Hydrometallurgy 59 2001. 5567 www.elsevier.

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Electrowinning of copper from sulfate electrolyte in presence of sulfurous acid

B. Panda, S.C. Das )
Council of Scientific and Industrial Research, Regional Research Laboratory, Bhubaneswar 751 013, Orissa, India Received 16 January 2000; received in revised form 21 July 2000; accepted 27 July 2000

Abstract The electrowinning of copper from acidic sulfate solution in the presence of sulfurous acid using a graphite anode was investigated. The effects of operating variables including sulfur dioxide concentration, copper concentration, sulfuric acid concentration, current density and temperature on the cell voltage, anode potential, power consumption, current efficiency, deposit quality, surface morphology, crystallographic orientations and polarisation characteristics were studied. Other anode materials such as PbrSb, PbrAg, Ti and TiIrO 2 were also used to examine their effects on electrocatalytic activity for oxidation of SO 2 and deposit quality. A rectangular stainless steel cathode of length 8 cm, width 5 cm and thickness 2 mm was used for copper electrowinning. Increases in SO 2 concentration, copper concentration, sulfuric acid concentration and temperature lower the power consumption. These variables have no effect on the current efficiency of copper deposition. The presence of SO 2 in the copper electrolyte affects both the cathodic and anodic polarisation curves. In addition, it causes shifting of preferred orientations from 220. 111. 200. 311. to 111. 200. 220. 311.. Changes in crystallographic orientation are also seen in the surface morphology of deposited copper. It is found that minimum power consumption together with maximum current efficiency and improved surface morphology can be achieved using a graphite anode. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: Electrowinning; Copper; Sulfate electrolyte

1. Introduction Copper extraction has undergone many developments in the past 20 years. Both pyro- and hydrometallurgical processes have been improved and totally

) Corresponding author. Tel.: q 91-674-581750; fax: q 91-674581750. E-mail address: director@csrrlbhu.ren.mc.in S.C. Das..

new processes have been reported w1x. The technoeconomic problem associated with the SO 2 emissions from copper smelting in pyrometallurgical processes has prompted the development of hydrometallurgical processes for recovery of copper from sulfide concentrates. The unit operations generally involved in these hydrometallurgical processes are roasting, leaching and electrowinning. In recent years, there has been a marked increase in the production of copper by electrowinning. A major drawback is the high energy requirement associated with

0304-386Xr01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved. PII: S 0 3 0 4 - 3 8 6 X 0 0 . 0 0 1 4 0 - 7

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B. Panda, S.C. Das r Hydrometallurgy 59 (2001) 5567

the copper electrowinning compared to electrorefining of copper. The process requires nearly 810 times more power 2.0 kW hrkg. than electrorefining 0.25 kW hrkg. w2x. This high energy requirement in copper electrowinning has prompted a number of investigations for reducing the energy consumption w3x. One such approach is to substitute an alternative anodic reaction in the place of oxygen evolution. The other possible alternative anode reactions suggested w3x may be given as follows: 2Clys Cl 2 q 2e Fe 2qs Fe 3qq e Cuqs Cu2qq e EB SHE s y1.36 V EB SHE s y0.77 V EB SHE s y0.15 V

affect the copper electrowinning process. A graphite anode was used and the effects of sulphurous acid on the cell voltage, anode potential, energy consumption, deposit quality, crystallographic orientations and surface morphology of cathode deposit and polarisation behaviour during copper electrowinning were studied. Other anode materials such as PbrSb, PbrAg, Ti and TiIrO 2 were used for comparison.

2. Experimental methods

1. 2. 3.
2.1. Apparatus and material The electrolytic cell used in the present work was a 250-ml pyrex beaker. It was covered with a perspex lid with a provision to insert anode and the cathode. The cathodes used were rectangular stainless steel sheets having the following dimensions; length 8 cm, width 5 cm and thickness 2 mm. For electrical connection to the cathodes, strips of the same material having dimensions; length 11 cm, width 1 cm and thickness 2 mm were welded at the center of the top edge of the rectangular sheets. The anodes used consisted of graphite, PbrSb 7%., PbrAg 1%., Ti and TiIrO 2 . The anodes were of the same dimensions as those of the cathode. A saturated calomel electrode SCE. was used as the reference electrode. A rectifier with a maximum capacity of 4 A and 30 V was used as the DC source. The cell voltage and anode potential were measured by inserting precision voltmeters in the circuit. A thermostat was used for maintaining the desired electrolyte temperature. The electrolytic solution was prepared from reagent grade copper sulfate CuSO4 , 5H 2 O., sulphuric acid, sulphurous acid and double-distilled water. The addition of sulfurous acid to the copper electrolyte was made by adding the appropriate volume of the reagent. The concentration of SO 2 in the stock sulfurous acid solution was analysed before preparing the electrolytic solution for each experiment. 2.2. Electrolysis Unless otherwise stated, the electrowinning experiments were carried out for 2 h at room temperature

2y H 2 SO 3 q H 2 O s SO4 q 4Hqq 2e

EB SHE s y0.18 V.

4.

The above reactions, except reaction 1. occur at lower potentials than the oxygen evolution reaction. However, reaction 4. is of more interest to the investigators w5x. Oxidation of dissolved SO 2 on carbon and graphite anodes has been studied by several investigators w6x. Wiesener w6x pointed out that carbon anodes are not suitable for the anodic oxidation of SO 2 . Pace and Stauter w7x found a power consumption of 1 kW hrkg of Cu produced as against twice that amount for conventional practice. Bharucha et al. w8x succeeded in designing a novel graphite anode for use in copper electrowinning. A mixture of air and 1215% SO 2 was sparged through a porous graphite anode. However, the work did not proceed beyond a limited number of trials at a laboratory scale. In the present work, an attempt was made to examine the effects of sulfurous acid on the copper electrowinning from sulfate electrolyte. Sulfurous acid was used as the source of SO 2 because it may be easier to trap the environmental formidable emissions of SO 2 as sulfurous acid and transport to the 2y copper cell house for their conversion to SO4 and simultaneously reducing energy consumption in the copper electrowinning. Other common compounds like Na 2 SO 3 and NH 4 . 2 SO 3 were avoided to prevent the formation of their respective sulphates in the copper electrowinning cell, which may ultimately

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30 " 18C. and at a current density of 150 Arm2 using a bath containing 20 grL copper, 30 grL H 2 SO4 and 4.16 grL SO 2 and graphite anode. In all the experiments, one cathode and one anode were taken and kept face-to-face 3 cm apart. During the electrowinning experiments, the cell voltage and anode potential were measured at 1-h interval. After electrolysis, the cathode was removed and thoroughly washed with tap water followed by distilled water and air dried after washing it in acetone. The current efficiency was calculated from the weight gained by the cathode. 2.3. Polarisation measurements Linear sweep voltammetry LSV. was used to examine the cathodic and anodic polarisation behaviours during copper electrowinning in the presence and absence of SO 2 . Platinum 1 cm2 . and graphite 1 cm2 . were used as working electrodes. A platinum wire and a SCE were used as counter electrode and reference electrode, respectively. Experiments were conducted taking 100-mL solution of different compositions. A PAR 175 Universal Programmer was used to drive a PAR 173 Potentiostat. The cathodic and anodic polarisation were studied between 0.0 to y1.6 V and q0.2 to q2.0 V, respectively, at a scan rate of 10 mVrs. The polarisation curves were recorded using a model RE0091 XY recorder. 2.4. Deposit examination X-ray diffractometry was carried out to determine the crystallographic orientations and the surface morphology of the deposits was examined by SEM.

100, 700 and 1000 mV, respectively. Pace and Stauter found a power consumption of 1 kW hrkg of copper in the presence of 1.3 grL of dissolved SO 2 in the copper electrolyte. In the present investigation, the influence of SO 2 concentration in the electrolytic bath was studied in the range 0.2524 grL. Figs. 1 and 2 show the effect of initial concentration of SO 2 on cell voltage, anode potential and power consumption, respectively. It can be seen from Fig. 1 that both the cell voltage and anode potential decrease rapidly with increase in SO 2 concentration up to 15 grL and then remained constant with further increase in SO 2 concentration. This is because SO 2 oxidises at a less positive potential than to the oxygen evolution reaction. The results obtained on cell voltage and anode potential at the end of 1- and 2-h electrolysis show that the cell voltage increases by , 0.3 V and anode potential by , 0.2 V. This may be due to decrease in SO 2 concentration in the copper electrolyte. The decrease in SO 2 concentration over the period of electrolysis may be attributed to the consumption and loss to atmosphere. Fig. 2 shows the plot of power consumption against SO 2 concentration. The trend in the fall in power con-

3. Results and discussions 3.1. Sulfur dioxide concentration The effect of different concentrations of sulfur dioxide on the reduction of anode potential during copper electrowinning has been studied w37x. Mishra and Cooper w3x reported that while sparging 10%, 20%, 100% SO 2 at a current density of 200 Arm2 , the reductions in anode potential are in the order of

Fig. 1. Effect of SO 2 concentration on cell voltage and anode potential. Cu concentration, 20 grL; H 2 SO4 concentration, 30 grL; current density, 150 Arm2 ; temperature, 308C; duration of electrolysis, 2 h; anode substrate, graphite.

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and power consumption during electrowinning of copper in the presence of sulfur dioxide. The concentration of copper was varied in the range 1050 grL. The cell voltage and anode potential values are plotted against copper concentration in Fig. 3. As expected, the cell voltage is relatively high at low copper concentrations, i.e., up to 30 grL and is almost constant beyond this. The anode potential does not show any significant change and also no significant change in the power consumption , 14001424 kW hrt of Cu. is observed in the range of copper concentration studied. The current efficiency is found to be , 98% in this range. 3.3. Sulfuric acid concentration The effect of sulfuric acid concentration during copper electrowinning was studied in the range 30 150 grL. The results on cell voltage and anode potential are given in Table 1. The cell voltage and anode potential decrease with increase in acid concentration up to 150 grL. However, the decreases in the voltages are marginal. The voltages at the end of 1 h for each sulfuric acid concentration studied are

Fig. 2. Effect of SO 2 concentration on power consumption. Cu concentration, 20 grL; H 2 SO4 concentration, 30 grL; current density, 150 Arm2 ; temperature, 308C; duration of electrolysis, 2 h; anode substrate, graphite.

sumption is similar to that shown by cell voltage or anode potential. It sharply decreased up to a SO 2 concentration of 15 grL and then remained constant. It is found that by adding SO 2 to the copper electrolytic bath, the power consumption during copper electrowinning can be lowered by , 550 kW hrt of Cu during 2-h electrolysis. The increase in the concentration of SO 2 has no effect on cathodic current efficiency and is found to be 98% throughout. 3.2. Copper concentration Pace and Stauter w7x obtained good quality cathodes with a current efficiency of 95% in copper electrowinning with a copper concentration from 10 grL down to 2 grL by circulating SO 2 sparged synthetic leach liquor at 498C. Mishra and Cooper w3x were successful to electrowin copper down to a level of 0.5 grL in the solution from an initial concentration of 20 grL of copper by sparging N2 q 5% SO 2 at 200 cm3rmin between the electrodes. As per Robinson w1x, concentration of Cu2q in the electrolyte affects the operating current density. In the present work, experiments were carried out by varying the concentration of copper in the electrolytic bath, to see its effect on cell voltage, anode potential

Fig. 3. Effect of copper concentration on cell voltage and anode potential. SO 2 concentration, 4.16 grL; H 2 SO4 concentration, 30 grL; current density, 150 Arm2 ; temperature, 308C; duration of electrolysis, 2 h; anode substrate, graphite.

B. Panda, S.C. Das r Hydrometallurgy 59 (2001) 5567 Table 1 Effect of H 2 SO4 concentration on cell voltage, anode potential and power consumption H 2 SO4 grL. 30 50 100 150 Cell voltage V. 1.62, 1.59 a 1.62, 1.56 a 1.56, 1.52 a 1.56, 1.52 a Anode potential V. 1.52, 1.51a 1.52, 1.51a 1.51, 1.49 a 1.51, 1.48 a % Current efficiency 98 98 98 98 Power consumption kW hrt of Cu. 1399 1399 1350 1350 Deposit morphology Bright, smooth, compact Bright, smooth, compact Bright, smooth, compact Bright, smooth, compact

59

Cu concentration, 20 grL; SO 2 concentration, 4.16 grL; current density, 150 Arm2 ; bath temperature, 308C; anode substrate, graphite; duration of electrolysis, 2 h. a Data obtained in 1 h of electrolysis.

less compared to those at the end of 2 h. The variation of sulfuric acid concentration has no significant effect either on current efficiency or power consumption. Similar results are also reported by Mishra and Cooper w3x. They electrowon copper from solutions containing a concentration of sulfuric acid as high as 170180 grL with only a slight drop in current efficiency. 3.4. Temperature The effect of temperature during electrowinning of copper from a solution containing iron and SO 2

has been studied by Cooper w9x. He concludes that temperature plays a major role in deciding the quality of cathode deposit. In the present study, the influence of temperature was studied in the range 30608C. Both cell voltage and anode potential decrease with increase in bath temperature where the fall is sharp beyond 508C Fig. 4.. No variation in the current efficiency is observed in the temperature range studied and is found to be 98% throughout. Fig. 5 shows the effect of temperature on power

Fig. 4. Effect of temperature on cell voltage and anode potential. Cu concentration, 20 grL; H 2 SO4 concentration, 30 grL; SO 2 concentration, 4.16 grL; current density, 150 Arm2 ; duration of electrolysis, 2 h; anode substrate, graphite.

Fig. 5. Effect of temperature on power consumption. Cu concentration, 20 grL; H 2 SO4 concentration, 30 grL; SO 2 concentration, 4.16 grL; current density, 150 Arm2 ; duration of electrolysis, 2 h; anode substrate, graphite.

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consumption. A significant decrease in the power consumption is observed with increase in temperature. The power consumption decreases almost linearly with increase in bath temperature. Higher temperature is found to improve the quality of the deposit. This is in good agreement with the results reported by Cooper w9x. 3.5. Current density The variation in current density during copper electrowinning was studied in the range of 100300 Arm2 and its effects on cell voltage, anode potential, power consumption and current efficiency were observed. Fig. 6 reports the effect of current density on cell voltage and anode potential. The results indicate that both the cell voltage and anode potential during copper electrowinning increase with increase in current density. The increase in the cell voltage and anode potential may be attributed to the increase in both cathodic and anodic polarisations. The power consumption is found to increase with increase in current density Fig. 7.. The current efficiency remains constant 98%. up to 200 Arm2

Fig. 7. Effect of current density on power consumption. Cu concentration, 20 grL; H 2 SO4 concentration, 30 grL; SO 2 concentration, 4.16 grL; temperature, 308C; duration of electrolysis, 2 h; anode substrate, graphite.

and powder deposit is formed when current density is further increased. This may be probably due to exceeding of critical current density as reported by Mishra and Cooper w3x. 3.6. Anode substrates Anode materials play an important role in the electro-oxidation of SO 2 w8x. In the present work, the effects of different anode materials on electrowinning of copper in the presence of SO 2 were investigated. The results are reported in Table 2 both in the absence and presence of SO 2 for comparison. Fig. 8 illustrates the trend in cell voltage for four different anodes such as: PbrSb, PbrAg, TiIrO 2 and graphite. In this set of experiments, electrowinning was carried out at 508C. Since in all the experiments bath composition, temperature, electrode distance, current density and cathode material were kept constant, the differences observed in the cell voltage may be attributed to the nature of different anode materials. The behaviour of each anode material is given below.

Fig. 6. Effect of current density on cell voltage and anode potential. Cu concentration, 20 grL; H 2 SO4 concentration, 30 grL; SO 2 concentration, 4.16 grL; temperature, 308C; duration of electrolysis, 2 h; anode substrate, graphite.

B. Panda, S.C. Das r Hydrometallurgy 59 (2001) 5567 Table 2 Effect of anode substrates on cell voltage, anode potential, current efficiency and power consumption Electrode material Cell voltage V. Anode potential V. 1.52, 1.53 a 1.66, 1.66 1.61, 1.62 1.46, 1.47 a 1.45, 1.44 a 1.61, 1.59 1.63, 1.59 a 1.46, 1.49 a % Current efficiency 98 98 94 97 Power consumption kW hrt of Cu. 1412 1498 1536 1338 Deposit morphology

61

In the absence of SO2 Graphite 1.64, 1.64 a PbrSb 1.74, 1.75a PbrAg 1.71, 1.72 a TiIrO 2 1.53, 1.55a In the presence of SO2 Graphite 1.50, 1.48 a PbrSb 1.69, 1.65a PbrAg TiIrO 2 1.68, 1.65a 1.54, 1.55a

Bright, smooth, compact Bright, smooth, compact Bright, smooth, compact Bright, smooth, compact

98 96 96 97.7

1292 1485 1476 1333

Bright, smooth, compact Non-uniform, granular deposit, adhering to the surface Non-uniform, granular deposit, adhering to the surface Non-uniform, granular deposit, adhering to the surface

Cu concentration, 20 grL; H 2 SO4 concentration, 30 grL; SO 2 concentration, 4.16 grL; current density, 150 Arm2 ; bath temperature, 508C; duration of electrolysis, 2 h. a Data obtained in 1 h of electrolysis.

The graphite anode shows better performance in comparison to the other anodes used in this investigation. The cell voltage and anode potential are

Fig. 8. Effect of anode substrates on time-dependence cell voltage and anode potential. Cu concentration, 20 grL; H 2 SO4 concentration, 30 grL; SO 2 concentration, 4.16 grL; current density, 150 Arm2 ; temperature, 308C; duration of electrolysis, 2 h; anode substrate, graphite.

found to be 1.64 and 1.53 V Table 2., respectively, in the absence of SO 2 . In the presence of 4.16 grL SO 2 , the cell voltage and the anode potential drop to 1.012 and 0.945 V, respectively, but they increase gradually during the electrowinning period up to 1 h and then remain almost constant Fig. 8.. The increase in both the cell voltage and anode potential with time may be attributed to the consumption and escape of SO 2 during the electrowinning process. The cathode deposits obtained either in the presence or absence of SO 2 are smooth and bright. The cell voltages and anode potentials with both PbrSb and PbrAg anodes are found to be higher than that with graphite both in the presence and absence of SO 2 Table 2.. This may be due to higher oxygen over-potential with these anode materials. In the presence of SO 2 , no change in either anode potential or cell voltage is observed. Fig. 8 shows the behaviour of cell voltage with time with these anodes. The trend in both the anodes is similar to that of graphite. The cathode copper in the presence of SO 2 with the anodes is completely different to graphite. In these cases, the deposits are non-uniform and granular when SO 2 is present. The use of Ti as anode substrate is found to be very unsatisfactory due to passivation of titanium under the experimental conditions.

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The IrO 2-coated Ti anode behaves differently to that of Ti alone. This anode is found to give better results compared to graphite, PbrSb and PbrAg in the absence of SO 2 . But no reduction in the cell voltage or anode potential is observed in the presence of SO 2 Table 2.. The plot of cell voltage with time is completely different in this case compared to the other anodes Fig. 8.. Non-uniform granular deposits are also formed in the presence of SO 2 with TiIrO 2 as for PbrSb and PbrAg anodes. The power consumption during electrowinning of copper in the presence and absence of SO 2 with these anodes is given in Table 2. The order of power consumption in the absence of SO 2 with different anode materials is PbrAg ) PbrSb ) graphite ) TiIrO 2 . But in the presence of SO 2 , the order changes to PbrSb ) PbrAg ) TiIrO 2 ) graphite. 3.7. Polarisation behaiour The anodic and cathodic polarisation behaviour of SO 2 during electrodeposition of copper on platinum

and graphite anode was investigated using LSV. Figs. 9 and 10 show the anodic polarisation behaviour of SO 2 on platinum and graphite electrodes, respectively. Fig. 11 shows the depolarisation effect of SO 2 on the kinetics of electrodeposition of copper on platinum electrode.

3.7.1. Anodic polarisation behaiour of SO2 The anodic polarisation behaviour of SO 2 on platinum and graphite anodes was studied between q0.2 and q2 V vs. SCE. Fig. 9 shows the effect of SO 2 on platinum anode with electrolyte of different compositions. The oxidation of SO 2 in 30 grL H 2 SO4 curve b, Fig. 9. shows a large plateau region, i.e., between q0.45 and q0.85 V compared to SO 2 oxidation in CuSO4 curve d. or CuSO4 q H 2 SO4 system curve f.. The plateau region obtained for curve d is between q0.8 and q1.1 V and for curve f is between , 0.8 and 1.0 V. These plateau regions correspond to the formation of sulfate ions from sulfite ions which varies with the

Fig. 9. Anodic potentiodynamic curves for electrolytes of different composition. Working electrode, Pt; scan rate, 10 mVrs; temperature, 308C. Key: a. H 2 SO4 concentration, 30 grL; b. H 2 SO4 concentration, 30 grL q SO 2 concentration, 4.16 grL; c. Cu concentration, 20 grL; d. Cu concentration, 20 grL q SO 2 concentration, 4.16 grL; e. Cu concentration, 20 grL q H 2 SO4 concentration, 30 grL; f. Cu concentration, 20 grL q H 2 SO4 concentration, 30 grL q SO 2 concentration, 4.16 grL.

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Fig. 10. Anodic potentiodynamic curves for electrolytes of different composition. Working electrode, graphite; scan rate, 10 mVrs; temperature, 308C. Key: a. H 2 SO4 concentration, 30 grL; b. H 2 SO4 concentration, 30 grL q SO 2 concentration, 4.16 grL; c. Cu concentration, 20 grL q H 2 SO4 concentration, 30 grL; d. Cu concentration, 20 grL q H 2 SO4 concentration, 30 grL q SO 2 concentration, 4.16 grL; e. Cu concentration, 20 grL; f. Cu concentration, 20 grL q SO 2 concentration, 4.16 grL.

electrolytic composition w10x. The results also indicate that oxidation of SO 2 takes place at relatively higher potential and is also inhibited in the presence of Cu2q ions. The increase in current starts at around q0.4 V for curves d and f whereas for curve b the same starts at around q0.32 V. The current decreases as potential increases for curves b, d and f. This decrease in current may be due to the formation of PtO, which inhibits the oxidation of sulfur dioxide w10x. The current increases again around , q1.34 V curve f. when the oxygen evolution begins. For curve b, the current decreases to 0 at q1.4 V, whereas for curves d and f some current is indicated indicating that the reaction oxidation of SO 2 . is not fully inhibited in the presence of copper ions until oxygen evolution begins. When carbonrgraphite electrodes are anodically polarised in a supporting electrolyte, evolution of a mixture of gases containing O 2 , CO and CO 2 may take place at the electrode surface w11x. The mechanism of formation of these gaseous substances has not been clarified, however, most studies mention

the anodic charge transfer of H 2 O or OHy prior to gas evolution w12x. Fig. 10 shows the anodic polarisation behaviour of SO 2 with graphite substrate with electrolyte of different compositions. It is seen from Fig. 10 that the anodic current for SO 2 oxidation at graphite electrode increases and does not show any inhibition of oxidation reaction as in the case of platinum substrates curves b, d and f.. The current starts increasing from q0.2 V and continues to increase with increase in potential. The initial increase in current in this case may be due to self-diffusion of electrons within the substrate followed by the anodic charge transfer of H 2 O or OHy w12x. In the present case, a weakly established plateau is observed in all the electrolyte compositions studied. Similar observations are also reported by Hunger and Lapicque w12x. In the case of d Fig. 10., i.e., oxidation of SO 2 in CuSO4 and H 2 SO4 electrolytes two plateau regions, i.e., between 0.250.45 and 0.71.3 V are observed. An oxide layer is also expected to be formed on the graphite electrode during anodic polarisation w10x. However, the experimental results show that the oxide layer formed does

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case of curves a, b and c Fig. 10. may be due to simultaneous discharge of OHy ions and SO 2 oxidation. For curves e and f Fig. 10., i.e., in CuSO4 and CuSO4 q SO 2 , respectively, the increase in current is negligible compared to curves a, b, c, and d Fig. 10. and no distinct plateau is observed. It is also observed that SO 2 oxidation is inhibited in the presence of Cu2q curves c, d, e and f. and also the presence of H 2 SO4 activates SO 2 oxidation curves b and d.. 3.7.2. Cathodic polarisation Curve a Fig. 11. shows the hydrogen evolution at a platinum electrode in H 2 SO4 electrolyte. H 2 starts evolving at a potential of 0.45 V vs. SCE. When SO 2 solution is added to H 2 SO4 , the H 2 evolution reaction is depolarised curve b., thus shifting cathode potential to a more positive value, i.e., y0.3 V vs. SCE. Besides, a plateau is observed in the potential range y0.55 to y0.65 V. This plateau may be ascribed to the reduction of H 2 SO 3 to S, leading to H 2 S formation w13x according to the following reactions: H 2 SO 3 q 4Hqq 4e EB SHE s 0.45 V S q 2Hqq 2e

Fig. 11. Cathodic potentiodynamic curves for electrolytes of different composition. Working electrode, Pt; scan rate, 10 mVrs; temperature, 308C. Key: a. H 2 SO4 concentration, 30 grL; b. H 2 SO4 concentration, 30 grLqSO2 concentration, 4.16 grL; c. Cu concentration, 20 grLqH 2 SO4 concentration, 30 grL; d. Cu concentration, 20 grLqH 2 SO4 concentration, 30 grLqSO2 concentration, 4.16 grL.

S q 3H O
2

H S aq..
2

EB SHE s 0.141 V. not disturb the SO 2 adsorption on the electrode surface w10x. For curve b Fig. 10., i.e., oxidation of SO 2 in H 2 SO4 alone the plateau is observed in between 0.25 and 1.2 V. The single plateau in the The formation of sulfur and H 2 S was also observed during the experiment. The polarisation for deposition of Cu is shown in curve c where the limiting current density plateau for copper deposition

Table 3 Cyrstallographic orientations under various experimental conditions using a graphite anode Cu grL. 20 20 20 20 50 20 20 20 H 2 SO4 grL. 30 30 30 30 30 150 30 30 SO 2 grL. 0 4.16 8.0 15.30 4.16 4.16 4.16 4.16 Current density Arm2 . 150 150 150 150 150 150 200 150 Temperature 8C. 30 30 30 30 30 30 30 50 Peak intensity IrI0 . %. 111. 200. 220. 74 100 100 100 100 100 100 100 47 32 36 22 51 46 36 32 100 29 21 33 32 30 27 45 311. 43 25 20 27 30 27 26 27

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starts at a potential of , 0.6 V vs. SCE. When SO 2 is added to the CuSO4 q H 2 SO4 electrolyte, two current plateaus are observed, the first one, i.e., , 0.800.85 V vs. SCE refers to limiting current density for Cu2q ion reduction, whereas the second one, i.e., y0.9 to y1.0 V vs. SCE refers to the

reduction of H 2 SO 3 curve d.. In the presence of SO 2 , the cathodic reduction of copper is depolarised and black deposits are found to be formed on the cathode at a more negative potential, i.e., beyond y1.0 V, which may be attributed to the formation of CuS. Lichusina et al. w14x also observed the depolar-

Fig. 12. SEM photomicrographs of copper deposits. Key: a. SO 2 concentration, nil; b. SO 2 concentration, 4.16 grL; c. SO 2 concentration, 15.3 grL; d. Cu concentration, 50 grL; e. H 2 SO4 concentration, 150 grL; f. temperature, 508C; g. current density, 150 Arm2 ; h. current density, 200 Arm2 .

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2y ising action of SO 3 during electrodeposition of copper. In addition, the reduction of H 2 SO 3 is also polarised curve d. in the presence of Cu 2q.

3.8. Crystallographic orientations The copper deposits obtained under different electrowinning conditions are examined by XRD method to determine the order of preferred crystal planes. The results are given in Table 3. The preferred crystallographic orientations of the copper deposit obtained in the absence of SO 2 are in the orders 220. 111. 200. 311.. But when 4.16 grL SO 2 is added to the copper bath, the most preferred crystal plane changes from 220. to 111. and the order becomes 111. 200. 220. 311.. Increase in SO 2 concentration 4.1615.30 grL. does not change the crystal growth significantly and the 111. plane remains preferred throughout. The variables such as copper concentration, H 2 SO4 concentration, bath temperature and current density do not change the habit of crystal growth where the 111. plane remains preferred throughout. However, some minor change in the order of planes is observed when the current density is increased. 3.9. Deposit morphology The morphology of copper deposits obtained from sulfate electrolyte in the presence of sulfurous acid under various experimental conditions are shown in Fig. 12. The surface morphology of copper deposit in the absence of SO 2 is given in Fig. 12a. Fig. 12b shows the deposit morphology in the presence of 4.16 grL SO 2 . Addition of SO 2 to the copper bath completely changed deposit morphology. Nodular growth is observed. Such abrupt change is also marked from the crystallographic orientations. The most preferred plane changed from 220. to 111.. The presence of SO 2 mainly increase the crystallite size. When the SO 2 concentration is raised to 1516 grL Fig. 12c., the size is further increased. The change in the deposit morphology and increase in the crystallite size on addition of H 2 SO 3 to the copper 2y electrolyte may be due to the presence of SO 3 , which depolarises the electrodeposition of copper. It has been reported w15x that during electrodeposition of copper, the polycrystalline growth is dependent on

the anion present in the bath. Story and Barnes w16x and Barnes et al. w17x, from their study on growth of habit of electrodeposited copper, observed that the deposit morphology of polycrystalline aggregates changes with the over-potential. Walker and Cook w18x also observed that addition of Cly shifts the morphology of copper deposits. With increasing concentration of Cly, the deposit appears to be coarser. Rouse and Anbel w19x reported that an increase in Cly concentration in the copper electrolyte decreases the cathode polarisation. Observations of Rouse and Anbel w19x were also supported by Lakshman et al. w20x. In addition, these authors w20x also reported change in the texture of the deposits. All this information suggests that anions, which depolarise the copper deposition process, affect the surface morphology by increasing the crystallite size. This is probably due to inhibition of nucleation of newer crystallites by surface coverage due to the adsorption 2y of SO 3 and thus the situation favours the increase in size of the crystallites, which are already grown. The present results, i.e., cathode depolarisation due 2y to presence of SO 3 associated with increasing crystallite size, are in agreement with the findings cited above. At higher copper concentration, the deposit seems to be more compact and uneven Fig. 12d.. When sulphuric acid concentration in the copper bath Cu 20 grL, SO 2 4.16 grL. is increased, a major change in the deposit morphology is observed Fig. 12e.. The crystallite size is now decreased but the size is relatively larger than that with deposit obtained in the absence of SO 2 Fig. 12a.. The morphology shown at lower current density, i.e., at 100 Arm2 Fig. 12g. is different to that at 150 Arm2 Fig. 12b. and is close to those obtained at either higher bath temperature or copper concentration Fig. 12d,f.. But when the current density is raised beyond 150 Arm2 , the deposit morphology is completely changed Fig. 12h. and a leaf-type growth is observed.

4. Conclusion The electrowinning of copper in the presence of sulfurous acid was studied. It was found that increase in SO 2 concentration in the electrolyte 1. decreased the cell voltage, anode potential and power consump-

B. Panda, S.C. Das r Hydrometallurgy 59 (2001) 5567

67

tion considerably, 2. increased the crystallite size of the copper deposits, 3. depolarised the copper cathode, and 4. did not alter the current efficiency of copper deposition. The oxidation of sulfur dioxide seems to be inhibited on PbrSb, PbrAg and TiIrO 2 anodes. Non-uniform granular deposits adhering to the cathode surface were formed when PbrSb, PbrAg and TiIrO 2 anodes were used in the presence of SO 2 with the a current efficiency of 98%. Copper concentration, H 2 SO4 concentration and temperature had no significant effect on current efficiency and deposit morphology of deposited copper. A current density up to 200 Arm2 gave sheet deposits. For current densities higher than 200 Arm2 rough, powder deposits were obtained. Graphite was found to be a better anode substrate for the continuous oxidation of SO 2 than PbrSb, PbrAg and Ti IrO 2 anodes. The conditions for obtaining smooth, bright and compact deposits with better surface morphology, maximum current efficiency and minimum power consumption were copper, 20 grL; sulfuric acid, 30 grL; sulfur dioxide, 4.1 grL; current density, 150 Arm2 ; temperature, 508C; a graphite anode.

Acknowledgements The authors are grateful to Prof. H.S. Ray, Director, R.R.L., Bhubaneswar and Dr. R.P. Das, Head, Hydro and Electrometallurgy Division R.R.L Bhubaneswar for their valuable suggestions and kind permission to publish this paper.

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