Ind. Eng. Chem. Res.

2002, 41, 6593-6599

6593

Some Studies on Sulfuric Acid Leaching of Anode Slime with

Additives
Jhumki Hait,*, R. K. Jana, Vinay Kumar, and S. K. Sanyal
National Metallurgical Laboratory, Jamshedpur 831007, India, and Chemical Engineering Department,
Jadavpur University, Jadavpur 700037, India

The most effective hydrometallurgical processing of anode slime is based on a chlorination route.
However, it requires special attention with respect to pollution problems and construction
materials. To minimize the problems, a new hydrometallurgical approach was pursued for the
recovery of valuable metals and metalloids from copper electrorefining anode slime. The process
involved the leaching of anode slime in sulfuric acid medium. At room temperature, sulfuric
acid leaching without any additive resulted in poor recoveries of metals other than copper. With
the addition of MnO2 to the leaching system at room temperature, an increase in the recovery
values of copper, selenium, and tellurium was found. The recovery was further increased to
90% Cu, 37% Se, and 66% Te with an increase in temperature to 80 C. However, the recoveries
of Ni (13%), Au (trace), and Ag (9.5%) were poor. Satisfactory amounts of copper, selenium,
tellurium, and gold were leached when both manganese dioxide and sodium chloride were added
during leaching. The maximum recoveries were 90% Cu, 80% Se, 79% Te, and 77% Au at 50 C
after 40 min of leaching. The effects of various parameters such as time, temperature, solid/
liquid ratio, amount of additives, and acid concentration on the recoveries of metals were studied.
The kinetics of leaching was also examined at different temperatures. The dissolution of metals
was observed to be very fast with both manganese dioxide and sodium chloride addition even at
room temperature. The leaching kinetics of selenium, tellurium, and gold with manganese dioxide
and sodium chloride additives followed the ash diffusion control model, whereas copper leaching
followed the mixed control (chemical and ash diffusion control) model. These leaching mechanisms
were further corroborated with SEM findings.
1. Introduction
Anode slime is the insoluble product deposited at the
bottom of an electrorefining tank during the electrorefining of copper. The composition of the slime depends
on the host ore that produces the anodes and also on
the dissolution mechanism and the physicochemical
characteristics of the impurities present in the anodes.
The various metals present in the anode slimes are Cu,
Ni, Se, Te, Ag, Au, platinum group metals (PGMs), Pb,
Fe, Ba, etc.,1,2 and the common mineral phases in the
anode slimes include CuSO45H2O, NiO, Cu2Te, Cu2Se,
Ag2Se, and CuAgSe, among others. The slimes are
collected periodically and sent to a byproduct metals
recovery plant for processing. Depending on the composition and morphology of the anode slime, a number
of processes following pyro-, pyrohydro-, hydropyro-, and
hydrometallurgical routes have been developed for the
extraction of valuable metals from anode slime. One of
the well-known pyrometallurgical processes is slime
smelting in a Dore furnace for the recovery of selenium
from the flue gases, followed by sodium nitrate treatment for the recovery of precious metals.3,4 The pyrohydrometallurgical method of processing the anode
slime includes oxidizing roasting with KNO3 at 400450 C, followed by leaching with sulfuric acid or dilute
NaOH at 80-100 C.5 Some of the hydropyrometallurgical processes are sulfuric acid leaching followed by
* Corresponding author address: Non-ferrous Process Division, National Metallurgical Laboratory, Jamshedpur 831007,
India. Fax no. 091-0657-270527, phone No. 091-0657-271806,
e-mail jhumki@nmlindia.org.
National Metallurgical Laboratory.
Jadavpur University.

sulfation roasting,6-8 sulfuric acid leaching followed by

oxidation roasting,9,10 and sulfuric acid leaching followed
by soda roasting.9,11-13 Wet chlorination is the only
hydrometallurgical process developed for anode slime.14,15
In the present investigation, an attempt has been
made to develop a suitable hydrometallurgical process
for the recovery of the valuable metals present in the
anode slime obtained from Indian Copper Complex,
Ghatsila, India. The process involves leaching of anode
slime in sulfuric acid medium with MnO2 and NaCl
additives for the recovery of valuable metals. This new
approach avoids problems such as the emission of
corrosive gases in pyrometallurgical and pyrohydrometallurgical processes and chlorine evolution and corrosion
problems encountered in the chlorine leaching process.
2. Materials and Methods
Anode slime from the copper electrorefining plant of
Indian Copper Complex, Ghatsila, India, was used for
the experiments. It contained about 12% Cu, 37% Ni,
10.5% Se, 3.38% Te, 1.54% Ag, and 0.1% Au. The slime
was ground to -200 mesh (BS) and dried in an air oven
to remove free moisture. Samples for chemical analysis
and leaching experiments were prepared by thoroughly
mixing the dried powder and then using the cone and
quartering method to prepare representative samples.
Leaching experiments were carried out in conical
flasks fitted in the clamps of a thermostatic water bath.
Each conical flask had a separate stirrer controller that
maintained the speed of the stirrer at 500 rpm. Each
flask was charged with 2.5 g of solids, and the liquid/
solid ratio was maintained at 10:1 unless otherwise
stated. AR-grade chemical reagents were used in all
experiments. Chemical analyses of the as-received

10.1021/ie020239j CCC: $22.00 2002 American Chemical Society

Published on Web 11/13/2002

6594

Ind. Eng. Chem. Res., Vol. 41, No. 25, 2002

Table 1. Recoveries of Metals in Sulfuric Acid Medium

without Any Additive
pressure
atmospheric
pressure

time
(min)

temp
(C)

acid conc
(vol %)

Cu

240
240
240

30
60
80

20
20
20

45
50
58

% recovery
Te
Se
10.0
9.5
9.5

poor
poor
poor

Ni
poor
poor
poor

sample and leach solutions were carried out by AAS,

ICP-AES, and conventional methods.
3. Results and Discussion
3.1. Sulfuric Acid Leaching without Additive.
Sulfuric acid is a good lixiviant, and therefore, it was
used for leaching of the anode slime without any
additive. Table 1 shows the recoveries of metals under
various conditions. It can be observed from the table
that, at ambient pressure, for an increase in leaching
temperature from 30 to 80 C the extraction of Cu
increased from 45 to 58%. The Te recovery, though poor,
remained almost constant at about 10% with the
increase in leaching temperature. However, only negligible amounts of Se and Ni were extracted at all
temperatures.
3.2. Leaching with Additives. 3.2.1. Sulfuric Acid
Leaching with Manganese Dioxide Addition. Effect
of MnO2 Addition. Leaching experiments with additives
were carried out in the next stage, as the acid leaching
without additive resulted in poor recoveries of all metals
other than copper.
Referring to the Eh-pH diagrams of selenium and
tellurium in water,16 it can be seen that these metals
can be leached at low pH and high oxidation potential.
Therefore, the addition of an oxidizing agent was
examined, as it might be helpful in the leaching of
selenium and tellurium present in the anode slime.
Manganese dioxide, a good oxidizing agent, was added
to the leaching system. Table 2 shows the effect of MnO2
addition on the recoveries of Cu, Se, and Te at a
temperature of 80 C. It was found that, with an
increase in MnO2 addition, the recoveries of all of the
metals increased considerably. Because the recoveries
of Ni, Ag, and Au were not appreciable, these metals
were not analyzed in most of the leaching tests. The
improvement in the recoveries with MnO2 addition
might be due to quadrivalent manganese in MnO2 being
reduced to divalent manganese and oxidizing Cu, Se,
and Te, as follows

Cu2Se + 4Mn4+ f 2Cu2+ + Se4+ + 4Mn2+

(1)

Cu2Te + 4Mn4+ f 2Cu2+ + Te4+ + 4Mn2+

(2)

The recoveries of the metals with the addition of 1.25

g of MnO2 in the sulfuric acid leaching system were
found to be about 90% Cu, 37% Se, and 66% Te (Table
2). Further increases in MnO2 addition did not improve
the recoveries of the metals appreciably.
Effect of Acid Concentration. Table 2 shows the effect
of the sulfuric acid concentration on the extractions of
Cu, Se, and Te in the leaching of anode slime with 1.25
g of MnO2 as an additive at 80 C. It can be observed
that, with an increase in acid concentration from 10 to
30 vol %, the Se recovery improved from 22 to 46%, and
the Te recovery increased from 42 to 75%. There was a
slight improvement in the recovery of Cu. However, it

was found that, with a 30 vol % acid concentration, the

extraction of nickel also increased considerably along
with those of Cu, Se, and Te. Nickel extraction at this
stage is undesirable, as it unnecessarily complicates the
separation process at a later stage. Therefore, 20 vol %
sulfuric acid was used as the leachant in other leaching
experiments.
Effect of Temperature. The results of leaching experiments carried out at different temperatures are also
shown in Table 2. It can be observed that, in 60 min of
leaching at 30 C, only 47% Cu and 10% Te were
extracted. During this period, a negligible amount of Se
(1.5%) was recovered. At 60 C, the recovery of Cu
increased to 65% in 60 min, whereas the recoveries of
Se and Te were only 9 and 17%, respectively. On a
further increase in temperature to 80 C, the Cu
recovery increased to about 82%, with the corresponding
values for Se and Te being 25 and 34%, respectively.
Thus, an increase in temperature was marked by an
improvement in the recoveries of Cu, Se, and Te.
Effect of Time. The leaching curves in Figure 1 show
that the extractions of the metals increased with
increasing time of leaching at 80 C. For an increase in
leaching time from 30 to 330 min, the recovery of copper
improved from 74 to 90%. Similarly, the Se and Te
recoveries also increased to 42 and 74%, respectively,
in 330 min of leaching. It was seen that only the Te
recovery depended strongly on the leaching time. However, no appreciable amounts of Ni, Ag, and Au were
recovered at 80 C even after 330 min.
Kinetics of Leaching. An attempt was made to study
the dissolution kinetics of Cu, Se, and Te in the leaching
of anode slime with MnO2 addition using the shrinkingcore model. This is the most widespread model describing fluid-solid reaction kinetics of dense particles. The
standard equations of this model are

x t: (i) film diffusion control, dense, constant-size

small particles, all geometries
(ii) chemical reaction control, dense, flat plate
particles
1 - (1 - x)2/3 t: (i) film diffusion control, dense,
shrinking spheres
1 - (1 - x)1/2 t: (i) film diffusion control, dense,
large shrinking spheres
(ii) chemical reaction control, dense, constant-size
cylindrical particles
1 - (1 - x)1/3 t: (i) chemical reaction control,
dense, constant-size shrinking spheres
1 - 3(1 - x)2/3 + 2(1 - x) t: (i) ash diffusion
control, dense constant-size spherical particles
x in the above equations is the fraction of metals
extracted at time t.
After examining the experimental results in comparison with the above equations, it was found that, at 80
C, the kinetics of Se and Te (Figure 2) followed the ash
diffusion control model, i.e., 1 - 3(1 - x)2/3 + 2(1 - x)
t. The proportionality constant (Kp) for the above equation is known as the chemical rate constant, and it is

Ind. Eng. Chem. Res., Vol. 41, No. 25, 2002 6595
Table 2. Effect of Various Parameters on Recoveries of Metals
effect of MnO2 additiona

effect of H2SO4 concentration

MnO2
(g)

Cu

% recovery
Se

Te

[H2SO4]
(vol %)

Cu

0.25
0.5
0.75
1.0
1.25

68
80
84
87
90

2.17
14
25.6
34
37.3

14
32
51
60
66

10
20
30
-

89
90
91
-

% recovery
Ni
Se
4.7
13
45
-

22.2
37.3
45
-

effect of temperature
Te

temp
(C)

Cu

% recovery
Se

Te

42
66
75
-

30
60
80
-

47.4
65
82.5
-

1.5
8.6
25
-

10.8
17
34.1
-

a Conditions: temperature ) 80 C, time ) 240 min, [H SO ] ) 20 vol %. b Conditions: temperature ) 80 C, time ) 240 min, MnO
2
4
2
) 1.25 g. c Conditions: time ) 60 min, [H2SO4] ) 20 vol %, MnO2 ) 1.25 g.

Figure 1. Effect of time on recoveries of metals at 80 C.

Figure 3. Scanning electron micrograph of untreated anode

slime: (1) BaSO4, (2) NiO, (3) selenides and tellurides of Cu and
Ag, (4) copper selenide.

Figure 2. Leaching kinetics with MnO2 addition at 80 C.

related to the other parameters as follows

Kp ) 2bMDC/Fr2 min-1
where D is the diffusion coefficient, F is the particle
density, r is the radius of the unreacted particle, M is
the molecular weight of the particle, C is the concentration of the reactants, and b is the stoichiometry factor.
Because Cu was leached appreciably during the initial
stage of leaching, its kinetics could not be determined.
The ash diffusion model was further confirmed by
examining the leached residue under scanning electron
microscope with EDX studies. The porous structure of
the Se-rich material provided an indication that elemental Se deposited during the early stage of leaching. This
deposited Se acted as a porous layer favoring ashdiffusion-controlled reaction kinetics. The SEM micrographs of the unleached anode slime and residue of the
leached anode slime (at 80 C) are shown in Figures 3
and 4.

Figure 4. Scanning electron micrograph of the residue after

leaching the anode slime at 80 C: (1) Mn and selenides and
tellurides of Ag, (2) selenides and tellurides of Cu and Ag.

3.2.2. Sulfuric Acid Leaching with Manganese

Dioxide and Sodium Chloride Addition. In the
preceding sections, it was shown that leaching with
manganese dioxide addition both at room temperature
and at high temperature did not yield high recoveries
for any metal other than copper. Hence, it was decided
to use sodium chloride as another additive in the
leaching system. Figure 5 shows the effect of leaching
duration with only sodium chloride addition at 80 C
on the recovery of metals from anode slime. It can be
seen that the Cu and Te recoveries increased with time
and that, in 180 min, 80% Cu and 31% Te could be
recovered. However, the recoveries of the other metals
were negligible.
Effect of MnO2 and NaCl Addition. The next set of
experiments was carried out with both manganese
dioxide and sodium chloride as additives in the leaching

6596

Ind. Eng. Chem. Res., Vol. 41, No. 25, 2002

Figure 5. Effect on leaching time with 3 g of NaCl on recovery of

metals.

Figure 7. Effect of H2SO4 on recoveries of metals.

the leaching system can be described as follows

MnO2 + 2NaCl + H2SO4 f MnSO4 + Na2SO4 +

Cl2 + H2O (3)
Ag2Se + Cl2 + H2O f AgClV + H2SeO3 + HCl

(4)

Cu2Se + Cl2 + H2O f CuCl2 + H2SeO3 + HCl (5)

Cu2Te + Cl2 + H2O f CuCl2 + H2TeO3 + HCl (6)

Figure 6. Effect of MnO2 on recoveries of metals.

system. The effects of various amounts of MnO2 addition

with 3 g of NaCl in the leaching system are shown in
Figure 6. The addition of NaCl was fixed to 3 g, because
preliminary experiments had shown that this was the
optimum amount. It can be seen from the figure that,
at 80 C, the Se and Te recoveries increased significantly
with the increase in MnO2 addition from 0.25 to 2.5 g.
It was also noted that, in 240 min of leaching with 1.25
g of MnO2, metal recoveries on the order of 76.4% Cu,
60% Se, and 62% Te were achieved. The recovery of Se
was much higher than that (35% Se) obtained by
leaching without sodium chloride addition in 240 min
(Figure 1).
One of the reasons for the increasing metal recoveries
might be the increase in H+ activity with sodium
chloride addition in the sulfuric acid medium.17 It is
known from the Eh-pH diagrams that increases in both
the acidity and the oxidation potential are beneficial for
the leaching of Se and Te.16 Thus, the increase in H+
activity upon sodium chloride addition might have
contributed to the enhanced recoveries of these metals.
Another reason was that, upon addition of sodium
chloride and manganese dioxide to dilute sulfuric acid,
chlorine was generated. Highly oxidizing chlorine, perhaps, took part in the reaction by disspoling Se and Te
more effectively. However, no chlorine evolution was
noted during leaching with MnO2 and NaCl additives.
Perhaps, whatever chlorine was generated was instantly
utilized in the leaching reaction.
The dissolution reactions of Se and Te with the
addition of sodium chloride and manganese dioxide in

NaCl + H2SO4 f Na2SO4 + HCl

(7)

MnO2 + HCl f MnCl2 + Cl2 + H2O

(8)

It might also be noted that the nickel recovery did

not increase to an appreciable level upon the addition
of sodium chloride along with manganese dioxide in the
leaching system. This might be beneficial for the present
system, as the decreased concentration of recovered
nickel would reduce the complications for metal separation by solvent extraction at a later stage. However,
nickel could be extracted from the residue in a second
stage of leaching with a higher acid concentration at
elevated temperature.18 There was no silver recovery,
which perhaps, precipitated as silver chloride with the
addition of sodium chloride in the leaching system. Gold
recovery was evaluated at a later stage when the effect
of time was studied.
Effect of Acid Concentration. Figure 7 shows the effect
of the sulfuric acid concentration on the extractions of
Cu, Se, and Te after 90 min of leaching at 80 C. There
was no significant change in the recoveries of Cu and
Te with increasing sulfuric acid concentration. However,
the Se recovery was a maximum (74%) at 20 vol % acid.
The maximum recoveries of Cu and Te were 88 and
78%, respectively, at 20 vol % sulfuric acid.
Effect of Time. It was found that the recoveries of Cu,
Se, Te, and Au almost reached their maxima in 30 min
of leaching at 80 C. However, the faster rate of recovery
of the metals resulted in difficulty in determining the
reaction kinetics at 80 C. Therefore, leaching experiments in the presence of manganese dioxide and sodium
chloride were performed at 30, 40, and 50 C for
different durations. Table 3 shows the leaching recoveries of the metals at 30, 40, and 50 C. The extraction of
the metals increased with increasing time of leaching
at different temperatures. It can be observed that the
maximum recoveries of Se, Te, and Au were 70, 70, and
71%, respectively, at 30 C. At 40 C, the recoveries of
the metals increased to 75% Se, 74% Te, and 77% Au.

Ind. Eng. Chem. Res., Vol. 41, No. 25, 2002 6597

Figure 8. Leaching kinetics for Se.

Figure 9. Leaching kinetics for Te.

Table 3. Effect of Time at Various Temperatures on

Recoveries of Metals
temp ) 30 C

temp ) 40 C

% recovery

% recovery

time
(min) Cu
5
15
25
35
40

70
78
83
85
86

Se

Te

30.2
50.8
63.3
67
70

25.4
46.5
59.5
66.8
70.4

Au Cu
29
52
63
69
71

72.4
79.3
86.7
87.7
88.9

Se

Te

39.2
56
66
73
75

36.3
53.4
64
72.7
73.8

temp ) 50 C
% recovery
Au Cu
37
56
68
74
77

81.6
86
88.8
91.2
91

Se

Te

Au

44
63.1
71.7
79
80

53.7
68.9
76
79
78

49
70
77
77
77

There were further improvements in the recoveries of

these metals at 50 C. An increase in extraction of Se
from 44% in 5 min to 80% in 40 min of leaching was
observed at this temperature. However, the recoveries
of Te and Au became constant at 50 C after 30 and 20
min of leaching, respectively. They were 79% Te and
77% Au.
It was also found that significant amounts of copper
were extracted in leaching at 30, 40, and 50 C (Table
3). At 30 C, in 5 min of leaching, 70% of the copper
was leached out, and the extraction increased with time
to 86% in 40 min of leaching. The recovery increased to
89% in 40 min when the leaching was performed at 40
C. At 50 C, the maximum recovery of 91% Cu was
obtained after 35 min of leaching, and it remained
constant upon further increases in the time of leaching.
Kinetics of Leaching. Attempts were made to determine the dissolution kinetics of Se, Te, and Au in the
leaching of anode slime with both manganese dioxide
and sodium chloride addition in terms of the shrinkingcore model. From the experimental results (Table 3) for
Se, Te, and Au, it was found that the data could be best
fitted according to the ash diffusion control model, i.e.,
1 - 3(1 - x)2/3 + 2(1 - x) t. However, the experimental
data for copper (Table 3) revealed that the mixed control
model, i.e., chemical reaction control [1 - (1 - x)1/3 t]
with ash diffusion control [1 - 3(1 - x)2/3 + 2(1 - x)
t], is fitted well.
The kinetics plots for Se, Te, Au, and Cu at all the
three temperatures (30, 40, and 50 C) are shown in
Figures 8-11. During the leaching process insoluble
silver chloride was formed, and this product layer might
have contributed to the ash diffusion reaction kinetics
of Se, Te, and Au. This was further confirmed by
examining the leached residue under scanning electron
microscope with EDX studies. The SEM micrographs
of leached anode slimes are shown in Figures 12 and
13.
To calculate the activation energy, the values of ln
Kp, where Kp ) [1 - 3(1 - x)2/3 + 2(1 - x)]/t, were plotted

Figure 10. Leaching kinetics for Au.

Figure 11. Leaching kinetics for Cu.

against 1/T (Arrhenius plot) in Figure 14 for Se, Te, and

Au. The activation energies of the overall reactions were
calculated to be about 1.95 kcal/mol for Se, 3.65 kcal/
mol for Te, and 3.89 kcal/mol for Au. The activation
energy value of a diffusion-controlled process is generally in the range of 1-3 kcal/mol.19 Therefore, this
further confirms that the sulfuric acid leaching of Se,
Te, and Au from anode slime in the presence of MnO2
and NaCl follows ash diffusion control reaction kinetics.
4. Conclusions
1. Sulfuric acid leaching of anode slime without any
additive results in poor recoveries of metals (Ni, Se, Te,
Au, and Ag) other than Cu.

6598

Ind. Eng. Chem. Res., Vol. 41, No. 25, 2002

79% Te, and 77% Au were observed after 40 min of

leaching at 50 C.
5. The reaction kinetics of Se, Te, and Au follow the
ash diffusion control model in sulfuric acid leaching
using both MnO2 and NaCl additives. SEM-EDX studies
confirm that the porous silver chloride product layer
formed during leaching contributes the ash diffusion
control kinetics. The reaction kinetics of Cu follows the
mixed control model.
6. The activation energies of the overall reactions are
found to be about 1.95 kcal/mol for Se, 3.65 kcal/mol
for Te, and 3.89 kcal/mol for Au.
Acknowledgment
Figure 12. SEM microstructure for the morphology of the residue
after leaching of anode slime with MnO2 and NaCl: (1) silver
selenide, (2) AgCl.

The authors are thankful to Shri Premchand, Head,

NFP Division, NML, Jamshedpur, India, for his advice
and help in various ways in carrying out this work.
Anode slime samples received from M/S ICC, Ghatsila,
India, are also thankfully acknowledged.
Literature Cited

Figure 13. SEM microstructure for the morphology of the residue

after leaching of anode slime with MnO2 and NaCl: (1) porous
structure of AgCl.

Figure 14. Arrhenius plots for Se, Te, and Au.

2. Leaching in sulfuric acid in the presence of MnO2

does not improve the recoveries of the metals significantly at room temperature, but at 80 C, maxima of
90% Cu, 42% Se, and 74% Te were recovered in 330 min
of leaching. The reaction kinetics for Se and Te at 80
C follow the ash diffusion control model.
3. Leaching of anode slime in sulfuric acid in the
presence of only NaCl does not improve the recovery of
the metals significantly.
4. With both MnO2 and NaCl addition in the sulfuric
acid leaching system, the recoveries of Cu, Se, Te, and
Au improve. Maximum recoveries of 91% Cu, 80% Se,

(1) Hoffmann, J. E. Processing slimes: The base case and

opportunities for improvement. JOM 1990, 42 (8), 38.
(2) Newton, Joseph; Wilson, C. L. Metallurgy of Copper; Chapman & Hall Ltd.: London, 1942.
(3) Dixon, C. P. Gold and silver refining at the electrolytic
refining and smelting company of Australia Ltd., Port Kembla,
N.S.W. In Mining and Metallurgical Practices in Australasia (The
Sir Maurice Mawley Memorial Volume); Woodcock, J. T., Ed.;
Monograph Series No. 10; The Australasian Institute of Mining
and Metallurgy: Parkvile, Victoria, Australia, 1980; pp 519-521.
(4) Dixon, C. P. Selinium recovery at the electrolytic refining
and smelting company of Australia Ltd., Port Kembla, N.S.W. In
Mining and Metallurgical Practices in Australasia (The Sir
Maurice Mawley Memorial Volume); Woodcock, J. T., Ed.; Monograph Series No. 10; The Australasian Institute of Mining and
Metallurgy: Parkvile, Victoria, Australia, 1980; pp 628-629.
(5) Jung, V.; Deierling, B.; Karl, R. Recovery of precious metals
from materials containing selenium, tellurium, arsenic and antimony. Chem. Abstr. 1983, 99, 198566z.
(6) Monahan, R. K.; Loewen, F. Treatment of anode slimes at
the Inco Copper Refinery. Presented at the Canadian Institute of
Mining and Metallurgy Annual Conference, Halifax, Nova Scotia,
Aug 1972.
(7) Tishchenko, A. A. Extraction of selenium and tellurium from
copper electrolytic slimes. Chem. Abstr. 1964, 61, 3955.
(8) Kunev, D.; Vasilev, Kh.; Chimbulev, M.; Karagozov, L.
Study of the sulfation roasting of electrolytic copper slimes.
Metallurgiya (sofia) 1977, 32 (8), 14-16; Chem. Abstr. 1978, 88,
64561.
(9) Cooper, W. C. The treatment of copper refinery anode slime.
JOM 1990, 42 (8), 45-49.
(10) Morrison, B. H. Slimes Treatment Process. U.S. Patent
4,047,939, Sep 13, 1977.
(11) Buketov, E. A.; et al. Shaft furnace sintering of electrolytic
copper slimes. Tsvetn. Met. 1965, 38 (4), 28-31; Chem. Abstr. 1966,
63, 12722.
(12) Shkodin, V. G.; Malyshev, V. P.; Evtyukhova, O. V.;
Malkov, V. E.; Galimova, S. A. Roasting-sintering of anode slimes
with soda in shaft furnaces. Tr. Ural. Nauch. Issled. Proekt. Inst.
Mednoi Prom 1969, 12, 204-208; Chem. Abstr. 1970, 72,
114078.
(13) Victorovich, G. S.; Bell, M. C.; Sridhar, R.; Raskauskas, J.
Novel soda ash process for the recovery of selenium from anode
slimes. Presented at the 109th AIME Annual Meeting, Las Vegas,
NV, Feb 24-28, 1980.
(14) Hoffmann, J. E. The wet chlorination of electrolytic
refinery slimes. JOM 1990, 42 (8), 50-54.
(15) Toraiwa, A.; Abe, Y. New hydrometallurgical process of
copper anode slimes at Saganoseki Smelter and Refinery. Presented at the Second International Conference on Processing
Materials for Properties, San Francisco, CA, Nov 5-8, 2000.

Ind. Eng. Chem. Res., Vol. 41, No. 25, 2002 6599
(16) Pourbaix, M. Atlas of Electrochemical Equilibrium in
Aqueous Solution; Pergamon Press: Oxford, U.K., 1966 (Translated by James A. Franklin).
(17) Majima, H.; Awakura, Y.; Yazaki, T.; Chikamori, Y. Acid
dissolution of cupric oxide. Met. Trans. 1980, 11B, 209-214.
(18) Morrison, B. H. Recovery of Silver and Gold from Refinery
Slimes at Canadian Copper Refiners. In Extractive Metallurgy
1985; The Institute of Mining and Metallurgy: London, 1985; pp
249-269.

(19) Habashi, F. Extractive Metallurgy, General Principles;

Gordon & Breach: New York, 1969; Vol. I.

Received for review April 1, 2002

Revised manuscript received September 11, 2002
Accepted September 13, 2002
IE020239J