REVIEW

Processing of copper electrorefining anode

slime: a review
J. Hait*1, R. K. Jana1 and S. K. Sanyal2
Anode slime is the insoluble product deposited at the bottom of the electrorefining tank during
electrorefining of copper. It generally contains Cu, Ni, Se, Te, Ag, Au, platinum group metals
(PGM), Pb, Ba, Fe, etc. Owing to the presence of valuable metals and metalloids in the anode
slime, numerous approaches have been made by the researchers to extract them following pyro-,
pyrohydro-, hydropyro-, hydrometallurgical, etc. routes. In the present paper the various
processing routes with the special emphasis on plant practice and precious metals recovery
from anode slime have been described systematically. Since the understanding of the process
chemistry is considerably aided by the formation and characterisation studies of the slime, these
Published by Maney Publishing (c) IOM Communications Ltd

aspects have also been included.

Keywords: Anode slime, Valuable metals, Metals recovery, Process

Introduction Formation of anode slime

During the dissolution of the anodes the impurities
Almost all copper in its final stage of production either
contained in them, depending on their physico-chemical
from ores or from concentrates is treated electrolytically.
characteristics, either dissolve in the electrolyte or are
The electrolysis is carried out for refining of impure
deposited on the bottom of the cell in the form of an
copper anodes to produce pure copper cathodes. An
insoluble precipitate, forming slime. Many of the
estimated amount of 12?4 million tonnes of Cu anode
impurities behave in two ways; they partly dissolve in
has been processed during 2005 (Green 2006). The
the electrolyte and partly precipitate in the slime. Some
copper anode contains many soluble and insoluble
of the impurities also pass into the cathodes in small
impurities. During the electrorefining insoluble anode
quantities. In addition to the insoluble impurities,
impurities, amounting about 3 to 5 kg/tonne of anode,
copper which falls from the anode in the form of light
fall to the bottom of the cell as slimes, which contain Cu,
scrap and copper compounds like Cu2O, Cu2Se and
Ni, Se, Te, Ag, Au, platinum group metals (PGM) along
Cu2Te and copper produced by the reaction:
with some amount of Fe, Pb, Ba, etc. The total amount
2CuzRCu2zzCu also pass into the slime (Isakov
of anode slime generated in the world is estimated to be
1970).
y55 000 t/year (Green 2006). Therefore, it is important
The distribution of copper and impurities between the
to recover the valuable metals from anode slime.
cathodes, electrolytes and slime depends on a number of
Extensive R&D work has been carried out on the
factors. The internal factors which affect the amount of
subjects which are reported in the literature. However,
slime include the type, concentration and form of
very few efforts, so far have been made to gather these
impurities which exist in the anode. The external factors
literature and to categorise them according to different
include the concentration of the dissolved oxygen and
processing routes for better understanding of extraction
the impurity ions in electrolyte and condition of
methods for recovering values from the slime. It is in this
electrolysis such as current density (Noguchi et al.
context in the present paper, it has been tried to
1991; Cifuentes et al. 1999). With increased current
categorise the different R&D work on anode slime density the amount of copper deposited in the slime
treatment according to the various processing routes like increases and in addition, a larger amount of impurities
pyrometallurgical, pyrohydrometallurgical hydropyro- passes into the cathode. A high electrolyte circulation
metallurgical, hydrometallurgical, etc. with their merits rate leads to an increase in the impurities deposited on
and demerits. Some literature on formation and the surface of the cathodes, particularly when large
characteristics of anode slimes have also been collected dendrites are present. The anode impurities show
and discussed as a prelude to the better understanding of different behaviour of dissolution state according to
the process chemistry involved in the processing anode the various forms of existence and the varying chemical
slime treatment. properties of these elements or compounds.

1
Metal Extraction and Forming Division, National Metallurgical Laboratory,
Characteristics of anode slime
Jamshedpur 831 007, CSIR, India At the time of electrorefining of copper from impure
2
Jadavpur University, Kolkata 700 032, India copper anode, impurities are deposited at the bottom of
*Corresponding author, email jhumesh@yahoo.com the refining cell. The low electrolyte temperature during

ß 2009 Institute of Materials, Minerals and Mining and The AusIMM

Published by Maney on behalf of the Institute and The AusIMM
Received 16 July 2007; accepted 16 August 2009 Mineral Processing and Extractive
240 DOI 10.1179/174328509X431463 Metallurgy (Trans. Inst. Min. Metall. C) 2009 VOL 118 NO 4
 Hait et al. Processing of copper electrorefining anode slime

refining can lead to the formation of a floating slime.
This slime adheres to the top parts of the anodes and
cathodes. At the end of the refining cycle, the anodes are
withdrawn and washed to recover the adherent anode
slimes. The refining cells are drained and the bottom
slimes also are collected. The slimes thereafter are water
washed to remove entrained electrolyte and sent to a
byproduct metals recovery plant for further processing
(Chen and Dutrizac 1988a).
The intricate physical, chemical and mineralogical
structures of the slimes present a challenging task to the
process engineers (Chen and Dutrizac 1990a). The
understanding of the process chemistry involved in
treatment of anode slimes depends considerably on these
characteristics of the slimes. Therefore, some informa-
tion on the characteristics of the anode slime have been
collected and presented in the following sections.
Chemical composition
Anode slimes are made up of those components of the
anodes which are not soluble in the electrolyte. They
contain copper, silver, gold, sulphur, selenium, tell-
Published by Maney Publishing (c) IOM Communications Ltd
the anode slimes washing steps employed (Chen and
Dutrizac 1988a, p. 97).
Mineralogical characteristics
Because of the finer, softer and water-soluble particles,
copper refinery slimes are difficult to be characterised as
the particles tend to lift out or dissolve from polished
sections during grinding and polishing (Chen and
Dutrizac 1990b). Despite the difficulties numerous
attempts have been made for the determination of
mineralogical phases in the anode slime. Some of the
important metal bearing phases detected in the anode
slime are Cu2Se, Ag2Se, Ag2Te, AgCuSe, Cu2O, NiO,
Cu–Ni–Sb, CuSO4.5H2O, CuSeO3.2H2O, SbAsO4,
PbSO4, etc.
A large number of selenide phases are present in the
raw anode slimes and these are the principal carriers of
Ag, Se and Te (Chen and Dutrizac 1988a, p. 97).
Selenium appears as ring like structures or broken
fragments of rings as well as compact masses often
associated with NiO. Sometimes the selenide spheroids
are hollow and sometimes the spheroid is filled with

urium, lead, arsenic, antimony, nickel, iron, silica, etc.
(Butts 1954; Hoffmann 1990; Newton 1942). However,
the composition varies from refinery to refinery depend-
ing upon the composition of the impure anode which in
turn depends upon the ore and other charged materials
added to the smelting furnace. It also depends upon the
extraction process. Some typical anode slime composi-
tion is shown in Table 1 (Cooper 1990).
Physical characteristics
The colour of the raw slimes is normally greyish black
and the particle size is about 200 mesh (BSS). Because of
the fine particle size involved, a siliceous filter aid is used
to improve filtration and part of this material inadver-
tently contaminates the slimes being processed. They are
three-dimensional and have smooth surfaces, round
edges, some of them having spherical shape and
crystalline structure, which favour their rapid deposition
on the bottom of the cell (Petkova 1990). The slimes of
the refining cell are agglomerated by phases such as
CuSO4.5H2O and Cu–Ni sulphates which persist despite
porous mass of elemental selenium (Chen and Dutrizac
1993a; Chen and Dutrizac 1993b). The silver in the raw
anode slimes occurs as Ag–Cu selenides. It is suggested
that silver dissolves during electrorefining and subse-
quently reacts rapidly with the Cu2Se particles in the
anode slimes layer (Petkova 1990). Silver enrichment
occurs at the expense of copper according to the
following reaction sequence (Chen and Dutrizac 1990c,
p. 293; Chen and Dutrizac 1989a; Chen and Dutrizac
1991a)
Cu2 SezxAgz ?(Cu2{x Agx )SezxCuz
(Cu2{x Agx )Sez(1{x)Agz ?AgCuSez(1{x)Cuz
AgCuSez(1{x)Agz ?(Ag2{x Cux )Sez(1{x)Cuz
(Ag2{x Cux )SezxAgz ?Ag2 SezxCuz
Most of the tellurium occurs dominantly in solid
solution in copper selenide (Chen and Dutrizac 1990a,

Table 1 Survey of anode slime composition in different refineries, wt-%

Refinery Cu Ag Au Pt Pd Se Te As Bi Sb Sn Pb Fe Ni

CCR (Noranda) 18.7 19.5 0.18 ... ... 10.0 1.2 1.14 0.77 1.68 ... 8.0 ... 0.67
Chuquicamata 27 12.0 0.07 ... ... 4 ... 5 ... 4 ... ... ... ...
Cu Refineries Pty 27 9.0 0.07 ... ... 0.7 0.03 5.8 0.25 0.45 ... 7.5 0.15 0.6
ER & S, Australia 13 9.0 0.10 ... 0.09 5.8 0.2 1.2 0.3 3 5.0 31.0 ... 2.0
El Salvador, Chile 5 24.0 1.4 ... ... 21 ... 0.7 ... 3 ... ... ... ...
Hibi Kyodo Co. Ltd, Tamano Smelter 21.5 9.6 0.50 ... ... ... ... ... ... ... ... 22.7 ... ...
IMI Refinery, UK 14 5.5 0.07 0.004 0.008 2 0.6 3.5 0.5 3.5 5 22 ... 9
Inco 21.0 6.37 0.12 ... ... 8.4 1.8 0.50 0.14 0.09 ... 1.7 ... 17.0
Indian Copper Complex, Ghatsila, India 12.29 1.54 0.1 ... ... 10.50 3.38 0.036 ... 0.01 ... 0.16 0.29 36.76
Kidd Creek 26.0 12.7 0.15 ... ... 19.5 0.05 0.45 0.28 0.09 ... 22 ... 0.03
Metallurgie Hoboken Overpelt 17.4 17.2 ... ... ... 5.1 0.95 6.8 0.74 6.8 0.35 23.2 ... ...
Mhangura Copper, Zimbabwe* 2 62 1.0 0.05 0.01 10 1.0 0.16 0.13 0.07 0.15 1.8 0.1 0.3
Minero Peru 41.0 20.0 0.04 ... ... 11 1.1 ... ... ... ... ... ... ...
Outokumpu* 8.5 16.8 0.3 ... ... 46 ... ... ... ... ... 8.0 ... 5.7
Palabora 53.4 7.8 0.33 0.05 0.07 3.6 2.2 0.15 0.01 ... ... ... ... 4.5
Phelps Dodge, El Paso 27.1 12.2 0.12 0.0007 0.006 8.8 3.1 1.7 ... 0.66 ... 4.65 0.08 0.64
Rabak, Turkey 24.7 4.8 0.11 0.0005 0.002 7.9 3.0 2.3 0.5 ... ... ... ... 0.05
Sakuysan, Turkey 26.7 4.73 0.10 ... ... 7.6 2.5 3.6 ... 1.3 ... 1.7 ... 0.82
Southwire, Georgia 10.0 4.1 0.02 0.08 0.35 0.6 ... 1.4 0.5 9.4 5.3 13.1 ... 8.4
*Composition of decopperised anode slime.

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2009 VOL 118 NO 4 241
 Hait et al. Processing of copper electrorefining anode slime
p. 39). The attempts to observe gold silver telluride and
copper telluride were unsuccessful, probably because of
the extremely small amounts present although the
elements have been found by chemical analysis (Zhou
et al. 1998). As the selenides become enriched in silver,
part of the tellurium remains in the Ag–Cu-selenides
(Chen and Dutrizac 1990c, p. 293), but part of this
seems to separate as discrete porous masses of Ag2Te
(Chen and Dutrizac 1988a, p. 97; Chen and Dutrizac
1990a, p. 39). Gold particles are rarely observed in
polished section mounts. Metallic gold particles are
found to be present in CuSO4.5H2O and in the oxidate
phase. The gold grains are usually rounded or spher-
oidal in contrast to the spike-like gold grains attached to
the selenides (Chen and Dutrizac 1990a, p. 39). Nickel in
the anode slime may be found in the form of NiO,
(Cu,Ni)SO4.5H2O or Kupferglimmer, a Cu–Ni–Sb oxide
(Chen and Dutrizac 1988b; Chen and Dutrizac 1989b;
Chen and Dutrizac 1990d; Chen and Dutrizac 1990e;
Forsen and Tikkanen 1982). BaSO4 originating from the
mould wash are simply liberated from the copper anode
during electrorefining and accumulates in the slimes
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layer (Chen and Dutrizac 1999). The most abundant
silicate species are silica gel, silica gel impregnated
copper sulphate and oxidate matrix phase, quartz and
K–Al silicate (Chen and Dutrizac 1991b, p. 173).
Anode slime processing
Anode slimes almost invariably contain Se, Te, Cu, Ag,
Au and traces of PGM. These elements normally
determine the sequence of processing steps for recover-
ing the metal values from slimes. Mostly the order of
recovery is Cu, Se, Te, Ag, Au and PGM. However, the
characteristics of anode slime also determines the metal
removal steps.
The production of precious and other technologically
important metals from copper anode slime is compli-
cated by the many components present in the slimes.
The precise constitution and impurities of the slimes is
determined by the original copper ore, the pyrometal-
lurgical processing treatments and the electrolytic
refining conditions. The first step in the treatment is
invariably decopperising. The decopperising process
normally eliminates most of the copper, the extent of
tellurium removal is often low and erratic. One possible
explanation for the low tellurium extractions is the
formation of refractory Te compounds in the slimes
layer. Preliminary studies have shown that the selenide-
telluride phases undergo extensive alteration in the
slimes layer and that some oxidation of the Se and Te
can occur. Therefore, it can be concluded that the
mineral forms of Te in the raw anode slimes impact on
the subsequent slime processing operations (Chen and
Dutrizac 1996). Presence of high amount of lead in the
anode slime also affects the processing step in the slime
treatment process. The Pb content necessitates a
modified slime treatment process which involves a
deleading operation after decopperising the slime
(Chen and Dutrizac 1993a). Similarly the presence of
NiO greatly complicates the subsequent processing of
the anode slimes. Nickel oxide is refractory and
conventional decoppering technologies are not effective
in solubilising the NiO. The presence of Kupferglimmer,
a Cu–Ni–Sb oxide is considered undesirable as this
phase either forms a refractory constituent or generates
242 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
float slimes which can contaminate the cathode product
(Chen and Dutrizac 1989b, Chen and Dutrizac 1988c).
Silica gel precipitates in the anode slimes complicates the
eventual recovery of the precious metals contained in
this phase. Furthermore, the silica content of the anode
slimes adds to the volume of the Dore furnace slag
generated during subsequent processing of the anode
slimes. The slag is recycled to the copper smelter and
contributes to the total inventory of the precious metals
(Chen and Dutrizac 1991b). Presence of high percentage
of barium sulphate in the slimes also causes considerable
extra problems in the recovery processes (Razavizadeh
and Gee 1989).
With the diversity in the raw materials, compositions
and characteristics each refinery has developed a slimes
treatment process suited to its own needs. However, the
objectives of any slimes treatment process should be
(Morrison 1985):
(i) maximum recovery of precious metals
(ii) minimum process steps to reduce the inventory
of metals being processed
(iii) clean separations of minor economic elements
such as selenium and tellurium
(iv) minimum environmental impact in gaseous or
liquid effluents
(v) economy of reagents and energy.
The traditional process steps including soda roasting,
selenium leaching, copper leaching, smelting, refining
and silver and gold electrolysis have problems like dust,
acid mist and selenium emissions which affect the internal
working environment as well as the external environment
(Ludvigsson and Larsson 2003). The byproduction of
sulphuric acid is also the troublesome aspect of the
roasting process because the economic marketing of
sulphuric acid depends strongly on site location.
Furthermore, even though the gas emission regulations
are followed harmful SO2 may be released (Amer 2002).
However, several improvements in the process have been
tried and made giving special emphasis on environmental
aspects and results. During mid-1980s a wet chemical
chlorination method replaced the gold electrolysis process
with a new gas cleaning system in which both chlorine gas
and sulphur dioxide gas were taken to separate absorption
tower. A few years ago the introduction of the Kaldo
furnace technology and a wet gas cleaning system for the
process gases has significantly improved the working
environment and substantially reduced emissions from the
precious metals plant to the atmosphere (Ludvigsson and
Larsson 2003). Among the methods of the processing of
copper anode slimes two of them have been widely used
on an industrial scale, namely roasting and pressure
leaching. The advantages of the roasting processes are:
simplicity and the available know-how worldwide. On the
other hand pressure leaching generally results in high
degree of extraction with the fact that the wastes can be
confined as stable solids (Amer 2002).
Depending on the industrial interest and applications
there are numerous approaches for the treatment of
anode slimes from electrolytic copper refining. Although
it is difficult to categorise distinctly these approaches
according to various metallurgical process routes, some
efforts have been made here to describe them in a
systematic way. The approaches may be broadly
classified into six categories:
(i) pyrometallurgical processing
2009 VOL 118 NO 4

(ii) pyro-pretreatment followed by hydrometallur-
gical processing
(iii) pyro-hydropretreatment followed by pyrome-
tallurgical processing
(iv) hydro-pretreatment followed by pyrometallur-
gical processing
(v) hydro-pyro-hydrometallurgical processing
(vi) hydrometallurgical processing.
The various processes under each of these categories are
discussed below.
Pyrometallurgical process
Direct smelting, one of the earliest methods is no longer
used unless the copper content is very low (Butts 1954).
The only known pyrometallurgical process exists is the
slimes smelted in Dore furnace with selenium recovered
from the flue gases followed by soda-nitre treatment
(Dixon 1980a; Dixon 1980b).
Makhmetov et al. (1980) tried to use lime and red mud
as additives in the oxidative roasting of copper anode
slimes. The resulted calcine was then melted in a
reverberatory furnace for the recovery of the dore alloy.
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The traditional pyrometallurgical method utilising
oxidation in a reverberatory furnace has numerous
shortcomings. Keeping in view of that, deep-bath
intensive smelting methods have been developed for
use in the larger refineries. The slime smelting is
superficially similar to copper converting. But it has
many unique features (Barbante 1994) which includes
the recovery of silver and gold from a selenium rich
material and use of air rather than pure oxygen
significantly affected only the selenium content of the
slag, reducing it to low levels.
Pyro-pretreatment hydrometallurgical process
Sometimes anode slimes are pretreated before the next
stage of processing. Sulphatising roast and oxidising
roast are the two pyrometallurgical based pretreatment
methods for anode slime processing.
Sulphatising roast
In the sulphatising roast (Monahan and Loewen 1972;
Hoffmann et al. 1976; Kunev et al. 1978; Tishchenko
1964) where sulphuric acid in presence of air is used,
sulphatisation of the base metals and oxidisation of
selenium and tellurium occur. Selenium is volatilised as
SeO2 and passes into scrubbers where it is converted to
selenious acid.
MSez4H2 SO4 ?MSO4 zSeO2 z3SO2 z3SO2 z4H2 O
An advantage of this process is that the sulphur dioxide
produced in the roast, reduces the selenious acid in the
scrubber solution to elemental selenium and the
sulphuric acid consumed in the roasting is regenerated
(Hoffmann 1984). However, there may be a possibility
of escaping SO2 to atmosphere if much care has not been
taken. The amount of SO2 produced should be adjusted
with the requirement of the selenium to get reduced. The
demerit of the process is that it is not well suited to
operations where large quantities of high selenium
slimes are treated (Hyvarinen et al. 1984).
Oxidising roast
The oxidising roast of anode slimes converts copper,
nickel and tellurium into acid soluble forms. The
roasting of granulated slimes in a shaft furnace at a
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
Hait et al. Processing of copper electrorefining anode slime
temperature range of 700–800uC results in the removal
of greater than 95% of the selenium as SeO2 (Greiver
1974; Titarenko et al. 1976), according to the following
reactions
Cu2 Sez2O2 ?2CuO:SeO2 (300{5000 C)
2CuO:SeO2 ?2CuOzSeO2 (500{6000 C)
2Ag2 Sez3O2 ?2Ag2 SeO3 (300{5500 C)
2Ag2 SeO3 ?4Agz2SeO2 zO2 (500{6500 C)
The gas stream is then scrubbed in a solution of NaOH
or Na2CO3 to recover selenium. It is recovered in the
form of Na2SeO3 according to the reaction
SeO2 zNaOH~Na2 SeO3 zH2 O
SeO2 zNa2 CO3 ~Na2 SeO3 zCO2
Oxidation roasting can also be used as a means of
eliminating selenium following sulphuric acid leaching
of the slimes (Morrison 1997).
The above pyro-pretreatment processes are generally
followed by hydrometallurgical treatment. Some pyro-
hydrometallurgical processings of anode slime are
described below.
Treatment in Daye Smelter
Pyro-hydrometallurgical route for slime treatment has
been adopted in the smelter of Daye Non-ferrous Metals
Company, China (Shijun and Youzheng 1998). The
process includes:
(i) sulphation roasting of anode slime, adsorption
and reduction of Se in scrubber, leaching of
copper and tellurium using sulphuric acid,
cementing Te with copper dust, separating Au
from leached residue by chlorination, precipitat-
ing Au with oxalic acid followed by electrorefin-
ing gold dust and casting it into Au-bullion
(ii) cementation of Pd and Pt by adding Zn dust into
Au separated solution, separating Ag from
solution with sodium sulphite, reducing Ag with
formaldehyde followed by electrorefining Ag dust
and finally casting it into Ag-bullion.
Production practice proves that the above process is
simpler and the process does not require much invest-
ment. The metals recoveries are high. But in this process,
the separation of Se and Te from the slime is difficult in
one stage. The direct recovery of Au and Ag is also low
and is hard to be improved. Au and Ag contents in final
residue are still high after treating the recycled Ag
separated residue and Pt and Pd concentrates cemented
by adding Zn dust into Au precipitated solution contain
relatively high Se and Te.
In some cases pyro-pretreatment is carried out after
initial hydrometallurgical treatment of anode slime.
Soda roasting is one such example, which is carried
out after sulphuric acid leaching of the slime.
Soda roast
The roasting of anode slimes with sodium carbonate has
been designed to effect the conversion of selenium to
water soluble sodium selenite and selenate (Buketov et
al. 1965; Shkodin et al. 1970; Victorovich et al. 1980).
The treatment is carried out after an initial sulphuric
2009 VOL 118 NO 4 243
 Hait et al. Processing of copper electrorefining anode slime
Published by Maney Publishing (c) IOM Communications Ltd
1 Slimes treatment flow sheet at SMM
acid leach of the slimes to remove copper and tellurium.
M2 SezNa2 CO3 zO2 ?2MzNa2 SeO3 zCO2
Although this approach dispenses with the need for gas
scrubbers, it has the disadvantage of having to recover
the selenium by the reduction of hexavalent selenium.
The behaviour of selenides in soda roasting is dependent
on the temperature and the sodium carbonate addition.
Other pyro-pretreatment hydrometallurgical processes
Jung et al. (J1983) proposed a method for the recovery
of Se, Te, Au and Ag from anode slimes by oxidising
roasting with 30–50% KNO3 at 400–450uC in a rotary
kiln. The roasting resulted in the formation of K-
selenate, tellurate, arsenate and antimonate. The method
also includes leaching at 80–100uC with dilute H2SO4,
precipitation of Se and Te from the mother liquor with
SO2 and recovery of precious metals from the leaching
residue. The metal recovery sequence in this process is
Se, Te, Ag and Au. The advantage of the process is the
recovery of Se and Te without any hazardous gaseous
emission.
Pyro-hydro-pretreatment pyrometallurgical
process
Sometimes for the processing of anode slime, pyrome-
tallurgical treatment is carried out after hydrometallur-
gical treatment which is preceded by pyro-pretreatment.
This sequence is adopted to recover selenium and copper
from anode slime before the recovery of other metals.
Anode slime is subjected to oxidising roasting for
selenium recovery and then sulphuric acid leaching of
the calcine for copper recovery. One such example is the
process followed in Niihama Copper Refinery of
Sumitomo, Japan.
Sumitomo process
The Niihama Copper Refinery of Sumitomo Metal
Mining Co. Ltd (SMM), Japan has developed an
244 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
efficient method (Shkodin et al. 1970), to recover
valuable metals from anode slimes and advanced
techniques to process the recovered materials. The raw
slimes treated at the Niihama Refinery are the copper
anode slimes generated at this and the Toyo Copper
Refinery. The process (Fig. 1) comprises:
(i) selenium and copper elimination
(ii) reductive smelting to produce bullion
(iii) dore metal or silver anode production
(iv) silver electrolysis
(v) gold electrorefining after some treatments of
silver anode slimes.
Metals recovery from secondary copper anode slime
The copper anode slime produced from anodes prepared
from recycled scrap copper is generally known as
secondary anode slime. This contains only negligible
quantities of selenium and tellurium but appreciable
quantities of tin, lead, antimony, gold, silver and nickel
(Bayraktar and Garner 1985). This type of anode slime
is first sulphatised with sulphuric acid to extract copper
and nickel. While copper is readily sulphatised in all
cases, nickel sulphation requires slightly more vigorous
conditions of baking temperature 175uC and the acid
strength of 70% H2SO4. Impurities like arsenic, anti-
mony and silver present in the copper and nickel
solutions are removed. After removal of copper, nickel
and arsenic by sulphation, the residue is processed by
alkali fusion and subsequently water leaching is done
under conditions favouring tin extraction. The solid
residue containing Au, Ag and Pb can be treated by
pyrometallurgical techniques. This process takes care of
recovery of precious metals even though there is high
amount of tin.
Hydro-pyrometallurgical process
In a majority of anode slime processing, sulphuric acid
leaching is performed with/without oxygen (Vzorodov et
al. 1982, Subramanian et al. 1980; Nippon Shin Kinzoku
1981; Savin 1965; Yildirim and Bor 1985, Decker and
Peteghem 1976) as an initial step followed by pyrome-
tallurgical treatment.
Figure 2 is a generalised flowsheet for anode slimes
treatment using sulphuric acid leach followed by an
oxidising roast. Further a furnace treatment is carried
out to the decopperised, partially deselenised and
detellurised slimes to produce dore metal. This com-
bined hydro-pyrometallurgical process appears to offer
the best solution to the processing of anode slimes and
has been the conventional approach. However, the
deficiencies inherent in this approach have directed
attention towards a simplification of the process in terms
of a direct pyrometallurgical treatment of the decop-
perised and detellurised slimes. The slimes from which
copper and tellurium had been extracted by a sulphuric
acid leach, were melted in a rotary kiln with sodium
nitrate, sodium carbonate and borax. The so-called
prealloy containing 75–95% Ag and Au was oxidised
with air to give dore metal containing 98% combined
silver and gold (Cooper 1990).
Hydro-pyrometallurgical routes followed in some of
the industries are described below.
Outokumpu process
The treatment of anode slime at Outokumpu Pori
Copper Refinery (Jarvinen 2000; Hyvarinen et al. 1984)
2009 VOL 118 NO 4

2 Generalised flow sheet for anode slimes treatment
Published by Maney Publishing (c) IOM Communications Ltd
using H2SO4 leaching and oxidising roasting
comprises the following process stages: the slime is first
treated in the autoclave for the removal of copper and
nickel. The batch from the autoclave is emptied into the
flash tank where silver and selenium can be precipitated
with SO2 gas. The solution is then filtered and the liquid
is led into the tellurium tank, where the tellurium can be
precipitated with copper. For selenium recovery the
slime from the flash tank is put into the roasting furnace
and selenium is obtained from the gases with water and
SO2 gas. The deselenised slime is fed into the TROF
(tilting rotating oxyfuel) converter with fluxes soda and
borax. In the converter two separate layers of slag and
dore metal are formed. The dore metal is cast to anodes
for the silver electrolysis. Gold is recovered from the
gold mud with the quick hydrochloric acid leaching
process. The important point in the leaching is to get
into contact the solid copper with the oxygen and liquid.
Outokumpu has an efficient agitator for this purpose.
The GLS-agitator (gas, liquid and solid) is powerful for
mixing oxygen, liquid and solid together. The current
production in Pori plant is 40 000 kg silver, 5000 kg
gold, 40 000 kg selenium and 100 kg platinum-palla-
dium concentrate.
Treatment at Norddeutsche Affinerie
The anode slime produced during copper refining are
leached with sulphuric acid to extract copper, nickel,
tellurium and arsenic. After drying they are melted and
oxidised to remove the impurities, to recover selenium
and to collect the precious metals in the form of silver
dore in a final cupellation process. Silver dore is treated
in a precious metal refinery to high quality Ag and Au
(Morrison 1989).
Treatment at Canadian Copper Refiners
At Canadian Copper Refiners Ltd (CCR, Montreal
East, Quebec, Canada) the caustic pressure leach was
developed to the pilot plant stage for slimes relatively
rich in selenium and tellurium contents (Plitzko 2001;
Morrison 1963; Lux et al. 1978). The caustic pressure
leach as the first step in slimes processing resulted in the
solubilisation of selenium; copper and tellurium were
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
Hait et al. Processing of copper electrorefining anode slime
3 Slimes treatment flow sheet at CCR
removed in a second step leaching. However, the process
had a number of short-comings, including the oxidation
of 10–15% of the selenium to the selenate form, thereby
necessitating two separate selenium reduction steps.
Complications associated with a caustic pressure leach,
specially with regard to the recovery of selenium, were a
major deterrent to the use of this approach on an
industrial scale. Therefore, use of caustic pressure
leaching among the major copper refineries has hardly
been practiced (Zarate and Gonzalez 1988).
Owing to the above reasons, an alternative process
was developed and this is shown schematically in Fig. 3
(Morrison 1985).
Here, the objective of oxygen-pressure leach is to
extract the maximum amount of copper and tellurium
without attacking selenium or silver. The semi-dry
leached slimes are then blended with purchased or tolled
slimes and 8% bentonite for pelletising. The resulting
green pellets are roasted at a temperature of 650uC
before charging them to the top blown rotary converter
where smelting is performed at a temperature .950uC.
Roasting of the green pellets is performed only for
converting Ag2Se to Ag2SeO3 form. During smelting the
melt is stirred at 1185uC for reducing the volatilisation
of lead so that lead compounds can be skimmed off in
the slag phase, leaving a silver selenide matte phase
which contains practically all of the precious metals.
After the lead converting stage, blowing of the matte
with oxygen volatilises selenium as the oxide. The
resulting dore metal is processed to recover silver, gold
and PGM (Cooper 1990). The process appears to have
several advantages over more conventional slime treat-
ment technologies. A separate roasting step for selenium
removal is not required. The tie-up of precious metals in
the refractories is greatly reduced and the time required
for slimes treatment in top blown rotary converter is
found to be quite favourable. Thus significant savings in
energy and labour costs are realised with the corre-
sponding increase in plant capacity.
2009 VOL 118 NO 4 245
 Hait et al. Processing of copper electrorefining anode slime
Published by Maney Publishing (c) IOM Communications Ltd

4 Flow sheet of new ferric leaching process: slimes treat-

ment at Hitachi Smelter

Treatment at the Hitachi Smelter and Refinery

A simple flowsheet to treat the anode slime by ferric
leaching process is shown in Fig. 4 (Sato et al. 1976). In
this process after copper removal by ferric sulphate 5 Slimes treatment flow sheet at Indian Copper Complex
leaching selenium removal was performed in a conveyer
type roaster to obtain a better quality selenium dioxide. leached for producing noble metals concentrate. This
The roasted slime was then melted in an electric furnace. treatment allows the separation and recovery of all the
valuable anode slimes components in high grade
Treatment at Indian Copper Complex, Ghatsila
fractions. The advantages of ammoniacal leaching over
At the Indian Copper Complex, Ghatsila, a constituent acidic leaching include fast dissolution of copper,
unit of Hindustan Copper Ltd, a precious metals plant complete iron rejection and non-demanding materials
for treating around 70 Mt/annum of anode slime was in requirements. The selective ammoniacal pressure leach-
operation based on a technology essentially supplied by ing of raw anode slimes extracts all of the copper and
M/S Outokumpu, Finland and based on an in house much of the selenium content of the feed. In the leaching
R&D effort (Sahu et al. 1989; Mohanty et al. 1982). of slimes containing 22%Pb in ammoniacal ammonium
Figure 5 depicts the main steps for processing the anode carbonate solution at 75uC and 350 KPa oxygen partial
slime. pressure with very short retention time of ,10 min, the
The anode slime treatment covers initial dilute acid investigators found that .99?5%Cu, .65%Se and
leaching for copper extraction followed by concentrated
acid leaching for nickel extraction. The residue from
furnace after selenium extraction is used for recovery of
precious metal, e.g. silver and gold.
Very recently Indian Copper Complex (ICC) has
stopped the processing of anode slime generated at their
plant. Now it is being sold to outside party.

Hydro-pyro-hydrometallurgical process
A novel process (Tan and Bedard 1988) (Fig. 6) is
developed based on the ammoniacal leaching of raw
copper refinery anode slime as an initial step whereby
copper and selenium are extracted selectively under mild
conditions and with short retention times. The ammo-
niacal pressure leaching is followed by soda ash roasting
in the next step and the roasted product is subsequently 6 Flow sheet based on ammoniacal pretreatment

246 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2009 VOL 118 NO 4
 Hait et al. Processing of copper electrorefining anode slime

,1%Ag were dissolved (Cooper 1990; Tan and Bedard
1989) Appreciable amounts of Ag are solubilised only at
higher temperatures and pressures and at retention times
greater than 1 h. The low dissolution of silver in this
process is desirable (Tan 1987) as explosive silver
compounds can form in the presence of potassium
hydroxide under conditions of no agitation, high purity
soluble silver species and concentrated ammonia. This
process produces a high grade noble metal concentrates.
However, the treatment profoundly alters the structure
of the slimes under very mild conditions. The proposed
ammoniacal pressure leaching step is reliable and
predictable, is flexible enough to accommodate large
variations in feed materials and is efficient in decopper-
ing and deselenising copper refinery anode slimes. It
opens up a whole spectrum of compatible byproduct
purification and recovery options. The clean separations
achieved in this process show that complicated flow-
sheets and noble metal recycle schemes are no longer
required. As a result, the associated problems of long
overall retention times, large process inventories and
poor byproduct grades and recoveries are eliminated.
Published by Maney Publishing (c) IOM Communications Ltd
themselves. The dissolution of copper from anode slime
in sulphuric acid solution with/without oxygen medium
is the most common process (Donmez et al. 1998).
Virtually all hydrometallurgical slimes processing tech-
nologies, including wet chlorination, address the extrac-
tion of selenium first. However, none of the reagents is
sufficiently aggressive to attack all the valuable con-
stituents in slimes at a time.
Some important hydrometallurgical processes are
described below.
Chlorination process
A number of studies have been carried out on the
chlorination of anode slimes (Cooper 1989). Chlorine
and chlorine-bearing oxidants are sufficiently aggressive
that most of the metallic constituents in the slimes,
irrespective of the form in which they are present, are
oxidised and converted to their chlorides (Hoffmann
1990). The basic concept in this approach is to separate
certain elements (notably selenium and silver) as
chlorides by the following reactions (Cooper 1990)

Recently a hydro-pyrometallurgical process has been Ag2 Sez3Cl2 ?2AgCl;zSeCl4

proposed for treatment of anode slimes obtained from
Egyptian copper electrorefining plant. The proposed SeCl4 z3H2 O?H2 SeO3 z4HCl
process consists of two leaching stages for extraction of
The copper remaining in the slimes reacts stepwise with
copper in sulphuric acid medium and silver in thiourea
chlorine first producing cuprous chloride then oxidising
leaching followed by pyrometallurgical treatment of the
it to cupric chloride.
remaining slimes for production of Pb–Sn soldering
alloy (Amer 2003). 2CuzCl2 ~Cu2 Cl2
Hydrometallurgical process
The pyrometallurgical treatment for recovering precious Cu2 Cl2 zCl2 ~2CuCl2
metals from anode slime is becoming more difficult to The other metals react with chlorine in the following
operate due to rising energy costs and strict pollution manners
regulations. The smelting and refining cycle require to
produce the bullion, which creates large in-process Sez2Cl2 ~SeCl4
inventories of precious metals and result in substantial
recycles of precious metal bearing slags. The smelting of Tez2Cl2 ~TeCl4
slimes also creates emission problems (Hoffmann 1994;
Ludvigsson and Larsson 2003). Selenium in particular is 3H2 OzSeCl4 ~H2 SeO3 z4HCl
largely volatilised, and because of its highly hydrophobic
nature, requires very high energy scrubbing techniques
to achieve acceptable levels in the final gaseous effluents 3H2 OzTeCl4 ~H2 TeO3 z4HCl
exiting the smelting operation. Recent improvements in
smelting technology, such as the use of a top-blown H2 SeO3 zCl2 zH2 O~H2 SeO4 z2HCl
rotary converter, have reduced smelting time substan-
tially. The use of complex, sophisticated, high energy H2 TeO3 zCl2 zH2 O~H2 TeO4 z2HCl
scrubbing system has reduced the environmental burden
of the smelting processes. However, a number of 2Auz3Cl2 ~2AuCl3
problems still exists, including the costly recycle of
precious metals in slag and high in-process inventories of
AuCl3 zHCl~HAuCl4
precious metals (Hoffmann 1990). Therefore, to over-
come these problems evolution of hydrometallurgical
process took place. The hydrometallurgical processing Ptz2HClz2Cl2 ~H2 PtCl6
of copper anode slimes has the advantages such as costs
are relatively low when compared to those for a smelter, Pdz2HClzCl2 ~H2 Pd Cl4
process may be applied to small and large operations, air
pollution by sulphur dioxide is eliminated, equipment 2AgzCl2 ~2AgCl
may be designed and installed in modules (Amer 2002).
A number of lixiviants are employed in the various PbSO4 z4HCl~H2 PbCl4 zH2 SO4
hydrometallurgical processes. These include sulphuric
acid, nitric acid, sodium hydroxide, etc. The process can The slimes chlorination process embodies of a number
be carried at normal temperature and pressure and at of unit processes. The unit processes employed are
elevated temperature and pressure. The nature of the oxidising/chlorination leach, selenium and gold reduc-
process is dictated by the composition of the slimes tion, selenium fluxing and distillation, gold recovery and

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2009 VOL 118 NO 4 247
 Hait et al. Processing of copper electrorefining anode slime
7 Wet chlorination of slimes
purification, PGM collection and recycle, tellurium pre-
cipitation, platinum and palladium recovery, silver reduc-
tion and recovery, and effluent disposal. In both the
oxidising leach and the subsequent wet chlorination,
several oxidant choices are available. These include
chlorine, hydrogen peroxide/hydrochloric acid and sodium
chlorate/hydrochloric acid. The oxidising leach is per-
Published by Maney Publishing (c) IOM Communications Ltd
formed with agitation to dissolve copper, arsenic and
antimony. Wet chlorination/oxidation (Fig. 7) is per-
formed with heating and agitation to oxidise and dissolve
selenium, tellurium, gold and PGM. However, silver is
converted to silver chloride. In the next step gold and
selenium are selectively precipitated by addition of the
stoicheometric amount of sulphur dioxide from which
highly pure (99?99%) selenium and gold (99?99% pure) can
be produced. This is followed by ammonium hydroxide
leaching for silver chloride extraction. The silver chloride is
converted to silver oxide which is reduced to silver in the
final step (Hoffmann 1990). The process has the advantage
of having modest reagent consumption and easily con-
trolled effluent streams. In spite of the advantages provided
by the wet chlorination of slime constituents, it gives rise to
a complex mixture of chlorides which has to be processed
to recover the remaining values (Hoffmann 1984).
As early as the first half of 1980s, wet chloridising
process for treating copper anode slime had been used
successfully in copper smelters in Yunan Smelter and
Fuchunjiang Smelter (Li et al. 1998).
Oxidative leaching treatment in a nitric acid solution
containing sodium chloride
Studies have been made on the acid leaching behaviour of
copper anode slime in dilute acid solution and the
oxidative leaching behaviour of acid leaching residue in
nitric acid solution containing sodium chloride (Sanuki
et al. 1989). After pretreatment of copper anode slime in
an acidic solution precious metals such as Au, Ag and Pt
remain in the acid leaching residue. The oxidative leaching
rates of the acid leached residue increase with an increase
in both concentration of nitric acid and sodium chloride in
the leaching solution. Precious metals such as Au, Pt and
Pd are dissolved in nitric acid solution containing sodium
chloride and thus it may be effective to carry out a
supplementary treatment for recovery of Ag from the
oxidative leaching residue of copper anode slime.
Some important hydrometallurgical routes followed for
treatment of anode slimes
INER process
The INER process (Wang et al. 1981; Hoh et al. 1982;
Hoh et al. 1983) is a novel hydrometallurgical process
248 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
8 INER process for treatment of anode slime
for recovering precious metals from copper refinery
anode slime which has been developed and tested
successfully in a pilot plant. The unit operations used
are mainly leaching, extraction and reduction. Based on
the pilot plant data a production plant with a capacity of
300 t anode slime per year is constructed in the republic
of China. The research and development work was
carried out at the Institute of Nuclear Energy Research
(INER) in Taiwan.
Figure 8 shows a block diagram of the INER process
for the recovery of precious metals from copper refinery
anode slime. The overall process includes four leaching
steps and five liquid–liquid extraction circuits. Sulphuric
acid leaching of anode slime is performed for copper
extraction which is followed by acetate leaching of the
residue according to the reaction
PbSO4 z4CH3 COONH4
~½Pb(CH3 COO)4
(NH4 )2 z(NH4 )2 SO4
The leach liquor mainly containing lead is treated for
metal extraction and the remaining solid residue is again
leached with nitric acid for the recovery of silver,
selenium and tellurium following the reaction
2Ag2 Sez8HNO3 ~2AgNO3 zAg2 SeO3
zH2 SeO3 z3NO2 z3NOz3H2 O
Finally the nitric acid leached residue is treated with
aqua regia for gold extraction.
This process provides a clean separation of the
valuable constituents of the slimes where gaseous
effluents are also minimised.
The INER process has the following advantages over
conventional pyrometallurgical processing:
(i) calculated energy consumption is significantly
lower (y11%) than for the pyrometallurgical
process (Hoh et al. 1983)
(ii) treatment of the waste is less expensive than in
the pyrometallurgical process
2009 VOL 118 NO 4

9 Anode slime treatment process at Saganoseki
(iii) the recovery of selenium is .95%, whereas for
the pyrometallurgical process it seldom exceeds
80%
(iv) about 99% gold and 98% silver can be recovered
Published by Maney Publishing (c) IOM Communications Ltd
directly without going through a gold–silver
alloy stage
(v) liquid–liquid extraction is suitable for recover-
ing metal from low content mother liquor. The
technique is suitable for continuous operation
and easy to operate
(vi) all of the organic and most of the mineral acids
are recycled.
In the last step (vi), after the recovery of silver chloride,
the Se, Te containing filtrate is sent to a denitration and
chlorination step that utilises liquid–liquid extraction by
TBP diluted with kerosene. The recovered nitric acid
with a nitrate ion level of 2?2M exits from the stripping
stage and is recycled to the nitric acid leach step. The
stripped organic extractant is recycled to the extraction
step (Hoh et al. 1983).).
In this process the overall recovery rates for lead,
silver, selenium, gold and tin were found to be about 96,
98, 98, 99 and 98% respectively. The final residue is
recycled to the copper smelter.
Processing at Saganoseki Smelter and Refinery
The copper anode slime treatment plant started by
Nippon Mining & Metals processes slimes in a chloride
media (Toraiwa and Abe 2000). The process has a wet
chlorination stage of decopperised slimes, a solvent
extraction and reduction stages of gold, a silver chloride
reduction stage and separative reduction stage of its gold
extraction raffinate. Copper anode slime is pulped and
copper in it is recovered by sparging oxygen under
pressure in the decopperising stage. Tellurium is also
Table 2 Developed processes for precious metals recovery
Treatment Product
Leaching with chlorine gas in Au ppt.
presence of H2O2/ferrous chloride
Leaching with chlorine gas and Au ppt.
precipitation by rotational copper disc
Leaching with HCl and sodium hypochlorite AgCl
Thiosulphate leaching followed by Metallic silver
electrochemical reaction
Thiourea leaching Au and Ag in solution
Nitric acid leaching Ag in solution Au in residue
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
Hait et al. Processing of copper electrorefining anode slime
10 Proposed anode slime treatment process developed
at NML
dissolved in this stage and precipitated with copper
metal. The oxidation leaching, called wet chlorination,
dissolves precious metals in decopperised anode slime
into aqueous solution of hydrochloric acid and converts
silver to silver chloride. Filtration separates chlorination
liquor and silver chloride. The chlorination liquor is
cooled to precipitate lead chloride and sent to gold
extraction stage. Silver chloride separated after wet
chlorination is pulped in water and reduced to crude
silver with iron. Oxidation cupel refines this crude silver
to produce silver anode in the Hitachi Refinery. Silver is
further refined by electrowinning. Gold in chlorination
liquor is recovered by solvent extraction with dibutyl
carbitol (DBC). Oxalic acid and/or sodium oxalate
reduce gold directly from gold loaded DBC by mixing
and heating together. Gold extraction raffinate includes
some precious metals and those are collected by
reduction with sulphur dioxide or hydrazine. The flow
sheet of the process is given in Fig. 9.
Recently developed process for metals recovery from anode
slime of ICC, Ghatsila, India
A process has been developed at the National
Metallurgical Laboratory (Jamshedpur, India) following
the hydrometallurgical route for the treatment of anode
slime of ICC (Ghatsila, India) (Hait et al. 2002; Hait
et al. 2004, Kholkin et al. 2005). The process flow sheet
is given in Fig. 10.
References
Okubo et al. 1984
Bunyamin et al. 2001
Bertha 1986; Bertha 1987a; Bertha 1987b
Arai et al. 1989
Yavuz and Ziyadanogullari 2000
Wang et al. 1980
2009 VOL 118 NO 4 249
 Hait et al. Processing of copper electrorefining anode slime

Table 3 Qualitative comparative study of some aspects related to various anode slime processing routes

Processing
Recovery status steps Effectiveness of Effluents Economy of energy
Process of precious metals involved elemental separation generation and reagents

Sumitomo Higher recovery of Large number Efficient separation Gaseous and High energy consumption
Au and Ag of Se and Au liquid effluents
Canadian Copper Higher recovery of Lesser number Efficient separation Gaseous and High energy consumption
Refinery Au and Ag of Au and Ag liquid effluents
Daye Smelter Higher recovery of Large number Not efficient separation Gaseous and Moderate energy consumption
Au and Ag of Se and Te liquid effluents
Outokumpu High recovery of Lesser number Efficient separation Gaseous and High energy consumption
Au and Ag of Se, Au and Ag liquid effluents
Indian Copper Higher recovery of Lesser number Efficient separation Gaseous and High energy consumption
Complex Au and Ag of Se, Au and Ag liquid effluents
Saganoseki High recovery of Lesser number Efficient separation Liquid effluents Low energy consumption with
Au of Au and Ag with minimum some of the reagents
gaseous effluents recycled and reused
INER Higher recovery of Large number Efficient separation of Liquid effluents Low energy consumption with
Au and Ag valuable metals with minimum most of the reagents
gaseous effluents recycled and reused

Some precious metals recovery processes 5. I. Bayraktar and F. A. Garner: ‘Hydrometallurgical processing of
secondary copper anode slimes for metals recovery’, Proc. Int.
Published by Maney Publishing (c) IOM Communications Ltd

A few processes developed for the recovery of precious
metals has been given in Table 2.
Conclusions
A number of methods have been developed world over
for the processing of copper refinery anode slime. The
processing routes are mainly based on pyro, pyro-hydro,
hydro-pyro and hydrometallurgical extraction. Some of
the process routes are already established in plant
practice. A brief over view of the processes by
categorising them according to the different routes are
presented in this paper. All these processes have their
own merits and demerits specially in relation to the
energy consumption and environmental point of view
which has been summarised in tabular form (Table 3). It
seems that hydrometallurgical processes such as INER,
Saganoseki process will be more economical due to their
low energy consumption and reuseability of the reagents
apart from the high recovery of precious metals.
Further, most of the processes are complex in nature.
However, the chemical and mineralogical characteristics
of the particular anode slime would play a vital role for
the procedure to be adopted.
Acknowledgements
The authors are thankful to Director, NML,
Jamshedpur, India for his support in carrying out this
work. Anode slime samples received from M/S ICC,
Ghatsila, India, are also thankfully acknowledged
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