Hydrometallurgy 105 (2010) 148154

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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

Treatment of copper ash smelter ue dusts for copper and zinc extraction and
arsenic stabilization
A. Morales a, M. Cruells b, A. Roca b,, R. Berg b
a
b

Universidad Catlica del Norte, Department of Metallurgical Engineering, Antofagasta, Chile

Universitat de Barcelona, Department of Materials Science and Metallurgical Engineering, Faculty Chemistry, Barcelona, Spain

a r t i c l e

i n f o

Article history:
Received 14 June 2010
Received in revised form 2 September 2010
Accepted 2 September 2010
Available online 9 September 2010
Keywords:
Copper smelter dusts
Arsenic stabilization
Copper and zinc extraction

a b s t r a c t
A ue dust sample of copper from ash smelting furnace has been extensively characterized. The main phases
of the dusts are magnetite, cuprospinel, chalcocyanite, zincosite, dolerophanite, and claudetite. As minor
phases, tenorite, arsenolite, delafossite and enargite were detected. In the sample studied, particles were
mainly spherical and less than 60 m. The leaching of ue dust sample with water dissolved copper sulfates
and zinc sulfates and, partially, arsenic oxides, in an exothermic process. The leaching of the residue after
water leaching in several acid media increased the dissolution of copper and arsenic oxides and small
amounts of zinc. A preliminary study by hydrocyclone classication was carried out with the objective of to
obtain two fractions: a coarse fraction rich in copper and a ne fraction rich in arsenic. However, results
obtained in this sample were not very successful. In the stabilization study, the residue obtained after leaching
the copper ash smelter ue dust with sulfuric acid was mixed with sludge from a paper factory (coinertization process). The smaller size fraction (N 12 m) obtained in the hydrocyclone was also mixed with
this sludge. Results obtained derived of the application of a standard leaching test over these residues indicate
that they were stabilized. Thus, the resulting mixtures should be dumped without generating major
environmental problems.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Copper smelter ue dusts are generated in the pyrometallurgical
process of copper extraction. The constituent elements, and their
concentrations, depend on: the characteristics of the sulfurated ores
that are processed, the species and their concentration, the reactortype used in the different stages of the process and the conditions
under which these stages operate. All these factors affect the chemical
and mineralogical characteristics of the smelting dusts, thus explaining their variability and, consequently, the processes chosen for their
treatment, which is based on the recovery of valuable elements and
the stabilization of undesirable elements present in the dusts (Biswas
and Davenport, 1976).
The treatment of ue dusts has been extensively studied by several
authors. The processes put forward or implemented at the pilot and/
or industrial scale, according to the reasons indicated, include:
roasting of the dusts and leaching (Sumitomo Metal Mining, 1982;
Yin et al., 1992; Mulale et al., 1999; Gorai et al., 2002), smelting and
leaching (Hanks et al., 1979; Smirnov et al., 1984; Zhang et al., 1992),
roasting (Carter et al., 1994; Fu et al., 2000), and smelting (Ermakov,
1979; Yu, 1987; Mochida and Iida, 1988). However, most studies focus

Corresponding author.
E-mail address: roca@ub.edu (A. Roca).
0304-386X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2010.09.001

on hydrometallurgical treatments of the dusts, using acid or alkaline

reagents (Baczek et al., 1982; Nez et al., 1985; Law et al., 1992;
Kunter and Bedal, 1992; Roman-Moguel et al., 1995; Gabb and Evans,
1997; Robles et al., 1999; Vircikova and Havlik, 1999; Ke and Qin,
2000, Martn et al, 2003).
An ideal process for the treatment of copper smelter ue dusts
should be a hydrometallurgical process, operating at room temperature and atmospheric pressure, with dilute reagents, few unit
operations and low energy costs, that converts the elements of lesser
value (or whose extraction is not protable) into a compact and inert
residue for landll.
In a previous paper (Morales et al., 2007), a hydrometallurgical
process for copper recovery and arsenic stabilization from copper
smelter ue dusts produced in a continuous smelting furnace was
studied. The mineralogical composition (XRD) of the ue dust sample
indicates that it is a complex material, consisting mainly of oxidized
species (chalcocyanite, zincosite, magnetite, cuprospinel, anglesite,
claudetite, arsenolite, tenorite, and cuprite) and also of sulfurized
species (digenite, bornite, cubanite, and anilite). The main elements in
this material were determined by XRF. The chemical composition
was: Cu (26%), Fe (14%), As (8.2%), S (5.6%), Pb (5.1%), Zn (4.6%), Bi
(1.1%) and Mo,Cd (b1.0%). Leaching this material with water led to
the partial dissolution of copper, zinc and arsenic (as sulfates and
basic sulfates, and arsenic oxides). The hydrocyclone classication of
the leaching residue gave a copper-rich coarse fraction (constituted

A. Morales et al. / Hydrometallurgy 105 (2010) 148154

mainly by spinel phases and sulfurized species), which can be

recycled to the smelting furnace, and an arsenic-rich ne fraction
that was mixed with wastewater sludge from a paper factory, to make
both residues inert (co-inertization process) before their disposal to
landll.
The objective of this paper is to study possible treatments of a ue
dust sample from a copper smelter ash furnace, for recovery of
copper and zinc, and the stabilization of the arsenic contained in these
materials. Complete characterization of the as-received material was
required, along with a study of their reactivity and their response to
hydrocyclone classication. Finally, the possibility of stabilization of
the arsenic concentrates jointly with sludge from the paper industry,
if necessary, is also put forward. A comparative study of the behavior
of copper smelter ue dusts from a continuous furnace (Morales et al.,
2007), and of that obtained in the present work from a ash furnace, is
also included.

149

Table 1
Chemical composition of the sample (XRF).
Element

Cu

Fe

As

Zn

Pb

Mo

Bi

Cd

Ca

% weight

27

11

7.5

13

5.8

1.5

0.54

0.21

0.16

0.52

2000) for comparative purposes in relation with the different

mixtures. The stirring rate was 0.5 min1. pH and conductivity were
measured after 15 min and 24 h of leaching and the solutions
obtained were analyzed using ICP. This process was also applied to
the smallest size fraction (T6), i.e. b12 m, obtained by hydrocyclone
mixed with sludge from a paper factory at ratios of 60/40 or 80/20
(weight/weight).
3. Results and discussion
3.1. Characterization of the copper ue dust sample

2. Materials and experimental procedure

2.1. Materials
The ue dusts studied here was a sample from a ash smelting
furnace. Several kg of this sample were collected from the furnace and
according to the researchers of the company is representative of the
copper smelter ue dust generated there. This sample was exhaustively characterized by X-ray uorescence (XRF), scanning electron
microscopy (SEM) in conjunction with microanalysis by energy
dispersive X-ray analysis (EDS) and X-ray diffraction (XRD). Some
of the solids obtained during this study were also characterized by
electron microprobe (EPMA).
For inertization purposes, sludge from the paper industry was used.
This material was mixed with the ue dust leaching residue and with the
b12 m fraction from hydrocyclone, to make the corresponding
materials inert. This material contains about 50% water and is made up
of calcium carbonate, kaolin and cellulose bers (Morales, 2006). It
contains: 22.7% Ca, 4.00% Si, 3.75% Al, 0.220% Fe, 0.49% Mg, 0.116% K, As
(20 g t1), Cu (45 g t1), Zn (29 g t1), Pb (7 g t1) and less than 5 g t1
of Cd, Cr, Hg and Ni. This sludge was used in a previous study, at pilot
plant scale level, for the treatment and inertization of electric arc furnace
ue dust from steelmaking to produce a residue which is environmentally acceptable for disposal (Grau et al., 2004).
2.2. Experimental procedure
In this study, the sample was leached with water during 1 h, at
room temperature, at a stirring rate of 700 min1 and with a solid
liquid ratio of 1/5 (weight/volume), to determine the reactivity of the
dusts. The residue of leaching with water was treated with different
acid systems: nitric, sulfuric and hydrochloric acids (0.1 M). Leaching
processes were developed during 1 h, at room temperature and with a
solidliquid ratio of 1/10 (weight/volume). All nal residues obtained
were characterized with the same techniques that were used for the
original samples. Dissolved elements were determined using emission
spectrometry from inductively coupled plasma (ICP).
Hydrocyclone experiments over the residue from water leaching were
conducted in a cyclosizer. The cut particle sizes were (in m): 44 (T1),
33 (T2), 23 (T3), 16 (T4), 12 (T5) and the fraction b12 m (T6). These
fractions were characterized by laser diffraction particle size analysis and
by XRF, XRD and SEM-EDS.
To develop the stabilization tests, the residue obtained after
leaching copper smelter ue dust with sulfuric acid was mixed with
the sludge from a paper factory (at a ratio 60/40, weight/weight) to
obtain pellets of approximately 10 mm in diameter. In a rst step, the
sludge was milled and then mixed with the residue, and the pellets
formed were dried at 100 C. Pellets obtained were leached with
water for 24 h, according to the leaching test DIN 38414-S4 (DOGC,

The moisture of the sample as received was less than 0.5%. Table 1
shows the characterization by XRF of this material. The major
elements were copper, iron, sulfur, zinc and arsenic.
The XRD characterization of the ue dust sample is shown in
Table 2 and Fig. 1. These results show the complexity of copper ue
dusts. They consist mainly of oxidized species and a few sulde
species. The sample showed a background that indicates the presence
of amorphous species, which were not identiable by XRD.
In the copper ue dust sample, spherical-shaped particles and
other irregular ones with particle sizes from tens of micrometers to
one micrometer are found (SEM-SE). Fig. 2 shows SEM images of a
complex particle (50 m size); image (A) was obtained with SEM-SE
and image (B) with SEM-BSE (backscattered electrons).
In the BSE image (Fig. 2B), the darkest part of the particle
corresponds to a cuprospinel phase. According to several EDS analysis
carried out, the spinel phase contains variable amounts of zinc. The
bright particles in the zone of cuprospinel crystals are copper oxides
(EDS analysis). The particles of sizes between 12 m were also
analyzed by SEM-EDS. Some of the particles analyzed are arsenic-rich
particles.
A complex particle ( 60 m size) is shown in Fig. 3. Image (A) was
obtained with SEM-SE and image (B) with SEM-BSE. According to the
analyses carried out by SEM-EDS, the upper part of the particle (1)
consists of a copper sulde, and the lower part (2), of iron and oxygen,
probably magnetite. Between the magnetite crystals, a vitreous iron
silicate phase appears.
3.2. Water leaching of the copper smelter ue dust sample
The water leaching process of copper smelter ue dust was carried
out at a solid-liquid ratio of 1/5 (weight/volume) for 1 h and at a
stirring rate of 700 min1. Table 3 shows the changes in acidity and
temperature during leaching with water.
The amount of dusts dissolved was of 54 wt.%. Preliminary
experiments indicated that the main part of the solids dissolved
were in the rst 5 min, that corresponds to the copper and zinc sulfate
dissolution. pH diminishes from the initial value of 6.10 to 2.80. The
process was exothermic, increasing the temperature by 9 C. Table 4
Table 2
Mineralogical characterization of the copper smelter ue dust (XRD).
Main components

Minor components

Magnetite Fe3O4
Cuprospinel CuFe2O4
Chalcocyanite CuSO4
Zincosite ZnSO4
Dolerofanite CuOCuSO4
Claudetite As4O6

Tenorite CuO
Arsenolite As4O6
Enargite Cu3AsS4
Delafossite CuFeO2

150

A. Morales et al. / Hydrometallurgy 105 (2010) 148154

Fig. 1. X-ray diffractogram of copper smelter ue dust: (1) cuprospinel, (2) chalcocyanite, (3) dolerofanite, (4) delafossite, (5) zincosite, (6) claudetite, (7) arsenolite, (8) tenorite,
(9) enargite.

shows the chemical composition of the residue obtained by XRF

(sample R) and the corresponding composition of solution (sample S).
After solidliquid separation and after several days, a precipitate
was formed in the ltrate (sample D). Table 5 shows the chemical
analysis of this precipitate, obtained by EPMA. The solid was also
characterized by XRD. The diffractogram indicates that the solid
generated was almost amorphous in nature, with little amount of

calcium sulfate appearing. EPMA analysis indicated that they are

formed by iron arsenate (majority phase) and calcium sulfate
(minority phase).
Fig. 4 shows the distribution of the elements Cu, Fe, As, S, Zn and Pb
and the general mass distribution between residue and solution.
Almost all the iron contained in the dusts remains in the residue,
because iron is in the original solids as magnetite and cuprospinel.

Fig. 2. Images of a complex particle (A, SEM-SE; B, SEM-BSE).

Fig. 3. Images of a complex particle (A, SEM-SE; B, SEM-BSE).

A. Morales et al. / Hydrometallurgy 105 (2010) 148154

Table 3
Changes in pH and temperature during leaching with water.

151

Table 5
Chemical composition of the precipitates formed in ltrate after leaching with water.

Time (min)

pH

T(C)

Precipitate

0
0.5
15
30
45
60

6.10

3.15
2.98
2.91
2.80

26
35
31
29
27
25

Amorphous
Crystals

3.3. Treatment of the residue generated after water leaching with

different acid media
The residue generated after leaching with water was subjected to
different treatments with nitric, sulfuric and hydrochloric acids
(0.1 M). These conditions were selected to accomplish the idea of a
process operating at room temperature, with dilute reagents, few unit
operations and low energy costs. Results obtained for the elements Fe,
Cu, Zn, As and Pb are given in Fig. 6. The amount of these elements
dissolved in the previous treatment with water is included for
comparative purposes. In acid media, extraction of copper and arsenic
increased and extraction of zinc increased slightly, whereas almost all
the iron remained in the residue. According to the diffractograms
obtained from the residues, dissolution of copper corresponds to its
oxide and perhaps additional amounts of basic copper sulfates.
Additional amounts of arsenic oxides were dissolved. Arsenic
extraction highly increased in nitric acid. Residues generated after
acid treatment consist basically of magnetite and cuprospinel and
another spinel phases in which appears zinc, that are not dissolved in
the experimental conditions employed. Leaching with sulfuric acid
was selected for the treatment of copper smelter ue dust sample. In
this case, the copper extraction was 8085% and the zinc extraction
was 65%. Both elements remain in the residue as a spinel phase.
3.4. Cyclosizer classication of the residue after leaching with water
The chemical composition of the different size fractions obtained
from the hydrocyclone classication of the residue generated during
leaching with water is included in Fig. 7. The XRD carried out on all the
size fractions showed that arsenic oxides are concentrated in the
nest fraction. In this gure, global correspond to the chemical
composition of the residue after leaching with water.
Results obtained indicate that copper composition is homogeneous in almost all the fractions (17% Cu), iron and arsenic are also
homogeneous in all the fractions ( 25% Fe, 19% As) except in the
nest fraction (19% Fe, 26% As), and zinc is concentrated in the middle
fractions (6.46.8% Zn).
Based on the chemical composition at different cut sizes and their
weights, a mass balance was carried out. Table 6 includes the
Table 4
Chemical composition of the residue and solution after leaching with water at a solid
liquid ratio of 1/5 (weight/volume).
Cu

Fe

As

Zn

Pb

Mo

Bi

R (%)
S (gL1)

17
27

20
1.0

0.20
17

19
1.4

5.1
4.7

2.5
0.013

0.82

0.38

Fe

Cu

As

Ca

3.5. Stabilization of the nal residues

The residue obtained after leaching the ue dust sample with
sulfuric acid (0.1 M) is named R1. This residue was mixed with sludge
from a paper factory at a ratio of 60/40 (dust weight/sludge weight).
Pellets of 10 mm diameter were made with the corresponding
mixtures. This residue is named R2.
Also, the b 12 m fraction from hydrocyclone was mixed with
sludge at ratios of 60/40 or 80/20 dust/sludge (weight/weight), and
pellets of 10 mm diameter were made with the corresponding
mixtures. These mixtures are named R3 and R4.
All the samples (R1, R2, R3, R4) were subjected to the leaching DIN
38414-S4 test (one part of solids with 16 parts water, for 24 h at room
temperature, at a stirring rate of 0.5 min1), for comparative
purposes. For R3 and R4 the leaching test was applied in samples of
particle size higher than 2 mm (coarse material) and also in samples
with particle size less than 100 m (ne material), to determine if the
stabilization process is chemical in nature. Table 7 shows the results of
the leaching tests.
The metals amount dissolved in R1 (residue after sulfuric acid
leaching) at 24 h was low, with the exception of arsenic (19 ppm).
Sample R2 (mixture of the former residue and sludge) shows a good
stabilization. Samples R3 and R4 (samples b12 from hydrocyclone)
also indicates a good stabilization, and this process can be considered
chemical in nature because the results obtained in the fractions
N2 mm and b0.1 mm were almost the same. No signicant differences
were detected using a ratio 60/40 or a ratio 80/20. New phases were
not detected in the nal mixture by XRD. For R2, R3 and R4, the
materials obtained could be dumped without generating major
environmental problems.
3.6. Treatment of copper smelter ue dusts
In a previous paper (Morales et al., 2007), a treatment of copper
smelter ue dusts from a continuous furnace was proposed. The dusts

100
80
60
40
20
0
Mass

Elements

32.32.0 0.420.1 22.52.0 2.720.2 28.62.0

51.61.5 17.20.5

29.70.9

distribution of the main elements corresponding to these fractions. It

can be observed that arsenic is concentrated in the nest fraction
(b12 m), whereas iron is concentrated in the coarse fraction (N 12 m).
However, concentration of copper in coarse fractions was not well
achieved.

Distribution (%)

Lead also remains in the residue. The copper dissolved is in the form of
copper sulfate and dolerofanite. Copper also appears in the residue as
cuprospinel, some residual suldes and copper oxides. Zinc sulfate
was dissolved, partially remaining in the residue as spinel. Arsenic
was partially dissolved from arsenic oxides. A lot of sulfur is in the
form of soluble sulfates, shown by sulfur dissolving to a high degree.
The presence of different species in the residues was conrmed by
XRD, Fig. 5.

% O

Cu

Fe

Zn
residue

As

solution

Fig. 4. Distribution of the elements during leaching with water.

Pb

152

A. Morales et al. / Hydrometallurgy 105 (2010) 148154

Fig. 5. X-ray diffractogram of residue after water leaching: (1) cuprospinel, (2) arsenolite, (3) claudetite, (4) scorodite, (5) enargite.

contained signicant amounts of residual suldes. The proposed

process consisted of leaching the dusts with water, with copper and
zinc recovery from solution using cementation, or solvent extraction,
and of precipitation of arsenic as iron arsenate or by using alternative
processes. The leach residue could be hydrocycloned with a cut size of
12 m, recycling the coarse fraction to the furnace (fraction formed by
residual suldes and spinel phases), and mixing the ner fraction with
sludge from a paper factory before pelletizing and landll.
The results obtained in the present work indicate:
Leaching with water dissolved copper, arsenic and zinc at levels of
27, 1.4, and 4.7 g L1, respectively. Leaching of the corresponding
80

Extraction (%)

70
60
50
40
30
20
10
0
Cu

Fe
water

Zn

nitric acid

As

sulfuric acid

Pb

hydrochloric acid

Fig. 6. Leaching of the water residue with different acid systems.

Composition (%weight)

Cyclosizer distribution
30

residue with sulfuric acid (0.1 M) additionally dissolved 2.9, 1.5 and
0.2 g L1 of these elements, respectively.
Concentration of copper in coarse fractions by hydrocyclone was not
well achieved. This is different to the behavior detected in a previous
work (Morales et al., 2007). There was not detected signicant
amounts of residual suldes in the coarse fraction of the dusts
generated in the ash furnace, as was previously detected in ue
dusts from the continuous furnace; and probably due to the
different furnaces used in both cases and the corresponding
operating conditions.
Mixtures of residues from the treatment of copper smelter ue dust
with sludge from a paper factory subjected to the standard leaching
test, released between 1.43.5 ppm Cu, less than 0.50 ppm As, and
less than 0.20 ppm Zn, whereas the residue from sulfuric acid
leaching released 1.7 ppm Cu, 19 ppm As and b 0.20 ppm Zn.
Consequently, the process to be proposed for the treatment of
copper ash smelter ue dusts can include the following steps:
1) Leaching the dusts with sulfuric acid 0.1 M (63% solids are
dissolved). From the solutions generated, copper can be
recovered by cementation. However, to prevent possible
problems of arsine formation during this step, solvent
extraction followed by electrowining is an alternative method
for recovering copper and zinc, leaving arsenic in solution.
After this, dissolved arsenic can be precipitated from the
resulting solutions by one of several well-established systems,
such as precipitation of crystalline or amorphous iron
arsenate (Dutrizac and Jambor, 1988; Vircikova et al., 1995)
or processes such as arsenic precipitation as beudantite or
alunite structures (Vials et al., 2010; Dutrizac et al., 1987;
Dutrizac & Jambor, 1987; Twidwell and Mehta, 1985). After
this, zinc can be recovered by precipitation.

25
Table 6
Distribution of the different size fractions obtained by cyclosizer.

20
15

10
5
0
> 44 > > 33 > > 23 >

>6>

> 12 >

Global

Fractions (micrometer)
Cu

Fe

Zn As

Fig. 7. Chemical composition of the different size fractions obtained by cyclosizer (XRF).

Mass
Fe
Cu
Zn
As

T1+

T1-

T2+

T2-

T3+

T3-

T4+

T4-

T5+

T6

N 44

b 44

N 33

b 33

N 23

b23

N16

b16

N12

b12

9
9
8
7
7

91
91
92
93
93

13
14
11
10
9

87
86
89
90
91

19
20
16
16
13

81
80
84
84
87

27
30
24
26
18

73
70
76
74
82

34
39
32
35
23

66
61
68
65
77

A. Morales et al. / Hydrometallurgy 105 (2010) 148154

153

Table 7
DIN 38414-S4 test conditions applied to the samples R1, R2, R3, and R4.
Sample

R1
R2
R3 (60/40)
R4 (80/20)

pH

( N 2 mm)
( b 0.1 mm)
( N 2 mm)
( b 0.1 mm)

7.10
7.43
7.40
7.35
7.80
7.70

Conductivity
(mS m1)
0.680
0.600
0.600
0.625
0.210
0.250

Concentration (mg L-1)

Cd

Cu

Pb

Zn

Ni

As

Cr

b0.040
b0.040
b0.040
b0.040
b0.040
b0.040

1.7
3.0
3.2
3.5
1.4
2.1

0.80
b0.40
b0.40
b0.40
b0.40
b0.40

b 0.25
b 0.25
b 0.25
b 0.25
b 0.25
0.13

b 0.10
b 0.10
b 0.10
b 0.10
b 0.10
0.10

19
b 0.20
0.20
b 0.20
0.40
0.55

b0.020
b0.020
b0.020
b0.020
b0.020
b0.020

2) The residue obtained after leaching with sulfuric acid can be

mixed with sludge from a paper factory, forming pellets of
10 mm diameter. Laboratory studies carried out in this work
indicate that the resulting mixture should be dumped without
generating major environmental problems. These results are
similar to those obtained in a previous work, (Grau et al.,
2004), consisting in the co-inertization of electric arc furnace
ue dust from steelmaking with sludge from a paper factory,
in a study developed at pilot plant level.
Alternatively, due to the fact that the residue after sulfuric
acid leaching is mainly formed by spinel phases (magnetite,
copper ferrite and so on) and enargite, this residue can be
recycled directly to the ash furnace, without any additional
treatment.
An alternative process could be the same, but not the best, as was
previously established by copper smelter ue dusts from a continuous
furnace (Morales et al., 2007): the residue from water leaching can be
hydrocycloned to obtain two fractions, one (coarse fraction) for
recycling to the furnace and the other (ne fraction, with high arsenic
content) for stabilization purposes by mixing with sludge from a
paper factory. However, the results obtained applying these steps
were not as successfully as those obtained by leaching with sulfuric
acid and co-inertization by mixing the former residue with sludge
from a paper factory.
In all the cases, this is a proposal of an hydrometallurgical process
operating at room temperature, atmospheric pressure, with dilute
reagents, few unit operations, low energy costs and environmentally
friendly.

4. Conclusions
The copper ue dust sample consists mainly of oxidized species
and a few sulde species. The main components are magnetite,
cuprospinel, chalcocyanite, zincosite, dolerofanite and claudetite. The
minor components are tenorite, delafossite, arsenolite and enargite.
The amount of dusts dissolved in water was 54%. Almost all the
iron remains in the residue (like magnetite and cuprospinel). Copper
dissolves as copper sulfate and dolerofanite, and remains in the
residue as cuprospinel, some residual suldes and copper oxides. Zinc
sulfate was dissolved, with zinc remaining in the residue as spinel.
Arsenic was partially dissolved from arsenic oxides. Almost all the
sulfur dissolved is as soluble sulfates.
Treatments of the residues after leaching with water in various
acid media, increases the extraction of copper and arsenic, slightly
increases the extraction of zinc, while almost all the iron remains in
the residue. Dissolution of copper corresponds to its oxides and
perhaps additional amounts of copper basic sulfates; therefore,
additional amounts of arsenic oxides were dissolved. Residues
generated after acid treatments consist basically of magnetite and
cuprospinel.
In the cyclosizer experiments, copper composition is homogeneous in almost all the fractions (17% Cu), iron and arsenic are also
homogeneous in all the fractions ( 25% Fe, 19% As) except in the

nest fraction (19% Fe, 26% As), and zinc is concentrated in the middle
fractions (6.46.8% Zn).
The leaching DIN 38414-S4 test over the residue after sulfuric acid
leaching indicated low elements dissolution, with the exception of
arsenic (19 ppm). The mixture of the former residue and sludge
shows a good stabilization. Samples b 12 from hydrocyclone mixed
with sludge at different proportions also indicates a good stabilization,
and this process can be considered chemical in nature because the
results obtained in the fractions N2 mm and b0.1 mm were almost the
same. All these materials could be dumped without generating major
environmental problems.
Acknowledgments
We are grateful to the Serveis Cienticotcnics de la Universitat
de Barcelona for their assistance in the characterization studies
developed in this work. Thanks are also due to Ms. Esther Vilalta and
Ms. Gemma Garcia for their assistance with the microscopy studies.
References
Baczek, F.A., Wojcik, B.C., Jueschke, A.A., Lewis, D.M., Otto, J.C., Tuttle, L.L. 1982.
Recovering copper from a copper-bearing source. US patent 4.290.865.
Biswas, A.K., Davenport, W.G., 1976. Extractive Metallurgy of Copper, First edition.
Pergamon Press Ltd, Oxford, England, pp. 161164.
Carter, M., Vance, E.R., Aldridge, L.P., Zaw, M., Khoe, G., 1994. Immobilization of arsenic
trioxide in cementitious materials. Australasian Institute of Mining and Metallurgy
275280.
Diari Ocial de la Generalitat de Catalunya (Ofcial Newspaper of the Catalan
Government), 2000.3/09.21 order, 26 September 2000.
Dutrizac, J.E., Jambor, J.L., 1987. The behavior of arsenic during jarosite precipitation:
arsenic precipitation at 97 C from sulfate or chloride media. Canadian Metallurgical Quarterly 26 (2), 91101.
Dutrizac, J.E., Jambor, J.L., 1988. The synthesis of crystalline scorodite FeAsO4.2H2O.
Hydrometallurgy 19, 377384.
Dutrizac, J.E., Jambor, J.L., Chen, T.T., 1987. The behavior of arsenic during jarosite
precipitation: reactions at 150 C and the mechanism of arsenic precipitation.
Canadian Metallurgical Quarterly 26 (2), 103115.
Ermakov, V.I., 1979. Complex treatment of ne dusts of uralian copper-smelting works.
Tsvetnye Metally 12, 2630.
Fu, Y., Jiang, L., Wang, D., 2000. Removal of arsenic from copper smelter ue dust by
calcinations. Yelian Bufen 6, 1416.
Gabb, P.J., Evans, J.P. 1997. Hydrometallurgical and leach processing of impurity
streams from the pyrometallurgy of copper sulde ores. US patent 5,616,168
Gorai, B., Jana, R.K., Khan, Z.H., 2002. Electrorening electrolyte from a copper plant
dust. Materials Transactions 43 (3), 532536.
Grau, J., Roca, A., Cruells, M., Vials, J. 2004. Process for inertization of inorganic
residues, European Patent, 04103069.3.
Hanks, R.J., Van der Zel, J.P., Chesney, P., Harris, G.B., 1979. Bismuth at Rokana copper
smelter, Zambia: its behavior and extraction from ue dusts. Transactions Institute
Mining Metallurgy Sect. C: Mineral Processing and Extractive Metallurgy 88,
99106.
Ke, J., Qin, R., 2000. Arsenic removal and bismuth recovery from copper smelter ue
dust. In: Young, C. (Ed.), Symposium Minor Elements 2000: Processing and
Environmental Aspects of Arsenic, Antimonium, Sellenium, Tellurium and Bismuth.
Society for Mining, Metallurgy and Exploration, USA, pp. 293298.
Kunter, R.S., Bedal, W.E., 1992. Chloride-process treatment of smelter ue dusts. JOM
Journal of the Minerals Metals and Materials Society 44 (12), 3538.
Law, H.H., Bohrer, M.P., O'Hara, P.A., Sapjeta, J., Tierney, V., 1992. Recovery of metals
from copper smelter furnace ue dust. In: Reddy, R.G., Imrie, W.P., Queneau, P.B.
(Eds.), Int. Symp. Process. Environ. Consid. TMS-AIME, Warrendale, PA, pp.
295310.
Martn, I.M., LpezDelgado, A., Lpez, F.A., Coedo, A.G., Dorado, M.T., Alguacil, F.J.,
2003. Treatment of copper converter ue dust for the separation of metallic/non

154

A. Morales et al. / Hydrometallurgy 105 (2010) 148154

metallic copper by hydrometallurgical processing. J. Chem. Eng. Japan 36 (12),

14981502.
Mochida, H., Iida, O., 1988. Copper smelter ue dust treatment. Jap. Kokai Tokkyo Koho,
3.
Morales, A. 2006. Caracterizacin de polvos de fundicin de cobre y establecimiento de
rutas de procesado. PhD Thesis. University of Barcelona, Barcelona, Spain.
Morales, A., Cruells, M., Roca, A., Berg, R., 2007. Characterization of ue dusts from a
copper smelter furnace, copper recovery and arsenic stabilization. In: Riveros, P.A.,
Dixon, D.G., Dreisinger, D.B., Collins, M.J. (Eds.), Cu2007, The John E. Dutrizac Symp.
on Copper Hydrometallurgy 4, book 2. : The Canadian Institute of Mining,
Metallurgy and Petroleum. Montreal, QC, Canada, pp. 177189.
Mulale, C.T., Mwema, M.D., Mashala, G.B., 1999. Retreatment of dust waste from the
copper smelter and converter. In: Gaballah, I., Hager, J., Solozabal, R. (Eds.), Global
Symposium on Recycling and Clean Technology, 2. TMS-AIME, Warrendale, PA, pp.
12011208.
Nez, C., Espiell, F., Roca, A., 1985. Recovery of copper, silver and zinc from Huelva
(Spain) copper smelter ue dust by a chloride leach process. Hydrometallurgy 14
(1), 93103.
Robles, A., Serna, A.E., Sandez, M., 1999. Alkaline arsenic leaching from smelter ue dust
and leaching solution regeneration. In: Daz, C., Landolt, C., Utigard, T. (Eds.),
Copper99-Cobre99. International Conf., TMS-AIME, Warrendale, PA, pp. 261272.
Roman-Moguel, G.J., Plascencia, G., Prez, J., Garcia, A., 1995. Copper recycling from
waste pickling solutions. JOM Journal of the Minerals Metals and Materials Society
47 (10), 1819.

Smirnov, M.P., Khvan, V.T., Bibenina, G.A., Kelyan, R.P., Il'yasov, N.I., 1984. Complex
treatment of lead and rhenium containing sulfate dusts from copper plants.
Tsvetnye Metally 6, 36.
Sumitomo Metal Mining. 1982. Metal recovery from ue dust containing copper. Japan
Patent 57.201.577.
Twidwell, L.G., Mehta, A.K., 1985. Disposal of arsenic bearing copper smelter ue dust.
Nuclear and Chemical Waste Management 5, 299303.
Vials, J., Sunyer, A., Torres, E., Beltran, V., Llorca, N., 2010. Arsenic inertization from
copper pyrometallurgy through phases of the alunite supergroup. In: Harre, J. (Ed.),
Copper 2010. Clausthal-Zellerfeld, Germany, pp. 20712086. Vol 5.
Vircikova, E., Havlik, M., 1999. Removing arsenic from converter dust by a hydrometallurgical
method. JOM Journal of the Minerals Metals and Materials Society 51 (9), 2023.
Vircikova, E., Molnr, L., Lech, P., Reitznerova, L., 1995. Solubilities of amorphous Fe-As
precipitates. Hydrometallurgy 38, 111123.
Yin, B.Z., Caba, E., Barron, L., Belin, D., Morris, W., Vosika, M., Bartlett, R., 1992. Copper
extraction from smelter ue dust by lime-roast/ammoniacal heap leaching. In:
Reddy, R.G., Imrie, W.P., Queneau, P.B. (Eds.), Int. Symp. Process. Environ. Consid.
TMS-AIME, Warrendale, PA, pp. 255267.
Yu, Z., 1987. Process for bismuth recovery from the ue dust of copper smelting.
Huaxue Shijie 28 (10), 465468.
Zhang, Z.W., Lu, W., Zheng, F., 1992. Separation and recovery of copper and zinc from
ue dust. Huanjing Kexue 11 (6), 10121016.