Dutrizac1992 PDF

tlydrometallurgy, 29 ( 1992 ) 1-45
Elsevier Science Publishers B.V., Amsterdam
The leaching of sulphide minerals in chloride

media
J.E. Dutrizac
Mineral Sciences Laboratories, CANMET, Energy, Mines and Resources Canada, Ottawa, Ont.,
Canada
(Revised version accepted November 15, 1991 )
ABSTRACT
Dutrizac, J.E., 1992. The leaching of sulphide minerals in chloride media. In: W.C. Cooper and D.B.
Dreisinger (Editors), Hydrometallurgy, Theory and Practice. Proceedings of the Ernest Peters In-
ternational Symposium. ttydrometailurgy, 29: !-45.
Recent studies on ~he ferric chloride and cupric chloride leaching ofchalcopyrite, galena and sphal-
erite are reviewed. Although the chloride leaching ofchalcopyrite concentrates has been proven at the
demonstration plant scale, the leaching reaction is difficult. In contrast, galena dissolves rapidly in
FeCI.a media, and both the leaching rate and lead solubility increase significantly with increasing chlo-
ride concentration. The hydrometallurgical treatment of lead concentrates seems to be technically
feasible. The sphalerite leaching rate is strongly affected by its solid solution iron content, and leach-
ing processes for iron-rich zinc concentrates could probably be developed. The importance of inter-
mediate sulphide phases and insoluble reaction products on the leaching of sulphides is discussed. In
addition, it is postulated that at least part of the elemental sulphur reaction product is formed via the
oxidation of dissolved HaS. The ability of chloride leaching processes to generate elemental sulphur
while leaving pyrite largely unaffected makes them especially useful tbr the treatment of pyritic com-
plex sulphides. Thus, recent chloride leaching technologies for complex sulphides are also reviewed.
INTRODUCTION
The leaching of copper from sulphide ore deposits occurs naturally; as early
as 1086 Chinese metallurgists were recovering copper from the natural drain-
age waters of such deposits [ l ]. Similar operations were carried out on a large
scale as early as 1737 to extract copper from the acid waters at Rio Tinto,
Spain. Natural weathering processes liberated both copper and iron from the
copper-bearing pyrite ores, and the copper was recovered by cementation on
iron. Subsequent natural evaporation of the solutions in the stream beds dur-
ing the dry season allowed ferrous sulphate to be recuperated as a by-product.
Correspondence to: J.E. Dutrizac, Mineral Sciences Laboratories, CANMET, Energy, Mines
and Resources Canada, 555 Booth Street, Ottawa, Ont. K IA 0G l, Canada.
0304-386X/92/$05.00 © 1992 Elsevier Science Publishers B.V. All rights reserved.

2 J.E. DUTRIZAC
Large-scale heap leaching of calcined ore began in 1876, and the heap leach-
ing technique was soon extended to unroasted, low-grade pyrites [2 ]. The
leaching of metallic gold in cyanide media to prepare solutions suitable for
gold electroplating has been employed since the mid-19th century. In 1887-
1888, MacArthur and the two Forrest brothers extended the cyanide leaching
technique to low grade gold ores and the tailings from gold gravity circuits
[3 ]. Most initial applications used vat leaching. Today, various cyanide
leaching techniques treat around 500,000,000 t/yr of ore, averaging about 5
ppm Au, to produce approximately 2,500 t of gold. This is certainly the larg-
est single application of modern leaching technology [ 4 ].
At about the same time as the cyanide process was bei~;g developed, Bayer
discovered that aluminum could be extracted from bauxite by leaching in
NaOH media under pressure and that pure aluminum hydroxide could be
prepared by seeding the cooled pregnant solution. This discovery laid the
foundations of pressure-leaching technology and also paved the way for the
rapid expansion of the electrolytic aluminum industry [ 5 ]. Today, the Bayer
process treats abo~,t 90,000,000 t/yr ofbauxite, containing approximately 40%
AlaO3, making this the largest single application of pressure leaching
technology.
Vat leaching and heap leaching methods were widely used to recover cop-
per from oxide ores during the 19th and early 20th centuries. The solubilized
copper was recovered either by cementation on iron or by direct electrolysis
[ 6 ]. As methods to extract copper selectively from the pregnant solutions did
not exist until recently, early operations were restricted to relatively high-grade
ores or to ores having low soluble iron contents. With the advent of modern
solvent extraction technologies, this constraint has been removed, and the
leach-solvent extraction-electr,~winning process is widely used to treat even
low grade oxidized copper ores. Currently, around 10% of the world's copper
production of 9,000,000 t/yr originates from leaching operations, and in the
U.S.A. it is as high as 25%. Shortly after the turn of the century, both carnotite
and pitchblende ores were being leached for uranium and/or radium produc-
tion [ 7 ], and these leaching techniques were developed into the sophisticated
methods which now account for all the world's uranium production of 40,000
t/yr.
The diversity, scope and ingenuity of the early leaching processes are per-
haps surprising. Equally surprising is the fact that these same processes,
essentially unaltered in principle, currently account for most of the world's
production of Au, AI and U. It is also remarkable that most of the above
leaching processes are based on "oxidized" feeds and that most employ low
cost H2SO4 or NaOH media. Early efforts were made to leach the common
base metal sulphides directly, but the results were disappointing. The need to
supply large amounts of oxidant for the oxidation of the sulphide ion was
difficult in an era lacking high shear mixing and tonnage oxygen. For eco-
LEACHING SULPHIDE MINERALS IN CHLORIDE MEDIA 3
nomic reasons, the practical chemical oxidants for base metal sulphides were
limited to ferric ion and air. Initial studies showed that ferric sulphate solu-
tions gave lower leaching rates than ferric chloride media [ 8 ], but efforts to
use hot concentrated FeCls-HCl media resulted in severe equipment corro-
sion and other problems which were not well understood at the time. As a
result, the leaching processes developed for sulphide ores usually involved a
roasting step to convert the sulphide to an "oxide". Thus, the development of
the electrolytic zinc process was based entirely on roasted sphalerite feeds
[91.
The brief historical review presented above indicates that leaching is a ma-
jor hydrometallurgical activity which is largely based on "oxidized" feeds.
The abundant sulphide ores of copper, lead and zinc are traditionally treated
by roasting and smelting technologies. Although these technologies have many
advantages, they are not without their inherent limitations. Current environ-
mental regulations demand nearly complete SO2 capture in any pyrometal-
lurgical operation. Although the technology to capture SO2 exists, its imple-
mentation commonly results in high capital and operating costs. It is estimated
that it costs an additional US$ 0.17/kg Cu for American copper smelters to
conform to current SO2 emission standards [ l 0 ]. A further difficulty is that
the marketing of the H2SO4 is coupled with that of the metal; depending on
the geographical location of the plant, the linkage can create major difficul-
ties. Ladle transfers, launders~ etc., all create in-plant hygiene problems which
are technically difficult to resolve.
Leaching technologies for sulphide feeds offer many potential advantages
over smelting processes [ l l, 12 ], and these include:
( l ) Formation of elemental sulphur or soluble sulphate such that SO2
emissions are entirely avoided.
(2) Ability to treat low grade or highly complex feeds.
(3) Pyrite is often "inert".
(4) Viable at either a small or large scale.
(5) Potential for lower capital costs and incremental plant additions.
(6) Potentially easier to instrument and control.
(7) Greater flexibility in product purity and form.
Set against these strengths are several disadvantages [ 11 ]"
(1) The need to demonstrate a significant advantage over existing
technologies.
(2) They are often energy intensive because of the high specific heat of
water and the use of electrochemical technologies.
(3) Water pollution problems.
(4) Recovery of Au and Ag by-products is difficult and requires additional
processing steps.
Steady progress, however, is being made on the leaching of sulphide feeds,
and many of the traditional difficulties are being overcome. For example, the
corrosion problems which plagued the early development of many leaching
4 J.E. DUTRIZAC
processes have been largely resolved through the use of engineered plastics
and thoughtfully selected metallic and ceramic components. Although com-
mercial leaching processes for sulphide feeds are limited in number, R&D
activities remain relatively strong. Thus, the purpose of this review is to sur-
vey the recent developments associated with sulphide leaching, and especially
the use of chloride media for such leaching processes~
CHLORIDE LEACHING PROCESSES FOR CHALCOPYRITE CONCENTRATES
Numerous leaching processes have been advocated for copper sulphide ores
and concentrates. Dutrizac and MacDonald [ 8 ] have reviewed the early lit-
erature on this subject. Ferric chloride or cupric chloride processing of copper
concentrates offers several potential advantages related to sulphur control,
metal purification/recovery options and process economics. Despite the
potential advantages of the chloride processing route for conventional chal-
copyrite-rich copper concentrates, the technology remains very much in the
developmental stage. Nevertheless, significant progress has been made [ 12 ],
and some of the recent advances in this area are noted below.
About 20 years ago, both the U.S. Bureau of Mines [13] and MINTEK
[ 14 ] developed relatively simple flowsheets for the treatment of chalcopyrite
concentrates. Leaching was carried out in a single stage near the boiling point
of the ferric chloride leaching medium (around 105 °C); high copper extrac-
tions were realized by grinding the copper concentrate to 95% - 3 2 5 mesh
and by prolonging the leaching time up to 8 h. The investigators recognized
that metal recovery and iron disposal were key factors. The Bureau of Mines
electrowon copper powder directly from the cuprous chloride solution', MIN-
TEK researchers used solvent extraction with LIX-64N to convert the cupric
chloride to a sulphate medium for conventional electrowinning. Both re-
moved iron by an oxidation-hydrolysis route. Fine grinding was considered
a necessary first step in both processes. An economic evaluation of the Bureau
of Mines' process [ 15 ] indicated capital costs ( 1975 US$ ) for an output of
54,000 t Cu/yr of $ 28,000,000 and operating costs of$ 0.22/kg Cu.
Cominco [ 16 ] carried out small scale test work and developed a ferric chlo-
ride process for copper concentrates which were ground to 97% - 325 mesh.
Leaching was carried out countercurrently in two stages, both of which oper-
ated at 95°C. Retention times of 9-12 h were required to achieve 99% Cu
extraction from solutions containing 50-200 g/l FeCl3. The long retention
times were probably a consequence of the 95 °C temperature used. As will be
seen later, the leaching of chalcopyrite is strongly temperature dependent, and
significant advantages are gained by leaching near the solution boiling point
(i.e., > 105 ° C). The spent iron chloride leach solution was regenerated under
pressure at 135-165 °C, and excess iron was precipitated as Fe203 in the iron
oxidation step. In the Cominco process, the hot-filtered leach solution was
treated with excess copper metal to reduce all the copper to the cuprous state.
Pure cuprous chloride crystals were formed on cooling the solution. Copper
powder was produced by hydrogen reduction of the cuprous chloride, with
the evolved HC! gas being used in the iron oxidation autoclave. The Cominco
process recognized the need to make high purity copper directly, and also
sought to avoid the high costs of electrowinning.
After experimenting with copper electrowinning directly from an iron
chloride leach solution, the Cyprus Metallurgical Corp. (Cymet) developed
a process based on a two-stage countercurrent leach in a FeCI3-CuCI2-NaCI
medium [ 17,18 ]. The concentrate was leached for 3 h in each stage at 98 °C
to achieve a copper recovery of 99%. The pregnant solution contained 100-
150 g/l Cu and 110-160 g/l Fe. Af:er thickening and filtration, the solution
was vacuum cooled to around 40°C to crystallize about half of the copper as
CuCI. The CuCI crystals were centrifuged, washed, dried, and then reduced
with H2 in a fluidized bed roaster at 500°C. Sand was used in the fluid bed
reactor to prevent sintering of the charge, and the Cu-sand product was sub-
sequently melted to yield bar copper. The spent leaching solution containing
approximately 50 g/l Cu and 110-I 60 g/l Fe was reoxidized at 95°C with 02
and HCI from the fluid bed reactor. About 3 h was required to reoxidize the
solution and control iron by the precipitation of sodium jarosite and fl
FeO.OH. The Cymet process was evaluated in a small continuous pilot plant
treating about 20 t/day of chalcopyrite concentrate. All parts of the process
were technically feasible and all corrosion problems were apparently over-
come. However, silver was extensively solubilized in the leaching circuit, and
unfortunately, much of the silver reports in the CuC! crystals and, thence, to
the metallic copper. The similar behaviour of silver and copper in ~:oncen-
trated chloride media is a continuing concern in all copper leaching processes.
The Cymet process demonstrated on a pilot scale that high copper leach ex-
tractions were achievable and that copper could be successfully recovered from
chloride media by non-electrowinning processes. The Cymet pilot plant was
closed in 1982, and the process has not been developed further since that
time.
The chloride hydrometallurgical process for treating chalcopyrite concen-
trates developed by the Duval Corporation and known as the CLEAR process
(Copper Leaching Electrowinning and Recycle) operated for a period of six
years and ultimately attained an output of 100 t Cu/day [ 19-21 ]. As shown
in Fig. 1, a two-stage countercurrent leach was used to achieve high overall
copper extractions. The first stage was carried out at 105 °C with 20 g/I CuCI:,
4 g/l FeCI3, 80 g/l NaCI and 44 g/I KCI. During process development, it
became apparent that high total chloride concentrations allowed higher leach
temperatures to be used with concomitantly higher extractions. The principal
leaching reactions were felt to be:
6 J.E.DUTRIZAC
FinelyGround
Cholcopyrite
Concentrote
!
FIRST
LEACH
STC1"
• 105"C Cu Powder
_~ ~ ,
r--... I _1 OUCT,O. w,r,I
[ S'~~"~ Cu POWDER ]
-I 1
/ LEACH ! 4 i ELECTROLY,StS ]
9P---~ Product
Residue
~ to
treotmenlor
disoosol
Fig. 1. Schematic tlowsheet for the CLEAR copper process for chalcopyrite concentrates, after
[211.
3CuCI?. + CuFeS, -,4CuC!-I- FeCI2 + 2S° (l)

FeCI~ + CuCI-, FeCI, + CuCI: (2)
Solution from the first stage leach was treated with copper metal to ensure
that all the copper was present as Cu +, and the clarified solqtion was sent to
the electrolysis unit. Residue from the first stage leach was re-leached at 150°C
under 330 kPa (50 psi) Ca pressure. Due to the high temperature and 02
pressure of the second stage leach, significant amounts of SOa were formed.
Sulphate and iron control was, therefore, effected by precipitating jarosite
and fl FeO.OH in the second stage leach reactor. The principal reactions are
as follows:
3FeCI3 + CuFeS, --,CuCI + 4FeCI2 + 2S° (3)
12FeCI.~ + 302 + 2H20--* 8FeCI3 + 4FeO.OH (4)
6FeSO4 + 12FeCI2 + 4.50., + 3KCI
(5)
+ 9H: O--, 3KFe3 (SO4)2 (OH)6 + 9FeCI3
4CUC1+O2 + 2H20--,CuCI2 + CuCI2.2Cu(OH)2 (6)
Copper metal is recovered from the pregnant solution from the first-stage
leach by electrolysis in a diaphragm cell. The use of high current densities and
mechanical agitation dislodged the copper crystals formed at the cathode onto
a collection belt. At the anode, half of the cuprous ions are oxidized to cupric
chloride, which is recycled to the second-stage leach. The relevant reactions
are:
C u + + e - --* C u ° (cathode) (7)

C u + _ e - _ ~ C u 2+ (anode) (8)
The CLEAR demonstration plant showed that chloride leaching processes

could achieve high copper extractions from chalcopyrite concentrates with-
out SO2 emissions. Few corrosion problems were encountered in the leaching
and materials handling parts of the plant; skillful use of fibre-reinforced plas-
tics and titanium adequately contained the chloride solutions. Although the
electrowinning reaction is supposed to generate only Cu and CuC12., some Cl2
gas was evolved. This created in-plant hygiene problems as well as extensive
corrosion of the cellhouse building. Careful control ofthe CuCl concentration
and the electrolysis parameters are necessary to avoid Cl2 generation. Fur-
thermore, the electrowon copper crystals contained most of the silver leached
from the concentrate, and efforts to remove the silver selectively from the
leach liquors were not successful. The copper product therefore required fur-
ther refining. On the other hand, the electrowon copper crystals were rela-
tively coarse, and could be handled and melted without significant oxidation.
The jarosite-FeO.OH-sulphur leach residue was digested with a small amount
of H2SO4 to form an effective soil conditioner (Iron-Sul) for the naturally
alkaline soils in the American southwest [22 ].
The CLEAR demonstration plant is a major milestone in the development
of chloride leach technologies. The large continuous scale of operation dem-
onstrated the general viability of the chloride route for a refractory sulphide
such as chalcopyrite. The processing costs were US$ 0.60/kg Cu in the early
1980's, and such costs were competitive with those then charged by local
smelters. The CLEAR demonstration plant also illustrated the need for fur-
ther work on solution purification and by-product recovery, and for better
methods of controlling the anode and cathode reactions in chloride electro-
winning circuits. The CLEAR demonstration plant was closed in 1982, pre-
sumably because of low copper prices.
Minemet Recherche piloted a C u C I 2 leaching process which addressed some
of the problems identified in the Cymet and CLEAR operations [ 23 ]. Leach-
ing is carried out countercurrently in two stages at about 100°C using a 3 h
retention time in each stage. The solution contains 50 g/l Cu E+ and 250 g/l
NaCl. Cu extraction is more than 98% and there is also formation of, predom-
inantly elemental, sulphur. The clarified pregnant solution is treated by sol-
vent extraction with LIX-65N. Oxygen is injected into the solution to convert
the copper to the Cu E+ state, which is the species extracted. The acid released
by the extraction of the Cu E+ ion is utilized in the Cu + oxidation reaction.
8 J.E. DUTRIZAC
The loaded organic is scrubbed to remove chloride and is then stripped with
H2SO4 to yield a conventional CuSO4-H2SO4 electrowinning solution. Silver
is not extracted with the Cu 2+ ions and accumulates in the raffinate. Presum-
ably, it could be recovered as a silver-rich product from the solution, but de-
tails of the silver recovery options have not been presented.
The principal advantage of the Minemet approach is that high purity cop-
per is recovered in compact form from a sulphate electrolyte using well-proven
technologies. Although the theoretical energy requirement for the plating of
copper from a cupric sulphate solution is considerably higher than that for
deposition from a cuprous chloride electrolyte, the metal produced is of a
higher purity. Unless major advances are made in ~i,e purification of chloride
leach solutions and in the control of the quality of the electrolysis product,
the transition to a copper sulphate electrolyte may be a practical solution to
the copper quality and silver recovery problems in chloride hydrometallurgy.
In a somewhat similar vein, the Henkel Corporation [24 ] has developed a
mixed organic e:aractant to transfer copper from a chloride leaching medium
to a conventional CuSO4-H2SO4 electrowinning solution. In principle, the
solvent extraction circuit can be incorporated in any ferric chloride leaching
process provided that an excess of Fe 3+ is maintained in the pregnant solu-
tion to ensure that all the copper is present as CuCl2. Such conditions can be
easily achieved in any ot'the processes described above by adjusting the ratio
oflixiviant to concentrate. The first component (di-isodecyl ester of pyridine
dicarboxylic acid) of the mixed organic, extracts the neutral CuCI2 species
from the concentrated acidic leaching medium. The reagent is selective for
copper such that most impurities, including silver, remain in the raffinate.
Presumably, a silver-rich product can be prepared from such a solution by
cementation, statphide precipitation, etc. After silver recovery, the raffinate is
subjected to oxidation hydrolysis to regenerate the FeCI3 lixiviant and to pre-
cipitate excess iron. Chlorine gas generated elsewhere in the process is the
principal oxidant. The copper-loaded organic phase is contacted with a NaOH
solution at pH 2.2 to wash out all the chloride. Due to the close pH control in
this operation, the copper is transferred from the first reagent to the chelating
extractant (L 1X 860) and the chloride ions liberated in the process are also
removed during washing. The aqueous phase from the washing operation is
directed to a conventional chlor-alkali cell to regenerate the NaOH and to
provide CI_~for the iron oxidation step. Finally, the loaded extractant is con-
tacted with spent H,~SO4-CuSO4 electrolyte to extract the copper as copper
sulphate. Ultimately, the copper is recovered as high-purity cathode using, well
established copper electrowinning technologies [ 25, 26 ].
The general disadvantages of this type of approach are well known. There
is a need for a large solvent extraction operation and the copper must be elec-
trowon from the higher valent cupric state. Furthermore, in the Henkel op-
tion, there is a requirement for a separate electrolysis step to generate C12 and
NaOH. These general disadvantages must, however, be weighed against the

significant benefits of producing compact, high-purity copper cathodes as well
as a silver by-product.
A somewhat different leaching-solvent extraction-electrowinning ap-
proach is followed in the Cuprex process [ 27, 28 ]. Chalcopyrite-containing
concentrates are leached in FeCl3 media to yield elemental sulphur and dis-
solved CuCl2. It is important that excess FeCl3 is present to ensure that all the
copper is present in the divalent form:
CuFeS2 + 4FeCI3 ~CuCI2 + 5FeCI2 + 2S ° (9)
CuFeS, + 3FeCI3 --, CuCI + 4FeCI2 + 2S° (lO)
CuCI + FeCI3 ~ CuCI2 + FeCb (ll)
It is well established thal eq. (11) heavily favours CuC12 and FeCI2 al-
though there is, of course, an equilibrium among the various species [29 ].
After liquid-solids separation, the solution is cooled, treated with CaCl2 to
precipitate gypsum and then contacted with ACORGA CLX50. Neutral cu-
pric chloride is selectively extracted and there is no need to adjust the pH of
the solution during extraction. After scrubbing to remove minor impurities,
the loaded organic is stripped with water at 65 °C to produce an aqueous CuCl2
solution containing > 100 g/l Cu 2+. The solution is electrolyzed in the Met-
clor cell originally developed by Tecnicas Reunidas and characterized by the
use of a cation-selective membrane [ 30 ].
Although the principal electrode reactions are the deposition of copper
powder and the evolution of C12 gas, some of the cupric ion is also reduced to
the cuprous state. Thus, it is necessary to oxidize the catholyte and extract the
remaining copper in a separate solvent extraction operation ("reforming")
using a high organic/aqueous ratio. The loaded organic from the reforming
stage is mixed with the organic feed to the principal solvent extraction (SX)
circuit.
The Cuprex process enjoys several advantages. High purity copper powders
are produced at high current efficiencies (94%) and with an energy consump-
tion of 2.66 kWh/kg Cu. The silver content of the copper is < l ppm and, in
fact, the Cuprex process should allow the recovery of a high-grade silver by-
product from the copper-depleted raffinate. The SX circuit is relatively
straightforward and does not involve in-circuit pH control. On the other hand,
the overall flowsheet is complex and the ion-selective membrane cells may be
difficult to maintain in a plant environment. Critics might argue that the Cu-
prex process suffers a double disadvantage: electrowinning is carried out from
the cupric state and particulate copper is produced. It is understood, however,
that efforts are being made to produce rod directly from the copper powders
(the CONFORM process) and such developments could help to overcome
these criticisms.
i0 J.E. DUTRIZAC
The Great Central Mines ( G C M ) hydrocopper process also produces par-

ticulate copper, but does not use solvent extraction purification [ 31 ]. As with
many chloride leaching processes, the initial step involves fine grinding of the
concentrate, to 80% minus 28 pm. As shown in Fig. 2, the ground concentrate
is then leached in a FeCla-NaCl solution to extract 99% of the Cu and 93% of
the Ag. Leaching is carried out countercurrently in two stages so that the preg-
nant solution contains only cuprous chloride and ferrous chloride. Impurity
control is effected by recycling part of the oxyhydrolysis iron precipitate to
the second-stage leach. The chloride solution is electrolyzed in a diaphragm
cell to yield a granular copper product and to regenerate a portion of the FeCl3
lixiviant:
CuCI+ H + + e - - ~ C u ° + HCI (cathode) ( 12 )

FeCI2 + HCI-~ FeCI3 + H + + e- (anode) ( 13 )
CuCI+ HCi-~CuCI2 + H + + e - ( anode ) ( 14 )
About 85% of the copper is produced in the main electrowinning cells, and
the remainder is recuperated from a stripper cell which treats the catholyte
bleed from the main cells. The magnitude of the catholyte bleed is governed
by the need to maintain the iron and water balances in the cell. The solution
GroundCopper
C°nc~f~r°'L
+.] L _l co,,+,
- .L
== L___3 SLvER
LEACH I ,ELECTROWlNNINGJ
Ir)n
Residue
F ANOLYTE I
-~
Copper-,m
roduct
~esidue for
gold recovery
Fig. 2. Schematic tlowsheet for the Great Central Mines (GCM) hydrocopper process for chal-
copyrite concentrates, after [ 31 ].
from the anolyte chambers is subjected to turbo-aeration to regenerate the

solutioa; no iron precipitates in this operation:
2FeCI2 + ½02 + 2HCI~ 2FeCI3 + H20 ( 15 )
The chalcopyrite leach process solubilizes all the iron in the CuFeS2 as well
as 0-12% of the iron present as pyrite. The excess iron is removed by oxyhy-
drolysis of a bleed stream using a Woodall Duckham spray roaster, and the
residue is discharged:
2FeCI2 "~"½02 +2H20-,Fe2Oa +4HC1 (16)
2FeCI3 + 3HEO-,Fe203 +6HCI (17)
The GCM process has been evaluated on a large laboratory scale. Based on
the laboratory scale data, operating and capital costs for a plant treating 850
t/day of 23% Cu concentrate were developed; the cost for the chloride leach-
ing route was compared to those for the Inco and Noranda smelting technol-
ogies. For the particular site considered, the capital cost of the GCM process
was $157,000,000 as compared to $ 64,000,000-$125,000,000 for the two
smelting options. The operating costs of all three routes were comparable.
The GCM process removes silver from the pregnant leach solution with solid
iodide, but details of the Ag removal/recovery process have not been pub-
lished. The GCM process, which is still being developed, achieves high cop-
per extractions, recovers silver, and produces a particulate copper product.
As the process has not been operated on a continuous pilot plant scale, the
quality of the copper product remains uncertain. Clearly, the GCM process is
most suited to specific sites where the marketing of H2SO4 from a smelter
would be prohibitive.
CHALCOPYRITEACTIVATION
The activation techniques summarized in Table 1 can be divided into three

general categories: changing the chalcopyrite to other sulphides by adding or
removing Cu, Fe or S, catalyzing the reaction with traces of Ag, and promot-
ing the rate by fine grinding and/or induced lattice strain. For economic rea-
sons, it is doubtful whether converting the chalcopyrite to other phases in a
separate operation will prove attractive. Silver catalysis seems to be effective
in ferric sulphate solutions, but not in chloride media. In any event, quanti-
tative silver recovery at low cost would be needed to make this option com-
mercially attractive and, as noted above, silver recovery is a continuing
concern in all chloride leaching processes developed to date.
Conventional fine grinding currently gives good copper extractions in ac-
ceptable retention times. Finer grinding in tower mills, for example, could
further accelerate both the rate and the extent of leaching and could provide
!2 J.E. DUTRIZAC
TABLE !
Activation methods for chalcopyrite
Method References Comments
Activation with 32,33 Pyrite and various Cu-S phases (nukundamite, idaite, bornite,
sulphur covellite, etc. ) formed. Significant improvement in rate and
extent of Cu leaching noted. Enhanced Fe rejection as pyrite.
Activation with 34 Covellite reacts to form bornite and pyrite. Rapid copper leaching
covellite and good iron rejection achieved in CuSO4 leach.
Activation with 35 Reaction forms Cu2S and FeS; hence high soluble Fe
copper concentrations realized during leaching. Significant rate increase
during O2-H2504 leaching.
Activation with 36,37 Forms Cu2S or Cu in addition to FeS. Copper is recovered by
iron FeCi3 leaching or flotation.
Activation with 38 Activated carbon increases the leachin~ rate in ferric sulpha:e
carbon media by up to 400%.
Activation by 39 Bornite and FeS formed; FeS removed by acid leaching. Bornite
sulphur removal product should be amenable to chloride leaching.
with H2
Activation by 40 Treatment at ~ 800°C forms intermediate solid solution, bornite
sulphur removal and FeS. Enhanced leaching rates noted in an H2504-O2 system.
in vacuum or in
inert gas
Activation by 4 !,42 Low concentrations of Ag+greatly accelerate leaching in ferric
silver catalysis in sulphate media, but have no effect in chloride solutions.
solution
Mechanical 43,44 Extensive grinding results in marked increase in leaching rate in
activation ferric sulphate or H202 solutions. Similar effect likely in chloride
media. Effect seems to be due to both the particle size and lattice
distortions in the chalcopyrite.
additional flexibility in the leaching stage. Also, it would be desirable to de-

velop improved methods/'or removing the few percent of the coarse, slowly
dissolving particles from the finely ground concentrates. Although not critical
to the success of chloride leaching, "activation" of the copper concentrates by
fine grinding could improve the overall economics of the process by reducing
the size of the leaching section. Nevertheless, there seems to be little commer-
cial interest in "activating" the chalcopyrite prior to leaching, despite the
number of fundamental studies of this aspect.
PRODUCT RECOVERY AND PURITY
In many of the processes cited above, there are serious problems related to
the purity of the copper product. Product purity depends to some extent on
the concentrate being treated. However, elements like Ag, Pb, As and Sb, are
all soluble in concentrated chloride media [45, 46 ] and all report to some
extent to the final copper product. Both the Cymet and Cominco processes
utilize CuCl precipitation to eliminate many of the objectionable impurities~
Silver, however, reported to the CuCl crystals and traces of other elements
will probably also co-precipitate if their concentrations in the leaching me-
dium are high. Consequently, CuC1 precipitation, by itself, is orobably not an
adequate purification process for yielding high purity copper. In most in-
stances a solution purification step will be required. Solvent extraction ~neth-
ods are being developed to produce a pure copper-bearing solution, and the
development of such technologies should be encouraged.
The principal by-products in most copper concentrates are silver and gold.
Silver generally dissolves more slowly than copper when chalcopyrite concen-
trates are leached, although the extent of silver dissolution depends on the
mineral form of the silver in the concentrate [ 47, 48 ]. Although some of the
solvent extraction processes result in a low-copper chloride solution contain-
ing most of the silver, the silver recovery methods themselves have not been
well defined. Unlike silver, gold is virtually insoluble in chloride media unless
a very high oxidation potential is maintained by Cl2, H202, etc. [49, 50 ].
Gold can be recovered from the leach residue by conventional cyanide leach-
ing, but the cyanide consumption is excessive because of the high elemental
sulphur content and gold extractions are generally low. Thiourea leaching has
been used to recover gold from sulphur-bearing leach residues [51 ]. Gold
recoveries of 60-85% were realized, but thiourea consumptions were 30 kg/t
residue. Due to the fact that gold is such an important economic factor in
most copper operations, the recovery of the precious metal from the chloride
leach residue will require more attention.
SULPHUR GENERATION AND CONTROL
One of the principal advantages of the chloride leaching route is the total
avoidance of SO2 emissions. Not only does this resolve concerns about SO2
air pollution, but it also separates metal production from sulphuric acid man-
ufacture. In the U.S. Bureau of Mines' process [l 3] only a "small amount"
of sulphate was formed and pyrite in the copper concentrate was largely un-
affected during leaching. It was proposed to recover the elemental sulphur
reaction product using an ammonium sulphide leach, with subsequent acidi-
fication to precipitate the sulphur. In the MINTEK process [14 ], less than
5% of the total oxidized sulphide ion reported as SO4; over 95% elemental
sulphur production occurred. Cominco [ 16] noted that elemental sulphur
was the dominant reaction product in their process and proposed to recover
the sulphur by flotation. Elemental sulphur recoveries ranging from 75% to
90% were realized. The Cuprex [ 27 ], GCM [ 31 ] and Henkel [ 24 ] processes
all noted mostly elemental sulphur formation, although the precise amount of
SO4 generated was not precisely defined and may depend on the mineralogi-
14 J.E. DUTRIZAC
cal composition of the concentrate tested. In the GCM process [ 31 ] elemen-

tal sulphur was recovered by pressure filtration at 150 ° C, but only 60-70% of
the sulphur was recuperated. In the Cuprex process [27], sulphur was
recovered by flotation followed by melting-filtration of the flotation concen-
trate. Difficulties were noted with this approach, however, and sulphur leach-
ing methods were being examined. All studies have reported that the sulphur
is contaminated by a number of impurities, notably selenium, which substi-
tutes for sulphur.
In contrast, the Cymet process [ 18 ], which leaches chalcopyrite concen-
trates at 98°C in 160 g/l Fe 3+ and 150 g/l Cu 2+ media, reported 25% SO4
formation. The reason for the significant level of SO4 generation in that pro-
cess is not known, but may be related to the concentrate used. The CLEAR
process [21 ] solubilizes copper by leaching initially at 105°C and subse-
quently at 140°C in an oxygenated CuCI2-FeCI3 medium. The high temper-
ature oxidation step is presumably responsible for the 15-25% SO4 formed in
that process.
Cominco [ 52 ] recently reviewed both the physical separation and leaching
methods available to recover sulphur from leach residues. Physical separa-
tion methods, such as hot filtration, pelletization and flotation, recover part
of the elemental sulphur, but their effectiveness depends on the nature of the
leach residue. These procedures, however, could be employed in an overall
sulphur recovery flowsheet to remove a significant fraction of the sulphur
early in the processing sequence. It was possible to leach the sulphur com-
pletely using limewater slurry, carbitol, ammonium sulphite and ammonium
sulphide solutions. All four reagents effectively leached the sulphur from the
residue, but carbitol produced the purest sulphur product. Drying of the res-
idue would, however, be required prior to the use of carbitol, or any organic
reagent.
A number of fundamental studies have been carried out on the FeCI3 or
CuCI_, leaching of relatively pure chalcopyrite [ 8, 12 ]. Most of the investiga-
tions reported > 90%, and often > 95%, elemental sulphur generation. For
example, Ravi et al. [ 53 ] recently observed 99.5% S° formation during chal-
copyrite leaching at 97°C. Majima and co-workers [54, 55] also observed
dominant elemental sulphur formation during the leaching of chalcopyrite
and noted significant variations in the morphology of the sulphur. Most re-
cently, Dutrizac [ 56 ] studied the relative amounts of elemental sulphur and
sulphate generated during the FeCI3 leaching of pure chalcopyrite. At temper-
atures < 100°C, more than 95% S° tbrmation was consistently achieved, to-
gether with < 5% SO~ generation. The relative amounts of S° and SO4 were
not affected by leaching times as long as 90 h, by FeCI~ concentrations as high
as 2.0 M, or by HCI concentrations to 3.0 M. It was noted that the presence
of air or O2 in the leach reactor had no effect on the amounts of S° and SO4
formed. It was confirmed that elemental sulphur itself is not attacked by FeCI3
solutions below the sulphur melting point [ 57 ].
Following the earlier work of Majima and co-workers [ 54, 55 ], it was shown
that the sulphur morphology was strongly affected by particle size, retention
time and the leaching conditions used [ 56 ]. The elemental sulphur agglom-
erates and coats the individual chalcopyrite particles, as noted in Fig. 3.
Although the sulphur coatings probably make the leaching somewhat more
difficult, the agglomeration certainly improves the thickening and filtration
properties of the leach residues. This is probably the cause of the good filtra-
tion rates noted by all investigators despite the often fine particle sizes in-
volved. Figure 4 shows the sulphur layer formed on a 50 ILtmchalcopyrite
particle leached for 24 h at 95 °C. The entire surface of the chalcopyrite is
covered with small particles and intergrown masses of elemental sulphur. Of
note, however, is the presence of many 15 ~tm euhedral sulphur crystals sim-
ilar to those observed by Majima and co-workers [ 54, 55 ]. The development
of large, well-formed sulphur crystals suggests that sulphur is deposited from
the leaching medium. The actual reaction sequence must involve, at least in
part, various dissolved H2S species:
Fig. 3. Secondary electron micrograph of 30 ~m chaicopyrite particles leached for 8 h at 95:C

in 0.1 3I FeCI3 solution. The particles are sulphur coated and are agglomerated into large masses
by the sulphur, from [56].
16 J.E. DUTRIZAC
Fig. 4. Secondary electron micrograph of 50 ~tm chalcopyrite particles leached for 24 h in O. I M

FeCI.~ media, a = sulphur-coated chalcopyrite; b= sulphur crystals with growth features, from
[561.
CuFeS, + 4HCI=.CuCi2 + FeCI2 + 2 ( H.,S ),,~.,olvcd

2 ( H~S )di,~,,,l~.d + 4FeCh ~) 4FeCI., + 4HCI + 2S °
CuFeS2 + 4FeCI3 -~ CuCI2 + 5FeCI2 + 2S° (20)

The dissolved H2S species formed at the surface of the chalcopyrite diffuse
from the reaction interface and are oxidized by ferric ions. Such a mechanism
readily explains the formation of S° as discrete globules on the chalcopyrite
surface, the protruding globular growth of the sulphur and, of course, the nu-
cleation and growth of euhedral sulphur crystals. A somewhat similar and
more detailed mechanism of sulphur formation was also advanced by Lotens
and Wesker [58 ]. They proposed that the sulphide ion in the chalcopyrite
was oxidized at the sulphide surface to S +, which was subsequently hydro-
lyzed to H 2 S : O 2 :
CuFeS2 + Fe 3+ -~ CuFeS. S + + Fe 2+ (21 )
2S + + 2H20-~ H2S202 + 2H + (22)
2H2 SaO2 --*H2SO3 + H 2 0 + 3S° (23)

H2SO3 "1-2H2 S--, 3H20+ 3S° (24)
Significant is the fact, however, that the proposed reactions predict only
75% S° formation, whereas the experimental evidence indicates a higher de-
gree of sulphur generation. Possibly reaction of the sulphite with dissolved
H2S species (the reaction in eq. (24) ) could account for the remainder of the
elemental sulphur formed.
Most FeCl3 and CuCl2 leaching processes generate some soluble sulphate.
The sulphate probably originates from the superficial oxidation of the sul-
phides prior to leaching (e.g., PbSO4 on galena) or by the sulphide leaching
reaction itself. Although little sulphate originates from chalcopyrite leaching,
the dissolution of associated minerals such as pyrite can contribute signifi-
cant sulphate. Elemental sulphur is stable in chloride media at 100°C, but
becomes more reactive above its melting point. Sulphate formation, accord-
ingly, becomes more prevalent in those processes employing elevated temper-
atures: up to 25% SO4 formation was observed in the CLEAR process.
In most chloride processes, sulphate is controlled by the addition of cal-
cium chloride to the solution to precipitate some form of calcium sulphate
(CaSO4"2H20, CaSO4" 1/2H20 or CaSO4). Sulphate can also be controlled
by precipitation of jarosite-type compounds, and the technique is especially
useful at higher leaching temperatures. Both sodium jarosite
(NaFe3(SO4)2(OH)6) and potassium jarosite (KFe3(SO4)E(OH)6) have
been employed [ 18, 21 ]. Dutrizac [ 59 ] investigated several sulphate control
techniques, which included the precipitation of calcium sulphate, lead sul-
phate, barium sulphate, sodium jarosite and potassium jarosite. Lead sul-
phate enjoys a considerable solubility in concentrated chloride media so this
compound was not useful for sulphate control. Jarosite precipitation required
a relatively low acid concentration and a high temperature to be effective; a
low terminal sulphate concentration could not be achieved. If a minor circu-
lating load of sulphate ( l 0 g/l SO4) is allowable in the process, however, po-
tassium jarosite precipitation is an effective method of sulphate control, as in
the CLEAR process. Barium chloride additions precipitate BaSO4, and the
reaction proceeds nearly stoichiometrically. Sulphate concentrations < 0.1 g/
I can be achieved. The presence of excess BaCI2 resulted in the precipitation
of BaCI2' H20 during the cooling of the solution, however, and this phase ad-
versely affected the filtration of the leach residue. Addition of CaCI2 effec-
tively controlled sulphate; provided that an excess of CaC12 was present, final
dissolved sulphate concentrations of 1-3 g SO4/1 could be maintained. It was
concluded that the "best" overall sulphate control strategy involved precipi-
tation of calcium sulphate.
18 J.E. DUTRIZAC
FUNDAMENTALS OF THE FERRIC CHLORIDE LEACHING OF CHALCOPYRITE
A great deal of fundamental research on the FeCl3 leaching of chalcopyrite

has been carried out and reviews of the relevant publications prior to 1984
have been published [ 8, 12 ]. The more recent investigations carried out to
elucidate the reaction of chalcopyrite in ferric chloride media are summa-
rized in Table 2.
Many electrochemical studies have shown the rapid initial formation of a
thin (around 3 nm) sulphide layer on the chalcopyrite during dissolution.
Parker et al. [ 61 ] described this as a metal-deficient polysulphide. Biegler
and Horne [ 65 ] postulated the selective dissolution of iron from the chalco-
pyrite to form a covellite-like phase:
CuFeS2 -~ 0.7 5CuS-i- 0.2 5Cu 2+ -I- Fe 2+
(25)
+ 1.25S°+ 2.5e-
In their studies on the galvanic coupling of chalcopyrite and pyrite, Murr
and Mehta [63 ] identified covellite (CuS), chalcocite (Cu2S), bornite
(CusFeS4), cubanite (CuFe2S3) and elemental sulphur by electron diffrac-
tion of the reaction scales. These products formed by the generalized reaction:
CuFeS2 --, Cu i _,v Fel _yS2_: -I- x C u 2+ -i- yFe 3+
(26)
+ zS°+ (2x + 3y)e-
Although it is certain that thin scales of sulphide form on chalcopyrite dur-
ing leaching, it has not been conclusively established that the 3 nm layers
significantly affect the macroscopic leaching of the chalcopyrite. That is, it is
not established that the sulphide layer passivates the entire surface in such a
way that the overall leaching rate is controlled by the dissolution of the inter-
mediate phase. The possibility exists that the bulk leaching reaction could
proceed simultaneously in two or more parallel paths:
CuFeS2 + 2Fe 3+ --,CuS + 3Fe 2+ +S ° (27)
CuS+ 2Fe a+-,Cu 2+ + 2Fe 2+ + S° (28)
CuFeS2 +4Fe 3+ --,Cu 2+ + 5Fe 2+ + 2S° (29)
FUNDAMENTALS OF THE CUPRIC CHLORIDE LEACHING OF CHALCOPYRITE
Various fundamental studies on the reaction of chalcopyrite with CuCI2

media have been reported, and a summary of the relevant information is given
in Table 3.
Table 3 indicates a number of inconsistencies in the reported parametric
dependencies for the leaching of chalcopyrite in CuCI2 media. In this regard,
TABLE 2
Recent fundamental studies on the leaching ofchalcopyrite in FeCI3 media
Material Reference Conclusions
Natural chalcopyrite 54 Leaching is 2 times faster in FeCl 3 than in Fe(SO4)~.5

single crystal media
Linear leaching kinetics
Activation energy 69 kJ/mol
Rate c~[ FeCla ] 0.5
Rate increases significantly with 0-2 M NaCi
concentrations
Rate independent of [ FeCl 2 ] in 0-1.0 M range
Natural chalcopyrite 55 Electrochemical mechanism advanced

single crystal Kinetics controlled by one-electron transfer
Theory explains effect of temperature, FeCla, FeCI2
Theory does not explain the effect of NaCl
CuCI2 formed during leaching accelerates
leaching rate
Natural high purity, 60,61 Electrochemical studies showed formation of ~ 3 nm

massive chalcopyrite sulphide film
Importance of CuCl2 reaction product shown
Catalysis by Ag2S explained
Natural chalcopyrite sawn 62,63 Electrochemical effects shown to be important in bacterial

massive and powders leaching of chalcopyrite
(purity not given) Galvanic interactions with pyrite demonstrated
Natural massive 64 Electrochemical studies suggested sulphide intermediale

chalcopyrite phases
Electro-oxidation of CuFeS2 gives Fe 3+ directly
Natural massive 65 Electrochemical studies showed an anodic prewave to

chalcopyrite, free of produce a ~ 3 nm sulphide intermediate
microscopic inclusions Subsequent leaching involves the thin sulphide
intermediate
Predicts that all chalcopyrites should leach at same rate
Sized, high purity natural 66 Leaching studies showed that the CuCl2 reaction product
chalcopyrite promoted the FeCl3 leach
Rate a [ FeCI3 ] 0.3-0.4
Rate increased slightly with [ HC! ]
FeCI2 slightly inhibited the reaction
Total Cu extraction depends on NaC! concentration
different mechanisms may prevail above and below 80°C. Low concentra-
tions of Cl adversely affect the reaction, but the rate may be chloride-
insensitive at higher ( > 2 M Cl) chloride concentrations. Most workers have
20 J.E. DUTRIZAC
TABLE 3
Recent fundamental studies on the leaching ofchalcopyrite in CuCI2 media
Material Reference Conclusions
Sized chaicopyrite 67 Linear leaching kinetics

concentrate containing Independent of stirring speeds > 400 rpm
27-30% Cu High activation energy, 135 kJ/mol
Rate independent of [CuCI:]
Rate independent of [CI ]
Electrochemicaliy controlled reaction
Sized chalcopyrite 68 Parabolic leaching kinetics

concentrate containing Activation energy 71 kJ/moi at > 80°C
c.80% chalcopyrite; Activation energy 335 kJ/mol at < 80°C
total Cu = 34%, Rate increases with ratio of CuCI2/CuC!
total Fe=25% Rate increases with [CI]
Diffusion controlled at > 80 °C
U nsized chalcopyrite 29 Postulates CuS |brmation at high Cu +/Cu 2+ ratios

concentrate containing High [Cl] favours reaction
26% Cu
Natural chalcopyrite crystals 69 Rate linear for first 200 h, but accelerates thereafter due
to surface roughening
Activation energy 82 kJ/tool
Rate increases as [CuCI2 ]o. 54
Rate decreases as [CuCI] -o.5
Rate increases with [ NaC! ] to -,, 2 M, but is insensitive
to higher concentrations
Rate electrochemically controlled by Butler-Volmer
equation
.-38 ~tm chalcopyrite 70 Linear kinetics

concentrates containing 27- Rate independent of [CuCI2] when 02 sparging used
32% Cu Rate increases with [Ci] to 90 g/i
Rate independent of surface area of chalcopyrite
Rate maximum at 85°C
observed linear kinetics together with a moderately high activation energy.

All workers noted that elemental sulphur is the dominant, if not exclusive,
sulphidic reaction product. There is a large body of data which suggests that
the CuCI2 leach, at high temperatures and high Cl concentrations, is electro-
chemically controlled [60, 61], and there is good agreement between the
mixed potential in cupric chloride media and the leaching rate [ 71 ]. That
CuCI2 solutions are more effective than FeCI3 media is attributed to the fact
that the Cu 2+/Cu + couple is faster and more reversible than the Fe 3+/Fe 2+
couple on a chalcopyrite surface in chloride media [ 61 ].
CHLORIDE LEACHING PROCESSES FOR LEAD CONCENTRATES
Galena (PbS) is the only lead sulphide mineral of any commercial signifi-
cance. Galena concentrates are readily processed by pyrometallurgical meth-
ods, but problems persist with fugitive SO2 emissions from some operations,
and all plants are concerned with potential in-plant hygiene problems caused
by Pb, Cd, TI, etc. In addition, the capital cost of replacing obsolete lead
smelters is high, and the future of small, independent smelters is in doubt.
Hydrometallurgical processing offers some promise of resolving these prob-
lems and numerous developmental and fundamental studies on the leaching
and recovery of lead have been carried out.
Although some work has been done on the reaction of galena in ferric sul-
phate media, that approach is limited to processes intending to leave the lead
as insoluble PbSO4 in the leach residue. Due to the moderately high solubility
of PbCI2 in concentrated chloride media [ 72, 73 ] and the potential to recover
a pure PbCI2 intermediate product by cooling the hot PbCl2-concentrated leach
solution, most processes have been chloride based. All early investigations
noted that galena is easily oxidized by eitheJ" FeCI3 or CuCI2 media, and those
early investigations have been reviewed [ 8, 12 ].
Early low-temperature leaching processes included those developed by the
Hecla Mining Company [74], Cominco Limited [75] and Hazen Research
[76]. Low temperature leaching is carried out at around 40°C in FeCI3 or
CuCI2 media to convert galena to PbCI2, which remains in the leach residue.
The residue is separated from the primary leach solution and is then re-leached
in hot concentrated brine to solubilize the PbCI2 selectively. Pure PbCI2 is
subsequently precipitated by cooling the solution:
40°C
PbS + 2FeCI3 ~ (PbCI2),olid + 2FeCI2 + S° (30)
(PbCl2)~olid + 2C1- 95°C (PbCI~-)~o~tio. (31)

25 °C
(PbCI24- )solution ' (PbC12)solia+ 2C1- ( 32 )
The advantage of the low-temperature leaching option is that it is relatively
selective for lead and impurity problems are minimized. The disadvantages
are that silver is not entirely extracted and the dissolution of some of the im-
purity elements cannot be entirely avoided.
Both the U.S. Bureau of Mines [ 77 ] and Minemet Recherche [ 78 ] have
developed high temperature leaching processes based on FeCI3. High lead ex-
tractions were consistently realized together with predominantly elemental
sulphur formation:
PbS+ 2FeCI3 ~ PbCI2 + 2FeC12 + S° (33)
22 J.E. DUTRIZAC
In both processes, silver extractions were 20-85%; the erratic values prob-
ably reflect variations in the silver mineralogy of the various concentrates
tested. The Bureau of Mines produced a PbCI2 intermediate product which
was subjected to fused salt electrolysis. In the Minemet process, the solution
was purified by Pb powder cementation and then by ion exchange. The ac-
cumulation of zinc was a lingering problem which was not completely re-
solved. Initially, Minemet recovered Pb from the leach solution by aqueous
electrolysis in a diaphragm cell such that the FeCI3 lixiviant was simultane-
ously regenerated:
P b 2+ + 2e- --, Pb ° (cathode) (34)
2Fe 2+ --, 2Fe 3+ + 2e- (anode) (35)
Subsequent developmental work, however, suggested that better product
purity and greater process flexibility could be achieved by crystallizing PbCl2
as an intermediate product [79 ]. The PbCl2 was subsequently dissolved in
concentrated NaCl solution for electrolysis in a high-flow cell of Minemet
design. Lead powder was obtained and this was compacted in briquetting rolls
to reject electrolyte and to minimize oxidation during subsequent melting:
P b 2 + + 2 e - .-, P b ° (36)
2CI- --,C12 + 2e- (37)
The chlorine gas evolved at the anode was used to regenerate the iron chlo-
ride lixiviant. Both of the above high temperature leaching processes were
tested in integrated pilot plants at a scale of 250 or 100 kg Pb/day. Both pro-
duced high purity lead, and neither encountered significant operational
difficulties.
More recently, St. Joe Minerals [80] carried out an extensive pilot plant
campaign to produce 2.7 t/day of PbCl2 by the FeCI3 leaching of conven-
tional high-grade lead concentrates. Their generalized flowsheet is presented
in Fig. 5. During the pilot program, over 360 t of PbCl2 were produced. The
lead concentrates were fed by a belt feeder to a tank where a 50% solids slurry
was prepared using regenerated leach solution. Leaching was then carried out
at 95 °C in three tanks in series with each tank fitted with a rubber lined, steel
agitator. The total leaching time in the 3 MNaCI-FeCI3 medium was only 0.5
h, but this was adequate to solubilize all the lead. The slurry was then thick-
ened and filtered at > 92°C to prevent PbCl2 crystallization. The clarified,
nearly saturated, PbCl2 solution was fed to a vacuum crystallizer and the
solution-PbCl2 crystal slurry exited the crystallizer at 25 °C. The slurry was
filtered on a belt filter so that good washing to remove the iron-bearing solu-
tion occurred. Copper and silver were recovered by cementation on iron. If
the cementation was carried out on the cooled solution, negligible precipita-
Lead
Concentrate
1
~ ResidueTreatment]----~erightS o
I
PbCl2 Residue J Ferric I
-IRegeneration ~
Crystallization
t J
etI
Aqueous
l 1
Lead ~Pb Metal
PbCl s -I ( l e c t r ° l y s i s ,I
I Copper I ~CuO
Cement |
/
Fe° ].~r Solution Bleed
Fig. 5. Schematic flowsheet for the St. Joe ferric chloride leach process for galena concentrates,
from [ 80 ].
tion of lead occurred. Finally, the solution was regenerated with chlorine gas,
which could be recovered from the electrolysis cells of a commercial operation.
Although the Leadex process [30] developed by Tecnicas Reunidas is
nominally based on aqueous Cl2 leaching, it can also be viewed as a dilute
FeCl3 leach in which the lixiviant is continuously regenerated by Cl2 gas. A
similar process was also advocated by the U.S. Bureau of Mines [ 81 ]. In the
Leadex process, leaching is carried out for 2.5 h at 90°C in a solution contain-
ing 2-10 g/l Fe 3+ and 200 g/l Cl; the redox potential is controlled at 550 mV.
Impurities, including Ag and Bi, are removed by cementation with a small
quantity of zinc dust. Next, lead is recovered by cementation on sheared zinc
cathodes in a trommel. Lead is totally removed from the solution and sepa-
rates cleanly from the zinc. The lead forms small pellets which are melted and
cast into ingots. The resulting zinc chloride solution is treated by solvent ex-
traction to produce a pure 70 g/l Zn solution for electrolysis in the company's
Metclor cell. Chlorine gas from the zinc electrolysis cell is employed in the
leaching operation. The process has been evaluated on a l kg Pb/h pilot plant
which ran for over 600 h, and achieved 99% Pb recovery as a 99.97% Pb
product. Silver recoveries were around 94% and sulphur was produced by
flotation of the leach residue. Zinc is used to cement the lead and the overall
energy consumption is 2.33 kWh/kg Zn, or about 0.9 kWh/kg Pb, a value
which is not excessive.
Although developed for copper, the Dextec process can also be used to re-
24 J.E. DUTRIZAC
cover lead from lead concentrates [82 ], and may be particularly useful for
deleading copper concentrates prior to subsequent smelting. In regard to the
latter application, Boliden Metall and Dextec operated a 3 m diameter by 4
m high pilot cell for about l year. The cell was operated in a batch mode using
10-12 h/day cycles. In the anode, or slurry, part of the cell, lead was selec-
tively solubilized at 90°C in a 250 g/l NaCl electrolyte maintained at a pH of
around 1.5 with HC1. A variety of dissolution reactions are probably involved:
PbS + 2FeCI3 --, PbCI2 + 2FeCI2 + S° (38)
PbS+ 2HCI--, PbCI2 +H2S (39)
P b S - 2e- -~ Pb 2+ + S° (40)
Any H2S evolved either would be oxidized by ferric chloride or would pre-
cipitate dissolved Ag, Cu, Zn, etc. In this regard < 1% of the copper, zinc and
iron in the concentrate was solubilized. The lead concentration of the solution
was 20 g/l Pb, and the lead migrated through the diaphragm and was depos-
ited as coarse crystals at the cathode. Concentrates containing 10-25% Cu,
4-20% Pb, 4-30% Zn and 100-20,000 ppm Ag were successfully treated.
Overall lead recoveries were 93% and the energy requirement was 0.6-0.7
kWh/kg Pb. During the pilot program, various improvements were made to
the cell design, and it was estimated that the capital cost of a 30,000 t/yr lead
refinery would be (1986 US$) $ 10,000,000 and that the operating costs,
exclusive of capital charges, would be $ 0.27/kg Pb. Although the Dextec pro-
cess would probably require extensive development to control all the impur-
ities present in conventional lead concentrates, it appears to offer a viable
means of de-leading copper concentrates with the concomitant production of
a marketable lead product.
Most of the lead leaching processes developed to date advocate the precip-
itation of a PbCl2 intermediate product. Such a step improves the final purity
of the lead metal and provides a "surge capacity" between the leaching and
metal recovery operations. Although the Minemet process initially proposed
electrowinning directly from the purified leach solution, the latest develop-
ments of that process incorporate an intermediate PbCl2 crystallization step.
Only the Dextec process proposes lead recovery directly from the leach solu-
tion, but it is doubtful if that option would be viable for "dirty" lead
concentrates.
Although the Hazen Research process [76 ] employed H2 reduction of the
PbCl2 crystals, most processes utilize electrolysis to recuperate the lead and
regenerate an oxidant. SNC Inc. and CANMET recently reviewed PbCI2 elec-
trolysis technologies and offered a conceptual design for an electrowinning
cell [ 83, 84 ]. Seven fused salt and eleven aqueous electrolysis cells were eval-
uated. It was concluded that the recovery of lead by either fused salt or aqueous
electrolytic procedures had been demonstrated at a pilot scale. Three pro-
L E A C H I N G S U L P H I D E M | N E R A L S IN C H L O R I D E MEDIA 25
cesses were found to be particularly advanced for commercial application: the

U.S. Bureau of Mines' mono-polar fused salt cell, Alcoa's bi-polar fused salt
cell and Minemet's aqueous electrolysis cell. Overall, it was felt that the fused
salt cells were simpler to operate, produced a molten product and probably
had lower operating costs. For a small scale operation, the Bureau of Mines'
mono-polar cell, which is shown schematically in Fig. 6, would seem to be the
preferred option. For a large lead producer, however, the better economics of
bi-polar cell electrolysis could be attractive. Regardless of the electrolytic route
followed, the purity of the PbCl2 crystals is a key factor for the smooth and
efficient operation of the cell. Iron and sulphate in the PbCI2 crystals are of
principal concern. Iron causes a reduction in the cell current efficiency, and
the accumulation of sulphate necessitates the frequent bleeding of electrolyte
to prevent impurity crystallization on the electrodes. Iron contamination can
be eliminated by good washing of the PbC12 crystals [ 80 ], and SO4 can be
controlled by the presence of CaCI2 in the leach and the rapid crystallization
of th: PbCl2 intermediate product [ 59, 80 ].
FUNDAMENTALSOF THE FeCI3AND CuCi2 LEACHINGOF GALENA
A number of fundamental studies have been carried out on the reaction of

galena (PbS) with either FeCI3 or CuCI2 media, and those investigations pub-
PbCI2 FEED PIPE PbCI2 FEED PIPE

CHLORINE HANDUNG
,,.~___
,~[__....~ ,..2.
MOLTEN LEAD 81PHONS
ANODE BUS BAR
I I.'.:I I:"41 II:'_',I r,.
I I AN6DES : I I
L___2 - L. . . . II !__-~
CATHODE
Fig. 6. Crosssectionthrough a conceptualcellfor the fused salt electrolysisof PbCI2,from [ 83 ].

26 J.E. DUTRIZAC
lished prior to 1984 have been reviewed [ 8, 12 ]. The more recent fundamen-
tal studies on the chloride leaching of galena are summarized inTable 4.
The various kinetic studies were reviewed by Kobayashi et al. [ 93 ] and the
individual investigations were Compared on a consistent basis. There is a con-
sensus that the rate increases directly as the surface area of the galena
increases or with increasing temperature. Most of the reported activation
energies lie in the relatively narrow range of 34-53 kJ/mol. The rate increases
with increasing total chloride concentration, and the effect is especially ap-
parent at the higher chloride levels. Concentrated HCI solutions accelerate
the rate, probably via the generation of H2S. Of some commercial significance
is the fact that two reaction regimes are identified depending on the FeCl3
concentration. This point is illustrated in Fig. 7 which is taken from the paper
ofKobayashi et al. [93 ]. For FeCl3 concentrations <0.1 M, the rate is strongly
dependent on the FeCl3 concentration, and linear kifietics may prevail. For
FeCl3 concentrations > 0. l M, the rate is nearly independent of the ferric ion
TABLE 4
Summary of recent fundamental investigations on the FeCI3 leaching of galena
Parameter Units Range studied Dependence Reference
Kinetics Parabolic 85,86

Linear 87,88
Complex 89
Parabolic 90
Linear 9I
Parabolic 92
Temperature ~C 28-95 dti* ---44 kJ/tool 85,86

range studied 27-57 dH* = 72 kJ/m~! 87,88
30-90 d i p = 34 kJ/tool 90
14-80 dH*=43 kJ/mol 91
FeCh M 0.1-2 ka [ FeCi3 ] -0..,7 85

concentration 0.008-0.8 ka [ FeCls ]o.,~ 87,88
0. !-0.8 k=constant 90
0.05-0.2 kot [ FeCI310,76 9i
NaCI M 1-4 ka [ NaCI ] t..,7 85,86

concentratiotl !-5 ka [ NaCi] ~.o 87,88
0-3 k = constant ai 90 ° C 90
HCI M 0. I-3 k = constant 85,86

concentration 3-6 ka [ HC! ] .t8 85,86
PbCl: M 0-saturation k = A - B [ PbCI2 ] 85,86

concentration
L E A C H I N G S U L P H I D E M I N E R A L S IN C H L O R I D E M E D I A 27
10 -2
.¢_ ~'" t41
E
"~ 10-3
m
c
ou
o
m 10 -4
7"
I I I
10"2 10-1 10 0
FeCl 3 conc (M)
Fig. 7. Effect of the FeCI3 concentration on the galena leaching rate as reported by various in-
vestigators, from [93 ]. 1 = [91 ]; 2= [88 ]; 3= [85 ]; 4= [90]; 5= [93 ]; 6= [93 ].
concentration and parabolic kinetics prevail. In the more concentrated FeCI3

media of commercial interest, the rate seems to be controlled by the outward
diffusion of the PbCI2 reaction product into the bulk solution.
The kinetics of dissolution of galena in CuC12 media [ 94 ] seem to be sim-
ilar to those observed in the analogous FeCI3 system. Near-parabolic kinetics
are observed, together with an activation energy of 33 kJ/mol. The rate is
independent of CuCI2 concentrations > 0.1 M, but increases with increasing
concentrations of NaCI or HC1. The rate decreases with the accumulation of
the PbCI2 and CuCI reaction products, and this effect is related to the reduced
diffusion gradient for the outward migration of the reaction products from
the galena surface, through the product layer, and into the bulk solution.
All workers agree that elemental sulphur is the predominant sulphidic re-
action product and that the sulphur is generated according to the following
overall reaction:
PbS + 2FeCI3 ~ PbCI2 + 2FeCI2 + S° (41 )
Dutrizac [ 85 ] determined both the elemental sulphur and sulphate formed
during galena leaching over a broad range of temperatures and ferric ion con-
centrations. The molar ratio of S°/(S ° + SO4) varied from 0.94 to 0.99, with
an average value of 0.97. Elemental sulphur is known to be the dominant
sulphidic reaction product formed during the electroleaching of galena [ 95 ],
and the passivating effect of the sulphur on the electro-dissolution process has
also been reported [ 96 ]. Microscopic studies [ 86 ] ofgalena particles leached
in 0.3 M FeCIa-0.3 M HCI-3.0 M NaCI media consistently showed a thin
continuous layer of PbCI2 between the unleached PbS and the porous elemen-
tal sulphur product layer. An example of this morphology is shown in Fig. 8.
The implication is twofold. First, it is clear that in even m.~derately concen-
trated FeCI3media, PbCI2 is generated more rapidly than it can diffuse from
28 J.E. DUTRIZAC
Fig. 8. Backscattered electron micrograph showing the continuous PbCI2 layer tbrmed on galena
after 7 h of leaching at 80°C in 0.3 M FeCl~-0.3 M HCI-3.0 M NaCI solution. The PbCl2 forms
a cominuous layer between the galena and the sulphur reaction product, from [86]. l -galena;
2 = PbCl~; 3 = sulphur.
the galena surface. Hence, the outward diffusion of the reaction products must
be at least partly rate controlling. Second, the separation of the elemental sul-
phur reaction product from the surface of the PbS, as well as the morphology
o1"the sulphur, suggests that the sulphur is liberated from the galena surface
as a soluble species:
PbS + 2 H El-* PbCl2 + ( H 2S ) solution (42)
The PbCI2 quickly saturates the solution at the reaction interface, and a
thin layer of solid PbCI2 is formed. The H2S species dissolves in the solution
and diffuses through the PbCI2 layer. Thence, the H2S reacts with FeCI3 to
form sulphur and the porous, globular texture of the sulphur is consistent
with such a reaction:
( H2S)solution + 2FeCI3 -~ 2FeCI2 + 2HCI+ S° (43)
The overall reaction is the same as for the direct FeCI3 leaching of the gal-
ena, but the formation of a soluble sulphur intermediary better accounts for
the morphology of the reaction products.
CHLORIDE PROCESSES FOR COMPLEX SULPHIDES
Complex sulphide ores commonly consist of massive pyrite together with

major amounts of sphalerite and lesser quantities of chalcopyrite, galena and
various silver minerals. The liberation sizes are often so fine that individual
concentrates can be prepared only at the expense of a significant sacrifice in
recoveries. A bulk concentrate containing all the metal values, however, can
usually be prepared with acceptable overall recoveries. Such bulk concen-
trates can advantageously be treated by chloride leaching, and an additional
benefit of the chloride leach approach is that the abundant pyrite remains in
the leach residue. In FeCl3 or CuCl2 leaching media, pyrite is nearly inert, as
has been noted in the recent reviews by Lowson [97 ] and Crundwell [98 ].
The following sections deal with chloride leaching processes for complex sul-
phide ores and the fundamentals of sphalerite leaching in chloride media.
Although there is little commercial interest in the chloride leaching of con-
ventional zinc concentrates, the behaviour of sphalerite in complex ores is of
considerable concern. The leaching of the other minerals commonly present
in complex sulphide ores, namely chalcopyrite and galena, was discussed
above.
Early developments in the leaching of complex ores and pyritic bulk con-
centrates have been reviewed [8, 12 ], and processes, such as those developed
by Minemet and Elkem, discussed. In addition, the various unit operations
involved in the production and processing of complex sulphide ores and con-
centrates were recently reviewed by Collins and Flett [99 ]. They noted the
complexity of the flowsheets required to recover four elements (Zn, Cu, Pb
and Ag) by hydrometallurgical methods, and also correctly observed that the
advantage of the chloride leaching option lies in better recoveries of high value
products and not in significantly reduced processing costs. That is, the key to
the treatment of complex sulphides lies in the production of a bulk concen-
trate with high overall recoveries.
The CANMET ferric chloride leach process [ 100 ] achieves > 99% Zn and
Pb extraction, as well as 97% Cu and 96% Ag extraction, from complex pyritic
bulk concentrates. As shown in Fig. 9, the process consists of a two-stage FeCl3
leach in FeCla-NaCl media with interstage thickening. The pregnant solution
is clarified and rapidly cooled to precipitate PbCI2 for eventual Pb and C12
recovery. Due to the fact that CaCl2 is added "o the leach solution to precipi-
tate calcium sulphate, sulphate contamination of the PbCI2 crystals is not a
serious problem. Iron powder is used to cement a mixed Cu-Ag product, but
this option is feasible only because of the relatively low Cu content of the
concentrates employed. Zinc chloride is selectively extracted from the solu-
tion with tributyl phosphate (TBP), and is stripped with spent chloride elec-
trolyte. The small amount of FeCl3 co-extracted with the ZnCl2 is eliminated
with mono ethylhexyl phosphoric acid, and trace impurities are removed by
30 J.E. DUTRIZAC
Bulk
Concenl~ae
Feed
Reagents~ ~
Leach Residue to
lb '~asto or to S"IAu
,v i~ecovely
1 Lead Chlo~le
E~'tro~ ! "- LEAD INGOT
bOll l l ~ 22
lh COPPER-SILVER
v CEMENTCAKE
Z]n~ Chlotldo m
Iron Removal by SX
~ m m
Sdvenl E1ec~d,/t, Pmllcatlon
Zn
Ramna
~ C~
~ ZINC CATHOOE
Clz Io CNo~nailon
Emuenl m m m m ~ CADMIUM
......... v[ Trealmerland Zn, Pb Chloride
Cadmium Remvi~,
.-- ii i
Emue~t Sol.fort.
" In wasle
P,Issidue to Waste
Fig. 9. Schematic flowsheet of the CANMET ferric chloride leach process for low-copper pyritic
bulk concentrates, from [ 100].
zinc dust cementation. A novel feature of the CANMET process is that zinc
is electrowon from the chloride solution as a compact plate; Cl2 gas is gener-
ated at the anode of the diaphragm cell and is used to re-oxidize the iron
chloride leach solution. Excess iron and other impurities are controlled by the
oxy-hydrolysis of a bleed stream from the SX raffinate.
An economic analysis of the CANMET ferric chloride leach process indi-
cated a higher return on investment than for conventional technologies for

the same amount of ore treated. Also, the process was shown to be economi-
cally viable for a level of zinc production as low as 35,000 t/yr. To date, little
work has been carried out on the recovery of sulphur from the leach residue
or on the leaching of gold from the residue after sulphur elimination. The
various parts of the CANMET process were tested on a small pilot scale and
a partner is being sought to carry out an integrated pilot plant campaign.
CENIM and LNETI have collaborated to develop a novel two-stage am-
monium chloride-P2 leach process for complex sulphide ores that achieves
> 95% recovery ofZn, Cu, Pb and Ag [-101,102 ]. As shown in Fig. 10, leach-
ing occurs initially in a near-neutral environment and according to reactions
of the type illustrated below for zinc:
ZnS+ ½02 +2NH~ - ~ Z n 2+ + 2 N H 3 + H 2 0 + S ° (44)
Z n 2+ +2NH3 ~Zn(NH3)~ + (45)
The significant observation is that ammonia is formed from the ammo-
nium ion during leaching and that the ammonia complexes the base metals.
Leaching is carried out at 105 °C and under a 150 kPa 02 pressure; CaCI2 is
added to precipitate gypsum and low concentrations of citric acid are main-
tained to give a compact gypsum cake. Due to the nearly neutral leach con-
ditions used (around pH 6), iron, sulphate and other impurities remain in
the residue, while Zn, Cu, Pb and Ag dissolve as amine complexes. Pyrite is
not leached as rapidly as the other minerals, but its dissolution generates
sulphate:
5 5
FeS2 + - - 0 2 "~'~ H20~2H2SO4 + ½Fe2Os 'H20 (46)
The initial, nearly neutral, leach is accelerated by the presence of low con-
centrations (e.g., 1.5 g/l Cu 2+ ) of cupric chloride, and it seems likely that a
cupric chloride leach is actually involved:
4ZnS+ 14Cu 2+ + 4H20--* 14Cu + + 4 Z n 2+ (47)
+ 8H + + 5042- "~"35 °
2Cu + +½02 + 2NH~ --, 2Cu 2+ + H 2 0 + 2NH3 (48)
The residue from the near-neutral leach is treated in an acidic environment
at 105 °C and 150 kPa 02 pressure. Sufficient HCI is added to solubilize all
the non-ferrous metals in the residue.
Silver in the pregnant solution from the first stage leach is recovered by
cementation on copper and a PbCI2 product is formed by vacuum crystalli-
zation at < 50 ° C. The PbCI2 is redissolved and cemented on zinc, following
the precedent of Tecnicas Reunidas [ 30]. Zinc is extracted at 50°C with
j'1 ~ J
I______ ____ 7.-
S~Nr(nbO
I 1
-'.1 II
1 i .1
e
Ao/HL
SdUino
Pyrite l
| ~oethll
i
9 Sulphu,
i
,_J
--~- [
I '
i. i ' ' ' I ,.~w,ww.
." I i .............. 1................................... ~ I i """mememm
i
. e.u ~ .~.N .....
i
: .................................. !'..... .1................... !.....
~J;7..-. -.7 ,F,...............................................
. J
i
[ WMIMn 0 01' UX ..- ,,~ ....... Wlmhln 0 ~ OEHPA Zn etw:lltllyldo

t , 1 .m
t~
M
1 N
Zinc
Copper
Fig. 10. Schematic flowsheet o f the C E N I M - L N E T I a m m o n i u m chloride leaching process for copper-rich pyritic bulk concentrates, from [ 101 ].
DEHPA and, because the metal is present as an amine complex, there is no

significant pH change during extraction:
Zn (NH3)~ + + 2RH---,R2Zn+ 2NH~- (49)
The loaded organic is scrubbed to remove Cu,Ca and Pb as well as any
chloride ions. Zinc is then stripped with spent H2SO4 electrolyte, and the metal
is recovered from a conventional sulphate electrolyte:
R2 Zn + H2504 ~ 2RH + ZnSO4 (50)
ZnSO4 + H20-~Zn + H2SO4 + ½02
After zinc solvent extraction, the solution is oxidized to convert Cu + to
Cu 2+. The cupric-containing solution is then treated with LIX 65N to extract
the copper, which is subsequently stripped with spent H2SO4 electrolyte. Fi-
nally, the copper is recovered by conventional electrowinning in a CuSO4-
HESO4 medium. The CENIM-LNETI process has been evaluated on a small
pilot plant scale, and is notable for its elegant use of ammonia chemistry to
control the acid generated during the solvent extraction operations.
The U.S. Bureau of Mines [51 ] developed a ferric chloride leach process
to recover gold and silver from complex ores. The leaching is carried out for
6 h at 40°C to convert the lead and silver to chlorides which are poorly solu-
ble at the 40°C leaching temperature. About half the zinc is solubilized but
the fate of copper was not discussed. Acidic thiourea leaching was then car-
ried out on the leach residue to recover around 85% of the gold and silver.
Lead chloride was next solubilized at 55 °C in concentrated brine and lead
was recovered electrolytically, with concomitant regeneration of the ferric
chloride lixiviant. It was assumed that Zn would be recovered by sulphide
precipitation. The process developed by the Bureau of Mines is really in-
tended to recover Au and Ag from complex sulphide ores, and it is not a fully
integrated process designed to recover all the metal values present. Further-
more, the low temperature leach is only effective for native silver and silver
in solid solution in galena; refractory silver minerals, such as tetrahedrite, are
probably not amenable to low temperature leaching [ 12 ].
FUNDAMENTALS OF THE CHLORIDE LEACHING OF SPHALERITE
A number of fundamental studies have been carried out on sphalerites hav-

ing different iron concentrations. Collectively, these investigations have sig-
nificantly advanced the understanding of the leaching reactions involved. The
parametric dependencies for the leaching of sphalerite in chloride media have
been discussed, and the results obtained by various investigators prior to 1984
reviewed [ 12 ]. The results of the fundamental studies carried out in the in-
terim are summarized in Table 5.
TABLE 5 *~
Recent fundamental studies on the leaching of sphalerite in FeCI3media

Material FeCI3/HCi 3H* Other parameters Kinetics Reference
dependence (kJ/mol )
Flotation concentrate Strong FeCI3 dependence 27 Electrochemical reaction 103

containing 54% Zn, 9% Fe Moderate HCI dependence
Two flotation concentrates Rate proportional to Linear kinetics 104

containing 3.6% and 5.3% Fe surface area Size distribution
eft~cts modelled
Iron-activated bulk concentrate k o t [ F e C l 3 ] °-s6 32 Elemental sulphur Parabolic kinetics 37

containing 8% Zn Rate increases slightly major reaction indicative of diffusion
with increasing HCI product control
Copper-zinc concentrate Rate a [ FeCI3] o.t4 40 Rate independent of Linear kinetics 105
containing 6% Zn stirring speed. NaC!
slightly increases rate
Fifteen sized, 39-811 Rate increased in a Linear kinetics for all 106
high-purity sphalerites linear manner with Fe contents
containing 0.04-15% Fe increasing Fe content
t Activation energy seems to decrease as solid solution Fe content increases.
.m
-t
N
N
g
Significant progress has been made in the understanding of the sphalerite

leaching reactions in ferric sulphate and ferric chloride media. There are many
similarities in the reactions in the sulphate and chloride systems, and in fact,
Zhang et al. [ 103 ] have shown that the free energies, enthalpies and entropies
of leaching were nearly identical in both systems. It appears that the leaching
reaction is electrochemical in nature and is controlled by charge transfer at
the sphalerite surface. Crundwell and Verbaan have reported an important
series of studies on the electronic properties of sphalerite [ 98 ] and on its
dissolution in ferric ion media [ 107, 108 ]. Leaching obeyed the Butler-
Volmer equation, with the potential of the sphalerite being dominated by the
Fe a+/Fe 2+ couple at the surface. The importance of the iron (III) complexes
present in the solution was demonstrated in the ferric sulphate system and, in
fact, a good correlation between the leaching rate and the sum of the concen-
trations ofthe Fe 3+and FeHSO42+ complexes was shown. The data presented
in Fig. 11 suggest the following relationship:
Rate a ( [Fe 3+ ] -I- [FeHSO42+ ] )0.45 (52)
The power dependence is close to the 0.50 value predicted by the Butler-
Volmer equation, and presumably similar species dependencies prevail in the
FeCIa system as well. It was postulated that the role of the Fe(II) reaction
I I
7{:
,ll
E
m
X I01 - -
_1 . / l i
Z
t
too I I
i0'~ I0"=
Fea+ + Fe HSO4~'+] ( mol/L )
Fig. 11. The effect of the combined concentrations of the F~ 3+ and FeHSO42+ species on the
rate of sphalerite dissolution at 60°C. The implication is that the FeSO4 + species is inactive.
From [ 109].
36 J.E. DUTRIZAC
product is related to its displacement of the active Fe(llI) species at the

sphalerite surface. Organics in the solution reduce the leaching rate because
they adsorb on the sphalerite surface and reduce the area available for charge
transfer [ 109 ]. By contrast, low concentrations of copper in solution result
in the precipitation of grains of CuS on the sphalerite surface that promote
dissolution via galvanic couples [ l l 0 ].
Buckley et al. [ l 11 ] used X-ray photoelectron spectroscopy to determine
the surface composition of sphalerite during leaching. It was shown that a
metal-deficient sulphide layer a few nanometres thick rapidly formed on the
sphalerite. Under weakly oxidizing conditions, Cu and Hg concentrated in
the sulphide layer, but copper was eliminated in the presence of ferric ion.
The implication of this study is that the charge transt~er reactions occur at a
surface which differs significantly from that of unleached sphalerite. A fur-
ther finding was that Pb present in the sphalerite (or in the concentrate?)
reacts to form a thin layer of lead jarosite (Pbo.sFe3(SO4)2(OH)6) on the
surface of the sphalerite. This effect is most prevalent in ferric sulphate leach-
ing media and helps to explain the refractory behaviour of some lead-rich zinc
concentrates in those solutions [ 108 ].
If charge transfer (hole injection/electron capture) is rate-limiting, the rate
should be dependent on the iron concentration of the sphalerite. In fact,
Crundwell [98] showed that the presence of an iron d orbital within the
sphalerite band gap creates a narrow, localized band that is more favourable
for electron transfer and also pins the Fermi level within the d orbital band.
Furthermore, he predicted that the oxidation rate of sphalerite should depend
directly on its solid solution iron content. Palencia Perez and Dutrizac [ 106 ]
recently reviewed the available literature on the effect of solid solution iron
on the sphalerite leaching rate, and presented new data for fifteen sphalerites
having iron contents ranging from 0.04 to 14.7% Fe. Some of their results
obtained in FeCI3-HCI media are presented in Fig. 12. It is apparent that the
leaching rate is strongly affected by its iron content, with low-iron sphalerites
dissolving very slowly. There was an approximate linear correlation between
the leaching rate and the iron content, as predicted by Crundwell. The impli-
cation is that all studies on sphalerite leaching should differentiate between
the solid solution iron content of the sphalerite and the total Fe content of the
concentrate.
The influence of the solid solution iron content of the sphalerite, as deter-
mined by a number of workers, is summarized in Table 6. There is a consen-
sus that the leaching rate in ferric chloride, ferric sulphate or H2SO4-O2
media increases, probably in a linear manner, with increasing solid solution
iron content in the sphalerite. Most workers, however, have reported "anom-
alous" sphalerites which leach significantly faster or slower than predicted.
The reasons for this anomalous behaviour are not always clear. There is also
an indication that the activation energy decreases with increasing solid solu-
0.8
0.3 M FeCI=, 0.3 M HCl, 80°C,
0.7
Bluebell 12.5% Fe
°6
OS II nau n79S* F
~- L Jt ~ Nanisivik6.0"/oFo
~" 0.4
Balmat 1.29% Fo
0.3
0.2 Santander 0.04% Fe

® •
0.1
0.0 I i
0 2 4 6 8 10 12 14 16 18 20 22
TIME (h)
Fig. 12. The effect of the solid solution iron content of sphalerite on its dissolution in FeCI3
media, from [ 106 ].
tion iron content, and that the effect is most pronounced in the, 0-2% Fe range.
This aspect, as well as the effect of the iron content on other leaching param-
eters, requires additional study.
CONCLUSIONS
Over the past decade, significant progress has been made in the ferric
chloride and/or cupric chloride leaching of sulphide concentrates. A demon-
stration plant treating chalcopyrite concentrates and various pilot plant cam-
paigns on lead, zinc and pyritic bulk concentrates have been carried out. Nu-
merous fundamental studies provide a sound foundation for process
development and have defined many of the important control parameters.
Demonstrated strengths of the FeCl3/CuCI2 leach option include high metal
recoveries, elemental sulphur generation, silver dissolution, lack of pyrite at-
tack and ease of solution regeneration. The avoidance of SO2 emissions and
the decoupling of metal production from acid manufacture are major advan-
tages. A number of economic studies suggest that chloride leaching/process-
ing routes are competitive with conventional technologies in some circum-
stances and especially for the treatment of non-conventional concentrates.
38 J.E. DUTRIZAC
TABLE 6
The effect of the solid solution iron content on the leaching of sphalerite
Material Leach Conditions Conclusions Reference
5 concentrates H2SO4-O2 pressure Rate increased linearly with Fe 112

containing leach at 150°C content for 4 sphalerites
0.43-8.88% solid
solution Fe;
-200 mesh, but not The sphalerite containing

sized 0.43% Fe leached much too
rapidly relative to the other
samples
9 sphalerites containing 5 g/l Fe(SO4)i.5- Rate increased as the logarithm !13

0.11-10.3% Fe; surface 50 g/l H2504 at 70°C of the Fe content
areas
measured with BET One sphalerite ( ,,, 1% Fe)
leached anomalously slowly Cu
accelerated the leaching
reaction
6 sphalerites containing 10 g/! Fe(SO4)1.5 Rate increased directly with

0.79-13.4% Fe -100 g/i H2SO4 at solid solution iron content
90°C
Two sphalerites (2.96 and 114
4.60% Fe) dissolved
anomalously fast
i 5 commercial 20 g/! Fe(SO4)l,s- Rate increased with increasing 115

concentrates, 90 g/! H_~SO4at 68°C solid
not sized solution Fe, but scatter of
results
Poor correlation between
sphalerite
conductivity and the leaching
rate
4 sphalerites containing 2 M HCI at 55°C Rate increased directly with 116

0.28-2.15% Fe the solid solution Ire content
5 sphalerites containing 0.2 M FeCi3-0.3 M Rate increased linearly with 117

HCI solid solution iron content
0.55-8.6% Fe; samples -2.0 M NaC! at 45,65 One sphalerite (8.02% Fe )
wet screened and 85°C leached anomalously slowly
15 sphalerites 0.3 M Fe (SO4)I.s Rate increased directly with 106

containing -0.3 M H2SO4and solid solution iron content
0.05-14.7% Fe 0.3 M FeCI3-0.3 M One sphalerite (4% Fe)
HCI leached anomalously slowly
at 50-90°C
Despite the successes and apparent advantages of the chloride route, there
has been little commercial activity. In fact, a number of key problems remain
to be resolved. Metal product purity and morphology, especially for copper,
are a concern. The use of solvent extraction techniques, possibly with conver-
sion to a conventional sulphate system, would probably resolve both
problems. The recovery of elemental sulphur from the leach residues needs
additional attention; total sulphur extraction must be achieved if gold is to be
leached from the residues. The selenium content of the sulphur remains a
general concern. Although the process residues are casually assumed to be
benign, this has not been widely demonstrated, especially for long term resi-
due impoundment.
The implementation of any FeCl3/CuCl2 leach process will entail a consid-
erable risk that must be balanced by significantly lower costs or by a major
technical advantage. Much of the impetus for chloride technology originated
from the need to control SO2 smelter emissions. With the development and
widespread commercialization of flash and bath smelting processes for Cu
and Pb, this consideration becomes less and less compelling. Hygiene aspects
and fugitive SO2 emissions are still a concern, however, and could provide
the incentive for a chloride process to treat conventional Cu, Zn or Pb con-
centrates. There seems to be an economic advantage in producing a bulk con-
centrate from complex sulphide ores, and chloride leaching technologies hold
considerable promise for the treatment of such feeds. Clearly more work is
needed, especially at the pilot plant level, if the potential of chloride metal-
lurgy is to be realized.
REFERENCES
1 Lung, T.N., The history of copper cementation on iron--The world's first hydrometal-
lurgical process from medieval China. Hydrometallurgy, 17 ( 1986 ): 113-129.
2 Taylor, J.H. and Whelan, P.F., Leaching and precipitation of copper at Rio Tinto, Spain.
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tlydrometallurgy, 29 ( 1992 ) 1-45

Elsevier Science Publishers B.V., Amsterdam

The leaching of sulphide minerals in chloride

0304-386X/92/$05.00 © 1992 Elsevier Science Publishers B.V. All rights reserved.

CHLORIDE LEACHING PROCESSES FOR CHALCOPYRITE CONCENTRATES

3CuCI?. + CuFeS, -,4CuC!-I- FeCI2 + 2S° (l)

C u + + e - --* C u ° (cathode) (7)

The CLEAR demonstration plant showed that chloride leaching processes

NaOH. These general disadvantages must, however, be weighed against the

The Great Central Mines ( G C M ) hydrocopper process also produces par-

CuCI+ H + + e - - ~ C u ° + HCI (cathode) ( 12 )

from the anolyte chambers is subjected to turbo-aeration to regenerate the

The activation techniques summarized in Table 1 can be divided into three

Activation methods for chalcopyrite

Method References Comments

additional flexibility in the leaching stage. Also, it would be desirable to de-

PRODUCT RECOVERY AND PURITY

SULPHUR GENERATION AND CONTROL

cal composition of the concentrate tested. In the GCM process [ 31 ] elemen-

Fig. 3. Secondary electron micrograph of 30 ~m chaicopyrite particles leached for 8 h at 95:C

Fig. 4. Secondary electron micrograph of 50 ~tm chalcopyrite particles leached for 24 h in O. I M

CuFeS, + 4HCI=.CuCi2 + FeCI2 + 2 ( H.,S ),,~.,olvcd

CuFeS2 + 4FeCI3 -~ CuCI2 + 5FeCI2 + 2S° (20)

2H2 SaO2 --*H2SO3 + H 2 0 + 3S° (23)

FUNDAMENTALS OF THE FERRIC CHLORIDE LEACHING OF CHALCOPYRITE

A great deal of fundamental research on the FeCl3 leaching of chalcopyrite

FUNDAMENTALS OF THE CUPRIC CHLORIDE LEACHING OF CHALCOPYRITE

Various fundamental studies on the reaction of chalcopyrite with CuCI2

Recent fundamental studies on the leaching ofchalcopyrite in FeCI3 media

Material Reference Conclusions

Natural chalcopyrite 54 Leaching is 2 times faster in FeCl 3 than in Fe(SO4)~.5

Natural chalcopyrite 55 Electrochemical mechanism advanced

Natural high purity, 60,61 Electrochemical studies showed formation of ~ 3 nm

Natural chalcopyrite sawn 62,63 Electrochemical effects shown to be important in bacterial

Natural massive 64 Electrochemical studies suggested sulphide intermediale

Natural massive 65 Electrochemical studies showed an anodic prewave to

Recent fundamental studies on the leaching ofchalcopyrite in CuCI2 media

Material Reference Conclusions

Sized chaicopyrite 67 Linear leaching kinetics

Sized chalcopyrite 68 Parabolic leaching kinetics

U nsized chalcopyrite 29 Postulates CuS |brmation at high Cu +/Cu 2+ ratios

.-38 ~tm chalcopyrite 70 Linear kinetics

observed linear kinetics together with a moderately high activation energy.

CHLORIDE LEACHING PROCESSES FOR LEAD CONCENTRATES

(PbCl2)~olid + 2C1- 95°C (PbCI~-)~o~tio. (31)

cesses were found to be particularly advanced for commercial application: the

FUNDAMENTALSOF THE FeCI3AND CuCi2 LEACHINGOF GALENA

A number of fundamental studies have been carried out on the reaction of

PbCI2 FEED PIPE PbCI2 FEED PIPE

I I.'.:I I:"41 II:'_',I r,.

Fig. 6. Crosssectionthrough a conceptualcellfor the fused salt electrolysisof PbCI2,from [ 83 ].

Summary of recent fundamental investigations on the FeCI3 leaching of galena

Parameter Units Range studied Dependence Reference

Kinetics Parabolic 85,86

Temperature ~C 28-95 dti* ---44 kJ/tool 85,86

FeCh M 0.1-2 ka [ FeCi3 ] -0..,7 85

NaCI M 1-4 ka [ NaCI ] t..,7 85,86

HCI M 0. I-3 k = constant 85,86

PbCl: M 0-saturation k = A - B [ PbCI2 ] 85,86