Hydrometallurgy, 27 ( 1991 ) 2 8 5 - 3 1 6

Elsevier Science Publishers B.V., A m s t e r d a m

285

Chloride hydrometallurgy*
Ren6 Winand
Universite Libre de Bruxelles CP 165, Department Metallurgy-ElectrochemisttT,
50 avenue F.D. Roosevelt, B-1050, Brussels, Belgium
(Received December 1, 1990; revised version accepted April 29, 1991 )

ABSTRACT
Winand, R., 1991. Chloride hydrometallurgy. Itydrometallurgy. 27: 285-316.
In hydrometallurgy, chloride solutions may be used instead of sulfate solutions. Due to complexation by chloride ions, most metals of interest in non-ferrous metallurgy are highly soluble in water.
Potential series are different from the standard ones. Electrochemical reactions are highly reversible.
The structure of metal deposits are worse for normal or intermediate metals but better for inert metals
in chloride than in sulfate solutions. Solutions are highly conductive. Leaching of sulfides usually
occurs more easily in chloride than in sulfate solutions. Regeneration of the leaching power can be
ach ieved by oxidation or by pyrohydrolysis. Solvent extraction is a very powerful tool for purification
of solutions.
A number of processes have been proposed in chloride hydrometallurgy. So far, with one exception,
only processes based on intermediate metallurgical products are still in operation. Recycling metallurgy and precious metals recovery will probably be developed next, followed later by complex sulfide
concentrates processing.

INTRODUCTION

In most hydrometallurgical processes, sulfuric acid is the main reactant and

sulfate solution chemistry is well known. However, other reactants can be
considered, as, for example, ammonia with or without sulfate or carbonate,
nitric acid, caustic soda and chlorides. Although the earliest use of chloride
ions in metallurgy seems to appear during the sixteenth century for amalgamation of silver, the next important process was the direct decomposition of
silver sulfide by cuprous chloride, developed in 1860 [ 1 ]. This can be considered as the start of the direct hydrometallurgy of sulfides. For almost a century, however, chloride hydrometallurgy was only applied in a few industrial
processes, mainly for nickel, cobalt and copper, and usually as a special part
of a more conventional metallurgical flowsheet.
*Based on a lecture given in the f r a m e of a professional s e m i n a r a n d short course entitled " F u n d a m e n t a l s a n d Practice of Aqueous Electrometallurgy", 20th A n n u a l Hydrometallurgical Meeting, Metallurgical Society of CIM, Montreal, Que. Canada, October 20-21, 1990.

0304-386X/91/$03.50

1991 Elsevier Science Publishers B.V. All rights reserved.

286

R, WINAND

The general philosophy of extractive metallurgy is to obtain commercial

grades of metals from ore material mined from the earth's crust. The final
metals are standardized and the general tendency is to increase the purity of
each of them, but ores are extremely diverse. The most c o m m o n way to go
from ore to metal is to concentrate the ore by a standard mineral dressing
operation, and to smelt the concentrate. Refining processes are then used to
obtain marketable grades of metals. The advantage is that, at smelting temperatures, the ore minerals lose their identity in a molten mass. Accordingly,
thermodynamics, mass transfer kinetics and phase separations are the main
factors controlling the process. Scientific knowledge and engineering experience lead to satisfactory reliability and predictability.
During the last twenty years, environmental pollution and energy shortages
have added two new constraints [2,3 ], especially for extractive metallurgy:
the tall stack has been identified as a visible source of pollution, and the metal
extraction industry has been put forward as a huge energy consumer.
Non-ferrous metallurgy is largely based on sulfide ores, because they are
relatively easy to concentrate. In smelting processes, sulfur supplies part of
the fuel energy. Of course, SO2 leakage into the atmosphere is prohibited, so
that conflicting situations appear between energy and environmental problems. Hydrometallurgy, on the other hand, appears at first sight as nonpolluting, especially if sulfur is recovered in the elemental state, but energy
consumption is high. Additionally, the world economic crisis and unsolved
political problems between industrialized and developing countries has led to
the need to investigate the possibility of processing complex sulfide ores,
eventually using new metallurgical routes. It is in this changing pattern that
chloride hydrometallurgy presents new opportunities. In this paper, literature
on the subject will be reviewed and discussed, beginning with the fundamental principles.
FUNDAMENTAL PRINCIPLES

Solubility
According to tables giving physical constants of inorganic compounds [ 4 ],
most chlorides of interest in non-ferrous metallurgy are highly soluble in water.
Two of them deserve further investigation: PbC12 and CuC1.
The saturated solubility of PbC12 in water is 0.99 g/100 g at 20 C and 3.34
g/100 g at 100 C. This solubility can be increased markedly by complexation
with excess chloride ions coming from hydrochloric acid or from alkaline or
alkaline earth chlorides. When HC1 is added to PbC12-H20 solutions, PbC12
solubility first decreases due to the so-called c o m m o n ion effect, but increases
after passing through a m i n i m u m whose value increases with temperature.
Fig. I shows that this kind of behavior is also observed with NaC1 and CaC12

CHLORIDE

287

H Y D R O M E T A L L U R G Y

i]

10

n i ]

I a I I

see [5]

R e f e r e n c e s :

o =
=
v =
=
[]=
=

Kendall
Muir
,
v. E n d e
Kendall
Muir,
Peters,

HCI

,
,

HCI
NaCI
NoCI

HCI

<>

C a C I

E
E

"g
o

3
o

~cF

....

1 0-1
Total

, ,,

I~0

Chloride

. . . . . . . .

1~)1

(mol/L)

Fig. 1. Overview of PbCI2 solubilities at 25 C in a number of binary aqueous chloride solutions

as a function of total chloride concentrations (from [5] ).

[ 5 ]. Some results are also available for solutions including C u C I 2 [ 6 ]. A thermodynamic approach to PbC12 solubility in more complex solutions gives only
approximate values [5,6 ]. Solubility limits are very important in this case
because, on the one hand, when leaching lead-bearing complex sulfide concentrates, they will impose the maximum process throughput and pulp density; on the other hand, the minimum solubility will allow precipitation of
pure PbC12 crystals; leaving in solution, however, a certain amount of PbC12,
that must be considered carefully for possible impact on downstream processes such as solvent extraction of other metals.
The solubility of CuC1 in cold water is about 0.006 g / 1 0 0 g water, but in
concentrated chloride solutions very high solubilities can be achieved. Again,
solubility limits are very dependent not only on the chloride ion concentration, but also on the type of chloride salt added to the solution [ 7 ]. Figure 2
shows solubility limits in the CuC1-NaC1-H20 system at various temperatures: on one side, CuC1 is precipitated and on the other NaC1. Figure 3 shows
what occurs in more complex systems at 30 C. As can be seen, all chlorides

288

R. WINAND

500

AO0
CuCI
solid
phase

!7 300

/ /

i:-

ip
NOl
solid
hose

!! 2oo
8

c] 100

I00

203

L00
50O
300
NoCI concentration,g / I

Fig. 2. Solubility data for the CuCI-NaCI-H20 system at various temperatures [8] Free Acid:
8-11 g/l HCI, [CulI] <2 g/l. O = 5 C ; = 2 2 C ; A = 5 0 C ; = 7 5 C (from [7]).
5r , ,

P i /qY

,' / /

~Ill

CuCt

,' ,,

~id

,' ,,,"/ l /

"J/Ill

z~

8
1
.jsJ~J~

/fJ~'~ ~)

NclCt

solid

13

10

11

C[iNaCI+HCI +~CI2+ZnCI2] concentrotion, mot /kg ofv~ter

Fig. 3. Cu(1)
lines = Zn (II)
tion: O =0;
M; 5= >--I M;

solubility in the CuCI-FeCI2-ZnC12-NaC1-HC1 system at 30C. Continuous

so-concentration; dashed lines = Fe (If) so-concentration; Zn (lI) concentra=0.64 M; =0.5 M; Fe(II) concentration: 1=0; 2=0.25 M; 3=0.5 M; 4=0.75
(from [7]).

are certainly not equivalent, especially FeC12 and ZnCI2: at constant NaC1
and HC1 concentration, FeC12 additions increase Cu (I) solubility, whereas
ZnCI2 additions decrease Cu (I) solubility. This is due to the fact that Fe (II)

289

CHLORIDEHYDROMETALLURGY

b
CuCt
solid

,"

/~
~/

' 1
L

,' / /

g
1 2 3 ~ s 6 7 8 ~1&11
(11- NaCI + HCI + FCI2ZnCI 2] concenfrQtion,
tool / kg of wafer

Fig. 4. Cu (I) solubilityin the CuCI-FeC12-ZnClz-NaCI-HC1-H20system. A = 90 C; = 30 C;

[NaCI+HCI] =4.9+0.2 M; [ZnC12]=0.5+0.03 M; 0_< [FeC12]-< 1.7 (from [7].
b

CuCt2 2H20
~Tid
pha~

_1_ M
~5
E4

3_ _..

"~...

\
\\\

7=
g
0

,,
i,

\\\
5

CV[NaCI. HQ] conc~ntrotion, mol /kg of w~tcr

Fig. 5. Solubility data in complex C u ( I I ) chloride solutions at 50 C. = CuCI2-NaCI-HCIH20 system; A =CuC12-ZnC12-NaC1-HC1-H20 system; 1 = [ Z n ( I I ) ] =0.5 M; 2 = [ Z n ( l I ) ]
= 1.5 M; =CuCI2-FeC13-NaCI-HC1-H20 system; 3 = [ F e ( I I I ) ] =0.5 M; 4 = [Fe(III) ] = 1
M; 5 = [ F e ( I l I ) ] = 1.5 M (from [7] ).

forms only weak complexes in chloride solutions, so that FeC12 acts as a C1ligand donor to C u ( I ) . In contrast to that, Z n ( I I ) ions are strongly complexed in chloride solutions, and ZnCI2 is in fact a C1- ligand acceptor to
Cu (I) complexes. This also has an influence on NaC1 solubility: in a system
free o f ZnCI2 but in the presence o f variable a m o u n t s o f F e ( I I ) , the NaCI
solubility is the same as in the CuC1-NaC1-HC1-H20 system, free from FeC12.
In contrast, ZnC12 additions shift the b o u n d a r y line in the direction of high

:).90

I0

R. W I N A N D

c~

c~ 8
~:
~5
L:

I
I20

CMC[212H20
sotid
phase

I
0

;
20

J
l.O

/
. /

[
r
r
50
80
100
femperatur~ C

120

Fig. 6. CuC12solubilityin water as function of temperature (data from [9 ] ).

chloride content. Of course, CuC1 solubility is strongly influenced by temperature, as shown in Fig. 4.
In oxidized copper chloride solutions, Fig. 5 shows that CuC12 solubility is
greatest when water is free from other ions. When NaC1 is added, Cu (II)
solubility decreases slightly down to the invariant point, M, where
CuC12.2H20 and NaC1 solid phases co-exist in equilibrium with a solution
containing 4 M NaC1 and 0.1 M HC1. At high total concentration of NaC1 and
HCI, NaC1 saturation results in a line, MN. Adding FeC13 or ZnC12 to this
system results in a decrease in CuCI2 solubility, stronger for FeC13 than for
ZnC12 additions. Moreover, adding ZnC12 to the solutions corresponding to
the invariant point M in Fig. 5 results in CuC12-2H20 precipitation, whereas
FeC13 additions precipitate NaC1. Again, temperature has a strong influence
on CuCl2 solubility, as shown in Fig. 6.
This discussion shows that solubility limits must be very carefully studied
for each specific system, taking into account also the oxidation level of the
solution, in order to avoid unwanted precipitation at any point in the process.

Complexation
Complexation is very important. On the basis of published stability constants [ 10 ] and of other available data, Berger and Winand proposed the following classification of the strength of C1- acceptors [ 7 ]: (CI- acceptors)
AgC1 > CuC1 > PbC12 > ZnC12 > CuCI2 > FeC13 > FeC12 > NiC12 > HC1, NaC1,
KC1 (C1- donors).
The species in solution change mainly as a function of chloride ion concen-

291

CHLORIDE HYDROMETALLURGY
TABLE 1
Complex chloride ions
Low C l - concentration

High C l - concentration Referencc

Cu(ll)

Cu 2+

Cu(I)

CuC17

CuCI +

CuCI2

Fe(III)

Fe 3+

Fe(ll)
Zn

Fe z+
Zn 2+

Pb

PbCI +
Ni 2+
Co 2+
Mn 2+
Cd 2+

PbC12

Ni
Co
Mn
Cd
Sb

SbCI 2+

SbCIJ-

SbC13

Bi

BiCI 2+

BiCI2~

BiCI3

ZnCI +

As
Ag

AgCIS-

Hg

HgCI +

CuCI3

CuCI 2

CuCI43FeCI 2+

FeCI~-

14

ZnCI2

ZnCI~-

FeCI +
ZnCI4-

14
15

CdCI2

CdCly

PbCI4
NiCI +
CoCI +
MnC1 +
CdCI4

16
11
14
14
15

SbCI4

SbCI 2

SbCI63

16

BiCI;

BiCI]

BiCI63

16

AgCI]

16

HgCI4

15

AsCI3
HgCI2

HgCly

24

20

1.6

1.2

>

0.8

u...I

11,12
) 13

PbCI3-

CdCI +

CuCI42
(orCu2CI4

0.4

-0.4

-0.8

- 1 .2
-2

I0

12

14

16

pH
Fig, 7. Potential

pH diagram for the copper-water system at 25C (from [ 17 ] ).

292

R. WINAND

tration. For cupric chloride, Cu 2+, CuCI + or CuCI2 are observed, the latter
being predominant at high chloride ion concentrations [ 11 ]. This distribution is somewhat controversial: others suppose also the presence of CuC1;and CuC12- [ 12]. For cuprous chloride, the increased solubility when chloride ions are added is explained by the successive formation of CuC17,
CuCI~- and finally CuC143-. Fontana, Van Muylder and Winand [ 13 ] determined, by spectrophotometry on highly concentrated CuC1-NaC1-HC1-H20
solutions, the fields of predominance of the various species observed, but
probably with Cu2C142- instead of CuC13-.
Table 1 summarizes the types of complex ions observed for various metals
in increasing chloride ion concentrations. The type of species in solution is
especially important for solvent extraction and also for electrode reactions
kinetic, and, of course, they strongly influence potential-pH diagrams.

Potential-pH diagrams
Figure 7 shows the copper-water potential-pH diagram, drawn without
taking into account any anion [ 17 ]. Figure 8 holds for the copper-sulfurwater system, including sulfides. If sulfides are neglected, the left part of Fig.
7 remains unchanged, but instead of hydroxide precipitation, a basic sulfate
2.0

;'
',

-z,

i-6

;' i

-6

I-4

1.6

1.2

, "--- ~

cUS,oq

>

- ~'~.~

03

031

"~.,

'

~--~--~.~.~

.o

-0.8

C)

CuO

o8 co-:
0.4

~.~

.........

HCuO"

--k

Cul
-1,2

I
I

-1.6

-2.0

- 2

H2S (rJq]

I
0

I
2

1
4

,
6

S--

H S -

I
8

lJO

. I \\\\\1
2

14

16

pH

Fig. 8. Potential - pH diagram for the copper-sulfur-water system at 25 C, for unit activities
of the sulfur ligands (from [ 17 ] ).

293

CHLORIDE HYDROMETALLURGY
2.0
1.6
t.2
0.8
0.4
>
u3 0
--0.4
-0.8
.-1.2
-1.6
-2/]
-2

I0

12

14

I(3

pH

Fig. 9. Potential-pH diagram for the c o p p e r - c h l o r i n e - w a t e r system at 25 ~C for unit activities

of the chlorine ligands ( f r o m [ 17 ] ).

is precipitated. Figure 9 shows the system copper-chlorine-water. Due to

strong complexation, copper metal can be obtained only at less positive potentials versus SHE, and basic cupric chloride precipitation is observed at a
more acid pH than in sulfate solutions. These diagrams are strongly influenced by chloride ion activities as shown in Figs. 10 and 11 [ 16].

Selectivity of metal deposition

Of course, important changes can be expected in the potential series in
chloride solution versus the standard series. For instance, Albert and Winand
[ 18 ] determined the molar equilibrium potentials of a number of systems in
a 4 M NaC1-0.5 M HCI solution. Figure 12 shows the results compared to
standard potentials [ 18,19 ].
This is important in assessment of the selectivity of a metal deposition process, provided that the electrochemical cathode reduction is sufficiently reversible. Without going into detailed mechanism analysis, it can be said that
cathode reactions are usually more reversible in chloride than in sulfate solutions. For copper, a further advantage comes from the fact that reduction
of Cu (I) species is possible in chloride solutions, with the need for only one
electron instead of two as in sulfate solutions. The exchange current density
for this reaction: Cu (I) + e ~ Cu, measured by a double impulse method was

294

R. WINAND

C"Z*

400'

C~Cl+

. . . . . . . . O. . . . .

C~Cl2

0 z_ ~ - -

. . . .

...CL . . . .

.LI:3-

200

I
PbCL +

PbCI2

IPbCI~ I

PbCI~-

-200

>

...... Im"

"~"

m ... . .~. . ... . ~.

Ld
-400

- BOO,

t
-1000
0.5

,t
0

CtcI-

IO

,,,
0.5

1
1.0

log aclFig. 10. E-log acl relationships for the Cu-Pb-Zn-Ni-CI--H20 system at 25C. Solid lines
are calculated from stability constants of chlorocomplexes at zero ionic strength; z~ =values
measured in NaC1 solutions; [] =values measured in CaC12 solutions, =values measured in
MgCI2 solutions; = values measured in CaC12 solutions (from [ 16] ).
a b o u t 2400 A / m 2 at 25 C in 0.5 M HC1; 4 M NaCI; 0.5 M CuCI solution
[ 20 ]. In sulfate solutions, e x c h a n g e c u r r e n t densities for the global r e a c t i o n
C u 2 + + 2e--,Cu are in the range o f 20 to 200 A i m 2. C a t h o d e r e d u c t i o n is ac-

295

CHLORIDE HYDROMETALLURGY

FeCI2]FeCI)

800.

FeCl 2

Cl
60C

t"
400
o

Ld

D
13

..

a t~*"

200

o
1

acl-

L
- o.5

".

o.5

log

10
I

1.o

acc

Fig. 11. E -log acl relationships for the Fe ( I I I ) / F e ( I I ) - C u ( I I ) / C u ( I )-Ag (I) Cu ( I ) - C 1 - - H 2 0

system at 25C. Solid lines are calculated from stability constants of chlorocomplexes at zero
ionic strength; A = are values measured in NaC1 systems: O--values measured in MgC12 system; D, i = v a l u e s measured in CaCI2 system (from [ 16] ).

cordingly mainly controlled by diffusion of a Cu (I) species in solution. Similarly, anodic oxidation of C u ( I ) to C u ( I I ) was also found to be highly reversible (Jo ~ 800 A / m 2) and diffusion was controlled by the same cuprous
species as in the cathode reduction. According to Moreau [ 21 ] and Hibbert
et al. [22 ] this species could be CuCI~-. Both papers suspect the presence of
an adsorbed intermediate c o m p o u n d at the surface of the electrode, probably
CuC1. For other bivalent metals, cathode reduction occurs in two single electron transfer steps, and some adsorbed species are also suspected to act as an
intermediate. For instance, for nickel [23]:

296

R. W I N A N D

NiCI + + e--, NiClads

NiClads + e--* Ni + CIAccording to Hurlen [24 ], the N i / N i (I) step occurs directly at kink sites
and is chloride-independent, whereas the Ni ( I ) / N i (II) step is independent
of kink sites and involves parallel reaction paths with chloride or nonchloride ions. Jousselin and Wiart [25] also assume the presence of an adsorbed Ni (I) species on the surface of the electrode. For cobalt, Scoyer and
Winand [26] showed that overpotentials were lower in chloride than in sulfate solutions.
Selectivity is also influenced by the metallographic structure of cathode deposits: dense, coherent and smooth deposits are better than isolated crystals
(whiskers), dendrites or nodules. Taking into account Fischer's classification
of deposits, as shown in Winand's diagram [27-29] (Fig. 13), and also the
fact that chloride ions are activating agents versus sulfate ions, in the absence
of any other additive, if a metal normally gives FT types of deposits in sulfate
solutions, it would give worse BR or FI deposits in chloride solutions. On the
other hand, ifa metal normally gives U D deposits in sulfate solutions, it would

R e v e r s i b l e p o t e n t i a l s in
a 4 M N a C l - 0.5 M HCI
s o l u t i o n at 30 C

Standard p o t e n t i a l s
E (mY)

lsoo --- A u 3 + / A u
1400

C12/CI- ---- 1242

A u ( l l I ) / A u . . . . 1012

C12/C1-

l:~o --

1200
1OO0
800

Fe(lll)/Fe(II) . . . . 681
Cu(lI) / Cu(I)

....

584

600

400
A g ( 1 ) / A g . . . . 335

~1 -- Cu+/Cu
3az --- Cu2+/Cu
32o .............. BiO++2H+ 3 e - - B i + H20

2O0
Bi(III)/Bi . . . . 91
Cu(1) / Cu . . . . 84
Ni(II) / Ni . . . . . 58

1~

---

Cu2+/Cu+
SHE

-200

-2~
.400

Fe(II) / Fe . . . . 458

--- N i 2 + / N i

_, ~ .... F e 2 + / F e

-600

-800

Fig. 12. M o l a r e q u i l i b r i u m p o t e n t i s l E M m e a s u r e d at 30 C in a 4 M N a C 1 - 0 . 5 M HCI s o l u t i o n

c o m p a r e d to s t a n d a r d p o t e n t i a l s at 25 C (from [ 18,19 ] ).

CHLORIDEHYDROMETALLURGY

297

J/CMeZ or J/Jdl
or no

FI

//

FI : f i e l d oriented isolated crystals;

BR: basis reprodu tc ion;

FT : field oriented texture type;
UD : unoriented dispersion type

In abcissa : mass transfer characterized by J/CMeZ+ or J/Jdl

J
: current density;
CMeZ+ : bulk concentration of metal ion to be discharged;
Jdl
: diffusion limiting current density.
In ordinate : inhibition intensity.
2D : b i d i m e n s i o n a l nucleation;
3D : tridimensional nucleation.

Fig. 13. Fields of stability of the main types of deposits (from [27-29 ] ).
give better FT deposits in chloride solutions. Similarly, metals of the type
giving FT in sulphates and bad BR-FI in chlorides would tend to be less sensitive to additives in chloride than in sulfate solutions.
This is in fact the case. For copper, it is well known that good FT deposits
are obtained in sulfate solution with only small amounts of additives (in electrowinning, 50 m g / l C1- and 4 m g / l gelatin; in electrorefining, some 1-2
mg/l thiourea is added as well as these ). However, in chloride solutions [20],
BR and FI structures are observed (Fig. 14), and it is necessary to add up to
300 m g / l o f gelatin to obtain a satisfactory F T - U D structure (Fig. 15 ). For
cobalt, deposits are usually nodular in acid sulfate solutions. In chloride solutions, deposits are much better, even without any additive [26]. Nickel
should give similar results. For zinc from chloride solutions, sponge-like

298

R. WINAND

Fig. 14. Optical micrograph of a copper deposit obtained in pure chloride solution without organic addition after 24 h, 250 A / m 2 30C. There is a thin layer of BR deposit, the rest is FI, in
places twinned (magnification 77) (from [20] ).

deposits were obtained without additives [30]; whereas 30 mg/1 glue was
fbund unsatisfactory to avoid nodular deposits, 15 mg/l tetrabutylammoniumchloride smoothed the surface and eliminated dendrites [31 ]. Lead also
gives dendritic non-adherent deposits in pure chloride solutions, and it was
necessary to add 2 g/l glue and 0.1 g/1 fl-naphthol to obtain a compact deposit
at 50 A / m 2 [ 32 ], while 0.4 g/l glue was not completely satisfactory at 100 A/
rn 2 [33].

CHLORIDE HYDROMETALLURGY

299

Fig. 15. Optical micrograph of a copper deposit obtained in pure chloride solution with 300
mg/l gelatine. Conditions: 24 h, 200 A/m 2, 30C. The structure is FT-UD, and the surface is
smooth (from [20] ).

Electrical conductivity
Ohmic voltage drop in the electrolyte is an important factor in specific
energy c o n s u m p t i o n for electrolysis. Chloride solutions usually have higher
conductivities than sulfate solutions. For instance, T h o m a s and Fray [34]
measured conductivities in the range o f 0.05-0.13 o h m - ~ c m - 1 at 25 C for
Z n C I 2 - N H 4 C I - H 2 0 systems. Berger and Winand obtained values between 0.2
and 0.4 o h m - ~ c m - ~ for the system C u C 1 - F e C I 2 - N a C 1 - H C 1 - H 2 0 at temperatures ranging from 31 to 52 C [ 7 ]. For comparison in conventional copper
electro-refining, the highly conductive 40 g/l Cu 2+, 150 g/1 H2SO4 solution
gives about 0.5 o h m -1 cm -~ at 60C.

Leaching thermodynamics and kinetics

Copper
Leaching of sulfides was rapidly recognized to occur by electrochemical
processes. Looking at the potential - p H diagram for the system C u - F e - S H 2 0 at 2 5 C with chloride ion at 1 M activity [2], in acid solutions, the
following possibilities m a y be envisaged depending on the oxidizing potential
o f the solution.
In strongly oxidizing solution, some sulfate formation is possible:
CuFeS2 + 8 H 2 0 +

1 6 o x ~ C u 2+ + F e z+ + 2 S O ] - + 16H + + 16ox-

in competition with elemental sulfur formation:

CuFeS2 + 4ox ~ Cu 2+ + Fe 2 + + 2S o + 4 o x In less oxidizing solutions CuS precipitation becomes possible:
CuFeS2 + 2ox--.CuS + Fe 2+ + S+ 2ox -

300

R. W1NAND

In strong acid solutions, H2S could be evolved while dissolving copper a n d /

or iron.
Experimental studies [ 35,36 ] have shown that, when the oxidizing couple
is Fe ( I l l ) / F e (II), the anodic reaction is:
CuFeS2 --, Cu (II) + Fe (II) + 2S + 4e
while the following cathodic reactions occur:
Fe 3+ + e ~ F e 2+
FeC12 + + e ~ Fe 2+ + C1FeCI~ + e ~ F e 2+ + 2C1FeC13 aq + e--'Fe2+ + 3C1Reactions are controlled by surface phenomena, with a rate exhibiting onehalf power dependence on total ferric iron concentration. The rate of dissolution also increases with chloride ion concentration up to 1 M, but becomes
independent from this parameter at higher chloride concentrations. The rate
of dissolution was found to be independent of hydrochloric acid, ferrous chloride and magnesium chloride concentrations. However, cupric chloride substantially increased the speed of dissolution, while small amounts of sulfate
ions reduced this speed. For large amounts of sulfate ions, the system behaves
like the slower ferric sulfate leaching medium. Figure 16 illustrates the mechanism for the dissolution of chalcopyrite with ferric chloride [35 ].
When the oxidizing couple is C u ( I I ) / C u ( I ) , MacDonald et al. [37] have
shown that the main reaction is:
CuFeS2+3Cu(II)

NaC1
H20'4Cu(I)+Fe(II)+2S

However, the reaction may not go to completion because this would result
not in the above mentioned reverse reaction, but in the reduction of elemental sulfur according to:
2Cu(I) + S - , C u S + C u ( I I )
High chloride concentration, high temperature, low pH and short leaching
times were found favorable to a high C u ( I ) / C u ( I I ) ratio. If almost Cu(II)free solutions must be made, a two-stage leach (or a reduction with copper
scrap) is needed.
If stronger oxidizing conditions than obtained by the Fe ( I I I ) / F e (II) system are achieved, iron can be directly precipitated [ 38 ]. This is the case when
leaching at 110 C, 2010 kPa 02 and 2 M HCI:
CuFeS2 + 2HC1 + 02 ~ CuC12 + FeOOH + H20 + 2S

CHLORIDE HYDROMETALLURGY

301

Anodic Site:
_....

CuFeS z ~
Cu+Z+ Fe+2+ 2S + 4,="

/
Cathodic Site:

C
Elemental
Sulfur
(Porous)

\.

FeCl~ -n) + eFe+z +

e-

- . .

Solution

_.__- F'eCl(n~'n)

nCl-

Vg 2

nCl-

Fig, 16. Mechanismfor the dissolution of chalcopyritewith ferricchloride (from [ 35 ] ).

and:
CuFeS2 + HC1 + 02 ~ CuC1 + FeOOH + 2S
The following drawbacks must be considered: a small part of sulfur is oxidized to SO~- ; CuFe204 precipitates if the pH is allowed to become higher
than 2.2, and CuC1 precipitates if the initial acidity is higher than 3 M.
Reduction of chalcopyrite by Cu (I) to chalcocite Cu2S or bornite CusFeS4
can be obtained according to the following reaction, iron entering the solution
as:

CuFeS2 + 4 C u ( I ) - , 2 C u 2 S + Fe (II) + Cu(II)

The reaction is rapid on fresh surfaces, but slows markedly as a film of
chalcocite (or bornite) is formed. It has been shown [39] that, if the reduction occurs in presence of copper metal, the reaction goes rapidly to completion and gives a material which is more readily leached by oxidizing agents
than is chalcopyrite. The probable net reaction is:

302

R.WINAND

CuFeS2 + Cu + 2Cu (I) --, 2Cu2 S + Fe (II)

Another "activation" m e t h o d consists in heating chalcopyrite with elemental sulfur at 475 C in order to obtain simple sulfides:
CuFeS2 + S ~ C u S + FeS2
It was, however, shown [40 ] that rapid extraction of copper was obtained
with a simultaneous high dissolution of iron.
Electrochemical studies [ 41-43 ] dealing with anodic dissolution of copper
sulfides Cu2S (chalcocite) and Cu9S8 (digenite) have shown that the first
stage of the reaction is a preferential dissolution of copper, resulting in a comp o u n d of approximate composition CuS, but with a decreasing C u / S ratio
with increasing temperature of treatment. The second state of reaction is the
decomposition of this material to cupric ion and elemental sulfur (see also
[ 44 ] ). This can result in an active-passive behavior. The rate of the dissolution process is accelerated by the formation of a CuC1s complex at high chloride concentrations. At low hydrochloric acid concentrations, electrochemical oxidation to sulfate is predominant. In the solution, at low anodic
potentials, C u ( I ) is the only species observed. At intermediate potentials
C u ( I ) and C u ( I I ) are formed, while at higher potentials C u ( I I ) is the main
product. At potentials above 0.55 V/SHE, sulfur is detected, but it does not
seem to be oxidized to soluble species provided enough chloride ions are
available.
Nickel
Looking at the potential-pH diagram for the N i - S - H 2 0 system [ 2 ] at 25 C,
the following reactions can be considered for nickel recovery from sulfide ores.
Alkaline oxidation with a m m o n i a is the well-known basis of the successful
Sherritt-Gordon process.
NiS + 5 H20 q- 8OX--*NiO + SO 2- + 10 H + + 8oxN i O + 2 NH + +4NH3--*Ni(NH3)62+ +H20
Acid oxidation according to:
NiS + 2ox ~ Ni 2+ + So + 2oxcertainly occurs during leaching of complex sulfide ores.
Acid decomposition through:
N i S + 2 H + - + N i 2+ + H 2 S
Ni3S 2 + 6H+-~3Ni 2+ + 2 H z S + H 2
is used in the Falconbridge matte leach process.
Finally, the reduction:

CHLORIDE HYDROMETALLURGY

303

Ni3S2 + 4 H + + 4R-~3Ni+ 2HaS + R +

is unlikely to continue after the first traces of nickel are formed, because of
too low a hydrogen overvoltage.
Ghali et al. [45-47 ] showed that, while leaching Ni3S2 with FeC13, an intermediate species fiNiS is formed. This species strongly influences the rate
of dissolution. It is, however, possible to transform most of the sulfide sulfur
into elemental sulfur, but studies devoted to anodic dissolution of fiNiS show
that satisfactory rates are only observed at potentials high enough to produce
HSO4 as well.
Zinc
On the basis of the potential-pH diagram for the system Z n - S - H 2 0 [ 2 ],
the following reactions can be expected to occur. Acid oxidation according to:

ZnS + 2ox--, Zn 2+ + SO+ 2oxZnS + 4 H 2 0 + 8ox--. Zn 2+ + SO 2- + 8H + + 8oxintegrates well with conventional roast-leach-electrowin-sulfate circuits, and
is used as a sulfuric acid-oxygen pressure leach at Cominco. In fact, the second reaction occurs only to a minor extent, and elemental sulfur is recovered.
Acid decomposition:
Z n S + 2 H + - + Z n 2+ + H 2 0
should occur under the same conditions as in the Falconbridge matte leach
process.
Reductive decomposition:
ZnS+2H + +2R-+Zn+HeS+2R +
Z n S + 2 R o Z n + S 2- + 2 R +
is very unlikely to occur because of the impurities that would reduce the hydrogen overvoltage on zinc.
Ferric chloride leaching has been studied in three different laboratories [ 4850 ] with very similar results. Elemental sulfur is formed at the surface of ZnS,
and the reaction kinetics follow the Crank, Ginstling and Brounstein law for
diffusion control through a layer of solid reaction product. Topochemical reaction occurs at the beginning of the process, and seems to be electrochemical, with eventually some adsorption. Only 5-15% of the sulfur is oxidized to
sulfate. Ferrous chloride accumulation slows down the reaction, but ZnC12
(or PbC12) has almost no influence. CuC12 substantially increases the rate of
dissolution. Too high an HC1 concentration results in H2S evolution.
Majima et al. [51 ] studied the non-oxidative leaching of sphalerite (ZnS)
by HC1, according to:

304

R.W[NAND

Z n S + 2 H + - + Z n 2+ +H2S
Kinetics are controlled by a chemical reaction at the surface o f sphalerite. The
dissolution rate is first order with respect to the H + activity in solution. The
presence of iron and mainly NaC1 additions greatly increase the speed of
reaction.

Lead
The P b - S - H 2 0 potential-pH diagram [ 2 ], includes PbS boundaries at 1 M
C1- and at 1 M H S O 4 . Indeed, the strong interactions between Pb z + and
SO42- or C1- must not be neglected.
Acid oxidation:
PbS + 2ox--, Pb 2+ + So + 2 o x is well known in perchloric, nitric, sulfamate and acetic acids, while:
P b S + 4 H 2 0 + 8ox-+PbSO4 + 8 H + + 8oxoccurs in a m m o n i u m sulfate leaching.
Acid decomposition:
PbS+ 2H+--+Pb 2+ + H z S
PbS + 2HCI-~ PbCI2 + H2 S
PbS + H 2 SO4 -+ PbSO4 + H2 S
is also possible.
Reductive decomposition:
PbS+2H + +2R--,Pb+H2S+2R +
P b S + 2R__+pb0+2R + + S 2gives a spongy metal including the same noble impurities as in pyrometallurgical lead bullion.
Electrochemical lead sulfide dissolution has been studied in HCl, and passivation was sometimes observed due to crystalline sulfur, lead chloride and
eventually lead sulfate [52,53]. However, Awakura et al. [54] studied the
non-oxidative dissolution of galena in HC1 according to:
P b S + 2H + --+Pb 2+ + H 2 S
and they found that the dissolution rate is first order with respect to hydrochloric acid activity, the kinetics being controlled by a chemical reaction at
the surface of galena. NaCl greatly enhances the speed o f reaction, either because the H + activity is increased or because of lead complexation. Anyway,
Majima et al. [ 51 ] showed that lead and zinc sulfides react in the same way,

CHLORIDEHYDROMETALLURGY

305

but that PbS dissolves faster than ZnS, making an eventual selective dissolution process feasible.
Iron
According to the potential-pH diagram for the F e - S - H 2 0 system [ 2 ], the
following reactions must be considered.
In acid oxidation:

FeS, + ( 4 x + 3 ) H 2 0 + 15ox--,Fe (OH)3 + 2SO 2- + ( 8 x + 3 )H + + 15oxFeS,_ + 2ox--, Fe 2+ + xS + 2oxPyrite (FeS2) reacts rather reluctantly, because it becomes protected either
by Fe (OH)3 or by So layers. This is not the case in acid decomposition:
FeS~ + 2H+ ~ F e 2+ -k-H2 Sq- ( x - 1 )S O

nor in reduction:
FeSx + 2xH + + 2 ( x - 1 ) R ~ F e 2+ +xH2 S + 2 ( x - 1 )R +
even if FeS of Fe is formed (which would be unlikely because of the rather
low hydrogen overvoltage on iron metal).
Pyrrhotite (FeS, usually non-stoichiometric) deserves more attention
[55,56 ]: the rates of dissolution may vary by orders of magnitude from one
sample to another, and an induction period is often observed. Only stoichiometric FeS seems to react according to the expected equation:
F e S + 2H + ~ F e 2+ q- H2 S
Non-stoichiometric species (iron deficient) must first be reduced to stoichiometric FeS before the spontaneous non-oxidative dissolution can occur. The
coupled reaction during the induction period is usually the oxidation of H2S
to elemental sulfur. If this sulfur layer is protective, the dissolution reaction
is very slow. Otherwise, dissolution proceeds very quickly.
Finally, the dissolution of metal ferrites and iron oxides by HC1 was studied
under oxidizing and reducing conditions [ 57 ]. The relative reactivity in 1 M
HC1 at 25C was found to be in the order:
F e 3 0 4 >> ZnFe204 > C u F e 2 0 4 > g F e 2 0 3 > NiFe204

The leaching of metal ferrites and iron oxides is enhanced by the presence of
0.01 M Cu ( I ) or Sn ( II ) but the leaching of NiO is enhanced by oxidants such
as 0.01 M C u ( I I ) .

Regeneration of lixiviant
Regeneration of the leaching power of solutions after metal winning can be
achieved by oxidation of Fe (II) to Fe (III) or of Cu (I) to Cu (II). These re-

306

R.WINAND

actions are rapid and controlled by the diffusion of oxygen at the liquid-gas
boundary on the solution side. For copper [ 58 ], the reaction is:
2CUC143- + 2H + + 02 ---,2CuCI~- + H20-t-2CICu (I) can also be oxidized to Cu (II) at the anode of an electrowinning cell.
The reaction is fully reversible [ 18-21 ].
Hydrochloric acid can also be regenerated by spray roasting of chloride solutions according to:
MeC12 + x H 2 0 - - , M e O + 2HCI+ ( x - 1 ) H 2 0

Solvent extraction
It is beyond the scope of this paper to discuss solvent extraction applied to
chloride hydrometallurgy: this would require a paper in itself. The field was
reviewed some years ago by Hudson [59] and Flett [60]. Solvent extraction
is especially attractive in chloride solutions. It is well known that cobalt and
nickel can be separated in chloride solutions by amine extraction [ 61 ]. Copper can also be separated from cobalt by solvent extraction with an amine
[62 ]. Iron and zinc can be extracted by TBP from concentrated COC12SOlUtions [64]. Water-immiscible nitriles extract selectively Cu (I) from aqueous
chloride solutions, even if the starting solution contains C u ( I I ) provided
Fe(II) is present: it will be oxidized to Fe(III) [65 ]. Copper (II) complexes
are extracted from hydrochloric acid solutions by alkylated hydroxyquinoline
[66] and by c~ hydroxyoxime [67]. It has been shown that the rate of extraction of copper by an oxime goes through a m a x i m u m at about 4 MNaC1 [ 68 ].

Summary
Highly concentrated solutions of most metals of interest in non-ferrous
metallurgy can be obtained through complexation by chloride ions. The potential series in chloride solutions is accordingly different from the standard
series. Most electrochemical reactions are more reversible in chloride than in
sulfate solutions. The structure of metal deposits are worse for normal or intermediate metals but better for inert metals in chloride than in sulfate solutions. Ohmic voltage drop in electrolysis is smaller in chloride than in sulfate
solutions. Leaching of sulfides occurs more easily in chloride than in sulfate
solutions with, however, kinetic limits due to a possible elemental sulfur protective layer, mainly for nickel (cobalt) and possible iron sulfides. Regeneration of the leaching power of the solution can be achieved either by chemical
or electrochemical oxidation or by pyrohydrolysis. Solvent extraction is a very
powerful tool for purification of solutions.

CHLORIDE HYDROMETALLURGY

307

PROCESSES

A number of processes have been proposed in chloride hydrometallurgy.

Some of them have been reviewed by Barbery et al. [69].
Processes based on ores
The C Y M E T Process [ 70 ] (Cyprus Metallurgical Processes Corporation ):
The original process was based on an electrolytic membrane cell, the concentrated ore undergoing anodic dissolution as a slurry. This idea was abandoned
in 1975. A pilot plant was then operated for 4 yr at 225 l b / h (100 k g / h )
copper rate.
The process chemistry involves a ferric and cupric chloride two-stage countercurrent leach in the presence of NaC1, at boiling point but at atmospheric
pressure. The solution from the first stage is cooled to crystallize CuC1, which
is then reduced by hydrogen in a fluid-bed reactor. Copper nodules are produced, suitable for fire-refining. Reagents are regenerated by oxidation of
Fe (II) to Fe (III) with oxygen after the first stage leach.
The C L E A R - D u r a l process [71,72 ]: This process includes a cupric chloride leach in two stages. In the first stage, the concentrate is partially reacted
at 107C to produce a reduced ( C u ( I ) ) pregnant liquor for feeding to the
electrowinning tankhouse, according to:

2CuFeS2 + 3CUC12 -* 4CuCI + FeC12 + 2S + CuFeS2

In the second leach stage, digestion is completed under oxygen pressure at
140 C to produce a spent solid residue, according to:
CuFeS2 + 2S + 2CUC12 + FeC12 + 02 + 3H2 O - , 3CUC12 + 2Fe (OH)3 + 4S
Some sulfate is formed, and helps to precipitate non gelatinous ferric hydroxide as a potassium jarosite plus beta ferric hydroxide.
Copper is electrowon in a diaphragm cell. At the cathode, Cu (I) is reduced
to copper metal, recovered continuously on a conveyor belt as a powder. At
the anode, C u ( I ) is oxidized to C u ( I I ) , regenerating the leach solution for
the first stage. Fe(II) is not oxidized at the anode.
The process was operated on a commercial basis at 40,000't/yr until it was
closed in 1983. The copper produced contained silver and other contaminants, and had to be melted and electrorefined. The leach residue contained
SOand pyrite.
The Z I N C E X p r o c e s s [ 73 ]: This process makes use of leach liquors coming
from pyrite cinders treatment through two different roast processes; one nonvolatilizing, the other volatilizing chlorides. Two separate circuits are thus

308

R.WINAND

necessary. The general idea is to prepare a conventional zinc sulfate electrolyte for zinc electrowinning. For the non-volatilizing roast process ( D K H ) , a
double solvent extraction process is necessary, including an anionic secondary amine and a cationic (D2EHPA) extraction. For the volatilizing roast
process (KOWA-SEIKO), the cationic extraction is enough because the leach
solution is pure enough and does not contain sulfate; however, chloride must
be recycled. In the cationic extraction, acidity is produced and must be neutralized by limewater. The Quimigal plant has operated since 1980 at 11,000
t / y r SHG slab zinc capacity.
The D E X T E C process [ 74,75 ]: The idea is to react the metal sulfide with
oxygen in the anode compartment of a diaphragm electrolytic cell, the metal
being deposited at the cathode. Current density at the anode is very low ( 100
A / m 2 ) , allowing the use of graphite anodes and polypropene filter cloth as
diaphragm with negligible wear. For chalcopyrite, the overall reaction is:
3
2CuFeS2 + ~O2
-~ 2Cu + Fe2 03 + 4S

and copper is recovered as a powder at a cathode current density of 1,500 A/

m 2. The same process was used with galena and with lead-containing sulfides,
without introducing air in the anode compartment.
In the anolyte, the following reactions occur:
PbS+2H+-~Pb
} t 2 S--+ S-t -

2+ + H 2 S

2H + + 2e

In the catholyte:
pb 2+ + 2 e _ , P b
()wing to leaching selectivity, the process seems able to give pure lead at the
cathode even with complex sulfides. Lead is also recovered as a powder. The
process was tested in a 10 m 3 pilot cell, at 8,000 A.
The E L K E M Process [69 ]: This process involves a ferric-cupric chloride
two-stage countercurrent leach at boiling point. PbC12 is crystallized from the
solution, and zinc is solvent extracted. Copper and zinc are produced by electrowinning from chloride solutions: at copper electrolysis, Cu (I) is oxidized
to C u ( I I ) , while at zinc electrolysis, chlorine is evolved at the anode. Reagents are regenerated by Fe (II) oxidation by air and by chlorine gas coming
out of zinc electrowinning. Silver reports to copper cathodes. The process was
piloted on a small scale at the end of the seventies. No details are available
concerning the copper and zinc cathode deposits.
The M I N E M E T R e c h e r c h e s processes: For copper and zinc extraction, this
process [76] includes a two-stage countercurrent cupric chloride leach at
boiling point. PbC12 is crystallized, silver is cemented on lead, iron is precipitated as goethite while blowing air in the solution to regenerate Cu (II). Sol-

CHLORIDE HYDROMETALLURGY

309

vent extraction with DEHPA leads to conventional copper and zinc sulfate
electrowinning. Air oxidation is used during copper solvent extraction to convert Cu (I) into Cu (II); this also controls pH. The leach residue contains So
and pyrite.
For lead, the process [77 ] includes a ferric chloride leach of galena in a
concentrated NaC1 solution according to:
PbS + 2FeC13 ---,2FeC12 + PbC12 + SO
Zinc, copper, silver and bismuth are also dissolved. In a first purification stage,
copper, silver and bismuth are cemented on lead crystals. The remaining copper and silver are quantitatively removed in the second purification stage by
an ion-exchange resin. Lead is recovered by electrowinning in a special cell
including a porous diaphragm. The purified lead chloride solution is fed to
the cathode compartment where lead is recovered as a powder that falls to the
bottom, from where it can be continuously removed. The solution flows then
to the anode where Fe (II) is oxidized to Fe (III). The unwanted chlorine evolution is avoided by keeping some unreacted Fe (II) in the exit solution. Zinc
can be removed by anionic solvent extraction. These processes were both piloted at medium scale during the late seventies and the early eighties.
USBMprocesses: Haver and Wong proposed a ferric chloride leach of chalcopyrite concentrates for 2 h at 106 C, copper being recovered by cementation on iron [ 78,79 ]. Iron is removed by pyrohydrolysis. The recovered HC1
is electrolysed to obtain chlorine, which is used to oxidize Fe (II) to Fe (III).
Elemental sulfur and silver are recovered from the leach residue by perchlorethene and cyanidation, respectively. The process was tried on a large laboratory scale, but was found to be too energy intensive.
After a ferric chloride leach, PbC12 crystals are precipitated, and lead is
recovered as a liquid in a molten salt electrolysis process [80,81 ]. This process was tried in a 3,000 A cell operated at 450C. Chlorine was used to reoxidize Fe(II) to Fe(III).
The C U P R E X process [82]: The concentrate is leached at atmospheric
pressure with a ferric chloride solution at 95 C. Sulfur remains in elemental
stale, and Cu(II) is obtained in solution. CuC12 is solvent extracted with a
kerosene solution of DS 5443 according to:
Cu ( I I ) ~q + 2 C1Zq+ 2 Lorg ---+L 2 CuCl2org
The organic phase is stripped by water at 65 C giving a highly concentrated
CuC12 solution which, after adding NaC1, is sent to the electrowinning cell.
Copper is recovered as granules. Chlorine is evolved at the anode. This chlorine is used to regenerate the catholyte Cu (I) to Cu (II). The electrolytic cell
(Metchlor cell) involves separation between catholyte and anolyte by a
cation-selective, ion exchange membrane such as Nation 117 made by Du-

310

R. WINAND

pont. This allows maintenance of the charge balance in the catholyte by transfer of Na + ions from the anolyte. The process was tested on a pilot scale.

Processes based on intermediate metallurgical products"

The Falconbridge matte-leach process [83]: The feed for this process is a
copper-nickel converter matte. After grinding, it is leached with chlorine in
copper-containing chloride solution at boiling point (about 110 C). This is
a Cu (II) leach, and sulfur remains in the elemental state. The leach slurry is
then heated in autoclaves at 140 C to dissolve residual NiS and to precipitate
CuS. The liquor is then treated by C12 and NiCO3 to precipitate the oxidized
iron. After cooling, the solution is contacted with tri-iso-octylamine to extract
cobalt. After further purification, nickel metal is recovered in electrowinning
cells. Chlorine is evolved at the anode on DSA electrodes protected by diaphragms. Cobalt is also electrowon from chloride electrolyte in similar cells.
CuS is roasted and dissolved in H2SO4 allowing conventional sulfate electrowinning. The process has been in commercial use since 1975.
SociOt~ le Nickel process [84,85 ]: The feed is a nickel-iron-cobalt matte.
The lixiviant is FeC13, with iron being re-oxidized by chlorine. The pregnant
solution is further oxidized by chlorine and is then contacted with TBP to
extract iron which is recycled to the leach. Cobalt is extracted by tri-iso-octylamine. Nickel is electrowon with chlorine evolution on DSA anodes. The process has been in commercial use since 1978.
Sumitomo nickel and cobalt refining process [ 86,87 ]: A mixture of nickel
and cobalt sulfides is pressure leached to give a nickel-cobalt sulfate solution.
This is converted to a chloride solution after solvent extraction by versatic
acid, the stripping being made with HCI. Nickel-cobalt separation is made by
amine solvent extraction. Both nickel and cobalt are electrowon from chloride solutions, with DSA anodes. Anode slime coming from the nickel matte
electrorefining was recently leached by chlorine. The process has been operated commercially since 1975.
A M A X nickel-cobalt chloride refining process [88,89 ]: The feed is an impure nickel-cobalt sulfide precipitate coming from an acid leach process for
nickel oxide ores. After a suitable pretreatment (partial hydrogen reduction,
dead roasting or matte smelting) necessary to ensure solubilization, dissolution occurs with HC1. Copper, zinc and iron are removed with TBP and cobalt with TIOA solvent extraction. Four solutions are obtained: a copper-zinc
solution, a ferric chloride solution, a cobalt chloride solution, and a nickel
chloride solution. Cobalt and nickel solutions are pyrohydrolized in fluidized
bed reactors to produce granular oxide and to recover HC1. The oxides are
reduced with hydrogen. The process was tested on a pilot scale during the
early eighties.
INER process for recovering precious metals from copper refinery anode

CHLORIDE HYDROMETALLURGY

31 1

slimes [90]: The complete process is complicated. After AgC1 precipitation,

a filtrate containing Cu, Pb, Se and Te is denitrated and chlorinated by HC1
in a TBP solvent extraction process. Tellurium is extracted from the chloride
solution by another TBP solvent extraction step. The process was tested on a
pilot scale in the early eighties.
CONCLUSIONS

Chloride electrometallurgy has the following advantages versus the conventional sulfate routes: Complex sulfide concentrates can be easily leached,
leaving elemental sulfur and giving concentrated chloride solutions. Purification can occur by solvent extraction, by oxidation and iron precipitation,
or by pure chloride precipitation. Regeneration of leachant can be achieved
by oxygen or chlorine blowing in the solutions or by pyrohydrolysis of chloride solutions to recover HC1. At chloride electrowinning, the high overvoltage oxygen evolution at the anode can be replaced by chlorine evolution on
DSA anodes, or by F e ( I I ) oxidation to Fe(III) or, even better, by C u ( I ) oxidation to Cu (II). Electrical conductivity is high, resulting in low specific energy consumption for electrolysis.
The following drawbacks must be mentioned: chloride solutions are corrosive, but this can be matched by choosing suitable materials for the equipment; cathode deposits of a n u m b e r of metals besides nickel and cobalt show
a tendency to be powdery, nodular or dendritic, with a weak sensitivity to
additives; solid residues should be thoroughly washed before being disposed
as wastes for environment protection. Further, among the above-mentioned
advantages, it should be noticed that pressure leaching of sulfides in sulfate
solutions can also leave elemental sulfur, as in the Cominco zinc pressure
leaching process.
Looking back over the past 25 years, it can be said that fundamental knowledge is satisfactory, but that research and development effort was dramatically reduced at the end of the seventies. Accordingly, only processes based
on intermediate metallurgical products, which came into commercial exploitation in the mid-seventies, are still in operation. Apart from the ZINCEX
process, all others were either shut down, like the CLEAR process, or did not
come to commercial exploitation.
1t is highly probable that chloride electrometallurgy will first find new applications in the treatment of other intermediate metallurgical products, in
recycling metallurgy and in precious metals recovery, and later in complex
sulfide concentrates processing. This could be hastened if international political instability makes high grade ore resources unavailable.

2;12

R. WINAND

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Vol. II Recovery of Metals, MacGraw Hill, New York, ( 1945 ) Chap. 17.
2 Peters, E., Direct leaching of sulfides: chemistry and applications. Met. Trans. B., 7 ( 1976):
505-517.
3 Winand, R,, Reflecting on the new goals in nonferrous extractive research. J. Metals, 42
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4 Weast, R.C., CRC Handbook of Chemistry and Physics. CRC Press, Boca Raton, Fl., USA,
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(1975).
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aqueuses chlorur6es de chlorure cuivreux, h concentrations 61ev6es. Hydrometallurgy, 11
( 1983): 297-314.
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