Separation and Purication Technology 37 (2004) 107116

Antimony removal from model acid solutions by electrodeposition

A. Sava Koparal a, , R. zgr a , . Bakir tveren a , H. Bergmann b s g
a

Environmental Engineering Department, Anadolu University, Cevre Muhendisligi Bolumu, 26470, Eskisehir, Turkey b Anhalt University of Applied Sciences, Bernburger Str. 55, 06366 Kthen, Germany Received 30 August 2002; received in revised form 3 September 2003; accepted 4 September 2003

Abstract The aim of this work is to investigate the feasibility of the removal of antimony from model acid solutions simulating copper electrorening and spent lead/lead oxide acid battery solutions by an electrochemical method. Although some data are available for advanced treatment methods such as adsorption, ion exchange and electrothermal methods, electrodeposition of antimony has not been studied extensively, yet. The data obtained from this work show that the electrodeposition of antimony on a copper electrode from acid solution is attainable and 100% removal is achieved practically depending on the effects of applied potential, current density and concentrations of acid and antimony. 2003 Elsevier B.V. All rights reserved.
Keywords: Acid recovery; Antimony removal; Battery wastes; Copper electrorening solutions; Electrodeposition

1. Introduction Antimony is a common impurity in copper electrorening and electrowinning from sulphate solutions. Many battery electrodes also contain some antimony that can be dissolved during the lifetime and deposited affecting the charge behaviour of the battery. Although some data exist from copper rening processes, there is no detailed information about antimony deposition [1,2]. Heavy metals such as antimony, copper, nickel, etc., can be removed from acid solutions by conventional
Corresponding author. Tel.: +90-222-3350580x6406; fax: +90-222-3239501. E-mail address: askopara@anadolu.edu.tr (A.S. Koparal).

and newly emerging metal treatment and recovery methods [3]. The conventional treatment methods based on precipitation are utilised for relatively nonselective treatment and always generate a sludge containing heavy metals, requiring disposal management. Newly-emerging treatment and recovery methods are evaporative recovery, ion exchange, membrane separation, reductive electrolysis, differential precipitation, extractive metallurgy and selective adsorption [3,4]. Among these methods reductive electrolysis is well established for certain metal recovery applications [5,6]. The removal of a metal by electrodeposition at source seems to be attractive due to the potential for a one-step clean method of metal recycle. The theory of electrolytic reduction (i.e. electrodeposition) is basically an oxidationreduction, which

1383-5866/$ see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.seppur.2003.09.001

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takes place at the surface of conductive electrodes in a chemical medium under the inuence of an applied potential [7]. At the cathode, the main reaction is reduction of metal, as given in Eq. (1). M2+ + 2e M (1)

and, in aqueous media, the reduction of the hydrogen ion or water occurs simultaneously (Eq. (2)). 2H+ + 2e H2 (2)

At the anode, the corresponding oxidation takes place and hydrogen ions and oxygen are formed in accordance with Eq. (3).
1 H2 O 2H+ + 2 O2 + 2e

(3)

The recovery of metal ion constituents along with other materials from disposable or spent batteries is a developing area for the application of electrodeposition [7]. There is one example for the recovery of lead from spent batteries [8]. The lead in the batteries is dissolved in an acid electrolyte and deposited on the cathode in a tank reactor. Only trivalent antimony among the metal ion impurities present in the electrolyte is co-deposited with the lead. Another example is using crushed batteries and separating metal pieces from electrolytic pastes [9]. The sludge is solubilized in an alkaline and acid process respectively, and the

puried solution is subjected to electrowinning. Calcium sulphate is the only solid waste. Electrical energy requirement for the whole process is reported to be 0.5 kWh kg1 . Recently, work has been done for antimony removal from spent lead/lead oxide batteries using divided and undivided cells and carbon cloth, lead, platinum, titanium, copper and graphite particle electrodes [10]. The best results have been achieved in divided cell on copper electrode due to the prevention of the oxidation of trivalent antimony at the anode. The lowest energy consumption and remaining antimony concentration are reported to be as 15 kWh m3 and 0.15 mg l1 , respectively. In this study, cathodic reduction of antimony from H2 SO4 solutions has been carried out in a divided cell containing copper or carbon cloth electrodes, examining the form of antimony deposited on cathode and the effects of parameters such as current density, initial antimony and acid concentrations.

2. Experimental Electrochemical deposition has been applied to remove and recover antimony from aqueous H2 SO4 solutions. A reactor with a volume of 200 cm3 , a height of 70 mm and a diameter of 60 mm is used as shown in Fig. 1. Anode and cathode chambers are separated by a ceramic cup lled with agar jelly. Either carbon

Fig. 1. Electrochemical cell used in electrodeposition of antimony.

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Fig. 2. Polarisation curves on copper cathode: (A) H2 SO4 of 4%; (B) H2 SO4 of 36%; (C) 5 mg Sb l1 in H2 SO4 of 36%.

cloth with a surface area of 55 cm2 or a copper sheet with a surface area of 120 cm2 is used as the cathode. A power supply (Statron; 16 V, 6.4 A), a digital voltmeter (OGSM 3900) and a magnetic stirrer to provide homogeneity in the solution (Electro-Mag) are used in the experiments. The remaining trivalent antimony concentration in the solution is determined by atomic absorption spectrometer (Varian Spectra AA 251). Deposited antimony at the surface of the electrode was examined by a X-ray diffraction (XRD) apparatus (Rigaku Rint 2200, Monochromatic Cu K radiation, = 1.5406 and scanning speed 2 min1 for 2). A solution of 100 cm3 of H2 SO4 of either 36% or 20% containing trivalent antimony with concentrations of 1500 and 3500 mg l1 has been used as a model solution. Percentage removal efciency and energy consumption as kWh g1 have been calculated using the equations Eqs. (4) and (5). C0 C removal (%) = 100 (4) C0 3 I V t 10 energy consumption = (5) C

where C0 is the initial Sb concentration, C the remaining Sb concentration, I the current passing reactor in ampere, V the potential applied to the reactor in volt, t the time in hour, and C the concentration difference. Arithmetic mean of the results obtained by repeating the experiments three times has been given as a datum. Since current density is an important factor affecting the efciency and energy consumption of an electrochemical system, current densities of 1, 2, 3 and 5 mA cm2 are examined. The very high sulphuric acid concentration, compared to the antimony concentration, is a problem for detailed kinetic studies because hydrogen evolution overlaps the main reaction as can be seen from Fig. 2 that is a representative picture of polarisation curves (EG&G Instruments potentiostat) on copper cathode with different acid concentrations.

3. Results and discussion In this study, the copper electrode was seen to be more effective than the carbon cloth for the removal of antimony even if the current density was as low as

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Fig. 3. The variation of residual concentration with time at carbon cloth: (A-1) 1 mA cm2 , (A-2) 2 mA cm2 , (A-3) 3 mA cm2 , (A-4) 5 mA cm2 ; and copper electrodes (B-1) 1 mA cm2 , (B-2) 2 mA cm2 , (B-3) 3 mA cm2 , (B-4) 5 mA cm2 (initial concentration: 3500 mg l1 , H2 SO4 of 20%).

1 mA cm2 as can be seen from Fig. 3. At a current density of 2 mA cm2 on the copper electrode, the nal concentration of 105 mg l1 for antimony with the removal efciency of 97% has been achieved with initial concentration of 3500 mg l1 in 3 h whereas 6 h were required for the same removal efciency with carbon cloth electrode. The energy consumption values were 0.03 and 0.20 kWh g1 , respectively. Qualitative data from XRD analysis shows that the deposited antimony is elemental antimony and antimony oxide when the copper electrode is used as shown in Fig. 4. Two different concentrations of H2 SO4 which are widely encountered are examined and the effect of the acid concentration on the removal efciency is shown in Fig. 5. It can be seen from this gure that the removal rate of antimony is slightly higher with 20% H2 SO4 than that with 36% H2 SO4 . Energy consumption values are not different in these two cases until maximum removal is achieved as can be seen in Fig. 6. The variation of current efciency with the concentration of H2 SO4 has been shown in Fig. 7. As can be seen from this gure, slightly better current efciency values are observed when H2 SO4 concentration is 20%. Besides current efciency, the nal concentration of the metal which is related with the initial concentration is important in terms of process feasibility. Thus, two different initial concentrations of 1500 and

3500 mg l1 for antimony are examined. The higher the initial concentration, the larger is the amount of antimony removed per unit time, the smaller is the energy consumed per gram of antimony, and the current efciency is higher at the same removal efciency of for example 99% as shown in Table 1. Several potential differences have been applied to obtain required current densities from 1 to 5 mA cm2 . These potential differences have been 22.8 V with higher concentration of 3500 mg l1 Sb and H2 SO4 of 36% in which the conductivity of solution was higher, whereas they have been 2.23.3 V with lower concentration of 1500 mg l1 Sb and H2 SO4 of 20% in which the conductivity of solution was lower. This explains the lower specic energy consumption with higher antimony concentration. The behaviour of the polarisation curves for both lower and higher H2 SO4 concentrations were similar as can be seen in Fig. 2. Therefore, hydrogen overlapping can also be a problem for the H2 SO4 concentration of 20%. Thus, it can be said for the Sb and H2 SO4 system that polarisation curves cannot be suitable to explain the kinetic behaviour of the system. An increase in current density results in an increase in removal efciency and energy consumption as can be seen from Figs. 8 and 9. The removal efciency of 93% for the current density of 1 mA cm2 is achieved in 5 h with an energy consumption value of 0.1 kWh

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Fig. 4. Qualitative analysis of antimony.

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100 Removal Efficiency (%)

80 H2SO4 (20%) 60 H2SO4 (36%)

40

20

0 0 1 2 3 Time (h) 4 5 6 7

Fig. 5. The variation of removal efciency with time using copper electrode (initial concentration: 3500 mg l1 , current density: 1 mA cm2 ).

per gram of antimony removed. The removal efciency is 99% in 5 h at 2 mA cm2 with an energy consumption value of 0.43 kWh g1 . It means that an increase of 6% in removal efciency due to an increase
1,4

in current density corresponds to an increase of more than four times in energy consumption. However, the removal efciency of 99% is achieved producing a solution of 35 mg l1 at 1 mA cm2 in 7 h with an energy

1,2

H2SO4 (36%) H2SO4 (20%)

Energy Consumption (kWh/g)

0,8

0,6

0,4

0,2

0 0 1 2
Time (h)

Fig. 6. The variation of energy consumption with time using copper electrode (initial concentration: 3500 mg l1 , current density: 1 mA cm2 ).

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100 90 Current Efficiency (%) 80 70 60 50 40 30 20 10 0 0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 Tim e (h)

113

H2SO4 (20%) H2SO4 (36%)

Fig. 7. The variation of current efciency with time using copper electrode (initial concentration: 3500 mg l1 , current density: 5 mA cm2 ). Table 1 Experimental results obtained in electrodeposition of antimony using copper electrodes Initial concentration of Sb (mg l1 ) 1500 Time (h) 0 0.25 0.5 1 2 0 0.25 0.5 1 2 3 4 Cell voltage (V) Remaining concentration of Sb (mg l1 ) 1500 237 181 100 16 3500 1366 1037 552 94 26 20 Removal efciency (%) 0 84.2 88.0 93.3 99.0 0 61.0 70.4 84.2 97.3 99.2 99.4 Current efciency (%) 53 28 15 8 90 52 31 18 12 6 Energy consumption (kWh g1 ) 0.00356 0.08392 0.19503 0.40932 0.00197 0.01474 0.03206 0.06874 0.31580 3.1158

3500

2.8

H2 SO4 of 20%, 5 mA cm2 .

120

100

Removal Efficiency (%)

80

60

1 mA/cm2 2 mA/cm2

40

3 mA/cm2 5 mA/cm2

20

0 0 1 2 3 Tim e (h) 4 5 6 7

Fig. 8. The variation of removal efciency with time at different current densities using copper electrode (initial concentration: 3500 mg l1 , H2 SO4 of 20%).

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0,5 Energy Consumption (kWh/g) 0,45 0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0

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1 mA/cm2 2 mA/cm2 3 mA/cm2 5 mA/cm2

3 Time (h)

Fig. 9. The variation of energy consumption with time at different current densities using copper electrode (initial concentration: 3500 mg l1 , H2 SO4 of 20%).

4000 3500

Remaining Concentration (mg/L)

3000 2500 2000 1500 1000 500 0 0 1 2 3 Tim e (h) 4 5 6 7 3500 mg/L 1500 mg/L

Fig. 10. Concentrationtime relationship at 1 mA cm2 (H2 SO4 of 20%).

Table 2 Mass transfer coefcients (km ) for the electrodeposition of antimony using copper electrodes Current density 3500 mg Sb l1 Time (h) 1 mA cm2 0 1 2 3 4 5 6 km (106 m s1 ) 1.043 0.994 1.077 1.167 1.246 1.569 1500 mg Sb l1 Time (h) 0 0.5 1 2 3 4 km (106 m s1 ) 4.399 3.178 3.03 3.018 2.498

A.S. Koparal et al. / Separation and Purication Technology 37 (2004) 107116 Table 2 (Continued ) Current density 3500 mg Sb l1 Time (h) 5 mA cm2 0 0.25 0.5 1 2 3 4 km (106 m s1 ) 8.71 5.63 4.275 4.186 3.783 2.99 1500 mg Sb l1 Time (h) 0 0.25 0.5 1 2

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km (106 m s1 ) 17.08 9.79 6.268 5.255

4000 3500

Remaining Concentration (mg/L)

3000 2500 2000 1500 1000 500 0 0 1 2 Tim e (h) 3 4 5 3500 mg/L 1500 mg/L

Fig. 11. Concentrationtime relationship at 5 mA cm2 (H2 SO4 of 20%).

consumption value of 0.2 kWh g1 . Thus, the removal efciency or the energy consumption may need to be selected for optimisation. Concentrationtime relationships for two current densities can be seen in Figs. 10 and 11. From these gures, a rst-order relation between time and concentration in a batch reactor represented with the equation (Cinitial /Cnal ) = ekL a (where is the reaction time) can be seen. Therefore, mass transfer coefcients have been calculated and tabulated in Table 2. From Table 2, the lower the initial concentration and the higher the current density, the larger are the mass transfer coefcients as expected. These results can also be seen from Figs. 10 and 11. Therefore, all results obtained before have been approved by the mass transfer coefcients.

4. Conclusions It is concluded from this study that antimony has been removed from H2 SO4 solutions of two different concentrations representing copper electrorening and spent battery solutions. The concentration of the acid is found not to be signicantly effective on the efciency of the process. Energy consumption is less than enough compared to those of the other processes showing that this process can be accepted as more economically applicable. The H2 SO4 solution after treatment may also be reused since the full removal of antimony is practically achieved. However, efciency and economy of the system will have to be investigated by studying with real

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A.S. Koparal et al. / Separation and Purication Technology 37 (2004) 107116 [3] J.W. Patterson, A.R. Minear, E. Gasca, C. Petropoulou, in: D.L. Ford (Ed.), Toxicity Reduction: Evaluation and Control, vol. 3, Water Quality Management Library, 1992. [4] I.R. Polivianny, A.I. Rusin, V.A. Lata, L.D. Khegay, S.T. Nourjigitov, Processes of wastes from lead/acid battery production, J. Power Sources 33 (1991) 279283. [5] J.P. Wiaux, The Recovery and Recycling of Metal Utilizing Electrolytic Techniques, Finishing (April) (1990) 3336. [6] R.D. Armstrong, M. Todd, J.W. Atkinson, K. Scott, Selective electrodeposition of metals from simulated waste solutions, J. Appl. Electrochem. 26 (1996) 379384. [7] K. Scott, Electrochemical Processes for Clean Technology, The Royal Society of Chemistry, UK, 1995. [8] M. Moja, Electrochemical Engineering, Int. Chem. Eng. Symp. Ser (1986) 98155. [9] U. Ducati, Italian Patent 23745 AA (1981). [10] H. Bergmann, A. Rittel, A.S. Koparal, T. Iourtchouk, U. Bakir Ogutveren, Antimony Removal From Concentrated Electrolytes, in: Proceedings of the 51st ISE Meeting, September 2000, Warshaw, Poland.

wastewaters from copper electrorening and spent lead/lead oxide acid battery.

Acknowledgements The authors thank to DAAD, Anadolu University and Anhalt University for the support of this work.

References
[1] H.K. Lin, X. Wu, P.D. Rao, Cathodic behaviour of antimony(III) species in chloride solutions, J. Appl. Electrochem. 24 (1994) 758766. [2] K. Ando, N. Tsuchida, Recovering Bi and Sb from electrolyte in copper electrorening, Met. Mater. Soc. J. 49 (12) (1997) 4951.