hydrometallurgy

ELSEVIER Hydrometallurgy 41 ( 1996) 255-267

Selective leaching of arsenic and antimony

contained in the anode slimes from copper refining
M.A. Fernhdez, M. Segarra, F. Espiell *
Received 10 June 1994; accepted 16 July 1995

Abstract

Selenium, tellurium, silver and gold are recovered from the anode slimes of copper electrore-
fining. Silver-copper selenide-telluride phases must be previously oxidized to obtain selectively
leachable compounds. Arsenic and antimony, present in anode slimes as As-Sb oxidized
compounds, may be selectively and almost completely dissolved in 0.4 M KOH at 80°C. After
this extraction, alkaline roasting of anode slimes in the presence of K *CO, at 600°C solubilizes Se
(99%) and less than 2% As and 0.1% of Sb. After Se leaching, Cu and Te can be dissolved in 1.2
M HCl at 25°C as well as in CuSO,-H,SO, solution. The residue contains BaSO,, PbSO,, SiO,,
Au, Ag and small amounts of Se, Cu and Te and can be smelted in order to obtain a bullion for
Ag and Au recovery by the conventional electrorefining process.

1. Introduction

Electrolytic refinery slimes contain those constituents of the copper anode which
remain insoluble during the refining process and ultimately sink to the bottom of the
electrorefining tank. Their composition depends on the origin of the copper anode and
may represent between 0.5% and 2% of its initial weight. They are periodically
recovered and processed for their precious metals contents. Anode slimes can be
considered as raw material for obtaining Se, Te, Au, Ag and platinum group metals. In
time, they may also be considered as a dangerous residue containing As, Sb, Se, Te, Bi
and easily soluble heavy metals such as Cu, Ni and Pb. Thus, the previous selective
removal of As and Sb may contribute to the reduction of environmental problems and
considerably simplify the flowsheets of the alkaline roasting processes for anode slimes
containing As and Sb, which are usually produced in the metallurgical treatment of
flotation concentrates of complex sulphide ores.

* Corresponding author.

0304-386X/96/$15.00 0 1996 Elsevier Science B.V. All rights reserved

SSDI 0304-386X(95)00061-5
256 M.A. Fermhdez et al. /Hydrometallurgy 41 (1996) 255-267

Dutrizac and Chen Cl], studying the anode slimes from Jnco’s Copper Cliff Copper
Refinery, found NiO crystals, Ag-Cu selenides, PbSO, and silicates as well as trace
amounts of Pb-Cu-Bi oxide, Ag,Te and BaSO,. Scott [2] suggests that, depending on
the silver and selenium content of copper anodes and the current density used in the
refining process, different compounds can be found in the anode slimes. Thus, if the
Ag:Se ratio in the anode is less than 1.7, AgCuSe is expected, whereas if it is greater,
selenium combines only with silver. On the other hand, if the current density is 220
A/m2 or more, metallic silver is found in the slimes. Lead is usually present as PbSO,.
Arsenic is dissolved from the anode and dissolves in the electrolyte as arsenic acid.
Antimony is solubilized, saturates the electrolyte and reacts with arsenic acid to give
either its basic arsenate or basic chloride [3]. Therefore, the arsenic content of anode
slimes depends on the As:Sb ratio in the initial copper anode. During electrorefining, the
gold in solid solution in the copper matrix is liberated in elemental form as either
spheroidal particles < 1 pm or as slightly larger spike-like grains physically attached to
selenides [4]. Some BaSO, is also present in anode slimes, because it is used as mould
wash.
Alternative processes should take account of three points of interest: yield, economy
and the environment. To develop a process including these three aspects, the appropriate
reagents and conditions in the leaching operations must be established in order to
achieve selective and complete separations.
The processes for treatment of anode slimes can be classified in two groups:
pyrometallurgical and hydrometallurgical. Pyrometallurgical processes are mostly based
on sulphation roasting, oxidation in converters, alkaline roasting and direct roasting in
air [5--91. Hydrometallurgical processes are based on nitric acid leaching, hydrogen
peroxide leaching, autoclave leaching, chlorination and sulphuric acid leaching [6, lo- 141.
As these processes dissolve most of the elements present in anode slimes, treatment of
the leaching solutions becomes complex, since the separation of the multiple compo-
nents is difficult.
In most of the pyrometallurgical processes arsenic is volatilized, mainly in the form
of As,O,, as well as selenium in the form of SeO,, forcing the elimination of arsenic
from exhaust gases if selenium is to be recovered. In the bibliography, As and Sb are
absent from the described processes for the treatment of anode slimes, although these
elements are present in most of the anode slimes produced in the different copper
refineries [3].
In this paper, a treatment of anode slimes is described which yields a solid with low
As and Sb contents. This can be further roasted in alkaline conditions to obtain easily
leachable compounds of Se and Te and a bullion which can be processed to recover
precious metals. Thus, a combination of selective leaching and pyrometallurgical
treatments of anode slimes is suggested to achieve selective and complete dissolution of
each of the elements present, yielding solutions from which the dissolved metals can be
recovered without the use of complex procedures.

2. Materials and procedure

Two samples were studied. Both correspond to a representative sample of the anode
slimes produced in the Rio Tinto Minera copper refinery at Huelva (Spain) during the
 MA. Fernhdez et al./Hydrometallurgy 41 (1996) 255-267 257

Table 1
Amount of each element present in anode slimes, NONOXID sample
Element Amount
(W)
cu 25.41
Se 8.23
Pb 2.89
AS 3.41
Sb 3.04
Te 1.27
Ag 14.54
Ba 8.01
S tOtal 7.20
SiO, 1.74
Bi 0.76
AW, 0.132
Au 0.382
Ni 0.0045
Fe 0.038
zn 0.008
co < 0.003
H,O 9.45

last half of 1990. Equal amounts were taken each day for 6 months and carefully mixed
in order to obtain a homogeneous sample. The sample named OXID was taken from the
anode slimes after filtering and drying, and was stored in air as it is usually made with
anode slimes marketed by RTM.
The other sample, named NONOXID, corresponds to the non-oxidized anode slimes;
that is, as they are produced. This sample was kept in the electrolyte of the copper
refining cells and transported in this manner.
Quantitative analyses were carried out using X-ray diffraction and fluorescence,
atomic absorption spectroscopy, electronic microscopy with EDS and EDAX and the
classical techniques of gravimetry and volumetry. The amount of each element is shown
in Table 1.
The observation with the electronic scanning electron microscope gave very similar
results to those published by Dutrizac and Chen [l]. The only difference found is the
very small nickel content in the RTM anode slimes compared with the sample observed
by Dutrizac, but the amounts of the rest of the elements are of the same order. The
compounds and their observed morphology are essentially the same: selenides as Ag,Se,
AgCuSe and Cu,Se, and CuSO,, PbSO, and BaSO, are the main constituents.
Anode slimes are stable while maintained in the electrolyte of the copper refining
cells, but when they are dried and in contact with air, selenides quickly oxidize to
copper and silver selenites and some significant aspects of their reactivity appear:
1. 50% of the total copper from OXID sample is soluble in 5% H,SO,; this amount
approached 100% 3 months after the sample was received and stored in air;
258 MA. Ferruindez et al./Hydrometallurgy 41 (1996) 255-267

2. copper from the NONOXID sample is not soluble, due to the presence of this
element as an insoluble phase in the form of copper sulphide and selenide;
3. selenides oxidize to selenites even at room temperature.
4. the amount of total sulphur is higher than the amount of sulphur contained in the
barite and PbSO,. Therefore, the sample contains some sulphur as sulphate and some
as sulphide. When treating oxidized anode slimes with concentrated hydrochloric
acid, soluble sulphates may be detected by precipitation with barium chloride (5.4%).

3. Results and discussion

.I. Leaching of As and Sb in KOH

Arsenates of alkaline metals are soluble at room temperature, and potassium anti-
monate is soluble in hot water. In order to establish the optimum conditions for As and
Sb leaching, the effect of alkali concentration, temperature and solid/liquid ratio in the
pulp were studied. Concentrations of As and Sb in the leaching dissolution were
analyzed by atomic absorption spectrophotometry.
Fig. 1 shows the effect of KOH concentration on the solubilization of As and Sb at
80°C. A concentration of 0.4 M KOH was enough to leach 80% of the As and Sb
present in the OXID sample of anode slimes whereas from the NONOXID sample, 90%
of each element was leached under the same conditions. When the KOH concentration
was 4 M, a temperature of 70°C was enough to solubilize 80% of each element (Fig. 2).

OXID

NONOXID

0 1 2345678 9 10 11

KOH Concentration (M)

Fig. 1. Effect of the KOH concentration on the solubilization of As and Sb from oxidized (OXID) and
non-oxidized (NONOXID) anode slimes. Conditions: 8O”C, 30 min, S/L ratio = l/40, 5 g of anode slime.
 MA. Fernhdez et al./ Hydrometallurgy 41 (1996) 255-267 259

‘Z
3 /
.-
z *’
3
0
0

2 60- OXID NONOXID

40 , I
50 60 70 80 90 100 110

Temperature (“C)

Fig. 2. Effect of the leaching temperature on the solubilization of As and Sb from oxidized (OXID) and
non-oxidized (NONOXID) anode slimes. Conditions: 4 M KOH, 30 min. S/L ratio = l/40, 5 g of anode
slime.

When the anode slimes were kept in the electrolyte (NONOXJD sample), more than
90% of As and Sb was solubilized at a lower temperature (60°C).
For the oxidized sample, solid/liquid ratio in the pulp had little effect on the As
leaching, while Sb needed a minimum ratio of l/10 when the experiment was
performed at 80°C with 4 M KOH (Fig. 3). When anode slimes have not been in contact
with air, the effect of solid/liquid ratio on the solubilization of both elements is
practically nil.
The solubilization of Se in the KOH leaching is shown in Fig. 4. The amount of Se
dissolved was strongly dependent on the degree of oxidation of the anode slimes: when
the sample was kept in the electrolyte avoiding its oxidation in air, only 2% of the
selenium was dissolved. The percentage of solubilized selenium can be reduced by
adding small amounts of hydrazine hydrate to the solution.
When anode slimes were oxidized, copper was partially leached in KOH (12% in 0.4
M KOH, at 80°C S/L ratio of l/10>, whereas, when anode slimes are kept in the
electrolyte, less than 100 mg/l of Cu are found in the KOH leaching solution under the
same conditions.
The optimum conditions for the As and Sb leaching are 0.5 M KOH, S/L ratio of
l/10 and temperature of SOT, working with oxidized anode slimes. Under these
conditions 85% As, 80% Sb and 20% Se are solubilized. For non-oxidized anode slimes,
almost all As and Sb and only less than 2% Se are solubilized under the same
conditions.
260 MA. Ferncinder et al./HydrometaNurgy 41 (1996) 255-267

l/l l/2 l/4 l/5 l/8 l/10 t/20 l/40 l/80 1

Solid I Liquid Ratio

Fig. 3. Effect of the solid/liquid ratio in the pulp on the solubilization of As and Sb from oxidized (OXID)
and non-oxidized (NONOXID) anode slimes. Conditions: 80°C. 4 M KOH, 30 min, 5 g of anode slime.

The previous elimination of As and Sb from non-oxidized anode slimes by leaching

in KOH would allow treatment of the resulting solid without the difficulties occurring
when these elements are present and give a solution practically free of impurities, as can

OXID NONOXID

NONOXID

0 1 2 3 4 5 6 7 8 9 10 11

KOH Concentration (M)

Fig. 4. Effect of the KOH concentration on the solubiiization of Se and Cu from oxidized (OXID) and
non-oxidized (NONOXID) anode slimes. Conditions: 8O”C, 30 min. S/L ratio = l/40, 5 g of anode slime.
 MA. Fenuindez et al./Hydrometallurgy 41 (1996) 255-267 261

Table 2
Percentage of each element solubilized by 4 M KOH, at 80°C. with a solid/liquid ratio of l/ 10, non-oxidized
anode slimes
Element Amount solubilized
(o/o)
CU < 0.01
Se 2.03
Pb < 0.01
As 98
Sb 97
Te < 0.01
Ag < 0.01
Au < 0.01
Ni < 0.01
Fe < 0.01
zn < 0.01
co < 0.01

be seen in Table 2, from which As and Sb can be recovered or co-precipitated as

insoluble sulphides after acidification. After KOH leaching, anode slimes seem suitable
for treatment by the alkaline roasting methods described by Hoffmann [6].

3.2. Alkaline roasting after KOH leaching

3.2.1. Leaching of Se
After leaching in KOH, the residue thus obtained was subjected to a wide range of
roasting conditions, by varying temperature, time and potassium carbonate/anode slime
ratios, to study the amount of selenium further solubilized in water at room temperature
after roasting in air atmosphere, and the selectivity of this operation. The amount of
selenium in the leaching solutions was determined by AAS.
Experiments were carried out by weighing 5 g of anode slime and carefully mixing
the sample with a suitable amount of potassium carbonate. All the experiments were
performed by covering the K,CO,/slimes mixture with a 3 mm thick carbonate coat to
prevent volatilization. Thus, by alkaline roasting the treatment of exhaust gases is
practically avoided. The mixture was placed in a crucible at the desired temperature and
for the time required.
The study of the K,CO,/slime weight ratio effect was performed at 500” and 600°C
(Fig. 5). A ratio of 0.2 is enough to solubilize all the selenium present in the anode
slimes when the roasting temperature is 6OO”C,but at 500°C the ratio must be 0.8.
Results obtained in the alkaline roasting experiments for NONOXID sample are similar
to those for the OXID sample.
If anode slimes have not been previously leached in KOH, As is also solubilized with
selenium after roasting. Fig. 6 shows the effect of K,CO,/slime ratio on As solubiliza-
tion for non-dearsenized slimes.
262 M.A. Fermindez er al./ Hydrometallurgy 41 (1996) 255-267

.-
6
/

40
0 0.2 0.4 0.6 0.0 1 1.2 1.4 1.6 1.8

K&O, i Slime Ratio

Fig. 5. Effect of the K,CO, /anode slime ratio when roasting and further water leaching at room temperature,
on the solubilization of Se. Conditions: roasting time = 6 h, leaching time = 30 min. 5 g of anode slime.

When anode slimes are roasted at 400°C only 50% Se is solubilized (Fig. 7), because
the oxidation of selenides is incomplete. The minimum temperature needed to solubilize
90% of Se is 500°C. Under these conditions only a few milligrams per litre of As were

I
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8

K&O, / Slime Ratio

Fig. 6. Effect of the K,CO, /anode slime ratio when roasting and further water leaching at room temperature,
on the solubilization of As for non-dearsenized anode slimes. Conditions: roasting time = 6 h, leaching
time = 30 min. 5 g of anode slime.
 MA. Ferncindezet al./ Hydrometallurgy 41 (1996) 255-267 263

-J
0 100 200 300 400 500 600 700 800 900

Temperature (“C)
Fig. 7. Effect of the temperature when roasting and further water leaching at room temperature, on the
solubilization of Se and As for non-dearsenized anode slimes. Conditions: K,CO, /anode slime ratio = 0.4,
roasting time = 6 h, leaching time = 30 min, 5 g of anode slime.

found in the solution when it had previously been leached with KOH. When As and Sb
were not previously eliminated by KOH leaching, arsenic was dissolved together with
selenium in amounts depending on the roasting temperature (10% at 500°C). After
roasting, tellurium remained in the solid.
The solutions obtained after leaching the roasted residues in water contain selenium
as potassium selenate. The alkaline roasting reaction of selenides can thus be written as:

(Cu,Ag,_,),Se + 0, + K&O,

--$2( 1 - x)Ag + 2 xCu0 + K,SeO, + CO, (1)

Fig. 8 shows the weight loss with time for anode slimes when roasted at different
temperatures in air atmosphere. Experiments were performed with 10 g anode slimes, 2
g K,CO, and with 2 cm bed thickness. Initially, there is an important weight loss due to
the water evaporation. After this step, the sample begins to gain weight, probably due to
the oxidation of selenides, until reaching a constant weight that indicates the end of the
roasting process.
Fig. 9 shows that the time needed to complete the roasting process is a function of the
roasting temperature and of the thickness of the K,CO, coating. The linearity observed
indicates that there is no resistance to the diffusion, nor to the transport of oxygen, from
the air through the bed of particles to the reaction surface, nor to the SeO, exit, as it
remains fixed as selenate. The optimum conditions for the Se solubilizing process are
264 MA. Fernhdez et al./Hydrometallurgy 41 (1996) 255-267

1 2 3 4

Time (h)
Fig. 8. Effect of temperature on the time needed to complete the roasting process. K,CO, /slime ratio of 0.2,
bed thickness 2 cm.

0 1 2 3 4 5

Bed thickness (cm)

Fig. 9. Relationship between bed thickness and time needed for complete reaction. Conditions: 6OO”C,
K,CO, /anode slime ratio = 0.4.
 MA. Fermindez et al./Hydrometallurgy 41 (1996) 255-267 265

Table 3
Percentage of each element solubilized by water leaching after roasting at 6OO”C,for 4 hours, K,CO, /slime
ratio of 0.2, non-oxidized and dearsenized anode slimes
Element Amount solubilized

CU < 0.01
Se 98
Pb < 0.01
As < 0.05
Sb < 0.01
Te < 0.01
Ag < 0.01
Au < 0.01
Ni < 0.01
Fe < 0.01
zn < 0.01
co < 0.01

the following: temperature of 6OO”C,time 4 h, K,CO,/slime ratio of 0.2, bed thickness

of 3 cm. Under these conditions 98% of the Se is solubilized in water. The solution of
potassium selenate thus obtained is clean and practically free of impurities, containing
only potassium sulphate and less than 50 mg/l of arsenic, if it has been previously
removed with KOH. Table 3 shows the analytical data for the water leach solution.
The solutions thus obtained can be treated with the methods found in the literature [6]
in order to recover Se, Te and Cu. The previous removal of As and Sb does not have
any significant effect on the behaviour of anode slimes during alkaline roasting in
relation to the published procedures, except for the selenium solutions obtained by water
leaching after roasting, which have a low As content.

3.3. Flowsheet

According to what has been said above, after As and Sb removal with KOH the
flowsheet for anode slimes treatment is analogous to those already published in which
alkaline roasting is performed [6]. Fig. 10 shows the suggested flowsheet for anode
slimes treatment. By leaching in 0.4 M KOH at 80°C with a solid/liquid ratio of l/10,
85% As and 80% Sb can be dissolved. From this solution, arsenic and antimony can be
recovered by precipitating their respective sulphides in acidic media. The solid resulting
from this step is mixed with potassium carbonate (K,CO,/slime ratio of 0.4) and
roasted at 600°C for 6 h. After this operation, the solid is leached with water at room
temperature. The leaching solution contains 98% Se in the form of selenate, which can
be recovered by reducing the solution with hydrazine dichlorhydrate in acidic medium.
The solid without selenium is afterwards leached with 0.5 M H,SO, in order to
dissolve 85% copper and some tellurium (18%). From the solution thus obtained, copper
can be selectively recovered by solvent extraction, obtaining a marketable copper
sulphate solution. Tellurium can be leached from the resultant solid by washing it with
266 M.A. Ferncindez et al./ Hydrometallurgy 41 (1996) 255-267

SLIMES
I

KOH !

1 LEAYHING / As' Sb

ALKALINE

r--J--l
1 LIiIg;NG k Cu, (Te)

e-- Tel (CU)

7
SMELTING

BULLION

Fig. 10. Suggested flowsheet for the treatment of anode slimes.

1.2 M HCl and adding metallic copper to the solution thus obtained. The resulting solid
without arsenic, antimony, selenium, copper or tellurium can be smelted, yielding a
bullion enriched in precious metals.

Acknowledgements

We would like to thank the European Community, Directorate General XII, for their
financial support, the Serveis Cientifico-T&cnics of the University of Barcelona and Rio
Tinto Minera S.A. from Huelva (Spain).
 MA. Ferncindez et al./Hydrometallurgy 41 (1996) 255-267 267

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