extractant and
metals are extracted through a cation exchange mechanism. It should be noted that a variety of
metals can be extracted by this reagent depending on the pH of the aqueous solution with
which it is in contact.
The overall reaction occurring in solvent extraction is:
[1]
-
where A represents R2P(O)O and the overbar represents a species in the organic phase.
During extraction the forward reaction is predominant, whereas for striping the reverse
reaction is favoured due to LeChateliers principle.
Occasionally to achieve better pH control and to alleviate water balance issues, the stripped
organic phase is contacted with NaOH at high concentration before being introduced into the
extraction circuit6:
[2]5
Testwork
Batch testwork
The order of metal extraction for Cyanex 272 with increasing pH is well established4 and is as
follows: Fe3+>Zn2+>Al3+>Cu2+>Mn2+>Co2+>Mg2+>Ca2+>Ni2+. It is, however, necessary to
obtain case specific data using the actual solution for verification purposes and as a basis for
further test work. The metal extraction from a feed solution using 18% (v/v) Cyanex 272 in an
aliphatic diluent at ambient temperature is shown in Figure 2.
It can be seen that the pH for optimum separation of cobalt from magnesium and nickel,
while still extracting a high proportion of cobalt, is between 5 and 5.5. Zinc is quantitatively
extracted, even at low pH values. Manganese is preferentially extracted, accentuating the need
to purify the feed to the cobalt solvent-extraction circuit.
Once the pH for extraction is selected, distribution isotherms can be produced in which the
feed solution is contacted with organic phase at varying phase ratios at a constant temperature
and pH. Distribution isotherm for the extraction of cobalt at pH 5.5 and an operating line are
shown in Figure 3. An organic-to-aqueous (O:A) phase ratio of 1 is assumed to produce an
operating line that achieves a maximum cobalt loading of about 7.5 g/l in the organic phase at
pH 5.5 from a feed liquor containing 7.5 g/lL cobalt.
The McCabe-Thiele plot method is used to predict the number of stages required in the
extraction circuit. Figure 3 shows the McCabe-Thiele plot at an O:A phase ratio of 1 with pH
controlled at 5.5. It can be seen that a cobalt content of less that 10 mg/l can be achieved in 4
stages.
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Figure 2. pH dependence of metal extraction at ambient temperature (with 18% (v/v) Cyanex 272)
Figure 3. Distribution isotherm for the extraction of cobalt by 18% (v/v) Cyanex 272 at pH 5.5 and ambient
temperature
The 18% (v/v) Cyanex 272 is then max-loaded to produce a loaded organic that would
represent that obtained on the pilot and full-scale plant. This loaded organic is used for
conducting stripping distribution isotherms in the laboratory.
The loaded organic phase and strip solution (8g/l sulphuric acid) is contacted at various O:A
phase ratios at ambient temperature. At high O:A phase ratios contacts are maintained at a pH
of <3.5 (as expected on the full-scale plant) with addition of 50g/l H2SO4.
The McCabe-Thiele plot method is used to predict the number of stages required for
stripping. Figure 4 shows the McCabe-Thiele plot at an O:A phase ratio of 0.67. It can be seen
that three stages are required to strip the loaded organic of cobalt.
Continuous testwork
Based on the batch test work, the start-up conditions for the piloting campaign are chosen.
The continuous test work utilizes 11 stages in the cobalt solvent-extraction circuit, namely 5
extraction stages, 3 scrub stages and 3 stripping stages as shown in Figure 5. 40g/l NaOH
solution is employed for pH control in the extraction stages and a pH profile as shown in
Table IV is recommended for start-up.
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Figure 4. Distribution isotherm for the stripping of cobalt from 18% (v/v) Cyanex 272 using 8g/l H2SO4
Figure 5. Schematic of cobalt solvent-extraction circuit for continuous test work
Table IV
pH Profile used for start up of pilot-plant campaign
Stage
E1
E2
E3
E4
E5
Sc1
Sc2
Sc3
S
S2
S3
pH
4.8 (controlled)
4.5 (controlled)
5.2 (controlled)
5.4 (controlled)
5.5 (controlled)
4.5
4.5(monitored)
4.5(monitored)
3.5 to 4.0 (controlled)
(not controlled)
(not controlled)
The pH profile in the extraction stages increases from pH 4.8 in the aqueous phase of E1 to
a value of 5.5 in the raffinate (E5). This profile ensures that a raffinate of <10 mg/l cobalt is
achievable by choosing extraction conditions that are favourable for cobalt (see Figure 2). The
co-extraction of magnesium is also enhanced but as the organic phase approaches E1 the pH
is lowered, thus forcing a portion of the magnesium from the organic phase before it exits the
extraction circuit.
The scrubbing stages operate at a high O:A ratio of approximately 40:1 and a pH slightly
lower than the extraction circuit using scrub liquor that contains 55g/l cobalt (the advance
electrolyte). These conditions provide a large driving force to scrub impurities from the
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loaded organic phase by displacing them with cobalt in the scrub liquor. The cobalt in the
scrub liquor is not intended to load the organic phase to a maximum, but rather to replace
impurities. The cobalt-depleted scrub liquor is normally directed to the extraction circuit but
can be removed from the circuit for separate treatment if water balance issues are of concern.
pH control in these stages is not required as scrub liquor is pre-adjusted to the desired pH
value. The extracted cobalt does not exchange hydrogen ions, but rather other metal
impurities, and the pH therefore remains constant.
The stripping circuit receives spent electrolyte containing approximately twice the amount
of hydrogen ions (produced in the electrowinning cells) required for stripping cobalt from the
organic. Thus pH adjustment is required only in S1 to make up for any deficit in hydrogen
ions. S2 and S3 are not controlled providing that the organic is completely stripped of metal
species before being recycled to the extraction circuit.
Extraction circuit
The extraction efficiencies for cobalt and magnesium and the pH in the final extraction stage
(E5) are shown in Figure 6. A reproducible extraction efficiency of 100% for cobalt is
achieved for the second half of the campaign. The co-extraction of magnesium averaged 13%,
hence substantiating the need for scrubbing in order to achieve less than 5% magnesium
reporting to the stripping circuit.
Initially cobalt is lost to the raffinate, i.e. low cobalt extraction efficiencies. The initial low
cobalt extraction efficiency is attributed to low pH in the final extraction stage (E5). The low
pH is due to the release of hydrogen ions (see Equation [1]) from the organic phase during
loading and 40g/l NaOH is insufficient for neutralization in this stage. A pre-neutralization
stage, where the organic phase is contacted with 10 M NaOH, is employed to achieve better
pH control in the final stages of the extraction circuit (see Equation [2]). Once the preneutralization stage is incorporated in the cobalt-solvent extraction circuit, the required
raffinate tenor of < 10 mg/l cobalt is consistently achieved. The pH profile automatically
increases to 4.9 in E1, to 5.7 in E4. Cobalt slippage occurred even when utilizing 5 extraction
stages. The extraction circuit can be reduced to 4 stages if a pre-neutralization stage is
introduced.
Figure 6. Extraction efficiencies of Co and Mg and pH values in the final stage of extraction
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The behaviour of magnesium in the aqueous solution in the extraction stages is shown in
Figure 7. Results show that the magnesium concentration increases from E1 to E3. The
concentration of magnesium falls from E3 to E4. At high pH values magnesium loads more
readily onto the organic phase and is scrubbed off at lower pH values and higher cobalt
concentrations present in stage E1. This results in a aqueous-phase recycle that builds up
magnesium in the extraction circuit until it eventually leaks out of the circuit via the raffinate
stream.
Figure 8 shows the magnesium concentration in the organic phase in the circuit. The
concentration of magnesium in E4 is high as it is co-extracted into the organic phase, hence
the low concentration of magnesium in the aqueous solution in E4. The loaded scrub liquor
exists at Sc1 in the aqueous solution. The concentration of magnesium in the organic phase in
the scrub circuit is lowered as the magnesium is displaced by the cobalt in the scrub liquor.
The scrub stage operates at a slightly lower pH than the extraction stages, thereby allowing
magnesium to be scrubbed.
Scrubbing circuit
The cobalt solvent-extraction circuit is started up utilizing 3 scrub stages and in the later phase
of the test work is reduced to one stage. As a result of the high phase ratio in the scrub
Figure 7. Magnesium concentration in the aqueous phase in the extraction circuit
Figure 8. Magnesium concentration in the organic phase
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section, and due to the limited duration of the pilot campaign, it is not possible to fully
optimize the scrubbing performance. This should be conducted during the full-scale plant
operation. The objective of achieving less than 5% of magnesium in the feed to the cobalt
solvent extraction circuit from reporting to the strip section is achieved with three scrub
stages; the results are summarized in Table V.
Figure 8 shows that the magnesium concentration in the organic phase on Sc1 is 50% of that
at E1, thus showing the effectiveness of the scrubbing stage.
Figure 9 shows the cobalt concentration of the organic phase in E1 and the final scrub stage
(Sc1). The results show that the cobalt concentration in the organic phase is generally slightly
lower in E1 than in Sc1. This is attributed to cobalt from the scrub liquor displacing
magnesium on the organic phase in the scrub circuit.
Stripping circuit
A phase ratio of 0.67 is employed in the strip circuit, which ensures that all loaded metal
species are completely stripped from the organic in S3 and that a 5g/l of cobalt is achieved
across the strip stages. The pH in S1 is maintained at 3.5 with the addition of 30g/l sulphuric
acid. This pH value is ideal for cobalt electrowinning.
Figure 10 shows the build-up of zinc in the stripping circuit. The concentration of zinc in the
feed to the cobalt solvent extraction is maintained below the analytical detection limit.
Figure 11 shows that zinc does not leak into the cobalt electrowinning circuit via the loaded
strip liquor but rather that it remains in the strip circuit. A pH value of 3.5 in S1 is conducive
to maintain the zinc loaded on the organic phase, thus preventing it from leaking into the
electrowinning circuit. Zinc is stripped in S2 and S3 due to the lower pH values in these
Table V
Percentage magnesium extracted, scrubbed and reporting to the strip liquor
Number of scrub stages
3
1
% Magnesium extracted
% Magnesium scrubbed
% Magnesium reporting to strip circuit
18
15
68
39
5
6
Figure 9. Comparison of cobalt concentration in organic phase of E1 and final scrub stage (Sc1)
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Figure 10. Zinc concentrations in aqueous and organic phase in S1
Figure 11. Zinc concentration in aqueous and organic phase in S3
stages, thus preventing zinc from exiting the strip circuit via the stripped organic, as seen in
Figure 9. The zinc in the strip liquor exiting S2 is re-extracted in S1. This internal recycle of
zinc gradually builds up, resulting in it eventually leaking into the cobalt electrowinning
circuit or remaining loaded on the stripped organic phase, leading to a low extraction capacity
of the organic phase and cobalt losses. A major concern is a spike of zinc existing in the
loaded strip liquor due to pH deviations in S1. If the pH in S1 decreases to less than 3 then
zinc will report to the cobalt electrowinning circuit, contaminating the electrolyte leading to
the production of off-specification cobalt cathode.
Impurity species build-up in the loaded strip liquor during the pilot-plant campaign. It is
thus recommended for a full-scale plant to incorporate a small bleed stream from the strip
circuit to remove these impurities in order to avoid accumulation to levels that would
compromise the metal product quality. The strip-liquor bleed can be recycled upstream to
remove zinc and recover cobalt.
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Table VI
Optimum operating conditions for cobalt solvent extraction
Extraction
Number of stages
Extractant
Diluent
O/A
pH profile
pH control
Pre-neutralization
4
18% (v/v) Cyanex 272
Aliphatic
1
4.9 to 5.7
40g/l NaOH
10 M NaOH
Scrubbing
Number of stages
Scrub liquor
O/A
pH profile
2
Advance electrolyte (~55g/l Co)
40
4.5 (monitored)
Stripping
Number of stages
Strip liquor
O/A
pH control in S1
3 (possibly a 4th)
Spent electrolyte (50g/l Co)
0.67
30g/l H2SO4
Conclusions and recommendations

Extraction circuit
It is shown that by increasing the pH profile in the extraction stages results in a marked
improvement in the recovery of cobalt resulting in less than 10 mg/l of cobalt in the raffinate.
The pH profile is inherently raised by pre-neutralization of the stripped organic with 10 M
NaOH. Greater than 99% extraction for cobalt is achieved in the extraction circuit with the
high pH profile. A pH profile of 4.9 in E1 to 5.7 in E4 and a phase ratio of 1.0 are
recommended for optimum results for the feed solution tested. Magnesium scrubbing is also
enhanced due to the decreasing pH profile from E4 to E1.
Scrubbing circuit
Scrubbing of magnesium is established during the pilot campaign although it is not optimized
due to the high phase ratio in the scrub circuit and the short duration of the pilot campaign.
The objective of <5% magnesium in the feed reporting to the loaded strip liquor is achieved
with three scrub stages and is shown to be possible with one stage, provided that the coextraction of magnesium is limited within the extraction circuit. 68% magnesium scrubbing is
achieved within three stages across the scrubbing circuit while only 39% is achieved with one
stage. It is therefore recommended to employ a minimum of two scrub stages that can be
optimised during the operation of the full-scale plant.
Stripping circuit
100% stripping of cobalt in the scrubbed organic phase is achieved in 3 strip stages providing
that the pH in S1 is maintained between 3.5 and 4.0 to achieve a delta of 5g/l cobalt across the
strip circuit. The pH in stage S1 is controlled by the addition of 30 g/l H2SO4. It is shown that
zinc accumulates within the strip circuit. Although zinc in the feed was kept below the
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analytical detection limit to prevent contamination of the cobalt cathode, the zinc does not exit
the strip circuit and over time builds up to concentrations that, with a slip in pH control in the
strip circuit, will contaminate the loaded strip liquor and ultimately the cobalt metal. The
build-up of zinc in the strip circuit will occur on the full-scale plant and provision must be
made for controlled periodic stripping of the organic phase at a low pH. A fourth strip stage
can be used for selective stripping of impurities. The strip liquor generated in a fourth stage
can be recycled to the cobalt upgrade step (see Figure 1) to minimize cobalt losses.
The optimum operating conditions for cobalt solvent-extraction determined in the piloting
campaign are given in Table VI.
REFERENCES
1. http://cobalt.bhpbilliton.com/ 31 August 2008.
2. SOLE, K. C., FEATHER, A. M., and COLE, P. M. Solvent Extraction in Southern
Africa: An update of some recent hydrometallurgical developments, Hydrometallurgy 78,
Elsevier, 2005. pp. 5278.
3. ROUX, L.M., MINNAAR, E., CILLIERS, P.J., BELLINO, M. and DYE, R. Comparison
of Solvent Extraction and Selective Precipitation for the Purification of Cobalt
Electrolytes at the Luilu Refinery, DRC, The South African Institute of Mining and
Metallurgy Base Metal Conference, Symposium Series S47, 2007. pp. 343364.
4. Cyanex 272 Handbook, Solvent Extraction Reagent, Cytec Industries, pp. 137.
5. DAUDINOT, A.M.M. and LIRANZA, E. G. Proceeding of the International Solvent
Extraction Conference, ISEC 2002, Johannesburg, pp. 964969.
6. BOURGET, C. and JAKOVLJEVIC, B. Operational Practices for Cyanex 272 Extractant
Circuits, Proceedings of ISEC 2008, vol. I, pp. 447452.
7. COLE, P.M. and FEATHER, A.M. Processing of African Copper-Belt Copper-Cobalt
Ores: Flowsheet Alternatives and Options, Proceedings of ISEC 2008, vol. I,
pp. 131138.
Tanja Knighofer
Process Engineer, TWP Matomo Process Plant, South Africa
After completing her Masters at the University of the Witwatersrand,
Tanja joined Minteks Hydrometallurgy Division where she worked on
various laboratory and pilot plant studies. Thereafter, she joined TWP
Matomo in the capacity of a Process Engineer on the Ruashi Cu/Co
project in the DRC. Currently she is involved in the MC plant
expansion project for Anglo.
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MULAUDZI, N. and MAHLANGU, T. Oxidative precipitation of Mn(II) from cobalt leach solutions using
dilute SO2/air mixtures. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and
Metallurgy, 2009.
Oxidative precipitation of Mn(II) from cobalt

leach solutions using dilute SO2/air mixture
N. MULAUDZI* and T. MAHLANGU
*Hydrometallurgy Division, Mintek, South Africa
Department of Materials Science and Metallurgy, University of Pretoria,
Pretoria, South Africa
The use of SO2/air gas mixtures as an oxidant to precipitate Mn from
Co(II) leach liquors was investigated. The effects of SO2/air ratio, pH
and temperature on Mn precipitation were evaluated. It was found that
the use of SO2/air gas mixtures resulted in significantly higher Mn
precipitation kinetics compared to using air or pure O2 alone.
The SO2/air ratio was varied from 0% to 6% SO2 (v/v) in air and
similar Mn removals were achieved at 0.75% to 3% SO2 at pH 3. The
solution pH was varied from pH 2 to pH 4; Mn precipitation did not
increase considerably from pH 2 to pH 3, but increased significantly
at pH values higher than pH 3. Cobalt co-precipitation also increased
as pH increased, with 1% Co co-precipitation at pH 3. An increase in
temperature from 30C to 60C also increased Mn precipitation and
100% Mn precipitated at 50C. Cobalt co-precipitation also increased
significantly with an increase in temperature. An activation energy of
25 kJ/mol was calculated from the Arrhenius plot, which is an
indication that the precipitation reactions were both chemically and
diffusion controlled.
XRD analysis showed that Mn precipitated in the form of Mn2O3
instead of MnO2 that was predicted from thermodynamic data. SEM
and XRD analysis also revealed that the precipitate consisted mainly
of gypsum or bassanite (99%), with the Mn containing phase (< 1%)
distributed within the gypsum phase. The co-precipitated Co reported
to the Mn phase.
Keywords: manganese precipitation; SO2/O2 gas mixtures; cobalt
solutions
Introduction
Manganese occurs in most cobalt, copper, nickel and zinc ores as an impurity, which reports
to the leach solution when the valuable metal is leached from the ore. The leach liquor
obtained from these ores often must be purified to an extent before the valuable metal is
recovered either by electrowinning or precipitation.
OXIDATIVE PRECIPITATION OF MN(II) FROM COBALT LEACH SOLUTIONS
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Some Mn(II), approximately 25 g/l, is desired in Co(II) electrowinning in order to form a

protective MnO2 layer on the lead anode surface, which limits corrosion of the anode.
Consequently, control of the manganese concentration in the advance electrolyte is not as
stringent if present at low concentrations. However, if the valuable metal has to be recovered
by precipitation of a relatively high quality cobalt salt, the level of Mn(II) in the purified leach
solution should be extremely low, in the range of 10 mg/l or less.
There are various methods that are used for the removal of Mn from leach solutions,
namely: ion exchange, solvent extraction and precipitation. Precipitation of manganese is a
cheaper and simpler alternative compared to solvent extraction and ion exchange. Several
research studies have been undertaken to investigate the use of SO2/O2 gas mixtures as an
oxidant to precipitate Mn from Zn(II), Co(II) and Ni(II) leach liquors (Menard et al., 2007;
Zhang et al. 2002; Zhang et al., 2007). The use of SO2/O2 or SO2/air gas mixtures as an
oxidant is attractive because it is cheaper compared to using other strong oxidants such as
ozone and hydrogen peroxide. The running costs for precipitating metals with SO2/O2 or
SO2/air gas mixtures can be reduced by using scrubbed SO2 from the sulphide ore roasting
operations if the plant is processing a sulphide ore.
The subject of this paper was to investigate ways to optimize the precipitation of manganese
from cobalt leach solutions to produce a less contaminated cobalt solution from which cobalt
can be recovered as a high quality precipitate. The effects of the SO2/air ratio, pH and
temperature were investigated to determine the optimum conditions for maximum Mn
precipitation with reasonably low cobalt losses (<1%). The use of pure oxygen instead of air
in the gas mixture was also compared.
Theory
Thermodynamic considerations
The possible reactions of Mn and Co can be predicted from the Pourbaix diagram, Figure 1,
which illustrates the regions where the various species that may form predominate. Oxidative
precipitation of Mn(II) to MnO2 becomes thermodynamically feasible if the redox potential of
Figure 1. The Pourbaix diagram for 2 g/l Mn(II), 6.5 g/l Co(II) and 4.8 g/l S(IV) at 30C and 1 atm as predicted by the
HSC thermodynamic model
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the system rises above that of the MnO2/Mn(II) line, represented by the long red line from pH
0 to pH 7. Precipitation of Mn(II) as Mn2O3 becomes thermodynamically possible at pH > 5,
represented by the region between the two parallel red lines from pH 5 to pH 7.
In the pH range investigated, namely pH 2 to pH 4, Co(II) is expected to remain in solution
at redox potentials below the Co3O4/Co(II) line as indicated by the purple line in Figure 1. If
the redox of the system rises above this line, oxidative precipitation of Co(II) as Co3O4
becomes thermodynamically feasible. The experimental conditions should therefore be
controlled such that the redox potential does not exceed Co(II) oxidation potentials at all pH
values.
Solubility of sulphur dioxide and oxygen
Sulphur dioxide is more soluble in water compared to oxygen. The solubility of and O2 at
25C has been reported to be 94.1 g/l and 0.04 g/l respectively (Brandt et al. 1994). Therefore
in the SO2/air system one would expect the mass transfer of O2 to be limiting due to its low
solubility compared to gas. Several authors have reported that O2 mass transfer is limiting for
oxidative precipitation of Mn(II) and Fe(II) using SO2/O2 gas mixtures (Menard et al. 2007;
Zhang et al. 2000). Zhang et al. (2000) also reported that an increase in temperature resulted
in a decrease in the optimum SO2/O2 ratio due to reduced O2 solubility as temperature
increases.
The solubility of SO2 is known to be pH dependent; the SO2 uptake in water droplets was
found to decrease with decreasing pH. As a result SO2 is less soluble in acidic water (Brandt
et al. 1994). The speciation of S(IV) oxides in water also varies with pH as illustrated in
Figures 2 and 3. Different S(IV) species are known to have different reactivities, with SO32reported to be 2040 times more reactive than HSO3 (Brandt et al. 1994). In addition Brandt
et al. (1994) cited Ali et al. who reported that for the oxidation of S(IV) by a Co(III) complex,
the reactivity of the S(IV) species was in the following order; SO32- > HSO3 > .H2O; where
SO32- was reported to be 16 times more reactive than HSO3 and HSO3 was 53 times more
reactive than SO2.H2O. It has been reported that pH affects the stability of the produced
transition metal complexes (Brandt et al. 1994). Zhang et al. (2000) reported that the optimum
SO 2/O 2 ratio was dependent on pH and it has also been shown that an increase in pH
-2
Figure 2. Distribution of sulphur(IV) oxide species as a function of pH (5 x 10 M Na2S2O5 , 25C)(Brandt et al. 1994)
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increased Mn precipitation kinetics (Zhang et al. 2002).

In the pH range investigated, pH 2 to pH 4, the dissolved is expected to be mainly in the
form of HSO3 as indicated in Figure 2. The Pourbaix diagram in Figure 3 also shows that
HSO3 is the predominant S(IV) species at pH 2 to pH 4 at relatively low potentials.
Proposed oxidation mechanism
A radical mechanism has been proposed for the autoxidation of S(IV) by O2 in the presence of
certain transition metal ions, namely: Cu(II), Fe(III), Ni(III), Co(III) and Mn(IV) (Brandt
et al. 1994; Berglund et al. 1994; Das et al. 1999). The proposed mechanism results in the net
oxidation of the transition metal ions as well as the oxidation of S(IV) species. The
mechanism proposed by Berglund et al. requires tetravalent metal ions to react with the S(IV)
species in order to form a complex, which is known to initiate the radical chain reactions.
Brandt et al. suggested that it was possible to form a similar complex with the divalent metal
ion and the S(IV) species, which also gives rise to radical formation. Huie et al. (1987)
reported that ultraviolet rays were required to initiate radical formation.
The mechanisms proposed by the various authors are similar; Brandt et al. studied the
mechanism using computer simulations and derived it as indicated by Equations [1] to [6].
Initiation reactions
[1a]
[1b]
In the presence of O2, the SO3*- radical reacts with O2 to form the peroxymonosulphate
radical, SO5*-, which is understood to control the redox cycle.
[2]
Propagation reactions
SO5*- is a more reactive oxidant than O2 and is believed to oxidize the divalent transition
metal ions and the S(IV) as follows:
[3a]
Figure 3. Pourbaix diagram for 4.8 g/l S(IV) at 30C and 1 atm as predicted by the HSC thermodynamic model
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[3b]
[3c]
The SO4*- radical is known to be a very strong oxidant with a standard reduction potential of
2.43 V vs. SHE, and is therefore expected to rapidly oxidize sulphite and transition metal ions
(Das et al. 1999). The produced SO4*- radical can participate in oxidation reactions as follows:
[4a]
[4b]
-
The HSO5 anion formed by the oxidation of S(IV) and M2+ by the SO5*- radical, together
with the SO 5*- radical open various reaction pathways. These reaction pathways may
influence both the decomposition process and the product formation as indicated by Equations
[5] to [6]
[5a]
[5b]
[5c]
[5d]
[5e]
Termination reactions
[6a]
[6b]
The recombination of SO4*- was proposed to be unlikely due to excess S(IV) and M2+ and
was therefore not included in the reaction scheme (Brandt et al. 1994).
Studies conducted by Das et al. (1999) on the reduction potentials of the SO3*- and SO5*radicals by pulse radiolysis revealed that the potential of the radicals was dependent on pH as
indicated in Figure 4. This indicates that redox reactions that involve the radicals shown in
Figure 4 are dependent on the pH of the system.
Reaction stoichiometry
The overall reactions for oxidative precipitation of Mn with SO 2/O 2 gas mixtures are
illustrated by Equations [7] to [10]. Mn is expected to precipitate as MnO2 at pH values below
pH 7 and high redox potential; and as Mn2O3 in the pH range of 5 to 7 at relatively high redox
potential values below those required for MnO2 precipitation (see Figure 1).
[7]
[8]
SO2 can also react with O2 to form sulphuric acid in the following side reaction:
[9]
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Figure 4. The redox potential of the SO3*-/SO32- and SO5*-/SO52- couples as a function of pH (Das et al. 1999)
Figure 5. Reactor set-up
Sulphuric acid produced by reactions 7 to 9 can be neutralized with hydrated lime to form
gypsum:
[10]
Experimental
Materials and apparatus
Synthetic solutions were prepared using sulphate salts of AR grade and 98% sulphuric acid.
The solutions prepared resembled the solution obtained from sulphuric acid cobalt leach
operations containing approximately 6.5 g/l Co(II) and 2 g/l Mn(II).
Laboratory tests were carried out in a 10 l glass reactor fitted with baffles and a flat-blade
impeller as shown in Figure 5; the solution volume for these tests was 4 l. The impeller and
baffles were designed to ensure efficient mixing and consequently efficient mass transfer of
the gas mixture into the liquid phase. The gases were mixed in the pipeline using a venturi
effect, where the smaller diameter SO2 line was inserted such that it bends into the bigger
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diameter air delivery line. The SO2 was mixed with the air in the T-piece before the gas
mixture was delivered to the reactor. The gas mixture was introduced into the reactor through
a glass frit located below the impeller. The temperature was controlled using a water bath,
with the thermocouple positioned inside the reactor. (Figure 5.)
All tests were performed at atmospheric pressure at an impeller speed of 500 rpm. The pH
and redox potential were monitored using Hamilton pH and Eh (Ag/AgCl) probes. Rotameters
were used to control the SO2 and air flow rates into the reactor while the pH was controlled by
addition of 17% (w/w) hydrated lime slurry using an autotitrator connected to a peristaltic
pump.
Experimental design
The experiments were designed to investigate the effects of the SO2/air ratio, pH, temperature
and the effect of using pure O2 versus air, as indicated in Table I. One parameter was varied at
a time. The same SO2 flowrate of 11ml/min was used in all tests. This flowrate was calculated
from the stoichiometric amount of SO2 required to precipitate 2 g/l Mn(II) according to
Equation [7] within a period of 5 hours. However, each test was run for 6 hours, hence some
excess reagents were introduced. All tests were conducted at 30C unless otherwise stated.
(see Table I.)
Solution analysis was performed using two instruments: Varian atomic absorption
spectrometer (AAS) and Varian inductively coupled plasma optical emission spectrometer
(ICP-OES). Solid samples were analysed with ICP-OES, X-ray Fluorescence (XRF), X-ray
diffraction (XRD) and scanning electron microscopy (SEM).
Effect of SO2/air ratio
The concentration of SO2 in the gas mixture was varied by changing the air flow rate while
keeping a constant SO2 flow rate of 11 ml/min. The various air flow rates used were;
170 ml/min, 231 ml/min, 352 ml/min, 714 ml/min, 1439 ml/min, which were equivalent to
6%, 4.5%, 3%, 1.5% and 0.75% SO2 (v/v) in air respectively.
The use of SO2/air gas mixtures resulted in faster kinetics for manganese precipitation
compared to using air alone, as indicated in Figure 6. Mn precipitation increased significantly
in the first 3 hours and thereafter little or no Mn precipitated further.
Table I
Experimental matrix
Parameter
pH
Temperature, C
SO2 in air, % (v/v)
SO2 flow rate, ml/min
Air flow rate, ml/min
SO2 in O2, % (v/v)
O2 flow rate, ml/min
Range
24
3060
06
11
1701439
3.523
36301
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Figure 6. Effect of % SO2 in air on Mn precipitation (2 g/l Mn(II); 6.5 g/l Co(II); pH 3; 30C)
Figure 7. Effect of % SO2 in air on Mn and Co precipitation at pH 3 (2 g/l Mn(II); 6.5 g/l Co(II); 30C; 6 hours)
The extent of Mn precipitation was similar for the dilute SO2 concentrations up to 3% SO2
in air, which is equivalent to 13% SO2 in O2, as indicated in Figures 6 and 7. This SO2/O2
ratio is similar to the optimum of 12% SO2 in O2 obtained by Schulze-Messing et al. (2006).
Menard et al. (2007) has, however, shown that at pH 4, Mn precipitation could still be carried
out at SO2/O2 ratios as high as 50% if adequate mixing is provided. The high SO2/O2 ratios,
however, result in slow kinetics compared to the low SO2/O2 ratios and therefore would result
in longer residence times.
Zhang et al. (2000) reported that the optimum SO2/O2 ratio is O2 mass transfer dependent,
with Mn precipitation increasing with the increase in O2 content in the gas mixture. This O2
mass transfer dependency of the system is likely because of the large difference in the
solubility of SO2 and O2. The slower kinetics observed at SO2/O2 ratios higher than the
optimum can be attributed to insufficient O2 supply in solution. Cobalt losses of 12% were
recorded for all the SO2/air ratios (Figure 7).
The relationship between SO2 efficiency and lime consumption versus the SO2/air ratio is
shown in Figure 8. The efficiency of SO2 was calculated by dividing the predicted moles of
SO2 used for Mn oxidation by the total moles of SO2 input. The efficiency followed the same
trend as Mn precipitation with maximum SO2 efficiency recorded at 3% SO2 in air. The total
lime consumption, however, remained relatively constant, which indicated that for less
oxidizing gas mixtures, the side reaction (Equation [9]) becomes dominant and consumes the
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Figure 8. Effect of % SO2 in air on SO2 efficiency and lime consumption at pH 3 (2 g/l Mn(II); 6.5 g/l Co(II); 30C; 6
hours)
Figure 9. Effect of % in air on the redox potential at pH 3 (2 g/l Mn(II); 6.5 g/l Co(II); 30C; 6 hours)
SO2 rather than Mn precipitation reaction (Equation [7]).

The relationship between the redox potential and %SO2 in air at pH 3 is illustrated in
Figure 9. The redox potential increased sharply on addition of SO2 in air and reached a
maximum potential of 1.1V vs. SHE at 3% SO2 and decreased thereafter. It can be deduced
from these results that the /air ratio controls the redox potential and therefore the oxidizing
strength of the solution, and consequently the extent of Mn precipitation.
The comparative oxidizing ability of SO2/air and SO2/O2 gas mixtures was investigated. The
same molar quantity of O2 was used in both instances. The extent of Mn precipitation
achieved using SO2/O2 gas mixtures was higher than that achieved with SO2/air gas mixtures
(Figure 10). This can be attributed to the higher partial pressure of O2 in the gas mixture and
consequently higher dissolved oxygen concentration when using pure O2 compared to air.
Effect of pH
The solution pH was varied from pH 2 to pH 4 at 30C and 3% SO2 in air. An increase in pH
resulted in increased Mn precipitation (Figure 11). At pH 4, all Mn was precipitated from the
solution after 5 hours, which represented a stoichiometric consumption of SO2 according to
Equation [7].
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Figure 10. Effect of % SO2 in O2 when using air and pure O2 on Mn precipitation (2 g/l Mn(II); 6.5 g/l Co(II); pH 3;
30C; 6 hours)
Figure 11. Effect of pH on Mn precipitation (2 g/l Mn(II); 6.5 g/l Co(II); 3% SO2 in air; 30C)
[7]
An increase in pH also resulted in increased Mn and Co precipitation, as illustrated in
Figure 12. Mn and Co precipitation was relatively constant at pH values less than 3, but a
sharp increase in precipitation of both metals was observed at pH values above pH 3, as
indicated in Figure 12. Zhang et al. (2002) also found the extent of Mn precipitation at pH
values less than 3 to be slow; but as pH increased above pH 4, the rate of Mn precipitation
became fast. It appears from these results that Mn and Co precipitation is relatively
independent of pH at pH values less than 3. A cobalt loss of 1% was recorded at pH 3 and the
cobalt loss increased linearly as pH was increased from pH 3 to pH 4. The higher cobalt
losses recorded at higher pH values are possibly due to higher Mn removal at those pH values,
which results in the presence of excess oxidant in solution, which consequently oxidizes the
Co(II). Therefore Co losses at higher pH values can be limited by stopping the process as
soon as sufficient Mn has been removed from solution.
The marked increase in Mn and Co precipitation at pH values above pH 3 shows the strong
influence of pH on the SO2/O2 system, as already reported by other authors (Menard et al.
2007; Zhang et al. 2000). The increase in Mn precipitation at pH values above pH 3 could be
attributed to a change in the speciation of the S(IV) species (Figure 2) as both Co(II) and
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Figure 12. Effect of pH on Mn and Co precipitation for 3% SO2 in air (2 g/l Mn(II); 6.5 g/l Co(II); 30C; 6 hours)
Figure 13. Effect of pH on Mn precipitation and redox potential at 3% SO2 (2 g/l Mn(II); 6.5 g/l Co(II); 30C;
6 hours)
Mn(II) are expected to remain in solution in the pH range of pH 2 to pH 4 (Figure 1).

From the S(IV) speciation diagram (Figure 2), it is observed that at pH 2 the SO2.H2O and
HSO3 species are equally dominant, but as pH increases from pH 2 to pH 4, HSO3 becomes
the dominant S(IV) species. It has been reported that the HSO3 species is 53 times more
reactive than the SO 2 .H 2 O species for the oxidation of S(IV) (Brandt et al. 1994).
Consequently, an increase in Mn and Co precipitation at pH values above 3 was possibly due
to improved kinetics caused by an increase in dominance of the more reactive HSO3 species
over the SO2.H2O species as pH was increased.
Figure 13 shows the effect of pH on Mn precipitation as well as redox potential for 3% SO2
in air. The redox potential decreased linearly as the pH increased but Mn precipitation
increased significantly, at pH values greater than 3. The redox potential followed the same
trend observed for the sulphite radical couples indicated in Figure 4. From these results it
appears that the redox potential alone is not responsible for the oxidative precipitation of Mn
since only half of Mn(II) was removed at the high redox potentials measured at pH 2 to pH 3,
whereas 100% Mn(II) removal was achieved at the lower redox potential measured at pH 4.
Figure 14 shows the redox potential measured for the 3% SO2/air gas mixture and the redox
potential measured when using O2 alone. The MnO2/Mn(II) line and the Co3O4/Co(II) lines
predicted by the HSC model in Figure 1 were also superimposed on the diagram.
Although the redox potentials measured for O2 followed a similar trend as the SO2/air gas
mixture, the extent of Mn precipitation by O2 alone was negligible (0.2%), compared to the
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Figure 14. Effect of pH on the measured redox potential for O2 at 700 ml/min and 3% SO2 in air at 362 ml/min
(2 g/l Mn(II); 6.5 g/l Co(II); pH 3, 30C, 6 hours)
Temperature, C
Figure 15. Effect of temperature on Mn precipitation (6.5 g/l Co(II); 2 g/l Mn(II); pH 3; 3% SO2; 6 hours)
extent of Mn precipitation by the 3% SO2/air gas mixture (50%). It can also be observed from
Figure 14 that the redox potential values measured for the 3% SO2/air gas mixture and O2
alone at various pH values lie within the (MnO2 + Co(II)) region in the Pourbaix diagram.
Hence, thermodynamically, MnO2 is expected to precipitate from pH 2 to pH 4, as it was the
case for the 3% SO2/air gas mixture; however, it was not the case for the O2 gas. These results
further highlight that high redox potential values alone are not responsible for the
precipitation of Mn, but the presence of reactive S(IV) species, which are responsible for the
radical mechanism, is probably required for Mn precipitation. The fact that Mn precipitation
increased significantly at pH values above pH 3 even though the measured redox for all the
pH values lies within the MnO2 predominance region, further emphasizses the dependence of
the kinetics on the S(IV) speciation.
From Figure 14 the measured redox potential crossed into the Co3O4 predominance region
only at pH 3.5, which indicates that cobalt oxidative co-precipitation is thermodynamically
feasible at pH 3.5 and higher. Only 1% cobalt was lost at pH 3.
Effect of temperature
The effect of temperature was investigated by varying the solution temperature from 30C to
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60C at pH 3 and 3% SO2 as indicated in Figure 15. The extent of Mn and Co precipitation
increased linearly with increasing temperature. The increase in the rate of reactions upon
increasing the temperature was expected due to the temperature dependence of reaction
kinetics. Complete Mn precipitation was achieved at 50C but at a cobalt loss of 17%. The
high cobalt loss could be due to the fact that all the Mn had been precipitated within this
period, leaving the oxidant free to oxidize the Co(II) in solution.
An activation energy of 25 kJ/mol was calculated from the Arrhenius plot at pH 3 and 3%
SO2. This activation energy is similar to the value of 23.5 kJ/mol obtained by Schulze
Messing et al. (2007). The activation energy calculated for these conditions lies between 20
and 40 kJ/mol, which indicates that Mn precipitation is under mixed reaction control and that
O2 mass transfer is most likely the dominant limiting factor compared to slow chemical
reaction steps. The dominance of mass transfer reaction control can be supported by the large
difference in the solubility of SO2 compared to O2 as well as the increase in Mn precipitation
observed when the quantity of O2 in the SO2/air and SO2/O2 gas mixture was increased.
Precipitation product
The precipitate was analysed using ICP-OES, SEM, XRF and XRD techniques. The XRD
results indicated that the precipitate consisted mostly of gypsum (CaSO 4), bassanite
(CaSO4.xH2O), calcite (CaO) and bixbyite (Mn3+,Fe3+)2O3. According to the XRD analysis,
Mn precipitated in the form of Mn2O3 and not MnO2 as predicted from the thermodynamic
data. The reason for this is still under investigation. The SEM micrographs in Figures 16 and
17 indicate the two phases that were present in the precipitate. The major phase in the
precipitate contained CaSO4 (99%), which is represented by the white areas in Figure 16. The
manganese precipitate phase (< 1%) is the bright white spot indicated by the arrow in
Figure 17. The cobalt that co-precipitated reported to the manganese precipitate phase as
indicated by the X-ray scan in Figure 17.
Conclusions
Precipitation of Mn with SO2/air gas mixtures resulted in higher Mn removal compared to
using air or oxygen alone. The use of pure O2 instead of air in the SO2 gas mixtures also
resulted in improved Mn precipitation. Solution pH was found to play a major role in the
precipitation reactions and the rate of Mn precipitation increased significantly only at pH
Figure 16. The SEM micrograph for the CaSO4 phase
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Figure 17. The SEM micrograph for the Mn precipitate phase
values above 3. The SO2 concentration in the gas mixture was found to control the redox
potential of the system and therefore the oxidizing strength of the solution to oxidatively
precipitate Mn. The oxidizing strength of the solution decreased at SO2/air ratios higher than
3% SO 2, which is equivalent to 13% SO 2 in O 2. The efficiency of SO 2 use for Mn(II)
precipitation also followed the same trend as the extent of Mn precipitation; however, lime
consumption did not decrease significantly at SO2/air ratios > 3%, which indicates that the
SO2 was mainly consumed by the side reaction of sulphuric acid production.
An increase in temperature resulted in both increased Mn precipitation and cobalt coprecipitation. An activation energy of 25 kJ/mol was calculated from the Arrhenius plot at 3%
SO2 and pH 3; which indicates that at these conditions, the reactions are both diffusion and
chemically controlled. Diffusion control could be more limiting given the possible O2 mass
transfer limitation.
Although pure O2 resulted in similar measured redox potentials compared to the 3% SO2/air
gas mixtures at pH 3, the extent of Mn precipitation with pure O2 was insignificant compared
to the extent of Mn precipitation by the 3% SO2/air gas mixture. It was evident from these
results that high redox potential values alone are not responsible for Mn precipitation and that
S(IV) species play an important role in the mechanism of Mn precipitation with SO2/air gas
mixtures. Therefore the reaction mechanism is possibly governed by both pH and redox
potential, depending on the oxidizing ability of the gas mixture. However, pH and
consequently the reactivity of the S(IV) species, had the most pronounced effect on the Mn
precipitation reactions.
XRD and SEM analysis revealed that the precipitate produced consisted mainly of gypsum
or bassanite (99%), with the Mn containing phase (< 1%) distributed within the gypsum
phase. The co-precipitated cobalt reported to the manganese phase. The manganese precipitate
was found to be in the form of Mn2O3 rather than MnO2.
Acknowledgements
I would like to acknowledge and thank my mentors from Mintek, Marthie Kotze and Johanna
van Deventer, who supported and advised me at different stages of the project. I also thank Dr
Brian Green for his inputs in the editing of this paper and all the other Mintek staff who
contributed to this work.
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References
1. BERGLUND, J. and ELDING, L.I. Reaction of peroxomonosulphate radical with
manganese(II) in acidic aqueous solution, Journal of Chemical Society Faraday
Transactions, vol. 90, no. 21, 1994. pp. 33093313.
2. BRANDT, C. and VAN ELDIK, R. Transition metal-catalysed oxidation of sulphur(IV)
oxides. Atmospheric relevant processes and mechanisms, Chemical Review, vol. 95,
1995. 1994. pp. 119190.
3. DAS, N.T., HUIE, R.E., and NETA, P. Reduction potentials of SO3*-, SO5*- and S4O6*3radicals in aqueous solution, Journal of Physical chemistry, vol. 103, 1999.
pp. 3583588.
4. HUIE, R.E. and NETA, P. Journal of Atmospheric Environment, vol. 21, 1987. p. 1743.
5. MENARD, V. and DEMOPOULOS, G.P. Gas transfer kinetics and redox potential
considerations in oxidative precipitation of manganese from an industrial zinc sulphate
solution with SO2/O2, Hydrometallurgy, vol. 89, 2007. pp. 357368.
6. SCHULZE-MESSING, J. ALEXANDER, D.C., SOLE, K.C., STEYL, J.D.T., NICOL,
M.J., and GAYLARD, P. An Empirical Rate Equation for the Partial Removal of
Manganese from Solution using a Gas Mixture of Sulphur Dioxide and Oxygen,
Hydrometallurgy, vol. 86, 2007. pp, 3743.
7. ZHANG, W., SINGH, P., and MUIR, D.M. SO2/O2 as an oxidant in hydrometallurgy,
Minerals Engineering, vol. 13, 2000. pp. 13191328.
8. ZHANG, W., SINGH, P., and MUIR, D.M. Oxidative precipitation of manganese with
SO2/O2 and separation from cobalt and nickel, Hydrometallurgy, vol. 63, 2002.
pp. 127135.
9. ZHANG, W. and CHENG, C.Y. Manganese metallurgy review. Part III: Manganese
control in zinc and copper electrolytes, Hydrometallurgy, vol. 89, 2007. pp. 178188.
Ndinanwi Mulaudzi
Metallurgical/Process Engineer in Training, Mintek
The author is a recent engineering post graduate; she obtained her
undergraduate degree, B.Eng Metallurgy, from the Department of
Materials Science and Metallurgical Engineering at the University of
Pretoria in 2005. In 2006 she obtained an honours degree in the same
discipline. She spent 2007 at Mintek conducting testwork for an
M.Eng Metallurgy thesis and became a Mintek employee in the
Hydrometallurgy division in March 2008. The thesis involved investigating the effects of pH,
SO2/air ratios and temperature on precipitation of Mn using SO2/air gas mixtures. The work
presented in the current paper is based on the thesis which is still
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MULLIGAN, M.C. and BRADFORD, L. Soluble metal recovery improvement using high density thickeners in
a CCD circuit: Ruashi II as case study. Hydrometallurgy Conference 2009, The Southern African Institute of
Mining and Metallurgy, 2009.
Soluble metal recovery improvement using high

density thickeners in a CCD circuit: Ruashi II
a case study
M.C. MULLIGAN* and L. BRADFORD
*FLSmidth Minerals (Pty) Ltd, South Africa
Metorex Ltd, South Africa
Counter current decantation (CCD) thickener circuits are used to

recover soluble metal as pregnant liquor solution from ore leach
residue. The basis of CCD operation is to concentrate suspended
solids thereby minimizing liquor content in underflow slurry that
flows in one direction. Then the underflow slurry liquor is diluted
with wash liquor, that flows in the opposite direction, and the
suspended solids are concentrated again and again.
The amount of liquor in the thickener underflow contributes to
determining the number of CCD stages required to recover the desired
amount of soluble metal. High density thickeners (HDT) are designed
to use gravity and compression, and minimize the amount of liquor in
the underflow, thus minimizing the number of CCD stages. This paper
reviews the process used to select HDTs versus high rate thickeners
(HRT) for the Ruashi II copper-cobalt hydrometallurgical process in
the Democratic Republic of Congo (DRC), from lab HDT
simulations, to CCD simulations and thickener design details.
Introduction
Copper at the Ruashi II plant is leached into solution in stirred tanks and is then recovered in a
counter-current-decantation (CCD) circuit. The pregnant liquor solution (copper-rich solution)
from the CCD circuit goes to a solvent extraction plant, followed by an electrowinning plant
where the final copper product is produced. The washing efficiency in the CCD circuit is
important to the overall copper production. The basis of CCD operation is to concentrate
suspended solids thereby minimizing liquor content in underflow slurry. The underflow slurry
liquor is diluted with wash liquor and the suspended solids are concentrated again.
The amount of liquor in the thickener underflow is a parameter in determining the number
of CCD stages required to recover the desired amount of soluble metal. Minimizing liquor in
the thickener underflow leads to a higher recovery of soluble metal. This paper reviews the
SOLUBLE METAL RECOVERY IMPROVEMENT USING HIGH DENSITY THICKENERS
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process used to select the best thickener technology for the Ruashi II copper-cobalt
hydrometallurgical process in the Democratic Republic of Congo (DRC), starting with lab
simulations, then to CCD simulations, and finally thickener design details.
Lab simulations
The process simulations of milling and leaching the ore was performed by Mintek. Various
leached samples were supplied to FLSmidth Minerals for thickening testwork. All post-leach
thickening testwork was done straight after the leach was done in order to prevent ageing of
the sample.
Thickening testwork
The thickener simulations used a combination of bench-scale batch tests and continuous fill
tests to measure the physical characteristics to be used in the size selection and design of the
thickeners.
Settling and flocculant flux curves
Figure 1 exhibits a summary of the measured suspended solids settling flux (kg/h/m2) versus
feed slurry suspended solids concentrations at different flocculant doses. A maximum settling
flux is identified at a suspended solids concentration of between 7 and 8 wt%. The thickener
feed slurry must be diluted to this concentration to optimize flocculation and suspended solids
settling flux.
Figure 2 exhibits a summary of the measured suspended solids settling versus flocculant
dose at different feed slurry suspended solids concentrations. The optimal flocculant dosage is
identified by a small change in settling flux at between 50 g/t and 60 g/t.
Batch and continuous thickener simulations
Various batch simulations were done at the optimal feed solids percent and optimal flocculant
dosage conditions. The average underflow density achieved in the batch tests was 55% solids
(by mass).
Various continuous simulations with rakes were done to check the effect of residence time
on underflow suspended solids concentration. Figure 3 exhibits the residence time required to
Figure 1. Optimal % solids
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Figure 2. Optimal flocculant dosage
Figure 3. Continuous test showing mud residence time vs. solids %
concentrate the slurry. These simulations are used to determine the suitability of using a high
density thickener rather than a high rate thickener. As one can see in Figure 3, the continuous
simulation achieved an underflow suspended solids concentration of 59 wt% when the mud
residence time is between 4 and 6 hours. This residence time is normally associated with high
density thickeners.
Rheology for thickener
Rheology measurements were taken using a Haake VT550 vane viscometer using FLSmidth
Minerals procedures. The slurry yield stress, the force required to produce movement from a
stationary bed, is measured at various underflow suspended solids concentrations. The yield
stress is a function of physical properties of the suspended solids (including chemical
composition, particle size distribution and concentration), flocculant type, flocculant dose,
and temperature.
The yield stress results are used to:
Define the limit to underflow density each thickener type can achieve based on ability to
discharge
Define the torque required to rotate the rakes during normal and abnormal operation. The
thickener rakes must be able to restart in unsheared slurry after an unscheduled
shutdown. FLSmidth Minerals thickener rake design and drive torque are designed to
overcome this most severe condition.
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Solids concentration
2/13/09
Yield stress (Pascals)
Underflow suspended solids concentration wt%
Figure 4. Underflow suspended solids concentration wt%
Figure 5. Underflow mud rheology
Figure 4 identifies a general relationship of thickener type to yield stress or underflow

suspended solids concentration. Typically conventional thickeners (CT) and HRT are designed
to consistently discharge underflow slurries exhibiting a yield stress of ~<25 Pa. FLSmidth
Minerals HDT is designed to consistently create and discharge underflow slurries exhibiting a
yield stress ~<100 Pa. FLSmidth Minerals deep cone paste thickeners (DCPT) are designed to
consistently create and discharge underflow slurries exhibiting ~<500 Pa.
The yield stresses measured at various slurry suspended solids concentrations for the Ruashi
post-leach sample is shown in Figure 5. As one can see on the graph, at an underflow density
of 55% the yield stress is 20 Pa, and at an underflow density of 59% the yield stress is 60 Pa.
At 60 Pa yield stress a FLSmidth Mineral HDT should be used. As was seen above, the
residence time to achieve 59 wt% underflow suspended solids was between 4 and 6 hours.
Counter current decantation (CCD) simulations
Once the laboratory thickener simulations were completed, measured data were used to
simulate various counter current decantation (CCD) design options. These CCD simulations
calculate soluble metal recoveries for changes in all the main variables affecting CCD wash
recovery, which are:
Suspended solids concentration in underflow slurry
Soluble metal content in wash liquor
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Suspended solids concentration in leach residue of CCD feed

Wash ratio (mass wash liquor/mass suspended solids)
Interstage mixing efficiency.
These different soluble metal recoveries form the basis for a sensitivity analysis of the CCD
circuit. (Figure 6.)
CCD wash recovery
Metorex Ltds feasibility study used a high rate thickener performance scenario for the CCD
soluble metal recovery. The underflow suspended solids concentration was 55 wt%.
Metorexs requirement was to achieve 99% soluble copper recovery in the CCD circuit. The
initial CCD Circuit design variables are shown in Table I below.
As shown in Figure 7, a minimum of 6 stages would have been required to obtain the wash
recovery of >99% at the HRT operating conditions.
Variables influencing wash recovery
The five variables shown in Table I are the variables that have an influence on the overall
CCD wash recovery. The wash ratio and underflow suspended solids concentration, however,
are the two variables that have the greatest influence on wash recovery.
Interstage
Mix
Wash Liquor
Flocculant
Leach Residue
Interstage
Mix
Interstage
Mix
Interstage
Mix
CCD5
Low Grade PLS
Leach Residue
CCD4
High Grade PLS

CCD3
CCD2
CCD1
Figure 6. High density thickeners

Table I
Variables used in CCD wash recovery calculations
Wash ratio
1.6
U/F suspended solids

concentration (wt%)
Interstage mixing
efficiency (%)
Soluble Cu in wash
liquor (g/l)
Feed suspended solids

concentration (wt%)
Soluble Cu
recovery (%)
55
95
0.0
30
+99
No. of stages
Figure 7. CCD high rate thickeners wash recovery
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Figure 8 below shows that a greater difference in wash ratio, from 1.1 to 2.1, has a
significant effect on CCD wash efficiency (% soluble metal recovery). Increasing the wash
ratio from 1.6 to 2.1 does not offer significant benefits at 5 stages of CCD and more. It can
also be seen from Figure 8 that 5 stages at a higher wash ratio of 2.1 can achieve the 99%
wash recovery rather than the 6 stages at a wash ratio of 1.6. The recommended wash ratio
will be between 1.6 and 2.1.
Figure 9 shows that a greater difference in underflow suspended solids concentration, from
55 wt% to 59 wt% has a significant effect on the number of stages required. An underflow
suspended solids concentration of 59 wt% can be produced by a high density thickener, 5
stages are able to achieve the 99% wash recovery rather than the 6 stages at underflow
densities of 55 wt%.
It is evident from Figures 8 and 9 that both wash ratio and underflow suspended solids
concentration have a big influence on the wash recovery (efficiency):
Increasing both the underflow (from 55 to 59 wt%) and wash ratio leads to an increase in
wash efficiencies
By increasing the underflow solids concentration from 55 to 59 wt% five stages are
required to achieve similar wash efficiencies as six stages at 55% as shown Figure 9
Keeping the number of stages and underflow solids concentration the same, a 0.51%
increase in wash efficiency can be realized by increasing the wash ratio from 1.6 to 2.1.
Figure 8. Sensitivity to wash ratio
Figure 9. Sensitivity to underflow suspended solids concentration
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The above is based on 95% interstage mixing efficiencies between CCD stages.
It can be seen in the above analysis, selecting high density thickeners rather than high rate
thickeners, means that 5 stages can be used instead of 6 stages to achieve the required wash
recovery. This means that the wash ratio of 1.6 can be used. By keeping the wash ratio at 1.6,
the soluble copper concentration reporting downstream to the solvent extraction plant is
greater and the plant does not need to be increased in size (i.e. if the wash ratio was 2.1 the
solvent extraction plant would need to increase in size to handle the additional solution
volume).
High-rate vs. high-density thickeners
CCD wash recovery
In the previous section one can see the impact of underflow suspend solids concentration on
the CCD wash recovery. The higher underflow suspended solids concentration means a
greater wash recovery of soluble copper. This thus means that with all other variables the
same, high density thickeners will always produce greater underflow suspended solids
concentration because of a combination of gravity, compression and altering of permeability
of the solids in the thickener. For Ruashi II this also means that with high density thickeners,
the required wash recovery can be achieved with one fewer stage.
Cost and payback implications
In general there is a perception that high rate thickeners have a lower cost than high density
thickeners. This is perhaps another reason for the preference for high rate thickeners in CCD
circuits. However, high density thickeners are always smaller in diameter than high rate
thickeners, allowing for a significant savings in installed cost. The use of high density
thickeners at Ruashi has, however, meant one stage fewer in the CCD circuit. The high
density thickener had an installed cost about the same as a high rate thickener, and with one
fewer thickener in the CCD circuit offered a significant capital and operating cost saving.
Even if the same number of stages were to be used with a high rate CCD circuit or high
density CCD circuit, the increase in wash recovery has a good payback. Table II is an
indicative increase in income due to a 0.61% increase in wash recovery. The extra copper
recovery leads to an extra 1.5 million dollars per annum. This increase in income leads to a
quick payback for the additional cost of the high density thickeners.
Differences in thickener design
There are some differences in the design between the high rate and high density thickeners.
The following list gives an overview of the main design differences between the two types of
thickeners.
Tank side wall depthhigh density thickeners use a combination of gravity and
compression to consolidate suspended solids. The mud residence time required to
increase the underflow suspended solids concentration is achieved by increasing the
sidewall height.
Tank floor slopedue to the greater rheology as a consequence of higher underflow
suspended solids concentration, a steeper floor slope is used to assists the slurry
movement to the centre of the thickener for discharge..
Rake drivesince high density thickeners are always smaller than high rate thickener,
the unit torque of K factor must be greater. Typically the same rake drive required for a
high rate can be used for a high density thickener and achieve a significantly greater unit
torque input.
Rake mechanismthe rakes are designed to minimize the cross-sectional area of the
mechanical members to minimize resistance or torque production and allow the most
dense underflow suspended solids to discharge from the thickener. High density
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Table II
Increase in income due to increase in copper recovery
Copper recovery for 45 000 tpa plant
Copper produced
Recovery
(tons/day)
130.00
(%)
98.78%
99.39%
Copper leached
(tons/day)
128.41
129.21
Production days
(days)
Copper produced
(tons/year)
350
44 945
Copper price
($/ton)
Income per annum
($/year)
242 901 639
Increase per annum
($/year)
1 500 000
45 222
5,404
244 401 639
thickeners also have pickets attached to the rake arms to alter the permeability of the
compacted solids. Pickets create paths for the liquor in the compacted solids to escape,
allowing solids concentration to continue
Thickener dischargehigh density thickeners are designed with discharge cylinders with
much more volume than cones to facilitate discharge and to minimize or prevent ratholing or underflow dilution.
Conclusions
The use of extensive laboratory thickening simulations to measure solid-liquid separation
properties and CCD simulations enabled good information to be gathered for the design of the
Ruashi II CCD circuit. The use of the CCD simulations showed that higher underflow
densities in the thickeners means 5 stages rather than 6 stages in the CCD circuit can be used
to achieve the same wash recovery of soluble copper. This thus led to the decision to use high
density thickeners in the CCD circuit rather than High Rate thickeners. The use of high
density thickeners allows Capex and Opex cost savings to be made due to the reduced number
of stages.
Acknowledgements
The authors would like to thank Metorex who kindly gave permission for this paper to be
published.
Mark Mulligan
Process Engineering Manager, FLSmidth Minerals (Pty) Ltd
Had a bursary from Sappi whilst studying BSc Chemical Engineering.
Worked in the Pulp and Paper industry for 6 years in Process and
Projects Engineering roles. Spent these years working on optimization
projects and large Capital projects in the Pulp, Liquor recovery, Leach
and Chlorine dioxide plants.Then spent a year working at Process
Projects in a Process Engineering position, primarily working on
projects in the Phosphoric acid and Fertiliser industries.
Have been with FLSmidth Minerals for 3 years in the Solid Liquid separation part of the
business, getting involved in all process related issues on all the projects relating to these
technologies.
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REOLON, M., GAZIS, T., and AMOS, S. Optimizing acid utilization and metal recovery in African Cu/Co
flowsheets. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and Metallurgy, 2009.
Optimizing acid utilization and metal recovery in

African Cu/Co flowsheets
M. REOLON*, T. GAZIS*, and S. AMOS*
*GRD Minproc Pty (Ltd), South Africa
Recent global demand for copper and cobalt has resulted in renewed
interest in developing the copper and cobalt deposits in the DRC. In
addition, recent dramatic increase in sulphur and sulphuric acid
prices, as well as the copper and cobalt prices, has led to the creation
of innovative ways to increase the utilization of reagents and recovery
of metals.
As a result of the potential in saving in operating costs, and the
possibility of increased recovery of metal, a series of trade-off studies
was performed to determine the cost benefits to several copper/cobalt
studies for projects in the DRC. The purpose of these trade-off studies
was to determine the feasibility of implementing any of the alternate
flowsheet options into the next phase of these projects.
This paper presents the base case and the various trade-off options
and includes a brief description of the flowsheets considered. Special
considerations specific to the base case are identified as these may
influence the benefits of the options for individual projects. The major
advantages and disadvantages are listed in order of importance to
indicate where capital, operating or latent risk costs are affected by
the options. High-level cost estimate ranges for capital, operating and
annualized risk are given for the various options. Where applicable,
comments on sensitivity to any identified parameters are discussed.
In order to compare the various options to each other, both process
and economic summary tables comparing the options are shown.
Discussion on the interaction of more than one of the options will
complete the comparisons.
Democratic Republic of the Congo

Introduction
The Democratic Republic of the Congo was initially established as the Belgian Congo in
1908. It subsequently gained independence in 1960. The early years of independence were
marked by social and political turmoil.
OPTIMIZING ACID UTILIZATION AND METAL RECOVERY IN AFRICAN CU/CO FLOWSHEETS
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In a coup in 1965, an army colonel, Joseph Mobutu seized power, renaming himself Mobutu
Sese Seko and the country Zaire. Under his presidency, social and economic conditions in the
country deteriorated further. In 1997, Mobuto was toppled by a rebel leader, Laurent Kabila.
Kabila restored the name of Congo in the form of the Democratic Republic of the Congo
(DRC). He, in turn faced a rebel movement backed by Rwanda and Uganda. Troops from a
number of African allies were flown into the country and the rebellion was put down and a
ceasefire signed in 1999. Kabila himself was assassinated in early 2001, and his son, Joseph
Kabila, was installed as president of the Republic.
Joseph Kabila subsequently negotiated the removal of Rwandan forces, and a peace
agreement was signed in South Africa in 2002. A transitional government was formed with
the objective of eventually holding democratic elections in the country. These elections were
held in July 2006, and resulted in the leading two presidential contenders each receiving less
than 50% of the vote, although Joseph Kabila did gain a significant majority over his leading
rivals. In the terms of the election rules, a run-off between the last two took place in
November 2006 with Kabila gaining an outright majority.
The United Nations were invited to install a peacekeeping force in the country at the end of
last century, and this force has contributed to a general improvement in the internal security of
the country, although, even today, there is continuing insecurity in the north-east of the
country. This area is quite remote from the main copper and cobalt mining province of
Katanga, where conditions have remained calm.
Economy
Since 2001, when Joseph Kabila became president, the economic policy of the country has
aimed at stabilization. Since about that date, there is little doubt that the mining and
construction sectors are improving, albeit from a low base. Gross national income is US$120
per capita, but since 2002, the economy has shown signs of expansion with a GDP growth in
2002 of 3.5%, 2003: 5.7%, 2004: 6.8%, 2005: 6.5%. The latter two figures are provisional.
The independent central bank has bought inflation under control in recent years, again
indicating a normalizing of the economic and social situation within the country.
The corporate tax and investment codes are being revised to continue to liberalize the
domestic business environment and attract foreign investment, and an increasing number of
foreign companies are establishing themselves in the country.
Gecamines
Prior to the departure of the Belgians from the Congo in 1960, the copper industry in the
Katanga area was owned and operated by Union Miniere de Haut Katanga (UMHK), a
company dating from 1906. After independence, nationalization of the copper industry was
inevitable, and UMHK were eventually dispossessed of their ownership of the industry, and a
state owned company, initially Generale Congolaise des Minerals and later La Generale des
Carriers et des Mines (Gecamines) took over as owners and operators of all the copper mines
in Katanga. Gecamines initially prospered throughout the 1970s and 1980s, but since the late
1980s, the company went through a series of increasing crises, until finally, by the late 1990s,
copper production was only 35 000 t of copper and 3 940 t of cobalt, compared to 437 000 t of
copper in 1987, plus 11 900 t of cobalt in the same year.
As a result of this poor performance, the Government started to seek ways of improving the
situation both within Gecamines and within the copper industry as a whole. As a result of
these initiatives, foreign private industry has been encouraged to enter into agreements with
Gecamines in an attempt to restore the industry. After some stumbling, these initiatives are
now beginning to bear fruit.
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Code Minier
A Code Minier has been introduced by the Government and provides a transparent legal
framework for investors in mining. The code has been gazetted in the French and English,
making it easier for foreign Anglophone companies to review the legislation.
Copper cobalt processthe base case
A typical hydrometallurgical copper cobalt flowsheet as used in southern Africa is shown in
Figure 1. This flowsheet is used as a base case against which the various options are
compared.
A predominantly oxide ore is crushed and milled to expose the copper and cobalt minerals
for leaching. The milling step is the main entry point for water in the process
The milled slurry then undergoes a solid/liquid separation stage in a thickener in order to
reduce the water entering the leach circuit. The separated water is recycled back to the mill.
The thickened slurry is sent to the leach reactors, where acid rich raffinate (from solvent
extraction) and makeup acid is blended with the slurry. Copper and other elements are leached
by the acid. The leach reaction is also performed under reducing conditions using sulphur
dioxide in order for the cobalt to be effectively leached.
After leaching the slurry is washed in a 6 stage counter current decantation (CCD) wash
circuit using slightly acidified process water. This step removes most of the metal containing
solutions from the leached solids. The washed solids are discharged to the tailings
neutralization step, and the metal containing solution is sent to the solvent extraction (SX)
step as pregnant leach solution (PLS)
The washed solids from the underflow of the last CCD thickener are pumped to the tailings
neutralization circuit. Iron/manganese precipitate is also neutralized in this step. Slaked lime
is used to control the pH at above 8. The neutralized tails are then pumped to the tailings
disposal site. Some of the water is decanted from the tailings dam and recycled to the process
water pond. The balance of the water remains in the tails. This is an exit point for water.
Figure 1. Base case process flowsheet
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The PLS is fed to the SX circuit where copper ions are selectively exchanged for acid (or
hydrogen ions) using a liquid organic solvent extraction medium. The discharge solution
(copper lean but acid rich) is discharged from the SX circuit as raffinate, which is recycled
and used in the leach step (see above). In order to maintain a water balance, and to bleed
cobalt and other metals out of this recycle stream, some of the raffinate is bled off and sent to
the cobalt production circuit.
The copper extracted by the SX organic is stripped with a strongly acidic electrolyte, where
the copper ions are exchanged for acid. The copper rich electrolyte is sent to the copper tank
house where the copper is electroplated, harvested and prepared for market. The
electrowinning (EW) process produces acid while plating copper metal.
The raffinate bleed that is sent to the cobalt production circuit is depleted of copper, but rich
in acid (from leach plus SX) and other accumulated metals. The cobalt circuit consists of a
series of stage-wise neutralization/precipitation reactions and solid/liquid separation steps.
The first stage is to remove primarily iron, manganese, aluminium and phosphates as
precipitates. This is done using limestone as a neutralizing agent controlled to pH of 33.5,
and a mix of SO2/air as an oxidizing agent for iron and manganese. The precipitate is
thickened, filtered, washed and transferred to tailings neutralization (see above).
The next stage is to precipitate residual copper at pH 55.5 using slaked lime. The
precipitate is thickened and pumped to the leach circuit for recycle of the copper and some coprecipitated cobalt.
The final stage is to precipitate cobalt as an impure hydroxide at pH 8 using slaked lime.
This cobalt product is thickened, filtered, dried and bagged for market.
The remaining solution from the cobalt circuit is sent to the process water pond for recycle
in the plant. Excess water is treated at this point for disposal.
Alternative flowsheets for the optimization of reagent utilization and copper/cobalt
recovery
The focus of the trade-off studies has primarily been on the reduction of acid consumption,
and the subsequent need to neutralize the acid with limestone, lime and other acid neutralizing
reagents. This drive for acid consumption minimization was particularly powerful during the
recent sulphur price increase during 2007 and 2008. Even though the sulphur price has
returned to the levels prior to this increase, there remains a significant cost to transport the
sulphur into the DRC, therefore one can always expect sulphur costs at substantially above
coastal sulphur costs.
The following list of options has been considered in recent projects, initially as trade-off
studies as well as inclusions in the feasibility studies and EPCM.
Split SX
Milling in raffinate
Pre-leach filtration
Acid tailings
Post-leach filtration instead of CCD.
The projects evaluated during mid 2007 to mid 2008 are located in the DRC and range in
size as follows:
ROM throughput1 300 000 to 4 500 000 t/a
Copper production30 000 to 80 000 t/a. the base case is centred around 40 000 t/a
Cobalt production1 500 to 7 000 t/a.
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Capital and operating costs are based on the costs received during the period given above. It
must be noted that these costs did vary significantly during this period. For this reason the
results given in this report are indicative only. An evaluation of this nature will need to be
performed on specific projects to obtain relevant data specific to the project under evaluation.
Split SX
Description
The base case flowsheets and design criteria have proposed that the leach product be washed
in a series of six CCD thickeners before passing the PLS (CCD1 overflow) to copper SX/EW.
At this point, this is the only place in the circuit where copper is removed.
By introducing the split SX option, the first CCD thickener will assume the function of a
post-leach thickener as well as a point of separation for the high grade and low grade PLS
streams. The high grade PLS stream will pass directly through the high grade copper SX/EW
stage where copper is removed. The resulting raffinate solution is recycled to the leach feed.
The low grade PLS stream will be passed through the remaining five CCD thickeners,
undergoing washing before being sent to the low grade copper SX/EW stage. The resulting
low grade raffinate is sent to the cobalt removal circuit.
The amount of Copper produced increases slightly in comparison with the Base Case, as
well as a slight increase in the production of Cobalt, resulting too in less Cu/Co settling out in
the tailings dam. (Figure 2.)
Analysis for splitting the SX stream into high grade and low grade streams
In comparing the mass balances for both the base case and for the split SX alternative, it is
observed that both the copper and cobalt production increase slightly (having fewer losses to
the tailings dam), with a significant decrease in total acid consumption. Due to splitting the
PLS and redirecting a portion of it to the high grade SXEW stage, the acid content of the CCD
Figure 2. Split SX flowsheet
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underflow to the tailings neutralization decreases as well as the acid content of the cobalt
bleed stream; therefore limestone required to neutralize this acid decreases. These changes are
used to determine the change of operating cost and revenue earned.
Advantages and disadvantages
Below is a list of advantages and disadvantages of the split SX option in relation to the base
case.
Advantages
Capital
Reduced lime plant
Reduced acid plant
Operating and revenue
Reduced acid costs
Reduced Co bleed and tails neutralization
Cu production increase
Co production increase
Risk
SX plant redundancy
Potential for additional SX throughput
Potential to continue partial operation on SX fire destroying one train
Disadvantages
Capital
Additional SX stream
Additional PLS pond
Additional raffinate pond
Additional plant operation (labour)
Risk
Operational complexity
Capital estimate
The capital cost changes for the implementation of the split SX option is based on the
following.
Reduction in limestone plant size
Reduction in acid plant size
Addition of a secondary copper SX/EW circuit as well as associated ponds.
The operating cost changes for the implementation of the split SX option is based on the
following.
Reduction in the consumption of limestone and acid
Increase in copper production
Increase in cobalt production.
Risk estimate
Annualized risk equivalent costs have been determined based on the following significant
risks.
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SX train redundancy
Partial production after a fire event.
Results
The summarized results for the split SX estimated capital costs, operating costs and revenues
earned, and annualized risk assessment is given in Table I.
The implementation of the split SX option will negatively affect capital, where the addition
of an extra PLS and raffinate pond capacity as well as supplementary SX costs will load the
capital expenditure by an additional $2 000 000. Capital advantage for reduced acid and lime
plant is also allowed.
An operating cost advantage of $4 200 000 is realized, however, in the split SX option. This
emanates greatly from the increased copper and cobalt revenue, as well as a reduction in the
consumption of both acid and limestone.
The costs associated with risk are advantageous in excess of $300 000 /a.
Recommendation
The split SX option offers both risk as well as operating and revenue advantages and is
recommended to be considered in any future hydrometallurgical copper cobalt projects.
Milling in raffinate
Description
The base case flowsheets and design criteria have proposed that the mill circuit uses process
water recycled from the downstream preleach thickener overflow and makeup process water.
This results in the addition of water into the leach circuit due to the slurrying of the relatively
dry ROM. Any water that passes into the leach circuit will need to be removed from the
process. The water trapped in the settled tailing is the only substantial outlet for water in the
plant. Any further water accumulation will have to be treated in the raffinate bleed.
By introducing the milling in raffinate option, recycled raffinate is used to slurry the crushed
ROM, thus reducing the water input into the process. This will have the net effect of reducing
or eliminating excess water accumulation in the plant, therefore reducing the raffinate bleed to
the cobalt plant.
Other benefits include better leaching and the elimination of the preleach thickener step,
reduced acid and limestone consumption. (Figure 3.)
Table I
Cost advantage summaries for the split SX option
Capital cost advantage
Operating/revenue cost advantage
Annualized risk advantage
Net annual advantage
Payback
-$2 000 000

$4 200 000
$300 000
$4 500 000
0.45 years
Positive cost values imply savings or financial gain to the project.

Negative cost values imply expenses or financial loss to the project.
Data indicative of 40 000 t/a copper production.
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Figure 3. Milling in raffinate flowsheet
Analysis of milling in raffinate compared to milling in water (base case)

In comparing the mass balances for both the base case and for the milling in raffinate
alternative it is observed that the acid consumption decreases. The acid content of the raffinate
bleed also decreases, therefore limestone to neutralize this acid decreases. Due to the reduced
size of the cobalt bleed, the tenor of cobalt will increase in the raffinate returning to leach.
This in turn will cause the cobalt loss to CCD underflow to increase, resulting in cobalt
production decrease. These changes are used to determine the change of operating cost and
revenue earned.
Below is a list of advantages and disadvantages of the milling in raffinate option in relation to
the base case.
Advantages
Capital
Cobalt plant feed and capital reduced
Acid plant size reduced
Limestone plant size reduced
No pre-leach thickener required.
Cobalt plant operating cost reduced
Acid consumption reduced
Limestone consumption reduced
No preleach op costs required
Reduced maintenance on acid and lime plants.
Risk
Co tenor therefore product purity increase.
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Disadvantages
Capital
Acid resistant mill required
Acid resistant mill area required.
Co production decrease
Additional mill maintenance.
Risk
Risk of mill and area corrosion
Added mill delivery schedule of approximately 20 weeks
HSE risk.
Capital estimate
The capital cost changes for the implementation of the milling in raffinate facility are based
on the following.
Reduction in the size of the cobalt plant
Reduction in the size of the acid plant
Complete removal of the preleach thickener area
Reduction in the size of the limestone plant
Additional cost for an acid resistant mill, stainless steel chute and plate work and
protected structural steel and concrete.
The operating cost changes for the implementation of the milling in raffinate facility are based
on the following.
Reduction in the consumption of acid and limestone
Reduced power, maintenance and consumable in the cobalt plant
Remove preleach thickener operating costs
Reduced operating cost in the acid and limestone plants
Additional mill operating costs
Reduced cobalt production.
Risk estimate
Annualized risk equivalent costs have been determined based on the following significant
risks:
Additional delay in delivery of the mill causing delayed revenue. This risk is highly
variable, and could be mitigated by earlier procurement, if such timing is available
Downtime and replacement of corroded mill shell
Increased HSE risk in the area.
Results
The summarized results for the milling in raffinate estimated capital costs, operating costs and
revenues earned, and annualized risk assessment is given in Table II.
The implementation of the milling in raffinate option will have an overall capital advantage
where the reduction of process and reagent plant capital more than offsets the additional cost
of the milling area. The reduction in the cobalt plant and acid plant result in the major capital
reduction.
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Table II
Cost advantage summaries for the milling in raffinate option
Operating / revenue cost advantage
Payback
$ 2 000 000
$ 5 000 000
$-5 000 000
$0
N/A

Data indicative of 40,000 t/a copper production.
An operating cost advantage of $5 000 000 is realized in the milling in raffinate option. The
largest contributor is from the reduction in sulphur and limestone reagent requirements.
The costs associated with risk have been shown to be about $1 000 000/a if the added delay
of production start-up can be avoided. If however the added delay can not be mitigated, then
the total annualized risk climbs to $5 000 000 /a.
Recommendation
In comparing milling in raffinate to milling in water, the result established that milling in
raffinate is potentially a high risk option, both technically as well as commercially. Delivery
times are high, and the need for expensive spares (mill shell), or prolonged shutdown are
typically unacceptable. Risk mitigation strategies may well swing this option positively. The
alternative option of preleach filtration vs. thickening offers similar benefits while eliminating
the high risk factor of milling in raffinate and is preferred where filtration is feasible.
Preleach filter
Description
The base case flowsheets and design criteria have proposed that the feed to leach be
dewatered in a thickener, thus allowing process water to be recycled back to the mill. Any
water in the underflow of this thickener will result in the addition of water into the leach
circuit. Any water that passes into the leach circuit will need to be removed from the process.
The water trapped in the settled tailing is the only substantial outlet for water in the plant. Any
further water accumulation will have to be treated in the raffinate bleed, resulting in the
neutralization (loss) of acid using limestone
By using the preleach filtration option, the water content of the slurry to leach is reduced
from 5060% to an estimated 2025%, thus reducing the quantity of water into the process.
This will have the net effect of reducing excess water accumulation in the plant, therefore
reducing the raffinate bleed to the cobalt plant and increasing raffinate utilization in the leach.
This will result in reduced acid and limestone consumption. (Figure 4.)
Analysis of preleach filtration as compared to the base case of preleach thickening
In comparing the mass balances for both the base case and for the preleach filtration
alternative it is observed that the acid consumption decreases. The acid content of the raffinate
bleed also decreases, therefore limestone to neutralize this acid decreases. Cobalt production
decreased due to increased tenor in the raffinate, resulting in increased losses to tails. These
changes are used to determine the change of operating cost and revenue earned.
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Figure 4. Preleach filtration flowsheet

Below is a list of advantages and disadvantages of the preleach filtration option in relation to
the base case.
Advantages
Capital
Reduce cobalt plant size
Reduce acid plant size
Eliminate preleach thickener
Reduce limestone plant size.
Reduce acid consumption
Reduce limestone consumption
Reduce cobalt plant operating cost
Eliminate preleach thickener operating cost.
Risk advantage
Increased co tenor possibly increased product concentration.
Disadvantages
Capital
Require a preleach belt filter
Increased complexity of preleach filteroperation and maintenance
Lower cobalt recovery.
Risk
Risk of increased operational shutdown.
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Capital estimate
The capital cost changes for the implementation of the pre-leach filter facility are based on the
following:
Reduction in the size of the cobalt plant
Reduction in the size of the acid plant
Complete removal of the preleach thickener area
Reduction in the size of the limestone plant
Addition of the preleach filter unit(s).
The operating cost changes for the implementation of the preleach filter is are based on the
following:
Reduction in the consumption of acid and limestone
Reduced power, maintenance and consumable in the cobalt plant
Reduced operating cost in the acid and limestone plants
Greater operating costs for filtration than thickener
Reduced cobalt production
Removal of the thickener operating costs.
Risk estimate
Annualized risk equivalent costs have been determined based on an estimated likelihood of
unplanned days shutdown of the filter plant.
Results
The summarized results for the preleach filtration estimated capital costs, operating costs and
revenues earned, and annualized risk assessment are given in Table III below.
The implementation of the preleach filter option will have an overall capital advantage of
about $5 000 000 where the reduction of process and reagent plant capital more than offsets
the additional cost of preleach belt filters. The reduction in the cobalt plant and acid plant
result in the major capital reduction.
An operating cost advantage of estimated $4 500 000 is realised in the preleach filtration
option. The largest contributor is from the reduction in acid and limestone reagent
requirements. Unfortunately a reduction of cobalt has been observed resulting in substantial
revenue losses, but this factor is outweighed by the other savings in operational costs.
Table III
Cost advantage summaries for the pre-leach filtration option
Capital cost dvantage
Payback
$5 000 000
$ 4 500 000
-$2 000 000
$2 500 000
N/A

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The cost associated with risk is based on an approximately 5 days of production throughput,
and is calculated at $2 000 000 /a.
Recommendation
Where filtration is reasonably possible, the preleach filtration option offers both capital and
operational cost savings, which offset any additional risk. It is therefore recommended to
implement the preleach filtration option into hydrometallurgical copper cobalt projects.
Recent results on a project have, however, shown that a preleach thickener underflow density
in excess of 65% solids was observed, thus the thickener option was retained.
Acid tails
Description
The base case flowsheets and design criteria have proposed that the CCD underflow slurry
stream be mixed with an iron and manganese impurity slurry, and then neutralized with lime
prior to being pumped to the tailings facility. The alternate proposal is to pump the CCD
underflow slurry directly to a modified tails facility. This will result in a tails facility operating
at approximately a pH of 3. The iron and manganese impurities stream will have to be placed
in a separate compartment of the tailings facility in order to prevent releaching of the
impurities into the acidic water in the acid tailings facility.
The major changes to the plant equipment are the lining of the tails facility, the creation of a
separate compartment in the tails facility for the impurities slurry, and the removal of the
neutralization circuit.
The conversion to an acid tails facility is expected to increase the utilization of acid,
increase the production of copper and cobalt, and possibly increase the leaching of copper and
cobalt in the acidic environment of the tails. These benefits are achieved by the recovery of
the clarified acidic water that is decanted off the top of the tails facility. This water, containing
the acid, copper and cobalt, is recycled to the plant as CCD wash water, where the acid and
metals have an opportunity to be extracted in downstream processes.
To enhance the recovery of tails leached material, it is suggested that a means of removing
recycle acidic water from the bottom of the tails pond is implemented; else most of the
leached copper will remain trapped in the tails sediment. (Figure 5.)
Analysis for the implementation of an acid tails facility
In comparing the mass balances for both the base case and for the acid tails alternative, it is
observed that the copper and cobalt production increases, while the acid consumption
decreased by a small amount. The acid content of the raffinate bleed also increases by a small
amount; thus more limestone is needed in the cobalt plant. These changes are used to
determine the change of operating cost and revenue earned.
Below is a list of advantages and disadvantages of the acid tails facility in relation to the base
case of neutralized tails.
Advantages
Capital
Remove tailings neutralization capital
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Figure 5. Acid tails flowsheet
Operating/revenue
Reduced tails neutralization costs
Recover some soluble copper and cobalt from CCD underflow
Reduce acid costs
Potential to continue leaching on tails pond.
Disadvantages
Capital
Acid tails lining costs
Require a separate compartment for Fe/Mn tails in pond
Tailings facility closure costs
Operating
Increased limestone consumption for Co plant
Storm water capacity.
Risk
HSE Risk if liner is breached in tailings.
Capital estimate
The capital cost changes for the implementation of the acid tailings facility are based on the
following:
The tails neutralization plant can be removed completely
The acid tails facility needs a lining to prevent the acid from entering the groundwater
The acid tails facility needs to be compartmentalized to keep the impurities separate from
the CCD underflow tails
Mine closure costs for the acid tails pond have not been included, but need to be
considered in evaluating this option.
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Operating cost and revenue income estimate

The operating cost changes for the implementation of the acid tailings facility are based on the
following:
An increase in the revenue from copper and cobalt due to better recoveries
Elimination of neutralization operating costs
Reduced acid consumption
A small increase in limestone consumption in the cobalt plant
Possibly none, but potentially some revenue from the continued leaching of copper and
cobalt in the acid tailings facility. The benefit from this source would have to be tested in
a laboratory or pilot plant for each project in order to confidently assign any benefits
from increased revenue.
Risk estimate
The main risk identified is that the liner of the acid tailings facility could be compromised
during the life of the mine. A significant outflow into the soil and groundwater system below
the tailings facility will result in environmental discharge requiring remedial actions to be put
in place.
An estimate for the scenario of liner failure has been made. The estimate is based on the
probability of a liner installations failing, an assumed cost to repair the failure, and
determining the annualized loss of revenue for such remediation actions.
Results
The result for implementation of the acid tails facility is presented in Table IV.
Operating cost and revenue earned values represent the annualized net gain including an
estimated income for the extended leaching advantage.
If the advantage of extended leaching is ignored, then the payoff of the capital occurs in
more than 10 years. These conclusions are based on current cost analysis only and may differ
considerably once further investigation of the cost of lining and lining maintenance of an acid
pond is taken into account. Furthermore, the cost of mine closure will further reduce the
performance of this option.
Recommendation
Further investigation into actual costs of constructing, lining and maintaining an acid proof
pond is required for specific projects considered, as no clear trend has been observed.
Table IV
Cost advantage summaries for acid tails option
Payback
$-6 500 000

$2 900 000
-$1 500 000
$1 400 000
4.6 years

Data indicative of 40,000 t/a copper production.
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Furthermore, the risk evaluation for tailings dam integrity is often subjective and therefore
difficult to determine. The specific findings of such an investigation significantly alter the cost
advantage summary.
Filtration vs. CCD
Description
The base case flowsheets and design criteria have proposed that the solids in the leached
stream be separated from the solution using a conventional CCD circuit operating with a wash
ratio of 1.26. This results in the addition of large quantity of water into the PLS stream.
By introducing the post-leach filtration option (which required an initial thickener to preconcentrate the filter feed), a lower wash water ratio of 0.8 is used, thus adding less water to
the PLS. Furthermore, it is anticipated that the recovery of copper, cobalt and acid through the
filter is improved due to more efficient washing and the production of a filter cake containing
less moisture than the CCD underflow to tailings. A smaller PLS stream also implies that the
raffinate bleed, hence the cobalt plant can be reduced in size, with subsequent savings on acid
and limestone. (Figure 6.)
Analysis of post-leach filtration compared to CCD (base case)
In comparing mass balances for both the base case and for the post-leach filtration alternativeit is observed that the acid consumption has increased, together with the raffinate bleed
stream. This is mainly due to increased copper production, causing an increased acid
production in the raffinate. Since a significant portion of this raffinate is neutralized, acid
consumption is increased. Copper and cobalt production has, however, increased due to better
recoveries from the tails. These changes are used to determine the change of operating cost
and revenue earned.
Figure 6. Postleach filtration flow sheet
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Below is a list of advantages and disadvantages of the post-leach filtration option in relation
to the base case.
Advantages
Capital
Remove CCD capital.
Remove CCD operating costs
Additional Cu production
Additional Co production.
Disadvantages
Capital
Add post-leach thickening and filter capital
Larger cobalt plant
Larger acid plant
Larger limestone plant.
Add thickener operating cost
Add filter operating costs
Additional acid consumption
Additional limestone consumption.
Risk
Loss of filter.
Capital estimate
The capital cost changes for the implementation of the post-leach filtration facility are based
on the following:
Remove the CCD, adding pre-filter thickener and filters
Increasing the cobalt plant
Increasing the acid plant
Increasing the limestone plant.
The operating cost changes for the implementation of the post-leach filtration facility are
based on the following:
Remove CCD operating costs but adding the pre-filter thickener and filters operating
costs
Adding copper and cobalt revenue
Increased acid and limestone consumption.
Risk estimate
Since a spare filter has been allowed for, the risk due to filter shutdown is considered to
be negligible.
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Results
The summarized results for the post-leach filtration estimated capital costs, operating costs
and revenues earned, and annualized risk assessment is given in Table V.
The implementation of the post-leach filtration option will have an overall capital cost of
$15 000 000. The cost of the filters represents the major capital increase.
An operating cost advantage of only $400 000 is insufficient to justify the extra capital
expense.
Recommendation
In comparing post-leach filtration to conventional CCD, the result established that post-leach
filtration is not a viable option as the capital costs far outweigh the operating cost advantages.
Improvement in the filtration properties may reduce the capital, but to date this appears
unlikely to make this option viable.
Overall summary of results
Table VI shows the averaged costing summaries for the various options considered in this
paper.
From the analysis of recent copper cobalt hydrometallurgical plants, it is clear that the split
SX and pre-leach filtration options offer a definite advantage in enhancing the performance of
the process plant. The milling in raffinate option can potentially offer advantage, however, the
risk is high, and thus there has been a tendency not to select this option. The acid tail and
post-leach filtration options are costly to implement, with limited returns, as reflected in the
payback periods.
The implementation of multiple options has been considered and analysed in individual
studies; however, no analysis has been attempted here.
Table V
Cost advantage summaries for the post leach filtration option
Payback
-$15 000 000

$400 000
$$400 000
37 years

Table VI
Averaged costing summaries
Split SX
Capital million US$
Cost 2.0
Operating and revenue million US$/a Save 4.2
Annualized risk million US$/a
Reduced 0.3
Payback, years
0.45
Mill in raffinate Pre leach filtration

Save 2.0
Save 5.0
Increased 5.0
N/A
Save 5.0
Save 4.5
Increased 2.0
N/A
Acid tails
Post-leach filtration
Cost 6.5
Save 2.9
Increased 1.5
4.6
Cost 15.0
Save 0.4
0
37
The data presented is indicative of 40,000 t/a copper production facility
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Marco Reolon
Principal Process Engineering, GRD Minproc, South Africa
Marco has extensive hydrometallurgical experience over a broad range of metals.
This includes: pressure leaching of nickel, cobalt and gold, copper leach SX/EW,
PGM refining and nickel/cobalt separation.
Experience
Principal Process Engineer, GRD Minproc (Pty) Ltd, December 2007 to present
As principal process engineer he is responsible for various projects and studies, and
for the development of the process engineering group focusing on copper/cobalt
projects and studies in Southern Africa. Project achievements to date include:
Teal, Kalumines Hydrometallurgical Plant Pre-Feasibility Study, Democratic Republic of the Congo, (2008)
Platmin Congo, Deziwa Copper/Cobalt Definitive Feasibility Study, Democratic Republic of the Congo,
(2008 - present)
CuCo Resources, Kisanfu Scoping Study, Democratic Republic of the Congo, (2008 - present).
Senior Process Engineer, Fluor Canada Ltd, January 2006 to November 2007
As a senior process engineer in the Mining and Metals business unit he is responsible for the process aspects of
predominately hydro-metallurgical and mineral processes. His major project achievements as Senior Process
Engineer and Process Lead are:
Barrick, Pueblo Viejo Feasibility Project, Gold Pressure Oxidation Leach and Base Metals Recovery,
Dominican Republic (2007 - Present)
Phelps Dodge, Safford Leach Project, Heap leach, Solvent Extraction and Electrowinning. Safford, Arizona,
USA (2006-2007)
Sociedad Contractual Minera, El Abra Sulfolix Project, Feasibility (2006).
Solaris Management Consultants Inc. Canada, September 2002 to December 2005
Coordinating process engineers and process activities within the company.
Process engineering including Studies, Flow sheets, P&ID, equipment sizing and specification.
Gas field development for energy companies.
Developing standards, procedures and forms for process engineering activities.
Developing Data Books, Operating Manuals and start-up assistance for new facilities.
Major project achievements as process engineer, construction or field engineer and commissioning engineer
include:
Strachan Gas Plant Flare and Relief Upgrade Study, Rocky Mountain House, Alberta (20022003)
Arc, Prestville Oil Battery, Manning, Alberta (20032004)
SESI, PCB Destruction Plant, Annacis Island, British Columbia (20042005)
Apache, Leafland Gas Plant Upgrade, Rocky Mountain House, Alberta (2005)
Encana, Resthaven Gas Plant Project, Cache Creek, Alberta (20042005)
Encana, Steeprock Gas Plant Project, Tupper, British Columbia (2005)
Minor well site, compression, gas plant and gas gathering projects. (20022005).
Flour Daniel Wright Ltd - Vancouver BC Canada, Melbourne and Perth Australia, Calgary and Ft McMurray
AB Canada, December 1995 to August 2002
As a senior process engineer in the Mining and Metals business unit he was responsible for the process
aspects of predominately hydro-metallurgical and mineral processes.
Major project achievements as process and Lead process engineer are:
Albian Sands, Muskeg River Oil Sands Project, Fort McMurray, Alberta, Canada (20002002)
Phelps Dodge, Morenci Mine for Leach, Solvent Extraction and Electrowinning. Arizona, USA (19992000)
Miramar Con Mine Re-commissioning, Yellowknife, NWT, Canada (1999)
Murrin Murrin Nickel Cobalt Project, Western Australia (19971999)
Lomas Bayas Copper Heap Leach, Solvent Extraction and Electrowinning Project, Chile (19961997)
Molecular Recognition Technology Development (19951996)
Several pre-feasibility and feasibility studies.
Process engineer
B.M.I Division of E.L Bateman, February 1994 to November 1995
Responsible for the process aspects of the project Enhanced Platinum Metals Refinery Study and Project,
Springs, South Africa (19941995).
The process utilized a hydrochloric acid process environment to ensure the solubility and appropriate chemistry
of the platinum group metals.
OPTIMIZING ACID UTILIZATION AND METAL RECOVERY IN AFRICAN CU/CO FLOW SHEETS 383
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Extraction and separation process includes Molecular recognition technologies, Ion Exchange, Distillation and
solid liquid separation.
SastechDivision of Sasol Ltd, January 1991 to February 1994
As a process engineer in the petrochemical, oil and gas business he was responsible for the process and business
development aspects of the new ventures group.
Worked on the following projects:
Acetic Acid Pilot Plant Commissioning, Secunda, South Africa (1994)
Hydrogen Sulfide Emission Reduction Study (1993)
Alpha Olefins Pilot Plant Re-commissioning, Sasolberg, South Africa (1993)
Alpha Olefins Pilot Plant Conversion, Sasolburg, South Africa (1992)
Refinery Feed Stream Simulation (1992)
Alpha Olefins Pilot Plant Commissioning, Sasolburg, South Africa (1991)
Cresylics Acid Plant Commissioning; Sasolburg, South Africa.
Impala Platinum Ltd, Projects Department, Refineries, January 1988 to December 1990
As a chemical engineer in the projects department he was responsible for the process design and
implementation of new projects.
Worked on the following projects.
Selenium/Tellurium Removal Plant Project (1990), as project engineer.
Chlorine Hydrochloric Matte Leach Upgrade Project (1990), as project engineer.
Bulk Chemicals Handling Facilities (1990), as project engineer.
Platinum Metals Refinery Pilot Plant Design (1990), as area engineer.
Pressurized Oxygen Nickel Leach Autoclave commissioning (19891990), as commissioning engineer.
Rhodium/Iridium/Base Metals Separation Pilot Plant Design (1988), as assistant project engineer.
Rhodium/Iridium/Base Metals Separation Research and Development (1988), as research engineer.
Overall experience
Tasks:
During his career he gained experience in the following work processes or project and operating activities.
Research and Development (literature surveys, laboratory and pilot test program, outsourcing test work, data
analysis, analytical technique development, flow sheet development, new product business development)
Pre-feasibility studies (estimation of deliverables).
Proposal (for studies, including schedules and execution plan)
Feasibility studies (design criteria, flow sheet, pilot plant data evaluation, process simulation, mass balance,
process description, equipment list and sizing, piping and instrumentation diagrams (P&ID), equipment and
piping layouts, equipment costing, operation costing)
Detailed engineering projects (as above, operating philosophy, process control and variables, instrument and
equipment data sheets, design and equipment reviews, batch operating schedule, HAZOP and PHA studies,
functional specifications, operating manuals)
Pre-commissioning (including construction completion and tracking, equipment inspection, water testing
system turnover,)
Commissioning and Process Optimization (pre-start-up piping and equipment checks, cold commissioning, hot
commissioning, equipment performance tests, operator training, optimization, data recovery, high rate trails,
equipment evaluation and plant data recovery.)
Plant Training (operations, trouble shooting and plant optimization, commissioning, production utilities and
maintenance scheduling, safety and loss control, plant supervisory training)
Technologies:
Platinum group metals hydrometallurgical processes
Nickel/Cobalt hydrometallurgical processes
Copper/Cobalt hydrometallurgical processes
Zinc hydrometallurgical processes
Oil Sands processes
Molecular Recognition Technology.
Synthol technology
Sulfur recovery technology
Plant Utilities (water treatment, steam and condensate, cooling water, air, vacuum, bulk storage)
Autoclave Leach Reactors (Pressure oxidation, acid and Chlorine/hydrochloric)
Heap Leach (acid)
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SWARTZ, B., DONEGAN, S., and AMOS, S. Processing considerations for cobalt recovery from Congolese
copperbelt ores. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and Metallurgy,
2009.
Processing considerations for cobalt recovery

from Congolese copperbelt ores
B. SWARTZ*, S. DONEGAN, and S. AMOS*
GRD Minproc Pty (Ltd), Perth, Australia
*GRD Minproc Pty (Ltd), Bryanston, South Africa
The resource market has seen a year of turmoil in 2008. During the
first five months of the year a spectacular increase in cobalt price was
observed peaking at around $50/lb but since July there has been an
equally spectacular decrease in the cobalt price to current levels of
around $16/lb. Prior to 2008, a consistent growth period, stretching
over a few years which, driven mainly by an increased demand from
the developing world, in particular China, resulted in an increased
demand for both copper and cobalt.
Introduction
The increased demand for copper and cobalt together with the increase in political stability in
the region, have resulted in renewed interest in developing the copper and cobalt deposits in
the Katanga Province of the Democratic Republic of the Congo (DRC). A number of projects,
in various stages of development, are currently underway in the DRC. The primary product
from most of these projects is copper; however, cobalt is often a significant and sometimes
major contributor to the project revenue.
Cobalt in the form of heterogenite is commonly associated with copper bearing oxide ores
and hence it is commonly co-extracted with copper. In order to extract cobalt with copper, a
reducing environment is created for reduction of Co3+ to Co2+ as divalent cobalt is soluble at
the pH values at which copper dissolution is conducted. Cobalt is then generally recovered
from a copper solvent extraction (SX) raffinate bleed stream.
The general trend in the development of these copper/cobalt projects is to produce an
intermediate cobalt product at start-up and progress to cobalt metal production once the
operation has proven to be viable for a period. The decision not to go all the way to cobalt
metal is generally due to the perceived risk associated with operating a complex cobalt
refinery in central Africa. Shifting from production of intermediate cobalt products to pure
metal is largely driven by increased revenues
The decision to produce an intermediate cobalt product vs. metal significantly affects the
processing routes employed subsequent to copper solvent extraction (SX). If an intermediate
product is to be produced, then removal of iron, manganese and copper will occur with little if
no emphasis placed on reducing the levels of other impurities. Production of cathode
necessitates stringent impurity control in the cobalt electrolyte, which is critical in ensuring
PROCESSING CONSIDERATIONS FOR COBALT RECOVERY
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that cathode metal specifications are met. Typical impurities, other than those mentioned
above, are nickel, zinc and aluminum. The methods for removal of these are precipitation, SX
and/or ion exchange (IX), and the choice of technology depends on impurity concentration,
relative capital costs for removal and associated operational preferences.
This paper discusses some of the processing options available for cobalt production and
provides an evaluation of the associated costs, risks and benefits applicable to the DRC.
Democratic Republic of the Congo
Introduction
The Democratic Republic of the Congo was initially established as the Belgian Congo in
1908. It subsequently gained independence in 1960. The early years of independence were
marked by social and political turmoil.
In a coup in 1965, army colonel Joseph Mobutu seized power, renaming himself Mobutu
Sese Seko and the country Zaire. Under his presidency, social and economic conditions in the
country deteriorated further. In 1997, Mobuto was toppled by a rebel leader, Laurent Kabila.
Kabila restored the name of Congo in the form of the Democratic Republic of the Congo
(DRC). He in turn faced a rebel movement backed by Rwanda and Uganda. Troops from a
number of African allies were flown into the country and the rebellion was put down and a
cease fire signed in 1999. Kabila himself was assassinated in early 2001, and his son, Joseph
Kabila, was installed as President of the Republic.
Joseph Kabila subsequently negotiated the removal of Rwandan forces, and a peace
agreement was signed in South Africa in 2002. A transitional government was formed with
the objective of eventually holding democratic elections in the country. These elections were
held in July 2006, and resulted in the two leading presidential contenders each receiving less
than 50% of the vote, although Joseph Kabila did gain a significant majority over his rivals. In
the terms of the election rules, a run-off between the two preferred candidates took place in
November 2006 with Kabila gaining an outright majority.
Economy
Since 2001, when Joseph Kabila became president, the economic policy of the country has
aimed at stabilization. Since about that date, there is little doubt that the mining and
construction sectors are improving, albeit from a low base. Gross national income is US$120
per capita, but since 2002, the economy has shown signs of expansion with a GDP growth in
2002 of 3.5%, 2003: 5.7%, 2004: 6.8%, 2005: 6.5%. The latter two figures are provisional.
The independent central bank has bought inflation under control in recent years, again
indicating a normalizing of the economic and social situation within the country.
The corporate tax and investment codes are being revised to continue to liberalize the
domestic business environment and attract foreign investment, and an increasing number of
foreign companies are establishing themselves in the country.
Gecamines
Prior to the departure of the Belgians from the Congo in 1960, the copper industry in the
Katanga area was owned and operated by Union Miniere de Haut Katanga (UMHK), a
company dating from 1906. After independence, nationalization of the copper industry was
inevitable, and UMHK was eventually dispossessed of its ownership of the industry, and a
state owned company, initially Generale Congolaise des Minerals and later La Generale des
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Carriers et des Mines (Gecamines) took over as owners and operators of all copper mines in
Katanga. Gecamines initially prospered throughout the 1970s and 1980s, but since the late
1980s, the company endured through a series of increasing crises, until finally, by the late
1990s, metal production was only 35 000 t of copper and 3 940 t of cobalt, compared to
437 000 t of copper in 1987, plus 11 900 t of cobalt in the same year.
As a result of this poor performance, the Government began to seek ways of improving the
situation both within Gecamines and within the copper industry as a whole. As a result of
these initiatives, foreign companies have been encouraged to enter into agreements with
Gecamines in an attempt to restore the industry. After some stumbling, these initiatives are
now beginning to bear fruit.
Code Minier
A Code Minier has been introduced by the Government and provides a transparent legal
framework for investors in mining. The code has been gazetted in French and English,
making it easier for foreign Anglophone companies to review the legislation.
Cobalt processing options
In the DRC there are typically three major saleable product types produced, namely:
A cobalt concentrate via gravity separation
An intermediate cobalt salt
Cobalt metal.
The value of the product increases as the level of refining increases; however, this is also
proportional to the capital and operating cost associated with the facility required to produce
the end product. The complexity of the operation also increases significantly from concentrate
production through intermediate to pure metal.
Introduction
Gravity separation is by far the cheapest and lowest cost method of producing a saleable
product from ore. Not all ore types are amenable to gravity separation and generally low
recoveries are achieved even for those materials that are amenable. Product grade and
recovery are ore specific and generally quite poor. Dense media separation is the most
common technology used and is often employed as a preliminary measure to generate cash
flow before proceeding to the production of a purer product.
This method is mentioned for completeness and will not be discussed further.
There are a number of different cobalt intermediate products that can be produced, namely:
Cobalt hydroxide
Cobalt carbonate
Cobalt sulphide
Cobalt sulphate.
In addition, there are a number of refined cobalt metal products that can be produced from a
copper raffinate bleed stream or any of the above intermediates:
Cobalt cathode by electrowinning (EW)
Cobalt powder/briquettes by hydrogen reduction.
Cobalt refining is not only complex, but product types vary considerably in terms of purity
(and hence market premium and transport costs) and by-product/effluent generation. It is
important, therefore, to establish factors with the greatest importance to and impact on the
project to be able to identify the optimum solution. Four main categories should be
considered:
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Operationally safe, robust and simple

Technically robust and proven technology
Environmentally compliant
Commercially acceptable.
Unfortunately there is no single technology, flowsheet and product that rank highly in all of
the above categories. It is therefore necessary to select a flowsheet that has an acceptable
ranking in all categories while providing the best return to the project. A decision diagram
(Figure 1) illustrates the options, ranked in environmental and operability terms.
Options producing high levels of soluble salt form the left-hand leg of the decision chart,
and those processes that minimize the production of soluble salt effluent are indicated in the
right-hand leg. Those processes on the right of the decision chart reduce soluble salt
generation by an order of magnitude. It should be noted that none of the options provides a
zero discharge scenario.
Process options with lower risk profiles are located at the top of the chart, whereas higher
risk options such as sulphide precipitation with hydrogen sulphide gas are located in the
bottom. For the purpose of this ranking, process risk includes operational safety, operability
and robustness.
Intermediate product options
There are four main cobalt intermediate product forms that can be produced from either
selective precipitation or evaporation/crystallization techniques:
Figure 1. Cobalt intermediate product decision tree
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Cobalt hydroxide (precipitation using lime, magnesia or caustic)

Cobalt carbonate (precipitation using sodium carbonate)
Cobalt sulphide (precipitation using sodium hydrosulphide)
Cobalt sulphate (crystallization of a cobalt sulphate solution).
For all of the above products the option exists to produce a crude or pure form. A crude
form is defined as the product obtained after limited impurity removal (only iron); a pure
product is defined as the product obtained after removal of the major typical impurities,
namely, iron, manganese, copper and aluminium.
The process description for impurity removal is similar for all four intermediate products
and is summarized below.
Impurity removal prior to intermediate product production
Fe/Mn/(Al) removal
Iron and manganese (and aluminium in the presence of phosphate) are removed from the
cobalt bleed stream (copper SX raffinate) using a patented process that uses an air/SO2
mixture to oxidize and precipitate Fe and Mn/Al in a single step. It must be noted that no Mn
or Al removal is required when producing a CoS product as these two metals do not
precipitate as sulphides.
This section is usually equipped with approximately four agitated, overflow tanks in series.
The feed liquor is often heated to around 50C via indirect heating and a residence time of up
to 5 hours is required for substantial (>90%) manganese removal.
The tanks will be equipped with gas spargers to inject the air/SO2 mixture. The addition of
the air/SO2 gas mixture is controlled by adding the air at a fixed volume and then controlling
the SO 2 into the tank at an approximate SO 2 content of ~0.5% by volume. The redox
controller ensures that the reaction remains in an oxidizing regime with a measured redox
potential above 600 mV by controlling the flow of SO2.
The pH is controlled by adding limestone to the solution to increase the pH to around 2.5 to
3.0 (a pH of ~3.5 is necessary for aluminum removal in the presence of phosphate). The pH
control at this stage is important to ensure that as little Co as possible is precipitated with the
Fe and Mn (Al).
The slurry coming from the Fe/Mn/(Al) removal tanks flows by gravity to a high rate
thickener where the supernatant liquor is decanted from the precipitated solids. The solids are
concentrated in the underflow to around 30%, following which they are pumped to the
Fe/Mn/(Al) removal filters. A thickener underflow recycle ratio of approximately 200% is
required for crystal growth.
The Fe/Mn/(Al) removal filters are used to separate the supernatant liquor left in the
thickened slurry from the solids. Two filters will normally be used in this application: one
operating and a standby. A counter current washing regime is used to minimize the wash
solution required while still achieving high wash efficiencies.
The washed cake is disposed of with the neutralized leach residue.
Secondary copper solvent extraction
Copper in solution can be removed via precipitation with lime (similar to Fe and Al removal)
or via SX. The SX route is generally the preferred route as the capital and operating costs
associated with the precipitation and thickening route are usually higher, and it imposes a
significant recirculating load of cobalt.
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The aqueous liquor from the Fe/Mn/(Al) thickener is contacted with a bleed of the stripped
organic from the primary copper SX circuit to remove minor quantities of copper. This
increases copper recovery and minimizes contamination of the cobalt product.
Copper extraction is usually completed in one or two mixer-settlers. Cu-loaded organic is
mixed with the loaded organic from the primary Cu SX in the primary loaded organic wash or
strip mixer-settler.
Aluminium removal
This step is often not required as aluminium is often precipitated to a sufficient extent as the
phosphate complex during iron removal. Al precipitation is not required when producing CoS
as Al is not precipitated as the sulphide. Al precipitation is completed in agitated tanks with a
combined residence time of around two hours. The precipitation is run at an elevated
temperature of around 50C usually via direct steam injection, and controlled to a pH of
around 5.5 using slaked lime (Ca(OH)2).
The underflow is concentrated to around 40% solids in the Al removal thickener. A large
underflow recycle is required to aid crystal growth and the underflow is recycled to the first
tank in the Fe and Mn removal stage.
The thickener O/F will still contain solids that need to be removed from the process before
the solution is pumped to the cobalt precipitation area. A pinned bed type clarifier is used as it
can efficiently take out these solids in a single stage.
Intermediate product production
Cobalt hydroxide precipitation
The Co(OH)2 intermediate product is formed by contacting Fe, Mn, Al and Cu free solution in
a series of agitated tanks at elevated temperature with a slurry of Ca(OH)2.
The reaction co-precipitates gypsum, which contaminates and significantly lowers the grade
of the product. Magnesium and residual manganese are also partially precipitated as
hydroxides, the extent of which is dependent on the terminal pH of the reaction sequence. The
combined cobalt hydroxide and gypsum slurry is thickened, filtered and washed, and the filter
cake dried before being loaded into bulk bags for dispatch.
A preferred method for producing the hydroxide product is by using milk of magnesia as the
precipitant. This route avoids gypsum contamination of the product, thereby producing a
purer cobalt hydroxide product than the milk of lime precipitation.
Sodium hydroxide may also be used as the precipitant with advantages similar to magnesia.
However, this will result in a final effluent containing sodium sulphate, which will have to be
disposed of or contained.
For all three precipitants, product purity may be increased further by utilizing a two-stage
precipitation process. The intent here it to precipitate ~90% of the cobalt at pH ~7.5 in the
first stage as a relatively pure cobalt hydroxide product, low in manganese and magnesium.
The resultant slurry is thickened, filtered, bagged and dried for dispatch.
The first stage thickener overflow solution is then subjected to a second precipitation step to
recover the remaining ~10% of cobalt. This is achieved with milk of lime addition at pH 8.0
to 8.5. The slurry is thickened and returned to a suitable place in the cobalt purification
circuit.
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Cobalt carbonate precipitation

A pure CoCO3 intermediate product is formed by contacting Fe, Mn, Al and Cu free solution
in a series of agitated tanks at elevated temperature with a slurry of Na2CO3. The resulting
CoCO3 slurry is thickened, filtered and dried before being loaded into bulk bags for dispatch.
If the product is to be refined further on site the drying is generally not required.
Cobalt sulphide precipitation
Cobalt sulphide can be precipitated using sodium hydrosulphide (NaHS) or hydrogen sulphide
(H2S). While it is possible to perform a hydrogen sulphide cobalt precipitation at atmospheric
pressure, this would recover only approximately 85 to 90% of the cobalt to the sulphide. The
remainder would thus need to be recovered by an additional precipitation step using, for
example, milk of lime, and perhaps recycled in this instance to the Cu scavenger
neutralization circuit for redissolution and subsequent reprecipitation.
The precipitation of a sulphide intermediate using hydrogen sulphide is a series of relatively
complex and, due to the toxic nature of hydrogen sulphide, high risk operations. The
requirement for hydrogen for the generation of hydrogen sulphide necessitates the installation
and operation of a hydrogen plant in addition to a hydrogen sulphide plant. The large volume
of purge gas for maintenance operations may also dictate the requirement for a small nitrogen
(air separation) plant. Each of these gas plants is complex and intricate, requiring a skilled
labor complement for their reliable and safe operation. For these reasons the use of hydrogen
sulphide will not be discussed further.
Neutralized secondary SX raffinate constitutes the feed to the Co sulphide precipitation
circuit. (Note that no specific Fe, Mn or Al removal step is required as Fe(II), Mn and Al will
not precipitate as a sulphide; however, some Fe(III) and Al removal may occur during
neutralization.)
Pure CoS intermediate product is formed by contacting Fe(III)-free solution in a series of
agitated tanks at elevated temperature with a solution of NaHS. The resulting CoS slurry is
thickened and filtered, and the filter cake loaded into bulk bags for dispatch.
Cobalt sulphate crystallization
Iron, manganese, aluminium and copper free solution constitutes the feed to the CoSO4
crystallizer plant.
The CoSO4 intermediate product is formed by first concentrating the feed solution in a large
falling film evaporator, and then crystallizing the concentrated liquor in a smaller
evaporator/crystallizer. Washing, drying and bagging facilities are provided to ensure a pure
crystal product with minimum contamination and moisture.
The operation of the crystallizer is complicated by the fact that a calcium saturated solution
is formed, resulting in gypsum precipitation and scaling in the crystallizer. This process will
also result in the co-crystallization of all impurities with the cobalt product, including
magnesium and calcium resulting in a low grade product.
Intermediate product comparison
The four product options listed above are compared and discussed with reference to a number
of key project drivers.
Capital cost (excluding effluent treatment)
Capital costs associated with the carbonate and hydroxide routes are similar. Both routes are
only partially selective for manganese and magnesium and thus a similar degree of
purification is required prior to final product precipitation. The sulphate route has the highest
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capital cost due to the requirement for an evaporator and crystallizer in addition to the
preceding impurity removal steps. The sulphide flowsheet is the cheapest option in terms of
capital cost, despite the requirement for closed vessels and off-gas scrubbing equipment.
Cobalt sulphide is selectively precipitated in the presence of manganese and aluminium and
thus the removal of these elements is not required.
Operating cost
The sulphate route has the advantage that no reagents are required for final product
production. However, a significant amount of energy is required for solution evaporation, and
this cost makes it the most expensive to operate. Operating costs for hydroxide, carbonate and
sulphide are similar; if lime is utilized for hydroxide precipitation that route is slightly
cheaper.
Metal recovery
The recoveries of all four routes are similar. For the hydroxide route a two stage precipitation
process is recommended to recover and recycle soluble cobalt. The disadvantage of the
sulphide route is that any off specification material is difficult to redissolve without
specialized equipment (autoclave).
This is often the most important factor to consider when choosing a preferred route. HSE
issues are more prevalent for the sulphide intermediate due to the potential for H 2 S
generation. In addition to this, the use of NaHS will result in a final effluent containing
sodium sulphate, which will have to be disposed of or contained. The problem associated with
sodium sulphate disposal is common for the hydroxide-caustic and carbonate route as well
and can often be a significant additional cost. Hydroxide (lime/magnesia) and sulphate
intermediates usually have lower HSE issues.
Product purity
The sulphide product contains the highest percentage of cobalt followed by the hydroxide
(caustic or magnesia), carbonate then the low-grade hydroxide (lime), while sulphate has the
lowest contained cobalt. The major impurity associated with the sulphide intermediate is
magnesium; with sulphate it is manganese, magnesium and calcium; with carbonate it is
manganese and calcium; and with the hydroxide it is manganese and either calcium or
magnesium, depending on the reagent used for precipitation, i.e. lime or magnesia.
Apart from the rejection of Al and Fe(II) by sulphide precipitation, there is negligible
selectivity in this application for the remaining minor elements (Cu, Zn, Ni) by all options.
Operability and maintenance
The sulphide process requires off-gas scrubbing and tight pH control during precipitation. In
addition to this, the handling and corrosive nature of NaHS must be considered. For the
production of sulphate, the operation of a crystallizer and evaporator is relatively complex and
maintenance intensive so is rated more difficult than the carbonate and hydroxide routes.
Large recycles required for the hydroxide route make the circuit cumbersome from an
operability perspective, and the relatively poor settling and filtration characteristics of the
hydroxide product aggravate this. Descaling will be required in all cases.
Sales and marketing
This will depend on product purity, but in general terms marketing information indicates that
the customer base for hydroxide, carbonate and sulphate is larger than for the sulphide. The
value received from sales for carbonate and sulphate is higher than that for hydroxide and
sulphide.
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Future cobalt metal production

In a number of cases clients wish to adopt a strategy of cobalt intermediate production in the
initial years of project life with the conversion to metal production as revenue from copper
and intermediate sales stabilizes and operational experience is gained. The sulphide
intermediate would potentially require ultra-fine grinding followed by pressure oxidative
leaching. Intermediate hydroxide and sulphate products would require additional manganese
impurity removal steps prior to cobalt EW. The carbonate would be the easiest to refine.
Those products containing significant gypsum will obviously produce calcium saturated
liquors upon dissolution, requiring additional consideration and control within the cobalt
refinery.
The above comparison is summarized in Table I below; the intermediate options are rated
14, with 4 being the preferred option.
Recommended intermediate product
The cobalt sulphate route is eliminated on the basis of cost and the production of a low purity
product. Cobalt sulphide production is by far the most complex process, and HSE as well as
operability issues eliminate this option.
The two best intermediate product routes are the carbonate and the hydroxide. The choice
between the two has to be made considering environmental issues associated with the disposal
of sodium sulphate effluent. If the plant is close to a large water body, the disposal of the
effluent via dilution may be possible. However, with increasingly stringent environmental
legislation, this is becoming less likely unless the effluent can be pumped to the sea. The
production of the hydroxide via magnesia (MgO) precipitation will result in a reasonably high
quality product, and the liming of the effluent to a pH of around 10.5 will result in a
magnesium free solution, which can be disposed of a conventional tailing dam. The
precipitate from the neutralization can be stored in a relatively small lined facility.
The production of cobalt hydroxide using a two-stage process is in most cases the
recommended route.
Pure metal product options
Cobalt metal can be produced via hydrogen reduction (powder or briquettes) or EW (full plate
cathode or rounds). EW is believed to be the preferred method in almost all cases in terms of
lower capital and operating cost, higher metal recoveries and less stringent operability and
Table I
Cobalt intermediate product ratings
Parameter
Capex
Opex
Recovery
HSE
Purity
Op and main
Sales and marketing
Future metal production
Total
Co(OH)2
CoCO3
CoS
CoSO4
2
3
2
4
2
3
2
2
20
3
4
4
2
3
4
3
4
27
4
2
1
1
4
1
1
1
15
1
1
3
3
1
2
4
3
18
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maintenance requirements, and for the purpose of this comparison only EW will be
considered. The production of cobalt rounds is a patented process, so this paper will
concentrate on the production of full plate cathode.
Two different processing routes will be considered; these are described below:
Cobalt hydroxide precipitation followed by redissolution, impurity removal and EW
Cobalt SX, impurity removal and EW.
Precipitation and redissolution
Cobalt precipitation
The primary cobalt hydroxide precipitate is the feed material to the cobalt metal plant. The
use of magnesia is unnecessary and a cheaper precipitant, i.e. milk of lime, is more suitable,
although calcium saturation issues and larger volumes of redissolution residue must be
considered. Primary precipitate, in the form of a filter cake, is advanced to the cobalt redissolution circuit; secondary precipitate (high manganese) is recycled to the
iron/manganese/(aluminum) precipitation circuit feed for recovery of the contained cobalt.
Cobalt redissolution
Primary cobalt hydroxide filter cake is dissolved using cobalt spent electrolyte and sulphuric
acid in a cascade of agitated tanks. Oxidation and partial neutralization of the leached slurry
may be used to scavenge iron and manganese using milk of lime and air/SO2 gas mixture.
Aluminum will redissolve and will remain largely inert in the refinery, unable to plate with
the cobalt. It will either exit as entrained liquor in the redissolution residue filter cake, or as
part of the spent electrolyte bleed.
Leached slurry is thickened and filtered and the filter cake is recycled upstream to recover
any undissolved cobalt. Filtrate is clarified in a polishing filter for final solids removal, and is
then diluted with clean water to ensure liquor advancing to the IX circuits is comfortably
below calcium saturation.
Zinc ion exchange (IX)
Zinc and residual copper are removed from the cobalt rich liquor using a macroporous aminophosphonic acid chelating resin within fixed-bed columns operated in a typical lead-lag
configuration. A split elution technique using sulphuric acid is used to maximize zinc-cobalt
selectivity. Weak eluate is recycled to cobalt precipitation, and strong eluate is disposed via
tails neutralization. Regeneration of the resin is achieved using a caustic solution.
Nickel ion exchange (IX)
Nickel is partially removed from the zinc and copper-free cobalt rich liquor using a
macroporous bis-picolylamine chelating resin. As electrowinning is selective for cobalt over
nickel, removal of nickel to ~0.2 g/l is generally sufficient to meet cathode specification.
Similar configuration and elution/regeneration techniques to the Zn IX circuit are used;
however, the inherently low nickel-cobalt selectivity and high unit cost of the resin, encourage
the use of smaller bed volumes and a consequent increased number of columns.
Cobalt electrowinning (EW)
Electrowinning is conducted at ~70C in standard undivided cells. Stainless steel permanent
blanks are used as cathodes, with Pb-Sn-Ca anodes at 120 mm cathode-cathode spacing. A
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rich electrolyte tenor of at least 50 g/l Co is achieved by adjusting spent electrolyte recycle to
the re-solution circuit. This permits EW operation with a cell drop of 5 g/l, producing a spent
electrolyte of 45 g/l Co and ~8 g/l H2SO4. Under these conditions, a current density of 250
A/m2 will typically give a current efficiency of ~80%.
The use of divided cell technology, particularly anode bags, would potentially allow higher
cell drops to be achieved (>20 g/l), thereby significantly reducing the flow through the
purification circuit. However, given the highly stressed nature of full-deposit cobalt cathode
and the resultant potential for frequent damage to the surrounding bags, significant
development is required to reduce process risk before this technology can be considered for
application in the DRC.
Cathodes are harvested live on a six/seven-day cycle. They are washed with hot water to
remove surface electrolyte and are then manually stripped. Stripped blanks can be treated with
dilute nitric acid for removal of residual metal deposits. Prior to return to the cells, stripped
blanks are dipped in gelatine to create a favorable deposit-blank bond strength.
Stripped cobalt cathode pieces are crushed to -70 mm, vacuum degassed to remove
contained hydrogen and nitrogen, and burnished in rotating drums to achieve the desired
product finish. Final product is packaged in sealed drums for dispatch.
Manganese that is oxidized at the anode forms insoluble MnO2. This is periodically washed
from the anodes and hosed from the cell bottoms.
Spent electrolyte is returned to the redissolution circuit as required. Surplus liquor is bled to
the cobalt precipitation circuit, providing an important outlet for such species as magnesium,
aluminium, sodium, sulphate and chloride.
Cobalt SX EW
For this refining configuration, liquor exiting the secondary copper SX stage forms the feed to
the cobalt SX circuit. Sufficient removal of organic from the secondary copper SX raffinate
must be performed to limit the transfer of copper extractant (oxime) to the Cobalt SX organic.
A diluent wash is considered to have good potential in this application due to the availability
of relatively large volumes of make-up diluent required in the primary copper SX circuit.
Cobalt SX
Cobalt is recovered from the partially purified bleed liquor in a multiple-stage SX circuit
utilizing a phosphinic acid organic extractant dissolved in a suitable hydrocarbon diluent.
Zinc, iron, aluminum, copper and manganese are all co-extracted, while calcium, nickel and
some magnesium are rejected.
The extraction circuit usually consists of four countercurrent stages. Each stage comprises a
single mixer providing a total of 1 minute mixing time and a settler for phase disengagement.
To maximize cobalt-nickel selectivity, pH is controlled within each stage by direct addition of
caustic solution to the mixers.
Two-stage organic removal is used for the raffinate, generally comprising a diluent wash
stage and Jameson flotation cell. Clean raffinate can be recycled within the process (e.g. CCD
wash water), with surplus advanced to tails neutralization. The use of sodium hydroxide
results in a raffinate containing sodium sulphate which, as per several of the intermediate
options, will have to be disposed of or contained.
Care must be used to avoid recycling cobalt SX extractant directly into the copper SX
circuits. Circuits containing solids generally act as good organic adsorbents, thereby
significantly reducing this risk.
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Cobalt loaded organic is scrubbed in a single stage to remove co-extracted and entrained
nickel (and magnesium). Demineralized water and sulfuric acid are contacted with the loaded
organic at a suitably low pH to achieve the required Co:Ni ratio on the scrubbed organic. A
bleed of cobalt loaded strip liquor can be added to the scrub stage to improve scrubbing
efficiency if required. Scrub raffinate is returned to the first cobalt extraction stage.
Scrubbed organic is stripped in two countercurrent stages to remove all loaded metals.
Cobalt spent electrolyte is used as strip liquor, the flow rate of which is adjusted to achieve
the required cobalt tenor for downstream electrowinning. Dilute sulphuric acid solution is
used to control pH in the first strip stage to ensure required stripping efficiency is achieved.
Stripped organic is returned to extraction via a stripped organic tank.
Zinc SX
Zinc (and ferric iron) is removed from the cobalt SX loaded strip liquor in a multiple-stage
SX circuit. While Di-Ethyl Hexyl Phosphoric Acid (DEHPA) is an option in this application,
the use of phosphinic acid is preferred due to the ability to reject calcium, relative ease of iron
stripping, and improved compatibility with cobalt SX (no extractant cross-contamination
issues, ability to use same crud treatment equipment, etc.).
The phosphinic acid extracts all zinc and ferric, whilst aluminium, copper, manganese and
cobalt are rejected. To ensure the target iron level is maintained in the zinc SX raffinate, all
ferrous in the cobalt loaded strip liquor is oxidized to the ferric form just prior to zinc
extraction using hydrogen peroxide in an in-line mixer.
Zinc is extracted in three countercurrent pH-controlled stages. Thorough removal of organic
is required for the downstream circuits, so a three-stage system is used generally consisting of
a Jameson cell, liquid-liquid coalescer and carbon columns.
Zinc loaded organic is scrubbed with water and sulphuric acid in a single stage to remove
co-extracted and entrained cobalt. Scrub raffinate is returned to the first zinc extraction stage.
Scrubbed organic is stripped with acidified water in two countercurrent stages to remove all
loaded metals. Stripped organic is returned to extraction via a stripped organic tank.
Entrained organic in the zinc loaded strip liquor is recovered using a liquid-liquid coalescer,
and the cleaned liquor is disposed via tails neutralization.
Copper IX
Residual copper is removed from the zinc SX raffinate using a macroporous aminophosphonic acid chelating resin within fixed-bed columns operated in a typical lead-lag
configuration. A single stage elution is used due to the ability to recover all eluted copper (and
cobalt) upstream. Regeneration of the resin is achieved using a caustic solution.
Cobalt EW
Cobalt electrowinning is carried out in identical fashion to that described in the
precipitation/re-dissolution process.
Spent electrolyte is returned to the cobalt SX strip circuit as required. Surplus liquor is bled
to the cobalt SX extraction circuit (blended with PLS) providing the only significant outlet for
such species as magnesium, aluminum, sodium, sulphate and chloride.
Metal production route comparison
The two general production routes described above are compared and discussed with
reference to a number of key project drivers.
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Capital cost (excluding effluent disposal)

Capital costs associated with both the precipitation and solvent extraction routes are similar.
For the second route, the additional cost of the cobalt SX circuit (organic inventory) is
effectively offset by the elimination of the nickel IX circuit, comprising a very expensive resin
inventory of its own.
Being solely dependant upon fixed bed IX, the precipitation/redissolution route is
considered to be more capital sensitive to the florate and composition of the cobalt rich liquor
feeding the purification steps. For this reason, the adoption of divided cell technology to
increase cell drop in the cobalt tank house would bring significant capital savings to the
precipitation/redissolution route (with smaller savings to the SX route).
Operating cost
The SX route consumes much larger amounts of caustic than the precipitation/redissolution
based route due to its use for primary cobalt recovery in the cobalt SX circuit. This is offset
by lower consumption of lime (effectively replaced by caustic) sulphuric acid and limestone
(reduced recirculating loads of cobalt and impurities). The operating cost differential between
the two options is therefore highly sensitive to the prevailing price of caustic; below US$800/t
(including delivery) the SX route is generally favoured.
Metal recovery
Due to the higher selectivity of the impurity removal steps, cobalt recovery for the SX route is
somewhat higher (~10%) than that for the precipitation/redissolution route. Cobalt loss with
both nickel and zinc is reduced considerably by the use of SX. Cobalt losses are also reduced
due to a significant reduction in the recirculating load of cobalt (elimination of secondary
cobalt precipitate, cobalt re-solution residue, weak eluates and a smaller electrolyte bleed).
Product purity
Both production routes have been compared on the basis of equivalent product purity. The SX
route, however, provides additional flexibility with respect to impurity removal, and could
tolerate higher than design levels of both zinc and nickel with greater ease than the
precipitation/re-solution based route.
Operability and maintenance
Both processing routes may be considered complex refineries, requiring steady operation and
tight control to achieve desired performance. The elimination of virtually all solid-liquid
circuits and consequent batch filtration steps is expected to provide an operability advantage
to the SX route.
The SX route also produces cobalt rich liquor (electrolyte) very low in calcium, as opposed
to the high calcium liquor produced via the precipitation/redissolution route. The need for
periodic de-scaling of the cobalt precipitation and redissolution circuits, and the potential for
downstream gypsum precipitation within the IX and EW circuits places the
precipitation/resolution route at a further disadvantage in terms of both operability and
maintenance.
Health, safety and environmental issues
The presence of larger volumes of organic solutions in the SX route requires increased
measures to control personnel exposure and fire risks.
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Environmentally, the SX route produces an effluent containing large amounts of sodium

sulphate that must be adequately disposed of or contained, whereas in its place the
precipitation/redissolution route produces gypsum, the disposal of which is quite straightforward.
The above comparison is summarized in Table II below; the metal production options are
rated 1 or 2, with 2 being the preferred option.
Recommended metal production process
Technically, the SX based route is equal or superior on most parameters, and excluding the
cost of effluent treatment, would be expected to give a superior return to the
precipitation/redissolution based route.
As with the choice of intermediate, however, the selection of a refining route is driven by
the costs and environmental issues associated with the disposal of a sodium sulphate
containing effluent.
The use of ammonia in place of caustic for the SX route would allow ammonia recovery
using a lime-boil process, producing a gypsum residue for disposal. The low concentration
and high volume of effluent to be treated, however, do not make this option particularly
attractive, and a cheap source of low pressure steam would be essential.
On this basis, the SX route is effectively eliminated, and the recommended route is
precipitation of a cobalt hydroxide using lime, redissolution in spent electrolyte, purification
and metal recovery via electrowinning.
Comparative nett present value (NPV) between hydroxide intermediate and metal
A high level NPV model has been applied to the following scenarios:
Cobalt hydroxide intermediate production
Cobalt hydroxide intermediate production followed by redissolution and cathode
production (i.e. conversion to a metal production circuit after operating an intermediate
production circuit)
Cobalt cathode production via intermediate production (i.e. direct metal production with
no saleable intermediate).
The following assumptions have been applied
15% discount rate
9 000 tpa cobalt metal production
US$16/lb cobalt metal
Cobalt hydroxide intermediate realizes 70% of the contained metal value.
Table III summarizes the input data for the NPV calculation.
Table II
Cobalt metal production route ratings
Parameter
Capex
Opex
Recovery
Purity
Op and main
HSE
Total
398
Precipitation and redissolution
SX
2
1
1
1
1
2
8
1
2
2
2
2
1
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Table III
NPV input data
Product
Hydroxide intermediate
Cathode from intermediate
Cathode via re-dissolution
Capex MUS$
Opex MUS$/a
Co product t/a
Revenue MUS$/a
28.4
99.8
87.4
60.3
81.0
81.0
9000
9000
9000
222.2
317.4
317.4
Capital cost
The costs listed above are high level estimates and meant for comparative purposes. The
estimate consists of costs for earthworks, civils, structural steel, plate work, mechanical
equipment, piping, electrical and instrumentation and buildings. It excludes indirect costs but
includes a 15% contingency. The battery limits covered are from the copper SX raffinate pond
to product dispatch, all internal recycles are costed, and effluent reporting to the copper circuit
is costed at a convenient point between the two plants. All reagent storage and utilities are
included.
The cost for the cathode from intermediate option is US$12.4 million higher than the
cathode via redissolution option, and this additional amount covers a second stage cobalt
precipitation, drying and bagging facility.
Operating cost
The operating cost is defined as the incremental cost (total cost being for the copper and
cobalt facility) required to produce the cobalt product. This includes labour, power, operating
and maintenance spares, vehicles, reagents (including SO2 for leaching), consumables
(including laboratory) and other.
The operating cost estimate is to the same level of accuracy as the capital cost and is meant
for comparative purposes.
Production and revenue
A cobalt production of 9 000 tpa has been assumed at a cobalt price of US$16/lb (spot price
on 21 November 2008). There will be some minor differences in cobalt recovery; however, at
the level of accuracy considered above this is regarded as being negligible.
NPV calculation
The NPV model shows an overwhelming financial benefit for production of cobalt metal.
Figure 2 summarizes the values.
From Figure 2 it can be seen that the NPV for the cobalt metal options is far larger than for
the intermediate option. This is due to the large increase in revenue associated with metal
production, as only 70% of the cobalt value has been assigned to the intermediate product,
and this is believed to be an optimistic view. The NPV for the intermediate option is
MUS$647 as opposed to MUS$894 for the cathode from intermediate option and MUS$905
from the cathode via re-solution option.
The relative change in NPV between the two metal production options is small.
Conclusions and recommendations
Numerous factors have been discussed, which affect the type of cobalt product that is
produced. It is often environmental considerations and operational complexity that determine
the optimum route.
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It most cases copper is the major contributor to project revenue but cobalt often makes a
significant contribution. In the early years of operation it is wise to follow the lowest
complexity route possible, and thus the production of cobalt hydroxide intermediate is
recommended. This also reduces the upfront capital required and lowers overall project risk.
Once operational experience has been obtained and cash flow realized, the conversion from
the intermediate product to metal should be considered as this returns greater value. The
complexity of cobalt metal production should not be underestimated, particularly in the DRC
where experienced operators are scarce. Cobalt metal production should not be undertaken
before understanding the complexity and risk.
Figure 2. Product NPV values
Steve Amos
Process Engineering Manager, GRD Minproc, South Africa
Graduated from Wits University in 1988 with a BSc Hons degree in
Applied Chemistry. As a JCI bursar I was assigned to Randfontein
Estates Gold Mine for in service training. After completion of this
training I was transferred to the JCI Minerals Processing Research
Labs (later Anglo Platinum Research Centre), where I was involved in
development work for the Anglo Platinum Precious Metals Refinery,
Anglo Platinum Base Metals Refinery and managed the pilot plant campaign for the ACP
project (Anglo Platinum Converting Process).
After this I was seconded to ATD (Anglo American Technical Division) where I was the
Senior Process Engineer on the Konkola High Pressure Leach Project, amongst other studies,
and worked for a short period at KCM in Zambia as Metallurgical Projects Manager. I
returned to Anglo Platinum Process Technology Division in early 2002 as a Senior Process
Engineer and worked projects and optimisation work associated for the Anglo Platinum
smelting and converting operations in Rustenburg and Polokwane, including the ACP project,
Waterval smelter upgrade, Waterval Slag Cleaning Furnace and Polokwane smelter project.
Joined GRD Minproc as a Senior Process Engineer in January 2006 and was promoted to
Process Engineering Manager in September of that year. I am currently responsible for all
process engineering activities in the South African office and have managed a number of
bankable feasibility studies.
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STEYL, J.D.T. Kinetic modelling of chemical processes in acid solution at t 200C. (i) thermodynamics and
speciation in H2SO4-Metal (II) SO4-H2O system. Hydrometallurgy Conference 2009, The Southern African
Kinetic modelling of chemical processes in acid

solution at t 200C. (i) thermodynamics and
speciation in H2SO4-Metal (II) SO4-H2O system
J.D.T. STEYL
Anglo Research, South Africa
Although thermodynamic theory has been widely applied to hightemperature hydrometallurgical processes to describe properties such
as solubility and acidity, few of those studies have attempted to
develop an accurate platform to interpret process kinetics. This study
utilized existing theoretical frameworks to model the ternary H2SO4MeSO4-H2O system up to 200C (where Me = divalent metal ions of
Cu, Zn and Fe) and less than 1 mol/kg sulphate, using MgSO4 as a
prototype salt. A qualitative interpretation of the chemistry at
quantum level was used as a complementary tool to add more
confidence to the ambiguous nature of the thermodynamic data
reported in the literature and to fill the gaps where no such data was
available at all. The Pitzer ion-interaction approach was used to build
a phenomenological model of this system but with the explicit
recognition of four contact ion pairs, i.e. HSO4 , H2SO4, MgSO4

and Mg(SO4)22. This required an iterative approach around the ioninteraction framework. The interaction parameters simulated the longrange electrostatic interactions and the formation of outer-sphere
complexes, while the explicit inclusion of the above complexes
recognized the important covalent interactions. Once parameterization
was optimized for the two binary systems (H2SO4-H2O and MeSO4H2O), three mixing parameters were derived for the ternary system.
Very limited experimental information has been reported for the
mixed system, especially at higher temperature. By selecting a
minimum number of adjustable interaction parameters, constraining
the system to the available thermodynamic data and incorporating the
observed species distributions at lower temperature, predictions at
higher temperature were made possible. Consistent and interesting
trends have been generated, some of which are presented in this paper.
The overall solution chemistry model was ultimately used as a tool to
interpret the kinetics of ferrous oxidation in acidic sulphate medium,
which is discussed in more detail in the second paper of the current
series.
KINETIC MODELLING OF CHEMICAL PROCESSES IN ACID SOLUTION
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Introduction
Despite the fact that sulphuric acid is a major chemical commodity, the effort expended to
describe the chemistry of sulphuric acid/base metal sulphate aqueous mixtures does not reflect
its industrial importance. This is especially prevalent at higher temperature, under conditions
frequently encountered in oxidative pressure leach applications. Although thermodynamic
theory has been widely applied to describe high-temperature hydrometallurgical processes,
focus has usually been directed, either towards calculating specific thermodynamic properties
(e.g. solubility in solution) or to calculate solution chemical properties such as acidity, derived
from potentiometric or conductivity measurement (examples in Liu and Papangelakis, 2005a,
2005b, Seneviratne et al., 2003 and, Baghalha and Papangelakis, 2000). This study attempts
to establish a simple thermodynamic model, with emphasis on the explicit recognition of the
minimum, but most important complex species in sulphuric acid/base metal sulphate solution,
temperatures below 200C and concentrations less than 1 mol/kg total sulphate. The chemical
model and peripheral arguments ultimately aims at developing a platform for interpreting
hydrometallurgical process kinetics.
Methodology
The methodology of modelling thermodynamic properties has traditionally followed an ioninteraction approach, i.e. based on complete electrolyte dissociation. The virial type of
equations of Pitzer (Pitzer, 1991), which is based on statistical mechanics, have been most
widely applied. However, certain electrolyte systems, such as H2SO4-H2O, require the explicit
recognition of the strong complexes (bisulphate inner-sphere complex, HSO4 in this case) in
order to accurately describe its thermodynamic properties (Pitzer et al., 1977). Although such
modifications introduce more interaction parameters, it is compatible with the fully
dissociation framework. At the other extreme, many researchers studying hydrometallurgical
systems frequently opt for a speciation-only type approach, for example to predict solubility
(Papangelakis et al., 1994) or to support proposed reaction mechanisms (Crundwell, 1987). In
cases where such speciation models also confirm independent measurement, for example
spectroscopic or pH, it becomes an attractive alternative to the interaction-type approach (e.g.
Casas et al., 2005a). Casas et al. (2005b) compared the performance of three different
chemical models, i.e. Debye-Hckel (DH) B-dot, Pitzer and Bromley-Zemaitis at high
temperature (>200C). Although the three models differed in complexity and recognized
species (equilibria), they demonstrated almost the same ability to fit the solubility of Mg and
Al in ternary systems. This illustrated that ion interaction parameters can make up for
differences in the number of explicitly recognized species and vice versa. Measured
information on species abundance is severely restricted in the open literature, especially at
higher temperature. It is therefore natural to limit the model to explicitly contain only the
complex species that are most likely to kinetic processes, the driving force behind this study.
These complexes are likely to be entropy driven and would therefore become even more
significant at higher temperature. An added advantage is that the interaction framework, based
on thermodynamic and speciation information at room temperature, can be used to infer the
speciation behaviour at higher temperature where only thermodynamic data are available.
Phenomological model
In view of the above discussions, the following interaction-type (some, also including
speciation) models have been considered for this study (references indicate recently applied
examples); Bromley-Zemaitis (Liu and Papangelakis, 2005a), Mixed Solvent Electrolyte
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(MSE) (Liu and Papangelakis, 2005b), Pitzer (Casas et al., 2005b) and Electrolyte NRTL
(Haghtalab et al., 2004). Although these models have successfully been applied to numerous
chemical systems, each having their own subtleties, the relatively low ionic strengths covered
in this study makes the choice somewhat ambiguous. Although the ion-interaction model of
Pitzer is more complicated, it has been widely applied to thermodynamic studies over the past
35 years and its theoretical framework was also adopted for this study.
Thermodynamic framework
The conventional unsymmetrical reference states of infinite dilution for the solute and pure
water for the solvent have been chosen for this low to medium ionic strength application. For
the same reason, the molality (temperature independent) scale was selected, treating the
proton as an unhydrated species. The standard Pitzer ion-interaction model is based on an
expression for the excess Gibbs energy of the solution, which consists of an extended DebyeHckel (DH) term and virial expansion terms. The relatively dilute electrolyte concentration
also makes ionic strength dependences of the third virial coefficients (Clegg et al., 1994)
redundant; these generalized equations can be found in numerous publications (e.g. Pitzer,
1991) and the important functions are reproduced here. The single-ion activity coefficient of a
cation (M), anion (X) and neutral ion (N) may respectively be represented as follows:
[1]
[2]
[3]
where the primed indices refers to summation over all distinguishable pairs, and:
[4]
[5]
and zi is the valency of ion, i. The water activity (aw), more appropriately expressed as the
osmotic coefficient, may then be written as:
[6]
The ionic strength (I) dependence of the DH terms may be represented as follows:
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[7]
[8]
The universal parameter, b has a value of 1.2 (kg/mol)1/2. In this study, the DH parameter for
the osmotic coefficient (A ) was directly calculated, following from the original DH
derivation (natural logarithm scale):
[9]
The dielectric properties reported by Bradley and Pitzer (1979) and the density reported by
Cooper and Le Fevre (1982) was used for pure water as the solvent. These properties for
water and the fundamental constants yielded an A value of 0.3914 (kg/mol)1/2 at 25C. The
binary (Bca) (and its derivative) and ternary (Cca) virial coefficients are expressed in terms of
their respective interaction parameters (ca and C ca) and their ionic strength functionalities:
[10]
[11]
[12]
[13]
The values of parameters 1 and 2 are usually set to 1.4 and 12 (kg/mol)1/2, respectively,
for 22 electrolytes but 2 and 0 (kg/mol)1/2, respectively, for other types of interactions (Pitzer,
1991). The functionalities may be represented as follows:
[14]
[15]
In mixed electrolyte systems, binary short-range interaction between ions of like charge ()
and various ternary interactions () may be accounted for. In this study, the long-range
electrostatic forces (denoted by E) were also included for unsymmetrical mixing. The binary
mixing term, , its derivative and the corresponding mixing term for the osmotic coefficient
are then expressed by Equation [16], [17] and [18], respectively. The values of the
electrostatic terms were calculated using Chebyshev approximations (see Pitzer, 1991).
[16]
[17]
[18]
As mention before, the Pitzer framework becomes more complicated when strong ion
associations are explicitly treated as a separate species. Thermodynamically, a complex
species is considered to be a new entity in solution when the mutual electronic attraction of
the individual ions is considerably greater that their thermal energy (Robinson and Stokes,
1959). In aqueous solution, water molecules are chemically bonded to the ion and this form
the inner coordination sphere. An inner-sphere complex is formed when water molecules are
replaced from the inner coordination sphere of the metal ion by a ligand ion (such as SO42)
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and then, for example, forming a direct chemical bond with the metal ion. When ligand ions
do not replace any water molecules from the inner-sphere, and is attached to the positive ions
only by virtue of electrostatic considerations, it forms an outer-sphere complex (Hancock,
1976). Activity coefficients for outer-sphere complexes are strikingly similar up to high
concentrations, and this is reflected in very similar values of their association constants. Innersphere complexes on the other hand, always show large differences in stability (Prue, 1966).
Inner- and outer-sphere complexes represent two extremes and although most ion complexes
would show predominance of one type, both are likely to be present. Aqueous species are
therefore present as simple and complex ions and the modelling objectives would dictate
which species need to be explicitly expressed. The ionic strength defines the charge in the
electrolyte solution and would obviously vary between these frameworks:
[19]
The ionic strength value corresponding to complete dissociation is referred to as the nominal
or formal ionic strength (independent of temperature). Whatever framework is used to
describe non-ideality in an electrolyte solution, the condition of electrical neutrality has to be
fulfilled:
[20]
If equilibrium is approached from an association perspective, either a step-wise or
cumulative description may be used, i.e., respectively:
[21]
[22]
By definition, the activity of an ion is related to its molality in the following manner (the
final term on the right incorporates the standard state, which is conveniently chosen at unit
molality, so that fi = mi = 1):
[23]
The thermodynamic association constant (denoted by ) at the thermodynamic transcendent
condition of infinite dilution for the step-wise (K) and cumulative () reaction may then be
represented as follows, respectively:
[24]
[25]
Thermodynamic models are used to set up a framework in which thermodynamic properties
can be regressed with experimental data. Colligative properties such as freezing point
depression, boiling point elevation, heat capacity, molar volume, the electromotive force
(e.m.f.) of cells, and isopiestic measurement (osmotic coefficient) are most often used in
correlation methods. Only the mean activity coefficient of a salt can be obtained from these
measurements (individual ions cannot be isolated during measurement). For a salt, M1X2 the
mean activity coefficient is defined as follows (Robinson and Stokes, 1959):
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[26]
The ion number ( ) of the salt is equal to the sum of the individual stoichiometric
coefficients (1, 2). Regression to solubility data is popular because its availability for both
pure and mixed electrolyte systems (e.g. Linke and Seidell, 1958 and 1965). The generalized
solubilization reaction for the hydrated salt may be written as follows:
[27]
The thermodynamic solubility product is derived by taking the activity of the solid phase as
unity (pure substance). The right-hand terms were respectively obtained after mathematical
substitution of Equations [23] and [26]:
[28]
The molalities and activity coefficients in Equation [28] obviously refer to the individual
ions, whereas the water activity is directly related to the osmotic coefficient as calculated in
Equation [6]. In order to maintain internal consistency, it may be necessary to convert the
calculated osmotic and mean activity coefficients to their formal (also called stoichiometric or
observed) values:
[29]
[30]
Finally, the molality scale is preferred scale in solution thermodynamics because it has the
advantage that it is independent of temperature and pressure. However, the concentration
scale has more practical significance and it may be necessary to convert between the scales.
The following relation is easily derived (where C refers to the molarity scale and is the
solution density in g/l):
[31]
The standard thermodynamic properties of an equilibrium reaction are constituted from the
sum of the primary components taking part in the reaction. Often, the partial molar properties
of a species are known only at the reference temperature, Tr (usually 25C) and sometimes,
not at all. The equilibrium constant can be calculated if the partial molar enthalpy of
formation of the constituent species, or the standard molar enthalpy of the reaction is known
as a function of temperature (or at the required temperature). This relationship is known as the
Vant Hoff isochore and is derived from classical thermodynamics (the derivation is beyond
the scope of this studysee Atkins, 1986):
[32]
Often heat capacity data is available and integration of Kirchhoffs Law (see Atkins, 1986)
may be used to calculate the enthalpy at the correct temperature:
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[33]
The temperature dependence of the heat capacity cannot be predicted and mathematical
correlation is therefore used to represent experimental data. The partial molar heat capacity of
a species is often reported by the following mathematical expression (also known as the
Kelley equationoriginal reference in Horvath, 1985):
[34]
The coefficients a, b, c, and d are temperature independent. The standard entropy of a
reaction is related to the standard heat capacity by the following relation (see Atkins, 1986):
[35]
The definition of the standard Gibbs free energy stipulates:
[36]
When no functional expression for the heat capacity is available, it is often assumed that the
heat capacity is constant, i.e. the enthalpy of reaction varies linearly with temperature (after
integration of Equation [33]):
[37]
The entropy value may then be estimated after integration of Equation [35]:
[38]
When no heat capacity data is available, it is often assumed to be zero, i.e. the enthalpy of
the reaction is constant. Integration of Equation [32] then yields:
[39]
This equation would give only an estimate over a very short temperature range. Predictive
methods have been developed to estimate the average heat capacity between T and Tr, such as
the method of Criss and Cobble (see Zemaitis et al., 1986). This method, is however,
questionable when applied the non-simple cations (like metal sulphate ions) and metal-oxyanions (like the bisulphate ion) (see Blakey and Papangelakis, 1996). Alternatively, a close
approximation of the value of K at higher temperature may be obtained using Helgeson
extrapolation (see description and original references in Liu and Papangelakis, 2005a).
However, this method may give an overestimation at higher temperatures (>100C)
(Papangelakis, 2004). The density function (Anderson et al., 1991) is remarkably accurate in
estimating equilibrium constants of reactions at higher temperatures when the molal heat
capacity value is known at the reference temperature. The model is based on the observation
of almost linear behaviour of lnK with ln and adopts the form as presented in Equation [40].
[40]
The density () and coefficient of thermal expansion () of water are well documented, e.g.
study of Anderson et al. (1991). In another approach, the Balanced Like Charge Method
(BLCM) utilizes equilibrium reactions with balanced like charges to extrapolate over
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temperature (see e.g. Papangelakis, 2004 and Oscarson et al., 1988). Lindsay (1980), referring
to these reactions as isocoulombic equilibria, found that because charge is conserved, their
heat capacity is usually constant with temperature and relatively small. Substitution of
Equations [37] and [38] into Equation [36] and simplifying yields the following relationship
and may be used to test the validity of the BLCM approach:
[41]
The following general equation (after substitution of Equations [33], [35] and [36] into
Equation [32] and rearranging) would still yield the superior result, i.e. if the heat capacity is
available as a function of temperature:
[42]
No V terms were included in any of the above equations since temperatures were limited
to 200C and, hence, to relatively insignificant pressure effects (at saturation).
Chemistry
This section briefly considers a quantum level interpretation of the chemistry and tries to add
more confidence to the ambiguous nature of the data reported in the literature. A basic
understanding of ion solvation is an essential part of this analysis. The concept of the
hydration shell has been verified for cations and anions by spectroscopic measurement and is
also supported by ab initio calculations (see e.g. Pye and Rudolph, 2001). An ion in water
may be considered to be surrounded by concentric shells of water molecules, where the
successive shells become more weakly bound to the preceding shells until a bulk water
structure is reached (Pye and Rudolph, 1998).
Calculation methodology
All calculations were carried out using the DMol3 (Delley, 1990) density function theory
(DFT) code imbedded in the Materials Studio (v.4.2) quantum chemistry package from
Accelrys Inc, i.e. the calculations were conducted within the Kohn-Sham formulism (Kohn
and Sham, 1965). In order to increase the chemical accuracy when treating the transition
metal complexes, an all electron scalar relativistic basis set was employed. The gradient
correction method (GGA = gradient generalized approximation) was employed throughout
utilizing two DFT Hamiltonians, i.e. the local spin density (LSD) method utilizing the Vosko
et al. (1980) (VWN) parameterization of the Ceperley-Alder Monte Carlo result for a
homogeneous gas; and the non-local spin density (NLSD) method, utilizing a combination of
the Becke (B) gradient corrected exchange energy (Becke, 1988) and the Pedrew (P) gradient
corrected correlation energy (Pedrew and Wang, 1992). Fully self-consistent field (SCF)
calculations were conducted using the VWN-BP functional throughout. High quality double
numerical atomic basis sets including polarization functions (DNP) were used throughout, i.e.
to yield best accuracy, especially since hydrogen bonding was an important aspect of this
study. Because these functions were treated numerically (rather than analytically) in DMol3,
basis set superposition errors (BSSE) were minimized (Delley, 1990after Materials Studio
help file). The aim of this chemical modelling exercise was more qualitative in nature and no
additional effort was therefore expended to quantify the effect of BSSE errors, or to test
alternative basis sets or exchange-correlation functionals.
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In addition to the use of explicit water molecules as described above, the Conductor-Like
Screening Model (COSMO) (Klamt and Schrman, 1993) was used to account for long
range electrostatic solvent effects, using the dielectric constant of pure water. COSMO is an
example of a continuum solvent model where the solvent molecules are not treated explicitly
but are expressed as a homogeneous medium characterized by a bulk dielectric constant. The
effect of the solvent is modelled by imposing charges on the continuum surface, which leads
to a polarization of the wave function within the solute cavity (Ziegler and Autschbach, 2005).
Therefore, the electronic structure and geometry of the solute is still described by the DFT
method, but the solute is placed inside a cavity which has the same shape of the solute
molecule. Outside of the cavity, the solvent is represented by a homogeneous dielectric
medium (Andzelm et al., 1995). The approach followed in this study is based on the default
DMol3/COSMO recommendations imbedded within Materials Studio. The DMol3/COSMO
can predict solvation energies for neutral solutes with an accuracy of about 2 kcal/mol
(Andzelm et al., 1995) and has been tested extensively (Klamt and Schrman, 1993, and
Andzelm et al., 1995). Although continuum models are effective when the impact of the
solvent is predominantly electrostatic in nature, the lack of an explicit solvent treatment is an
oversimplification and neglects specific information on the intermolecular interactions, such
as hydrogen-bonding in the first hydration shell. Therefore, in this study, the total
coordination of the cation and the composite, polyatomic sulphate anion was restricted by
explicitly using water as a coordination filling species in the first hydration shell, while
treating the effect of the solvent beyond this level via the COSMO methodology. The most
important simpler structures were confirmed to be minima via analytic second derivative
calculation. Since neither the vibrational energy, nor the entropy of the solvated species could
be obtained using the above methodology, the enthalpy rather than the total free energy
formed the basis of comparison with reported literature values. It was assumed that the
enthalpy could be represented by the potential energy; hence, it was assumed that the kinetic
energy (translational, rotational, etc.) cancels approximately for reactions between solvated
ions at constant temperature.
First principles perspective
The objective of this simulation exercise was to create a thermodynamic framework from a
first principles perspective and consistent with reported standard state properties of ions and
neutral species in aqueous solution (e.g., NBS tables, Wagman et al., 1982). The modelling
was conducted at the thermodynamic condition of infinite dilution in water. Within the
context of the conventionally defined zero Gibbs energy of formation of the proton at any
temperature, the hydrogen electrode was the appropriate starting point. The absolute electrode
potential in electrochemistry is the difference in electronic energy between the Fermi level
energy of a metal electrode and a universal reference system (without any additional metalsolution interface) (see Trasatti, 1986). The standard hydrogen electrode (SHE) is a redox half
cell and forms the basis of the thermodynamic scale of oxidation-reduction potentials:
[43]
This reaction can be achieved at a practical level with the use of a platinum electrode
because it possesses the ability to catalyse the reduction of the proton to form hydrogen gas at
a high exchange current density, and vice versa. The recommended value of the absolute
electrode potential (Eabs, often referred to as the vacuum scale potential) of this cell in water is
4.440.02 V at 25C (Trasatti, 1986). This number is the required link between the
electrochemical potential scale and the physical energy scale. Reported literature values vary
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considerably for such an important quantity, with an average around 4.6 V (see details in
Bockris and Khan, 1993). The absolute value of the solution energy of a single ion is just one
of the uncertainties that have to be dealt with. The exact nature of the hydrated proton at
infinite dilute is clouded by the fact that the proton is geometrically very small and forms
fluctuating hydrogen bonds with the surrounding water molecules. Senanayake and Muir
(1988) used e.m.f. measurement (with some extra-thermodynamic assumptions) in chloride
media to estimate ionic activities and hydration numbers. The hydration number of 7 obtained
for the proton in dilute solution indicated further hydration beyond the first hydration cell.
Based upon the acidity function and other physical evidence (Bell, 1959, and Bockris and
Reddy, 1977), the existence of this well-defined species is usually assumed to predominate in
strongly acid solutions. However, the more recent and insightful paper of Marx et al. (1999)
suggests that both the H5O2+ and H9O4+ species are important only in the sense of ideal
structures and that numerous unclassifiable situations exist inbetween. Ab initio path integral
simulations were used to show that the hydrated proton actually forms a fluxional defect in
the highly structured, hydrogen-bonded network of water. This protonic defect can assume
many different structures, so that an unambiguous distinction between H5O2+ and H9O4+ can
no longer be achieved (Marx et al., 1999). In view of these discussions, a thermodynamic
basis needed to be established using the molar enthalpy of hydration as reference. The
thermochemical (Born-Haber) cycle consisted of atomizing the gas, ionizing the gas, followed
by solvation in water medium and finally, reduction on a platinum electrode to again form
hydrogen gas (see Equation [44]). Since neither the vibrational energy, nor the entropy of the
solvated species could be explicitly calculated within the context of the DMol3/COSMO
framework, the enthalpy (rather than the total free energy) formed the basis of comparison.
[44]
Comparison between the calculated and reported enthalpy of hydration (Table I) suggests
that either the H3O+ or the H5O2+ species could be used as basis. A similar conclusion can be
drawn by comparing Hred, obtained by difference of the reported total ionization enthalpy
and the hydration enthalpy. Therefore, for the purpose of this study, the following reaction
was used as thermodynamic basis:
[45]
This approach yields the free enthalpy of hydration, Hhyd of the proton as -1114 kJ/mol
and the reduction enthalpy, Hred as -429 kJ/mol. If an entropy change of -131 J/mol.K (NBS
Tables) is used for the hydration reaction, a value of 4.65 V for the absolute potential of the
hydrogen reaction is obtained. This is in good agreement with the average value reported in
Bockris and Khan (1993), i.e. 4.6 V.
The next step was to define a thermodynamic basis for the sulphate dianion. The most direct
approach was to use the enthalpy of dilution of concentrated sulphuric acid to calibrate the
system:
[46]
The ions refer to the formal species in excess water. The structure of a H2SO4 molecule in
concentrated sulphuric acid consists of extensive hydrogen-bonded networks. This is evident
from its exceptionally high dielectric constant () of 110 (Lide, 1991). Kazansky and Solkan
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Table I
Calculated and literature values of the various energy contributions to the Born-Haber cycle for the hydrogen system
Energy
Step (Born-Haber Cycle)
Hat+Hion
H(g) H
+
Calculated
(kJ/mol)
Literature
(kJ/mol)
References
+
(g)
1543
1536
Wagman et al. 1982 (NBS tables)
-524
-1081
-1147
-1185
-1216
1103
Marcus, 1987
-1019
-462
-396
-358
-327
Hhyd, 25C
H (g) H (aq)
+
+
H (g) + H2O(aq) H3O (aq)
+
+
H (g) + 2H2O(aq) H5O2 (aq)
+
+
H (g) + 3H2O(aq) H7O3 (aq)
+
+
H (g) + 4H2O(aq) H9O4 (aq)
Hred, 25C
H (aq) H(g)
+
H3O (aq) H(g) + H2O(aq)
+
H5O2 (aq) H(g) + 2H2O(aq)
+
+
-424
Bockris and Khan, 1993: 4.6 Vred
aCalculated
(Reaction [45]) from average reported absolute potentials and the entropy of hydration, Shyd = -131 J/mol.K
(Wagman et al., 1982)
Table II
Calculated molecular energies and average hydrogen bond lengths of the symmetrical complexes of H2SO4 in 100%
sulphuric acid (bulk permittivity of 110)
Molecule
Etot (hartrees)
Ediff (hartree) (per sulphur)
Distance () H-Bond(OO)
Distance () H-Bond(OH)
[H2SO4]
[H2SO4]2
[H2SO4]3
-702.0775021
-1404.1582559
-2106.2385225
-0.0016259
-0.0003795
2.74 (avg.)
2.74 (avg.)
1.72, 1.74
1.70, 1.78
(2003) used ab initio quantum chemical calculations, whereas Walrafen et al. (2000) used
experimental methods, to show that these hydrogen bonds form very definite ionic clusters.
These localized structures may be cationic, anionic or neutral in nature, e.g., in the case of the
dimer, [H3SO4 H2SO4]+, [HSO4 H2SO4] or [2H2SO4], respectively. The modelling of periodic
structures, using a number of interacting molecules (e.g., Arrouvel et al., 2005), would
obviously yield the best results. In the context of this study, only the most stable electroneutral complexes, as reported by Kazansky and Solkan (2003), were used. The average OH
distance of 1.74 is close to the average calculated values of Kazansky and Solkan (2003) of
1.8 . The total electronic energies (Table II) suggests that the neutral trimer is a sufficiently
stable (23% change per mole sulphur) to be used as basis to define the sulphate dianion
structure in water solvent.
A description of the structure of the sulphate ion in water is important because it would
affect its interaction with cations, such as the proton and divalent metal ions. The formation of
a contact ion pair between magnesium and sulphate ion was postulated as a temperature
dependent equilibrium with the hydrated sulphate and the hexaaquo magnesium ion (see Pye
and Rudolph, 1998). In a later publication (Pye and Rudolph, 2001), water was proposed to
coordinate with the sulphate ion in a bidentate fashion to form two hydrogen bonds per pair of
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sulphate oxygen atoms. Structural energetic and vibrational characteristics of isomers

containing less than six waters in the primary hydration shell were considered. However,
comparison between calculated and experimental S-O bond lengths suggested that more than
six waters should be present in the primary hydration shell. Cannon et al. (1994) presented
evidence, using ab initio calculations, that this tetrahedral dianion strongly interacts with
water; roughly three water molecules were coordinated with each of the sulphate oxygen
atoms. Therefore, unlike most anions, sulphate can be considered a structure-making ion with
respect to the solvent around it (Cannon et al., 1994). The model developed by Cannon et al.
orientated the water with one hydrogen pointing towards sulphate oxygen and the other
hydrogen pointing towards the neighbouring water oxygen. The number of waters in the first
hydration shell of the sulphate ion has been reported to be approximately 6 to 14, based on
diffraction data (see Cannon et al., 1994). A more recent study by Vchirawongkwin et al.
(2007), the hydrated sulphate ion was characterized using ab initio quantum mechanical (QM)
charge field (QMCF)molecular dynamics (MD) simulation and large angle X-ray scattering
(LAXS) methods. The LAXS data showed an average coordination number (i.e. hydrogen
bonded to sulphate ion) of up to 12, while the QMCF-MD simulation displayed a range of
between 8 and 14. Experimental investigations in several sulphate solutions (see references in
Vchirawongkwin et al., 2007) have been conducted and coordination numbers between 6 and
2
8 were assumed. The study of Wang et al. (2000) indicated that isolated SO4 is unstable in
the gas phase (strong Coulomb repulsion between the two excess electrons) and a minimum
of three water molecules is necessary to stabilize the dianion. Around 12 water molecules
were claimed to be present in the first hydration shell, with four water molecules, each
forming two direct hydrogen bonds with the sulphate oxygen atoms. The first principles study
of Gao and Liu (2004) considered a large number of isomers in two structural series, using ab
initio molecular dynamics simulations. They considered up to 12 water molecules in the
primary hydration shell at 100K. However, when the induced conditions approached 200 K, a
crowding-out of the first hydration shell was observed, with four molecules moving to the
second shell and eight remaining the primary hydration shell. As pointed out by Cannon et al.
(1994), the above wide range of values for the hydration number in the primary hydration
shell exemplifies the difficulties involved in building solvation models for polyatomic ions.
The more accurate approach would be use the QM-MD formulation (as suggested by Sterzel
and Autschbach, 2006), but since this was outside the scope of this study, the thermodynamic
reference framework defined above (for the sulphuric acid system) was expanded to define
the sulphate ion and its complexation with cations.
The sulphate ion is a polyatomic group with the double charge evenly distributed over the
four oxygen atoms in tetrahedral symmetry. The hydrogen bond network in this first shell
must adapt to the geometry imposed by the sulphate group (Gao and Liu, 2004). The Td
structure of Pye and Rudolph (2001) was used as starting point and geometrically optimized
using the calculation methodology described earlier. The starting structure consisted of each
H2O molecule acting as a bidentate hydrogen bond donor to two sulphate oxygen atoms. Eight
optimizations, each time modifying the starting structure slightly, were conducted and on each
occasion the structure relaxed to form only one direct hydrogen bond to sulphate oxygen for
each H 2O molecule, while the other hydrogen orientated itself towards the dielectric
continuum. However, at least one and often two H2O molecules donated their free hydrogen
to another H2O oxygen in the same group for hydrogen bonding. This phenomenon suggested
that water molecules are likely to form clusters in the primary hydration sphere. In fact, as
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illustrated by Gao and Liu (2004), the geometrical coincidence of the sulphate group with its
tetrahedron structure either form cyclic rings (up to 3 molecules) to accommodate more H2O
in the primary hydration shell, or alternatively a crowding-out effect of the first hydration
shell is observed at finite temperature, with some molecules moving to the second shell. With
this in mind, the H2O molecules was arranged either in 2 or 3 clusters; for example, with
6 molecules in the primary hydration shell, either 2 clusters of 3 H2O molecules or 3 clusters
of 2 H2O molecules could be considered. As expected, the highest combination of 3 cyclic
rings always resulted in the lower overall energy for the total structure. In most cases, one of
the H2O molecules in the 3 cyclic clusters orientated itself towards the dielectric continuum.
This is in line with the observations of Gao and Liu (2004): the hydrogen bond network in
the first shell must adapt to the geometry imposed by the requirement to solvate the sulphate
group, which introduces strain in the network and even repulsion among the first H2O
molecules. The calculated energies are listed in Table III. It is important to realise that these
structures may not be the true minima but that further modifications are likely to result only
in marginal improvements of the calculated reaction enthalpy for the general association
reaction:
[47]
Besides disagreement between calculated and reported reaction enthalpies, the asymmetrical
nature of the lower complexes suggests at least 8 H2O molecules in the inner hydration sphere
at infinite dilution. This is a simplified approach and if the reality is in fact more molecules in
the primary hydration sphere, the bonding is likely to be less structured than depicted in
Figure 1. This may be the case since the calculated value of the absolute standard molar
enthalpy of hydration for the sulphate ion (-1213 kJ/mol) is lower than the reported value
+
+
(-1026 kJ/mol, Marcus, 1987, based on H (g) H (aq): H = -1103 kJ/mol). Figure 1 presents
a static snapshot of the sulphate ion in water solvent; the more accurate approach would be to
consider a dynamic simulation (e.g., Vchirawongkwin et al., 2007), as mentioned above.
Nevertheless, the static approach was considered sufficient for the purpose of this study.
Typical calculated hydrogen bond lengths (Steyl, 2008) were in reasonable agreement with
measured (Vchirawongkwin et al., 2007) and calculated (Gao and Liu, 2004) values from the
literature.
Table III
2
Calculated molecular energies of SO4 (H2O)n (n = 6-9) and the corresponding reaction enthalpy (Reaction [47])
Molecule
H2O
2
SO4 (2H2O)3
2
SO4 (3H2O)2
2
SO4 (2H2O)2(3H2O)
2
SO4 (2H2O)4
2
SO4 (2H2O)(3H2O)2
2
SO4 (2H2O)3(3H2O)
2
SO4 (3H2O)3
-76.6240464
-1160.989182
-1160.993309
-1237.624055
-1314.254551
-1314.260114
-1390.889044
-1390.894635
aCalculated
Etot (hartrees)
Hrx,calc (kJ/mol)
38.8
49.6
67.2
84.1
98.7
111.6
126.2
NBS tables (kJ/mol)
95.3
95.3
95.3
95.3
95.3
95.3
95.3
(absolute) energies of molecular species; bCalculated (potential) energies of Reaction 47; cWagman et al. (1982)
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Figure 1: Optimized structures for the lowest energy complexes of SO4 (H2O)8
Table IV
Calculated molecular energies of HSO4 (H2O)n (n = 3-5) and H2SO4(H2O)2, reaction enthalpies and equilibrium
(protonation) constants
Molecule
HSO4 (H2O)3 (a)
HSO4 (H2O)3 (b)
HSO4 (H2O)4
HSO4 (H2O)5 (a)
HSO4 (H2O)5 (b)

H2SO4(H2O)2
Etot
(hartrees)
-931.546511
-931.547928
-1008.180816
-1084.809288
-1084.811148
-855.3544882
Hrx,calc
(kJ/mol)
51.3 (Rx 52)

55.1 (Rx 52)
78.3 (Rx 52)
89.9 (Rx 52)
94.8 (Rx 52)
7.7 (Rx 53)
Hrx,lit
(kJ/mol)
Log (K)
(Calculated)
Log (K)
(Literature)
73.35
73.35
73.35
73.35
73.35
dpK2: 2.2
fpK1: -1.3
c1.99; e1.96
g-4.7 to -2.0
aCalculated
(absolute) energies of molecular species; bCalculated (potential) energies of corresponding reactions; cWagman
et al. (1982); dSrx = 111.7 J/mol.K (Wagman et al. 1982); eDickson et al. (1990); fSrx = 0 J/mol.K; gPerrin (1982)
The bisulphate, HSO4 ion and H2SO4 molecule were the next species to consider. In view
of the strong interaction between the acidic hydrogen and the oxygens around the sulphur, the
smaller overall charges, and the unsymmetrical geometries, that these species would be less
hydrated than the solvated free sulphate ion. The bond distance between the proton and the
sulphate oxygen is so short (~1) that the proton and one water is not enough to form a cyclic
ring between two sulphate oxygens. However, the proton and two or three waters may form
cyclic rings, as suggested in the study of Arrouvel et al. (2005) for the hydrated H2SO4
molecule. The measured Raman frequencies of Walrafen et al. (2000) in sulphuric acid
+
solutions pointed to strong hydrogen bonding, resulting from direct H3O -HSO4 ion pair
interaction. They suggested 3 or 4 H2O molecules in association with the bisulphate ion in
more dilute acid environment. To be consistent with the way the hydration of the proton was
dealt with in this study, a single H2O molecule was bound to each of the O-H groups of the
+
bisulphate ion and acid molecule, i.e. to form the hydronium ion, H3O . The rest of the H2O
molecules were then arranged in either 2 or 3 cyclic rings, similarly to the approach followed
for the hydrated sulphate ion. The acid molecule was modelled by adding one H2O molecule
to each of the protons. It should be noted that these unconstraint hydronium ions resulted in
several structures which were very close in energy. The overall association reaction for the
first protonation of the sulphate ion may be represented as follows:
[48]
Comparison between the calculated and literature data (Table IV) suggests that the sulphate
ion sheds half its water upon protonation, i.e. forms HSO4 (H2O)4. Taking into consideration
the crude assumptions made thus far, the calculated pK2 of 2.2 is in reasonable agreement
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with values listed in the literature (~2) (the pK refers here to the negative logarithm of the
ionization constant). This calculation included the reaction entropy of 111.7 J/mol.K from
Wagman et al. (1982). Assuming that the H2SO4(H2O)2 molecule (as modelled above) is an
accurate enough description, the following reaction may be written for the protonation of the
bisulphate ion:
[49]
The calculated pK1 of -1.3 (assuming zero reaction entropy) is slightly higher than typical
values listed in the literature, but is considered acceptable in view of the spread of the
reported values (see Figure 6).
The next and final step in the quantum level description of the chemistry of the system was
to build a basis for the metal ion and its interaction with the sulphate ion to form contact ion
pairs. Since Mg2+ fulfilled the role of surrogate metal for the all the other divalent metal ions
in solution, a description of its solvation was the logical starting point. This alkaline earth
element has a hexagonal crystal structure. The unit cell, consisting of two atoms, was
modelled using space group P63/mmc and the experimental cell dimensions of a = 3.2088
and c = 5.2099 (ICSD Database, 2008). The optimized energy, using periodic DFT
calculation, was calculated as -400.837182 hartrees, while keeping the number of k points
within reasonable limits. The optimized cell dimensions were calculated as a = 3.1811 and
c = 5.1493 . The optimized energy of the Mg atom in vacuo was calculated as -200.360445
hartrees, allowing the cohesive energy, Ecoh to be obtained as follows:
[50]
where n in this case is the number of atoms in the unit cell. The calculated value of -1.58 eV is
in good agreement with the literature value (Kittel, 1996) of -1.51 eV. The work required to
decompose the metal into a single atom (atomization) is thus 153 kJ/mol, which compares
well with the NBS Tables value of 148 kJ/mol. Divalent transition metal cations, like Mg2+
and the other metals encountered in this study (Cu2+, Fe2+ and Zn2+), are strongly hydrated at
room temperature in dilute aqueous environment and consist of 6 waters (see Horvath, 1985)
in an octahedral arrangement in the primary hydration shell. The studies of Pye and Rudolph
(1998) and Rudolph et al. (2003) confirmed the hexaaquo magnesium complex by Raman
Spectroscopy (RS) and ab initio calculation. The calculated energy of the Mg2+ ion in the gas
phase of -199.533566 hartrees may be compared to the gas phase value of the atom (listed
above) to yield the calculated enthalpy of ionization of 2171 kJ/mol. This compares well with
the literature value of the ionization enthalpy of 2201 kJ/mol (Wagman et al., 1982). The free
enthalpy of hydration may be calculated according to the following reaction and is seen to be
in close agreement with the literature (Table V):
[51]
In order to complete the thermodynamic cycle, the standard reduction potential may be
written as follows:
[52]
Since the difference in the energy of the electron between the gas (vacuum) and the metal
(Fermi level) of the hydrogen electrode has been calculated as 4.65 V (previous discussions),
the standard reduction potential (Reaction [52]) is easily calculated as -2.57 V. This is
reasonably close to the literature value of -2.36 V (Atkins and De Paula, 2006). The
conventional molar entropy of hydration of Mg2+(aq) (-138.1 J/mol.K) and the entropy change
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for the hydration reaction, H2(g) 2H (aq) (-131 J/mol.K) are very similar (values from
Wagman et al., 1982). The fact that the entropy change for the overall reaction is small (~7
J/mol.K), explains why the calculated reduction potential agrees reasonable well with the
literature value. As mentioned before, this study also neglects any kinetic energy changes; it is
assumed that these energies cancel approximately, at least for reactions between solvated ions
2
and at constant temperature. The reaction between the solvated Mg2+ and SO4 ions to form
the first metal contact ion pair, may now be evaluated:
[53]
If the Mg2+ ion bonds to a sulphate oxygen in a monodentate fashion, the removal of
sulphate water may be analogous to the way the bisulphate molecule was formed, i.e. half of
2
the H2O molecules from the SO4 (H2O)8 ion were shed. The primary hydration shell around
2
the Mg2+(H2O)6 ion is stronger and more structured compared to the SO4 (H2O)8 ion.
Assuming only one H 2 O molecule will be lost from the Mg 2+ (H 2 O) 6 ion due to this
monodentate bond, three cases may be considered for the contact pair: (H2O)5MgSO4(H2O)3,
(H2O)5MgSO4(H2O)4 and (H2O)5MgSO4(H2O)5. The calculated energies are summarized in
Table V. Comparison between the estimated reaction enthalpy from Akilan et al. (2006a) and
the calculated values of the complexes, suggests 8 or 9 waters of hydration for the contact ion
pair. The optimized structure of the MgSO4(H2O)9 complex, is illustrated in Figure 2.
Table V
2+
Calculated molecular energies of Mg(H2O)6 and monodentate MgSO4 contact ion pairs, reaction enthalpies and
equilibrium constants
a
Molecule
Etot
(hartrees)
2+
Hrx,calc
(kJ/mol)
Hrx,lit
(kJ/mol)
Log (K)
(Calculated)
Log (K)
(Literature)
e-2.06
g-0.96
e1.05
g2.15
f1.21
f1.21
Mg(H2O)6
MgSO4(H2O)8 (a)
MgSO4(H2O)8 (b)
-660.024857
-1514.529050
-1514.523722
-1961 (Rx 55)
44.55 (Rx 57)
c-1949
MgSO4(H2O)9
-1591.1545255
26.74 (Rx 57)
d32
MgSO4(H2O)10
-1667.787060
-10.08 (Rx 57)
d32
d32
aCalculated
(absolute) energies of molecular species; bCalculated (potential) energies of corresponding reactions;

+
+
(1987) (expt.), based on H (g) H (aq): H = -1103 kJ/mol; dAkilan et al. (2006a); eSrx = 110 J/mol.K (Akilan
et al., 2006a); fAtkinson and Petrucci (1966); gSrx = 131 J/mol.K (see discussion below)
cMarcus
Figure 2. Optimized structure for the lowest energy complex of MgSO4(H2O)9
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Dielectric spectroscopy (DRS) (Akilan et al., 2006a) and ultrasonic relaxation values
(Atkinson and Petrucci, 1966) have proven the existence of a stepwise mechanism, commonly
referred to as the Eigen mechanism:
[54]
[55]
[56]
The above mechanism presents a general description of the association of free hydrated ions
to first form a double solvated ion pair, then solvent-shared ion pair, and ultimately, the
contact ion pair. The enthalpy and entropy terms for the overall inner-sphere complex
reaction, as reported in Table V, was obtained by summing the thermodynamic contributions
of each of the mechanistic steps. The alternative value of 131 J/mol.K for the reaction entropy
was obtained from the ultrasonic relaxation data reported by Atkinson and Perucci (1966): the
enthalpy for each of the mechanistic steps were fixed at the values reported by Akilan et al.
(2006a), while the entropy was calculated to give the average thermodynamic equilibrium
constants in Atkinson and Perucci (1966). This value of the reaction entropy gives log(K) =
2.15 and illustrates the sensitivity of the equilibrium constant to the reaction entropy.
Various studies (e.g. Zhang et al., 2002 and Rudolph et al., 2003) speculate on the
possibility of a bidentate contact ion pair. The optimized structure (9 waters of hydration) is
illustrated in Figure 3, while the calculated energy values are listed in Table VI. By comparing
these energies with the literature enthalpies (Akilan et al., 2006a), it becomes clear that the
bidentate complex may explain the formation of a second type of contact ion pair. Although
the reported thermodynamic values of Akilan et al. (2006a) are qualitative in nature, they do
provide estimates of the enthalpy and entropy contributions of the various equilibria steps.
The DRS study of Akilan et al. (2006) identified the formation of a possible triple ion at
higher ionic strengths, assumed to be Mg2SO42+. Although the existence of a triple ion is
2
supported by RS (Rudolph et al., 2003), the presence of the corresponding anion, Mg(SO4)2
cannot be ruled out. This is because the geometry of this anion would be close to linear and
therefore, have a zero dipole moment (cannot be detected by DRSsee Akilan
et al., 2006a and Buchner et al., 2004). The study of Zhang et al. (2002) even considered
2
larger Mg2+-SO4 clusters. Since modelling of the primary contact ion pair has revealed that
2
the SO4 (H2O)8 ion may lose half its waters to form the Mg(H2O)5SO4(H2O)4 monodentate
or the Mg(H2O)4SO4(H2O)5 bidentate complex, no waters are likely to be directly associated
with the anionic component if the Mg2SO42+ triple ion is formed, i.e.:
Figure 3. Optimized structure for the lowest energy complex of MgSO4(H2O)9 (bidentate)
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[57]
[58]
Various structures were considered for the Mg 2 SO 4 2+ (H 2 O) 10 (monodentate) and
Mg2SO42+(H2O)8 (bidentate) ion pairs, but the minor electronic energy differences between
the structures had almost negligible effects on the calculated equilibrium constants. The
values reported in Table VI clearly suggest that the Mg2SO 42+ complex is an unlikely
candidate for the second contact ion pair, even when using a larger reaction entropy change of
2
130 J/mol.K. The more likely triple ion contact ion pair is the Mg(SO4)2 species, as can be
seen from the values reported in Table VI. The corresponding optimized symmetrical
structure is illustrated in Figure 4 and the overall reaction is represented by Equation [59].
[59]
The structure presented in Figure 4 was obtained by adding another partially hydrated
2
SO 4 (H 2 O) 4 ion to the optimized Mg(H 2 O) 5 SO 4 (H 2 O) 4 monodentate structure in a
symmetrical fashion. The presence of this species is in line with the potentiometric study of
Fedorov et al. (1973), who assumed the formation of a series of anionic sulphate complexes
Table VI
x
Calculated molecular energies of possible second Mg-SO4 contact ion pairs, reaction enthalpies and equilibrium
constants
a
Molecule
Etot
(hartrees)
Hrx,lit
(kJ/mol)
Log (K)
(Calculated)
Log (K)
(Literature)
43
43
43
43
43
43
43
-6.21
-0.95
e-10.40
f -5.18
e-23.32
f-18.10
e -6.98
g-3.5
-0.22
-0.22
-0.36
MgSO4(H2O)8 (bidentate)
MgSO4(H2O)9 (bidentate)
Mg2SO42+(H2O)10 (monodent.)
-1514.511298
-1591.1467755
-1868.033131
77.17 (Rx 57)

47.14 (Rx 57)
68.32 (Rx 61)
Mg2SO42+(H2O)8 (bidentate)
-1791.381005
142.04 (Rx 62)
-2522.275826
48.77 (Rx 63)
Mg(SO4)2 (H2O)12 (monodent.)
Hrx,calc
(kJ/mol)
d
d
-0.36
-0.36
aCalculated
(absolute) energies of molecular species; bCalculated (potential) energies of corresponding reactions;

et al. (2006a); dSrx = 140 J/mol.K for the (overall) second contact ion pair (Akilan et al., 2006a).
eSrx = 30 J/mol.K (Akilan et al., 2006a) for triple} ion formation: Reactions [57], [58] and [59];
fSrx = 130 J/mol.K;
gSrx = 100 J/mol.K
cAkilan
Figure 4. Optimized structure for the lowest energy monodentate complex of Mg(SO4)2 (H2O)12
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for Zn(SO4)n{2-2n} and Cd(SO4)n{2-2n}, up to n=5 at high ionic strengths. It should, however, be
mentioned that this claim of a high degree of anionic pairing is controversial and has been
questioned on the basis anion exchange data (see Rudolph, 1998). On the other hand, the
formation of inner ferric, Fe(SO4)n{3-2n} complexes are known to form (e.g. Magini, 1979) and
although it can be partially explained by virtue of the high positive charge of the hydrated
ferric ion, it does suggest that this kind of anionic pairing may, although to a lesser extent, be
present in the divalent case. This may specifically be true at higher temperature, especially if
the reaction entropy is higher than the estimated value of 30 J/mol.K of Akilan et al. (2006a).
A reaction entropy of about 100 J/mol.K yields log(K) of -3.5. It is concluded that the
presence of this species could be significant at higher temperature, especially in the case of a
softer transition metal cation (cf. the harder Mg alkali-earth cation), e.g. Cu2+. That the
entropy for the formation of the anionic triple ion may be closer to 100 J/mol.K (cf.
30 J/mol.K), stems from a comparison between the change in the solvent cavity volume of the
various reactions, as computed within the continuum solvent methodology. The calculated
volume increase for the first contact ion pair formation (Reaction [53]) was approximately
203, while the entropy change for this reaction was estimated to be about 130 J/mol.K
(Table V). The calculated volume change for the formation of the anionic triple ion
2
(Mg(SO4)2 (H2O)12), via Reaction [59], was very similar, i.e. around 233. The triple anion
carries a net negative charge that would result in some structuring effect in the secondary
solvation shell and beyond. An estimated entropy change of 100 J/mol.K is justified on the
grounds that the disruptive effect caused by the accommodation of this large molecule in the
surrounding solvent is only partially compensated for by its structuring effects.
The above results should be viewed as qualitative in nature due to the static modelling
approach followed. It should also have been extended to the divalent transition metals (Cu2+,
Fe2+ and Zn2+). However, available thermodynamic data were largely limited to the Mg case
(next section), especially for the ternary system, and such a study was not justified within the
current context (a static model of the Fe2+/sulphate system is presented in Steyl, 2008).
Model regression
This section requires some quantitative thermodynamic values, while the chemical modelling
(previous section) has generated only qualitative information.
Thermodynamic data
The first association of the proton (second protonation of acid, H2SO4) may be written as
follows:
[60]
The thermodynamic values of this association constant (K1) was obtained from the study of
Dickson et al. (1990). They measured (potentiometrically) the dissociation constant of HSO4
in NaCl background solution and fitted the data to a series of equations. The following
expression (molality scale) was directly incorporated into the solution chemistry model and
gives the thermodynamic association constant up to 250C:
[61]
where T (kelvin) and the vector, p = [562.7097,-13273.75,-102.5154,0.2477538,-1.117033E4]. Various researchers have in the past used the thermodynamic values of Marshall and Jones
(1966). They determined the equilibrium constant from solubility measurements of CaSO4 in
sulphuric acid solution (01 mol/kg) from 25350C. However, their results have been
criticized by various authors (e.g. Shock and Helgeson, 1988 and Dickson et al., 1990)
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because they ignored the presence of the neutral aqueous species, CaSO4 and H2SO4, which
may exist in significant amounts, especially at high temperatures. The study of Dickson et al.
(1990) also acknowledged the most important results from the literature between 1952 and
1990 and incorporated some of it into their expression (Equation [61]). One of the most
important studies during that period was the work of Pitzer et al. (1977), but their equations
are valid only to 55C.
Figure 5 compares the performance of the Equation [61] against other thermodynamic data
reported in the literature. The broken lines represent the calculated equilibrium constant after
integration of the enthalpy and entropy terms (Equation [42]), using reported heat capacity
parameters (Equation [34]). The data points were obtained from a random scan of published
values in the open literature (Steyl, 2008). The equation of Dickson et al. (1990) performed
well up to high temperatures (>200C) and was therefore adopted for this study. The HSC
(2006) heat capacity parameters, imbedded within the software, were obtained from Helgeson
extrapolation (Shock and Helgeson, 1988). The second association of the proton (first
protonation of acid, H2SO4) may be represented as follows:
[62]
Reported thermodynamic values for this association constant (K2) is very rare because the
concentration of the neutral species, H2SO4, can be accurately determined only at high
temperature and concentration. In most studies of the dilute sulphuric acid system, even at
high temperature (e.g. Marshall and Jones, 1966, Dickson et al., 1990 and Rudolph, 1996),
the formation of the neutral species was ignored. Some of the older Raman studies (e.g.
Young and Blatz, 1948 and Young et al., 1959) and the Nuclear Magnetic Resonance (NMR)
study of Hood and Reilly (1957) quantitatively took the existence of the neutral ion pair into
account, even at low temperatures (<50C), albeit at high acid concentrations. The RS study
of Rao (1940) suggested (qualitatively) around 95% dissociation of the neutral species in
1 mol/litre acid. More recent work include the RS (structural) investigation of Walrafen et al.
(2002), the spectroscopic measurements of Xiang et al. (1996) and the flow calorimetric work
of Oscarson et al. (1988), all at high temperatures (>150C). Agreement between the studies
of Xiang et al. and Oscarson et al. is good, and the published equations of latter were used as
the primary source of data for this study. The isocoulombic reaction was obtained by
considering the water dissociation reaction in addition to Reaction [62], i.e.:
[63]
Both the assumption of zero reaction heat capacity and the BLCM model for the
isocoulombic reaction fit their respective linearity assumptions very well over the 150200C
range (Steyl, 2008). The thermodynamic data reported by Sweeton et al. (1974) was used for
Figure 5. Effect of temperature on the thermodynamic association constant (K1)
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the water dissociation reaction. The Density and BLCM models predicted very similar values
of log(K2) at 25C, i.e. -1.7 and -1.8, respectively. The considerable spread in reported values
exemplifies the difficulties in measuring this equilibrium constant in dilute sulphuric acid
solution, i.e. the neutral molecule is not present in measurable quantities at room temperature.
The thermodynamic values reported by Oscarson et al. (1988) at the reference temperature of
150C (see Table VIII) were therefore used in the phenomenological model, along with the
Density model to extrapolate to other temperatures.
Earlier discussions highlighted the lack of information on the structure and thermodynamic
properties of contact ion pair formation of the divalent metal sulphates. Spectroscopic studies
of MgSO4 solutions (Akilan et al., 2006a, Buchner et al., 2004, Rudolph et al., 2003), CuSO4
solutions (Akilan et al., 2006b), ZnSO4 solutions (Rudolph et al., 1999a and 1999b), CdSO4
solutions (Rudolph, 1998), FeSO4 solutions (Rudolph et al., 1997) and, NiSO4 and CoSO4
solutions (Chen et al., 2005) have provided a major contribution to the understanding of
species complexation in the metal sulphate self-medium. However, the reported
thermodynamic values undoubtedly contain uncertainties (see Akilan et al., 2006a). The RS
study of Rull et al. (1994) has even gone as far as dismissing the presence of contact ion pairs
altogether in solutions, up to 2.9 mol/kg MgSO4 and 80C. Figure 7 compares the overall
(SIPs+CIPs) equilibrium data with various extrapolated lines. The data (open symbols) at high
temperature, used in the models of Baghalha and Papangelakis (1998) and Casas et al. (2005),
were calculated using Helgeson extrapolation, while the model of Liu and Papangelakis
(2005) used the Density model. The lines in Figure 7 were calculated using the Density model
and thermodynamic reference data from various spectroscopic studies. This figure exemplifies
Figure 6. Extrapolation of the thermodynamic association constant (K2) to 25C
Figure 7. Experimental data vs. extrapolated values of the overall thermodynamic constant, K3(tot)
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the disagreement in the literature, especially when extrapolating to higher temperature. From a
phenomenological modelling perspective, Casas et al. (2005) illustrated that explicit
recognition of species are not actually required. In fact, numerous studies (e.g. Holmes and
Mesmer, 1983, Phutela and Pitzer, 1986 and Reardon and Beckie, 1987) used an ion
interaction approach without any explicit species recognition to describe the thermodynamics
of metal sulphate systems up to high temperatures. However, as pointed out by Akilan et al.
(2006), models that take no note of the actual species present cannot be much more than
exercises in numerology, with little physical significance.
Since this study was concerned with building a framework to assist with the interpretation of
kinetic processes, it was important to recognize the existence of the contact ion pairs, despite
the lack of thermodynamic data. In view of the rationale followed thus far, the total free
metal ion molality refers to the sum of the actual free hydrated ions and all the solvent
separated ion pairs (SSIPs):
[64]
where y refers to the mole fraction of apparent unassociated metal ions (m) and mf refers to the
formal metal salt molality (CIP refers here to the first contact ion pair, MgSO4 and CIP is the
fraction contact ion pairs):
[65]
and z is the true mole fraction of unassociated ions. This equation may be combined with
some of the thermodynamic relationships presented earlier, the yield the following equation of
equilibrium constant (Steyl, 2008):
[66]
The activity coefficient of the neutral contact ion pair is not likely to be 1, especially since
the previous section suggested that the ion pair may still be hydrated. Errors in species
distributions would ultimately be absorbed in the rate constants of the kinetic processes. The
more important issue was an accurate description of the changes in species predominance
with solution concentration and temperature changes. The value of log( 3) of 1.5 was
therefore retained for the MgSO4 contact ion pair (Table VIII). No distinction between
different bonding mechanisms, i.e. monodentate or bidentate was made in the
phenomenological model. This is because monodendate bonding was assumed to be only
present in the case of the alkali earth element, Mg and not in the case of the divalent metal
ions of Cu, Fe and Zn (Steyl, 2008).
Table VII
Reported thermodynamic values from the literature
System
MgSO4-H2O
FeSO4-H2O
CuSO4-H2O
ZnSO4-H2O
Method
RS
DRS
RS
RS
RS
log(3)
Reference
~1.5
~1.6
b
~l.5
c
1.0
~1.5
Rudolph et al. (2003)

Akilan et al. (2006a)
Rudolph et al. (1997)
Akilan et al. (2006b)
Rudolph et al. (1999a)
Average calculated value (Equation [66]), using reported data above 0.1 mol/kg (from the corresponding reference)
b
and assuming unit activity coefficient for the contact ion pair; Stoichiometric mean activity coefficient from
c
Reardon and Beckie (1987); Value taken directly from the literature
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Table VIII
Thermodynamic values used in the regression of the phenomenological model
Reaction
+
2H (aq) + SO4 (aq) = HSO4 (aq)
+
o
H (aq) + HSO4(aq) = H2SO4 (aq)
2+
2o
Mg (aq) + SO4(aq) = MgSO4 (aq)
2o
2SO4(aq) + MgSO4(aq) = Mg(SO4)2 (aq)
No.
K1
K2
3
K4
log(K)
1.964
-1.05
1.5
-3.5
Hrx (kJ/mol)
22.8
19.62
c
10
d
49
Srx (J/mol.K)
114
b
26
c
62
d
97
Reference
a
Dickson et al. (1990)

Oscarson et al. (1988)
This study
This study
Equation [61] is used to extrapolate over temperature; Value at 150C (Cp = 113 J/mol.K), using Equation [40] to
c
extrapolate over temperature;
Average enthalpy from RS measurement ~10 kJ/mol for various divalent metal sulphates
d
(see Rudolph, 1998, Rudolph et al., 1997, 1999a and 1999b) and S calculated (no Cp estimate); H estimated from
ab initio calculation, S calculated and assumed Cp = 0 J/mol.K (Akilan et al., 2006a)
Ab initio calculation suggested the possibility of triple-ion pair formation. This was
confirmed for the Mg system (Akilan et al., 2006a, Buchner et al., 2004 and Akilan et al.,
2006a) and the Ni and Co systems (Chen et al., 2005), but not in the Cu system (Akilan et al.,
2006b). However, calculations in the previous section suggested that this triple ion may be the
2
anionic complex, Mg(SO4)2 , which would not be detectable by DRS. The thermodynamic
data for this stepwise reaction, as estimated by crude ab initio modelling (previous section),
was therefore adopted for the phenomenological model. The positive enthalpy values of all
the above reactions may be ascribed to the energy required to break the coordinated H2O
molecules of the constituent species prior to bonding. However, the positive entropy values
may be ascribed to the release of H2O molecules (reflecting less structure around the ion
pairs), which compensates for the positive enthalpies, especially at higher temperature, i.e.
these reactions can be viewed as being entropically driven. No explicit interactions between
HSO4 and the metal cations were taken into account because the HSO4 anion has a noble
gas electronic structure (similar electronic structure to perchlorate, ClO4 ion) and is not
expected to form contact ion pairs (Tremaine et al., 2004 and Rudolph et al., 1997).
The following subsections discuss the binary and ternary systems up to 200C, i.e. the
H2SO4-H2O, MgSO4-H2O and H2SO4-MgSO4-H2O systems, respectively.
H2SO4-H2O system
Although the thermodynamic properties of this system have been studied extensively, there
still exists discrepancy in the actual species molalities in the dilute system. At higher
temperatures, very little data are available at all. The MSE model of Liu and Papangelakis
(2005b) suggests almost 40% H2SO4 in a 0.5 mol/kg acid solution at 200C. Wang et al.
+
(2006) adjusted this model by explicitly treating of the proton as the hydrated species, H3O ,
and adjusting the interaction parameters to reflect experimental measurements (e.g. Hood and
Reilly, 1957, Young et al., 1959 and Walrafen et al., 2000). However, as pointed out earlier,
current experimental techniques have not yet developed to a level where quantitative
information about minor species abundance, such as H2SO4, can be provided in the dilute
(<1 mol/kg) range at high temperatures. Due to the relative dilute range of this study, it was
not deemed necessary to follow the hydrated cation approach of Wang et al. (2006). With, (i)
careful selection of the important equilibrium constants (discussed previously), (ii) selecting a
minimum number of adjustable interaction parameters, (iii) constraining the system to
measured thermodynamic properties (salt and water activity), and (iv) incorporating the
experimentally observed (at lower temperature) distribution of the primary species (HSO4
and SO42), predictions at higher temperature should be realistic.
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Table IX
Optimized interaction parameters for the H2SO4-H2O system (with inclusion of the long-range electrostatic terms)
(0)HB
(1)HB
BS
p1(kg/mol)
103 p2 (kg/mol)
0.2291
0.3736
0.1151
-0.4641
0.0498
-0.1788
Table X
Objective functions and their relative deviations for the H2SO4-H2O system
a
Temp (C)
25
50
75
100
a
Objective function
/3 + /3 + /31
+
+
+
AARD (%) (, , ) Temp (C) Objective function AARD (%) (, , )

0.31, 0.22, 2.49
0.49, 0.40, n/a
0.12, 0.34, n/a
0.06, 0.39, n/a
The error of property, p, defined as: p = (|pi calc/pi exp 1|;

respectively
125
150
175
200
+
+
+
+
0.13, 0.42, n/a

0.09, 0.22, n/a
0.14, 0.05, n/a
0.67, 0.74, n/a
Absolute average relative deviation of , and ,
The studies of Pitzer et al. (1977), Clegg et al. (1994) and Clegg and Brimblecombe (1995)
present excellent literature reviews of the important thermodynamic studies of the H2SO4H 2O system over the years, all of which were limited to below 60C. The only high
temperature study based on own experimental measurement and where a description of the
self-medium was attempted, is the isopiestic study of Holmes and Mesmer (1992). The most
important experimental data were incorporated into a regression analysis, using the model
described above and minimizing the objective function (the relevant regression information is
presented in Table X). The symbol 1 refers to the degree of dissociation of the bisulphate
ion. Various combinations of the interaction parameters ((0)HB, (1)HB, CHB, (0)HS, (1)HS,
CHS, BS, HBS) were attempted. The activity coefficient of the neutral complex was assumed
to be unity, i.e. no interaction parameters involving the neutral acid molecule was included.
The subscripts H, B and S refer to the proton (H+), bisulphate (HSO4 ) and sulphate ions
2
(SO4 ), respectively. In order to simplify this task, a scan of their relative influences was
conducted, both with and without the inclusion of the long-range electrostatic parameters. The
best fit with the minimum number of adjustable parameters was achieved with the parameters
presented in Table IX. A power series was used to calculate the temperature dependence of the
interaction parameters (after Holmes and Mesmer, 1992):
[67]
with the maximum value of i = 4, Td = T 298.15K and To = 1K. Due to the lack of
thermodynamic data and species abundance, especially at higher temperatures, the interaction
parameters were allowed to vary only linearly (i = 2). The lower end of the regression was
limited to 0.1 mol/kg H2SO4 at higher temperatures (>50C) because isopiestic measurements
(Holmes and Mesmer, 1992) are generally not regarded as accurate at the lower molalities. A
comparison between the experimental data and the model output are represented in Figures 8
and 9. Figure 10 presents the speciation diagram at 1 mol/kg H2SO4 and suggests that the
neutral species (H2SO4) plays a minor role (less that 5%), even at a temperature of 200C.
This is in line with the predictions of Wang et al. (2006).
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Figure 8. Comparison between the experimental values of the osmotic coefficient and the model output (this study)
for the H2SO4-H2O system at 25C intervals
Figure 9. Comparison between the experimental values of the fraction HSO4 dissociated (1) and the model output
(this study) for the H2SO4-H2O system at 25C intervals
Figure 10. Sulphate species (fraction of the total sulphate molality) as a function of temperature for the H2SO4-H2O
system at 1 mol/kg acid
MeSO4-H2O system
Thermodynamic data of the base metal sulphates encountered in this study (CuSO4, ZnSO4,
FeSO4 and MgSO4) in water medium is scattered through the literature, with significant
variances. The most important sources of measured and reported osmotic and mean activity
coefficient data can be found in Robinson and Stokes (1959), Pitzer (1972) and Majima et al.
(1988). The more recent paper of Quendouzi et al. (2003) also gives a good summary of
reported data and it compares well with their calculated values for various metal salts in water.
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Additional data for the CuSO4-H2O system was found in Harned and Owen (1958), Downes
and Pitzer (1976) and Majima and Awakura (1988). The more recent measurements of
Albright et al. (2000) and Miladinovic et al. (2002) provided useful information on the
ZnSO4-H2O system. However, only the study of Oykova and Balarew (1974) revealed
information about the FeSO4-H2O system, which exemplifies the difficulties in obtaining
accurate experimental data for this system. Additional information for the MgSO4-H2O
system was obtained from the measurements of Snipes et al. (1975), Archer and Wood
(1985), Phutela and Pitzer (1986) and, especially, Archer and Rard (1998) for the osmotic
coefficient, and Pitzer and Mayorga (1974), Rard and Miller (1981) and Holmes and Mesmer
(1983) for the mean activity coefficient. Agreement between the above studies is reasonable,
except for the measurements of Majima et al. (1988). Their data were not included for the
ZnSO4 and MgSO4 systems. Figure 11 presents the average reported values of the mean
activity coefficients (at 25C). The observed mean activity coefficient is relatively insensitive
to the type of divalent metal salt. Although uncertainty exists to the degree of contact ion pair
formation, earlier discussions emphasized that it would vary significantly between the
different salts. Notwithstanding, Figure 11 suggests that contact ion pair formation is not
significant at 25C (~10% at 1 mol/kg MgSO4; see Rudolph et al., 2003) and also reflects the
similarities in the solvent-separated ion pairs between these salts. This is also evident from the
very similar values of the total thermodynamic equilibrium constants of these salts at 25C, as
reported in various publications (e.g. Nair and Nancollas, 1958 and 1959, Helgeson, 1967,
Pitzer, 1972 and Hgfeldt, 1982). The overall equilibrium constants are therefore dominated
by electrostatic forces (see Pitzer, 1972). Previous discussions and information from the
literature (e.g. Rudolph et al., 1997, 1999a, Rudolph, 1998 and Akilan et al., 2006a) suggests
that contact ion pair formation increases rapidly with temperature. In an attempt to gauge if an
increase in temperature would transpire into significant differences between salts, their
reported thermodynamic values were compared. For example, the emf study of Nair and
Nancollas (1959), conducted up to 45C, yielded very similar enthalpy (20.3 kJ/mol and 16.8
kJ/mol) and entropy (111 J/mol.K and 102 J/mol.K) values for MgSO 4 and ZnSO 4 ,
respectively. Helgeson extrapolation (Helgeson, 1967) yielded similar equilibrium constant
values at 100C (consistent with other reported conductivity results, see e.g. Hgfeldt, 1982),
and log(K) = 4.8 and 4.6, respectively, at 200C.
No reported data could be found for CuSO4 and FeSO4 at higher temperatures. Since there
were no data available at high temperatures to suggest otherwise, this study assumed that
these salts behave similarly up to 200C, which justifies the Mg surrogate approach, albeit
artificially (e.g. Pitzer, 1972, suggested that possible triple ion pair formation is expected to be
more prominent in the case of Cu2+ as compared to Mg2+). Experimental data for MgSO4
were incorporated into a regression analysis. Numerous combinations, from a minimum of
Figure 11. Average mean activity coefficients of various metal sulphates in water (data points represent averages)
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3 to a maximum of 6 parameters were tested, involving the main interactions between ions
((0)MS, (1)MS, (2)MS, CMS, (0)MT, (1)MT, CMT, ST, MST). The subscripts M, C and T refer to
2
the metal, first contact ion pair (MgSO4) and the triple ion pair (Mg(SO4)2 ), respectively.
Reactions [68] and [69] represent the first and triple contact ion pair reactions, respectively:
[68]
[69]
The above interaction parameters were later extended to include binary interactions
involving the neutral contact ion pairs ( MC , SC , CC , CT ) and then also to ternary
interactions (MCC, SCC, CCC, MSC). The best regressions at 25C with a minimum number
of 4 parameters was obtained with the parameters (0)MS, (1)MS, (2)MS, with explicit
2
recognition of MgSO4 and Mg(SO4)2 , in addition to one of the following CMS, SC, or MC.
Although previous studies of MgSO4 at high temperature (e.g. Holmes and Mesmer, 1983,
and Phutela and Pitzer, 1986) only utilized the parameters, (0)MS, (1)MS, (2)MS and CMS, the
explicit inclusion of the two contact ion pairs demanded a modified approach. Excellent
results at high temperatures were obtained with the inclusion of one of the neutral interaction
parameters, SC or MC. The inclusion of these parameters may be perceived to capture the
electrostatic interactions between the dipole of the first contact ion pair and the charged
sulphate anion or metal cation, respectively. The inclusion of the (2) MS term in the
conventional treatment of 22 electrolytes (see Pitzer and Mayorga, 1974) is related to the
rapid decrease in the ion activity coefficients in the dilute range (~0.03 to 0.1 mol/kg), which
in turn, is related to a maximum degree of association found for typical 2-2 electrolytes in this
dilute range. With optimized (2)MS values for MgSO 4 in the range -37.23 (Pitzer and
Mayorga,
1974)
to
-32.7 (Rard and Miller, 1981), its value needed to be adjusted because of explicit contact ion
pair formation. In order to prevent the regression from getting stuck in local minima, the
initial (2)MS values were systematically varied before each optimization. Figure 12 illustrates
the results of this scan, suggesting an optimum (2)MS value in the region of -29 (kg/mol) and
maintaining the 22 electrolyte parameters, 1 and 2, at 1.4 and 12 (kg/mol)1/2, respectively.
Although the trough is relatively shallow around the minimum, it is (as expected) different
than what the conventional treatment requires, i.e. the explicit recognition of ion pairs lowers
the absolute value of (2)MS.
The optimized interaction parameters at 25C are presented in the first column of Table XI.
In order to determine the temperature dependence of the various interaction parameters,
Equation [67] was again utilized. However, as may be recalled from Table VIII, no heat
capacity information was available for the formation of two contact ion pairs (MgSO4 and
Figure 12. Residual sum of squares versus the second virial coefficient at 25C
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Table XI
Optimized interaction parameters for the MgSO4-H2O system
(0)MS
(1)MS
(2)MS
SC
Reaction [68]
Reaction [69]
p1 (kg/mol)
102 p2 (kg/mol)
105 p3 (J/mol.K)
Cp (kg/mol)
0.2575
3.1890
-29.2839
-0.0990
0.1532
0.4970
-7.1213
-0.5775
0.5653
-0.6343
-3.1555
1.3769
267.5036
Mg(SO4)2 ), and hence, no accurate description of their enthalpy and entropy changes with
temperature could be made. The heat capacities of these two reactions were therefore
incorporated into the regression via Equations [34] and [42]. Experimental data at higher
temperatures for the MgSO4-H2O system were limited to the heats of dilution measurements
of Snipes et al. (1975) (up to 80C), the isopiestic vapour pressure measurements of Holmes
and Mesmer (1983) (at 110C) and the heat capacity measurements of Phutela and Pitzer
(1986) (up to 150C). The studies of Archer and Wood (1985) and Archer and Rard (1998)
also included other data sources (most of them limited to 150C) and their model outputs
provided excellent generalizations of all available data up to 150C. Although the study of
Phutela and Pitzer (1986) extended up to 200C, this information was limited to very low
molality (~0.1 mol/kg), with questionable accuracy (discrepancies with the Archer and Wood
model above 140C). It was important for this study to include additional information in the
regression at high temperatures (>150C). Incorporation of the solubility of the monohydrate
(kieserite) was ideally suited for this purpose:
[70]
A major unknown was the thermodynamic equilibrium constant, Ksp at higher temperatures
and more specifically, the partial molal heat capacity of the crystal phase. This study used a
Cp25C value of 145 J/mol.K, while the study of Archer and Rard proposed a value of
126 J/mol.K and the study of Pabalan and Pitzer (1987) suggested 134 J/mol.K (value adopted
in the study of Liu and Papangelakis, 2005a). The temperature dependence of Ksp would
obviously also depend on the specific choice of thermodynamic parameters for the other
species taking part in Reaction [70]. Baghalha and Papangelakis (1998) and Casas et (2005b)
used Helgeson extrapolation to calculate K sp at high temperatures, whereas Liu and
Papangelakis (2005a) calculated slightly larger values, using the Density model. The data
chosen for this study originated from the HSC (2006) database and resulted in the following
thermodynamic values for Reaction [70] at 25C: log(Ksp) = 0.0662, Cp = -355.92 J/mol.K
and H = -52.43 kJ/mol. Equation [6] was used to obtain the water activity. This value and
the mean activity coefficient were then plugged into Equation [28] during the regression
analysis to obtain the calculated value of the solubility at different temperatures. The
experimental solubility values for the kieserite phase were obtained from Marshall and
Slusher (1965), and Linke and Seidell (1965).
Because the exact heat capacity values of the two metal contact ion pair reactions had a
significant influence on the optimized interaction parameters, a systematic manual scan was
first conducted. Figure 13 presents a surface plot of the area close to the global minimum and
supports the assumption of Akilan et al. (2006a) of zero heat capacity for triple ion formation
reaction (Reaction [69]). The overall regression was subsequently conducted, initializing Cp
(Reaction [68]) at 270 J/mol.K. In order to prevent overparameterization, no temperature
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Figure 13. Residual sum of squares versus Cp for the first (CIP1) and triple (CIP2) contact ion pairs
Table XII
Objective functions and their relative deviations for the MgSO4-H2O system
a
Temp (C)
25
45
65
80
100
110
120
a
Objective function
/3 + /3 + /3
1
1
/3 + /3 + /3
+
+
+
+
+
AARD (%)
(, , )
Temp (C)
0.85, 1.65, 1.14

1.04, 2 .14, n/a
1.61, 1.55, n/a
1.50, 1.63, n/a
1.14, 0.96, n/a
1.37, 1.02, n/a
1.37, 2.39, n/a
130
140
150
170
180
190
200
Objective function
AARD (%)
(, , log Ksp)
+
+
+
102 log(Ksp)
102 log(Ksp)
102 log(Ksp)
102 log(Ksp)
1.34, 3.42, n/a

1.26, 4.32, n/a
0.35, 6.58, n/a
n/a, n/a, 0.55
n/a, n/a, 0.16
n/a, n/a, 0.01
n/a, n/a, 0.16
The error of property, p, defined as: p = (|pi calc/pi exp 1|; Absolute average relative deviation of , and (or log
Ksp), respectively
dependence of the reaction heat capacities was deemed necessary, i.e. the enthalpy and
entropy expressions reduced to Equations [37] and [38], respectively. A power series
(Equation [67]) was once again used to calculate the temperature dependence of the
interaction parameters. However, higher order (i = 3) terms needed to be included to represent
the solubility of kieserite at the lower temperature end, i.e. 170C. All the optimized
parameters are listed in Table XI. The objective functions and their relative deviations (at their
corresponding temperatures) are summarized in Table XII. Figure 14 illustrates the goodness
of the regression by comparing the model prediction with the measured solubility of MgSO4
in the kieserite region.
The performance of the phenomenological model from this study is compared to the
published data in Figures 15 and 16. Except for the data of Phutela and Pitzer (1986), the
model gives an excellent representation of the experimental osmotic coefficient and observed
mean activity coefficient of MgSO 4 up to high temperatures. Figure 17 compares the
calculated fraction contact ion pairs with the available experimental data (25C). The model
predictions at higher temperatures are also illustrated, emphasizing the preferential ion
association at low molalities (discussed previously). These trends also suggest that the
2
formation of the triple ion (Mg(SO4)2 ) becomes increasingly important at high temperatures
and at the expense of the first contact ion pair (MgSO4).
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Figure 14. Comparison between the model output (this study) and the measured solubility of the kieserite crystal
phase in the MgSO4-H2O system
Figure 15. Comparison between the experimental values of the osmotic coefficient and the model output (this study)
for the MgSO4-H2O system at selected temperatures
Figure 16. Comparison between the experimental values of the mean stoichiometric activity coefficient of MgSO4 and
the model output (this study) for the MgSO4-H2O system at selected temperatures (the broken line artificially exceeds
the solubility limit)
H2SO4-MeSO4-H2O system
Reliable experimental information on this ternary system is rare, which is surprising in view
of its industrial importance. The most comprehensive set of experimental data was generated
by Majima et al. (1988) at 25C, but its accuracy is questionable (elaborated upon later in this
section). Valuable information was obtained from the isopiestic measurements of Rard and
Clegg (1999) for the H2SO4-MgSO4-H2O system at 25C. The isopiestic measurements of
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Figure 17. Model predictions of the fraction (of total Mg) MgSO4 (3) and Mg(SO4)22 (4) and the experimental
values for the MgSO4-H2O system. The dotted line refers to 3, while the solid line represents the fraction total
contact ion pair formation (3+4) (the broken line artificially exceeds the solubility limit)
Majima et al. (various acid-salt mixtures) and the vapour pressure and emf measurements of
Tartar et al. (1941) (H2SO4-ZnSO4-H2O system) is also compared (see the data of Rard and
Clegg). References to other data sources for these ternary systems can be found in Rard and
Clegg, but were not considered for this study since they were all limited to 25C. Only one
paper was found that reported thermodynamic data at higher temperature, i.e. the study of
Jaskula and Hotlos (1992) for the H2SO4-CuSO4-H2O system at 60C. It was unfortunately of
little use to this study because no comparative values were reported for the same system at
25C. Various researchers have applied the Pitzer ion interaction model to these types of
ternary systems, e.g. Guerra and Bestetti (2006) (H2SO4-ZnSO4-H2O system, 45C), Rard
and Clegg (1999) (H 2SO 4-MgSO 4-H 2O system, 25C) and Reardon and Beckie (1987)
(H2SO4-FeSO4-H2O system, 90C). Due to the relatively dilute nature of the solutions and
the explicit recognition of selected contact ion pairs, this study had to derive its own unique
mixing parameters. The poor agreement between the experimental data of Majima et al. and
the other studies mentioned above prevented an accurate derivation of the mixing parameters.
In order to compare the results of the various studies, the relative mean activity coefficient,
was defined as follows:
[71]
This equation allowed the mean activity coefficient in the ternary system to be normalized
to its value in the pure binary system and thus provided a more suitable basis of comparison.
Figure 18 compares the relative mean activity coefficient of sulphuric acid in ternary mixtures
and suggests reasonably close agreement, even for different divalent metal salt systems.
However, Figure 19 illustrates a considerable spread of the relative mean activity coefficient
of metal sulphate between the different salts in ternary mixtures with sulphuric acid and water.
The relative mean activity coefficient of MgSO4 from Rard and Clegg (1999) is also
significantly different from the values reported by Majima et al. (1988). Only the data of Rard
and Clegg provided consistency between the mean activity coefficient of MgSO4 and the
osmotic coefficient (Figure 20), and was therefore the only source of data used in the
regression analysis. Due to the lack of data, only three mixing parameters were selected.
Because of the relative obscurity of the contact ion pairs, especially in acidic media (see
Rudolph et al., 1997), their mixing parameters were not considered. Only combinations of the
following mixing parameters were therefore considered: (0)MB, (1)MB, CMB, HM, HMB,
HMS and MBS. The subscripts H, M, B and S refer to the proton (H+), metal (Mg 2+),
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Figure 18. Relative mean activity coefficient of sulphuric acid in ternary mixtures from different studies (the surface
represents the average fit through all the data points)
Figure 19. Relative mean activity coefficient of the metal sulphate in ternary systems from different studies (the
surface represents the best fit through the data points of Rard and Clegg, 1999, for the H2SO4-MgSO4-H2O system)
Figure 20. The osmotic coefficient of the H2SO4-MgSO4-H2O system. The surface represents the best fit through the
data points of Rard and Clegg (1999), while the solid lines represent the model output from this study for the two
binary systems
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bisulphate (HSO4 ) and sulphate (SO42), respectively. Various combinations were tested,
ultimately suggesting that at least two of the binary interaction terms (0)MB, (1)MB or HM
needed to be included. The study of Rudolph et al. (1997) also suggested that mixing of Me2+
and HSO4 ions, although not forming contact ion pairs, should be approached from an ioninteraction perspective. The limited experimental data available for the mixed system made
the choice of the third (ternary) interaction term somewhat arbitrary. It was therefore decided
to use the same ternary interaction term as used in the work of Reardon and Beckie (1987),
i.e. HMB, but with the inclusion of the long-range electrostatic terms, E HM and E HM.
Figure 21 illustrates the goodness of the regression by comparing the model prediction with
the measured data of Rard and Clegg and its comparative offset with the data of Majima et al.
(1988).
The optimized parameters (at 25C) are summarized in Table XIII, corresponding to an 1
value of 2 (kg/mol)1/2. The objective functions and their relative deviations are summarized in
Table XIV. The only thermodynamic data found for the H2SO4-MgSO4-H2O system at higher
temperatures was the solubility data of kieserite at 200C from Marshall and Slusher (1965).
This lack of data could only justify a linear dependency on temperature (i = 2), using Equation
[67]. Figure 22 illustrates the excellent agreement between the measured solubility data in the
ternary system and the model output, even though some areas (dotted lines) lie outside the
range used in the regression at 25C.
The theoretical framework provided by the Pitzer ion-interaction approach was used to model
the ternary H2SO4-MeSO4-H2O system, using MgSO4 as the surrogate salt to represent other
Figure 21. Comparison between the experimental values of the mean stoichiometric activity coefficient of H2SO4 in
ternary mixtures with MgSO4 and H2O, and the model output from this study
Table XIII
Optimized interaction parameters for the H2SO4-MgSO4-H2O ternary system (with inclusion of the long-range
electrostatic interaction terms between H+ and Mg2+)
(0)MS
(1)MS
HMB
p1 (kg/mol)
102 p2 (kg/mol)
0.2606
2.0949
0.2930
0.0121
1.3823
-0.1662
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Table XIV
Objective functions and their relative deviations for the H2SO4-MgSO4-H2O ternary system
Temp (C)
25
200
a
AARD (%) (, , log Ksp)
Objective function
+ , MgSO4
log(Ksp)
3.09, 8.03, n/a

n/a, n/a, 0.03
b
The error of property, p, defined as: p = (|pi calc/pi exp 1|; Absolute average relative deviation of , and log Ksp
respectively
Figure 22. Comparison between the experimental values of kieserite solubility in the ternary system, H2SO4-MgSO4H2O at 200C and the model output from this study (the dotted line refers to the model prediction outside the
regression range)
divalent metal sulphate electrolytes. Since this study aimed at developing a platform for
interpreting hydrometallurgical process kinetics in acidic metal sulphate solutions, the most
important inner-sphere complexes were explicitly recognized. Thermodynamic data was used
to constrain the phenomenological model, thereby inferring the speciation behaviour at higher
temperatures were no qualitative experimental information was available.
Due to the relatively dilute nature of the electrolyte modelled in this study, all
thermodynamic expressions referred back to the transcendent position of infinite dilution. A
qualitative interpretation of the quantum level chemistry was used as a complementary tool to
add more confidence to the ambiguous nature of the thermodynamic data reported in the
literature. Molecular geometries were optimized within a DMol3/COSMO framework. The
total coordination of aqueous species were restricted by explicitly using water as a
coordination filling species in the first hydration shell, while treating the effect of the solvent
beyond this level via the continuum solvent methodology. Since neither the vibrational
energy, nor the entropy of the solvated species could be explicitly calculated within the
context of the DMol3/COSMO framework, the enthalpy rather than the total free energy
formed the basis of comparison with reported literature values. It was assumed that the
enthalpy was represented by the potential energy; hence, it was assumed that the kinetic
energy (translational, rotational, etc.) cancels approximately for reactions between solvated
ions at constant temperature. The thermodynamic basis for the proton yielded an average
hydration of between H3O+ and H5O2+, while a structured and static approach to the solvation
of sulphate suggests the dianion to have 8 H2O molecules in the primary hydration shell. It
was estimated to lose half its H2O molecules when reacting with the proton to form the
bisulphate ion. With zero reaction entropy, the pK1 was estimated to be around -1.3, assuming
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the hydrated sulphuric acid molecule consists of two H2O molecules in its primary shell. The
first contact ion pair of MgSO4 was likely a monodendate complex, but the presence of a
second contact ion pair could also be explained by the MgSO4 bidentate complex. The
presence of a monodentate Mg2SO42+ triple ion (reported in the literature) could not be
2
verified by calculation. Instead, its anionic analogue, Mg(SO4)2 seemed more probable,
especially at higher temperatures (significant entropy contribution). The log(K) was
calculated as -3.5, using an estimated reaction entropy of 100 J/mol.K.
The equation of Dickson et al. (1990) gave a good description of the experimental second
ionization constant of acid up to high temperatures, and was adopted for this study. The first
ionization constant, estimated from a quantum level treatment, compared very well with the
thermodynamic data of Oscarson et al. (1988) (the Density model was used to extrapolate the
reported high-temperature data to 25C). The association constant for the first contact ion pair
for different metals was estimated from spectroscopic data (reported in the literature) to be
about 1.5, despite having different bonding mechanisms. The Density model was used to
extrapolate to higher temperatures, using an average reported reaction enthalpy of 10 kJ/mol.
Since no heat capacity value was available, it was considered a variable in the regression
analysis. The reaction enthalpy of 49 kJ/mol for the formation of the triple ion was adopted
from ab initio calculations, with a linear dependence of log(K) on the inverse temperature,
i.e. zero reaction heat capacity.
The explicit recognition of the four contact ion pairs, i.e. HSO4 , H2SO4, MgSO4 and
2
Mg(SO4)2 required an iterative approach around the ion-interaction framework. Using the
thermodynamic values and extrapolation techniques described above, selecting a minimum
number of adjustable interaction parameters, constraining the system to the available
thermodynamic data and incorporating the experimentally observed lower temperature species
distributions in the regression routine, speciation predictions at higher temperature were made
possible. The binary H2SO4-H2O and MgSO4-H2O systems were first regressed, using the
interaction parameters {(0)HB, (1)HB, BS} and {(0)MS, (1)MS, (2)MS, SC}, respectively. The
neutral acid species, H2SO4, was found to play an insignificant role, even at 1 mol/kg H2SO4
and 200C, which is in line with recent predictions from the literature. Although the pure
MgSO4-H2O system introduces an oversimplified approach to complexities of a mixed system
of various divalent metal sulphates, their thermodynamic values agree to such an extent that
the Mg-surrogate approach could be justified. These values and also very similar overall
equilibrium constant values, reflect the fact that these salts consist predominantly of outersphere complexes at room temperature, i.e. they are dominated by electrostatic forces. The
interaction parameters may be regarded as capturing the long-range electrostatic effects and
the formation of outer-sphere complexes, while the explicit inclusion of equilibrium constants
recognizes the important covalent interactions. The formation of the first contact ion pair,
MgSO4, was found to become more important at higher temperatures (using a regressed and
constant reaction heat capacity of 268 J/mol.K), while the second contact ion pair,
Mg(SO4)22, started to become more prevalent at even higher temperatures (>150C) and at
the expense of the first contact ion pair. The disadvantage of the Mg-prototype approach is
that softer transition metal cations, such as Cu2+, may be expected to form more prominent
first and second contact ion pairs with the sulphate dianion. Since this study was concerned
with trends, rather than exact values, these discrepancies may be absorbed in the kinetic rate
constants when modelling process reactions.
Reliable experimental data was found to be rare for the mixed H2SO4-MgSO4-H2O ternary
system, especially at higher temperatures. Once parameterization have been optimized for the
binary systems, three adjustable mixing parameters were required for the ternary system
(ignoring the role of the two higher-order contact ion pairs), i.e. (0)MB, (1)MB and HMB.
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These parameters were varied linearly with temperature because only one set of data was
available in the dilute range ( 1 mol/kg total sulphate) at higher temperature, i.e. the
solubility of kieserite at 200C. The model was found to behave in a consistent manner, even
beyond the range used in the regression. In conclusion, the following two figures illustrate
typical trends that may be expected. Figure 23 presents the variation in the unassociated
proton fraction (0.2 mol/kg H2SO4) with changing metal sulphate molality. The fraction
unassociated H+ is clearly more sensitive to the total metal sulphate molality at higher
H2SO4:MeSO4 ratios. Put differently, the fraction unassociated H+ is more sensitive to the
total acid at lower total MeSO4 molality.
Figure 24 represents the total fraction metal sulphate contact ion pairs
(MeSO4+Me(SO4)22) with varying acid molality and temperature. Contact ion pair formation
is clearly favoured at higher temperature and lower acid conditions. At low metal sulphate
molalities, the temperature and acid concentration has a relatively smaller effect on the total
fraction contact ion pairs present.
The above model provides a powerful tool that may be used to interpret the kinetics of
reactions occurring in hydrometallurgical processes.
Figure 23. Predicted trends of the fraction unassociated H+ (0.2 mol/kg H2SO4) with varying metal sulphate molality
in the ternary system, H2SO4-MgSO4-H2O, at various temperatures: (a) Surface plot; (b) Contour plots (the dotted
line represents the 150C contour at 0.1 mol/kg H2SO4)
Figure 24. Predicted trends of the total fraction metal sulphate contact ion pairs with varying acid molality in the
ternary system, H2SO4-MgSO4-H2O, at various temperatures: (a) Surface plot at 0.5 mol/kg MgSO4; (b) Contour
plots at varying MgSO4
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Acknowledgements
The author is grateful to Dr. Maggie Burger for helpful discussions on the quantum level
chemistry aspects of this study, whilst Prof. Vladimiros Papangelakis is thanked for his
objective commentary regarding the phenomenological model. Anglo American plc is
acknowledged for financially supporting this work. The author would also like to thank Luke
Ngubane for sourcing the numerous references so efficiently.
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Johann Steyl
Technical Specialist, Anglo Research, South Africa
Johann started his employment at Mintek in 1994, after graduating
from the University of Pretoria with a degree in Chemical
Engineering. He joined Anglo Research in 2001 and is currently
working as technical specialist in the Technology Division. His
research focuses mainly on the development of new processes for the
treatment of ores and concentrates.
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VENTER, R. and BOYLETT, M. The evaluation of various oxidants used in acid leaching of uranium.
The evaluation of various oxidants used in acid

leaching of uranium
R. VENTER* and M. BOYLETT*
*GRD Minproc Pty (Ltd), Bryanston, South Africa
Uranium in the tetravalent state has very low solubility in acid and
alkaline solutions and needs to be oxidized to the hexavalent state to
become soluble. In acid leaching of uranium the uranium is oxidized
by ferric iron, which in turn is reduced to ferrous iron. The reduced
iron needs to be oxidized to the ferric form to allow the uranium
dissolution reaction to proceed.
This paper considers the known and proven oxidants used in acid
leaching of uranium. These include manganese dioxide, sodium
chlorate, hydrogen peroxide, ferric iron, oxygen and sulphur
dioxide/air (oxygen). The reaction chemistry of each oxidant as well
as the practical applications are considered and discussed.
All the oxidants discussed work adequately in acid leaching of
uranium and it is possible to engineer solutions for the use of the
oxidants in acid leaching on plant scale. The availability and supply
of the oxidant as well as the cost and environmental impact of the
oxidant plays a major role in the selection of a suitable oxidant. The
location of the plant will also have an impact on these issues.
Introduction
Dissolution of uranium is the first hydrometallurgical process in the extraction of uranium
from the uranium containing minerals in the ore. Leaching procedures selected for dissolving
uranium are dependant in part on the physical characteristics of the ore such as: type of
uranium mineralization, ease of liberation, and the nature of other constituent minerals
present.
In nature uranium occurs in the tetravalent and hexavalent oxidation states. Tetravalent
uranium has a low solubility in both dilute acid and carbonate (alkali) solutions. To achieve
economic recovery of uranium in the tetravalent state, oxidation to the hexavalent state is
essential. It is therefore important to maintain proper oxidizing conditions during leaching of
these minerals to achieve high uranium extraction.
A number of oxidants have historically been used and are currently used to oxidize
tetravalent uranium to hexavalent uranium in acid and alkaline circuits. When selecting an
oxidant to be used on commercial scale, consideration must be given to a number of factors.
Apart from the effectiveness of the oxidant to maintain an oxidizing environment, the
availability and cost of the oxidant must be considered. Part of this is the logistics of getting
the oxidant to site and administering it to the leach. The latter could introduce a number of
THE EVALUATION OF VARIOUS OXIDANTS USED IN ACID LEACHING OF URANIUM
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engineering challenges to the flowsheet.

This paper considers different oxidants typically used in acid leach uranium circuits,
namely:
Manganese dioxide (MnO2) as milled pyrolusite
Sodium chlorate (NaClO3)
Hydrogen peroxide (addition as H2O2 or Caros acid (H2SO5))
Ferric iron, frequently as roaster calcine from a pyrite burning acid plant
Oxygen in pressure leach circuits and
Sulphur dioxide/air(oxygen) mixture.
The reaction chemistry and application of each oxidant, as well as engineering issues on
plant scale and the availability and logistics are discussed.
Mineralogy
Uranium in typical uranium bearing minerals occur in the tetravalent (U4+) and hexavalent
(U6+) oxidation states. Primary uranium ores are predominantly in veins or pegmatites but are
also found in sedimentary and placer deposits. Primary ores include uraninite and pitchblende
(UO2) (Kinnaird and Nex, 2008).
Secondary uranium ores are found in weathered zones of primary deposits and precipitated
in sediments. These include autinite (Ca(UO 2 ) 2 (PO 4 ) 2 .10H 2 O), torbernite
(Cu(UO 2 ) 2 (PO 4 ) 2 .10H 2 O), uranophane (Ca(UO 2 ) 2 SiO 3 (OH) 2 .5(H 2 O)), carnotite
(K2(UO2)2[VO4]2.3H2O) and schoepite ((UO2)8O2(OH)12.12(H2O)) (Yan and Connely, 2008).
Multiple oxides are complex associations of uranium with rare earths, tin, tantalum, niobium
and titanium with extensive crystal lattice substitutions that makes them extremely refractory.
These include davidite ((La,Ce, Ca)(Y, U)(Ti, Fe3+)20O38), brannerite ((U, Ca, Ce)(Ti, Fe)2O6)
and betafite ((Ca, U)2(Ti, Nb, Ta)2O6(OH)) and are more difficult to process, and products can
pose environmental issues (Yan and Connely, 2008.)
The silicates, uranothorite ((Th, U)SiO4) and coffinite (U(SiO4)1-x(OH)4x), having the zircon
structure, would be expected to be refractory, but in practice readily dissolve in oxidizing acid
or carbonate solutions (Lunt, et. al, 2007.)
Uraninite and coffinite occur in the tetravalent state (Lunt, et al., 2007). In the Southern
African context examples of uraninite are the Witwatersrand ores in South Africa (Ford,
1993) and Rssing in Namibia (Kinnaird and Nex, 2008). Kayelekera in Malawi is an
example of coffinite (Chilumanga, 2008).
Minerals occurring in the hexavalent state typically include carnotite found at Langer
Heinrich and Trekkopje in Namibia (Kinnaird and Nex, 2008). In phosphate deposits uranium
is found in the hexavalent form in the apatite structure. Examples of the phosphate deposits
are Bakouma in the Central African Republic, Florida and other commercial phosphoric acid
producers from which uranium is a possible by-product (Merrit, 1971:22). There are also
minerals described as refractory, such as brannerite, which require more aggressive leach
conditions, but the basic chemistry is unchanged (Yan and Connely, 2008).
Simple chemistry
Uranium is typically recovered in acid circuits using sulphuric acid, or in alkaline circuits
using a sodium carbonate bicarbonate mix. Acid leach is the preferred method, but in cases
where the acid consumption is very high, mostly caused by gangue minerals, it makes more
sense to consider alkaline leach. The selection of acid or alkaline leach is based on a number
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of key process drivers. These are discussed elsewhere (Lunt et al., 2007).
In typical extraction circuits, after dissolution, uranium is usually extracted using strong
base resins and/or alamine 336 in a solvent extraction plant. Solvent extraction is used only
for acid circuits (Lunt et al., 2007). In these circuits the uranium is solubilized in its
hexavalent form. This is true for both acid and alkaline circuits:
Hexavalent uranium dissolves as the UO22+ ion and produces complex uranyl anions:
Uranyl sulphate [UO2(SO4)3]4- and
Uranyl carbonate [UO2(CO3)3]4The focus of this paper is on oxidation in acid circuits and to leave the alkaline circuitry as a
separate issue. A typical uranium acid leach flowsheet can be seen in Figure 1.
The typical flowsheet comprises comminution to reduce the particle size to a size acceptable
to the leach. A pre-concentration step could also be included where the ore is upgraded. The
material is then leached in sulphuric acid at atmospheric or elevated pressure and ambient or
elevated temperature. Leaching is followed by liquid/solids separation in countercurrent
decantation (CCD) thickeners or on belt filters, followed by solvent extraction (or ion
SULPHURIC ACID
AND OXIDANT
WASH WATER
TAILS
TO WASTE
ELUATE
YELLOW CAKE
Figure 1. Typical acid leach flowsheet (Lunt and Holden, 2006)
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exchange or both) and finally product precipitation/recovery. Variations in ion exchange

methodology include fixed bed ion exchange (FIX) and countercurrent ion exchange (CCIX).
An alternative to liquid/solid separation is resin in pulp (RIP) the development of which will
closely parallel the gold CIP designs.
Uranium dissolution chemistry in acid
Tetravalent uranium must be oxidized to the hexavalent form before dissolution occurs in
sulphuric acid. Ferric iron (Fe3+) acts as the principal oxidant of tetravalent uranium in acid
leaching circuits. Iron is generally present, either as a constituent in the ore, or introduced as
metallic iron as a result of wear and abrasion in the grinding circuit. Iron can also be added on
demand.
The mechanism for the dissolution of uranium in sulphuric acid is therefore based on the
following reactions:
The Fe3+ oxidizes the tetravalent uranium (U4+) in the solution to the soluble hexavalent
uranium (U6+). The Fe3+ is then reduced to Fe2+. The oxidant is added to regenerate the Fe2+
to Fe3+ so that the leach reaction can continue. In practice it is found that the Fe3+/Fe2+
mechanism is to be considered more than the uranium reaction. The mechanisms are
described by the following reactions with MnO2 as oxidant (Merritt, 1971:64):
Thus, the Fe3+/Fe2+ couple facilitates the leach process by acting as the electron carrier
during oxidation.
The intention of this paper is to consider various ways of achieving the oxidation of ferrous
to ferric iron in acidic conditions.
Source of iron
Iron needs to be present in the leach solution. If insufficient iron is present it can be added by
adding ferrous or ferric sulphate or adding steel in some form. Iron can also be added via
solution recycle streams from downstream processes.
Oxidants
Following is a discussion of each of the oxidants typically used in acid leaching of uranium.
Manganese dioxide (MnO2)
This is the traditional oxidant used for Witwatersrand ores and elsewhere, e.g. Ranger in
Australia. The oxidation takes place according to the following equation:
From the equation it is clear that each mole of MnO 2 requires 2 moles of acid.
Commercially available pyrolusite typically contains in the order of 30% to 50% MnO2 with
the remainder potentially being acid consuming gangue minerals. These gangue minerals
could also be a source of iron needed for the leach reaction to take place.
Manganese dioxide (as pyrolusite) was the first choice in the Witwatersrand as it was freely
available as surface outcrops near to the mines and cheap sulphuric acid was locally produced
from pyrite in the ore. Vaal Reefs South Uranium Plant operates with this exact flowsheet and
has done so for almost 30 years.
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In the 1950s through to 1990s in excess of 20 Witwatersrand uranium plants used pyrolusite
as oxidant in the leach in preference to the auto oxidation process, which introduced SO2 and
air into the leach to oxidize the ferrous iron to ferric iron, as a result of cheap sources of
pyrolusite being available (Ford, 1993). It is easy to mill and is added as a slurry under redox
control. No special agitation is therefore necessary and the MnO2 does not deactivate or
dissociate in the slurry if it does not react with the iron immediately, as is the case with some
of the other oxidants (e.g hydrogen peroxide).
At Randfontein, Cooke Plant, the nearest supply was from a small pit at the top of the access
road. Today most of this pit is surrounded by housing.
The apparent lack of availability and environmental considerations weigh against the use of
pyrolusite today. South Africa is a major exporter of manganese ores from the Northern and
Eastern Cape and a producer of electrolytic manganese dioxide. All of these products would
be suitable but with increasing distances from site transport costs increase. Outside the
Witwatersrand, for example in Namibia, the most likely source of supply is from Ghana. It is
practical via the port of Walvis Bay, but also expensive.
The environmental aspect involves the production of Mn2+ in solution. In theory this will be
deposited on the slimes dam as the hydroxide. In practice, the pH to achieve this is high and
must be maintained, which equates to high neutralization costs. Pyrite oxidation will lower the
dam pH in the long term, thus soluble manganese may enter water tables and water courses.
This is a greater problem on the Witwatersrand than in Namibia for instance. Namibian ores
are essentially pyrite free and the climate is dryer, compared to the pyrite containing ores in a
wetter climate on the Witwatersrand. The higher pH needed to precipitate the manganese still
holds true for Namibia.
The relatively low MnO2 concentrations in the pyrolusite cause relatively high volumes of
pyrolusite to be shipped to site, which introduces logistical challenges. The acid consuming
gangue minerals in the pyrolusite can also significantly increase acid consumption in the
leach.
Sodium chlorate
Sodium chlorate was traditionally the first choice oxidant in North American uranium plants.
The oxidation reaction takes place according to the following equation:
From the equation it is clear that each mole of sodium chlorate requires 3 moles of acid.
In Southern Africa sodium chlorate was not considered as an oxidant due to availability of
cheaper and more convenient alternatives (i.e. pyrolusite).
Sodium chlorate is added to the leach slurry as a solution. No special agitation is therefore
necessary. During the reaction with sodium chlorate in the leach, chloride ions go into
solution with the possible adverse effects on ion exchange loading and materials of
construction.
Sodium chlorate is expensive. It is also used as oxidant in PGM refining. Partial reduction
leads to intermediate products, such as chlorite and hypochlorite. Sodium chlorate powder has
an auto-ignition risk when in contact with organic. It therefore needs procedures and proper
engineering for safe handling.
Hydrogen peroxide (H2O2)
Hydrogen peroxide was used as oxidant in acid leaching in the nineteen eighties. Lucas et al.
(1983) describe plant trials performed in Queensland where pyrolusite was replaced by Caros
acid as oxidant. De Vries (1984) patented a process that utilizes hydrogen peroxide in an acid
leach of uranium ore.
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Hydrogen peroxide can be used as is or can be made up as Caros acid or

peroxymonosulphuric acid (H2SO5) by mixing with concentrated sulphuric acid according to
the following reaction:
The oxidant regenerates the ferric iron (Fe3+) from ferrous iron (Fe2+). In the case of Caros
acid the reaction is as follows:
In the case of hydrogen peroxide the reaction is as follows:
From these equations it is clear that one mole of acid is consumed for every one mole of
Caros acid or hydrogen peroxide.
Lucas et al. (1983) reported similar uranium extractions to using pyrolusite with a reduction
in acid consumption and oxidant consumption. They also reported a reduction in lime
consumption for neutralization of acid effluent but this could not be fully quantified. Mention
was also made that excluding manganese from the leach liquors should reduce the
neutralization requirement for the manganese and pyrolusite gangue minerals. Test work
performed by GRD Minproc and Mintek supports the reduction in acid and oxidant
consumption.
From the plant trial and other operations the main benefits of using hydrogen peroxide (or
Caros acid) as oxidant were claimed to be:
Better process control
Oxidant savings
Sulphuric acid savings
Lime savings
Cleaner oxidant handling
Simplified effluent treatment.
On the downside, hydrogen peroxide will dissociate if it does not react rapidly with the iron
in solution. The dispersion of the hydrogen peroxide through the slurry is therefore very
important. It is reported that difficulties with dispersion of the hydrogen peroxide in the leach
slurry was experienced during scale-up to plant scale at Rssing and Western Areas (Boylett,
2008). It is also reported that using Caros acid will reduce the hydrogen peroxide
consumption as a result of more efficient use of the hydrogen peroxide (James, 2008).
Hydrogen peroxide can also be used for precipitation of uranium as uranyl peroxide
(UO4.xH2O) instead of the more traditional ammonium diuranate (ADU), which eliminates
the use of ammonia as a precipitation reagent. Uranyl peroxide is also reported to be easier to
thicken and filter or centrifuge and requires only drying and not calcining for dispatch. It is
also reported to produce a purer product. This is the subject of another paper but it is
sufficient to say that this product is the more common end product of an alkaline leach circuit
than from an acid circuit. It is the end product from Langer Heinrich for example. As
hydrogen peroxide becomes more popular for precipitation in acid circuits this might change.
Hydrogen peroxide was often discounted based on its relatively high price. It is very
favourable from an environmental perspective as the reaction chemistry produces only water.
Production of Caros acid was traditionally a challenge as a result of high heat generation by
the reaction between the acid and the hydrogen peroxide. Manufacturers of hydrogen peroxide
claim that they now have simple methods of producing Caros acid for use in the uranium
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leach circuit (James, 2008). It is now made in situ by feeding sulphuric acid and hydrogen
peroxide into a funnel device. The high heat of reaction is immediately dissipated into the
slurry below.
For those gold plants using hydrogen peroxide for cyanide destruction the storage, use and
availability of peroxide is an advantage. The greater use of peroxide by the gold plants
enhances its applicability and availability in remote areas. Hydrogen peroxide is supplied in
large volumes to a number of operations throughout Africa, for instance gold producers in
Ghana. Suppliers maintain that availability and logistics of hydrogen peroxide is not a
problem.
Ferric iron from roaster calcine
Calcine from the roasting of pyrite, which has been treated with concentrated sulphuric acid,
is also used as oxidant in acid leaching of uranium. The resulting slurry is combined with the
return filtrate and contacted with sulphur dioxide in flotation cells. The auto-oxidation
reaction results in the conversion of ferrous iron to ferric iron with the formation of additional
sulphuric acid. The process is described by the following reactions (Ford, 1993):
This process not only produces a concentrated source of ferric iron, but also liberates any
uranium and gold present in the calcine for subsequent recovery.
A number of plants practise milder forms of calcine digestion by adding sulphuric acid to
the calcine slurry in air-agitated pachucas at between 70C and 90C. Pyrolusite is also added
to maximize the concentration of ferric iron. This practice is followed by Rssing and was
followed by Hartebeesfontein uranium plant amongst others.
Oxygen
Uranium ores containing sulphidic minerals can be leached by the addition of oxygen only at
elevated temperature and pressure. The addition of sulphides to ores that do not contain
sulphidic minerals has also been proposed.
Sulphuric acid and ferric sulphate are generated in situ during pressure leaching by the
reaction of oxygen with the sulphides. If pyrite and uraninite are present the following
reactions might be expected:
Pyrite is oxidized to produce soluble iron and acid:
Ferrous iron is oxidized to ferric iron by oxygen:
As the temperature increases above 170C ferric iron is removed from the solution through
iron hydrolysis reactions:
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Jarosite also forms during the hydrolysis reaction as described by the following general
reaction (Guise and Castro). M indicates the cation.
An additional source of dissolved iron is from steel from the crushing and grinding plants:
The following reactions represent the dissolution of uranium:

Tetravalent uranium is oxidized by ferric iron:
The dissolution of tetravalent uranium by oxygen:
Hexavalent uranium will dissolve in the presence of sulphuric acid alone:
Acid consuming gangue, including carbonates, is leached by acid:
These reactions proceed more rapidly to completion at high temperature and with the
increased solubility of oxygen in solution at increased pressure. Temperatures of above 170C
are suggested. Oxygen consumption is in the order of 2 tons of oxygen per ton of sulphur.
Pressure leaching is utilized in the treatment of refractory ores and is performed in
autoclaves at elevated temperature and pressure. Autoclaves were trialled at the Western Deep
Levels plant in the late 70s (Bovey and Stewart, 1978). Acid leaching in autoclaves, based on
these plant trials, were used most recently in the design of the autoclaves for the Dominion
Reefs plant owned by Uranium One.
Indicated advantages of the pressure leaching process include: improved extraction,
decreased operating costs, a decreased amount of impurities and free acid in the leach
solutions and improved slurry filtration properties. Pressure leaching also results in increased
recovery of gold and uranium from the pyrite.
Disadvantages include increased corrosion and maintenance. Another disadvantage is the
production of soluble SiO2 that contaminates resin in ion exchange circuits and forms crud in
solvent extraction circuits.
Sulphur dioxide/air (SO2/air)
It is a well known fact that a mixture of SO2 gas and air acts as an oxidant in hydrometallurgy
(Ho and Quan, 2003). It is used in iron and manganese removal in cobalt circuits, although it
has not been proven commercially yet. It was first suggested by workers in the USA and the
operating conditions and detailed chemistry was determined by the Government Metallurgical
Laboratories (GML) in South Africa in the 1950s (Ford, 1993). It has also been suggested for
use in leaching of uranium in an oxidizing sulphuric acid solution as an alternative to MnO2.
(Ho and Quan, 2007).
In the case of SO2/air mixture as oxidant, oxygen in the air together with the SO2 is
responsible for oxidizing the Fe2+ to Fe3+ according to the following reaction:
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Both oxygen and SO2 are required in solution for the reaction to proceed, but due to the
lower solubility of oxygen compared to SO2/O2 mass transfer limits the maximum reaction
rate. The Fe2+ oxidation rate is controlled by the SO2/O2 ratio and the rate of oxygen mass
transfer. It is independent of Fe2+ concentration.
Higher oxidation rates can be obtained in solutions compared to slurries, as the solids in the
slurries decreases the rate of oxygen transfer. Ho and Quan (2007) focused on producing a
ferric solution that can be added to the leach slurry rather than in situ addition of SO2/air to
the leach.
Earlier work by Ho and Quan used sodium sulphite as the source of SO2; however, at a
metallurgical plant direct sparging of SO2 would be preferred. The measured Fe2+ oxidation
rates using SO2 were very similar when sodium sulphite was used compared to SO2 gas.
Ho and Quan found that the SO2/O2 volumetric ratio plays a major role in the oxidation rate.
At relatively low SO2/air ratios where there is an excess of oxygen in the solution, the reaction
rate is proportional to the SO2 dissolution rate into the solution. However, once the SO2 flow
rate exceeds the maximum rate of oxygen mass transfer, the Fe2+ oxidation rate decreases as a
result of reducing conditions caused by SO2.
The main contributor to the reduced SO2 efficiency is the side reaction of SO2 to produce
sulphuric acid, according to the following reaction:
A SO2/O2 ratio of greater than 0.36 caused the Fe2+ oxidation rate to become variable.
Unlike most of the other oxidants, SO2/air is not an acid consumer.
From a large-scale implementation point of view, SO2/air has a number of challenges. For
slurries dispersion agitation is necessary with more installed and utilized power. If an acid
plant is running on site, SO2 can be sourced from the acid plant. Care must, however, be taken
to ensure that the SO2/air ratio from the burning sulphur is satisfactory, as this gas stream
might have a higher nitrogen content compared to when pure SO2 gas is mixed with air. Any
SO2 escaping from the leach tanks needs to be collected and passed through a scrubbing
system. The relatively low SO2 concentration in the gas stream can also give rise to large gas
flow rates into the leach.
Introduction of the SO2/air mixture into the leach tanks also presents a challenge as it will
probably need to be introduced against high slurry heads. This can influence the partial
pressures of the different gases in the gas mixture. The solubility of SO2 is higher than oxygen
and if the SO2/oxygen ratio in the solution gets too high it will cause reducing conditions and
affect the reaction kinetics.
Oxidizing iron in a solution stream added to the leach will be easier to achieve. Care should,
however, be taken to ensure that sufficient iron is oxidized to the ferric state to oxidize the
uranium.
As far as is known to the authors, at the time of writing this paper, no commercial operation
exist that uses SO2/air as oxidant in acid leaching of uranium.
Conclusion
Traditionally the tendency in Southern Africa was to use pyrolusite as oxidant in acid leach of
uranium. Availability and logistical issues as well as environmental issues seem to be
changing this tendency.
SO2/air has been tested on many occasions and has proved to work satisfactorily; however,
administering the SO2/air gas mixture to the leach on large scale presents a number of
challenges. SO2 is an attractive option if acid is produced on site and if sulphur prices are low.
It also reduces the number of reagents required to be shipped to site.
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Hydrogen peroxide is also an alternative. It has no environmental effects and leads to a

reduction in acid and oxidant consumption compared to pyrolusite. Handling and transport of
hydrogen peroxide, as well as availability, may still be an issue. Hydrogen peroxide might
also become costly compared to the other oxidants.
Sodium chlorate is not really considered as a result of introduction of chlorides into the
system and the adverse effect it has on ion exchange resins and corrosion of materials of
construction. Sodium chlorate also has an explosion risk.
All the oxidants described work adequately in acid leaching of uranium. It is also possible to
engineer solutions to introduce the oxidant into the leach slurry on plant scale. The factors
that play a significant role in selecting a suitable oxidant will include the availability and
supply of the oxidant, the cost of the oxidant and the environmental impact of the oxidant. All
three of these issues will be affected by the location of the plant and possible sources of
oxidant close to the operation.
Acknowledgements
The authors would like to thank the management of GRD Minproc (Pty)Ltd for permission to
publish this paper and to acknowledge the input of their colleagues in undertaking uranium
projects and uranium feasibility studies.
References
BOVEY, H.J. and STEWART, L.N. Pressure Leaching of Uranium Bearing Witwatersrand
Ores, SAIMM, 22 March 1978.
BOYLETT, M. Personal communication. 2008.
CHILUMANGA, P. An Overview of Uranium Mining Development in Malawi,
Implementation of Global Best Practice in Uranium & Processing IAEA HQs
VIENNA. 2008.
DEVRIES, F.W. Hydrogen Peroxide in Sulfuric Acid Extraction of Uranium Ores, United
States Patent 4,425,307, January, 10, 1984.
FORD, M.A. Uranium in South Africa, Journal of the South African Institute of Mining and
Metallurgy, vol. 93, no. 2, 1993. pp. 3758.
GUISE, L. and CASTRO, F. Purification of Sulphuric Acid Solutions from the Leaching of
Nickelliferous Laterites, University of Minho, Department of Mechanical Engineering,
Azurem 4800 Guimaraes - Portugal.
HO, E.M. and QUAN, C.H. Iron(II) Oxidation by SO2/O2 in Uranium Leach Solutions,
ANSTO, Australia. Hydrometallurgy 2003.
HO, E.M. and QUAN, C.H. Iron(II) oxidation by SO2/O2 for use in uranium leaching,
JAMES, A. Sales and Technical Marketing Manager Exports, Solvay SBU H2O2, Email
communication. 2008
KINNAIRD, J.A. and NEX, P. Assessing the Geological Occurrences of Uranium in Africa
Implications for Mining and Processing, Uranium Mining and Exploration Conference,
Johannesburg, March 2008.
LUNT, D., BOSHOFF, P., BOYLETT, M., and EL-ANSARY, Z. Uranium Extraction The Key
Process Drivers, The Southern African Institute of Mining and Metallurgy Namibian
Branch Uranium in Namibia. 2007.
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LUNT, D. and HOLDEN, A. Uranium Extraction The Key Issues for Extraction, ALTA
Uranium Conference, Perth, Western Australia, May 2006,
LUCAS, G.C., FULTON, E.J., VAUTIER, F.E., WATERS, D.J., and RING, R.J. Queensland
Mines Plant Trial with Caros Acid, Proc. Australas. Inst. Min. Metall., 287, September
1983.
MERRITT, R.C. The Extractive Metallurgy of Uranium, Colorado School of Mines. 1971.
YAN, D. and CONNELLY, D. Implications of Mineralogy on Uranium Ore Processing. ALTA
2008 Uranium Conference, Perth, Western Australia, June 2008.
Riaan Venter
Senior Process Engineer, GRD Minproc, South Africa
Riaan has 10 years of metallurgical and process control experience in
the minerals processing industry. His experience includes various
positions at Anglo Platinum where he started his career in 1998 where
he gained production and technical experience on precious metals
refining, and research, design and optimization experience on various
concentrator plants, smelters and refineries. He moved to GRD
Minproc in 2007 as a senior process engineer and has been involved in
projects and feasibility studies for platinum, gold and uranium extraction facilities as well as
techno economical evaluations of projects. Riaan is registered as a Professional Engineer at
ECSA.
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BAZHKO, O. Application of redox titration techniques for analysis of hydrometallurgical solutions.

Application of redox titration techniques for

analysis of hydrometallurgical solutions
O. BAZHKO
Mintek, South Africa
Regular analysis of different streams is important for the control of

hydrometallurgical processes. Various physical and physical-chemical
methods are applied for this purpose. Many modern methods require
costly equipment and are subject to interferences. Therefore, redox
titration methods remain of interest. The use of different types of
oxidizing and reducing agents as well as redox indicators enables
many cations and anions to be rapidly and accurately analysed.
Sometimes redox titrations require the prior preparation and addition
of masking agents. Selective, sensitive and low-cost methods of redox
titration of copper and SO2 in plant conditions are described.
Introduction
Hydrometallurgical processes involve the removal of metals from different types of ores,
concentrates, and waste products by aqueous solutions containing different chemical reagents.
Processes include a number of sequential steps such as ore preparation, leaching,
precipitation, extraction, ion exchange, cementation and electrodeposition. Successful
realization of metal recovery requires accurate analyses of feedstock composition,
intermediate and auxiliary solutions, and final products. Effective analytical methods provide
the opportunity to manage and improve a process.
The main problems of analysis in hydrometallurgical processes are associated with the
complicated compositions of solutions. Raw materials usually contain many components and
can include base metals such as Fe, Co, Ni, Cu, Cr, Mn, Al, Pt and U groups of metals, and
rare-earth metals. These metals as a rule are in the form of different salts or oxides. After the
leaching process the solutions also contain an excess of leaching reagent. The most commonly
used leaching agents are sulphuric acid (Cu, Zn), sodium carbonate (U, V, Mo, W), sodium
hydroxide (W), ammonia (Cu, Ni), cyanide and thiosulphate (Au, Ag), sulphite (Sb, Hg),
chlorine and chloride (platinum group metals and rare-earth metals).
Selection of an appropriate method of analysis is based on criteria such as accuracy,
precision, sensitivity, urgency for results, costs per analysis, number of samples to be
analysed, amount of sample available, and avoidance of chemical and physical interferences1.
This paper summarizes methods used to analyse hydrometallurgical solutions, with titration
methods receiving particular attention.
APPLICATION OF REDOX TITRATION TECHNIQUES
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Physical and physical-chemical methods

At present different physical and physical-chemical analytical methods are widely applied in
hydrometallurgy. These include various spectral techniques based on the absorption, emission,
or scattering of electromagnetic radiation. Atomic absorption spectroscopy (AAS) with flame
and atomization, atomic emission spectroscopy (AES), inductively coupled plasma-mass
spectroscopy (ICP-MS), and X-ray fluorescence analysis (XRF) can be considered the most
sensitive detection methods for about 30 elements. Important characteristics of spectral
techniques are the short time of analytical signal registration, low detection limit, and wide
calibration ranges, which give the advantage of minimal sample preparation2. Along with
these complicated methods, photometry and spectrophotometry are effectively and widely
used by analysts. There are many selective organic and inorganic reagents that form the
coloured substances that absorb light in visible or ultraviolet regions and provide the
opportunity to determine almost all elements of the Periodic system.38 Electrochemical
methods such as voltamperometry, coulometry, and potentiometry are also used in
hydrometallurgy for analysis, but generally for single-component samples.911
Titration methods
In spite of intensive development of physical-chemical methods, titration has not lost its
importance for chemical analysis. This method of analysis is easy to use and fast. Titration
does not require complicated and expensive devices or equipment and is based on selective
reactions. It is usually used to determine medium and high concentrations of elements.
Furthermore, titration gives reliable results even in field conditions.
One of the titration methods used in hydrometallurgy is an oxidation-reduction (redox)
titration. Redox titrimetry is used to analyse a wide range of inorganic analytes. Although
many of these methods have been replaced by newer ones, a few of them continue to be listed
as standard methods of analysis.
Redox titrimetry is based on a redox reaction between the analyte and titrant. The oxidizing
and reducing agents most commonly used in hydrometallurgy12, 13 are shown in Table I.
In some cases samples require preparation before the titration. Sometimes substances
analysed by titration with an oxidizing agent must be converted into a reduced state with
auxiliary reducing agents. There are several ways to prereduce an analyte quantitatively.
Reductors could be used: a Jones reductor is a column filled with granular Zn coated with a
Zn(Hg) amalgam14, 15, and a Valden reductor contains spongy, granular Ag coated with HCl.
In other cases preoxidation is necessary. For ferric reduction to ferrous, the treatment with
stannous chloride, and the addition of HgCl2 to destroy any excess of SnCl2 are often used. To
transform a substance into an oxidized state, auxiliary oxidizing agents are used, for example,
ammonium peroxydisulfate and hydrogen peroxide. These reagents are capable of oxidizing
2
Mn2+ to MnO4 , Cr3+ to Cr2O7 , and Ce3+ to Ce4+. Any excess of auxiliary oxidizing agents is
easily destroyed by a short boiling of the solution.
There are several methods to find the end point in redox titrimetry. A few titrants, such as
permanganate, have oxidized and reduced forms whose colours in solution are significantly
different, and it is not necessary to use any indicator. Specific indicators are substances that
indicate the presence of oxidized or reduced species. For example, starch forms a dark blue
complex with iodide; thiocyanate forms a red complex with ferric. The most important class
of redox indicators are substances that may be reversibly oxidized and reduced, and change
the colour upon oxidation or reduction. Redox indicators impart a colour that depends on the
solutions electrochemical potential. A list of general redox indicators16, 17 is shown in
Table II.
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Table I
Common oxidizing and reducing agents
Agent
Redox half-reaction
Standard reduction
potential (v)
Ions that can be determined
+ 1.7
As (III), Cu (I), Fe (II), V (IV), Mo (V),

Ti (III), U (IV)
+1.49
Fe (II), Sb (III), Mn (II), V (IV), W (V),

U (IV), Tl (I), Cr (III), H2O2, (indirect
determination Cr (II), V (II), Ti (III),
Nb (III), Mo (III), Cu (I), Sn (II),
Ca (II), Cd (II), Zn (II), Pb (Il),
(II), Ni (II))
+ 1.42
As (III), Sb (III), Fe (II)
+ 1.33
Fe (II), As (III), Cu (I), U (IV),

Sn (II), Te (IV), W (III), Mo (III),
2Ti (III), V (IV), SO3 , Ag (I),
Ba (II), Pb(II)
+ 0.994
Fe (II), As (III), Hg (I), T1 (I), Sn (II),

Sb (III), Ti (III), V (III), Mo (III, V),
2W (V), U (IV), SO3
Oxidizing agents
2-
Cerium IV Ce4+ IV
Ce(ClO4)6 + e- =
Ce3+ + 6 ClO4
-
Permanganate MnO4
Bromate BrO3
MnO4 + 8 H + 5 e =
2+
Mn + 4 H2O
BrO3 + 6 H + 6 e = Br + 3 H2O
2-
Dichromate Cr2O7
2-
Cr2O7 + 14 H + 6 e =
3+
2 Cr + 7 H2O
Vanadate VO3
2+
3+
2+
+ 0.771
Cu (I), U (IV), Sn (II), U (IV)
+ 0.521
As (III), Sn (II), SO3 , Sb (III)
2+
+ 0.771
VO3 , Cr2O7 , MnO4 , MnO2
+0.521
Fe (III), Cu (II) ), Cr2O7
VO2 + 2 H + e = VO + H2O
Ferric Fe3+
Fe + e = Fe
Iodine I2
I2 + 2 e = 2 I
2-
Reducing agents
3+
Ferrous Fe2+
Fe + e = Fe
Iodide I
I2 + 2 e = 2 I
Ascorbic acid C6H606
3 C6H606 + 6 H + 6e = 3 C6H8O8
4+
Stannous Sn2+
2+
2-
2-
2-
2-
3-
+ 0.185
VO3 , CrO4 , MnO4 , AsO4 ,

Ce (IV), Sn (IV), Ag (I), Hg (II),
PbO2, MnO2
-
2-
2+
+ 0.15
Cu (II), Fe (III), VO3 , Cr2O7 , MnO4
3+
+ 0.1
Cu (II), Fe (III), Sb (V), Cr2O7 ,

MoO4
+ 0.09
Cu (II), Fe (III), VO3 , Sb (V),

2Cr2O7 , MnO4 , MnO2
TiO + 2 H + e = Ti + H2O
Thiosulphate S2O3
2-
Sn + 2 e = Sn
Titanium III Ti3+
2-
S4O6 + 2 e = 2 S2O3
2-
Another method for locating the end point of a redox titration is the potentiometric method.
It is based on the use of an appropriate electrode to monitor the change in electrochemical
potential as titrant is added to a solution of analyte. The end point can then be found from a
visual inspection of the titration curve.1
While selecting the method for analysis it is necessary to estimate the composition of
analytes and possible chemical interferences that can cause erroneous analytical results.
Unfortunately, analytical methods are rarely selective toward a single species. Different
separation techniques such as precipitation, extraction, or chromatography can be used to
remove either the analyte or the interferent from the sample matrix. A simpler variant that
analytical chemists use to reduce matrix effects to either a negligible or a minimal magnitude
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Table II
Redox indicators
Indicator
Transition
potential (v)
Colour of Ox
form
Colour of red
form
N-phenylantranilic acid (2-carboxy-diphenylamine)
+ 1.08
purple
colorless
Ferroin (tris-(1,10-phenanthroline) iron (II) sulphate)
+ 1.06
cyan
red
o-Dianizidine (5,3 '-dimethoxybenzidine)
+ 0.85
red
colourless
Sodium diphenylamine sulfonate
+ 0.84
red-violet
colourless
Diphenilamine
+ 0.76
violet
colourless
Diphenylbenzidine
+ 0.76
violet
colourless
3,3'-Ddimethylnaphtidine
(3,3'-(dimethyl-4,4'-diamino-1, 1 '-dinaphthyl))
+ 0.7
purple red
colourless
Variamine blue (4-amino-4 '-methoxy-diphenylamine)
+ 0.575
violet blue
colourless
Nitroferroin (tris(5-nitro-1, l0-phenanthroline) iron (II) sulphate)
+ 1.25
cyan
red
5,6-Dimhethylferroin
(tris-(5, 6-dimethyl-1, I 0-phenanthroline) iron(II) sulphate)
+ 0.97
yellow-green
red
Sodium o-Cresol indophenol
+ 0.62 (pH =0)

+ 0.19 (pH =7)
blue
colourless
Methylene blue
(Bis-3,9-dimethylamino phenazothionium chloride)
+ 0.53 (pH =0)

+ 0.01 (pH =7)
blue
colourless
Thionine (diaminophenathiozine)
+ 0.56 (pH =0)

+ 0.06 (pH =7)
violet
colourless
Indigocarmine (indigodisulfonic acid)
+ 0.29 (pH =0)

- 0.13 (pH =7)
blue
colourless
Phenosafranin
+ 0.28 (pH =0)

- 0.25 (pH =7)
red
colourless
Safranin T
+ 0.24 (pH =0)

- 0.29 (pH =7)
red-violet
colourless
Neutral red
+ 0.24 (pH =0)

- 0.33 (pH =7)
red
colourless
pH independent indicators
pH dependent indicators
is masking. Masking is technically not a separation technique because the analyte and
interferent are never physically separated from each other. The masking agent binds the
interferent as a soluble complex or changes the oxidation number of the interferent,
preventing it from affecting determination of the analyte. A wide variety of ions and
molecules are used as masking agents (Table III).
Titration methods of Cu and SO2 in hydrometallurgical solutions
One of the most important applications of redox titration in hydrometallurgy is a
determination for copper. Various redox titration methods have been developed for copper
analysis including iodometry, chromatometry, cerimetry, mercurometry, or
permanganatometry.18 For analysis of copper electrowinning solutions an iodometric titration
of copper is used.
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Table III
Masking agents
Masking agent
Ions that can be masked
Cyanide CN
Fe (II), Fe (III), Co (II), Ni (II), Cd (II), Zn (II), Hg (II), Ag (I), Au (III), Pt (II), Pd (II)
Fluoride F
Al (III), Fe (III), Mg (II), Ca (II), Sr (II), Ba (II), Ti (IV), Cr (III)

3-
2+
Phosphate PO4
Fe (III), UO2
2-
Thiosulphate S2O3
Ag (I), Fe (III), Pb (II), Cu (II), Au (III), Pt (II), Pd (II), Hg (II), Cd (II)
Hydroxylamine NH2OH
Fe (III), Co (II), As (V), Sb (V)
Thiourea CS(NH2)2
Fe (III), Hg (II), Cd (II), Ag (I), Sb (III)

2-
EDTA (CH2N)2(COOH)2(COO)2
2-
Citrate (CH2)2C(OH)(COO)3
2-
Tartrate (CHOH)2(COO)2
Fe (III), Cu (II), Co (II), Ni (II), Cd (II), Zn (II), Mg (II), Mn (II)

Ag (I), Fe (III), Sb (III), Cu (II), Hg (II), Cd (II)
Fe (III), Al (III), Cu (II), Hg (II), Cd (II), Pb (II), Zn (II)
Ascorbic acid C6H606
Fe (III), Sn (IV)
The iodometric determination of copper is a type of displacement redox titration. Cu2+ reacts
with an excess of potassium iodide in an acid medium:
[1]
The reaction is accompanied by the liberation of a stoichiometric amount of iodine. A large
excess of potassium iodide is also necessary to minimize the losses of iodine by evaporation
from the solution. Free iodine is not lost in the presence of excess KI, due to the formation of
I3 ion:
[2]
Once the reaction is complete the iodine produced is titrated with sodium thiosulfate:
[3]
The end point of the iodine titration with thiosulfate is indicated by the colour change of the
starch indicator. The amount of standard sodium thiosulphate solution required to titrate the
liberated iodine is equivalent to the amount of copper.
2Ions that reduce iodide such as Fe3+, As (V), and Sb (V), or oxidize iodine such as Cr2O7 ,
As (III), and Sb (III) can exert an influence on the copper determination. Pb and Bi form
coloured substances with iodide and create difficulty for titration; they must be masked or
removed. Since iron forms stable fluoride complexes, Fe 3+ can be masked by sodium,
ammonium or potassium fluoride. As (V) and Sb (V) react with iodide only in strong acid
media.
The samples that are usually analysed at Mintek originate from hydrometallurgical
processes and contain not only Cu but Fe (II), Fe (III), Co (II), Ni (II), Zn, (II), Mn (II), and
Cr (III). Thus, addition of fluoride only is sufficient for accurate copper determination. The
procedure for analysis includes the following steps:
NaF is added for ferric masking
an excess of KI is added and the mixture is shaken. After about 10 minutes the solution
becomes deep-brown and contains solids
the mixture is titrated with the standard thiosulfate solution until the slurry has a light
yellow tint. At this step, 1 ml of starch indicator is added and titration must be continued
until the mixture in the flask turns white.
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The use of this method for real solutions provided good results. Moreover, titrations were
performed on plant samples, quickly, without additional capital inputs for equipment.
Sulphur dioxide and sulphites are often used in hydrometallurgy as reducing agents for
metal recoveries.19, 20 Their concentrations can be determined by oxidizing titrations, but if
the analyte contains other reducing agents interferences occur. Our objective was to analyse
samples that contained both sulphite and ferrous ions. In this case we determined sulphite by
indirect titration.
2In the first step the amount of Fe 2+ and SO 2 (SO 3 ) can be determined by a
dichromatometric method, which is based on reactions:
[4]
[5]
The titration is performed in an acid medium (the addition of sulphuric acid). Phosphoric
acid is added to mask ferric ions. Diphenylamine is used as a reversible oxidation-reduction
indicator.
In the second step the amount of iron (III) is determined by titration with EDTA. Iron (III)
forms with EDTA stable complex at pH value of 2 or lower. Other base metals do not react
with ADTA at low pH. Sulphosalicylic acid is used as indicator for titration of iron (III).
And in the third step the amount of iron (II) and iron (III) is determined by titration with
EDTA after oxidizing Fe2+ with hydrogen peroxide and decomposing of peroxide excess by
heating. The concentration of sulphite ions is calculated by subtracting the results of the
second and third steps from the result of the first titration.
This method of redox titration was applied successfully for analysis of the solution after the
SO2 leaching of an ore.
References
1. HARVEY, D. Modern analytical chemistry, 2000. 798 pp.
2. International conference ANALYTICAL CHEMISTRY AND CHEMICAL ANALYSIS
(AC&CA-05), devoted to 100 anniversary of Anatoly Babko / Book of abstracts: Kyiv Ukraine. September 1218, 2005, 480 p.
3. MAKSIMOVA, I.M., KOROLEV, D.N., MOROSANOVA, E.I., and YU, A. Zolotov
Photometric determination of metal ions in continuous-flow systems in the presence of a
surfactant J. Analyt. Chem., vol. 50, no. 9, 1995. pp. 842845.
4. SAMCHUK, A.I. and PILIPENKO, A.T. Analytical chemistry of minerals, Utrecht, The
Netherlands. VNU Science Press, 1987.
5. BULATOV, M.I. and KALINKIN, P.I. Textbook for photocolorimetric and
spectrophotometric methods of analysis. Leningrad, Ghemistry, 1976. 376 pp. (Russian).
6. PESHKOVA, V.M. and GROMOVA, M.I. Methods of absorption spectroscopy in
analytical chemistry, 1976 (Russian).
7. BARKOVSKY, V.F. and GANOPOLSKY, V.I. Differential spectrophotometric analysis,
1969 (Russian).
8. MARCHENKO, Z. Photometrical determination of elements. M.:Mir, 1971 (Russian)
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9. BARD, A.J. and FAULKNER, L.R. Electrochemical methods such as voltamperometry,

coulometry, potentiometry are also used for purpose of analysis in hydrometallurgy but
often for single component samples. Electrochemical Methods. Wiley: New York, 1980.
10. GARCIA-ARMADA, P., LOSADA, J., and DE VICENTE-PEREZ, S. Cation Analysis
Scheme by Differential Pulse Polarography, J.Chem. Educ., 1996, vol. 73, pp. 544547.
11. EVANS, A. Potentiometry and Ion-Selective Electrodes. Wiley: New York, 1987.
12. KOROSTELEV, P., BERKA, A., VULTERIN, J., and ZYKA, J. New redox methods in
analytical chemistry. 1968, p. 13758. (Russian)
13. LAYTINEN, G.A. and HARRIS, V.E. Chemical analysis. 1979.
14. NOROOZIFAR, M. and KHORASANI-MOTLAGH, M. The Application of the SolidPhase Jones Reagent as a Reductant in the Speciation Flow Injection Analysis of Fe(III)
and Fe(II) in Real Samples. Chem. Anal., Warsaw, vol. 49, 2004. 929 pp.
15. MORAIS, C.A. and CIMINELLI, V.S.T. Recovery of europium from a rare earth
chloride solution, Hydrometallurgy, vol. 49, no. 12, June 1998, pp. 167177.
16. HULANSKY, A. and GLAB, S. Redox indicators. Characteristics and applications. Pure
& Appl. Chem., vol. 50, 1978. p. 463498.
17. LURIE, U.U. Handbook for analytical chemistry. Chemistry. 1971. 456 p. (Russian)
18. KOROSTELEV, P.P. Titrimetric and gravimetric analysis in metallurgy. Handbook.
Moscow. 1985. 320 p. (Russian)
19. DAS, G.K., ANAND, S., DAS, R.P., MUIR, D., and SINGH, P. Sulfur dioxidea
leachant for oxidic materials in aqueous and non-aqueous media. Mineral Processing and
Extractive Metallurgy Review, vol. 20, no. 46, 2000.
20. NAIK, P. and SUKLA, L.B. Aqueous SO2 leaching studies on Nishikhal manganese ore
through factorial experiment. Hydrometallurgy, vol. 54, no. 23, Feb. 2000.
Volha (Olga) Bazhko

Post-doctoral fellow, Mintek, South Africa
20032007: Analytical Chemistry Department of Chemical Faculty,
Belarusian State University, Republic of Belarus, teaching staff.
Research in the field of sorption and ion-exchange, synthesis and
investigation of immobilized sorbents, developing of quick analytical
methods, investigation of environmental behaviour of metals and other
toxicants. Presently: Hydrometallurgy division, Mintek, South Africa,
Post-doctoral fellow. Developing of titrimetric, spectrophorometric and atomic absorption
methods for the determination of base and noble metals, uranium and other components in
the hydrometallurgical streams.
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MASIYA, T.T. and GUDYANGA, F.P. Investigation of granular activated carbon from peach stones for gold
adsorption in acidic thiourea. Hydrometallurgy Conference 2009, The Southern African Institute of Mining and
Metallurgy, 2009.
Investigation of granular activated carbon from

peach stones for gold adsorption in acidic thiourea
T.T. MASIYA* and F.P. GUDYANGA
*Institute of Mining Research, University of Zimbabwe, Zimbabwe
Department of Metallurgy, University of Zimbabwe, Zimbabwe
This paper reports on an investigation into the effectiveness of using

granular activated carbon produced from peach stones, an agricultural
waste, for the adsorption of gold from acidified thiourea solutions. In
this work the activated carbon was produced by chemical activation
of the peach stones with either phosphoric acid or zinc chloride. The
effects of several parameters on the adsorption kinetics and equilibra
were examined. Gold adsorption was found to depend significantly
on: solution pH, rate of stirring, activated carbon dosage, carbon
particle size, and the initial concentration of gold and thiourea. The
adsorption equilibrium experimental data fitted well both the
Langmuir and Freundlich isotherm models with high correlation
coefficient. The adsorption capacity calculated from the Langmuir
isotherm was 31.2 mg Au/g for phosphoric activated peach stones and
69.0 mg Au/g for zinc chloride activated peach stones.
Introduction
The ability of activated carbon to adsorb dissolved metal species has been known for a
considerable time. It has found increasing application, especially in the mining industry, as an
adsorbent for the extraction of gold from leached solutions (Petersen and van Deventer, 1994;
Hurter, 1986). The adsorption of gold cyanide onto activated carbon, especially of coconut
shell origin, has been studied extensively and is well known (Yapu et al., 1994; Van Deventer
and Van der Merwe, 1993; Marsden and House, 1992; Adams and Fleming, 1989). Activated
carbon has also been used for gold recovery from non-cyanide solutions (Haque, 1989).
Lignite and activated bagasse were successfully assessed for adsorption of gold from acidic
thiourea solutions (Syna and Valix, 2003; Zouboulis et al., 1994).
It is of both technological and economic interests to examine the potential of activated peach
stones for the adsorption of gold species from acidic thiourea solutions. Peach stones are
agricultural by-products that are currently of no economic value, and have a hard
lignocellulosic material shell that gives them the potential to be used as raw materials for
production of granular activated carbon. In Zimbabwe more than 90% of the activated carbon
used by the mineral industry is imported at a very high cost (Thixton, 1998).
INVESTIGATION OF GRANULAR ACTIVATED CARBON FROM PEACH STONES
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The peach stones used for this study were activated chemically by phosphoric acid and zinc
chloride. The effect of different process conditions such as pH, particle size, carbon dosage,
stirring speed, initial gold and thiourea concentration on per cent gold recovery was
investigated to ascertain the mechanism for adsorption.
Experimental
The activated carbon particles used in this study were manufactured from peach stones by
chemical activation with either phosphoric acid or zinc chloride. Except where stated
otherwise, the activated carbons in the size range -1.0 +0.5 mm were used for the
investigations.
ZnCl2 activation
3.3 g of ZnCl2 was dissolved in 100 ml distilled water. 100 g of the raw peach stones were
then soaked in this solution for 24 hours. At the end of this time, the solution was filtered and
the impregnated peach stones were dried in an oven overnight at 105C after which they were
activated at 700C for 2 hours in a muffle furnace. The sample was then removed from the
furnace, allowed to cool and then washed in hot HCl solution and rinsed in distilled water
until the wash water was almost neutral.
H3PO4 activation
The raw peach stones were impregnated with 43 wt% H3PO4 for 24 hours in the weight
ratio 1:1 (peach stones: H3PO4), followed by drying in an oven overnight at 105C. The dried
sample was then activated in a muffle furnace at 300C for 1 hour. The sample was allowed to
cool and subsequently washed first in hot NaOH solution followed by a series of soaking and
decanting in hot distilled water until there were no traces of phosphates (identified by adding
a few drops of Pb(NO3)2 into the wash water, which turns to a white precipitate in the
presence of phosphates).
Equilibrium adsorption studies
Equilibrium data was collected by taking 200 ml solution of known gold concentration into a
series of 500 ml containers. To each container, different activated carbon dosages (0.05 to 2.0
g) were added. Prior to their use activated carbon samples were washed thoroughly with water
until most of the fines were removed, and then dried at 105C in an oven for 24 hours. The
containers were sealed and bottle rolled for 72 hours until equilibrium was assumed to have
been reached. The solutions were filtered and the filtrates were analysed for residual gold
concentration using the Spectra Atomic Absorption Spectrometer (AAS).
Batch kinetic adsorption studies
The kinetic adsorption studies were carried out by stirring between 0.25 g and 1.0 g of
activated carbon with 300 ml acidified aqueous gold-thiourea solution of desired initial
concentration in a series of 800 ml Duran beakers on a magnetic stirrer (HeIdolph type) with
an adjustable stirring speed. Temperature was maintained at room temperature during the
investigations. Aliquots of 10 ml were withdrawn regularly (after 15, 30, 45, 60, 90, 120, 180
and 240 minutes) and filtered through a filter paper. Filtrates were analysed for residual gold
concentration using an atomic absorption spectrometer (AAS).
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Effect of pH on gold adsorption
Gold adsorption on peach granular activated carbon and commercial granular activated carbon
as a function of initial pH was studied for the pH range 1 to 12, and the results are shown in
Figure 1. In the pH range 1.4 to 4 the per cent gold recovery initially decreases for both
activated carbons as the initial pH is increased. As solution pH is increased above pH 4.1 a
sharp increase in gold recovery is observed, especially with activated peach stones. This is
attributed to the fact that beyond pH 5, thiourea is known to decompose to sulphur and
cyanamide through an intermediate product, formamidine disulphide.
[1]
Zouboulis et al. (1994) attributed this observed increase in gold recovery in the alkaline
range to increased adsorption capacity by the finely divided elemental sulphur formed.
Figure 2 presents the effect of initial pH value on the kinetics of gold adsorption from
thiourea solutions. The gold adsorption kinetic is faster at lower initial pH than at higher
initial pH values. The adsorption of metal ions depends on solution pH, which influences
electrostatic binding of ions on the activated carbon to corresponding metal groups in
solutions (Ahalya et al., 2005).
Effect of activated carbon particle size on gold adsorption
Figure 3 presents gold adsorption behavior of -0.150 mm peach activated carbon particles as a
function of contact time in comparison with that of the fraction -1.0 +0.5 mm of the same
activated carbon. As is expected, the smaller the size of granules, the faster the rate of
adsorption of gold by the activated carbon. Smaller particle size, for the same mass of
activated carbon, enhances gold adsorption (Yannopoulos, 1990). This is attributed to increase
in surface area for adsorption and reduced mean pore length through which gold species travel
within the activated carbon particles as particle size decreases. The ultimate carbon loading
Figure 1. Effect of initial solution pH on equilibrium gold adsorption on peach granular activated carbon (PGAC)
and commercial granular activated carbon (CGAC) from thiourea solutions (initial solution concentration = 7.5 mg
Au/L; solution volume = 200 ml; carbon dosage = 0.2 g)
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Figure 2. Effect of initial pH on the rate of gold adsorption from acidic thiourea solutions (initial solution volume =
300 ml, carbon dosage = 0.5g, initial gold content = 10.5 mg/L)
Figure 3. The effect of activated carbon size on rate of gold adsorption from thiourea solutions
Figure 4. Variation of gold recovery with time for different stirring speeds (initial solution volume = 300 ml; initial
gold content = 5.0 mg/L; pH = 1.7; carbon dosage = 0.5 g)
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capacity, however, is virtually independent of particle size (Marsden and House, 1992).
However, the use of fine activated carbon is not recommended, especially in carbon-in-pulp
plants as it will result in higher gold losses via the carbon fines.
Effect of stirring speed on kinetic adsorption of gold from thiourea solutions
The effect of stirring (Figure 4) of the adsorbent/adsorbate system in acidic gold thiourea
solutions was investigated for cases where agitation resulted in activated carbon being fully
suspended in the gold solutions (i.e. between 200 and 400 rpm). Below 200 rpm it was
observed that some of the carbon remained on the base of the beaker and at 500 rpm the
magnetic follower became unstable. The observed increase in rate of adsorption of gold with
stirring speed in the range 200 to 400 rpm is attributed to the improvement in contact between
the gold species in solution and the active sites on the carbons, thereby promoting effective
transfer of adsorbate ions to the adsorbent site.
Effect of initial gold concentration on equilibrium adsorption
The equilibrium removal of gold from solution decreases as the initial gold concentration of
the solution is increased for both carbon dosages investigated (see Figure 5).
This is because at lower concentration, the ratio of the initial moles of gold species to the
available surface area is low and subsequently the fractional adsorption becomes independent
of initial concentration. However, at higher concentration the available sites for adsorption
become fewer compared to the moles of gold species present and hence the percentage
removal of gold is dependent upon the initial gold concentration, i.e. there is increased
competition among gold species for the available active sites on the carbon surface. For the
same initial gold concentration there is an increase in per cent gold removal as the carbon
dosage is increased from 0.25 g to 0.5 g. This is because there was an increase in number of
available active adsorption sites for the same number of moles of gold species as carbon
dosage was increased
Figure 6 shows the variation of the actual amount of gold adsorbed per gramme of activated
carbon with time. An increase in the initial gold concentration leads to an increase in the
adsorption capacity of gold on activated carbon. This indicates that the initial gold
concentration plays an important role in the adsorption capacity of gold on activated carbon.
Figure 5. Effect of initial gold concentration on equilibrium gold recovery for two different initial activated peach
carbons concentrations (bottle rolled; solution volume = 200 ml; contact time = 5 hours; pH = 1.7)
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Figure 6. Variation of amount of gold adsorbed as a function of time for two different initial gold concentrations
(initial solution volume = 300 ml; carbon dosage = 0.5 g; pH = 1.7)
Figure 7. Effect of initial thiourea concentration on gold recovery (bottle rolled: initial gold concentration = 4 mg /L;
solution volume = 200 ml; carbon dosage = 0.25 g and 0.5 g; contact time = 5 hours; pH = 1.8)
Effect of initial thiourea concentration on gold recovery

The effect of the amount of free excess thiourea concentration on equilibrium gold-thiourea
complex adsorption on activated peach stones was examined and the results are presented in
Figure 7.
The loading capacity for gold on activated carbon was found to decrease as the amount of
free excess thiourea concentration was increased. Thiourea concentration is an important
parameter when considering the adsorption of gold from thiourea solutions on activated
carbon. Thiourea is an organic molecule that has a high tendency to adsorb on activated
carbon. When there is not enough carbon, or the number of surface active sites is not
sufficient for adsorbing both gold-thiourea complexes and free thiourea, then thiourea will be
loaded preferentially over gold, and gold adsorption will be suppressed (Petersen and van
Deventer, 1994; Zouboulis et. al., 1994).
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However, when there is excess activated carbon, or the number of surface active sites
exceeds the total number of molecules to be adsorbed, then free thiourea does not interfere
with adsorption of gold-thiourea complexes.
Deschenes and Ghali (1988) explained this decline in gold adsorbed differently. They
attributed it to the fact that thiourea is less stable at high concentrations and decomposes to
cyanamide and elemental sulphur. Similar observations were also reported by Amer (2002).
They believed that the elemental sulphur formed blocks on some of the macropores on the
carbon, resulting in gold species being blocked from reaching the micropores.
Adsorption isotherm equilibria
To quantify the adsorption capacity of activated peach stones for removal of gold from acidic
thiourea solutions, the adsorption isotherm data was evaluated using the Langmuir and
Freundlich adsorption isotherms.
The basic assumption of the Langmuir adsorption process is the formation of a monolayer of
adsorbate on the outer surface of the adsorbent and after that no further adsorption takes place.
A linear form of the Langmuir equation is given by:
[2]
where Qe is the equilibrium quantity of gold adsorbed on activated carbon (mg/g), Qm the
maximum monolayer adsorption, KL the langmuir equilibrium constant for the adsorption
reaction (L/mg) and Ce the equilibrium gold concentration in the solution (mg/L).
A linear plot of 1/Qe versus 1/Ce was employed to give the values of Qm and KL from the
intercept and slope of the plot (Figure 8).
The Freundlich adsorption isotherm, on the other hand, is an indicator of the extent of
heterogeneity of the adsorbent surface. A linear form of the isotherm is given by:
Figure 8. Comparison of the Langmuir isotherms for ZnCl2 and H3PO4 granular activated peach carbons (GAC) and
commercial activated carbons (CGAC) (bottle rolled for 72 hours; pH = 1.8; initial gold solution = 11.5 mg/L)
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Figure 9. Comparison of the Freundlich isotherms for ZnCl2 and H3PO4 granular activated peach carbons (GAC)
and commercial activated carbons (CGAC) (bottle rolled for 72hours; pH = 1.8; initial gold solution = 11.5 mg/L)
Table I
Adsorption isotherm constants for chemically activated peach and commercially activated carbons
Langmuir constants
KL (L/mg)
H3PO4 GAC
ZnCl2 GAC
C.GAC
15.3
48.3
63.0
Qm (mg/g)
31.2
69.0
158.7
Isotherm
Freundlich isotherm constants
R2
KF (mg/g)
R2
0.9802
0.9033
0.9758
26.5
110.6
203.4
3.8
3.0
3.9
0.9067
0.9938
0.9696
[3]
where KF and n are the Freundlich constants and represent the significance of adsorption
capacity and intensity of adsorption, respectively.
Values of KF and n are calculated from the intercept and slope of the plot log Qe versus log
Ce (Figure 9), which is a straight line.
The constants for the two isotherms, as calculated from the plots in Figure 8 and Figure 9,
are shown in Table I, together with their correlations coefficients.
Conclusions
It can be concluded that the adsorption of gold (I) ions from acidic thiourea solutions by
activated peach stones is dependent on several parameters, which include: solution pH, rate of
stirring, carbon dosage, gold and thiourea concentration in solution and carbon particle size.
Zinc chloride activated peach stones fitted well the Freundlich isotherm, with a very high
correlation coefficient (R2 = 0.9938), while the phosphoric acid and commercial activated
carbons produced good fits with the Langmuir isotherm, with high correlation coefficients
(R2 = 0.9802 and 0.9758 respectively).
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References
ADAMS, M.D. and FLEMING, C.A. (1989), The mechanism of adsorption of aurocyanide
onto activated carbon, Metallurgical and Materials Transactions B, vol. 20B, 1989.
pp. 315325
AHALYA, N., KANAMADI, R.D., and RAMACHANDRA, T.V. Biosorption of Chromium
(VI) from aqueous solutions by the husk of Bengal gram (Cicer arientinum),
Environmetal Biotechnology: Electronic Journal of Biotechnology, vol. 8, no. 3, 2005.
AMER, A.M. Processing of copper anode-slimes for extraction of metal values,
Physicochemical Problems of Mineral Processing, vol. 36, 2002. pp. 123134.
DESCHENES, G. and GHALI, E. Leaching of gold from chalcopyrite concentrate by
thiourea, Hydrometallurgy, vol. 20, no. 2, 1988. pp. 179202.
HAQUE, K.E. Gold Leaching from Refractory Ores-Literature survey, Mineral Processing
and Extractive Metallurgy Review, vol. 2, no. 3, 1987. pp. 235253.
HURTER, M.F. A review of advances and established procedures in the carbon in pulp (CIP)
gold recovery plant at Western areas Gold Mining Company Limited, Proceeding of
Internatioanl Conference on Gold, vol. 2, Extractive Metallurgy of Gold, SAIMM, 1986.
pp. 335351.
KADIRVELU, K. and NAMASIVAYAM, C. Agricultural by-products as metal adsorbents:
sorption of lead (II) from aqueous solutions onto coir-pith carbon, Environmental
Technology, vol. 21, no. 10, 2000. pp. 10911097.
MARSDEN, J. and HOUSE, C.I. The chemistry of gold extraction, Ellis Horwood, London.
1992.
MCKAY, G., BLAIR, H.S., and GARDENER, J.R. Adsorption of dyes on Chitin I:
Equilibrium studies, Journal of Applied Polymer Science, vol. 27, no. 2, 1982.
pp. 151155.
PETERSEN, F.W. and VAN DEVENTER T.S.J. Comparative performance of porous
adsorbents in presence of gold cyanide, organic foulants and solid fines, Hydrometallurgy
94, IMM and SCI, Cambridge, 1994. pp. 501515.
SYNA, N., and VALIX, M. Assessing the potential of activated bagasse as gold adsorbent for
gold-thiourea, Minerals Engineering, vol. 16, no. 6, 2003.
THIXTON, D.H. Carbon technology for the recovery of gold: A comprehensive guide to
current carbon technology for the recovery of gold with special reference to practice in
Zimbabwe, Ministry of Mines, Environment and Tourism, Publication No. 21, Dept. of
Metallurgy. 1998.
VAN DEVENTER, J.S.J. and VAN DER MERWE P.F. The reversibility of adsorption of gold
cyanide on activated carbon, Metallurgical and Materials Transactions B, 1993.
pp. 433439.
YANNOPOULUS, J.C. The extractive metallurgy of gold, Van Nostrand Reinhold, New York.
1990.
YAPU, W., SEGARRA, M., FERNANDEZ M., and ESPIELL, F. Adsorption kinetics of
dicyanoaurate and dicyanoargentate ions in activated carbon, Metallurgical and
Materials Transactions B, 1994. pp. 185191.
ZOUBOULIS, A.I., KYDOS, K.A., and MATIS, K.A. Adsorption of gold-thiourea complex
on Greek lignite, Hydrometallurgy 94, July, 1994. pp. 546559.
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Francis Gudyanga
Secretary for Science and Technology Development, Zimbabwe
Professor Francis Gudyanga is currently the Permanent Secretary of
the Ministry of Science and Technology Development in Zimbabwe
while at the same being on the academic staff on a part-time basis in
the Department of Metallurgical Engineering at the University of
Zimbabwe (UZ). He obtained (1988) a PhD in Minerals Technology
and a DIC in Electrochemical Engineering from the Royal School of
Mines, Imperial College, after working on the electrohydrometallurgical reduction of cassiterite associated with sulphide minerals. In 1989 he joined he
teaching staff in the Department of Metallurgy, UZ, carrying out research in hydrometallurgy
principally in the reductive decomposition of sulphidic mineral ores. He was Deputy Dean
(19911994) and Dean (19941997) of Engineering at UZ. He worked at Bindura Nickel
Corporations refinery on the production of Ni, Cu and Co by the Outokumptu process. He
spent a years sabbatical (1996) at Mintek, Randburg, South Africa, working on the bacterial
leaching of sulphide ores. In 2000 he was appointed Deputy Director General (Technical) of
the Scientific and Industrial Research and Development Centre (SIRDC) in Harare. He was
Chairman of the Research Council of Zimbabwe (20002007). He has been on the board of
the Zimbabwe Mining and Development Corporation and/or its subsidiaries since 1991. He
was a Member of the Executive Board of the International Council for Science (ICSU)
(20022008) and is a member of the ICSU Regional Committee for Africa since 2004. He
serves on several other board and committees.
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JEFFREY, M., PLEYSIER, R., and BUNNEY, K. Elution behaviour of metals from carbon. Hydrometallurgy
Elution behaviour of metals from carbon

M. JEFFREY, R. PLEYSIER, and K. BUNNEY
Parker Centre (CSIRO Minerals), Australian Minerals Research Centre, Australia
This study investigated the elution of precious and toxic metals from
activated carbon. Gold and mercury are of primary interest, due to
their value and environmental impact respectively. A laboratory
elution rig was commissioned to simulate industrial Zadra and AARL
carbon elution conditions. Mercury was found to elute most
effectively in strong caustic cyanide solutions; gold was found to
elute most effectively in hot low ionic strength solutions. As cyanide
decomposes on contact with activated carbon at high temperatures,
optimum elution conditions for gold conflicts with those for mercury
no practical compromise in conditions was found. However,
sequential elution allowed reasonable recovery of both metals.
Ongoing work is looking at the deportment of other metals under
elution conditions.
Introduction
Gold can be extracted industrially from ores by a variety of processes, and one of the most
successful methods is the carbon-in-pulp (CIP) process. In CIP processing, ore is mined,
ground, and leached with alkaline cyanidic solution to solubilize the gold as a gold cyanide
complex. The gold cyanide is adsorbed by activated carbon, which is subsequently eluted to
produce a concentrated gold solution. The eluted solution is electrowon to recover the
precious metals (alternatively, zinc precipitation may be used), and the carbon is treated in a
kiln under a flowing steam atmosphere to reactivate its surface for reuse.
Many gold plants process ores containing traces of mercury, but the deportment of mercury
through the entire plant under different operating conditions is poorly understood. It is known
that generally mercury follows gold through the cyanide circuit (Zrate, 1985) and loads onto
the activated carbon, but only partially elutes with the gold. This partial elution compounds
the treatment difficulties, since a portion of the mercury reports to the electrowinning cells,
and the remainder reports to the carbon regeneration kilns.
Mercury is a heavily regulated effluent from industrial processes and, in Western Australia,
is listed as a controlled waste under Schedule 1 of the WA Environmental Protection
(Controlled Waste) Regulations 2004. Compounds or solutions of mercury may not be
discharged into the environment under Schedule 1 of the WA Environmental Protection
(Unauthorized Discharges) Regulations 2004, as it is classified as waste that can potentially
accumulate in the environment or living tissue under Part 3 of the WA Environmental
Protection Regulations (1987).
ELUTION BEHAVIOUR OF METALS FROM CARBON
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This paper presents results from fundamental studies of the elution behaviour of mercury
and gold under simulated industrial conditions. Conditions that favour mercury and gold
desorption have been established, and a process for the treatment of mercury-containing CIP
carbon is proposed.
Method
Elution rig
A laboratory-scale elution rig was commissioned to simulate Zadra and AARL carbon elution
conditions, see Figure 1. The majority of the system was constructed from stainless steel
tubing and Swagelok fittings. The elution column was ~600 mm long with an internal
diameter of 25 mm, and a capacity of ~100 g of granulated activated carbon per experiment.
The void volume of the system, when loaded with carbon, was ~150 mL. Solutions were
pumped through the column with a high pressure positive displacement pump with a flow rate
of 9.9 mL/min unless noted otherwise. A pressure relief valve (Figure 1) was set to
1 400 kPag as a safety precaution, but was not triggered in the experiments as routine
operating pressures were well below this threshold.
Heat was maintained with electrical heating tape wound around the main column, controlled
by a thermocouple inserted through the top of the column, connected to a PID controller.
Temperature control was accurate to within 2C over the normal course of an experiment.
Solutions were preheated prior to entering the column by five turns of tubing, wound with the
same heating tape. Metal foil loosely bound around the column and heating tape provided
convective insulation for the system.
Samples
Samples of granulated activated carbon were received from an industrial CIP plant. The
samples were either barren, loaded, or acid washed (barren was taken after elution but before
regeneration, loaded was from the adsorption train, and acid washed was taken immediately
before elution). The metal loadings on each sample are given in Table I. Gold loadings were
measured by FAAS on aqua regia digestions of ashed carbon samples, while mercury loadings
were measured by CVAAS on microwave-assisted acid digestions of as-received samples.
Figure 1. Photograph of the elution rig
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Table I
Metals on carbon samples
Sample
C1 loaded
C1 acid washed
C2 acid washed
Gold loading (g/ton)
Mercury loading (g/ton)
909
1 140
355
187
229
92
Due to the greater ease and precision with which higher element concentrations can be
measured, the majority of experiments were performed with representative portions of C1
acid washed carbon.
Conditions
The standard operating procedure was to load the column with a known weight of acid
washed carbon, fill the rig with deionized water, pump 150 mL of 2% w/v NaCN + 2% w/v
NaOH solution into the rig, seal and soak the carbon at 130C for ~30 minutes, then pump 9.9
mL/min of deionized water through at 130C (AARL type elution). Output from the rig was
collected in ~100 mL portions, weighed, and assayed for gold and mercury concentrations.
Pressure inside the elution rig was maintained by restricting the flow rate from the outlet
manifold with the PD piston pump able to maintain pressures in excess of 1 MPa in the
system. When pumping was stopped (such as during the soak stage), the rig was sealed to
maintain the high pressures required to prevent the solution boiling.
Variations on this base method are noted for each run. The effects of modifying temperature,
pressure, cyanide concentration and eluant composition were investigated.
The concentration profiles shown are calculated from the metal assays of each sample and the
masses of each solution. The recovery profiles shown are calculated as the normalized
integrated concentrations of each metal, assuming that the density of each solution sample is
equal to that of pure water. Simple density measurements on selected solution samples
indicated this to be a reasonable approximation.
Commissioning data
During the commissioning of the column, a number of experiments were conducted at various
temperatures and pressures to ascertain that the elution circuit was operating with similar
characteristics to that of industry. Initially the C2 acid washed carbon was eluted at a typical
elution pressure and temperature of 200 kPag and 130C. The gold profile data is shown in
Figure 2. The elution profiles (closed symbols) represent the metal assays from each sample
with the recovery profiles provided by the cumulative metal values (open symbols). From the
concentration profile, it was clear that during the initial stages of elution, which corresponds
to the flushing of the NaCN + NaOH solution from the column, the elution of gold was poor.
However, as the soak solution was displaced with distilled water, there was a large peak in the
concentration profile, followed by a tail which was typical of elution processes. The recovery
profile showed that within 2 200 g of eluant (~15 BV), the recovery of gold was >90%, and
the profile was similar to that reported in the literature (Marsden and House, 2006). An
elution experiment was also carried out at 700 kPag, and the data (Figure 2) showed that both
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Eluant mass (g)
Figure 2. Effect of pressure on the concentration of gold in the eluant and the cumulative recovery for an AARL style
elution at 130C
the recovery and concentration profiles were similar at the two elution pressures. Such a result
was not surprising, as it would be expected that pressure would not impact on the elution
process, providing that it was maintained above the vapour pressure of the eluant solution.
An important operational observation from the elution experiments at the two different
pressures, however, was that pressure control was less reproducible at 200 kPag. The outlet
valve needed to be continually manipulated to prevent large changes in pressure, and hence
flow rate, which affected the stability of the column temperature. In contrast, at 700 kPag, the
elution operated more smoothly, with little change required in the valve position during the
course of the experiment. This variability is evident in the gold concentration profile, where
the main peak is less uniform at the lower pressure. Therefore, the remainder of the
experiments were conducted at the higher column pressure to take advantage of the improved
pressure, flow and temperature control.
The gold elution profiles at 130C and 700 kPag for the other two carbon samples, C1 acid
washed, and C1 loaded were compared to the profiles for the C2 acid washed carbon, as
shown in Figure 3. From the gold recovery curves, it was evident that both the C1 and C2
carbon samples eluted in a very similar manner, despite the loading for the C2 carbon being
significantly less than the C1 carbon. It was also clear that the acid washing stage had little
impact on the elution of gold.
For each of the carbon samples eluted at 130C and 700 kPag, the concentration and
recovery profiles for mercury were also measured, as shown in Figure 4. These profiles are
significantly different from those for gold, with the concentration of mercury peaking in the
second eluant batch collected, and then rapidly dropping to zero. The recovery profiles
indicated that only < 60% of the mercury had been eluted from the carbon, compared to >
90% for gold. These results indicate that distilled water is not effective at eluting mercury
from carbon. The recovery of mercury from both the acid washed carbon samples was similar
at ~57%, but recovery from the loaded (not acid washed) carbon was significantly lower at
41%. The mechanism by which acid washing improves mercury desorption has not yet been
determined.
During the commissioning trials, elutions were conducted at a range of temperatures, with
data obtained at 130 and 160C, as shown in Figure 5. As expected, the elution of gold was
more effective at higher temperatures, producing a sharper gold concentration profile, and
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Eluant mass (g)
Figure 3. The concentration of gold in the eluant and the cumulative recovery for an AARL style elution at 130C of
three difference carbon samples
Eluant mass (g)
Figure 4. The concentration of mercury in the eluant and the cumulative recovery for an AARL style elution at 130C
of three difference carbon samples
Eluant mass (g)
Eluant mass (g)
Figure 5. Effect of temperature on the concentration of gold and mercury in the eluant and the cumulative recovery
for an AARL style elution
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hence a more concentrated pregnant eluant at the higher temperature. The overall recovery
was also superior at the higher temperature, 97%, compared to 93% at 130C. These results
are consistent with the data reported in the literature (Marsden and House, 2006). An
interesting observation was that the elution of mercury was less effective at the higher
temperature, with the peak concentration and recovery of mercury, lower at 160C (40%
recovery) than at 130C (57% recovery). The data shown in Figure 4 suggest that cyanide is
important for the elution of mercury, since the peak mercury concentration corresponded to
the period in which the caustic cyanide soak solution was flushed from the column. The data
obtained at 160C are consistent with this hypothesis, since cyanide is known to decompose
on activated carbon at elevated temperatures, resulting in a lower free cyanide concentration
at higher elution temperatures.
Effect of cyanide concentration in the AARL soak stage
The effect of varying the cyanide concentration in the soak stage of the AARL elution on the
metal elution was investigated. This work was undertaken as the commissioning data
suggested that cyanide played an important role in the elution of mercury. The C1 acid
washed carbon was soaked at 130C in 2% w/v NaOH solutions containing 0, 2, and 5% w/v
NaCN prior to the standard deionized water elution. The results are shown in Figure 6.
The data obtained for the gold profiles indicate that although a soak solution containing no
cyanide could be utilized prior to the elution, the recovery of gold under these conditions was
slow and that the recovery of gold was incomplete. Gold elution rates increased with
increasing NaCN in the soak solution, with profiles approaching a similar overall recovery of
gold. This data is also consistent with the literature, which shows the rate of gold elution from
carbon utilizing a Zadra system at 95C increases with increasing cyanide concentration.
(Adams and Nicol, 1986). Mercury desorption was even more markedly affected by the
presence of cyanide, with the peak mercury concentration very low from a caustic-only soak,
resulting in an overall mercury recovery of only 6%. This data clearly indicated the
importance of cyanide in the elution of mercury, and were consistent with the data in Figures
4 and 5. When 5% NaCN was adopted in the presoak, the concentration peak and overall
recovery of mercury were higher, but still nowhere near complete (<65%). The reason for this
is that for the AARL type elution, cyanide is used only in the presoak solution, and hence the
elution of mercury ceases once this is flushed from the column with the distilled water.
Eluant mass (g)
Eluant mass (g)
Figure 6. Effect of cyanide concentration in the soak stage on the concentration of gold and mercury in the eluant and
the cumulative recovery for an AARL style elution
480
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Pressure Zadra elution with high cyanide

The effectiveness of eluting metals with cyanidic eluant in place of deionized water was tested
by utilizing a pressurized Zadra type elution at 130C with 2% w/v NaCN + 2% w/v NaOH.
This was undertaken in an attempt to establish whether the Zadra type systems are more
effective at eluting mercury than the AARL process. The gold and mercury profiles are shown
in Figure 7. It is interesting to note that the concentration profile for gold was poorer for the
Zadra system, which was expected due to the high ionic strength of the eluant. However, the
elution had not reached a plateau when the experiment was ceased, and the recovery profile
indicates that given more time, the ultimate recovery of gold would be comparable to the
AARL elution. The concentration profiles for mercury do not tail off as rapidly for the Zadra
elution as they do for the AARL elution, providing further evidence that the presence of free
cyanide is necessary to elute mercury from carbon. Even though the recovery of mercury with
the pressure Zadra system was higher than the AARL system (76% and 56% respectively), the
barren carbon still retained significant concentrations of mercury.
It should be noted that there is a small hump in the gold profile after 1 200 g of eluant; at
this point, the flow was ceased, the column sealed and soaked at 130C for 30 minutes prior to
recommencing the flow. This was primarily done to assess whether additional soaking would
improve the mercury elution. It is clear from Figure 7 that the gold concentration peaks and
the mercury concentration dips temporarily, most likely as a result of the increased
degradation of cyanide during the 30 minute soak period.
A further Zadra style elution was performed at the lower temperature of 110C with 2% w/v
NaCN + 2% w/v NaOH solution and no soak stage. The resulting profiles for gold and
mercury are shown in Figure 8, along with the standard AARL elution profiles for
comparison.
At 110C, not surprisingly, the gold elution was significantly curtailed due to the combined
effect of the higher ionic strength and lower temperature. The maximum gold concentration
was only 19% of the peak value obtained with the AARL elution, and the gold recovery was
only 34% after 1 900 g of eluant. Mercury elution, however, was much more effective at the
lower temperature with cyanide, with an overall recovery of 87% being obtained. These
results indicate that at 110C, the degradation of cyanide in the column is significantly
reduced, resulting a higher cyanide concentration, and hence better mercury recovery at the
lower temperature.
500
1000
1500
Eluant mass (g)
2000
2500
500
1000
1500
Eluant mass (g)
2000
2500
Figure 7. Comparison of Zadra and AARL style elution systems showing the concentration of gold and mercury in
the eluant and the cumulative recovery of each metal at 130C
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500
Page 482
1000
1500
2000
2500
500
1000
1500
2000
2500
Eluant mass (g)
Eluant mass (g)
Figure 8. Comparison of Zadra elution at 110C and AARL elution at 130C, showing the concentration of gold and
mercury in the eluant and the cumulative recovery of each metal
500
1000
1500
2000
Eluant mass (g)
2500
3000
500
1000
1500
2000
2500
3000
Eluant mass (g)
Figure 9. Split (two-stage) elution, with Zadra type eluant for the first 1 500 g, then a soak, followed by AARL elution
at 130C
Split elution: recovery of mercury and gold in separate eluant streams

An ideal elution is rapid, complete, and produces a concentrated solution of the metal of
interest. The results presented so far indicate that optimum elution of mercury occurs under
Zadra type conditions with a high concentration of cyanide and low temperature. In contrast,
the optimum conditions for gold elution requires hot solutions with low ionic strength solution
(i.e. AARL conditions). These conditions are mutually exclusive, and no viable balance
between them was found where a high recovery of gold and mercury was obtained with a
single eluant in a reasonable period of time. However, a split elution could be adopted where
the mercury is initially eluted with a cyanide solution, followed by gold elution with distilled
water. Figure 9 shows the profiles for such an arrangement, where ~1.5 L of NaCN + NaOH
solution was passed initially at 90C, followed by a soak stage at 130C, and then ~1 L of
deionized water. It can be seen that in this arrangement, almost complete mercury recovery
was obtained within the first stage of elution. In the second stage of elution, the gold
concentration profile was similar to the standard AARL profiles, and the recovery incomplete
only as the experiment was truncated.
The split elution produces a gold-rich/mercury-cyanide-poor stream, and a mercurycyanide-rich/gold-poor stream, and hence there is the possibility of treating the two streams
separately. For example, the mercury-rich stream could be treated with sulphide to precipitate
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the mercury as cinnabar (HgS, see Equation [1]) before recycle to avoid loss of gold, while
the gold-rich stream can be directly electrowon.
[1]
Conclusions
Under the conditions employed, mercury elutes only in the presence of free cyanide. Gold
elutes best in low ionic strength solutions at high temperatures (after being soaked in
concentrated cyanidic solution). Cyanide decomposes on hot activated carbon, so mercury and
gold elution require opposing conditions for efficient desorption. A split (or two-stage) elution
system may allow for the practical elution of both metals and the possibility of separate
treatment for each stream.
Future work
Optimization of the split elution conditions to achieve economic recovery and better
separation of the two metals of interest are underway. Investigation of the deportment of other
trace metals under elution conditions is also in progress.
References
Environmental Protection Act. Environmental Protection Regulations 1987. Western
Australia, www.slp.wa.gov.au. 1987.
ADAMS, M.D. and NICOL, M.J. The kinetics of the elution of gold from activated carbon.
Fivaz, C.E. and King, R.P. (eds.) Gold 100. 2nd ed. Johannesburg, South Africa, The
South African Institute of Mining and Metallurgy. 1986.
MARSDEN, J.O. and HOUSE, C.I. The Chemistry of Gold Extraction, Littleton, Colorado,
Society for Mining, metallurgy, and Exploration, Inc. 2006.
ZRATE, G. Copper and Mercury Behaviour In Cyanidation of Gold and Silver Minerals.
Oliver, A.J. (ed.) 15th Annual Hydrometallurgical Meeting. Vancouver, Canada, CIM
Metallurgical Society. 1985.
Matthew Jeffrey
Research Program Leader, CSIRO, Australia
Matthew Jeffrey was awarded a Bachelor of Engineering (Chemical)
with first class honours from the University of New South Wales in
1994, and a Doctor of Philosophy, from Curtin University (AJ Parker
CRC for Hydrometallurgy) in 1998. Matthew has extensive research
experience in hydrometallurgy, being based at Monash University for 8
years as a senior lecturer prior to joining CSIRO Minerals. He has
published over 70 papers in the field, and holds a patent. Matthew is
currently the CSIRO Research Program Leader for Gold Hydrometallurgy, and the Parker
Centre gold market leader. Matthews expertise and research interests include:
Processing of gold using cyanide or thiosulfate
Leaching and electrochemistry of gold and base metals
Electrowinning
Resin and carbon adsorption and elution
Modelling and solution speciation
Ion chromatography (for determining sulphur and cyanide speciation).
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The Southern African Institute of Mining and Metallurgy

The SAIMM Southern African

Hydrometallurgy Conference 2009

THE SOUTHERN AFRICAN INSTITUTE OF MINING AND METALLURGY

SYMPOSIUM SERIES S54

The SAIMM Southern African

HYDROMETALLURGY CONFERENCE 2009

2426 February 2009

MISTY HILLS, MULDERSDRIFT, GAUTENG

Lognormal-De Wijsian Geostatistics for Ore Evaluation

An Introduction to Geostatistical Methods of Mineral Evaluation

Increased Underground Extraction of Coal

Rock Mechanics in Mining Practice

Assay and Analytical Practice in the South African Mining Industry

The Extractive Metallurgy of Gold in South Africa,

Mineral and Metal Extraction An Overview

Rock Fracture and Rockburstsan illustrative study

THE SPECIAL PUBLICATIONS SERIES

Proceedings, Underground Transport Symposium

Backfill in South African Mines (1988)

Treatment and Re-use of Water in the Minerals Industry (1989)

COREX Symposium 1990

Measurement, Control, and Optimization in Mineral Processing

Handbook on Hard-rock Strata Control

Rock Engineering for underground coal mining

SUPPLEMENT TO THE SAIMM JOURNAL

THE SYMPOSIUM SERIES

Mathematical Statistics and Computer Applications in Ore Valuation (1966)

Published by The Southern African Institute of Mining and Metallurgy

Printed by Camera Press, Johannesburg

The progression of metallurgical testwork during heap leach design

Mixing system design for the Tati Activox autoclave

Stabilization of supersonic vent gas from autoclave pressure oxidation

Recent advances in BIOX technology

Systematic characterization of the mixing process for the BIOX reactor

SOLVENT EXTRACTION AND ELECTROWINNING

Developments in organic holding tank structure for solvent extraction processes

SOLVENT EXTRACTION AND ELECTROWINNING (Continued)

Solvent extraction design consideration for the Tati Activox plant

BASE METALS REFINERIES

COPPER, COBALT, NICKEL, ZINC HYDROMETALLURGY

Optimizing acid utilization and metal recovery in African Cu/Co flowsheets

Processing considerations for cobalt recovery from Congolese copperbelt ores

Elution behaviour of metals from carbon

The organisers of the conference wish to

Protea Mining Chemicals

MIP Process Technologies

HYDROMETALLURGY CONFERENCE 2009

Leaching of the arsenopyrite/pyrite flotation

This paper describes experimental investigations into the reductive

HYDROMETALLURGY CONFERENCE 2009

HYDROMETALLURGY CONFERENCE 2009

LEACHING OF THE ARSENOPYRITE/PYRITE FLOTATION CONCENTRATES

Results and discussion

HYDROMETALLURGY CONFERENCE 2009

FeAsS + 2H+ + 2e- = Fe + As + H2S

HYDROMETALLURGY CONFERENCE 2009

LEACHING OF THE ARSENOPYRITE/PYRITE FLOTATION CONCENTRATES

300 minutes, a slight decrease in total arsenopyrite/pyrite decomposition is also observed.

HYDROMETALLURGY CONFERENCE 2009

Sieve analysis and precious metal deportment in the flotation concentrate

HYDROMETALLURGY CONFERENCE 2009