5/21/2016

Hydrometallurgy
Assignment
High Pressure Multi stage Oxidative
leach circuit

Onkarabile Matome

Contents
Introduction .................................................................................................................................................. 1
Objectives ..................................................................................................................................................... 1
Reaction Equations ....................................................................................................................................... 2
Mass Balance ................................................................................................................................................ 3
Electrowinning section .................................................................................................................................. 5
Question 5 ..................................................................................................................................................... 5
References .................................................................................................................................................... 6
Appendix ....................................................................................................................................................... 7

List of Tables
Table 1 Mass balance evaluations on the extraction of Ni process in high pressure leach system ............. 3
Table 2 : pH values and Ca calculations. ....................................................................................................... 4
Table 3 Specifications on for the electrowinning sections. .......................................................................... 5
Table 4 : Equilibrium voltage and Area of the Cathode summary table ....................................................... 5

List of Figures
Figure 1 Process Flow Diagram of the extraction of Ni from pentlandite in a high pressure leach circuit .. 1

Introduction
Pressure autoclave circuits are utilized in the leaching of concentrates, ores and mattes for the recovery
of metals into solution (B.D Phaphane et al, 2013). Once this has been done, valuable minerals can then
be extracted and recovered using hydrometallurgical methods such as electrowinning, precipitation and
many others. This report is a summary of the analyses carried out in the extraction of Nickel (Ni) from
pentlandite (NiSFeS) concentrate. The metal concentrate is treated in a multi stage high-pressure
oxidative leach circuit using oxygen in the pressure autoclaves. Figure 1 below is a process flow diagram
that describes the material flow in the system
NiS.FeS
feed

O2 gas

Pressure
Leach

H2SO4 & H2O

make-up

Leach Residue

Ni electrowinning

SX circuit

Ni Cathode

Gypsum & Impurity

precipitation

Process water recycle

Ca(OH)2

Precipitate to landfill

Figure 1 Process Flow Diagram of the extraction of Ni from pentlandite in a high pressure leach circuit

Objectives
The objectives of this report follows questions outline in the main problems statement. Listed below is
the summary of these objective;

Determine the reaction equations in the system and balance them accordingly, show that acid
consumption in the electrowinning unit is the same as the stoichiometric acid in the reactor.
Establish a complete mass balance for Ni, Fe, S and Ni cathode, Oxygen requirements, make up
acid and production of the mass of the filter cake and effluent solution flowrates.
Determine the required mass of Ca(OH)2 using table 2 in the report.
Determine the equilibrium voltage for the Ni electroplating process under the conditions given in
table 3.
And lastly adding some recommendations on the configurations of the process flow with
reference to acid in the system.
1

Reaction Equations
Leaching
The main purpose of the leach circuit is to selectively dissolve metals from the fine milled flotation
concentrates (Dunn, 2009). The resultant metal-rich liquor is then oxidized by introducing oxygen in the
autoclave which in turn forms exclusively (notes, 2013) elemental Sulphur, dissolved Ni and ferrous iron.
Iron in the system reacts further with oxygen to form ferric iron which then precipitate to hematite
(2 3 ). Below are the reactions equations in the leach reactor.
2 + 22 4 + 2 2+ + 2+ + 2 0 + 22 + 24 2
3

2+ + 4 2 2 2 3

Equation 1
Equation 2

Overall : 2 + 22 4 + 4 2 2+ + 2 2 3 + 2 0 + 22 + 24 2

Equation 3

SX Circuit and Electrowinning

In this section an overview analysis is adopted. Thus the only important reaction in this joined unit is the
electroplating of Ni. This governing reactions equations are as follow.
Anode : 22 2 + 4 + + 4

Equation 4

Cathode : + + 2 0

Equation 5

Overall : + + 2 0 + 0.52 + 2 +

Equation 6

Precipitation
2+ + 4 2 4

Equation 7

() dissolution
()2 2+ + 2

Equation 8

Acid Neutralization
2 + 2 4 22 + 4 2

Equation 9

Other Metal precipitation

+ + ()

Equation 10

Acid Calculations
Stoichiometric Acid consumption
N(2 4 ) = 2N(2 ) = 2 (

178.8

5000

) (0.8)(0.96) = 42.98

Acid generated in the electrowinning process

N(2 4 ) = 2 = 2 (

100058.7

16181 75

) = 42.98

Mass Balance
An overall mass balance was conducted on the whole process, followed by unit to unit analysis. The first
step was to determine the volumetric flow rate of the process which was determined by analyzing the

leach reactor. 5 of Ni is returned to the reactor and 80 is in the output stream. This imply that 75 is

introduced from the . From this a volumetric flow rate of 16818 is determined. Further
evaluations are performed and the summary of the analysis is given in table 1 below.
Table 1 Mass balance evaluations on the extraction of Ni process in high pressure leach system
Summary
Process Flow
NiFeS2
Ni Feed
Solid sulphur Feed
Stoich O2 feed
SO4 feed
H+ feed
Ni Production
Ca(OH)2 feed
Waste
balance

16818
32000
10511
11496
9627
33220
691
10091
138
34514
-2148

L/h
t/a
t/a
t/a
t/a
t/a
t/a
t/a
t/a
t/a
t/a

As it can be observed from table 1, mass balance is off by value 2148 t/a. this can be attributed to some
of the assumptions made during the process evaluations and calculations. An example is the water
balance within the system was not calculated assuming water in the system will be equal to the water out
of the system. But this might not be the case due to H+ reactions in the water molecule.
() required
To calculate the required Ca(OH)2 in the process, reaction equations of precipitating metals must first be
determined. Equations to calculate pH were established based on a general metal reaction with the
hydronium ion. The summary of which equations determined and used is given below following the results
obtained in table 2.

Table 2 : pH values and Ca calculations.

Metal
Ni
Fe(III)
Zn
Cd
Mn
Cu
H+
Ca min

conc.
[mg/L]
5000
1000
400
120
500
200

pKs

permissible
conc. [mg/L]

15.2
38.8
15.52
14.35
12.8
19.32

0.5
10
0.5
0.1
50
0.5

22.85263 g/L

conc.
[mol/L]
293.5
55.9
26.2
13.5
27.5
12.7
0.025554
914.1052

Ca
0.051938 kmolh
Ca(OH)2 3.843436 kg/h
pH must be controlled between 0.484 and 6.881

3+ + 3 ()3

2+ + 2 ()2
2+ + 2 ()2
2+ + 2 ()2
2+ + 2 ()2
2+ + 2 ()2
Metal Equations in the precipitation unit
+ + ()
[() ] = [] + []
= [ + ] + [ ]
[() ] = [] + ([ [ + ])
1
[ + ] = ( ([ ) [() ] + [ ])

pH calculation on a general metal reaction with a Hydronium

pH

Molar
Mass

5.166
0.484
5.531
6.260
6.881
3.788

58.69
55.85
65.38
112.41
54.94
63.55

Electrowinning section
To calculate the voltage at equilibrium, specifications in table 3 were used and the obtained results were
summarized in table 4 below. Equations A1 and A2 in the appendix were used to following the
electrochemical cell analogy (notes, 2013).
Table 3 Specifications on for the electrowinning sections.

E0
T
n
R
[Ni]

Cathode
-0.26 V
313 K
2
8.314 J/mol/K
0.0852 mol/L

E0
T
pH
R

Anode
1.23 V
313 K
0.3
8.313 J/mol/K

Table 4 : Equilibrium voltage and Area of the Cathode summary table

Ni production rate
Current Density
Current Effeciency
r
n
F
A
E cell

21.48853
400
0.92
0.002073
2
96500
3130
1.448665

kmol/h
A/m2
%
mol/s/m2
C/mol
m2
V

Question 5

Positions of the bleed stream is a function of economics, thus depending on what costs less a
decision can be made, however it should be noted that maintaining an acidic process induces
operational costs. Thus yes it would make sense to more the bleed stream before the SX circuit.
Elemental Sulphur is generally environmentally acceptable rather than sulphate ion which is
associated with sulphuric acid (J Petersen,H.F Fuls, 2013).

References
B.D Phaphane et al. (2013, june). scielo. Retrieved from kinetic studied on leaching reactions in the
autoclave circuit of the tati hydrometallurgical demonstration plant :
http://www.scielo.org.za/pdf/jsaimm/v113n6/06.pdf
Dunn, G. (2009). Hydromet: Increasing capacity of existing exothermic autoclaves. Retrieved from
SAIMM: http://www.saimm.co.za/Conferences/Hydro2009/043-056_Dunn.pdf
E Muzenda, F. N. (2014, May). SCIELO South Africa. Retrieved from Journal of the South Africa Institute
of Mining: http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0038223X2013000500008
J Petersen,H.F Fuls. (2013, May). SCIELO South Africa. Retrieved from Journal of the Institute of South
African Mining: http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0038223X2013000500008
notes, C. (2013). Introduction to hydrometallurgy.

Appendix
A. Equations used in the Electrowinning section
Cathode : = 0

[2+ ]

Anode : = 0 2.030

Equation A1

Equation A2

Equation A3