Hydrometallurgy 108 (2011) 199204

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

The role of arsenic in the homogeneous precipitation of As, Sb and Bi impurities in

copper electrolyte
Xue-Wen Wang a,, Qi-Yuan Chen b, Zhou-Lan Yin b, Ming-Yu Wang a, Fang Tang a
a
b

School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China

a r t i c l e

i n f o

Article history:
Received 10 January 2011
Received in revised form 24 February 2011
Accepted 18 April 2011
Available online 28 April 2011
Keywords:
Copper electrorening
Electrolyte purication
Arsenato antimonic acid
Arsenato antimonate

a b s t r a c t
The role of arsenic in the homogeneous precipitation of impurities arsenic, antimony and bismuth in copper
electrolyte was studied. Experiments found that though the formation of arsenato antimonates is one of the
control-steps in the homogeneous precipitation and antimony is absolutely necessarily for arsenato
antimonates formation, arsenic played an important role for the homogeneous precipitation as well. Arsenic
(V) is not only a reactant of arsenato antimonates formation but also an oxidant of Sb(III) oxidation. Arsenic
(V) can oxidize antimony from Sb(III) to Sb(V) in copper electrolyte. If the concentration of arsenic (V) is over
6 g/L and the mole ratio of As(III)/As(V) is less than 0.09, the oxidation can be taken place at room
temperature, and the equilibrium value of the As(V)/As(III) is about 0.606 in the electrolyte. Under these
conditions, the precipitation rate of antimony from the electrolyte can be reached over 97%. Arsenic (III) can
promote arsenato antimonates formation and depress oating slimes formation simultaneously. The higher
the arsenic (III) concentration is, the easier the formation of arsenato antimonates will be. If arsenic (III) is
lack, the copper electrolyte is prone to be over oxidized, which will result in the formation of oating slimes.
Floating slimes and arsenato antimonates have a similar chemical composition. To distinguish arsenato
antimonates from oating slimes, the most effective way was thermal decomposition.
2011 Elsevier B.V. All rights reserved.

1. Introduction
In copper electrorening, the impurities of arsenic, antimony and
bismuth are dissolved along with copper from the anode to the
electrolyte. If no electrolyte is bled from the electrorening circuit, the
impurities would gradually accumulate in the electrolyte, which
would result in a variety of intolerable problems, such as contamination of the cathodes and passivation of the anodes. Therefore, a
number of methods have been proposed for the purication of copper
electrolyte besides the typical treatment, such as prevention the
supersaturation of arsenic, antimony and bismuth in copper electrolyte with stannic acid (Schuize, 1972), adsorption antimony and
arsenic from the electrolyte with activated carbon (Navarro and
Alguacil, 2002; Toyabe et al., 1987), co-precipitation of bismuth and
antimony from the electrolyte by adding a carbonate of barium,
strontium, or lead (Hyvarinen, 1979), removal antimony and bismuth
from the electrolyte using ion exchange resins (Cunnigham et al.,
1997), extraction of antimony and bismuth from copper electrolyte
with LIX1104SM (Navarro et al., 1999), adsorption bismuth and
antimony with an adsorbent containing antimony (Wang et al., 2003),

Corresponding author.
E-mail address: wxwcsu@163.com (X.-W. Wang).
0304-386X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.04.007

removal bismuth from copper electrolyte solutions using MRT (Izatt

et al., 2010), and separation and concentration arsenic from the
copper electrolyte using electrodialysis (Cifuentes et al., 2002).
It is well known that a part of the impurities arsenic, antimony and
bismuth dissolved from the anode can spontaneously precipitate from
the electrolyte to the anode slimes during copper electrorening and
the volume of the copper electrolyte withdrawn to be puried per ton
cathode (VPTC) is diverse in different copper reneries. Even in the
same renery with the same anode, the VPTC value is not the same
under different electrorening conditions (Wang, 2003), which
indicates that the efciencies of homogeneous co-precipitation of
impurities arsenic, antimony and bismuth are different, i.e., the
fraction of arsenic, antimony and bismuth dissolved from the anode
and then deposited to form the anode slimes vary under different
electrorening conditions.
It was found that the homogeneous co-precipitation of impurities
arsenic, antimony and bismuth in copper electrolyte is dominant in
the forms of arsenato antimonates (Wang et al., 2006), and there are
two control-steps in the homogeneous co-precipitation, one is the
oxidation of antimony from Sb(III) to Sb(V) and the other is the
formation of arsenato antimonates (Wang et al., 2011). Although
antimony is absolutely necessarily for the formation of arsenato
antimonates (Wang et al., 2006), recently it was found that arsenic
also plays an important role in the formation of arsenato antimonates
(Wang et al., 2011). The aim of this paper is to present the roles of

200

X.-W. Wang et al. / Hydrometallurgy 108 (2011) 199204

arsenic (V) and arsenic (III) respectively in the formation of arsenato

antimonates.

Table 2
Composition of industrial copper rening electrolyte, g/L.

2. Experimental

Cu

H2SO4

As(III)

As(V)

Sb(III)

Sb(V)

Bi

46.71

184.68

0.54

4.97

0.42

0.07

0.32

2.1. Materials, apparatus and analysis

(V) was added into. The electrolytes placed in the beakers with cover
for ageing without stirring and thermal retardation, and white
precipitates formed in all the electrolytes during the aging. After
aging for a week, ltration was carried out, and the concentrations of
As, Sb and Bi in the ltered electrolytes were listed in Table 3.
From Table 1 and Table 3, it can be worked out that after aging, the
precipitation rate of antimony in the 4#, 5#, 6#, 7# and 8#
electrolytes is over 97%, while that in the 1#, 2# and 3# electrolytes
is below 65% though the initial concentrations of antimony in the
electrolytes were almost the same (about 1.5 g/L Sb, see Table 1) at
about 80 C. After the As(V) adding in, it was observed that the
temperature of the precipitates begin to form in the 4#, 5#, 6#, 7# and
8# electrolytes was over 65 C, while that in the 1#, 2# and 3#
electrolytes was below 50 C. When the aged 1#, 2# and 3#
electrolytes were heated over 60 C under stirring, the precipitates
formed in them were dissolved, which indicates that the precipitates
formed in the aged 1#, 2# and 3# electrolytes are Sb(AsO4) (Wang,
2003) or amorphous antimonious acid (Petkova, 1997) as the
solubility of them increase with temperature increase, while the
precipitates formed in the aged 4#, 5#, 6#, 7#, and 8# electrolytes
couldn't dissolve even if under boiling.
In order to differentiate the precipitates formed in the aged 4#, 5#,
6#, 7# and 8# electrolytes from those formed in the aged 1#, 2# and
3# electrolytes, after ltration the precipitates were washed with
dilute sulfuric acid and distilled water respectively, and then dried at
60 C under vacuum till their weights were constant. Table 4 gave the
compositions of the precipitates formed in 3# and 4# electrolytes.
From Table 4 it can be seen that the precipitates contain antimony (V),
and the content of antimony (V) in the precipitate formed in 4#
electrolyte is much higher than that in the precipitate formed in 3#
electrolyte, and some of the As(V) was changed into As(III) in the
electrolytes, see Table 3, which indicates that some of the Sb(III) was
oxidized to Sb(V) by the added As(V). The precipitate formed in 4#
electrolyte should be arsenato antimonates because the precipitate
couldn't dissolve under boiling. The formation of arsenato antimonates in the electrolyte can be expressed by the following equations
(Wang et al., 2006):

To properly understand the role of arsenic in the formation of

arsenato antimonates, synthetic and industrial copper rening
electrolytes were used. Sulfuric acid, hydrogen peroxide solution
(30 vol.%), CuSO45H2O, As2O3, 99.99% Sb, 99.99% Bi, distilled water
and the powder of arsenato antimonic acid of AAAc(1:1) were used in
the experiments. The AAAc(1:1) powder contains As 21.35 wt.% and
Sb 35.08 wt.%, and the arsenic and antimony in it both are
quinquevalent.
The electrolytes used in the experiments contained the basic
components: 3436 g/L Cu, 180185 g/L free H2SO4, and the impurities
arsenic, antimony and bismuth. They were synthesized at about 80 C
and then placed in beakers for ageing without stirring and thermal
retardation. The initial concentration of the synthetic electrolytes is
shown in Table 1. The industrial copper rening electrolyte was taken
from Guixi smelter, and its composition is listed in Table 2.
The Sb(III) and Bi(III) added into the electrolytes were respectively
prepared by dissolving metallic antimony and bismuth in concentrated sulfuric acid and diluting with water. As2O3 was rstly
dissolved in water under heating and stirring, then oxidized with
the hydrogen peroxide solution to obtain As(V). The excess H2O2 was
decomposed by boiling the solution for about half an hour. The AAAc
(1:1) solution was obtained by dissolving the AAAc(1:1) powder in
distilled water.
The composition of experimental samples was determined by
inductively coupled plasma emission spectroscopy (ICP) with a PS-6
PLASMA SPECTROVAC, BAIRD (USA). The valence of elements was
determined by standard chemical methods (Chemistry Department and
Hangzhou University, 1982). The IR spectrum was obtained using the
KBr disk method with an AVATAR 360 (Nicolet) spectrophotometer
operating in the range of 4000400 cm1. TG/DTG curves were obtained
on a METTLER TOLEDO Thermogravimetric Analyzer (TG/SDTA851e) in
the temperature range of 251100 C at a heating rate of 5 C min1
under dynamic argon (70 ml min1) atmospheres.
3. Results and discussion
3.1. Oxidation of antimony from Sb(III) to Sb(V)

H3 AsO4 SbO 3H2 O HAsO2 HSbOH6  H

It is well known that antimony and arsenic dissolve electrochemically from copper anodes as trivalent ions and then are oxidized to
pentavalent ions by the air (O2) dissolved in copper rening
electrolytes. Furthermore, As(III) oxidizes before Sb(III). Under
certain conditions, the higher the concentration of arsenic is, the
faster the oxidation of antimony from Sb(III) to Sb(V) in copper
electrolyte will be (Wang et al., 2011).
To properly understand the role of arsenic in the oxidation of
antimony from Sb(III) to Sb(V), the prepared Sb(III) and/or Bi(III)
were rst added into the synthetic copper electrolytes under stirring
at above 65 C to avoid them hydrolyzation, and then the prepared As

aH3 AsO4 bHSbOH6 

cMeO Mec Asa Sbb O3a5bc=21 Ha5b2c2 xH2 O cH

a b c=21xH2 O; where Me
AsIII; BiIII and SbIII; a1; b1; c3a b:

The IR spectrum of the precipitate formed in the 4# electrolyte is

shown in Fig. 1, where the main bands can be, respectively, assigned
to s and as of OH (3403.7 and 1631.3 cm1) (Losilla et al., 1998),
of OH (1383.2 and 1349.5 cm1) (Nali and Mhiri, 2001), of AsOH

Table 1
Initial concentrations of impurities As, Sb and Bi in the synthetic copper electrolytes, g/L.
Electrolytes

1#

2#

3#

4#

5#

6#

7#

8#

As
Sb
Bi
Cu
H2SO4

0.000
1.550

34.12
181.4

4.021
1.548
0.505
35.27
183.7

5.009
1.544

35.74
184.5

6.013
1.558

34.65
182.8

7.050
1.542
0.524
35.68
184.7

8.078
1.536

34.85
180.8

9.042
1.532

36.01
184.2

10.002
1.533
0.544
35.86
183.7

X.-W. Wang et al. / Hydrometallurgy 108 (2011) 199204

7#

8#

7.030
7.440
0.030

7.397
7.884
0.021

10.461
11.025
0.019
0.116

and SbOH (1126.6 cm1) (Nali and Mhiri, 2001; Qureshi and
Kumar, 1971), as of AsOH (1031.6 cm1) (Colomban et al., 1989),
as of As-OX(X = As, Sb) (816.9 cm1) (Myneni et al., 1998), as of Sb
OH (618.6 cm1), and as of SbOY(Y = As, Sb) (502.6 cm1)
(Colomban et al., 1989; Qureshi and Kumar, 1971). There are AsO
Sb, SbOSb bonds formed among As(V), As(III), Sb(V), and Sb(III) in
the precipitate, which are the characteristic bands of arsenato
antimonates (Chen et al., 2004). Therefore, the precipitates formed
in the 4# electrolyte is arsenato antimonates, so are the precipitates
formed in 5#, 6#, 7#, and 8# electrolytes.
From reactions (1) and (2), it can be seen that arsenic (V) is not
only an oxidant for antimony oxidation from Sb(III) to Sb(V) but also a
reactant for arsenato antimonates formation in copper electrolyte.
The concentration relationship between the arsenic (V) and the
antimony in the aged electrolytes was shown in Fig. 2. As seen in
Fig. 2, the concentration of antimony declined sharply when the As(V)
concentration is over 4.5 g/L in the aged electrolytes. From Table 1 and
Table 4, it can be found that Sb(III) can be obviously oxidized to Sb(V)
by As(V) when the initial As(V) concentration was more than 6 g/L in
the electrolytes.
Under normal conditions, it is difcult for arsenic (V) to oxidize
antimony from Sb(III) to Sb(V) because the difference of the standard
electrode potentials oAs(V)/As(III) (0.559 V) and oSb(V)/Sb(III) (0.720 V) is
over 0.15 V (Dean, 1985). However, when Sb(V) and As(V) react with As
(III), Sb(III), and Bi(III) to form the precipitates of arsenato antimonates,
the concentration of Sb(V) decreases remarkably in the electrolyte, and
the Sb(V)/Sb(III) becomes less than or equal to the As(V)/As(III), thus
arsenic (V) can oxidize antimony from Sb(III) to Sb(V) in copper
electrolyte.
The relationship between the As(III)/As(V) mole ratio and the
antimony concentration in the aged electrolytes was given in Fig. 3. As
seen in Fig. 3, the concentration of antimony increased rapidly when the
value of As(III)/As(V) mole ratio was higher than 0.09 in the nal
solutions, in other words, the formation of arsenato antimonates made
antimony concentration decreased rapidly under the nal As(III)/As(V)
mole ratio less than 0.09, which means that As(III)/As(V) mole ratio 0.09
is near the equilibrium value that arsenic (V) can oxidize antimony from
Sb(III) to Sb(V) in copper electrolyte at room temperature, or the
equilibrium value of the As(V)/As(III) and Sb(V)/Sb(III) both are about
0.606 if the concentration is close to the activity for As(III) and As(V)
respectively in the electrolyte. In fact, reaction (1) could take place in all
the electrolytes listed in Table 1 except the 1# electrolyte when the
prepared As(V) was added into, but only the formation of arsenato
antimonates can promote reaction (1) proceeding till Sb(III) concentration very little.
It was found that, by heating the aged 6# electrolyte at 85 C under
stirring for about 0.5 h, the precipitates formed in it were turned from
arsenato antimonates into antimonate. The XRD pattern of the
antimonate was shown in Fig. 4. This further conrmed that arsenic
(V) can oxidize antimony from Sb(III) to Sb(V) in copper electrolyte.
Table 4
Compositions of the precipitates formed in 3# and 4# electrolytes, wt.%.

80
60
40
20

4000

As

As(V)

Sb

Sb(V)

3#
4#

27.23
26.12

25.86
24.98

47.85
43.51

0.30
4.73

1000

2000

Wavenumbers (cm-1)
Fig. 1. IR spectrum of the precipitates formed in 4# electrolyte.

Above experimental results indicate that the oxidation of

antimony from Sb(IIII) to Sb(V) by As(V) depends on not only the
concentration of As(V) but also on the mole ratio of As(III)/As(V) and
the temperature of copper electrolyte. Thus it can be seen that the
oxidation of antimony from Sb(IIII) to Sb(V) during copper electrorening can follow the indirect oxidation mechanism, namely the
oxidation of arsenic from As(III) to As(V) by the air (O2) dissolved in
the rening electrolyte and the subsequent oxidation of antimony
from Sb(IIII) to Sb(V) by the As(V).

3.2. Prevention copper electrolyte over oxidation

During test it was found that by adding sufcient hydrogen
peroxide solution into the aged 3# electrolytes (listed in Table 3) to
oxidize the Sb (III), only about 40% of the antimony was precipitated
in the form of arsenato antimonates. After ltrating, the electrolyte
was boiled for half an hour, and some suspending white precipitates
appeared, and then the white precipitates were separated from the
electrolyte by ltration again. The lter cake was dried at 60 C under
vacuum till its weight was constant, and its chemical composition was
analyzed. The analyses results showed that the lter cake contains As
(V) 17.98 wt.% and Sb(V) 37.26 wt.%. It is interesting that the lter
cake can be dissolved in distilled water at about 50 C under stirring,
which indicates that the electrolyte was over oxidized and the
arsenato antimonic acid of AAAc(1:1) was formed in it (Wang et al.,
2004a). The AAAc(1:1) has the structure of (HO)3AsOSb(OH)4O
Sb(OH)4OAs(OH)3 and the suspending precipitates are the hydrolyzates of AAAc(1:1) (Wang et al., 2004a; Wang et al., 2005). The

0.6

0.4

0.2

0.0

Samples

3000

618.57
502.56

6#

5.541
5.900
0.037
0.135

816.90

5#

4.589
4.973
0.038

1631.27
1597.00

4#

3.821
4.359
0.544

3403.65

3#

2.846
3.333
0.654
0.476

% Transmittance

2#

0.0
0.0
0.660

Sb / g.L-1

1#

As(V)
As
Sb
Bi

1383.18
1349.49
1126.62
1031.56

100

Table 3
Concentrations of the impurities in the electrolytes listed in Table 1 after ageing, g/L.
Electrolytes

201

10

As(V) / g.L-1
Fig. 2. Effect of As(V) concentration on antimony concentration in the aged electrolytes.

X.-W. Wang et al. / Hydrometallurgy 108 (2011) 199204

Sb concentration, g/L

202

0.6

0.4

0.2

0.0
0.00

0.03

0.06

0.09

0.12

0.15

0.18

Mole ratio of As(III)/As(V)

Fig. 3. Effect of As(III)/As(V) mole ratio on antimony concentration in the aged
electrolytes.

formation of the hydrolyzates in the electrolyte can be expressed by

the following equations (Wang, 2003; Wang et al., 2005):
H3 AsO4 HSbOH5 HH2 AsO3 OSbOH5  H2 O

2HH2 AsO3 OSbOH5 

HO3 AsOSbOH4 OSbOH4 OAsOH3 H2 O

AAAc(1:1) + H2O (HO)3AsOSb(OH)4OSb(OH)5H + H3AsO4

(5)

(HO) 3 AsOSb(OH) 4 OSb(OH) 5 H + H 2 O HSb(OH) 5 OSb

(OH)5H + H3AsO4
(6)
aHSbOH5 OSbOH5 H
bHO3 AsOSbOH4 OSbOH5 HH3 AsO4 b Sb2ab Oabc
OH10a9b2c H2ab cH2 O; where a 0; b 0; a b 2; c 1:
7
The hydrolyzation of AAAc(1:1) is harmful for cathode copper
quality as the essential component of the hydrolyzates is antimony
(V) which has a good adsorbability for the impurities arsenic,
antimony and bismuth in copper electrolyte (Wang et al., 2003).
When some of the impurities were adsorbed by the hydrolyzates, the
so-called oating slimes were formed in the electrolyte (Wang, 2003).

To conrm that the formation of oating slimes is caused by the

hydrolyzation of AAAc(1:1) in copper electrolyte, the industrial
electrolyte was placed in a beaker with cover under stirring and
external polarization in a thermostatic water bath. Maintaining the
temperature at about 65 C, the AAAc(1:1) solution was slowly
dropped in the electrolyte till white precipitates appeared. After
ageing for 24 h, ltration was performed. The compositions of the
ltrate and the lter cake were listed in Table 5. The composition of
the oating slimes obtained by ltering the electrolyte of Daye
Smelter copper electrorening circulating system was listed in Table 5
as well. It can be seen that the oating slimes and the hydrolyzates
formed in the electrolyte have the similar chemical composition,
which indicates that they might be the same compounds, and
antimony (V) is the essential component of oating slimes (Abe and
Takasawa, 1987).
Commercial operations found that when arsenic concentration
was below 5 g/L, the amount of oating slimes formed in copper
electrolyte increases obviously. This indicates that the copper
electrolyte is easy to be over oxidized if the anode is shot of arsenic
(Baltazar et al., 1987; Noguchi et al., 1995). In order to reduce oating
slimes formation, the most effective way is to improve the
homogeneous co-precipitation of impurities arsenic, antimony and
bismuth in copper electrolyte (Wang et al., 2011), i.e., the most
effective way is to speed-up the formation of arsenato antimonates.
From reactions (1) to (4), it can be seen that the formations of
arsenato antimonates and arsenato antimonic acid AAAc(1:1) are
competitive for impurities arsenic, antimony and bismuth in copper
electrolyte. Arsenic (III) is one of the reactants of reaction (2).
Quantum chemical calculations showed that the reaction of H3AsO4
and HSb(OH)6 with As(III) to form arsenato antimonates is more
easily than that with Sb(III) or Bi(III) (Chen et al., 2004), that is to say,
arsenic (III) plays an important role for the formation of arsenato
antimonates as well. By increasing arsenic concentration, the
formation of arsenato antimonates can be improved provided that
the mole ratio of Sb/As/Bi in the anode is suitable for arsenato
antimonates formation (Wang et al., 2011) as, maintaining the mole
ratio of As(III)/As(V) constant, the concentration of arsenic (III)
increases with the total arsenic concentration increase.
Although oating slimes are by-products of copper electrorening,
and a lot of oating slimes formed in copper electrolyte might not be
encountered for several years under normal conditions because
arsenic (III) is generated constantly during copper electrorening,
which not only avoids the copper electrolyte over oxidation but also
speeds-up the formation of arsenato antimonates. However, in 1987
and 1988, this was occurred two times in Guixi Smelter copper
electrorening cells. The oating slimes not only oated on the
surface of the cells but also suspended in the electrolyte, and a lot of
knots were formed on the surface of the cathodes (Wu, 1988). By
investigation, it was found that the oating slimes formation derived
from the addition of the decoppered solution of copper anode slimes
to the circulating system. The added solution contained 2535 g/L Cu,
0.12.5 g/L Se(IV) and 0.52.0 g/L Te(IV). The H2SeO3 and H2TeO3 can
oxidize not only arsenic from As(III) to As(V) but also antimony from
Sb(III) to Sb(V) completely, which suggests that the added solution
made the electrolyte over oxidation. This further shows that it is
difcult to avoid oating slimes formation with the lack of arsenic (III)

Table 5
Compositions of the oating slimes formed in commercial copper electrorening
electrolyte and the precipitate obtained by making AAAc(1:1) hydrolyzed in the
electrolyte listed in Table 2 and then ltering.

Fig. 4. XRD pattern of the precipitates formed in 7# electrolyte by heating at 85 C

under stirring for about 0.5 h.

Filtrate, g/L
Filter cake, wt.%
Floating slimes, wt.%

As(V)

As(III)

Sb(V)

Sb(III)

Bi

Cu

H2SO4

5.52
9.81
8.76

0.38
3.16
0.57

0.38
41.73
37.24

0.12
5.87
4.55

0.25
1.38
7.74

46.54
0.10

186.12

X.-W. Wang et al. / Hydrometallurgy 108 (2011) 199204

0.2
36

27

-0.2
TG
DTG

18
50

3.3. Distinction between oating limes and arsenato antimonates

100

150

-0.4

200
39.6

dw/dt (mgoC-1)

0.0

Weight (mg)

in copper electrolyte. In order to minimize the formation of oating

slimes, partial arsenic was reduced from As(V) to As(III) (Braun et al.,
1976; Petkova, 1997), or the solution containing arsenic (III) was
added into the copper electrolyte (Demaerel, 1987; Xiao et al., 2007)
to enhance the homogeneous co-precipitation of impurities arsenic,
antimony and bismuth in copper electrolyte, and the concentration of
arsenic is maintained over 7 g/L in many copper reneries. This
indicates that maintaining arsenic (III) sufcient can effectively
prevent oating slimes formation in copper electrolyte.

203

-0.6

38.4

4. Conclusion
Arsenic (V) and arsenic (III) are both important for the formation
of arsenato antimonates in copper electrolyte. When the arsenic (V)

37.2

200

400

600

800

1000

-0.8

Temperature (oC)

0.05
40

30

-0.05
TG
DTG

20

-0.10
-0.15

10

dw/dt (mgoC-1)

Weight (mg)

0.00

-0.20
0

-0.25
0

200

400

600

800

1000

Temperature (oC)

9
0.002
8
7
-0.004
TG
DTG

-0.006
-0.008

dw/dt, mgoC-1

0.000
-0.002

Wight, mg

The oating slimes and the arsenato antimonates formed in copper

electrolytes both contain As(V), As(III), Sb(V), Sb(III) and Bi(III), and
they are both white amorphous precipitates and have no xed
composition (Wang, 2003; Wang et al., 2006). Therefore, to
differentiate oating limes from arsenato antimonates is necessary.
Thermal decomposition is one of the most effective ways used to
distinguish the amorphous solids. Fig. 5 shows the TG/DTG curves for
the thermal decomposition of AAAc(1:1) (Wang et al., 2005), arsenato
antimonates (Wang et al., 2004b) and the oating slimes listed in
Table 5. Fig. 5a showed that the curve of AAAc(1:1) decomposition
process is divided into four stages. The rst, which occurs from 25 C
to ~ 200 C, is attributed to the dehydration till three and a half H2O
molecules. A clear plateau is reached at about 210 C when the
decomposed product of As2O5Sb2O53.5H2O was formed. The second
stage occurs from ~ 350 C to ~410 C, which could be inferred to the
reaction of As2O5Sb2O53.5H2O 2AsSbO4 + 3.5H2O + O2. The second clear plateau is reached above 410 C with the existence of
AsSbO4. The third stage occurs between ~ 870 C and ~ 975 C, which
corresponds to the reaction of 2AsSbO4 Sb2O3 + As2O3 + O2. The
fourth stage is caused by Sb2O3 evaporation.
Although oating slimes are the hydrolyzed products of AAAc(1:1),
their TG/DTG curves are not the same, in Fig. 5b, not only the rst stage
vanished but also the second stage diminished markedly because many
(HO)3As- and HO-groups were lost through the reactions (5), (6) and
(7). In Fig. 5c, the rst and second stages all vanished as there are few
HO-groups and no (HO)3As-groups in the arsenato antimonates.
Moreover, the positions and the shapes of the third stage are
different among the three TG/DTG curves. In Fig. 5a, AsSbO4 is a pure
substance, it has a xed decomposition temperature, and the As2O3 is
very easy to be volatilized at about 975 C, so the DTG curve is very
sharp at the temperature. In Fig. 5c, the stage occurs between ~682 C
and ~738 C, which could be inferred to the reactions of As2O5 As2O3 + O2; Sb2O3 + O2 Sb2O5; Sb2O3 + Sb2O5 2Sb2O4; As2O3 +
Sb2O5 2AsSbO4; Bi2O3 + Sb2O5 2BiSbO4 (Wang et al., 2004b). The
TG curve for the stage is similar to a polygonal line, which is due to not
only the As2O3 quick-volatilizing but also the structure of As(III), Sb
(III), and Bi(III) linking directly with Sb(V) and As(V) through \O\
bands in the arsenato antimonates because the reactions of the As(V)
with the Sb(III) and the Sb(V) with the As(III), Sb(III), or Bi(III) are
very easy to carry out at 682738 C. In Fig. 5b, the third stage shows
that the similar reactions were occurred in the oating slimes as the
composition of the oating slimes is similar to that of the arsenato
antimonates, and the reaction temperatures are almost the same at
the stage, but the As(III), Sb(III), and Bi(III) in the oating slimes were
adsorbed by the surface of AAAc(1:1) hydrolyzates, most of the
adsorbed As(III), Sb(III), and Bi(III) can't react with the Sb(V) and As
(V) till they diffuse to the inner of the hydrolyzates, which made the
reactions speed slow and the TG/DTG curves of the oating slimes at
the stage be different from that of the arsenato antimonates.

-0.010
4

-0.012
0

200

400

600

800

1000

Temperature,oC
Fig. 5. TG and DTG curves for the thermal decomposition of AAAc(1:1), oating slimes
and arsenato antimonates. a, AAAc(1:1); b, oating slimes; c, arsenato antimonates.

concentration is over 6 g/L and the mole ratio of As(III)/As(V) is less

than about 0.09, the oxidation of antimony from Sb(III) to Sb(V) by As
(V) can occur in copper electrolyte, and the equilibrium value of the
Sb(V)/Sb(III) is about 0.606 in the electrolyte. Under these conditions,
the precipitation rate of antimony from the electrolyte can be reached
over 97%. Maintaining the mole ratio of As(III)/As(V) constant, the
increase of arsenic (III) concentration can improve the combination of
the Sb(V) with As(V), As(III), Sb(III) and Bi(III) to form the precipitate
of arsenato antimonates. By increasing arsenic concentration, the
homogeneous co-precipitation of impurities arsenic, antimony and
bismuth can be promoted obviously provided that arsenic (III) in
copper electrolyte is sufcient and the mole ratio of Sb/As/Bi in the
anode is suitable for arsenato antimonates formation, which is the
most efcient way to prevent oating slimes formation.

204

X.-W. Wang et al. / Hydrometallurgy 108 (2011) 199204

Acknowledgement
The authors acknowledge nancial support from the National
Natural Science Foundation of China (No. 50274075).
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