Separation and Purification Technology 142 (2015) 116–122

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Separation and Purification Technology

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Selective leaching and recovery of bismuth as Bi2O3 from copper smelter

converter dust
Tae Kyung Ha, Bok Hyun Kwon, Kye Sun Park, Debasish Mohapatra ⇑
Metals & Materials Research Laboratory, LS Nikko Copper Inc., Ulsan 689-892, South Korea

a r t i c l e i n f o a b s t r a c t

Article history: Secondary materials such as converter dusts from the copper smelters are rich in bismuth and other valu-
Received 11 December 2014 able metals. This paper describes an economically viable Bi recovery process from the converter dust by a
Received in revised form 2 January 2015 hydrometallurgical method. The results showed that, Bi could be effectively leached out from the con-
Accepted 3 January 2015
verter dust using a combination of H2SO4 and NaCl as leaching reagent with a leaching efficiency of
Available online 9 January 2015
92% under the optimum conditions. Small amount of impurities such as Ag, Pb, Te and Se were removed
from the leach solution by SO2 reduction. Bismuth was separated from the leach solution as crude BiOCl
Keywords:
cake by hydrolysis method. The final bismuth product, Bi2O3 was synthesized by NaOH treatment of the
Converter dust
Acidic-chloride leaching
crude BiOCl cake at elevated temperature. The purity of the Bi2O3 product was about 97.8%, As, Pb and Sb
SO2 being the major impurities. Based on the feasibility study, the process was deemed technically feasible
Hydrolysis and its product commercially saleable.
Bi2O3 Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction [2–6]. The copper smelters usually prefer hydrometallurgical treat-

Dust treatment is an age old problem in the copper smelting
industry and the problem has been aggravated with time due to
the lack of quality copper ore and increasing amount of impurities.
There is no one-fit-all solution to the dust handling problem.
Usually, copper smelters adopt their own in-house technology to
overcome the dust problem. The mass of the dust produced in
the smelting furnace and the composition of elements present in
the dust depends on several factors such as, the type of furnace,
mineralogy of the concentrates and grade, oxygen enrichment,
fluxes and circulating material (slag, dust, etc.) and their respective
proportions [1]. Usually, volume of the dusts generated during cop-
per smelting process represents around 5–10% of the total input.
These materials are important sources of Cu and precious metals
because of their high content; however, the significant amount of
impurities such as As, Bi, Sb, Pb, and Cd prevents easy and com-
plete reprocessing in smelting or converting furnaces. Consequent-
ly, dusts captured from the off-gas represent an ideal stream to
remove those impurities from the system.
The treatment of copper smelter converter dust has been exten-
sively studied during last 2–3 decades. However, most of the lit-
eratures related to hydrometallurgical treatment of dust are
confined to the copper recovery and arsenic removal/stabilization
⇑ Corresponding author. Tel.: +82 52 231 0182; fax: +82 52 231 0183.
E-mail address: m_debasish2001@yahoo.com (D. Mohapatra).
ment of the converter dust to recover Cu values followed by treat-
ment of the Pb rich leach residue by pyro-metallurgical process
[6–8]. Plant water, fresh H2SO4 or spent electrolyte from the tank
house is used as leaching reagent and copper is recovered by sul-
fide precipitation, electro-winning and in some cases by solvent
extraction. The leach residue rich in Pb, Bi and precious metals is
sold to the Pb smelters for further processing. Such residues con-
tain a significant amount of silver (0.15%) and therefore represent
a valuable source for its Ag content alone. The full economic poten-
tial of such residues are undervalued due to the penalties imposed
on deleterious impurities such as the bismuth, copper or due to
undeveloped technology for the recovery of major components.
Specifically, Pb smelters do not accept secondary raw materials
containing more than 0.02% of bismuth. The reason for this penalty
is that, bismuth is known to interfere with the recovery of silver
values and also alter the physical properties of the metallic lead
with respect to its ductility [9]. So, the limitation of Bi content in
refined lead is limited to 50–100 ppm [10]. Therefore, such resi-
dues must be sold elsewhere at less than the premium price it
would otherwise demand if the bismuth were not present or were
present in amounts less than about 0.02%. Also, in order to re-cycle
the dusts to the copper smelting system, minor elements par-
ticularly bismuth need to be removed from the dust, since Bi is
one of the most deleterious impurities affecting the quality of elec-
tro refined copper metal [10]. In any case, the selective removal of
Bi from the dust is of considerable interest. Most of the commercial

http://dx.doi.org/10.1016/j.seppur.2015.01.004
1383-5866/Ó 2015 Elsevier B.V. All rights reserved.
 T.K. Ha et al. / Separation and Purification Technology 142 (2015) 116–122 117

Bi recovery process from the converter dust is based on pyro-met- dust was investigated by a JSM-7001F, JEOL (Korea) Scanning elec-
allurgical technique. The acidic-chloride based leaching of dust is tron Microscope with energy dispersive X-ray analyzer (SEM–
the most promising among those that have not found industrial EDX). The sulfur analysis was done by a LECO SC-432 analyzer.
applications yet, particularly for high Bi content dust [11–13].
The mechanism is that, the formation of chloro-complexes
3. Results and discussion
enhance the solubility of Bi, Sb, Cu to a much higher order com-
pared to Ag and Pb, the solubility of which are quite low in
3.1. Characterization of copper converter dust
H2SO4 medium [14].
The objective of the paper is to develop a hydrometallurgical Bi
The particle size analysis of a represented dust sample is pre-
recovery process from the converter dust generated in the Cu
sented in Fig. 1. As expected, the dust particles were fine with an
smelting industry. In the first stage, Cu, Zn, Cd and As was leached
average size (d50) of 15 lm. It can be seen that majority of the par-
out from the dust using a diluted H2SO4 solution. The un-dissolved
ticles lie within the 5–50 lm size range. The chemical analysis and
residue was used as the starting material for the Bi recovery pro-
X-ray diffraction pattern of the dust sample are presented in
cess. The purpose of the leaching test was to selectively dissolve
Table 1 and Fig. 2, respectively. The dust contains about 10.9% of
the Bi values and at the same time minimize the extent of Pb
Cu apart from considerable amount of Pb, As, Zn, Bi, etc. Major
and Ag dissolution. The leaching tests were carried out in an
phases detected by XRD included hematite (Fe2O3), cuprospinel
acidic-chloride medium where H2SO4 was used as an acid source
(CuFe2O4), anhydrous copper sulfate (CuSO4) and lead sulfate
and NaCl as the chloride source. The Bi rich leach solution was sub-
(PbSO4). SEM observations revealed that, a majority of the particles
ject to an impurity removal step by SO2 reduction, followed by
has an inner core consisting of oxide phases such as CuFe2O4 and
BiOCl precipitation by hydrolysis. Finally, marketable Bi2O3 was
Fe2O3, with an outer crust consisting of sulfates such as PbSO4,
synthesized by mixing BiOCl with NaOH solution at elevated tem-
ZnSO4 and CuSO4, indicating that most of the particles had not
perature. The optimum conditions for leaching, impurity removal
been thoroughly sulphatised. The complicated background of the
and Bi2O3 preparation has been examined and discussed in this
dust XRD pattern indicates that other minor elements may exist
paper.
as amorphous species, which are not identifiable by XRD. The che-
mical state of Bi and Ag could not be determined due to their low
concentrations. However, it is postulated that minor elements such
2. Experimental
as Bi and Ag present as oxides in the dust.
The dust samples were collected from our smelter and used as
such for all further experiments. As a pre-treatment, the dust was 3.2. Pre-treatment of converter dust
first leached with a pre-determined concentration of H2SO4 and
pulp density. Since operational cost is as important consideration Because of the higher content of Cu in the dust, it makes eco-
in the industrial process, care was taken to perform the leaching nomic sense to recover it in the first place. The Cu recovery tech-
test under atmospheric pressure and temperature conditions. After nique which consists of a H2SO4 leaching followed by an
the solid liquid separation the un-dissolved leaching residue was appropriate recovery method has been practiced by several smel-
used as-such as the starting material for the Bi leaching process. ters throughout the world. The process parameters vary from smel-
At this point drying was avoided to minimize the influence of the ter to smelter governed by several factors such as, Cu phases in the
temperature. Pulp density calculations were done taking into dust, impurities in the dust, end use of the leach solution and leach
account the moisture content in the leach residue. All chemicals residue. A similar approach has been adopted in this case also,
used were of analytical reagent grade obtained from Daejung che- since this is the most economical and practical way to recover
micals, Korea. the Cu values from the dust. The Cu recovery part is beyond the
All leaching experiments were performed in a glass reactor of scope of the discussion, so only a brief summary is presented in
2000 mL, with a Teflon cap in the central hole in which the axis this paper for the benefit of the readers. Since most of the copper
of a Teflon stirrer with adjustable revolutions was placed. The flask exist as sulfate and oxide phases in the present material, a dilute
was heated by an electrical mantle fitted with a temperature con- H2SO4 leaching was chosen to leach out Cu values to the aqueous
trolling thermostat maintained at an accuracy of ±1 °C. For each phase. In this particular case, the objective was to selectively dis-
run, 1000 mL of leach solution containing pre-determined concen- solve the Cu values to a maximum extent possible. Care was taken
tration of chemicals were charged into the reaction flask and heat- to minimize Bi dissolution at this stage. Any Bi leached to the
ed to the required temperature. The residue was added to the flask
after the attainment of desired temperature. The contents were
stirred at 300 rpm and the reaction time was counted after addi-
tion of dust. To avoid evaporation loss, a condenser was fitted to
the reactor with continuous water flow. Except temperature varia-
tion experiments, all other experiments were carried out at room
temperature (24 ± 1) °C.
Metal concentration in the aqueous phase was determined by
ICP-AES (Varian) after suitable dilution and also by conventional
titration methods if and when required. The particle size distribu-
tion of the dust samples was investigated by means of a Malvern
Mastersizer 2000 laser diffraction particle size analyzer. An ethanol
media with an ultrasound bath prior to the grain size analysis was
used in order to avoid potential dissolution of salts. The mineralogy
of solid samples was determined by powder X-ray diffraction
(X’pert PRO, PANalytical) with monochromatic Cu Ka radiation
operated at 40 kV and 40 mA, between 10° and 100° of 2h range,
and a step size of 0.05° and 3 s/step. The morphology of converter Fig. 1. Particle size analysis of the converter dust sample.
118 T.K. Ha et al. / Separation and Purification Technology 142 (2015) 116–122
Table 1
Chemical composition of the converter dust sample (wt.%).
Elements Ag As Bi
Before H2SO4 leaching 0.05 7.1 1.9
After H2SO4 leaching 0.15 2.9 5.3
Fig. 2. XRD pattern of the converter dust.
aqueous phase was difficult to recover, so considered as a net loss.
The copper leaching efficiency was directly related to the type of
Cu phase present in the dust. At the optimum leaching condition
of 50 g/L H2SO4, 300 g/L pulp density, room temperature and
60 min reaction time, the Cu leaching efficiency varied between
80% and 90%. Dusts containing higher sulfate, resulted higher
leaching efficiency of Cu. On the other hand, presence of copper
sulfide phase and other insoluble Cu phases in the dust resulted
in lower Cu leaching efficiency. Appreciable amount to Zn, Cd
and As was also leached out at this stage. Additionally, a large frac-
tion of sulfur was removed as sodium sulfate. The un-dissolved
part of the dust which represents the leach residue was the source
of Bi, hence used for the Bi recovery process. The major compo-
nents of the leach residue derived from the dilute H2SO4 leaching
are presented in Table 1. It contained 42% Pb, apart from consider-
able amount of Bi, As, Zn and Cu. The XRD studies of the sample
showed that Pb in the sample was present in the form of PbSO4
(Fig. 3). Bismuth content was as high as 5.3%, which was deemed
to be economically feasible for its recovery. Silver content in the
leach residue was 0.15%. Some Cu still remain in the leach residue
which was mostly in sulfide form.
Fig. 3. XRD pattern of the converter dust after dilute H2SO4 leaching.
Cd Cu Fe Pb Sb Te Zn
1.3 10.9 1.6 14.2 0.1 0.2 7.8
0.1 1.9 4.8 42.0 0.45 0.65 2.4
3.3. Bismuth leaching
Like many other metallic compounds, Bi leaching to the aque-
ous phase also depends on the type of Bi phase exists in the solid
material. Sulfuric acid alone does not readily and completely dis-
solve Bi compounds for the reason that Bi sulfate in a diluted sul-
furic acid solution hydrolyzes with precipitation of basic bismuth
sulfate. On the other hand, bismuth oxide is insoluble in chloride
medium alone, at higher pH values. However, bismuth sulfate is
readily soluble in chloride medium; hence enough sulfuric acid
should be added to the medium to convert the oxides of bismuth
to the sulfate, which is subsequently dissolved in chlorine medium.
The chemical equation can be presented as below:
Bi2 O3 ðsÞ þ 3H2 SO4 ! Bi2 ðSO4 Þ3 ðsÞ þ 3H2 O ð1Þ
Bi2 ðSO4 Þ3 ðsÞ þ 6NaCl ! 2BiCl3 ðaq:Þ þ 3Na2 SO4 ð2Þ
Consequently, for the recovery of Bi an acidic-chloride based
leaching process was adopted where, H2SO4 and NaCl were used
as H+ and Cl ion sources, respectively. The choice of H2SO4 and
NaCl was based on their easy availability and low cost compared
to similar other alternatives. The sodium chloride having a higher
dissociation constant provide higher activity of Cl/mole compared
to other salts/acids in the order; NaCl, KCl > HCl > FeCl2 > CuCl2 >
FeCl3 > ZnCl2 [14]. The other advantage of using H2SO4 as the acid
source is, Ag and Pb dissolve to a somewhat lesser extent in a chlo-
ride solution that contains some sulfate ions [15].
Based on the theoretical aspects and practical constraints from
the industrial prospective, five important variables such as, tem-
perature, sulfuric acid addition, sodium chloride addition, pulp
density and time were studied and laboratory scale optimum con-
ditions were developed. Conditions were sought which resulted in
the maximum Bi leaching efficiency and minimum amount of Pb
and Ag in the aqueous phase. The effect of H2SO4 concentrations
on the Bi leaching efficiency was determined as a function of time
and graphically presented in Fig. 4. The other parameters those
maintained constant during the process were, NaCl 60 g/L, tem-
perature 70 °C, rpm 300 and pulp density (PD) 10%. According to
Fig. 4, H2SO4 concentration and leaching time were critical
Fig. 4. Effect of H2SO4 concentrations on the Bi leaching efficiency as a function of
time.
 T.K. Ha et al. / Separation and Purification Technology 142 (2015) 116–122
variables affecting the leach-ability of bismuth. The leaching effi-
ciency of Bi was enhanced significantly by an increase in the level
of each of those variables. This was more visible at lower H2SO4
concentration compared to higher H2SO4 concentrations. Without
H2SO4 (only 60 g/L NaCl used for leaching), the leaching efficiency
of Bi was under 2% even after 180 min of leaching time. Since the
leaching solution pH was about 5.0 when H2SO4 was not used, it
was expected that Bi precipitated as BiOCl and subsequently
remained in the solid phase. Increasing H2SO4 concentration in
the leaching medium significantly improved the Bi leaching effi-
ciency. Bismuth leaching efficiency increased from 37% to 92%
when H2SO4 concentration in the leaching medium increased from
25 g/L to 100 g/L. However, further increasing the H2SO4 concen-
tration to 150 g/L improved Bi leaching efficiency by only 3%. The
acid sensitivity on the Bi leaching efficiency suggests that Bi may
be present as oxide phase in the dust [9]. The initial rate of Bi
leaching was also increased with increasing H2SO4 concentration.
For example, 17% Bi was leached within 10 min of leaching when
25 g/L H2SO4 was used, that increased to 58% when 150 g/L
H2SO4 was used as leaching reagent. After the initial surge, the bis-
muth dissolution reaction rate slowed down appreciably. As far as
leaching time was concerned, maximum Bi leaching was achieved
within 120 min, after that the extent of reaction did not improve
significantly. The silver dissolution was under 2 ppm in most of
the cases studied and relatively insensitive to the H2SO4 concentra-
tion and temperature. Lead dissolution actually decreased from 1%
to 0.3% when H2SO4 concentration increased from 100 g/L to 150 g/
L at 70 °C. The above results probably indicate a difference in the
solid state activity of the Bi, Ag and Pb in the dust matrix.
The NaCl concentration is another important parameter critical
not only for the Bi leaching but also for the impurity dissolution
behavior. The variation of NaCl concentration was studied at a
fixed H2SO4 concentration of 100 g/L, temp 70 °C, time 180 min
and 10% PD. According to the results presented in Fig. 5, the leach-
ing efficiency of Bi increased from 72.8% to 92% when NaCl concen-
tration increased from 45 g/L to 60 g/L. Higher NaCl concentration
was found to have no such significant effect on the Bi leaching
behavior since the chloride demand by the Bi had been satisfied.
However, significant amount of Ag dissolution occurred when NaCl
concentration increased beyond 60 g/L. By increasing the NaCl con-
centration by 50%, Ag dissolution increased by 20-fold. When the
concentration of Cl was higher, AgCl dissolved to form AgCl1+X
complex with Cl ion as represented by the following equation
[16]:
 in the aqueous phase Bi exist as BiCl3, lead as H2PbCl4 and Ag as
Agþ þ Cl ! AgCl ðsÞ
 
AgCl ðsÞ þ Cl ! AgCl2 ðaq:Þ
Fig. 5. The NaCl concentration as a function of Bi leaching efficiency.
119
Moreover, the addition of NaCl increased the concentration of
Cl ion in the solution which also promoted the dissolution of
other non-ferrous metal ions by forming coordination ions, thereby
significantly increasing the impurity level in Bi leached solution
[14]. Also, when the mass of NaCl was higher, it promoted the for-
mation of more Na2SO4 by consuming H2SO4, thereby creating
potential sealing problem in the pipeline.
The effect of temperature was studied at three different tem-
perature conditions such as room temperature, 50 °C and 70 °C.
When experiment was carried out at room temperature no exter-
nal heat was applied; however, the reaction temperature increased
spontaneously up to 35 °C due to the exothermic nature on the
reaction. For other two temperature tests, external heat was used.
Temperature tests exceeding 70 °C was avoided due to the practi-
cal constraints. As demonstrated in Fig. 6, increased temperature
significantly improved the Bi leaching efficiency. Bismuth leaching
efficiency increased linearly with reaction temperature, from 57%
at room temperature to 92% at 70 °C when other operational para-
meters were kept constant i.e., 100 g/L H2SO4, 60 g/L NaCl and
120 min. Reaction temperature had negligible effect on the leach-
ing behavior of Pb and Ag. In all the three temperature conditions
studied, Ag concentration under the 2 ppm and Pb concentration
less than 500 ppm was reported in the leached solution.
Pulp density is an important parameter that influences the
leaching kinetics, process cost and downstream treatment process.
Therefore, to determine the effect of this parameter on the leaching
behavior of Bi, Ag and Pb, experiments were carried out at four dif-
ferent pulp densities such as 10 wt.%, 20 wt.%, 30 wt.% and 40 wt.%
solid to liquid ratio by volume. Parameters that kept constant were,
H2SO4 100 g/L, NaCl 60 g/L reaction time 120 min and reaction
temp 70 °C. As presented in Fig. 7, Bi leaching efficiency which
stood constant at 92% between 10% PD and 20% PD, subsequently
decreased to 87% for 30% PD and 74% for 40% PD. At the same time,
the concentration of Pb decreased steadily from 390 ppm at 10% PD
to 45 ppm at 40% PD. The decrease in dissolution of Bi and Pb when
operating at higher pulp density was due to the inadequate chemi-
cal amount for mineral surfaces. The concentration of Ag in the
leach solution was quite low to get any concrete conclusion. So,
the optimum Bi leaching conditions derived from the above results
are 100 g/L H2SO4, 60 g/L NaCl, 70 °C, 120 min, 20% PD with a Bi
leaching efficiency of 92%. The composition of a typical Bi leach
solution is presented in Table 2. At the best leaching conditions,
the concentration of Bi, Pb and Ag dissolved into the aqueous phase
were 9.6 g/L, 420 ppm and 1 ppm, respectively. It is expected that,
ð3Þ
AgCl2.
ð4Þ
Fig. 6. Effect of temperature on the Bi leaching efficiency.
120 T.K. Ha et al. / Separation and Purification Technology 142 (2015) 116–122

Table 3
Chemical composition of the filtrate cake after SO2 blowing (wt.%).

Elements As Bi Cu Fe Pb Sb Te Zn
Composition 1.6 0 28.2 0 12.1 1.2 57.1 0

Fig. 7. Effect of pulp density on the Bi leaching efficiency.

3.4. Purification of leach solution

Recovery of bismuth from the pregnant leach solution by

hydrometallurgical route is technically challenging and sometimes
economically not feasible. Although there are several processes
available such as hydrolytic precipitation, sulfide or carbonate pre-
cipitation, cementation, solvent extraction, ion exchange, elec-
trolysis; each process has its own limitations [17]. Choosing the
right recovery/purification process for Bi, depends on several fac-
tors such as leaching solution medium, Bi content in the leach solu-
tion, type of impurities, Bi end product, market/sale price of the
product, waste water treatment cost, and solid waste disposal
issues. In this study, we have recovered bismuth as Bi2O3 from
the pregnant leach solution using a three stage purification
process.
I. Removal of impurities such as Ag, Pb, Cu, Te and Sb from the
leach solution using gaseous SO2 as reducing agent.
II. Separation of Bi as BiOCl from the leach solution by
hydrolysis.
III. Conversion of BiOCl-cake to Bi2O3 using an alkali solution.
Fig. 8. Precipitation efficiency of Bi, Cu, Fe and As, as a function of dilution factor
and pH.
The bismuth was recovered from the purified solution by
hydrolysis route using H2O as precipitating reagent. Hydrolysis is
the reaction of a compound or ion with water forming a basic salt.
Many of these basic salts are insoluble in water, which accounts for
their precipitation. The transformation of BiCl3 to BiOCl by hydro-
lysis is a multi-step process represented by the following
equations:
BiCl3 þ H2 O ¼ BiðOHÞCl2 þ HCl ð5Þ
BiCl3 þ 2H2 O ¼ BiðOHÞ2 Cl þ 2HCl ð6Þ
The basic salt so formed may also loose water, as shown in the
equation:

Removal of impurities from the leach solution is a key part of
the process to get better purity and saleable price for Bi2O3 prod-
uct. Impurities such as Ag, Pb, Fe and Sb are considered as toxic
to the Bi2O3 product, so it is essential to remove such impurities
from the final product. In the present study, SO2 reduction process
was used to remove the impurities. Results showed that, at a favor-
able reducing condition of 100 mV to +100 mV reduction poten-
tial and at a temperature 70 °C, contact time 60 min, 82% Te, 85%
Pb and 100% Ag precipitated as corresponding metals and subse-
quently removed from the solution. About 30% As and 45% Cu also
precipitated along with the above elements. The role of tem-
perature in this case was to accelerate the rate of reaction. At a
lower temperature, for example at 40 °C, similar results were
obtained but after a prolonged period of SO2 blowing. The chemical
composition of the cake generated by the SO2 blowing is presented
in Table 3 and represents an ideal case to be returned to the smel-
ter for precious metal recovery. The SO2 blowing also reduced most
of the Fe3+ to Fe2+ in the leach solution, which was advantageous
for the purification requirement of the subsequent process.
BiðOHÞ2 Cl ¼ BiOCl þ H2 O ð7Þ
Because of the lower solubility product constant (Ksp) of BiOCl
(1.8  1031, 25 °C) compared to BiOOH (4  1010, 25 °C) and a
large quantity of Cl anion in the solution, the formation of BiOCl
was preferred compared to the hydrated bismuth oxide. Fig. 8
shows the precipitation efficiency of Bi, Cu, Fe and As, as a function
of dilution factor and pH at room temperature (24 ± 1) °C. It was
observed that bismuth precipitation efficiency was 86% when solu-
tion volume increased by 5 times by diluting with water. The
precipitation efficiency increased to 99% when dilution factor
was 10 times and 99.9% when dilution factor was 25 times. The
pH of the solution which is directly proportional to the dilution
factor is a critical factor for the precipitation of Bi. In the present
study, the solution pH was 0.25, 0.45 and 1.2 for the dilution fac-
tors 5, 10 and 25 times, respectively. The degree of Bi precipitation
increased with the increase of solution pH. At the same time, Cu
and Fe, the two major constituents in the leach solution precipitat-
ed to a much lesser extent. For all the three dilution factors, Cu and
Fe precipitation was under 1%. Unfortunately, almost all of the As

Table 2
Chemical composition of the leach solution.

Elements Ag As Bi Cu Fe Pb Sb Te Zn
Concentration (g/L) 0.002 0.41 9.6 1.10 6.5 0.42 0.15 0.82 3.5
Leaching efficiency (%) 0.01 14 92 29 68 0.5 17 63 74
 T.K. Ha et al. / Separation and Purification Technology 142 (2015) 116–122
co-precipitated with Bi and reported to the solid phase. The effect
of temperature was studied to access the Bi precipitation efficiency
during hydrolysis. It was observed that, higher temperature
(>50 °C) improved Bi precipitation efficiency by a factor 5–10%.
However, considering the energy cost associated with the elevated
temperature, it was conclude to operate the hydrolysis test at the
room temperature. Based on the results, about 10 times of dilution
factor was considered suitable to precipitate >99% Bi from the
leach solution. After solid liquid separation the waste water was
channeled to some other process for re-use, which was specifically
important considering the large quantity of water consumed in the
process.
The resulting BiOCl precipitate that contained small amount of
As, Sb and Sn was treated further to synthesize Bi2O3. The chemical
analysis showed that the BiOCl precipitate contained 76.3% Bi, 0.3%
Cu, 0.1% Fe, 0.7% Sb and 2.25% As. The transformation of BiOCl into
Bi2O3 is a process that depends mainly on two factors, i.e., NaOH
concentration and temperature [18]. The chemical reaction for this
transformation can be written as below:
2BiOCl þ 2NaOH ! 2BiOOH þ 2NaCl
2BiOOH þ Heat ! Bi2 O3 þ H2 O
Combining Eqs. (8) and (9), can be presented as:
2BiOCl þ 2NaOH þ Heat ! Bi2 O3 þ 2NaCl þ H2 O
According to the Eq. (10), theoretically two moles of BiOCl react
with two moles of NaOH to produce one mole of Bi2O3. In other
words, 521 g of BiOCl consume 80 g NaOH to produce 466 g of
Bi2O3. Top of that, some excess NaOH should be added to the leach-
ing medium to make the solution sufficiently alkaline to dissolve
desired alkali soluble impurities such as As and Sb from the
Bi2O3 product in order to give it maximum purity. Three different
concentrations of NaOH i.e. 50 g/L, 100 g/L and 150 g/L, were cho-
sen to study its effect on Bi2O3 conversion and impurity removal at
a fixed PD of 300 g/L, temperature 80 °C and reaction time 120 min.
When 50 g/L NaOH was used, BiOCl transformation to Bi2O3 was
not completed, understandably due to the lack of OH ion in the
aqueous medium. In the case of 100 g/L NaOH, complete transfor-
mation of Bi2O3 happened and most of the alkali soluble impurities
also dissolved into the aqueous phase. Increasing NaOH concentra-
tion to 150 g/L did not give any significant improvement in terms
of product purity or product quality. The final product Bi2O3 was
separated by filtering, washed with deionized water and then dried
at 105 °C to a constant weight. The X-ray diffraction pattern con-
firmed the presence of Bi2O3 phase in the product (Fig. 9). The che-
mical composition for the final Bi2O3 product as presented in
Fig. 9. X-ray diffraction pattern for the final Bi2O3 product.
121
Table 4
Chemical composition of the final Bi2O3 product (wt.%).
Elements As Bi Cu Fe Pb Sb Te Zn
Composition 0.35 88 0.2 0.1 0.3 1.2 0 0
ð8Þ
ð9Þ
ð10Þ Fig. 10. Process flow diagram for Bi recovery from converter dust.
Table 4 showed the mass fraction of Bi as 88% which is very close
to the theoretical value of 89.7%. Small amount of impurities pre-
sent in the Bi2O3 were As, Sb and Pb. The purity of the Bi2O3 pro-
duct was calculated to be 97.8%. Finally, a process flow diagram
to recover Bi as Bi2O3 from the converter dust has been presented
(Fig. 10). To the best of our knowledge, the product has good mar-
ket and commercial value.
4. Conclusion
A hydrometallurgical process based on acidic-chloride leaching
has been developed to recover Bi as Bi2O3 from the converter dust.
Process conditions for unit operations have been optimized base on
laboratory tests. Parameters such as H2SO4 concentration and chlo-
ride concentration were found to have significant effect on the
leaching behavior of Bi and impurities. Under the optimum leach-
ing conditions (100 g/L H2SO4, 60 g/L NaCl, 20% PD, 70 °C and
120 min contact time), 92% Bi leaching efficiency was achieved
with minimum levels of impurities in the leach solution. Substan-
tial amount of impurities such as Pb, Ag, Te and Cu were removed
from the leach solution using SO2 as reducing agent. A dilution fac-
tor of 10 times was found suitable to precipitate out >99% of Bi as
BiOCl from the solution. The appropriate conditions for synthesiz-
ing Bi2O3 from the crude BiOCl were, 100 g/L NaOH, 80 °C, PD
300 g/L and reaction time of 120 min. Using this method, recovery
of Bi as Bi2O3 product of 97.8%, purity was achieved.
Acknowledgements
The authors are thankful to the Chief Technology Officer (CTO)
of LS Nikko Copper for his kind permission to publish the paper.
References
[1] A.K. Biswas, W.G. Davenport, Extractive Metallurgy of Copper, third ed.,
Pergamon, London, 1994.
[2] M. Vitkova, V. Ettlet, J. Hyks, T. Astrup, B. Kribek, Leaching of metals from
copper smelter flue dust (Mufulira, Zambian Copperbelt), Appl. Geochem. 26
(2011) 5263–5266.
122 T.K. Ha et al. / Separation and Purification Technology 142 (2015) 116–122
[3] A. Morales, M. Cruells, A. Roca, R. Bergo, Treatment of copper flash smelter flue
dusts for copper and zinc extraction and arsenic stabilization,
Hydrometallurgy 105 (2010) 148–154.
[4] Zhi-feng Xu, Q. Li, Hua-ping Nie, Pressure leaching technique of smelter dust
with high-copper and high-arsenic, Trans. Nonferr. Met. Soc. China 20 (2010)
176–181.
[5] F. Bakhtiari, M. Zivdar, H. Atashi, S.A. Sayed Bagheri, Continuous copper
recovery from a smelters dust in stirred tank reactors, Int. J. Min. Process. 86
(2008) 50–57.
[6] R. Ichimura, H. Tateiwa, C. Almendares, G. Sanchez, Arsenic immobilization
and metal recovery from EI Teniente smelter dust, in: P.A. Riveros, D.G. Dixon,
D.B. Dreisinger, M.J. Collins (Eds.), The John E. Dutrizac Symposium on Copper
Hydrometallurgy, vol. IV, Canadian Institute of Mining, Metallurgy and
Petroleum, Montreal, Canada, 2007, pp. 191–204.
[7] P.J. Gabb, D.L. Howe, D.J. Purdie, H.J. Woerner, The Kennecott smelter
hydrometallurgical impurities process, in: W.C. Cooper, D.B. Dreisinger, J.E.
Dutrizac, H. Hein, G. Ugarte (Eds.), Copper 95, vol. III, The Metallurgical Society
of CIM, 1995, pp. 591–606.
[8] J. Hino, T. Kawabata, Removal and recovery of minor elements in copper
smelting, in: W.C. Cooper, D.B. Dreisinger, J.E. Dutrizac, H. Hein, G. Ugarte
(Eds.), Copper 95, vol. III, The Metallurgical Society of CIM, 1995, pp. 617–627.
[9] J.D. Miller, J.L. Sepulveda Jimenez, Selective removal of bismuth from oxidized
particulate materials, U.S. Patent 3,966,461, 1976.
[10] A. Sandstrom, J.E. Sundkvist, Method for the treatment of bismuth containing
sulfide ores or concentrates of such ore, U.S. Patent 5,961,940, 1999.
[11] Ya Chen, T. Liao, G. Li, B. Chen, X. Shi, Recovery of bismuth and arsenic from
copper smelter flue dusts after copper and zinc recovery, Miner. Eng. 39 (2012)
23–28.
[12] N.L. Piret, Optimizing bismuth control during copper production, J. Met. 10
(1994) 15–18.
[13] R.S. Kunter, W.E. Bedal, Chloride process treatment of smelter flue dusts, J.
Met. 44 (1992) 35–38.
[14] D.M. Muir, Principles and Applications of Strong Salt Solutions to Mineral
Chemistry, Extractive Metallurgy Symposium’85, The Institute of Mining and
Metallurgy, London, 1985. pp. 65–91.
[15] R. Leimula, O. Hyvarinen, Method of removal of impurities from gold
concentrate containing sulfides, U.S. Patent 6,861,037, 2005.
[16] L. Liu, J. Wu, X. Li, Z. Gong, Preparation of high purity nanometer bismuth
trioxide from silver–zinc slag, Adv. Mater. Res. 156–157 (2011) 785–
793.
[17] C.M. Flynn, T.G. Carnahan, R.E. Lindstrom, Recovery of bismuth from chloride
process solutions, U.S. Patent 4,285,912, 1981.
[18] O. Monnereau, L. Tortet, P. Liewellyn, F. Rouquerol, G. Vacquier, Synthesis of
Bi2O3 by controlled transformation rate thermal analysis: a new route for this
oxide, Solid State Ionics 157 (2003) 163–169.