Powder Technology 177 (2007) 133 139 www.elsevier.

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Recovery of nickel powder from copper bleed electrolyte of an Indian copper smelter by electrolysis
Archana Agrawal , D. Bagchi, S. Kumari, V. Kumar, B.D. Pandey
Metal Extraction and Forming Division, National Metallurgical Laboratory, Jamshedpur - 831 007, India Received 10 December 2005; received in revised form 17 January 2007; accepted 12 March 2007 Available online 23 March 2007

Abstract When nickel concentration increases in the copper sulphate electrolyte during electrolysis, it starts electrodepositing on the copper cathode thereby affecting the purity of the copper. In order to produce high quality copper cathodes with less than 1 ppm Ni, it became necessary to bleedoff large volumes of foul electrolyte contaminated with nickel and other impurities. The study reported in this paper was part of the effort aimed at devising a cost effective and an ecofriendly method for the production of value added powders from a waste stream, for P/M application. A part of copper salts and regenerated acid was used back into the system. As discussed in our paper on copper recovery from copper bleed stream (CBS), a process involving decopperisation and crystallisationsolvent extraction (SX) separationelectrowinning (EW) has been attempted as an alternative to the conventional process. Optimum conditions for nickel recovery from this type of solution have been investigated through a series of experiments carried out in a rectangular electrolytic bath with SS as cathode and PbSb as anode. A quantitative and selective recovery was found for nickel deposition under suitable conditions. The purity of the electrolytic nickel powders so produced was found to be 99.89%. The compact density of the annealed nickel powder was 7.72 g/cc. Other properties of the nickel powders such as flow-ability, particle size, etc. were also evaluated to assess its suitability for its use in P/M applications. 2007 Elsevier B.V. All rights reserved.
Keywords: Nickel powder; Copper bleed stream; Electrolytic powder; Powder properties

1. Introduction Being a strategic metal nickel finds its application in electroplating industry and in the production of various grades of stainless steel and alloy steel. Boldt [1] described the treatments of oxide ores where the nickel is recovered from solution after ammonia leaching as a hydroxide carbonate which is then calcined to NiO. Also, metal has been recovered by hydrogen reduction from a sulphuric acid leach. Possibly in the future similar leach solutions could be treated by electrolysis to recover nickel, although hydrogen reduction would seem to be the preferred method [2]. About 50% of nickel [3,4] is recovered by electrorefining and electrowinning process world over. Electrocrystallisation is one of the most widely used industrial methods for the production of high purity metal powder [5,6]. Properties of metal powder deposited on the cathode depend upon the various
Corresponding author. E-mail address: archana_nml03@yahoo.com (A. Agrawal). 0032-5910/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.powtec.2007.03.032

parameters such as concentration of ions, pH, bath temperature, current density, presence of additives in the electrolyte etc. A number of studies have been reported on electrowinning of nickel [79] from their sulphate solutions. The pH of the electrolyte
Table 1 Chemical composition of different copper bleed electrolyte Typical copper bleed electrolyte of modern copper refineries (g/L) Components Cu 4050 H2SO4 170200 Impurities Ni As Fe Sb Bi Cl Upper limits (g/L) 20 10 2 0.5 0.2 0.03 Copper bleed stream from ICC, Ghatsila (g/L) 39.86 194.04 Synthetic copper bleed solution (g/L) 38.42 171.5

9.577 NA 0.255 NA 0.108 NA

19.37 NA 0.757 NA 0.2 NA

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current density results in an increase in the grain size of nickel deposit. To control the quality of the electrodeposits some additives are usually added during winning [6,8]. The grain size of nickel can easily be reduced to nano-range by using additives such as coumarin and saccharin [7,9]. Wang et al. [8,10] have produced copper and nickel powder of size less than 100 nm by ultrasonic electrolysis. Recently, the processing of secondary materials for the recovery of valuable metals in an environmentally acceptable manner with low energy, capital and operating costs has been given due attention in the metal extraction/recovery. Copper bleed solution (CBS) is one of the streams generated in copper smelters [14] during electropurification of the impure copper anode to produce copper cathode. This solution contains high concentration of copper and nickel besides several other impurities. In order to recover copper and nickel as value added product from the bleed stream generated in a copper smelter, a process comprising of decopperisation and crystallisationSX separationelectrowinning steps has been developed at NML. In this paper effect of various parameters on the electrowinning of nickel powder has been presented. Properties of nickel powders have also been evaluated. 2. Experimental
Fig. 1. Copper bleed solution treatment following decopperisationcrystallisationsolvent extractionelectrowinning.

2.1. Materials required CuSO4, NiSO4, H2SO4, NaOH, LIX 84, Cyanex 272, (NH4) H3BO3, thiourea, all of Merck.

2SO4,

plays an important role on crystallite size of the electrodeposited nickel powder [10,11]. Recently, studies were conducted on the nickel deposition at about pH 3, using pure sulphate solutions with and without sodium sulphate and boric acid additives. A current efficiency of 7481% was obtained at a temperature more than 60 C [12,13]. The experiments reveals a sharp fall in the current efficiency with a decrease of pH and the corresponding energy consumption for unit weight (kg) of metal increased more than 3.4% due to the increase in H+ concentration of the electrolyte, and consequently hydrogen evolves over metal deposition. Further, it has been established that increasing the
Table 2 Preparation of the electrolytic nickel powder on bench scale at different pH Parameters Current density (A/m2) Average current (A) Average voltage (V) pH Volume of the spent solution (L) Powder (g) Current efficiency (%) Energy consumption (kWh/kg) % Ni recovery BS A 8.5 8.99 4.5 0.75 11.045 47.47 17.29 69.03 BS B 4000 8.5 8.48 5.5 0.75 11.411 48.46 15.79 71.32

2.2. Methods The process route developed at NML for the recovery of copper and nickel powders from the copper bleed stream of an Indian copper smelter comprises of the following steps: partial decopperisationmixed salt crystallisationsolvent extraction and electrowinning. The copper bleed solution obtained from an Indian copper smelter contains 39.86 g/L Cu, 9.58 g/L Ni, 0.26 g/L Fe, 0.108 g/L Bi, 0.007 g/L As, 0.055 g/L Sb, 198.04 g/L H2SO4.

BS C 4000 8.5 8.33 6.5 0.75 11.225 48.24 15.78 70.34

BS D 5000 12.5 11.30 4.5 0.75 14.473 42.37 19.52 90.45

BS E 5000 12.5 9.72 5.5 0.72 14.65 42.83 16.58 91.59

BS F 5000 12.5 9.44 6.5 0.72 14.31 41.85 16.49 89.43

BS ABS F: Bench scale experiment A to bench scale experiment F. Feed solution (g/L): 20Ni, 40(NH4)2SO4, 10H3BO3 , 0.2 CS(NH2)2. Volume: 0.8 L, Time (h): 2.5. Cathode: SS sheet (1No): 16.6(l) 3.7(b) 0.2(t) cm. Anode: PbSb(6%) (2No): 16.1(l) 4.0(b) 0.2(t) cm.

A. Agrawal et al. / Powder Technology 177 (2007) 133139 Table 3 Preparation of the nickel powder on large scale by electrolysis with 10 g/L of Ni in aqueous feed Parameters Time (h) pH Current densities (A/m2) Av. Voltage (V) Av. current (A) Energy consumption (kWh/Kg) Volume of the spent electrolyte (L) Analysis of the spent electrolyte (g/L) Weight of the dry nickel powder ( g) Current efficiency (%) Recovery of the nickel on solution basis (%) Deposit character LS A 1.75 5.50 5000 11.31 87.00 26.80 08.50 01.38 64.26 38.55 86.2 Dendritic powder with bright lustre LS B 1.90 5.25 5000 09.30 87.00 19.86 08.50 01.32 77.39 42.75 86.80 Dendritic powder with bright lustre LS C 2.06 5.16 4500 9.6 80.00 20.37 08.40 01.44 77.50 43.05 85.60 Dendritic powder LS D

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2.32 5.21 4000 09.60 70.00 20.93 08.85 01.47 74.49 41.89 85.30 Dendritic powder

Loss of powder during washing. LS ALS D : Large scale experiment A to large scale experiment D. Feed solution (g/L): 10Ni, 10H3BO3, 40(NH4)2SO4, 0.2 CS(NH2)2. Volume of the electrolyte: 9.0 L. Cathode: cylindrical rod (SS): 29.9(l) 2.5(d) and 29.4(l) 2.5(d) cm (2No). Anode: PbSb (6%): 18.0(l) 15.4(b) 0.4(t) cm (2No).

To optimise the experimental conditions a synthetic solution containing (g/L): 38.42 Cu, 19.37Ni, 171.5 H2SO4 was prepared (Table 1). The partially decopperised bleed solution, containing equal amounts of copper and nickel was evaporated in single stage and two stages to crystallise mixed crystal of copper nickel sulphate. The crystals obtained in the second stage of the two stage of crystallisation were washed with water,

Table 4 Large scale preparation of the nickel powder by electrolysis with 20 g/L of Ni in aqueous feed Parameters Time (h) pH Current densities (A/m2) Average voltage (V) Average current (A) Energy consumption (kWh/Kg) Volume of the spent electrolyte (L) Nickel in the spent electrolyte (g/L) Weight of the dry nickel powder (g) Current efficiency (%) Recovery of the nickel powder (%) LS E 3.97 4.66 5000 9.30 87.00 19.05 08.50 0.15 168.18 44.47 99.6

and dissolved. The solution was neutralized with NaOH to bring down the pH to 3.54.0, aerated for 24 h to precipitate iron as hydroxide and filtered. The filtrate so obtained was subjected to solvent extraction using LIX 84 and CYANEX 272 to separate copper from nickel. The loaded copper was stripped with H2SO4 and was electrolyzed to give pure copper powder. Nickel left in the raffinate was used to produce nickel powder by electrolysis. Analyses of the samples for low concentration of metallic contents were carried out by an Atomic absorption spectrometer. Solutions containing high metals were analyzed by conventional method. All the chemicals used for the chemical analysis were Analar grade reagents. 2.3. Bench scale electrolysis of nickel sulphate solution: 0.8 L of synthetic electrolyte containing 20 g/L Ni, 40 g/L (NH4)2SO4, 10 g/L H3BO3, 0.2ng/L thiourea was used for the production of the nickel powder in the bench scale electrowinning. The dimension of cathode was 16.6(l) 3.7(b) 0.2(t) cm made of stainless steel. The anode was made of lead antimony (6%) alloy with dimension of 16.6(l) 4.0(b) 0.2(t) cm. The current density was maintained in the range 40005000 A/m2
Table 6 Comparison of the nickel powder produced and metal depletion in solution with time on large scale(Set 9: Table 20) Time in (h) 0 0.5 1.0 1.5 1.9 Nickel in solution (g/L) 89.79 62.06 42.26 19.28 11.18 Nickel powder produced (g) 0 27.73 47.54 70.51 78.61 Current efficiency (%) 0 65 52 51 43 Energy consumption (kWh/kg) 0 14.61 15.27 14.50 16.99

LS E : Large scale experiment E. Composition (g/L): 19.37Ni, 40(NH4)2SO4 , 10H3BO3, 0.2CS(NH2)2. Volume of the electrolyte: 9.0 L. Cathode: Cylindrical rod (stainless steel): 29.9(l) 2.5(d) and 29.4(l) 2.5(d) cm (2No). Anode: PbSb (6%): 18.0(l) 15.4(b) 0.4(t) cm (2No).

Table 5 Comparison of current efficiency for copper and nickel powder synthesis in large scale experiments Current efficiency (%) Cu (38g/L) Ni (10g/L) Ni (20g/L) LS A 82.8 38.55 44.47 LS B 69.36 42.75 LS C 85.32 43.05 LS D 88.15 41.89

Feed solution (g/L): 10Ni, 10H3BO3, 40(NH4)SO4, 0.2 CS(NH2)2. Volume of the solution: 9.0 L, current density: 5000 A/m2, average current: 80 A.

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A. Agrawal et al. / Powder Technology 177 (2007) 133139 Table 7 Size analysis of the nickel powder produced on large scale by electrolysis Particle size (m) 212 212150 150106 10675 7563 6345 4538 b 38 Mesh size (BSS) +72 72 + 100 100 + 150 150 + 200 200 + 240 240 + 325 325 + 400 400 Percentage by weight Sample LS B 12.59 29.67 10.75 07.39 05.51 05.24 11.64 16.06 Sample LS D 15.30 30.73 10.18 05.89 03.38 03.90 08.59 20.40 Sample LS E 22.66 30.10 13.94 8.61 4.44 3.98 8.09 7.67

Fig. 2. Plot of nickel metal fall/powder produced vs time. Feed solution (g/L): 10Ni, 10H3BO3, 40(NH4)SO4, 0.2 CS(NH2)2 V: 9.0 L, current density: 5000 A/m2, average current: 80 A.

Samples: LS BLS E (after annealing at 973 K).

to see the effect on the powder deposit. The average voltage was also measured as in the case of copper. The experiments were carried out in the pH range of 4.56.5. The pH was adjusted by the addition of dilute NaOH with intermittent mixing which also leads to the dissolution of any nickel hydroxide formed during the electrolysis. Since the gap between the cathode and anode was 3.5 cm, constant stirring of the electrolyte was not required because the amount of nickel deposited on the cathode could be replenish by the diffusion of nickel from the electrolyte. 2.4. Large-scale electrolysis of the nickel sulphate solution The 9.0 L solution obtained from the solvent extraction step of the actual copper bleed stream containing 10 g/L Ni, 40 g/L (NH4)2SO4, 10 g/L H3BO3 and 0.2 g/L thiourea was used as the electrolyte. Two cylindrical rods of 29.9(l) 2.5(d) cm dimension made of stainless steel were used as cathodes and the anode (2No) were made of lead antimony (6%) alloy with dimension as 18(l) 15.4(b) 0.4(t) cm. Distance between cathode and anode was kept in between 5 to 6 cm. Since the experiment was done on a large-scale cylindrical cathode was found to be better than the plate type cathode for a good powdery deposit because under high current density, which is a requirement for powder synthesis, the transport of metal ions from the bulk solution to the small area available for depositing is very fast so the sheet deposit will not take place and the powder can be removed easily from the cathode. The variation of pH in the range 5.25.5 has been studied to see the effect on

the nickel deposition in this set of electrowinning operation. The experiments were carried out at the current density in the range 40005000 A/m2 with corresponding high voltage. Boric acid and (NH4)2SO4, were added in the electrolyte as the buffering action of boric acid at the cathode surface favours the deposition process by decreasing H2-evolution rate [15] and a lower precipitation of insoluble Ni(OH)2 [16]. The powder was recovered from the bath and also from the cathode at the end of the experiments. The nickel powder thus produced was subjected to annealing in an electrically heated tubular furnace at the desired temperature (973 K) with a flow of hydrogen gas (510 L/min). The hydrogen loss of nickel powder was determined at 1318 K under hydrogen environment (510 L/min) for half an hour and then its properties were examined for P/M applications. 3. Result and discussion In order to recover nickel from the copper bleed solution from an Indian smelter, a process followed consists of decopperisation of copper till the concentration of copper ion in the solution is brought down to the level of nickel. After the decopperisation step, crystallisation was carried in single and two stages to see the possibility of getting the mixed crystals. The solution obtained after partial decopperisation of the synthetic CBS contained 17.65 g/L Cu, 21.18 g/L Ni, 205.8 g/L sulphuric acid. In a two-stage crystallisation, the mixed crystals obtained with the chemical composition of 21.72 %Cu, 2.3 % Ni, in the first stage indicate that copper crystallisation takes place before nickel which can further be used for making powder or can be recycled for copper make up in the refinery. In the second stage of crystallisation mixed metal sulphates with high nickel (15.6%) and low copper (8.1%) were obtained. The crystal obtained from the single stage evaporation (80%) had
Table 8 Properties of the nickel powder produced at large scale by electrolysis Sample no. LS B LS C LS D LD E Hydrogen loss (%) 0.70 0.85 0.30 Apparent density (g/cc) 4.29 Flow rate (s/50 g) 20 21 20 21 Acid insoluble (%) 0.37 0.29 0.32 0.13

Fig. 3. Plot of current efficiency and average voltage with time for the production of nickel feed solution (g/L): 10Ni, 10H3BO3, 40(NH4)SO4, 0.2 CS (NH2)2, V: 9.0 L, current density: 5000 A/m2, average current: 80 A.

A. Agrawal et al. / Powder Technology 177 (2007) 133139 Table 9 Chemical analysis of the unannealed electrolytic nickel powder produced at large scale Sample no. Fe (%) Cu (%) Co (%) Pb (%) Bi (%) Sb (%) Purity (%) LS A LS B LS C LS D LD E
#

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Table 11 Compactibility and green density of annealed electrolytic nickel powder [Set LS D and LS E] Sample Annealed no. nickel powder LS D LS E Weight of Nil powder (g) Weight of the compacted metal (g) 16.17 19.12 Length of the compacted metal (mm) 14.5 15.00 Diameter of the compacted metal (mm) 14.5 14.5 Green density (g/ cm3) 6.75 7.72

0.048 0.013 0.012 0.013 0.0187

0.189 0.039 0.046 0.016 0.011

0.048 0.039 0.046 0.042 0.031

0.122 0.098 0.084 0.051 0.048

NF NF NF NF NF

NF NF NF NF NF

99.59 99.81 99.84 99.88 99.89

(b 152m) 16.43 (b 104m) 20.07

Copper contamination from the old bath.

Load applied = 8 tonne.

chemical composition as: 12.13% Cu, 13.48% Ni, 0.539% Fe, 0.046% Bi and 15.03% H2SO4. For the recovery of copper and nickel, the crystals obtained from the second stage crystallisation of the two stages crystallisation were leached with water to give the aqueous solution with the composition of 8.39g/L Cu, 13.67g/L Ni, 0.5g/ L Fe and 20g/L H2SO4. Fig. 1 shows the overall treatment steps for the recovery of copper and nickel powders by decopperisationcrystallisation solvent extraction and electrowinning route. Presence of iron being deleterious for solvent extraction was removed from the leach solutions obtained as above. The leach was treated with NaOH solution with a constant stirring to increase the pH of solution from 1.12 to 3.42 and aerated for a period of 24 h at room temperature to precipitate iron as ferric hydroxide thereby bringing down the iron content from 0.522 to 0.0041 g/L. The iron free solution was subjected to solvent extraction using LIX 84 and CYANEX 272 to separate copper from nickel [14]. Copper goes into the solvent during solvent extraction leaving nickel in the raffinate. This raffinate was used to recover nickel as powder. Thus, different sets of the experiments were carried out to optimise the parameters for the recovery of the metal as powder by electrolysis on bench scale and were verified on large scale. A number of experiments were performed at current density of 4000 A/m2 and 5000 A/m2 with the average current at 8.5A and 12.5A at different pH varying from 4.56.5 (Table 2). The recovery of the nickel powder was low at 4000 A/m2 current density irrespective of the pH. But with the increase in current density to 5000 A/m2 the recovery was above 91% at pH 5.5. The current efficiency and energy consumption are found to be 4748%, 4142% and 1617 kWh/kg, 1720 kWh/kg at the current density of 4000 A/m2 and 5000 A/m2 respectively. High
Table 10 Chemical analysis of the annealed electrolytic nickel powder produced at large scale S. no. LS A LS B LS C LS E LS F Fe (%) 0.074 0.021 0.026 0.053 0.017 Cu (%) 1.267 a 0.050 0.053 0.034 0.0148 Co (%) 0.047 0.041 0.039 0.044 0.032 Pb (%) 0.111 0.101 0.074 0.053 0.434 Bi (%) NF NF NF NF NF Sb (%) NF NF NF NF NF Acid insoluble 0.37 0.29 0.32 0.13 Purity (%) 99.59 99.81 99.84 99.88 99.89

voltage is noticed at the current of 12.5 A corresponding to the current density of 5000 A/m2, at a lower pH of 4.5. The parameters optimised on the bench scale were then substantiated by a few large-scale trials. A 9.0 L nickel pregnant solution containing different amounts of nickel along with other components (Tables 3 and 4) was taken for the electrolysis of nickel at the current density in the range 40005000 A/m2 at pH 5.25.5. It can be seen that the high current density leads to higher amount of nickel deposition. The nickel recovery is around 86% and current efficiency being in the range 3944% with energy consumption of 2021 kWh/kg. If we compare the current efficiency on large-scale electrolysis of copper and nickel (Table 5), the efficiency of latter is almost half to that of the former. It is due to the occurrence of secondary semi reaction of hydrogen production during the production of nickel powder (Eqs. (1)(3)) hence a large amount of current is consumed in reducing protons instead of nickel. Cathode : Ni2 2e Ni Anode : 2H2 OO2 4H 4e The overall cell reaction is 2NiSO4 2H2 O2Ni 2H2 SO4 O2 3 1 2

A similar effect on the current efficiency was observed by Rambla et al.[17], where they found that the current efficiency increases with the increase in the concentration of nickel in the electrolyte. There was also a difference in the bench scale and

NF: Not found. a Increased copper concentration due to contamination with residual copper powder in annealing furnace.

Fig. 4. SEM picture of annealed nickel powder.

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Fig. 5. XRD of annealed nickel powder.

large-scale results, which may be attributed to the different geometry and disposition of electrodes and the geometry of the whole system in both the cases. About 87% of nickel is recovered at 5000 A/m2 for a feed of pH 5.25. But from the solution of 20 g/L nickel at pH 4.66, the recovery of the nickel goes above 99% in 3.97 h under the similar conditions (Table 4)). Thus it is possible to recover total nickel with increase in time with the energy consumption of 19 kWh/kg. Rate of nickel powder produced can be seen from Table 6. A rise in nickel powder precipitated and a fall in metal concentration in the aqueous feed are noticed (Fig. 2), which is more or less similar to that for copper . Voltage also decreases with time but becomes almost constant at the later stage (Fig. 3). Current efficiency also shows an initial increase at a current density of 4500 A/m2 and then a fall with time is noticed. A few additives are known to improve the quality and quantity of nickel powder produced. As found earlier, the addition of boric acid Kumar et al [12] acts as a buffering agent, whereas thiourea increases the brightness of the powder produced. Ammonium sulphate also helps in maintaining the pH of the electrolytic bath.

3.1. Properties of nickel powder produced by electrolysis To ensure the quality of powder for the P/M applications, it was annealed in the electrically operated tubular furnace. A known amount of the powder was charged in the constant zone of furnace and heated to 973 K for 1 h in the reducing atmosphere of the H2. The flow rate of the gas was initially 5.2 L/m but after having reached the temperature the flow was increased to 10 L/m. A very bright powder was obtained. The particle size for all the samples was found to be in the range 213 to b 38 m with maximum amount ( 30%) of 212150 m size (Table 7). Apparent density of the nickel powder was found to be 4.29 g/cc (Table 8). The flow rate of the powder was 2021 s/ 50 g sample and acid insoluble was in the range 0.130.37%. Hydrogen loss of the powder was determined in an electric furnace at the temperature 1318 K under the reducing atmosphere of H2 (Table 8). The hydrogen loss is minimum in sample LSE (0.3%) and maximum in sample LSD (0.85%). The purity of the nickel powders was ascertained by the chemical analysis for annealed and unannealed powders

Table 12 Deposition rate constant Kd during Ni electrolysis on bench scale at different pH and at two current densities SL no. 1 2 3 4 5 6 CD (A/m2) 4000 4000 4000 5000 5000 5000 c1 (mg dm 3) 16000 16000 16000 16000 16000 16000 c2 (mg dm 3) 4960 4640 4800 1600 1280 1696 pH 4.5 5.5 6.5 4.5 5.5 9.37 6.5 9.44 800 9000 0.001525 Average volt (V) 8.99 8.48 8.33 11.3 800 9000 0.001717 V (cm3 ) 800 800 800 800 Time (s) 9000 9000 9000 9000 Kd (cms 1) 0.000796 0.000841 0.000818 0.001565

A. Agrawal et al. / Powder Technology 177 (2007) 133139 Table 13 Deposition rate constant Kd during Ni electrolysis on large scale at different time SL no. 1 2 3 4 CD (A/m2) 5000 5000 5000 5000 c1 (mg dm 3) 89.79 89.79 89.79 89.79 c2 (mg dm 3) 62.06 42.26 19.28 11.18 Temp (C) 55 55 55 55 Average volt (V) 9.3 9.3 9.3 9.3 V (cm3 ) 9000 9000 9000 9000 Time (s) 1800 3600 5400 6840

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Kd (cms 1) 0.0038 0.0039 0.0052 0.0056

(Tables 9 and 10) and was found to be maximum of 99.89% for sample LSE (with and without annealing); the lowest purity was for sample LSA (99.60%). The green density (Table 11) of the nickel powder was found out by taking calculated amount of the powder in a die of cross sectional area 0.2738 in.2 under the applied load of 8 tonne; the required load is 30 tsi. The density was found to be 7.72 g/cc for sample LSE. SEM pictures of annealed nickel powder produced at 5000 A/m2 as represented in Fig. 4 shows that nickel powder produced was dendritic in nature with an advantage of better compaction for P/M application. The nickel powder dendrite showed well-defined growth in thickness as compared to copper. The X-ray analysis confirmed that the produced powder was metallic Ni as shown in Fig. 5. The 2 h values fit with those reported in the literature (011260 of Power Diffraction File). 3.2. Deposition rate constant Deposition rate constant Kd (cm s 1) were calculated using Eq. (4) as reported by Fornari et al [18] Kd 2:303V logc1 =c2 =St 4

6. On compaction of b 104 m size powder, the green density was found to be 7.72 g/cc. Acknowledgements Authors are thankful to the Director, NML, Jamshedpur for giving permission to publish the paper. Thanks are also due to the Dept. of Mines, Govt. of India for sponsoring the activity to NML. References
[1] J.S. Boldt Jr, The Winning of Nickel, Methuen, London, 1967. [2] D. Gilroy, The electrowinning of metals, in: A.T. Kuhn (Ed.), Industrial Electrochemical Processes, Elsevier, Amsterdam, 1971, pp. 175217. [3] R. Wu, M. Oliazadeh, A.M. Alfantazi, J. Appl. Electrochem. 33 (2003) 10431047. [4] R. Walker, A.R.B. Sandford, Chem. Ind. 19 (1979) 642647. [5] V. Kumar, B.D. Pandey, D.D. Akkerkar, Hydrometallurgy 24 (1990) 189201. [6] F. Ebrahimi, G.R. Bourne, M.S. Kelly, T.E. Matthews, Nanostruct. Mater. 11 (1999) 343350. [7] F. Ebrahimi, Z. Ahmed, J. Appl. Electrochem. 33 (2003) 733739. [8] L. Oniciu, L. Muresan, J. Appl. Electrochem. 21 (1991) 565. [9] J.K. Dennis, J.J. Fuggle, Electroplat. Met. Finish. 17 (Jan 1968). [10] J. Wang, X. Zhao, J. Pan, X. Yin, Mater. Sci. Eng. 18 (2000) 7074. [11] K. Biswas, W.G. Davenport, Extraction metallurgy of copper, 3rd Edition, Pergamon Press, UK, 1994. [12] V. Kumar, B.D. Pandey, D.D. Akerkar, Electrowinning of nickel in the processing of polymetallic sea nodules, Hydrometallurgy 24 (1990) 189201. [13] B.D. Pandey, V. Kumar, Extraction of copper and nickel from ammoniacal leach liquors of Indian sea nodules, Hydrometallurgy 26 (1991) 3545. [14] A. Agrawal, S. Kumari, M.K. Manoj, B.D. Pandey, V. Kumar, D. Bagchi, Premchand, in: V.N. Mishra, S.C. Das, K.S. Rao (Eds.), Proceedings of Int. Symp. on Solv. Extr., Bhubaneswar, Allied Publishers Pvt. Ltd., 2002, pp. 3442. [15] J. Ji, W.C. Cooper, D.B. Dreisinger, E. Peters, J. Appl. Electrochem. 25 (1995) 642. [16] E. Ku zeci, R. Kammel, S.K. Gogia, J. Appl. Electrochem. 24 (1994) 730. [17] J. Rambla, E. Brillasi, J. Casado, Nickel electrowinning using a Pt catalysed hydrogen-diffusion anode, Part II: batch tank with a sulphate bath, J. Appl. Electrochem. 29 (1999) 12111216. [18] P. Fornari, C. Abbruzzese, Copper and nickel selective recovery by electrowinning from electronic and galvanic industrial solutions, Hydrometallurgy 52 (1999) 209222.

where V is the volume of the feed solution (cm3 ), S is the area of the cathode cm2 , c1 and c2 are the concentration of the nickel in the solution at time 0 and t. The results of Kd.for the nickel powder produced on the bench and large scale and are given in Tables 12 and 13 respectively. The conditions are mentioned in the table. 4. Conclusion 1. 87% of nickel powder recovery could be achieved at 5000 A/ m2 for a feed of pH 5.25. But, the recovery of the nickel goes above 99% in 3.97 h under the similar conditions from the solution of 20 g/L nickel at pH 4.66. 2. SEM shows that the powder is dendritic in nature. 3. The current efficiency for nickel powder production by electrolysis was found to be in the range of 3944% with energy consumption in the range 2021 kWh/kg. 4. Purity of the annealed nickel powder was found to be 99.89%. 5. The annealed powder has apparent density to be 4.29 g/cc, flow rate of the powder was 2021 s/50 g sample and acid insoluble was in the range 0.130.37%.