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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 International Symposium. ttydrometailurgy, 29: !-45.
Recent studies on ~he ferric chloride and cupric chloride leaching ofchalcopyrite, galena and sphalerite 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 chloride 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 leaching processes for iron-rich zinc concentrates could probably be developed. The importance of intermediate 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 complex 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 drainage 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 during 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.
J.E. DUTRIZAC
Large-scale heap leaching of calcined ore began in 1876, and the heap leaching 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 18871888, 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 largest 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 copper 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 production [ 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 perhaps 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-
nomic reasons, the practical chemical oxidants for base metal sulphides were
limited to ferric ion and air. Initial studies showed that ferric sulphate solutions gave lower leaching rates than ferric chloride media [ 8 ], but efforts to
use hot concentrated FeCls-HCl media resulted in severe equipment corrosion 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 major 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 environmental regulations demand nearly complete SO2 capture in any pyrometallurgical operation. Although the technology to capture SO2 exists, its implementation 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 difficulties. 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
J.E. DUTRIZAC
processes have been largely resolved through the use of engineered plastics
and thoughtfully selected metallic and ceramic components. Although commercial leaching processes for sulphide feeds are limited in number, R&D
activities remain relatively strong. Thus, the purpose of this review is to survey 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 literature 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 chalcopyrite-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 extractions 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', MINTEK researchers used solvent extraction with LIX-64N to convert the cupric
chloride to a sulphate medium for conventional electrowinning. Both removed 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 chloride process for copper concentrates which were ground to 97% - 325 mesh.
Leaching was carried out countercurrently in two stages, both of which operated at 95C. 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 100150 g/l Cu and 110-160 g/l Fe. Af:er thickening and filtration, the solution
was vacuum cooled to around 40C 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 500C. Sand was used in the fluid bed
reactor to prevent sintering of the charge, and the Cu-sand product was subsequently 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 95C 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 overcome. 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 ~:oncentrated chloride media is a continuing concern in all copper leaching processes.
The Cymet process demonstrated on a pilot scale that high copper leach extractions 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 concentrates 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:
J.E.DUTRIZAC
FinelyGround
Cholcopyrite
Concentrote
STC1"
FIRST
LEACH
105"C
_~
r--...
Cu Powder
[ S'~~"~
-I
/
~
,
_1 OUCT,O. w,r,I
Cu POWDER ]
LEACH
9P---~
! 4 i ELECTROLY,StS ]
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)
(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 150C
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)
(4)
(5)
(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
C u + _ e - _ ~ C u 2+
(cathode)
(7)
(anode)
(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. Presumably, it could be recovered as a silver-rich product from the solution, but details of the silver recovery options have not been presented.
The principal advantage of the Minemet approach is that high purity copper 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 solution 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 precipitate 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 contacted 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 electrowon from the higher valent cupric state. Furthermore, in the Henkel option, there is a requirement for a separate electrolysis step to generate C12 and
(9)
(lO)
(ll)
It is well established thal eq. (11) heavily favours CuC12 and FeCI2 although 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 cupric 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 Metclor 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 consumption 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 byproduct 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 Cuprex 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 particulate 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 pregnant 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 )
(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
Copper
L _l co,,+,
Ground
Cnc~f~r'L
+.]
-
.L
==
m
Ir)n
Residue
L___3 SLvER
LEACH
I ,ELECTROWlNNINGJ
F
ANOLYTE
-~
Copper-,m
~esidue
for
gold recovery
roduct
Fig. 2. Schematic tlowsheet for the Great Central Mines (GCM) hydrocopper process for chalcopyrite concentrates, after [ 31 ].
11
( 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 oxyhydrolysis of a bleed stream using a Woodall Duckham spray roaster, and the
residue is discharged:
2FeCI2 "~"02 +2H20-,Fe2Oa +4HC1
(16)
(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 leaching route was compared to those for the Inco and Noranda smelting technologies. 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 published. The GCM process, which is still being developed, achieves high copper 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
!2
J.E. DUTRIZAC
TABLE !
Activation methods for chalcopyrite
Method
References
Comments
Activation with
sulphur
32,33
Activation with
covellite
Activation with
copper
34
Activation with
iron
Activation with
carbon
Activation by
sulphur removal
with H2
Activation by
sulphur removal
in vacuum or in
inert gas
Activation by
silver catalysis in
solution
Mechanical
activation
36,37
35
38
39
40
4 !,42
43,44
additional flexibility in the leaching stage. Also, it would be desirable to develop 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 commercial 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
13
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 medium are high. Consequently, CuC1 precipitation, by itself, is orobably not an
adequate purification process for yielding high purity copper. In most instances a solution purification step will be required. Solvent extraction ~nethods 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 concentrates 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 containing 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 leaching, 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 manufacture. 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 unaffected during leaching. It was proposed to recover the elemental sulphur
reaction product using an ammonium sulphide leach, with subsequent acidification 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 ] elemental 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 concentrate. Difficulties were noted with this approach, however, and sulphur leaching methods were being examined. All studies have reported that the sulphur
is contaminated by a number of impurities, notably selenium, which substitutes for sulphur.
In contrast, the Cymet process [ 18 ], which leaches chalcopyrite concentrates at 98C 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 process is not known, but may be related to the concentrate used. The CLEAR
process [21 ] solubilizes copper by leaching initially at 105C and subsequently at 140C in an oxygenated CuCI2-FeCI3 medium. The high temperature 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 separation 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 completely 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 residue 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 investigations reported > 90%, and often > 95%, elemental sulphur generation. For
example, Ravi et al. [ 53 ] recently observed 99.5% S formation during chalcopyrite leaching at 97C. 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 recently, Dutrizac [ 56 ] studied the relative amounts of elemental sulphur and
sulphate generated during the FeCI3 leaching of pure chalcopyrite. At temperatures < 100C, more than 95% S tbrmation was consistently achieved, together 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
15
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 agglomerates 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 filtration rates noted by all investigators despite the often fine particle sizes involved. 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 similar 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:
16
J.E. DUTRIZAC
[561.
CuFeS, + 4HCI=.CuCi2 + FeCI2 + 2 ( H.,S ),,~.,olvcd
2 ( H~S )di,~,,,l~.d + 4FeCh ~) 4FeCI., + 4HCI + 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 nucleation 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 hydrolyzed to H 2 S : O 2 :
CuFeS2 + Fe 3+ -~ CuFeS. S + + Fe 2+
(21 )
2S + + 2H20-~ H2S202 + 2H +
(22)
17
(23)
(24)
Significant is the fact, however, that the proposed reactions predict only
75% S formation, whereas the experimental evidence indicates a higher degree 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 sulphides 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 significant sulphate. Elemental sulphur is stable in chloride media at 100C, but
becomes more reactive above its melting point. Sulphate formation, accordingly, becomes more prevalent in those processes employing elevated temperatures: up to 25% SO4 formation was observed in the CLEAR process.
In most chloride processes, sulphate is controlled by the addition of calcium 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 sulphate, barium sulphate, sodium jarosite and potassium jarosite. Lead sulphate 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 circulating load of sulphate ( l 0 g/l SO4) is allowable in the process, however, potassium 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 adversely affected the filtration of the leach residue. Addition of CaCI2 effectively 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 precipitation of calcium sulphate.
18
J.E. DUTRIZAC
(25)
+ 1.25S+ 2.5eIn 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 diffraction 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)eAlthough it is certain that thin scales of sulphide form on chalcopyrite during 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 intermediate 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)
(28)
(29)
19
TABLE 2
Recent fundamental studies on the leaching ofchalcopyrite in FeCI3 media
Material
Reference Conclusions
Natural chalcopyrite
single crystal
54
Natural chalcopyrite
single crystal
55
60,61
62,63
Natural massive
chalcopyrite
64
Natural massive
chalcopyrite, free of
microscopic inclusions
65
66
different mechanisms may prevail above and below 80C. Low concentrations of Cl adversely affect the reaction, but the rate may be chlorideinsensitive 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
concentrate containing
27-30% Cu
67
Sized chalcopyrite
concentrate containing
c.80% chalcopyrite;
total Cu = 34%,
total Fe=25%
68
U nsized chalcopyrite
concentrate containing
26% Cu
29
69
70
Linear kinetics
Rate independent of [CuCI2] when 02 sparging used
Rate increases with [Ci] to 90 g/i
Rate independent of surface area of chalcopyrite
Rate maximum at 85C
21
Galena (PbS) is the only lead sulphide mineral of any commercial significance. Galena concentrates are readily processed by pyrometallurgical methods, 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 problems 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 sulphate 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 40C 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:
40C
PbS + 2FeCI3 ~
(PbCI2),olid + 2FeCI2 + S
(30)
(31)
25 C
' (PbC12)solia+ 2C1-
( 32 )
(PbCI24- )solution
(33)
22
J.E. DUTRIZAC
In both processes, silver extractions were 20-85%; the erratic values probably 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 accumulation of zinc was a lingering problem which was not completely resolved. Initially, Minemet recovered Pb from the leach solution by aqueous
electrolysis in a diaphragm cell such that the FeCI3 lixiviant was simultaneously regenerated:
P b 2+ +
2e- --, Pb
(cathode)
(anode)
(34)
(35)
(36)
(37)
The chlorine gas evolved at the anode was used to regenerate the iron chloride 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 produced 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 conventional 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 thickened and filtered at > 92C 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 solution occurred. Copper and silver were recovered by cementation on iron. If
the cementation was carried out on the cooled solution, negligible precipita-
23
Lead
Concentrate
~
PbCl2
ResidueTreatment]----~erightS o
I
Residue
Crystallization
J
PbCl s
Copper I
Cement |
l 1
etI
Aqueous
Lead
-I ( l e c t r l y s i s
,I
J Ferric I
-IRegeneration ~
~Pb Metal
~CuO
/
Fe
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 90C in a solution containing 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 separates 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 extraction 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 selectively solubilized at 90C 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)
(39)
P b S - 2e- -~ Pb 2+ + S
(40)
Any H2S evolved either would be oxidized by ferric chloride or would precipitate 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 deposited 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 process would probably require extensive development to control all the impurities 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 precipitation 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 developments of that process incorporate an intermediate PbCl2 crystallization step.
Only the Dextec process proposes lead recovery directly from the leach solution, 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 electrolysis technologies and offered a conceptual design for an electrowinning
cell [ 83, 84 ]. Seven fused salt and eleven aqueous electrolysis cells were evaluated. 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-
25
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
CHLORINE HANDUNG
,,.~___
,~[__....~
,..2.
L___2
I.'.:I
AN6DES
L. . . .
I:"41 II:'_',I
r,.
II
!__-~
CATHODE
26
J.E. DUTRIZAC
lished prior to 1984 have been reviewed [ 8, 12 ]. The more recent fundamental 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 consensus 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 apparent 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
Kinetics
Dependence
Reference
Parabolic
Linear
Complex
Parabolic
Linear
Parabolic
85,86
87,88
89
90
9I
92
Temperature
range studied
~C
28-95
27-57
30-90
14-80
85,86
87,88
90
91
FeCh
concentration
0.1-2
0.008-0.8
0. !-0.8
0.05-0.2
ka [ FeCi3 ] -0..,7
ka [ FeCls ]o.,~
k=constant
kot [ FeCI310,76
85
87,88
90
9i
NaCI
concentratiotl
1-4
!-5
0-3
ka [ NaCI ] t..,7
ka [ NaCi] ~.o
k = constant ai 90 C
85,86
87,88
90
HCI
concentration
0. I-3
3-6
k = constant
ka [ HC! ] .t8
85,86
85,86
PbCl:
concentration
0-saturation
k = A - B [ PbCI2 ]
85,86
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
._
E
10 -2
"~
10-3
~'"
27
t41
m
c
ou
o
10 -4
7"
10"2
10-1
FeCl 3 conc
10 0
(M)
Fig. 7. Effect of the FeCI3 concentration on the galena leaching rate as reported by various investigators, from [93 ]. 1 = [91 ]; 2= [88 ]; 3= [85 ]; 4= [90]; 5= [93 ]; 6= [93 ].
(41 )
28
J.E. DUTRIZAC
Fig. 8. Backscattered electron micrograph showing the continuous PbCI2 layer tbrmed on galena
after 7 h of leaching at 80C 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 sulphur 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 +
(43)
The overall reaction is the same as for the direct FeCI3 leaching of the galena, but the formation of a soluble sulphur intermediary better accounts for
the morphology of the reaction products.
29
30
J.E. DUTRIZAC
Bulk
Concenl~ae
Feed
Reagents~ ~
Leach Residue to
lb '~asto or to S"IAu
,v i~ecovely
Lead Chlo~le
E~'tro~
bOll l l ~
22
lh COPPER-SILVER
v CEMENTCAKE
Z]n~ Chlotldo
Sdvenl
Iron Removal by SX
~
E1ec~d,/t, Pmllcatlon
Zn
Ramna
.........
C~
Emuenl
Trealmerland
v[
Cadmium Remvi~,
.--
ii
ZINC CATHOOE
Clz
Io CNo~nailon
m m m m ~ CADMIUM
Zn, Pb Chloride
"
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 generated 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-
31
(44)
(45)
+2NH3 ~Zn(NH3)~ +
The significant observation is that ammonia is formed from the ammonium 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 maintained to give a compact gypsum cake. Due to the nearly neutral leach conditions 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
FeS2 + - - 0 2
"~'~ H20~2H2SO4
+ Fe2Os 'H20
(46)
The initial, nearly neutral, leach is accelerated by the presence of low concentrations (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+
+ 8H + +
(47)
5042- "~"35
(48)
e.u
."
'
I
.1
,_J
.~.N
Wlmhln 0 ~ OEHPA
'
"""mememm
,.~w,ww.
Zinc
Zn etw:lltllyldo
.....
Sulphu,
Pyrite
Ao/HL
II
~oethll
-'.1
'
SdUino
S~Nr(nbO
i .............. 1...................................
'
WMIMn 0 01' UX
7.-
j'1
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 ].
: ..................................
i.
Copper
____
--~-
I______
.m
t~
33
(49)
(50)
A number of fundamental studies have been carried out on sphalerites having different iron concentrations. Collectively, these investigations have significantly 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 interim are summarized in Table 5.
39-811
40
Fifteen sized,
high-purity sphalerites
containing 0.04-15% Fe
Copper-zinc concentrate
containing 6% Zn
32
Rate increased in a
linear manner with
increasing Fe content
Rate independent of
stirring speed. NaC!
slightly increases rate
Elemental sulphur
major reaction
product
k o t [ F e C l 3 ] -s6
27
Other parameters
Rate proportional to
surface area
Flotation concentrate
containing 54% Zn, 9% Fe
3H*
(kJ/mol )
FeCI3/HCi
dependence
FeCI3media
Material
TABLE 5
Linear kinetics
Parabolic kinetics
indicative of diffusion
control
Linear kinetics
Size distribution
eft~cts modelled
Electrochemical reaction
Kinetics
106
105
37
104
103
Reference
-t
.m
*~
35
(52)
)0.45
The power dependence is close to the 0.50 value predicted by the ButlerVolmer equation, and presumably similar species dependencies prevail in the
FeCIa system as well. It was postulated that the role of the Fe(II) reaction
7{:
,ll
E
m
X
W
I01
_1
. / l i
Z
t
too
I
i0'~
I
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 60C. The implication is that the FeSO4 + species is inactive.
From [ 109].
36
J.E. DUTRIZAC
37
0.8
0.3 M FeCI=, 0.3 M HCl, 80C,
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
0
10
12
14
16
I
18
i
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 parameters, 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 demonstration plant treating chalcopyrite concentrates and various pilot plant campaigns on lead, zinc and pyritic bulk concentrates have been carried out. Numerous 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 attack and ease of solution regeneration. The avoidance of SO2 emissions and
the decoupling of metal production from acid manufacture are major advantages. A number of economic studies suggest that chloride leaching/processing routes are competitive with conventional technologies in some circumstances 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
containing
0.43-8.88% solid
solution Fe;
H2SO4-O2 pressure
leach at 150C
112
9 sphalerites containing
0.11-10.3% Fe; surface
areas
measured with BET
6 sphalerites containing
0.79-13.4% Fe
!13
114
i 5 commercial
concentrates,
not sized
115
4 sphalerites containing
0.28-2.15% Fe
2 M HCI at 55C
116
5 sphalerites containing
0.2 M FeCi3-0.3 M
HCI
-2.0 M NaC! at 45,65
and 85C
117
0.3 M Fe (SO4)I.s
-0.3 M H2SO4and
0.3 M FeCI3-0.3 M
HCI
at 50-90C
106
39
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 conversion 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 residue impoundment.
The implementation of any FeCl3/CuCl2 leach process will entail a considerable 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 concentrates. There seems to be an economic advantage in producing a bulk concentrate 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 metallurgy is to be realized.
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