Parametros de Calidad Analitica
Parametros de Calidad Analitica
Parametros de Calidad Analitica
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.
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 Cd Cu Fe Pb Sb Te Zn
Before H2SO4 leaching 0.05 7.1 1.9 1.3 10.9 1.6 14.2 0.1 0.2 7.8
After H2SO4 leaching 0.15 2.9 5.3 0.1 1.9 4.8 42.0 0.45 0.65 2.4
Fig. 2. XRD pattern of the converter dust. Bi2 ðSO4 Þ3 ðsÞ þ 6NaCl ! 2BiCl3 ðaq:Þ þ 3Na2 SO4 ð2Þ
Consequently, for the recovery of Bi an acidic-chloride based
aqueous phase was difficult to recover, so considered as a net loss. leaching process was adopted where, H2SO4 and NaCl were used
The copper leaching efficiency was directly related to the type of as H+ and Cl ion sources, respectively. The choice of H2SO4 and
Cu phase present in the dust. At the optimum leaching condition NaCl was based on their easy availability and low cost compared
of 50 g/L H2SO4, 300 g/L pulp density, room temperature and to similar other alternatives. The sodium chloride having a higher
60 min reaction time, the Cu leaching efficiency varied between dissociation constant provide higher activity of Cl/mole compared
80% and 90%. Dusts containing higher sulfate, resulted higher to other salts/acids in the order; NaCl, KCl > HCl > FeCl2 > CuCl2 >
leaching efficiency of Cu. On the other hand, presence of copper FeCl3 > ZnCl2 [14]. The other advantage of using H2SO4 as the acid
sulfide phase and other insoluble Cu phases in the dust resulted source is, Ag and Pb dissolve to a somewhat lesser extent in a chlo-
in lower Cu leaching efficiency. Appreciable amount to Zn, Cd ride solution that contains some sulfate ions [15].
and As was also leached out at this stage. Additionally, a large frac- Based on the theoretical aspects and practical constraints from
tion of sulfur was removed as sodium sulfate. The un-dissolved the industrial prospective, five important variables such as, tem-
part of the dust which represents the leach residue was the source perature, sulfuric acid addition, sodium chloride addition, pulp
of Bi, hence used for the Bi recovery process. The major compo- density and time were studied and laboratory scale optimum con-
nents of the leach residue derived from the dilute H2SO4 leaching ditions were developed. Conditions were sought which resulted in
are presented in Table 1. It contained 42% Pb, apart from consider- the maximum Bi leaching efficiency and minimum amount of Pb
able amount of Bi, As, Zn and Cu. The XRD studies of the sample and Ag in the aqueous phase. The effect of H2SO4 concentrations
showed that Pb in the sample was present in the form of PbSO4 on the Bi leaching efficiency was determined as a function of time
(Fig. 3). Bismuth content was as high as 5.3%, which was deemed and graphically presented in Fig. 4. The other parameters those
to be economically feasible for its recovery. Silver content in the maintained constant during the process were, NaCl 60 g/L, tem-
leach residue was 0.15%. Some Cu still remain in the leach residue perature 70 °C, rpm 300 and pulp density (PD) 10%. According to
which was mostly in sulfide form. Fig. 4, H2SO4 concentration and leaching time were critical
variables affecting the leach-ability of bismuth. The leaching effi- Moreover, the addition of NaCl increased the concentration of
ciency of Bi was enhanced significantly by an increase in the level Cl ion in the solution which also promoted the dissolution of
of each of those variables. This was more visible at lower H2SO4 other non-ferrous metal ions by forming coordination ions, thereby
concentration compared to higher H2SO4 concentrations. Without significantly increasing the impurity level in Bi leached solution
H2SO4 (only 60 g/L NaCl used for leaching), the leaching efficiency [14]. Also, when the mass of NaCl was higher, it promoted the for-
of Bi was under 2% even after 180 min of leaching time. Since the mation of more Na2SO4 by consuming H2SO4, thereby creating
leaching solution pH was about 5.0 when H2SO4 was not used, it potential sealing problem in the pipeline.
was expected that Bi precipitated as BiOCl and subsequently The effect of temperature was studied at three different tem-
remained in the solid phase. Increasing H2SO4 concentration in perature conditions such as room temperature, 50 °C and 70 °C.
the leaching medium significantly improved the Bi leaching effi- When experiment was carried out at room temperature no exter-
ciency. Bismuth leaching efficiency increased from 37% to 92% nal heat was applied; however, the reaction temperature increased
when H2SO4 concentration in the leaching medium increased from spontaneously up to 35 °C due to the exothermic nature on the
25 g/L to 100 g/L. However, further increasing the H2SO4 concen- reaction. For other two temperature tests, external heat was used.
tration to 150 g/L improved Bi leaching efficiency by only 3%. The Temperature tests exceeding 70 °C was avoided due to the practi-
acid sensitivity on the Bi leaching efficiency suggests that Bi may cal constraints. As demonstrated in Fig. 6, increased temperature
be present as oxide phase in the dust [9]. The initial rate of Bi significantly improved the Bi leaching efficiency. Bismuth leaching
leaching was also increased with increasing H2SO4 concentration. efficiency increased linearly with reaction temperature, from 57%
For example, 17% Bi was leached within 10 min of leaching when at room temperature to 92% at 70 °C when other operational para-
25 g/L H2SO4 was used, that increased to 58% when 150 g/L meters were kept constant i.e., 100 g/L H2SO4, 60 g/L NaCl and
H2SO4 was used as leaching reagent. After the initial surge, the bis- 120 min. Reaction temperature had negligible effect on the leach-
muth dissolution reaction rate slowed down appreciably. As far as ing behavior of Pb and Ag. In all the three temperature conditions
leaching time was concerned, maximum Bi leaching was achieved studied, Ag concentration under the 2 ppm and Pb concentration
within 120 min, after that the extent of reaction did not improve less than 500 ppm was reported in the leached solution.
significantly. The silver dissolution was under 2 ppm in most of Pulp density is an important parameter that influences the
the cases studied and relatively insensitive to the H2SO4 concentra- leaching kinetics, process cost and downstream treatment process.
tion and temperature. Lead dissolution actually decreased from 1% Therefore, to determine the effect of this parameter on the leaching
to 0.3% when H2SO4 concentration increased from 100 g/L to 150 g/ behavior of Bi, Ag and Pb, experiments were carried out at four dif-
L at 70 °C. The above results probably indicate a difference in the ferent pulp densities such as 10 wt.%, 20 wt.%, 30 wt.% and 40 wt.%
solid state activity of the Bi, Ag and Pb in the dust matrix. solid to liquid ratio by volume. Parameters that kept constant were,
The NaCl concentration is another important parameter critical H2SO4 100 g/L, NaCl 60 g/L reaction time 120 min and reaction
not only for the Bi leaching but also for the impurity dissolution temp 70 °C. As presented in Fig. 7, Bi leaching efficiency which
behavior. The variation of NaCl concentration was studied at a stood constant at 92% between 10% PD and 20% PD, subsequently
fixed H2SO4 concentration of 100 g/L, temp 70 °C, time 180 min decreased to 87% for 30% PD and 74% for 40% PD. At the same time,
and 10% PD. According to the results presented in Fig. 5, the leach- the concentration of Pb decreased steadily from 390 ppm at 10% PD
ing efficiency of Bi increased from 72.8% to 92% when NaCl concen- to 45 ppm at 40% PD. The decrease in dissolution of Bi and Pb when
tration increased from 45 g/L to 60 g/L. Higher NaCl concentration operating at higher pulp density was due to the inadequate chemi-
was found to have no such significant effect on the Bi leaching cal amount for mineral surfaces. The concentration of Ag in the
behavior since the chloride demand by the Bi had been satisfied. leach solution was quite low to get any concrete conclusion. So,
However, significant amount of Ag dissolution occurred when NaCl the optimum Bi leaching conditions derived from the above results
concentration increased beyond 60 g/L. By increasing the NaCl con- are 100 g/L H2SO4, 60 g/L NaCl, 70 °C, 120 min, 20% PD with a Bi
centration by 50%, Ag dissolution increased by 20-fold. When the leaching efficiency of 92%. The composition of a typical Bi leach
concentration of Cl was higher, AgCl dissolved to form AgCl1+X solution is presented in Table 2. At the best leaching conditions,
complex with Cl ion as represented by the following equation the concentration of Bi, Pb and Ag dissolved into the aqueous phase
[16]: were 9.6 g/L, 420 ppm and 1 ppm, respectively. It is expected that,
in the aqueous phase Bi exist as BiCl3, lead as H2PbCl4 and Ag as
Agþ þ Cl ! AgCl ðsÞ ð3Þ
AgCl2.
AgCl ðsÞ þ Cl ! AgCl2 ðaq:Þ ð4Þ
Fig. 5. The NaCl concentration as a function of Bi leaching efficiency. 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
Removal of impurities from the leach solution is a key part of BiðOHÞ2 Cl ¼ BiOCl þ H2 O ð7Þ
the process to get better purity and saleable price for Bi2O3 prod- Because of the lower solubility product constant (Ksp) of BiOCl
uct. Impurities such as Ag, Pb, Fe and Sb are considered as toxic (1.8 1031, 25 °C) compared to BiOOH (4 1010, 25 °C) and a
to the Bi2O3 product, so it is essential to remove such impurities large quantity of Cl anion in the solution, the formation of BiOCl
from the final product. In the present study, SO2 reduction process was preferred compared to the hydrated bismuth oxide. Fig. 8
was used to remove the impurities. Results showed that, at a favor- shows the precipitation efficiency of Bi, Cu, Fe and As, as a function
able reducing condition of 100 mV to +100 mV reduction poten- of dilution factor and pH at room temperature (24 ± 1) °C. It was
tial and at a temperature 70 °C, contact time 60 min, 82% Te, 85% observed that bismuth precipitation efficiency was 86% when solu-
Pb and 100% Ag precipitated as corresponding metals and subse- tion volume increased by 5 times by diluting with water. The
quently removed from the solution. About 30% As and 45% Cu also precipitation efficiency increased to 99% when dilution factor
precipitated along with the above elements. The role of tem- was 10 times and 99.9% when dilution factor was 25 times. The
perature in this case was to accelerate the rate of reaction. At a pH of the solution which is directly proportional to the dilution
lower temperature, for example at 40 °C, similar results were factor is a critical factor for the precipitation of Bi. In the present
obtained but after a prolonged period of SO2 blowing. The chemical study, the solution pH was 0.25, 0.45 and 1.2 for the dilution fac-
composition of the cake generated by the SO2 blowing is presented tors 5, 10 and 25 times, respectively. The degree of Bi precipitation
in Table 3 and represents an ideal case to be returned to the smel- increased with the increase of solution pH. At the same time, Cu
ter for precious metal recovery. The SO2 blowing also reduced most and Fe, the two major constituents in the leach solution precipitat-
of the Fe3+ to Fe2+ in the leach solution, which was advantageous ed to a much lesser extent. For all the three dilution factors, Cu and
for the purification requirement of the subsequent process. 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) 116–122 121
co-precipitated with Bi and reported to the solid phase. The effect Table 4
of temperature was studied to access the Bi precipitation efficiency Chemical composition of the final Bi2O3 product (wt.%).
2BiOCl þ 2NaOH þ Heat ! Bi2 O3 þ 2NaCl þ H2 O ð10Þ Fig. 10. Process flow diagram for Bi recovery from converter dust.
Acknowledgements
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
Fig. 9. X-ray diffraction pattern for the final Bi2O3 product. (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 [10] A. Sandstrom, J.E. Sundkvist, Method for the treatment of bismuth containing
dusts for copper and zinc extraction and arsenic stabilization, sulfide ores or concentrates of such ore, U.S. Patent 5,961,940, 1999.
Hydrometallurgy 105 (2010) 148–154. [11] Ya Chen, T. Liao, G. Li, B. Chen, X. Shi, Recovery of bismuth and arsenic from
[4] Zhi-feng Xu, Q. Li, Hua-ping Nie, Pressure leaching technique of smelter dust copper smelter flue dusts after copper and zinc recovery, Miner. Eng. 39 (2012)
with high-copper and high-arsenic, Trans. Nonferr. Met. Soc. China 20 (2010) 23–28.
176–181. [12] N.L. Piret, Optimizing bismuth control during copper production, J. Met. 10
[5] F. Bakhtiari, M. Zivdar, H. Atashi, S.A. Sayed Bagheri, Continuous copper (1994) 15–18.
recovery from a smelters dust in stirred tank reactors, Int. J. Min. Process. 86 [13] R.S. Kunter, W.E. Bedal, Chloride process treatment of smelter flue dusts, J.
(2008) 50–57. Met. 44 (1992) 35–38.
[6] R. Ichimura, H. Tateiwa, C. Almendares, G. Sanchez, Arsenic immobilization [14] D.M. Muir, Principles and Applications of Strong Salt Solutions to Mineral
and metal recovery from EI Teniente smelter dust, in: P.A. Riveros, D.G. Dixon, Chemistry, Extractive Metallurgy Symposium’85, The Institute of Mining and
D.B. Dreisinger, M.J. Collins (Eds.), The John E. Dutrizac Symposium on Copper Metallurgy, London, 1985. pp. 65–91.
Hydrometallurgy, vol. IV, Canadian Institute of Mining, Metallurgy and [15] R. Leimula, O. Hyvarinen, Method of removal of impurities from gold
Petroleum, Montreal, Canada, 2007, pp. 191–204. concentrate containing sulfides, U.S. Patent 6,861,037, 2005.
[7] P.J. Gabb, D.L. Howe, D.J. Purdie, H.J. Woerner, The Kennecott smelter [16] L. Liu, J. Wu, X. Li, Z. Gong, Preparation of high purity nanometer bismuth
hydrometallurgical impurities process, in: W.C. Cooper, D.B. Dreisinger, J.E. trioxide from silver–zinc slag, Adv. Mater. Res. 156–157 (2011) 785–
Dutrizac, H. Hein, G. Ugarte (Eds.), Copper 95, vol. III, The Metallurgical Society 793.
of CIM, 1995, pp. 591–606. [17] C.M. Flynn, T.G. Carnahan, R.E. Lindstrom, Recovery of bismuth from chloride
[8] J. Hino, T. Kawabata, Removal and recovery of minor elements in copper process solutions, U.S. Patent 4,285,912, 1981.
smelting, in: W.C. Cooper, D.B. Dreisinger, J.E. Dutrizac, H. Hein, G. Ugarte [18] O. Monnereau, L. Tortet, P. Liewellyn, F. Rouquerol, G. Vacquier, Synthesis of
(Eds.), Copper 95, vol. III, The Metallurgical Society of CIM, 1995, pp. 617–627. Bi2O3 by controlled transformation rate thermal analysis: a new route for this
[9] J.D. Miller, J.L. Sepulveda Jimenez, Selective removal of bismuth from oxidized oxide, Solid State Ionics 157 (2003) 163–169.
particulate materials, U.S. Patent 3,966,461, 1976.