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Atmospheric Chloride Leaching of Base Metal Sulphides

197

Atmospheric Chloride Leaching of Base Metal Sulphides


Bryn Harris (1), V Lakshmanan(2), T. Magee(1), R. Sridhar(2)
(1) Jaguar Nickel Inc., Toronto Canad
(2) Process Research Ortech Inc., Missisauga Canad
bryn.harris@mcgill.ca

Abstract
The Jaguar Nickel Atmospheric Chloride Leach Process, recently developed for nickel laterite ores, has been successfully
adapted to the atmospheric leaching of base metal sulphide feeds. Results are presented showing that greater than 95% of
the contained copper, nickel and cobalt can be solubilised from base metal sulphide concentrates irrespective of the PGM
content of the feed, and that substantially all of the sulphur can be removed and recovered as an elemental product suitable
for sale. The paper discusses the roles of the important parameters, net chloride concentration, pH, Eh and temperature, on
the extraction kinetics and overall recovery of the metals. Speciation of sulphur and the deportment of PGMs is also
discussed. A conceptual flowsheet is presented.

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198

Introduction
Jaguar Nickel Inc., with the assistance of Process Research ORTECH, has been developing a novel chloride-based flowsheet for
the recovery on nickel and cobalt from Guatemalan laterites [1,2,3]. A logical consequence of this development was to see if
the chemistry could be equally applied to sulphide ores as well as oxide ores, and this paper reports on results obtained in the
laboratory using a modified version of the chloride-based circuit developed for oxidic feeds. The immediately obvious
differences are that sulphide feeds both require an oxidant to effect leaching and also have much higher values of paymetals
relative to gangue and impurities than do laterites, and cognizance of these differences has been taken into account in
looking at sulphide feeds.
Chloride chemistry, particularly in strong salt solutions, is complex, and can be quite different from that found in
corresponding sulphate systems. The two most important factors in concentrated chloride salt solutions (brines) to note are
firstly that the activity of water is <<1, and secondly, that the activity of the hydrogen ion, H+ (or, more importantly, H3O+), is
significantly increased. It follows, then, that in concentrated brines such as magnesium chloride considered for the Jaguar
Process, in general, a small amount of acid can achieve much more than a similar amount in more dilute chloride solutions or
in sulphate systems. It is also necessary to appreciate that base metals, with the exception of nickel, form a variety of chlorocomplexes, and that these also have a bearing on the properties of the system, and, hence, efficient impurity removal and
better product recovery.
Considering the above, the behaviour of ferric iron is of great interest. The reduced activity of water offers the opportunity to
1
readily hydrolyze any iron that enters solution, and at a significantly lower apparent pH than can be achieved in sulphate.
Provided that the overall chloride concentration is maintained such that FeCl4- does not form to any extent, in which case
hydrolysis would be very difficult, then it should be possible to leach out base metals from sulphide feeds, and with
appropriate control of the redox manipulate the form of sulphur produced, and such has formed the basis of the flowsheet
presented in this paper.

The Chemistry of Chloride Systems


The fundamental background to the chloride chemistry which forms the basis of the work reported in this paper has been
discussed at some length in a previous publication [3], and is therefore not reproduced here. Nevertheless, it is pertinent to
revisit certain of these fundamentals as they apply to base metal sulphide feeds.
Chloride metallurgy has for many years been primarily the domain of precious metals production, but is increasingly being
considered as an alternative process for the production of base and refractory metals. Many metal chlorides are found to be
considerably more soluble than their corresponding sulphate salts, thus allowing the use of more concentrated solutions.
The solubility of CuSO4.5H2O, for example, is about one fifth that of CuCl2.2H2O, and both nickel and ferrous chlorides are also
more soluble than their sulphate counterparts [4].
Additionally, and with particular relevance to sulphide feeds, the enhanced leachability of minerals in chloride solutions can
be attributed to, in part, the high oxidizing potential of both the Fe(III)/Fe(II) and Cu(II)/Cu(I) couples, as well as the high
stability of the chloro-complexes of many transition metals. This lowers ionic activities and potentials for sulphide corrosion,
as well as imparting moderate solubility of these complex species in stronger brine solutions.

Redox Potentials and Chloride Complexation


The standard reduction potentials for some of the reactions of interest are provided below:

Oxygen
O2 + 2H+ + 2e-

H2O

Iron
Fe2+ + e=
Fe(s)
Fe3+ + e=
Fe2+
FeOOH + 3H+ + e-=
Fe2+ + 2H2O
1

1.23V

(1)

-0.44 V
0.73V (1.0N HCl)
0.74V

(2)
(3)
(4)

It should be noted that pH can be a very misleading term when applied to strong brines due to both the low activity of water
and the enhanced activity of the hydrogen ion.

Hydro-Sulfides 2004

Atmospheric Chloride Leaching of Base Metal Sulphides

FeO42- + 3H2O + 3e-

199

FeOOH + 5OH-

0.80V

(5)

Nickel
=
Ni2+ + 2e-

Ni

-0.24V

(6)

Cobalt
Co2+ + 2e=
Co3+ + e=

Co
Co2+

-0.28V
1.92V

(7)
(8)

Copper
Cu+ + e=
Cu2+ + e=
Cu2+ + 2e=

Cu
Cu+
Cu

0.52V
0.16V
0.34V

(9)
(10)
(11)

Magnesium
Mg2+ + 2e- =

Mg

-2.36V

(12)

The potential-log [Cl-] shown in Figure 1 indicates that at a concentration of 10M Cl- (354.5 g/L of Cl-) and 0.73V, iron will be
present as ferric chloride, whereas ferrous chloride is the most predominant from 1.0M Cl- (35.45 g/L of Cl-) and higher and
between 0.4V and 0.73V. The reduction potential for the Ni++/Ni couple is 0.3V as against its standard reduction potential of
-0.24V [5], and, therefore, the dissolution of nickel is highly favorable in this system, where the reduction of oxygen will
provide the required dissolution potential for nickel and iron. A similar argument also holds for cobalt and for copper.
Furthermore, it can be seen that the oxidation of iron to the ferric state is also favorable under these conditions, which in turn
could contribute to the dissolution of nickel and other base metals as it reduces to the ferrous state.
1.6

Cl2

Eh / V

Cl-

AuCl4Au

1.2

O2
H2O
Fe3+

0.8

FeCl2+

FeCl2+

FeCl3

2+

Fe

AgCl2
0.4

Cu

CuCl+

2+

CuCl32-

Pb2+
Pb

2+

H
H2
+
PbCl

CuCl2

2+

BiCl6

Fe
Fe

FeCl

3-

AgCl32-

Cu

FeCl2

PbCl4

2-

Ni2+
Ni

ZnCl3

Zn2+
-0.8

ZnCl2

ZnCl

-0.4

BiCl4-

BiCl5

BiCl2+

Ag

Bi

CuCl2

Zn

ZnCl42-

-1.2
-2

-1

1
-

log[Cl ]
Figure 1. Eh-log[Cl-] diagram at 25oC [5]

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Bryn Harris

200

Chloride Hydrometallurgical Practices


Apart from the precious metals plants (which of necessity have to operate in chloride), there have been relatively few
commercial hydrometallurgical operations treating sulphide feeds which have been conducted entirely in chloride media. A
review of these processes can be found in an earlier publication [3]. Despite this, a chloride-based atmospheric leach process,
whilst unusual, is far from unique. Noranda operated the Brenda Leach Process, employing a high temperature (105-110oC),
high-strength chloride (CaCl2+NaCl+HCl) atmospheric leach of copper-molybdenum sulphide concentrates until the mine
shut down in the 1990s [6]. The process essentially leached out all of the copper, lead and calcium from molybdenum, and
the only real factor of concern was to maintain the lagging on the piping in winter to prevent the high strength brine from
crystallizing [7].
Falconbridge operates a chloride process at its nickel-cobalt refinery in Kristiansand, Norway, which was initially a
hydrochloric acid leach, but more latterly a chlorine leach [8,9,10]. These and other plants such as those operated by
Jinchuan [11], Sumitomo [12] and SLN [13] in a mixed chloride-sulphate medium, clearly demonstrate that chloride-based
circuits are perfectly feasible, and that any material-handling issues associated with a chloride environment can be and are
being overcome.
One major unit operation sometimes associated with chloride flowsheets is pyrohydrolysis of the final chloride liquor, and
over the years, this has become a very mature technology, particularly in the steel pickling industry for the treatment of
ferrous chloride solutions. There are essentially two ways of operating, in a spray roaster or in a fluid bed [14]. When treating
a magnesium chloride feed solution, the former generates a fine, caustic powder, suitable for use as a neutralizing and
precipitating agent within the process, whereas the latter generates coarser particles, more suitable for handling and sale.
Significant work has been recently reported on the pyrohydrolysis of such solutions, a process which is operating successfully
on predominantly magnesium chloride liquors at Rio Tinto Iron and Titanium (QIT) in Quebec [15,16]. It is also worth noting
that at its Goro plant in New Caledonia, Inco plans to use pyrohydrolysis for the production of nickel oxide and to recycle HCl
within the solvent extraction circuit [17].

Chloride Metallurgy for Base Metal Sulphide Feeds


Beginning in the 1970s and early 1980s, when it was firmly believed by hydrometallurgists that aqueous processing would
confine smelting to the history books, there was a great deal of interest in and research into developing chloride-based
hydrometallurgical processes for the treatment of (primarily) copper sulphide concentrates [18,19,20]. Of these early
attempts, only Duvals CLEAR (Copper (chloride) Leach Electrowin And Regeneration) Process [21,22,23,24,25,26] attained
commercial operation, and this only from 1976 until 1982, when it was shut down for economic reasons. The Cyprus CYMET
Process [27,28,29,30,31,32] attained a pilot operation at 45kg/h, but none of the others, those of Minemet Recherche (Imetal)
in France [33,34,35], Dextec in Australia [36,37,38,39,40,41], Elkem in Norway [42,43], the USBM Process [44,45,46,47], the
Canadian Great Central Mines Process [48,49,50], Phelps Dodge [51], and UBC/Cominco [52], with the exception of Dextec
which has transmogrified itself into the Intec Process [53,54,55,56,57], seem to have progressed at all. Although the literature
contains many references to ferric and cupric chloride leaching of chalcopyrite concentrates [20], of which the studies by
Dutrizac [58,59], Majima et al.[60], and Holdich and Broadbent [61] are of interest, none of the processes really overcame the
difficulties associated with precious metals recovery, electrowinning of copper from a chloride medium, and the effective
recycle of lixiviant, whether ferric or cupric. The following summarises some of the salient features of these early processes.

CLEAR Process (Duval) [21,22,23,24,25,26]


The CLEAR (Copper (chloride) Leach Electrowin And Regeneration) was probably the most developed of all of the sulphide
hydrometallurgical copper processes [18,21,22]. It comprised a two-stage leach, with 50% of the copper in concentrate being
recovered in a reduction leach with CuCl2, generating a cuprous chloride solution suitable for electrowinning. The balance
of the copper was recovered in an oxidation leach with ferric chloride; iron leached from the concentrate was precipitated as
goethite, and the recirculating load of iron was oxidized with oxygen in a pressurized reactor at 140C. The only major
consumable was oxygen, and virtually all of the sulphur in the feed reported to the leach residue in elemental form. A small
proportion of the sulphur was oxidized to sulphate, which was precipitated as jarosite. Solvent extraction was introduced
into the flowsheet for the control of impurities such as zinc [23,24], and arsenic, antimony and bismuth remained largely in
the leach residue. However, concentrations above 50 mg/L As, Sb or Bi resulted in unacceptable copper [25]. Silver in the
concentrate leached and reported to the copper product [25,26], although efforts were made to recover it from solution by
amalgamation [26]. Gold normally reported to the leach residue, although it was shown that it could be recovered by
leaching with high chloride cupric chloride solution, with subsequent electrowinning of the gold [62]. The process operated
from 1976 until 1982, and was shut down for economic reasons (along with a number of other U.S. copper operations, it
might be added).

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201

CYMET Process (Cyprus Metallurgical Processes) [27,28,29,30,31,32]


This was one of the first copper hydrometallurgical processes treating a sulphide feed and proceeded as far as a 45 kg/h pilot
plant [27]. The process that was piloted was not the original one, (which was based on anodic dissolution and suffered from
pollution problems [27]). In the revised flowsheet [27,28,29,30,31,32], copper was leached by a mixed cupric/ferric chloride
solution in two stages at 90-95C. Copper was recovered by cuprous chloride crystallization followed by hydrogen reduction.
The lixiviant was regenerated by oxydrolysis of the crystallizer mother liquor, which also yielded jarosite and ferric hydroxide
for disposal. Reagent requirements were for hydrogen, oxygen and alkali (for jarosite precipitation). According to Flett [18],
the process did not appear to have been investigated for complex sulphides, and it would seem that any feed with substantial
lead and bismuth contents caused serious impurity problems in the cuprous chloride crystals. A separate recovery step
(amalgamation) was included for silver recovery, but any gold was lost with the residue.

MINEMET Process [33,34,35]


This process was developed by Minemet Recherche (Imetal) for the recovery of cathode copper from chalcopyrite
concentrates [33,34]. For copper concentrates, leaching was by two stages of cupric chloride/sodium chloride at close to the
boiling point. Copper was recovered by solvent extraction and conventional sulphate electrowinning; any cuprous copper
present in the leach liquor being oxidized by air sparging during solvent extraction. For more complex sulphide concentrates
[33], especially those containing lead, the lixiviant was ferric chloride/sodium chloride, and the copper was removed from
solution along with silver and bismuth by lead cementation. Lead was recovered by electrowinning.

DEXTEC Process [36,37,38,39,40,41]


In this Australian-developed process, chalcopyrite concentrate was converted to copper powder, ferric oxide and elemental
sulphur in an electrolytic diaphragm cell. The reaction was carried out at 90C in near-saturated sodium chloride solution
under air sparging. For lead concentrates, the temperature was 70C without air sparging [38]. Silver was leached and
reported with the copper powder, but gold reported to the leach residue, where it could be recovered by cyanidation or a
proprietary Dextec process [40]. Bismuth, lead and zinc were leached selectively from the concentrate, and arsenic reported
to the leach residue (presumably as a ferric arsenate-type material).
The process was tested on a number of concentrates at the pilot scale (100-L cells), and a commercial cell (8 m3) was reported
to be operating at Port Kembla [40], with the pilot lead version subsequently operating at a European smelter.

ELKEM Process [42,43]


This process was developed by Elkem in Norway, specifically to treat concentrate from a small Norwegian copper mine [18]. It
was piloted at 150 and 1500 kg/day on a number of concentrates, and comprised a two-stage ferric chloride leach,
crystallization of lead chloride and electrowinning of copper/silver powder. Zinc was recovered from the spent catholyte by
solvent extraction with TBP. As with the other processes, sulphur reported to the leach residue in elemental form, iron was
oxidized and precipitated as goethite, jarosite (from the small amount of sulphur oxidation) and ferric arsenate (along with
arsenic). Impurity control was by neutralization of a bleed stream. Behaviour of gold was not mentioned, but it is likely that it
remained in the leach residue.

USBM Process [44,45,46,47]


This was also a ferric chloride leach process at 104C, followed by copper recovery by electrowinning in a diaphragm cell. The
copper product also contained the silver leached from the concentrate. Gold remained in the leach residue along with
elemental sulphur. Iron was controlled (presumably also arsenic) by oxydrolysis and precipitation as hydrated oxide, which
also appeared to act as scavenger for all other impurities, except sulphate and lead [47]. The process, as described, was only
tested on chalcopyrite concentrates.

GREAT CENTRAL MINES Process [48,49,50,51]


This could be regarded as the being the last of the plethora of processes developed in the late seventies and early eighties,
and was developed by Bacon, Donaldson and Associates [48,49] using HBMS concentrates. The process [49] was basically a
two-stage cupric chloride leach, with elemental sulphur reporting to the residue, as with the other processes. Silver was
recovered from the leach liquor by a proprietary process, and copper was recovered by electrowinning. Iron was removed by
hydrolysis and precipitation of spent catholyte. Gold was not mentioned, but again presumably reported to the leach

Hydro-Sulfides 2004

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202

residue. A proprietary modification of the leach chemistry when dealing with complex concentrates dealt with impurities
[51].

More Recent Developments


The late 1980s and early 1990s saw a renewed interest in chloride-based processes, primarily for the treatment of complex
base metal sulphide feeds which were not amenable to smelting. Those of particular interest in addition to the advent of the
Intec Process mentioned earlier, were the CANMET FCL (Ferric Chloride Leach) Process [63], the Cuprex process of ICI and
Tecnicas Reunidas in Spain [64,65], otherwise known as CMEP or later, Cuzclor [78], and the CENIM-LNETI Process, developed
in Portugal, and which interestingly employs an oxidising leach in a strong ammonium chloride solution [66]. However, to
date, once again, none of these appears to have reached commercialisation.
The past few years has seen the continued development of the Intec Process, which uses a mixed bromine/chlorine oxidant,
BrCl2-, denoted Halex, and the advent of Outokumpus HydroCopper Process, which makes novel use of a chlor-alkali cell
[67,68,69,70]. Also being pursued at the present time is chloride-assisted sulphate pressure leaching, originally developed as
Norandas Antlerite Process in the 1970s [71], a variation and modification of which is the CESL Process [72,73,74], and most
recently the basis of the process proposed by Inco for Voiseys Bay [75].
There have also been processes reported for simply the upgrading of chalcopyrite concentrates, particularly from complex
sulphides, the most interesting of which in the context of the Jaguar Process was that described by Dyson and Scott using
acidic magnesium chloride solutions [76]. In these processes, the copper component of the concentrate largely remains
unaltered, while the iron (and zinc) components are selectively removed. Finally, one other process of interest was that
proposed by Adamson and Naden [77], wherein sulphide feeds were pressure leached in a magnesium chloride medium
under an oxygen atmosphere. The purpose of the magnesium chloride was to promote the formation of elemental sulphur,
as well as the retention of iron in the leach residue. However, as with all of the other processes mentioned above, it seems
not to have progressed beyond the developmental stage.

DISCUSSION OF PUBLISHED PROCESSES


Flett [78] recently published a review of the applications of chloride hydrometallurgy to complex sulphides, concluding that
whilst there were no current operating processes, the Intec Process seemed the most likely, if any, to achieve
commercialisation. Even more recently, Senanayake and Muir [5] have looked at the fundamentals of processing sulphide
feeds, demonstrating that it should, indeed, be possible, to develop a chloride-based process for sulphide feedstocks.
The chloride-based processes essentially solubilise base metals with either cupric and/or ferric ions, with copper recovery
generally being proposed by electrowinning from cuprous chloride, which is theoretically less energy intensive than
conventional sulphate electrowinning, but which has never really been made to operate satisfactorily. Iron was rejected as
goethite (which acts as an impurity scavenger), or as jarosite if appreciable sulphate formation occurred. Most of the
deleterious impurities (As, Sb, Bi) were claimed to remain in the leach residue along with elemental sulphur. Zinc, if present,
could be recovered by solvent extraction/electrowinning after copper recovery, and lead crystallized as chloride from the hot
leach liquor by cooling. Silver was usually leached and reported to the copper, if a separate recovery step was not introduced.
Gold and the PGMs generally remained in the leach residue, and were difficult to separate and recover.
The three major problem areas were therefore copper recovery, sulphur production and PGM recovery. As noted above,
direct electrolysis of cuprous chloride was never really successful, but this is easily overcome by employing solvent extraction,
transferring into sulphate and carrying out conventional electrowinning. The issues of sulphur formation and PGM recovery
were never satisfactorily addressed. Whilst appearing to be logically attractive, the formation of elemental sulphur directly in
the leach process always led to subsequent problems, whether they were environmental in nature or were related to the
subsequent separation and recovery of both the sulphur and the precious metals.
In developing the process outlined in this paper, the authors have taken cognizance of the particular difficulties associated
with elemental sulphur, as well as generating an intermediate concentrate from which it is relatively simple to isolate and
recover the precious metals. Effluent treatment has been minimized by recycling the lixiviant, leading to an environmentally
friendly flowsheet.

Magnesium Chloride as a Lixiviant Medium


It is apparent from the discussion presented in a previous paper [3] that high strength chloride brines, and in particular those
of magnesium chloride, have some unusual properties that can be advantageous in leaching circuits:

High H+ activity enables only a small amount of acid (HCl) to effect leaching of the value metals. This is because
the high hydrogen ion activity provides a very much higher driving force than for equivalent acid strength in more

Hydro-Sulfides 2004

Atmospheric Chloride Leaching of Base Metal Sulphides

203

dilute solutions, and in many instances, the amount of acid added need be only marginally higher than the
stoichiometric amount required for the base metals.

Low water activity coupled with the high solubility of base metal chloride salts, permits more effective control of
iron in the liquor through hydrolysis and re-precipitation. Essentially, there is insufficient capacity for the brine to
hold high levels of ferric iron in solution, since ferric has the lowest pH of hydrolysis amongst any of the ions
present, although the low iron levels in sulphide feeds relative to oxides still results in high iron extraction.

High magnesium concentration leading to low water activity and, through the common ion effect, minimises
the dissolution potential of magnesium.

High chloride concentration stabilises base metals in solution and leads to increased solubility. However, care
has to be taken that the chloride levels are not so high as to promote the formation of ferric anion complexes such
as FeCl4-, which are difficult to hydrolyse and precipitate from solution once formed.

Pyrohydrolysis the alkali and alkaline earth chlorides do not decompose during pyrohydrolysis, unlike
magnesium chloride. Therefore, using MgCl2 permits the recovery and recycle of both hydrochloric acid and caustic
(highly reactive) magnesia, the acid being recycled to the leaching step, and the MgO being used for neutralisation
and precipitation within the flowsheet downstream of the leach circuit.

Sulphur removal the high proton activity achievable with low acid concentration means that reductive leaching
can readily be attained, enabling the elimination of sulphur as hydrogen sulphide very easily and efficiently.

A further, and often overlooked, property of magnesium chloride is that it is a very effective desiccant. The result of
this is that the leach solids tend to be partially dehydrated by the leaching medium, and thus both settle and filter
somewhat more efficiently than might be anticipated from their behaviour in sulphate media.

Testwork and Results


Initial laboratory testing has been conducted in order to test the hypotheses discussed above with reference to sulphide
concentrates. Unfortunately, the timing of the conference (April, 2004) means that only limited data can be reported in this
paper, but they nevertheless confirm that the magnesium chloride system potentially offers a viable route to treating base
metal sulphides.
Based on work conducted with the laterite project [1,2,3], process conditions were chosen as 95oC, 4 hours leaching time, with
an initial lixiviant solution of 400 g/L total chloride, comprising 4N HCl, with the balance of the chloride from MgCl2. Feed
solids pulp density was 5%, this level being chosen to ensure that salt crystallization did not take place. The analysis of the
first two sulphide concentrates tested is shown below in Table 1, one of which was from the northern hemisphere, and the
other from the southern. Concentrate II contained appreciable values of precious metals, whereas Concentrate I had
negligible PGM content.

Table 1. Analysis of Sulphide Feeds Used in Testwork


Fee
d

I
II

Ni

Fe

Cu

Co

Zn

So

S2-

Au

Ag

Pt

Pd

Rh

pp
m

pp
m

pp
m

pp
m

pp
m

18.
7
18.
0

26.
6
29.
0

1.3
8
1.4
0

0.1
9
0.2
5

0.01

0.01
3

1.4
3

0.2
7

7.0

1.1
4

3.8
8

0.4
4

20.
1
23.
8

A series of leach tests was carried out for each concentrate, using a variety of oxidants, and the results obtained to date are
summarized below in

Table 2. The results clearly show that:

Hydro-Sulfides 2004

Bryn Harris

204

High base metal extraction can be achieved with several different oxidants, although this is undoubtedly a function
of the concentrate and the oxidant used. Test 11 gave the best results with concentrate I, using oxidant F.
Unfortunately, the results for concentrate II with oxidant F were not available for inclusion in the paper.

Sulphur elimination was generally >99.9% (as hydrogen sulphide). Negligible elemental sulphur was seen in the
leach residues, and very low levels of sulphate were observed in the final leach liquor (

Table 2). This is a highly effective and efficient means of eliminating sulphur from base metal sulphide
concentrates.

Iron extraction was high (predominantly as ferrous), but such is not a problem in this flowsheet compared to
laterites, since the Fe/base metals ratio is very much lower with sulphide feeds. High iron extractions still give
relatively low iron in solution compared to the base metal content, and this can very easily be removed in a chloride
medium by precipitation with recycled reactive magnesia with almost negligible co-precipitation of base metals.

As anticipated, no dissolution of gold, platinum or palladium was observed. In the test conducted where there were
significant precious metals values in the concentrate, minor rhodium was seen to dissolve, but silver dissolution was
high. Unless recovered separately, by, for example, cementation or with activated carbon, this silver will likely
report with the copper.

Tes
t
No

Co
n

T1

T2
T5
T8
T3
T11
T9
T17
T18
T16

II

Table 2. Results of Initial Base Metal Sulphide Leaching Experiments


Metal Extraction, %
Sulphur
Final
Remova
ORP
Oxidant
P
SO42Cu
Ni
Co
Fe Au Ag
Pt Rh
l
d
mg/L
mV
%
47.
79.
67.
80.
A
190
>99.9
10.5
4
4
7
4
30.
12.
61.
B
475
0.7
>99.9
18.4
1
3
0
81.
90.
77.
85.
C
440
>99.9
3.7
3
0
4
2
99.
89.
73.
88.
D
405
>99.9
3.8
9
5
0
6
58.
46.
30.
64.
>99.9
42.4
E
250
7
5
3
1
99.
94.
82.
95.
F
398
>99.9
23.1
9
9
7
0
99.
89.
99.
72.
G
365
>99.9
6.9
9
6
9
0
50.
53.
56.
71.
66.
13.
C
425
0
0
0
>99.9
*
0
4
7
4
7
7
78.
99.
87.
92.
G
260
*
*
*
*
*
>99.9
*
8
3
1
5
H
575
58.
58.
37.
83.
* *
*
*
*
>99.9
*

Hydro-Sulfides 2004

Atmospheric Chloride Leaching of Base Metal Sulphides

205

5
6
3
- results not available at the time of publication.

flowsheet
The flowsheet shown in Figure 2 is a generic version for using the atmospheric chloride leach process for treating sulphide
feeds. The main operations to be considered are:

Leaching of the sulphide feed at 90-100oC in recycled magnesium chloride/hydrochloric acid with the addition of an
oxidant to control the redox potential. This is crucial both to ensure that the sulphur is eliminated as hydrogen
sulphide gas, and that no precious metals dissolve. Direct oxidation to elemental sulphur occurs at a higher redox
potential, one that is often commensurate with effecting dissolution of the precious metals. This has always been a
drawback of previous chloride-based leaching flowsheets. The use of different oxidants over and above the normal
choices of oxygen and/or chlorine permits the manipulation of the redox potential and kinetics. However, this has
to be weighed against the introduction and possible build-up of alkali and alkaline earth metal cations in the circuit,
and furthermore, the impact of any such cations on the pyrohydrolysis reaction.

Treatment of the hydrogen sulphide gas in a Claus Reactor to recover elemental sulphur, suitable for sale or direct
storage, and recovery of the intrinsic energy contained in the sulphide as it is oxidised to elemental sulphur. The
recovered energy can be used elsewhere in the flowsheet, notably in the pre-evaporative step for pyrohydrolysis.
An option would be to use the gas as a precipitant within the flowsheet to form separate base metal sulphide
products for sale if desirable.

Solid/liquid of the leach slurry, optimally on a vacuum belt filter. The residue contains all of the PGMs, and can
either be sold as-is, upgraded in a second chloride leach with a higher oxidation potential, or be fed directly to a
PGM processing plant.

Solvent extraction of copper. In a chloride medium, this can be achieved with relatively high levels of iron and base
metals in solution. At a given pH, solvent extraction is more efficient than in the corresponding sulphate medium,
and in fact extraction can occur at a much lower pH due to the lower water activity and enhanced hydrogen ion
activity [79,80,81,82]. Stripping can be into sulphate followed by conventional electrowinning, since copper
recovery by electrolysis from a chloride medium is somewhat more difficult than it is from sulphate, and the
potential advantages of the single electron change are rarely realised.

Precipitation of impurities by lime and recycled magnesia (from the pyrohydrolysis step). Depending on the feed,
this will likely be a two or three-stage process. Initially, iron will be precipitated by magnesia experience with the
laterite flowsheet has shown that this can be very effective using magnesia in a magnesium chloride matrix, to give
a pure, easily settleable and readily filterable goethite product. Arsenic, if present, is easily removed as scorodite,
whereas antimony and bismuth can be precipitated as the respective oxychlorides as the pH is raised. Selenium and
tellurium may require separate treatment in a bleed stream by, for example, reductive precipitation.

Zinc, if present in commercially viable levels, can be recovered by a separate solvent extraction step, analogous to
copper. Such a step would likely be incorporated after iron removal. Otherwise, the laterite flowsheet has indicated
that zinc can be removed to low levels simply by pH adjustment with magnesia.

Although the test data obtained to date indicate virtually no sulphate formation, any that is formed can easily be
controlled by replacing some of the magnesia used for pH control with lime in order to precipitate gypsum. This
will also control minor lead impurities as well as barium, should it be present. Significant lead values can be
controlled by cooling crystallization of lead chloride from the leach liquor. Calcium in pyrohydrolysis is not a
problem, although if calcium chloride shows signs of building up too high, then it too can readily be treated in a
bleed stream.

Hydro-Sulfides 2004

Bryn Harris

206

Sulphide Feed

HCl from
Copper Circuit

O2

CLAUS
REACTOR
Energy

H2S

Oxidant

BASE METALS
ATMOSPHERIC LEACH

Elemental
Sulphur

Chloride Lixiviant

Precious Metals Concentrate


Upgrade, refine or sell

Loaded Organic
To Copper Circuit
COPPER SOLVENT
EXTRACTION
Stripped Organic
From Copper Circuit

Copper Raffinate

2-3 STAGE
PURIFICATION

(Lime)

NICKEL/COBALT
PRECIPITATION

MgO

To Disposal
or Recycle

MgO

MgCl2 Brine
18% HCl

Nickel/Cobalt
Hydroxide Product

PYROHYDROLYSIS

Energy

Figure 2. Conceptual Flowsheet for the Treatment of Sulphide Feeds


Recovery of nickel and cobalt. The flowsheet of Figure 2 indicates precipitation with recycled magnesia as a mixed

nickel/cobalt hydroxide, which is the currently preferred option for the laterite flowsheet. However, in a chloride
medium, separation of nickel and cobalt is relatively easily by solvent extraction with amines, phosphine oxides,
phosphate esters., etc offering the option of separate nickel and cobalt products, should such prove to be attractive.
The final step is pyrohydrolysis of a portion of the final magnesium chloride brine, consistent with the hydrochloric
acid and magnesia requirements of the flowsheet. Pyrohydrolysis is normally quite energy intensive, but in this
flowsheet, there is considerable energy available from the sulphur formation step, and this will significantly reduce
the energy requirements of pyrohydrolysis.

Hydro-Sulfides 2004

Atmospheric Chloride Leaching of Base Metal Sulphides

207

As can be seen, this flowsheet is not only extremely efficient, but it also extremely environmentally friendly. Elemental
sulphur is formed in a separate dedicated step, and it will likely be of sufficiently high purity such that it may be sold.
Otherwise, it can be melted and blocked, making it easily disposable. There will be a small amount of leach residue,
comprising mostly gangue minerals, which is a small volume for disposal. Should PGMs be present, then this will form a
concentrate suitable for sale, upgrading in a second chloride leach or direct feed to a PGM refinery. The point to note here is
that this residue can also be readily processed in a chloride medium even if the precious metals comprise mostly gold, and
therefore that no cyanidation step is required. There will also be intermediate precipitates, and although these will be of
relatively small volume, they will nevertheless require dedicated disposal areas.
The magnesium chloride process is able to handle most of the common impurities by suitable control of redox and/or pH.
The only possible problems normally encountered in sulphide feed concentrates are likely to be selenium and tellurium, and
these only if they attain their higher valence states.

conclusions
This paper has presented some initial results on the application of the Jaguar Nickel Atmospheric Chloride Leach Process to
sulphide feedstocks. The process, initially developed for laterite feeds, involves leaching of the sulphide in a mixed
magnesium chloride/hydrochloric acid lixiviant together with an appropriate oxidant. A number of oxidants have been
tested, and the choice revolves around ensuring that the redox potential is kept within a range to ensure that sulphur is
eliminated as hydrogen sulphide, and at the same time preventing any precious metals in the concentrate from being
solubilised.
It is considered that the formation of hydrogen sulphide, and its subsequent conversion to elemental sulphur, at the same
time liberating all of its intrinsic energy, is a major step forward in the processing of base metal sulphides. Eliminating the
sulphur in this manner avoids any risk of coating the base metal and PGM minerals with molten sulphur, and simultaneously
effects a very clean separation of sulphur from the solids. Treating the hydrogen sulphide in a Claus Reactor is very common
practice, generating both a clean sulphur product and liberating substantial quantities of energy for use elsewhere in the
flowsheet.
As an alternative, the hydrogen sulphide could be used to precipitate separate copper, nickel, cobalt and zinc sulphides,
should the marketing of these prove more attractive. This would depend on the location of the mine and associated
infrastructure to a large extent.
Coincidentally, adjusting the redox potential to promote the formation of hydrogen sulphide also maintains it at a level which
is not conducive to any precious metals leaching. Therefore, this process overcomes two of the major problems previously
encountered with chloride-based base metal sulphide leach processes, by eliminating the sulphur from the leach residue, and
leaving a precious-metals rich concentrate after the base metals have been leached out. The precious metals concentrate can
be sold as-is, treated directly in a PGM refinery, or upgraded in a second, more oxidizing leach step, again depending upon
the economics of the particular location.
Finally, the process is extremely environmentally friendly. A separate elemental sulphur product, minimal leach residue, and
low volume intermediate precipitates are produced. No effluent treatment is required, since the magnesium chloride lixiviant
is recycled within the process flowsheet. The authors believe that an approach based on this flowsheet offers appreciable
advantages over both conventional smelting and/or pressure oxidation processes for the treatment of base metal sulphide
feeds, both with and without precious metal values.

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