EPD Congress 2011

TMS (The Minerals, Metals & Materials Society), 2011

OTI
EPD Congress

Practice and Theory

of Chloride-Based
Metallurgy
Pyrometallurgy and
Acid Regeneration
Session Chairs
Kamal Adham
Lisa E. Helberg

EPD Congress 2011

TMS (The Minerals, Metals & Materials Society), 2011

CHLORIDE METALLURGY
- PROCESS TECHNOLOGY DEVELOPMENT Edgar Peek
Xstrata Process Support, 6 Edison Road, Falconbridge, Ontario, Canada
epeek@xstrataps.ca
Keywords: pyrometallurgy, hydrometallurgy, chloride, sulphides, oxides

ABSTRACT
The two dominant metallurgical problems in treating most base metal sulphide concentrates in both
the chloride and sulphate system are iron removal and sulphur elimination, respectively [1-3]. In
this paper the opportunities, limitations and fundamentals of the chloride metallurgy system are
described against this background. Only the treatment of oxide and sulphide ores is considered.
Both hydrometallurgical and pyrometallurgical unit process operations are highlighted, since most
successful base metal processes are based on a combination of the two. Hence, an overview of the
technical and also some economical aspects of chloride metallurgy are presented.
This overview summarizes the successful applications of chloride metallurgy, but it will not give
exhaustive process and plant descriptions. It predominantly focuses on the essential technical
features of the metallurgical unit process operations, while providing numerous references
separately.

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INTRODUCTION - ORE TO METAL

In Figure 1 a simplified representation of the production of metal from any mined ore has been
given. This elementary four step processing route will be used to explain the opportunities and
limitations of chloride metallurgy. Hence, after highlighting the advantageous properties of
chlorides, the extraction of metals from concentrates, the purification options of either the solution
or off gas and the recovery of metals from solution will be addressed in consecutive order.

BENEFICIATION
crushing/grinding/screening
gravity/magnetic/electrostatic separation
sintering/pelletization
flotation

EXTRACTION
acidic leaching (H 2 S0 4 /HCI/HN0 3 )
base leaching (NH3/NaOH)
reduction (CO/H2)
sulphide roasting and smelting
(reduction) volatilization

PURIFICATION
selective precipitation/cementation
solvent extraction/ion exhange
fractional distillation
converting (oxidation)

RECOVERY
electrowinning and refining
hydrogen reduction
carbonate/oxide precipitation

Figure 1: From Ore to Metal in Four Stages A simplified representation

including examples of unit process operations

CHARACTERIZATION OF METAL CHLORIDES

In order to truly appreciate the opportunities and restrictions of chloride metallurgy, it is essential to
recognize some important physical and chemical properties of (metal) chlorides. In chloride
hydrometallurgy some important characteristics of chlorides are:

470

v
v
v

Chlorides are far more soluble than sulphates. Most metal chlorides are extremely soluble in
water, lead, silver and mercury chloride being the relevant exceptions. This property means
that very concentrated metal chloride solutions can be made, which subsequently reduce the
size of solid/liquid separators, solvent extraction/ion exchange units and other process
equipment.
Hydrochloric acid is a true lixiviant. In chloride solutions the hydrogen ion has a very high
activity compared to sulphate solutions. This proton activity increases markedly with
enhanced chloride concentrations, giving rise to fast leaching rates and high unit capacities.
As a result only moderate leaching temperatures are required. However, the vapour pressure
of HCl over the solutions is also enhanced demanding the use of closed equipment.
Specific metal solubilization is possible by control of the acidity and oxidation-reduction
potential. In contrast to the sulphate system, a high redox potential is possible in the
chloride system across the entire pH-range, ferric chloride and cupric chloride leaching
being the well-known examples. This enables (oxidative) leaching and electrowinning
under very diverse conditions.
Lixiviant (H+) and/or oxidant (e-) regeneration (HCl, Cl2, CuCl2, FeCl3) is often possible as
an integral part of the flow sheet. Two technically demonstrated and economically viable
options are metal chloride pyrohydrolysis and electrowinning. If chlorine is to be
regenerated, then this inherently implicates that an oxidative (chlorine) leaching step should
be incorporated in the process, and vice versa.
Metal separation from solution by ion exchange or solvent extraction is facilitated by the
fact that metals form anionic or cationic complexes of differing stability. For instance, the
stronger cobalt anionic complexes can be separated from nickel cobalt chloride solutions
via solvent extraction using amines like Alamine 336. The combination of strong chlorocomplexes and high proton activity raises the ionic activity and thus promotes the solubility
of these complexes.
Due to high metal chloride concentrations, solutions will have a high conductivity and
viscosity. This lowers the energy requirements in electrowinning and allows electrolyte to
flow through diaphragms and filters.
In chloride hydrometallurgy elemental sulphur can be produced instead of the undesirable
sulphur dioxide (SO2) and sulphuric acid. Pyrite (FeS2), an important and mainly barren
constituent of sulphide ores, is hardly attacked during leaching.
The chloride system is renowned for being a very corrosive environment. This has inhibited
the application of chloride hydrometallurgy for a long time. However, with the discovery of
new construction materials (plasticizers and synthetics, i.e. chlorinated hydrocarbons),
corrosion has become a manageable phenomenon.

Some characteristic features of metal chlorides at elevated temperatures (pyrometallurgy) are now
highlighted. It is interesting to note that some properties such as for instance stability and reactivity
are independent of temperature. The significant properties are:
v

Metal chlorides, especially the base metal ones, are in general very volatile at relatively low
temperatures as demonstrated in Figure 2 [4-5]. Metal sulphates on the other hand
decompose at elevated temperatures.

471

The volatility of chlorides differs from metal to metal, which makes their separation
physically possible (selective volatilization or fractional distillation).

Figure 1: The Vapour Pressures of the Most Common (Base) Metal Chlorides as a
Function of Temperature. Notice the Big Difference between Zinc and Cuprous
Chloride Volatility.
v

v
v
v
v
v
v

Both chlorine and hydrogen chloride (not dry) are highly reactive, which makes the use of a
carbonaceous reductant obsolete in the case of most metal oxides. The well-known
exceptions are of course the very stable oxides such as for example zirconium and titanium,
which do require a reductant (carbo-chlorination).
Metals can be volatilized in the di- or trivalent state instead of metallic state. Hence, most
metal chlorides are very stable.
Every metal chloride has a different susceptibility for hydrolysis, i.e. reaction with water
vapour. This can facilitate selective metal removal.
The technical feasibility of hydrogen reduction of metal chlorides is also often mentioned as
a perceived processing advantage. However, it should be noted that elevated temperatures
are needed resulting in volatile metal chlorides and reduction to metal everywhere.
Hydrogen chloride gas can be used for salting out metal chloride solutions, i.e. initiate metal
chloride crystallization.
Lixiviant regeneration by pyrohydrolysis is an established technology for HCl.
Corrosion does occur at elevated temperatures, but it is very slow compared to corrosion in
solution. Hence, corrosion usually occurs at those places where chlorides are allowed to
condense. The corrosion rate is then highly dependent on compounds such as oxygen, any
metal chloride and water vapour, which promote the formation of oxide or metallic scales
that will provide temporary protection.

Figure 2 clearly demonstrates that for most metal chlorides the volatility increases dramatically, if
the temperature is raised about 200 0C above the melting point. Therefore, the melting and boiling
points of many metal chlorides from both groups Ib to VIIIb and groups IIIa to VIa of the periodic
system have been given in Figures 3 and 4, respectively, to provide a more comprehensive image
on metal chloride volatility. The phrase "unknown" usually indicates decomposition of the

472

compound. The volatility of earth-alkaline metals (group Ia and IIa) will be touched upon later
when the topic of salt roasting is described.

Figure 2: Melting and Boiling Points of Metal Chlorides from Groups IIb, Ib, VIIIb,
VIIb, VIb and IVb of the Periodic System of Elements [4,5].

Figure 3: Melting and Boiling Points of Metal Chlorides from Groups IIIa, IVa, Va
and VIa of the Periodic System of Elements [4-5].
In view of these characteristic properties of metal chlorides at both room temperature and elevated
temperatures, the opportunities and limitations of metal oxide and metal sulphide treatment in the
chloride system will be discussed. A distinction will be made between hydro- and pyrometallurgy.
Firstly, the fundamentals of metal extraction will be explained, while examples of metal recovery
will be described separately.

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FUNDAMENTALS - CHLORIDE PROCESS TECHNOLOGY DEVELOPMENT

Pyrometallurgical Treatment Metal Oxides
Only the very refractory metals, like for instance zirconium and titanium, have to be treated via
chloride chemistry, because process engineers have not been able to develop an economically
viable alternative processing route which could produce the same or better high purity product
(pigment) desired. Hence, metallurgists were forced to commercialize the well-known and
successful concept of carbo-chlorination in both the titanium and zirconium industry, despite the
corrosive nature of the chloride system. It should be mentioned that the sulphate route for titanium
dioxide was developed prior to the chloride route, but gives a mineralogically different TiO2
product at higher cost, i.e. anatase instead of rutile.
The carbo-chlorination concept has been given in reaction 1. In practice, this technology is only
required for the very stable tetravalent metal oxides. In reactions 1a (rutile) and 1b (ilmenite) the
application of carbo-chlorination for titanium ores has been exemplified. Both minerals are
chlorinated at about 1000 0C, usually in a fluidized bed, yielding titanium tetrachloride and ferric
chloride, which are subsequently separated from each other through fractional distillation. The latter
technique combined with partial oxidation is also required to remove vanadium compounds,
usually as oxychlorides. Pure TiO2 pigment is obtained by oxidizing the purified TiCl4.
MeO(s) + C(s) + Cl2 (g) = MeCl2 (s,l,g) + CO(g)

(1)

TiO2 (s) + 2C(s) + 2Cl2 (g) = TiCl4 (g) + 2CO(g)

(1a)

2FeTiO3 (s) + 6C(s) + 7Cl2 (g) = 2TiCl4 (g) + 2FeCl3 (g) + 6CO(g)

(1b)

The thermodynamic stability of metal chlorides against oxidation has been reviewed by Kroll [6].
He established that the metal chloride stability in air or oxygen diminishes in the following
sequence, i.e. AgCl, Hg2Cl2, PbCl2, CdCl2, CaCl2, LiCl, MnCl2, CuCl2, ZnCl2, SnCl2, NiCl2, FeCl2,
MgCl2, CrCl3, SnCl4, TiCl4, ZrCl4, AlCl3 and SiCl4. Hence, it is obvious that a very low partial
oxygen pressure is required to chlorinate the latter five metal oxides. However, for most metal
oxides a carbonaceous reductant is not required. Chlorine and hydrogen chloride gas by itself can
react completely and at a sufficient rate with the metal oxide. The chlorination (Cl2) and
pyrohydrochloridization (HCl) mechanism has been presented in reactions 2 and 3, respectively.
Pyrohydrochloridization is thermodynamically slightly more favourable than chlorination.
MeO(s) + Cl2 (g) = MeCl2 (s,l,g) + O2 (g)

(2)

MeO(s) + 2HCl(g) = MeCl2 (s,l,g) + H2O(g)

(3)

Chlorination of (base) metal oxides has predominantly been carried out on pyrite cinders, laterite
ores and ilmenite [7-17]. The treatment of pyrite cinders with chlorine is relatively new, but salt
roasting of this raw material has been commercially practised since 1876, as will be described later.
For clarification, pyrite cinders are another term for roaster calcines obtained from roasting pyrite
for sulphuric acid production. The chlorination treatment involves the volatilization of nonferrous
metals in an air-chlorine mixture containing 5 to 17 vol.% Cl2 at 1000 0C in a shaft furnace [7].

474

Duisburger Kupferhtte and Lurgi [7] successfully piloted this process in 1965-1966 on a 100
tonnes/day scale. It was found that chlorine consumption varied between 1.2 and 2 times the
theoretical requirement. The volatile nonferrous metal chlorides were separated from the off gas
using a venturi scrubber and electrostatic precipitators. Operating experience with the pilot unit
resulted in a modified furnace design where combustion and chlorination were separated from each
other [14]. Hence, pelletization and preheating of the charge was carried at 1200 0C in stage one of
the shaft furnace while chlorination was done in a second stage. In this way metal chloride
oxidation could be minimized. The use of fluidized beds for pyrite cinders treatment has also been
reported [12].
Laterite ores [12] have been the subject of many chlorination proposals. In most cases the laterite
ore is first reduced, before either a high temperature or low temperature processing route is
followed. Chlorination at about 950 0C results in the volatilization of nickel, cobalt and iron
chlorides. Metal separation is carried out via fractional distillation, followed by selective high
temperature oxidation and subsequently hydrogen reduction to metal powder. The chlorination at
350 0C also results in metal chloride formation, but volatilization can not take place. The nickel and
cobalt chloride formed has to be leached from the chlorinated residue. Then solvent extraction
(anionic SX, secondary amines) can be applied to separate nickel from cobalt.
Treatment of TiO2 bearing feed stocks [15] has already been introduced. Reaction 1b is an
undesirable (and usually unavoidable) side reaction during the production of TiO2, since it
consumes both a lot of chlorine and coke. Furthermore, titanium tetrachloride purification will
require more stages at higher iron loads. Hence, pigment producers preferentially want to process
high grade titanium ores with a low iron, and especially low earth-alkaline metals content. The
latter elements form non-volatile metal chlorides. Unfortunately, such high grade ore deposits are
rare. This has initiated a lot of research and development on the selective chlorination of iron from
ilmenite with and without a carbonaceous reductant prior to TiO2 production. Both reducing
chlorination (reaction 2a) and oxidizing pyrohydrochloridization (reaction 3a) have been
investigated in Egypt and India, respectively. Chloride recovery from FeCl3 determines the
economics of such ilmenite beneficiation processes. The example on ilmenite upgrading indicates
that both chlorine and hydrogen chloride can have the same result. However, the latter example also
reveals an essential difference.
2FeTiO3 (s) + 2CO(g) + 3Cl2 (g) = 2TiO2 (s) + 2FeCl3 (g) + 2CO2 (g)

(2a)

2FeTiO3 (s) + 6HCl(g) + O2 (g) = 2TiO2 (s) + 2FeCl3 (g) + 3H2O(g)

(3a)

Water vapour is highly undesirable during chlorination, since HCl formation and re-oxidation of
metal chlorides can occur upon cooling down the off gases, not to speak of corrosion. Hence,
hydrogen chloride formation is unacceptable. Furthermore, some hydrogen can be formed under
these highly reducing conditions, due to a reaction of water vapour with CO, and hydrogen
reduction of the metal chlorides at elevated temperatures can take place for a number of (base)
metal chlorides. The metallic phase formed is usually not volatile and separation efficiency will
decrease dramatically. In addition, metals have a much higher density, which might cause practical
problems such as defluidization. The desired absence of water vapour requires externally heated
reactors, hydrogen free (carbonaceous) reductants or a very low partial oxygen pressure.

475

Pyrohydrochloridization is characterized by the presence of large amounts of water vapour. This

facilitates the use of hydrocarbons as a fuel, while hydrogen formation is negligible. Internally
heated reactors such as fluidized beds are possible. However, excess oxygen needed for complete
combustion can cause chlorine formation in the offgas upon cooling. This also hampers lixiviant
regeneration. This oxygen dilemma suggests that stoichiometric or slightly reducing
pyrohydrochloridization should be investigated. This subject will surface on several occasions in
this paper.
Pyrohydrochloridization (high temperature HCl treatment) has been suggested and applied as a
metal extraction process for laterite ores, manganese deep sea nodules [18-26] and low grade tin
ores. In the case of laterites only a low temperature (200-300 0C) treatment was considered.
Subjects of controversy were whether the ore should be pre-reduced or not and how the iron
chloride should be removed from the nickel and cobalt chlorides. Very different HCl/H2O gas
mixtures are required for either maximizing nickel and cobalt recovery or minimizing iron
chloridization. Fluidized beds and multiple hearth furnaces were suggested or employed in these
investigations, which were not extended beyond the laboratory scale.
The treatment of low-grade tin ores through pyrohydrochloridization and salt roasting has attracted
a lot of attention [27-35]. The N.V. Billiton Maatschappij piloted reducing pyrohydrochloridization
in a fluidized bed at 900 0C. The reducing conditions, which are created by burning light oil with a
deficit of air, are required to prevent re-oxidation of the stannous chloride. The combustion gases
are mixed with chlorine at 600 0C, before they are fed to the fluidized bed. Due to the presence of
water, the chlorine exothermically reacts to HCl and raises the temperature to 900 0C. At Warren
Spring Laboratories the research focused on salt roasting in vertical retorts at 800 0C, also under
reducing conditions. The general principles of salt roasting will be described below. However, it is
important to note that both approaches never became successful mainly due to low tin prices.
The most simplistic form of salt roasting has been given in reaction 4. This reaction is not a true
and practical extraction step. It is more a purification step, i.e. a high temperature "metathesis"
reaction. Reactions 5a to 5c on the other hand do represent the overall mechanism of nonferrous
metals extraction via salt roasting from for instance laterites (nickel and cobalt oxides), deep sea
manganese nodules [36-42], low grade tin ores (reductant needed, reaction 5c) and refractory
copper ores (Torco process). However, the mechanism shown is usually not the rate determining
step. The salts utilized in practice are usually sodium and calcium chloride. However, potassium
and magnesium chloride have also been ventured. In reactions 6a and 6b the overall mechanism for
salt roasting of pyrite cinders has been given. The sulphur dioxide shown is derived from the
residual sulphur present in cinders. In both cases, i.e. reactions 5 and 6, a mono- (NaCl or KCl) or
divalent (CaCl2 or MgCl2) salt appears to be the actual chloridizing agent. However, this
assumption is not valid as will be exemplified by brief descriptions of both the Torco process and
pyrite cinders treatment later in this section. First of all, salt roasting will be explained and justified.
MeO(s) + Me""Cl2 (s,l,g) = MeCl2 (s,l,g) + Me""O(s)

(4)

MeO(s) + SiO2 (s) + Me""Cl2 (s,l) = MeCl2 (s,l,g) + Me""O.SiO2 (s)

(5a)

"

MeO(s) + SiO2 (s) + 2Me Cl(s,l) = MeCl2 (s,l,g) +

476

Me"2O.SiO2 (s)

(5b)

MeO2 (s) + C(s) + Me""Cl2 (s,l) + SiO2 = MeCl2 (s,l,g) + Me""O.SiO2 (s) + CO(g)

(5c)

MeO(s) + SO2 (g) + O2 (g) + Me""Cl2 (s,l) = MeCl2 (s,l,g) + Me""SO4 (s)

(6a)

MeO(s) + SO2 (g) + O2 (g) + 2Me"Cl(s,l) = MeCl2 (s,l,g) + Me"2SO4 (s)

(6b)

Salt (NaCl) roasting is one of the oldest applications of chloride pyrometallurgy. The reason for that
is simple. Salt has been readily available long before hydrogen chloride and chlorine were
produced. For instance, the first industrial production of hydrogen chloride was carried out via
reaction 7 at 840 0C in a so called Mannheim furnace. An improved version of this operation is the
Hargreaves process, which can be symbolized by reaction 8. Nowadays, hydrogen chloride is
mainly produced by combusting hydrogen and chlorine (reaction 9) and as a by-product of
chlorinated hydrocarbon production via for example reaction 10. In Peek [0] the production of
chlorine from salt and HCl was already addressed.
2NaCl(s,l) + H2SO4 (l) = 2HCl(g) + Na2SO4 (s)

(7)

4NaCl(s,l) + 2SO2 (g) + O2 (g) = 4HCl(g) + 2Na2SO4 (s)

(8)

H2 (g) + Cl2 (g) = 2HCl (g)

(9)

C6H6 (l,g) + 2Cl2 (g) = C6H5Cl2 (l,g) + 2HCl(g)

(10)

In addition to its availability, salt has only one other advantage, i.e. it is relatively inexpensive.
However, the application of salt as a metallurgical reagent also has numerous disadvantages,
especially when compared to HCl and Cl2. Illustrative examples are:
v
v
v
v
v

Salts (NaCl, KCl, CaCl2, MgCl2) are usually required in a large stoichiometric excess in
order to attain appreciable reaction rates.
Salts have a melting point below 800 0C (Figure 5), which causes melting phenomena in the
charge. In the case of externally heated reactors local hot spots can cause sintering of the
charge.
From a thermodynamical point of view, salt is a very poor chloridizing agent.
Most salts have a significant tendency to hydrate, which makes them difficult to handle both
in storage and transport.
Earth-alkaline salts are hardly volatile (Figure 6). This might be considered as an advantage
for metal separation. However, in many places residual chlorides in the roasting residue are
environmentally unacceptable. Hence, an additional (costly) purification step is demanded.

477

Figure 4: Melting and Boiling Points of Metal Chlorides from Groups Ia and
IIa of the Periodic System of Elements [4-5].

Figure 5: Vapour Pressures of the Most Common Earth-Alkaline Chlorides Used in

Salt Roasting. The CaCl2 Vapour Pressure has been Calculated.
In the beginning of this century the benefits outweighed the disadvantages and the Torco process
[43-51] and salt roasting of pyrite cinders [52-58] were developed.
The concept for the Torco (Treatment Of Refractory Copper Ores) process was discovered by
accident in 1923 [51] when a silica bearing Chilean copper ore, fortunately containing a small
amount of sodium chloride, was being prepared by reductive roasting for an ammoniacal leaching
process. It was established that copper had been segregated during roasting from the original copper
bearing minerals, mainly chrysocolla (copper silicate). Metallic copper had been formed and for
then unknown reasons had been deposited on the outside of the chrysocolla particles. This intrigued
many metallurgists and initiated forty years of research and development on the treatment of
478

siliceous or refractory copper ores via salt roasting. The term refractory relates to the unresponsive
nature of the ore towards flotation and leaching. Beside chrysocolla, the copper can also be locked
up in the form of copper bearing vermiculite, i.e. hydrated aluminum silicate. Large deposits of
these minerals can be found on the Zambian copper belt and in Mauritania.
The most ardent proponent of the Torco process was a French metallurgist called Rey. He made a
large contribution towards unravelling the complicated reaction mechanism [44]. The chemistry of
the process in its simplest form can be represented by reactions 11a to 11c.
2NaCl(s,l) + SiO2 (s) + H2O(g) = Na2SiO3 + 2HCl(g)

(11a)

3Cu2O(s) + 6HCl(g) = 2Cu3Cl3 (g) + 3H2O(g)

(11b)

2Cu3Cl3 (g) + 3H2 (g) = 6Cu(s) + 6HCl(g)

(11c)

The hydrogen reduction step (reaction 11c) takes place at the surface of coke or coal particles.
These particles can and were recovered via flotation for copper extraction. It is evident that both
water vapour and hydrogen chloride is continuously regenerated, which implicates that a salt
quantity of much less than stoichiometric is sufficient. It is clear that HCl is the active chloridizing
reactant, not NaCl.
Rey also established that the biggest problem in this process is heat transfer to the material being
treated. Furthermore, the process requires a large gas/solid contact area, intimate mixing of the salt,
ore and fuel particles in the charge and construction materials resistant to the corrosive gases
generated. In the early attempts (1925-1950) to commercialize the segregation process, shaft, hearth
and rotary kiln furnaces were employed. However, these reactors did not satisfy all the conditions
specified. Due to predominantly technical problems of varying nature (mainly mechanical), but also
political instability and fluctuating copper prices, these research and development operations were
abandoned.
However, in the early nineteen sixties the Anglo-American Corporation proposed the use of
fluidized beds (at that time a relatively new reactor in extractive metallurgy). The fluidized bed
does provide efficient heat transfer and can oxidize copper sulphides at the same time. A 10
tonnes/per day pilot unit was built in Nchanga, Zambia. The ore was heated in the fluidized bed
while the segregation took place in a separate non-fluidized chamber inside or just beside the
fluidized bed at 750-800 0C [46,47,49]. It was found that the preheated refractory copper ores
reacted almost completely within 2 minutes in the segregating chamber, if salt and coal particles
were provided in the optimum manner and ratio. The quantity and size of the coke particles is very
important, since it is known to determine both copper metal nucleation and grade and recovery
during subsequent flotation. It was revealed that silver could also be segregated while bismuth,
selenium, tellurium, arsenic and antimony stayed behind. These encouraging results initiated in
1965 the construction and commissioning of a 500 tonnes/day commercial pilot unit at Rhokana,
Zambia. After some start-up problems, this plant operated successfully and continuously for 7
years. Based on the promising operating experiences at Rhokana, the first full scale 3600
tonnes/day plant was constructed in Akjoujt, Mauritania in 1970. The plant consisted of four 900
tonnes/day fluidized beds and produced its first copper concentrate, averaging more than 60% Cu,
in 1971. Unfortunately, political and economic factors discontinued the application of this
technology around 1975. However, research and development still continue, especially for nickel
oxide ores.
479

The treatment of pyrite cinders by means of salt roasting dates back to 1842, when Longmaid was
the first to patent the concept [58]. Until 1950 the process was carried out at about 500 0C in usually
a multiple hearth furnace using 8-10 wt% sodium or calcium chloride. In the charge the process
chemistry can be summarized by reactions 12a to 12f.
3FeS2 (s) + 8O2 (g) = Fe3O4 (s) + 6SO2 (g)

(12a)

2SO2 (g) + O2 (g) = 2SO3 (g)

(12b)

2NaCl(s) + 2SO3 (g) = Na2SO4 (s) + SO2 (g) + Cl2 (g)

(12c)

Cl2 (g) + H2O(g) = 2HCl(g) + O2 (g)

(12d)

MeO(s) + Cl2 (g) = MeCl2 (s,l) + O2

(12e)

MeO(s) + 2HCl(g) = MeCl2 (s,l) + H2O(g)

(12f)

The off gases in this process consisted of HCl, H2O, O2, SO2 and SO3. After de-dusting and
condensation a dilute acid containing sulphuric, sulphurous and hydrochloric acid was formed. The
chloridized residue was leached with this acid to extract the nonferrous metal chlorides. Lead, gold
and silver were not recovered, since they stayed behind as insoluble PbSO4, probably metallic gold
and AgCl. The iron-rich residue (61-63 wt% Fe) was dried, filtered, mixed with lime and coal,
agglomerated and sintered, before it was charged to an iron blast furnace. A lead-silver alloy has
been recovered at the bottom of those blast furnaces. The nonferrous metal chlorides leached
(copper, zinc, cobalt, nickel, indium, thallium, cadmium) were recovered in an ingenious
hydrometallurgical operation (Duisburger Kupferhtte) consisting of cementation (using both
metallic copper and iron), aqueous chlorination (cobalt oxidation), crystallization (sodium sulphate
removal), precipitation and electrolysis steps. Pyrometallurgical steps such as calcination and
reduction were also incorporated. However, nonferrous metal grades were insufficient to pay for the
processing costs and the residues contained too much nonferrous metals for direct use in
ironmaking. To resolve this problem, chloridizing volatilization processes were developed after
1950.
In the early nineteen fifties the first pyrite cinder pellets were made and chloridizing volatilization
was carried out in a shaft furnace using calcium chloride at Vuoksenniska, Finland. Due to
presumably corrosion problems, high fuel consumption and considerable amounts of unburned
sulphur in the residue, the operation closed down shortly after start-up. However, in Japan research
and development continued on this concept. This resulted in the establishment of a 350 tonnes/day
rotary kiln operation by Kowa-Seiko (Japan) in the early nineteen sixties. Later on bigger plants
were built in Spain and Portugal. In these plants chlorides of Cu, Zn, Pb, Co, Au and Ag are
volatilized at 1250 0C from 15 mm pellets containing cinders and 30 wt% calcium chloride. The
residual iron-rich pelletized residue can be fed directly into a blast furnace, while the nonferrous are
recovered by electrochemical procedures [54]. The success of this process is partly based on the
high extraction efficiencies of nonferrous metals. The presence of precious metals in the KowaSeiko cinders, especially silver, also significantly contributes to the economics. It should be
emphasized that the use of chloride metallurgy for recovering precious metals is widely
acknowledged [59-63]. However, in the case of pyrite cinders the most important precondition is

480

the need for a profitable sulphuric acid market. Furthermore, milling engineers always try and can
lower the nonferrous metal content in the pyrite, mainly by flotation techniques (=competition).
Pyrometallurgical Treatment of Metal Sulphides
Since the bulk of the base metals are recovered from sulphide deposits, it is not surprising that
pyrometallurgical processing of sulphides in the chloride system has been investigated. In most
cases the objective was to develop an alternative processing route for sulphide concentrates, which
avoids the environmental drawbacks of conventional roasting and smelting. In addition, an
economically and environmentally acceptable route for iron disposal (e.g. fayalite) or iron
utilization should be available. Hence, the production of sulphur dioxide and sulphuric acid should
be prevented, while on the hydrometallurgical side an alternative for the goethite and jarosite
precipitation steps is highly desirable. Again the sequence chlorination, pyrohydrochloridization
and salt roasting will be followed. However, no process details will be presented since it warrants a
separate study. The inquisitive reader is encouraged though to consult the references provided [6472].
The fundamentals of high temperature sulphide chloridization can be represented by reactions 13 to
15. Chlorination, shown in reaction 13a and 13b, has been practised on pyrite/galena mixtures
(Ashcroft and Swinburne process, Broken Hill, Australia) and nickel/ copper sulphide concentrates
(research and development work). Reaction 13a is the desired mechanism, while excess chlorine
will result in the formation of unwanted sulphur mono- or dichlorides (reaction 13b). This
chlorination option offers the interesting opportunity to recover elemental sulphur. In contrast to
oxides, the chlorination of sulphides is carried out at much lower temperature, usually ranging from
300-500 0C. Hence, the metal chlorides are recovered through volatilization or solubilization in the
next processing step. In view of the earlier presented topic on the detrimental effects of water
vapour during chlorination, externally heated reactors appear to be required for industrial purposes.
Given the history of the Torco process, only an (externally heated) fluidized bed would seem to
qualify. It should also be noted that the presence of oxygen is also unacceptable (SO2 formation).
Hence, the fluidization gases should either be inert or reducing, and hot.
MeS(s) + Cl2 (g) = MeCl2 (s,l,g) + S2 (s,l,g)

(13a)

MeS(s) + 1Cl2 (g) = MeCl2 (s,l,g) + S2Cl2 (g)

(13b)

Pyrohydrochloridization of metal sulphides has not received a lot of attention. This is probably
due to the obnoxious nature of the hydrogen sulphide formed. This gas might be considered as a
deleterious constituent, since there is no direct application for H2S. However, it should be
underlined that after condensation or leaching of the metal chlorides H2S can be converted into
elemental sulphur by the Claus process, reaction 14b and 14c. Another alternative is the highly
exothermic reaction with chlorine yielding hydrogen chloride and elemental sulphur (reaction 14d).
The latter option requires the complete integration of chlorides into a sulphide processing flow
sheet (chloride electrowinning and HCl leaching or pyrohydrochloridization). Care has to be taken
in designing the reactor and choosing suitable construction materials, since processes involving
elemental sulphur are preferentially (kinetics) carried out just above the melting point of sulphur,
i.e. in the temperature range 120-150 0C. Higher temperatures promote sulphide (pS2) volatility.

481

MeS(s) + 2HCl(g) = MeCl2 (s,l,g) + H2S(g)

(14a)

H2S(g) + O2 (g) = SO2 (g) + H2O(g)

(14b)

2H2S(g) + SO2 (g) = 3S0(s,l) + 2H2O(g)

(14c)

Cl2 (g) + H2S(g) = 2HCl(g) + S0(l)

(14d)

The discussion on pyrite cinders already introduced the role of sulphides in salt roasting. In
reactions 15a to 15c the essential mechanisms have been summarized. Salt roasting of metal
sulphides is executed at 300-500 0C. The reactors investigated were predominantly multiple hearth
and rotary kiln furnaces. The raw materials treated were nickel/copper sulphide and lead/zinc
sulphide concentrates. The biggest problem encountered was the chloridization of iron compounds.
The use of steam and oxygen was proposed to selectively oxidize the iron chlorides.
MeS(s) + M""Cl2 (s,l) = MeCl2 (s,l,g) + M""S(s)

(15a)

MeS(s) + M""Cl2 (s,l) + 2O2 (g) = MeCl2 (s,l,g) + M""SO4 (s)

(15b)

"

MeS(s) + 2M Cl(s,l) + 2O2 (g) = MeCl2 (s,l,g) +

M"2SO4 (s)

(15c)

Nowadays, there are few commercial pyrometallurgical chloride extraction processes for both
metal sulphides and oxides due to a combination of factors. Pigment (TiO2) production is of course
the most well-known exception. Important aspects for the failure and absence of pyro- but also
hydrometallurgical processing incentives in the chloride system are:
v
v
v
v
v
v

Economic boundary conditions, such as metal and sulphur prices, process capacity versus
capital investment, processing costs and maintenance expenditures.
The shortage or absence of suitable construction materials. However, nowadays that
argument is based upon insufficient knowledge or high equipment costs compared to
sulphate based metallurgy.
Metallurgical ignorance with respect to the feasibility of both metallurgical and especially
chemical chloride processes, which do exist.
Insufficient knowledge of the market demand for a certain metal, especially its physical
properties. The final product(s) tend(s) to be overvalued.
Technological problems, such as outlined throughout this overview.
Lack of chloride practitioners, i.e. a psychological effect. Development costs tend to be
higher, due to the unforgiving aggressiveness of chloride systems. This can rapidly
discourage management.

Hydrometallurgical Processing of Both Metal Oxides and Sulphides

In view of the number of research and development projects carried out, one might get the
impression that chloride hydrometallurgy is much more popular than chloride pyrometallurgy. This
perception is the result of a significant age difference between hydro- and pyrometallurgy, which is
reflected in the metallurgical history of almost every base metal. Furthermore, hydrometallurgical
tests are easier to do. In this overview only the essential aspects of chloride hydrometallurgy will be
highlighted. Some process applications will be discussed in a separate section to demonstrate their

482

significance as a meaningful unit process operation now or in future combined pyro- and
hydrometallurgical chloride processes. Especially, the economic aspect of lixiviant regeneration
will be emphasized. Industrial and academic process descriptions have been outlined in the
enclosed references [73-98].
Irrespective of the method applied (i.e. aqueous chlorination, HCl leaching, metal chloride
metathesis), chloride leaching of metal oxides is relatively easy as long as the metal chloride is
more stable than the metal oxide in solution. This is true for almost every metal with the exception
of the very refractory ones like for instance Si, Al, Ti and Zr. In reactions 16 to 18 the three possible
leaching mechanisms have been presented.
MeO(s) + Cl2 (aq) = MeCl2 (aq) + O2 (aq)

(16)

MeO(s) + 2HCl(aq) = MeCl2 (aq) + H2O(l)

(17)

MeO(s) + Me""Cl2 (aq) = MeCl2 (aq) + Me""O(s)

(18)

Aqueous chlorination has been investigated for treating both nickel/cobalt oxides [90] (laterites)
and zinc oxides [96]. Oxygen sparging has been suggested as a means for selectivity, i.e. aqueous
hydrolysis. Hydrogen chloride leaching appears to have been tried or carried out for every base
metal oxide. In Peek [0] HCl leaching of the iron oxide layer on steel plates, i.e. steel pickling, and
the subsequent recovery of the chloride content via pyrohydrolysis, i.e. a high temperature reversal
of reaction 17, is exhaustively described (Chapter III). Reaction 18 is more a purification
(metathesis) step and is in general not regarded as a leaching mechanism. Lack of selectivity and
high reagent consumptions have in most cases prevented the application of chloride
hydrometallurgy for metal oxides.
In addition to the context of geochemistry, it is evident that chloride hydrometallurgy for metal
sulphides is quite a popular subject. Again a distinction has been made between the use of chlorine,
HCl and metal chlorides. Reaction 19 gives the opportunities and limitations of aqueous
chlorination. Reaction 19a gives the ideal mechanism in which elemental sulphur is produced.
However, accurate control on both the chlorine feed rate (oxidation-reduction potential) and pH are
necessary to prevent reactions 19b and 19c, i.e. metal sulphate and sulphuric acid formation,
respectively. Oxygen sparging has been used to reject undesirable constituents such as iron as
hydrated iron oxides. The technique has been applied to copper sulphide minerals, complex
lead/zinc concentrates and nickel-copper sulphide concentrates. Only the latter option has been
commercialized in Norway, by Falconbridge [75]. Some operational aspects will be highlighted
later.
MeS(s) + Cl2 (aq) = MeCl2 (aq) + S0(s)

(19a)

MeS(s) + 4Cl2 (aq) + 4H2O(l) = MeSO4 (aq) + 8HCl(aq)

(19b)

MeS(s) + 4HCl(aq) = MeCl2 (aq) + H2SO4 (aq) + 2HCl(aq)

(19c)

Non-oxidative HCl leaching is symbolized by reaction 20a. Finely ground iron, nickel and cobalt
sulphide can dissolve under strongly acidic conditions, but copper sulphide can only be solubilized
483

if the redox potential of the solution is raised. Under the latter conditions elemental sulphur will be
formed (reaction 20c). Non-oxidative HCl leaching gives hydrogen sulphide, which has to treated
via for instance the Claus process (reaction 14c and 20b), since there is little demand for H2S in
metallurgy. The difficulties surrounding reactor design for this option have already been stipulated.
The HCl leach has been suggested for chalcopyrite ores (oxidizing leach), nickel bearing pyrrhotites
(non-oxidative leach) and lead/zinc sulphide concentrates. It was Falconbridge again, which started
development in 1953 by piloting non-oxidative HCl leaching of matte [74]. The great advantage of
non-oxidative HCl leaching is that H2S is nearly insoluble in chloride solutions, hence a free and
"easy" metal/sulphur separation is attained. The biggest concerns are leaching rates (sulphur
coatings around particles), dissolution of iron and complete elimination of sulphur from the matte
or concentrate. Especially the need for recovering chlorides from the dissolved iron units (lixiviant
regeneration) presents an economic barrier. Processes such electrolysis, hydrogen reduction and
pyrohydrolysis have been proposed for recovering the HCl. These subjects will be addressed in the
next section.
MeS(s) + 2HCl(aq) = MeCl2 (aq) + H2S(g)

(20a)

2H2S(g) + SO2 (g) = 3S0(s) + 2H2O(g)

(20b)

MeS(s) + 2HCl(aq) + O2 (aq) = MeCl2 (aq) + H2O(l)+ S0(s)

(20c)

Extensive test work has been carried out on metal chloride leaching of base metal sulphides. A
distinction can be made between ferric chloride (reaction 21a) leaching and cupric chloride
(reaction 21b) leaching attempts. An alternative might be provided by oxidative ferrous chloride
leaching. Ferrous chloride is readily available as pickle liquor at many places and the iron can be
directly rejected as iron oxide. However, lixiviant regeneration does not occur, i.e. depending on the
nonferrous metal chloride recovery route chlorine or HCl will be obtained, not FeCl3 or CuCl2. The
chemistry of these options has been given in reaction 21a to 21c.
MeS(s) + 2FeCl3 (aq) = MeCl2 (aq) + FeCl2 (aq) + S0(s)

(21a)

MeS(s) + 2CuCl2 (aq) = MeCl2 (s,l,g) + Cu2Cl2 (aq) + S0(s)

(21b)

2MeS(s) + FeCl2 (s,l) + 1O2 (aq) = 2MeCl2 (aq) + Fe2O3 (s) + S0(s)

(21c)

Ferric chloride leaching has been exercised on a laboratory scale for pyrrhotite, lead/zinc sulphide
matte, galena, chalcopyrite and nickel sulphide. Only the treatment of chalcopyrite by the Cuprex
process was extended to the pilot plant scale by the Cyprus Metallurgical Process Company in
Tucson, Arizona. Cupric chloride leaching has been investigated for both chalcopyrite and zinc/lead
concentrates. A well-known other example is the Clear process (chalcopyrite). In both cases cupric
and ferric chloride leaching have actually been combined. The purification and metal recovery
process steps developed neatly illustrate the advantages of working in the hydrometallurgical
chloride system. As with sulphate hydro-metallurgy, considerable research and development work
needs to be carried out on the role and elimination of impurities. It is obvious that lixiviant
regeneration, environmentally acceptable and/or economical iron (oxide) rejection and removal of
elemental sulphur are also the key issues in chloride metallurgy.

484

The pyrometallurgical and hydrometallurgical chloride process technology options discussed have
been summarized in Figures 7 and 8. Now, the purification of off gases and solutions and the
recovery of metals from the purified solutions will be explained.

Figure 6: Overview of the Research, Development and Application of Chloride

Pyrometallurgy on Various Raw Materials. Italics Indicate Industrial Establishment
in Past or Present.

485

Figure 7: Overview of the Research, Development and Application of Chloride

Hydrometallurgy on Various Raw Materials. Italics indicate Industrial
Establishment in Past or Present.

PROCESS TECHNOLOGY - PURIFCATION AND METAL RECOVERY

Solution purification in the chloride system can be achieved via selective precipitation as metal
sulphides or carbonates, solvent extraction, crystallization, ion exchange and fractional distillation.
Metal recovery can be accomplished via electrowinning, hydrogen reduction and oxide
precipitation. All these subjects [99-125] will be described using existing or dismissed, but
formerly successful, examples of unit process operations in the chloride system.
Pyrite Cinders Leach Liquor Treatment
In Figure 9 the solution purification steps for the low temperature chloridization of pyrite cinders by
the Duisburger Kupferhtte (1876-1965) has been given. It is clear that selective precipitation was
the only method commercially available in those days to purify the complex leach liquor containing
both nonferrous metal chlorides and sulphates. The simplified flow sheet shows that the first
purification step consisted of copper cementation using metallic iron. This method was
discontinued because of ferrous chloride disposal problems. It was replaced by a two stage copper
precipitation in which cupric chloride was first reduced to cuprous chloride using metallic copper
followed by addition of lime water to precipitate cuprous oxide for further processing.
486

Subsequently, the sodium and large amounts of the sulphate were recovered through crystallization
of hydrated sodium sulphate. Then lime was added to the solution to precipitate both gypsum
(sulphate removal) and ferric hydroxide. Chlorine was added in this step to oxidize ferrous to ferric
iron. Chlorine has also been used to oxidize cobalt, if a nickel cobalt separation was required. Next
indium and cadmium were removed by cementation using metallic zinc. Finally, zinc was
precipitated as zinc hydroxide which is subsequently calcined, while the lime added converted to
calcium chloride which was discarded. Nickel precipitated together with zinc and was ultimately
recovered by thermal reduction of the zinc oxide residue. It is understandable that reagent
consumption was high, while lixiviant regeneration (both chloride and sulphate) was very limited.
Hence, as mentioned previously processing costs were too high in the long run.

Figure 8: Purification of Duisburger Kupferhtte Pyrite Cinders Leach Liquors

(Low Temperature Salt Roasting) via Cementation.
Due to the absence of sulphates and certain alkali metals the purification steps for the high
temperature salt roasting process for pyrite cinders (Kowa-Seiko operation) was less complicated
and thus profitable. However, a significant improvement was made when solvent extraction (SX)
was incorporated in the process flow sheet. In Figure 10 a two-stage solvent extraction operation for
removing zinc from the leach liquor has been presented. This modification known as the Zincex
[110-112] or Espindesa process was commercialized in 1976 at the Bilbao plant of Metalquimica
del Nervion in Spain. At Bilbao 8000 tonnes per year zinc are produced via the Zincex process.
Given this successful operation, an 11000 tonnes per year zinc Espindesa plant was built in
Portugal in 1980 (Quimigal-Barreiro pyrite cinders treatment). The Zincex process consists of a
primary anionic SX step in which the zinc is extracted from the impure leach liquor as ZnCl42using a secondary amine (Amberlite LA-2) and a secondary cationic SX step where after careful pH
control the Zn2+ cation is removed from the solution using D2EHPA (di-2-ethyl-hexyl phosphoric
acid). The loaded organic from the secondary SX step can be stripped with spent electrolyte

487

yielding a zinc sulphate solution suitable for conventional sulphate electrowinning. The raffinates
can, depending on the nonferrous metal content, be returned to leaching or sent to other purification
steps. The D2EHPA also co-extracts some ferric iron, which cannot be stripped from the organic
with spent electrolyte. Therefore, a D2EHPA bleed stream is treated with strong HCl to remove the
iron. In order to minimize chloride losses a secondary amine SX step is necessary to separate HCl
and FeCl3. The latter chlorides are lost.

Figure 9: Two-Stage Solvent Extraction of Zinc from Pyrite Cinders Leach Liquors
(High Temperature Salt Roasting), i.e. Zincex or Espindesa Process.
Processing of Galvanized Steel Pickle Liquors
Galvanizing pickle liquors vary widely in composition, i.e. 80-130 g/l Fe2+, 20-120 g/l Zn2+ and 1 to
2 wt% free HCl. They are formed as a result of HCl or ferrous chloride pickling of galvanized
sheets or any other objects. The use of ferrous chloride is preferable, since it is low cost, is very
effective owing to the cementation effect of ferrous chloride in solution and requires no additional
baths or handling equipment. Normally ferrous chloride pickle liquors are processed through
pyrohydrolysis. However, chloride recovery from these zinc bearing pickle liquors poses a problem,
because zinc chloride builds up in a conventional pyrohydrolysis unit. Therefore, zinc has to be
removed prior to conventional pyrohydrolysis. This can be done via ion exchange (IX) in the so
called Metsep process [106,107] developed by the National Institute of Metallurgy in South Africa
and Woodall-Duckham in 1973-1975. In Figure 11 a simplified outline of the process has been
given.
A weak-base ion exchange resin (Relite MG) is used to extract zinc as R2+(ZnCl4)2- from the pickle
liquor in a semi-continuous counter-current series of ion exchange columns. The resin is fluidized
by the upward flow of the liquor, while hydraulic transport to the next stage (column) occurs when
the feed is temporarily discontinued. Elution is carried out with water and some zinc chloride eluate
to minimize dilution. The zinc chloride is then transferred to the conventional sulphate system by

488

solvent extraction with D2EHPA. The zinc free pickle liquor is processed via pyrohydrolysis in a
spray roaster yielding ferric oxide. A 31 m3/h (pickle liquor feed rate) IX plant was operated
successfully for at least two years until changes in the market situation forced the plant to be closed
down [113].

Figure 10: Simplified Flow sheet of the Metsep Process for Zinc Recovery from
Galvanizing Pickle Liquors via Ion Exchange.
An alternative option for treating galvanizing pickle liquors is the MeS process developed by MXProcessor AB in Sweden. In this process zinc is extracted as ZnCl42- with tri-butyl phosphate
(TBP). To avoid co-extraction of iron, it is essential that all the iron is in the divalent state.
Otherwise a separate strong HCl organic strip similar to the one found in the Zincex process is
required. However, the iron-free organic is stripped with water or dilute sulphuric acid and then
mixed with additional sulphuric acid in a boiler where the HCl is evaporated and chloride-free zinc
sulphate is crystallized for electrowinning. The ferrous chloride raffinate containing less than 100
ppm zinc could be used in water treatment. This MeS has been successfully piloted in The
Netherlands.
Falconbridge Matte Leach Processes -HCl and Cl2The Falconbridge Matte Leach Process [74,75] was based on leaching Ni-Cu matte from its
Sudbury smelter with strong hydrochloric acid in rubber-lined equipment at 70 0C, i.e. a nonoxidative HCl leach yielding hydrogen and hydrogen sulphide gas. The simplified flow sheet of
this operation has been given in Figure 12. This plant was operated from 1968 to 1983 [119] in
Kristiansand, Norway as a precursor to the present chlorine leach (oxidative leach), which will also
be discussed here. The former process consisted of two solvent extraction stages, i.e. one unit for
ferric iron removal using TBP and one unit for cobalt (and some copper) extraction using TIOA

489

(tri-iso-octyl amine), a NiCl2.4H2O crystallization step, followed by crystal drying and NiCl2.H2O
pyrohydrolysis which yielded NiO granules (1600 kg/h) and HCl gas. The pyrohydrolysis step is
outlined by Peek [0] (Chapter III). After absorption the HCl was recycled to the leaching process,
while the NiO was reduced in a rotary kiln with hydrogen gas to give metallic nickel granules for
sale. Some HCl gas was also used in nickel chloride crystallization (salting out effect). The copper
sulphide leach residue containing precious metals is processed through the conventional RLE
sulphate route.

Figure 11: Simplified Flow sheet of the Falconbridge Matte Leach Process from
1968-1983. The Process Comprised of HCl Leaching and NiCl2 Pyrohydrolysis.
In 1981-1983 the chlorine leach process was introduced at Nikkelverk A/S, Kristiansand, Norway.
An important reason for doing this was the need for a different nickel end-product via a less energyintensive, more simplistic and more profitable treatment route. The simplicity of the chlorine leach
can be exemplified in two ways. Firstly, the chlorine leach displaced the super-azeotropic HCl
leaching step which required constant and laborious control of the water balance. Secondly, the
nickel chloride crystallization, drying and pyrohydrolysis unit process operations were replaced by
pregnant liquor purification, non-acidic filtration (pH=2) and nickel chloride electrowinning. The
process has been outlined in slightly more detail below.
The Ni3S2-Cu2S-Ni0.7Cu0.3 matte is leached at 100 0C in agitated vessels at a high redox potential,
which is continuously measured in order to maintain the desired Cu2+/Cu+ ratio. For every ton of
Cl2 added one ton of water is boiled off. This is beneficial for the water balance of the system. The
important leaching reactions are given below:
6Cu+(aq) + 3Cl2 (g) = 6Cu2+(aq) + 6Cl-(aq)

(22a)

Ni3S2 (s) + 2Cu2+(aq) = 2NiS(s) + Ni2+(aq) + 2Cu+(aq)

(22b)

490

2NiS(s) + 4Cu2+(aq) = 2Ni2+(aq) + 4Cu+(aq) + 2S0(s)

(22c)

2Cu2S(s) + 2S0(s) = 4CuS(s)

(22d)

Roughly 92% of the nickel is extracted during chlorine leaching yielding a solution consisting of
230 g/l Ni and 50 g/l Cu. Nickel solubilization is lower than in the MLP resulting in a higher
tonnage of residue, which is a serious drawback. Consequently, the copper-nickel bearing slurry is
treated in an autoclave at 140-150 0C (second aqueous chlorination step) in order to maximize
nickel and copper dissolution. Subsequently, the slurry is sent to copper precipitation, where in two
stages at 80 0C and 65 0C, respectively, the copper is removed via metallic nickel and matte
addition at a much lower redox potential. The precipitation or metathesis mechanism is given in
reactions 23a to 23d.
2Cu+(aq) + S0(s) + Ni3S2 (s) = Cu2S(s) + Ni2+(aq) + 2NiS(s)
Ni0(s)

S0(s)

2Cu+(aq)

= Cu2S(s) +

Ni2+(aq)

(23a)
(23b)

Cu2S(s) + S0(s) = 2CuS(s)

(23c)

S0(s) + 2Cu+ = CuS(s) + Cu2+(aq)

(23d)

The elemental sulphur and copper sulphide residue is treated via the conventional sulphate route
after extensive washing (chloride removal) and filtration. The leach liquor is then sent to the iron
precipitation steps where the pregnant nickel chloride solution is treated to oxidize ferrous to ferric
using chlorine and nickel carbonate (neutralizer). Then cobalt is extracted via solvent extraction
using TIOA. Most of the lead and manganese is also removed, which requires additional
precipitation steps in the cobalt and nickel electrolytes. Thus, both a purified nickel and cobalt
chloride solution are obtained. Both metals are recovered via chloride electrowinning.
The introduction of chloride electrowinning in metallurgy initially focused on fused salt
electrolysis using graphite anodes from the chlor-alkali industry. These anodes have numerous
drawbacks like for instance low electrical conductivity, high overvoltage for chlorine production,
graphite oxidation, formation of graphite slimes and their size [120]. This changed with the arrival
of DSA's in 1960-1970, i.e. dimensionally stable anodes developed by De Nora in Italy. These
anodes had good electrical conductivity, chemical resistance against Cl2, dimensional freedom and
stability, and low chlorine overpotential, even at high current densities. They are not used for fused
salt solutions, but are applied in the chlor-alkali industry for NaCl solutions. DSA's consist of
titanium sheets or expanded Ti mesh coated with an electro-active layer of a refractory (platinum
group) metal oxide such as for instance ruthenium oxide. The discovery of these anodes made
cobalt and nickel chloride electro-winning technically and economically viable. At Nikkelverk,
electrolyte is fed to cells which are equipped with diaphragms, although membranes can also be
used to separate the anolyte from the catholyte. The chlorine recovery demands a complex, but
reliable collection system. Typical operating parameters for the nickel chloride solution EW step
are a current density of 220 A/m2, a current efficiency of 98%-99%, a temperature of 60 0C, a Ni
concentration in the anolyte of 54 g/l and a nickel concentration in the catholyte of 60 g/l. Hence,
chloride electrowinning has become an established technology for both nickel and cobalt.

491

Zinc Chloride Electrolysis -Chlorine RouteIn view of the treatment of complex zinc/lead sulphide ores and other zinc bearing raw materials, it
is interesting to mention that zinc chloride electrowinning has been known for quite a long time. In
the mid-1890's commercial zinc chloride EW plants were built and operated in both Germany and
England using the old chlor-alkali technology, i.e. diaphragm cells and graphite anodes [121].
However, the use of DSA's for zinc chloride electrowinning has only been demonstrated on a
laboratory scale [117]. It is reported that metallic zinc can be deposited from a 15 g/l Zn electrolyte
(0.12 mol/l HCl) using 15 mg/l TBACl (tetra-butyl ammonium chloride) to prevent dendritic
growth. The current density was 323 A/m2 while the current efficiency amounted more than 93%.
Thomas and Fray [96] investigated the electrowinning of zinc from an 80 g/l zinc chloride solution
(and higher concentrations) at a current density of about 2500 A/m2 in a cell without a diaphragm.
Below 9 0C solid chlorine hydrate was formed at the anode, while above this temperature chlorine
gas was evolved. Current efficiency was about 92% using periodic current reversal. These two
examples illustrate that there is room for divergence in this field.
HCl and Metal Recovery via Electrowinning
The regeneration of HCl is highly desirable when an HCl leaching step is utilized. In
electrowinning one option would be to develop an electrowinning cell in which chloride ions can
not reach the anode to form chlorine. The introduction of such a cell would simplify and change
tank house design drastically. At the Delft University of Technology the use of a three compartment
or two membrane electrolytic cell is being explored [122,123].

Figure 12: Simplified Representation of the Two Membrane Electrolytic Cell for
HCl Regeneration. The HCl is made in the Ampholyte [122,123].

492

Figure 13: Nickel Electrowinning a Perspex Two Membrane Electrolytic Cell

yielding Metallic Nickel, Hydrochloric Acid and Oxygen.
In Figures 13 and 14 a schematic cross section of such a two membrane electrolytic cell and the
possible application for nickel chloride, respectively, has been presented. The investigations have
been carried out in a Perspex cell consisting of three compartments of equal dimensions separated
by one piece of cation exchange membrane and one piece of anion exchange membrane. Leadantimony (10% Sb) anodes and DSA's have been tested in combination with nickel cathodes.
Electrowinning experiments were done at a current density of 200 A/m2 and 50 0C. A 1 M NiCl2
solution was used as the catholyte, a 0.2 M NiCl2 solution as the ampholyte and a 1 M H2SO4
solution as the anolyte. It was found that cathodic current efficiencies of more than 95% could be
attained with an acceptable cell voltage of 2.7-3.1 V depending on the anode employed. Up to 1
mol HCl per kilogram solution was obtained in the ampholyte. Optimization and commercialization
of this concept is dependent on membrane selectivity (both anion and cation exchange membranes),
long term membrane performance (durability) and membrane (operating) cost. Test work on this
subject was done in the late 90s.
Fractional Distillation of Metal Chlorides
The application of (counter current) fractional distillation of metal chlorides is in practice restricted
to the treatment of precious metals, most likely because of the associated energy requirements. An
example (FeCl3 separation from TiCl4) was already given when discussing carbo-chlorination of
rutile. If metal chlorides have boiling points or sublimating points so close together that their
separation through distillation becomes impractical, then partial oxidation or reduction of the metal
chlorides to a lower valency might be a solution in some cases. Vanadium removal from titanium
tetra chloride through partial oxidation has already been mentioned as an example. Distillation
usually requires inert or highly reducing atmospheres to preserve precious metal chloride stability.
Hydrogen Reduction of Metal Chlorides
The decomposition of metal chlorides into metals via a reaction with hydrogen can be carried out at
relatively high temperatures (100-800 0C), i.e. in molten salts, and at low temperatures in aqueous
solutions. Apart from the reaction kinetics involved, the technical feasibility of the concept (e.g.
equipment design) and the need for metal complexes in aqueous solutions above pH=7, the most

493

important precondition for the application of hydrogen reduction is that hydrogen needs to be
generated somewhere in the overall process flow sheet. Otherwise hydrogen becomes a
consumable.
Non-oxidative leaching could provide H2 gas. One successful operation was the Peace River
Mining and Smelting Process [124,125]. In this process, high surface area scrap (steel turnings, cast
iron borings and detinned cans) was dissolved in hydrochloric acid at 95 0C yielding an impure
ferrous chloride solution and hydrogen gas. After solution purification the ferrous chloride was
crystallized, dried, briquetted and then reduced to sponge iron in a shaft furnace at 700-800 0C with
the hydrogen generated during leaching. The sponge iron was ground to iron powder. A 50,000
tonnes per year plant was built in Amherstburg, Ontario, Canada. Due to insufficient capital and
lack of understanding of the iron powder market, this enterprise failed. This was unfortunate, since
this elegant concept could have provided an impetus to chloride metallurgy.
Oxide Precipitation
Oxide precipitation has already been mentioned with respect to lixiviant regeneration, i.e. high
temperature metal chloride hydrolysis. It is not a genuine metal recovery option, since the metal
oxide needs to be treated in order to attain the metal. Consequently, pyrohydrolysis is more energy
intensive than electrowinning for recovering metals. However, pyrohydrolysis has the potential to
become an integrated metal extraction and lixiviant regeneration process.
Concluding Remarks
It is evident from the many processing technology examples presented in this chapter that chloride
metallurgy has great potential. In this perspective this paper is offered as a source of encouragement
to all those metallurgists that attempt to further knowledge and advancement of all these extensive
and complex processing opportunities in the chloride system.

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