Journal of Hazardous Materials 181 (2010) 908915

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Journal of Hazardous Materials

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The recovery of zinc from hot galvanizing slag in an anion-exchange membrane electrolysis reactor
Xiulian Ren, Qifeng Wei , Surong Hu, Sijie Wei
College of Ocean, Harbin Institute of Technology at Weihai, Weihai 264209, PR China

a r t i c l e

i n f o

a b s t r a c t
This paper reports the optimization of the process parameters for recovery of zinc from hot galvanizing slag in an anion-exchange membrane electrolysis reactor. The experiments were carried out in an ammoniacal ammonium chloride system. The inuence of composition of electrolytes, pH, stirring rate, current density and temperature, on cathodic current efciency, specic power consumption and anodic dissolution of Zn were investigated. The results indicate that the cathode current efciency increases and the hydrogen evolution decreased with increasing the cathode current density. The partial current for electrodeposition of Zn has liner relationship with 1/2 (: rotation rate). The highest current efciency for dissolving zinc was obtained when NH4 Cl concentration was 53.46 g L1 and the anodic dissolution of zinc was determined by mass transfer rate at stirring rate 0300 r min1 . Increase in temperature benets to improve CE and dissolution of Zn, and reduce cell voltage. Initial pH of electrolytes plays an important role in the deposition and anodic dissolution of Zn. The results of single factor experiment show that about 50% energy consumption was saved for electrodeposition of Zn in the anion-exchange membrane electrolysis reactor. 2010 Elsevier B.V. All rights reserved.

Article history: Received 21 December 2009 Received in revised form 17 May 2010 Accepted 21 May 2010 Available online 1 June 2010 Keywords: Galvanizing slag Zinc recovery Ion-exchange membrane electrolysis

1. Introduction There are large amounts of zinc slag produced by hot dip galvanizing industry each year. For those wastes are zinc-rich resources, many methods have been developed to recover zinc [1]. The recovery processes are pyrometallurgical or hydrometallurgical. Generally, the pyrometallurgical ways are more power consumption and complex, while the hydrometallurgical processes are more environmentally benign and economical [1]. Usually, sulfuric acid [26], hydrochloric acid, acetic acid [2] ammonia/ammonium carbonate, ammonium chloride [7,8] and carboxylic acid are used as leaching medium for the dissolution of zinc [2]. The metal from the leaching solution is recovered by different methods such as precipitation [24], crystallization [2,3], solvent extraction [9], ion exchange [10] and electrowinning [1013]. The zinc slag used in this study contains mainly metallic zinc, aluminum and alloy formed by them. As far as this slag is concerned, it is not advisable to leach it with acid, for a great deal of lixiviating reagent would be consumed. Besides, the corrosion of equipments would also be very serious. So, the conventional hydrometallurgical

Corresponding author at: Department of Marine, Harbin Institute of Technology, Wenhua West Road 2#, Weihai, Shandong 264209, PR China. Tel.: +86 0631 5687691; fax: +86 0631 5687210. E-mail address: weiqifeng163@163.com (Q. Wei). 0304-3894/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.jhazmat.2010.05.098

process is not favorable for treating such slag. To our knowledge, this zinc slag can be directly melted into anodes and electrorened to produce high purity zinc, at the same time, aluminum can be turned into saleable Al(OH)3 . Concerning the electrolysis, it is essential to select a suitable electrolyte system, the ammoniaammonium chloride system (NH3 NH4 Cl) has been used [13], showing a promising prospect. Ammonia/ammonium chloride discharged from cathode compartment was reused as lixiviant of hot galvanizing slag and anolyte in this study. The concentrated ammonia/ammonium chloride waste can be crystallized as production of ammonium chloride after neutralization and purication. In this system, impurities in the electrolyte cannot co-deposit with zinc, and do not affect the current efciency and the quality of cathodic zinc as electrodeposition happens in sulfuric acid electrolyte. As the slag was used as anodes, it dissoluted in the process, insoluble solid particles produced by the hydrolyzation went into solution, contaminating the electrolyte and metallic zinc deposited on cathode, which made the electrolysis processing abnormal. At the same time, saleable Al(OH)3 was intended to be produced in this process, hence, an anion-exchange membrane can be used to separate the cathode and anode in order to collect the anodic reaction products and to avoid their effects on the cathode reaction. The ion-exchange membrane has been widely used to selectively transport counter ions through them based on unique property [14,15], it will be much suitable to separate anolyte and catholyte in this experiment.

X. Ren et al. / Journal of Hazardous Materials 181 (2010) 908915 Table 1 Chemical composition of the slag (%). Elements wt.% Al 56.17 Zn 41.38 Fe 2.01

909

Insoluble 0.44

2.2. Preparation of the slag anode The slag was melted by heating to 600 C and cast into a steel mould (20 mm 40 mm 2 mm) to form anodes and cooled to room temperature in the argon atmosphere. The anodes were polished with ne silicon carbide paper and degreased by immersion with acetone in an ultrasonic bath, and then were rinsed with distilled water. 2.3. Analytical methods 2.3.1. Zinc concentration The zinc concentration in solution was determined by EDTA titration, which was taking in the hydrochloric acidhexamine buffer system and xylenol orange was used as the indicator. The chemical composition of the slag and deposited metallic zinc was determined by ICP analysis (Inductive Coupled Plasma Emission Spectrometer). 2.3.2. pH pH was measured using a pH meter (Jenco 6010). 2.3.3. Stirring rate The stirring rate was measured using a laser speed detector (DT2857, China).
Fig. 1. Schematic ow chart of the utilization of the slag.

The ow chart of our novel approach to recovery zinc from the slag in an anion-exchange membrane electrolysis reactor is shown in Fig. 1. The slag was smashed into powder and was leached by ammonia/ammonium chloride to obtain solution containing desired concentration of Zn, this mixture containing desired concentrations of NH4 Cl and ammonia was used as anolyte. After a period of electrolysis, the mixture was discharged from anode compartment and its pH was adjusted by adding ammonia or HCl. The ltrate of the mixture was fed into the cathode compartment and was used as catholyte. The lter cake washed thoroughly was used as raw material to produce Al(OH)3 by separating impurities. The slag was also casted into a rectangular parallelepiped which was used as anodes. In order to achieve long-period deposition, the known additives were employed to inhibit the growth of dendrites. Compared with the conventional hydrometallurgical process, the major advantages of this process are the simplicity, sufcient exploitation of the slag and comparatively low power consumption. In this study, our work was focused on the optimization of conditions for electrolysis. 2. Experimental 2.1. Characterization of the hot galvanizing slag A representative sample of hot galvanizing slag was employed in this study. The composition of the slag is listed in Table 1. Chemical analysis was determined by ICP analysis. The mineralogical composition was examined by XRD analysis. The results in Fig. 2 showed that the slag was consisted of metallic aluminum, metallic zinc, solid-melt formed by aluminum, zinc and iron.

2.3.4. Calculations of current efciency and specic energy consumption Cathode current efciency (CCE) was determined as the ratio of the weight gain of zinc deposited at the cathode with electrical charge q, to the theoretical weight of deposited metal calculated using Faradays law. It was calculated as follows: CCE m 103 100% tqI (1)

where CCE is the cathode current efciency (%), m is the actual weight gain of deposited zinc (kg), t is the duration time (h), q is the electrochemical equivalent of zinc (g/A h), and I is the current through the cell (A).

Fig. 2. X-ray diffraction pattern of the slag.

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X. Ren et al. / Journal of Hazardous Materials 181 (2010) 908915

Specic energy consumption was calculated as follows: W= V 1000 q CCE (2)

where W is the specic energy consumption (kWh kg1 ), V is the cell voltage (V), CCE is the current efciency (%) and q is the electrochemical equivalent of zinc (g/A h). 2.3.5. XRD analysis X-ray diffractions were performed on the slag powder and the product zinc foil using XRD-6000 with Cu target anode, graphite monochromator, X-ray tube voltage of 40.0 kV, X-ray tube current of 30.0 mA, scan range of 1080 , scan speed of 8.000 min1 and sampling interval of 0.02 . 2.4. Experimental cell 2.4.1. Electrochemical membrane reactor The experiments were carried out in a divided cell, and the electrolysis membrane reactor was made of acryl glass in our laboratory. The volumes of anolyte vessel and catholyte vessel were of 0.45 and 0.75 L. The electrolyte was agitated with a mechanical stirrer in both compartments. The system featured an electrolytic membrane reactor and an adjustable DC power supply. The cathodes used were ASTM 301 stainless steel sheets of xed dimensions, and a thin layer of lacquer was applied on one side of the cathode. Practically, aluminum is usually used as a cathode in the electrolyte of zinc from sulfate solution, but it is used as a blank cathode to prepare the starter-sheet blanks in the zinc electrowinning. However, in this study, zinc deposition was weighted, the oxidation of the polished cathode surface will affects the accuracy of experimental results, and therefore, ASTM 301 was used as the cathode. The casted slag was used as the anode, the plate with an effective physical dimension of 20 mm 40 mm 2 mm. The anode and cathode were separated by an anion-exchange membrane. The DC current (WYK-3020 constant current regulator, 020 A, 030 V) was applied to the reactor, and the cell voltage was recorded at regular intervals. The temperature of the electrolyte was controlled with a variation of 1 C using a thermostatic control. The initial bath pH was measured using a pH meter. 2.4.2. Anion-exchange membrane The PE-203 was employed as an anion-exchange membrane with polyethylene as substrate, RN+ (CH3 )3 as functional group, exchange capacity of 2 0.2 mequiv./g (dry membrane), water content of about 35%, resistance of about 4.5 cm2 , thickness of about 0.3 mm and selectivity of 96%, was purchased from Shanghai Qiulong Chemical Company, Ltd. Before use, the membrane was equilibrated with sulfuric acid solution for one night and then rinsed with demineralized water. 2.5. The electrolysis procedure The cathode compartment was lled with a ltrate of mixture from anode compartment containing zinc chloride, ammonium chloride and ammonia of known strength. The anode compartment was lled with the leachate of slag containing hydrolysis product, ammonium chloride, zinc chloride and ammonia of known strength, the initial pH was adjusted with ammonia. The anode and cathode were placed at a constant distance of 15 mm from the anion membrane. Voltage was applied across the electrodes to achieve the desired current density. During the electrolysis process, the electrolyte was stirred with a motor stirrer at constant rotate speed. After electrolysis, the cathode and anode were removed and washed thoroughly with distilled water, and dried in an oven in the

argon atmosphere. The deposited plate was weighted and deposition was scraped off carefully from the cathode surface. The current efciency was calculated from the weight gain. The concentration of Zn2+ in anolyte was determined by EDTA titration to calculate the concentration of Zn2+ and the partial anode current efciency. The effect of the following parameters on the current efciency and specic power consumption were studied: Zn2+ concentration, NH4 Cl concentration, cathode current density, bath temperature and initial pH. All electrolysis tests were conducted for at least 1 h in each solution. Linear sweep voltammetry was used to examine the cathodic and anodic polarization behaviors under different conditions. Experiments were conducted taking 50 mL solution of different compositions with a chi 600 electrochemistry workstation in a small electrolysis reactor. The cathodic and anodic polarizations were studied in the potential range of 0.5 to 1.1 V, and of 0.71.1 V at a scan rate of 10 mV s1 , respectively. A casted slag plate with uncovered surface of 1 cm2 was used as the anode, ASTM 301 was used as cathode, platinum plate (1 cm2 ) was used as counter and a saturated calomel electrode (SCE) was used as the reference electrode. To minimize iR-drop effects, a Luggin capillary was employed to connect the reference electrode compartment to the working electrode. The electrolysis of over-time was completed in the optimized conditions in a 4-h period. The product zinc was detected by XRD and its chemical composition was analyzed by ICP. 3. Results and discussion 3.1. Effect of cathodic current density Usually the current density applied to the electrolysis process is restricted by the limiting current, when the current density is higher than this value, cathode current efciency decreases and specic energy consumption increases, and serious deterioration in the quality of the cathode deposit is achieved. In order to obtain the maximum CCE and the minimum specic energy consumption, the electrolysis was conducted by varying the cathode current density from 300 to 600 A m2 in the presence of 50 g L1 of ammonium chloride at 25 C, pH 8, and stirring rate of 300 r min1 with 53.58 g L1 Zn2+ . The electrolysis was performed for 1 h. The effect of cathode current density on the cathode current efciency (CCE) is plotted in Fig. 3. Fig. 3 indicated that: when the cathodic density was below 500 A m2 , the CCE increased with current density increasing.

Fig. 3. The effect of current density on cathode current efciency.

X. Ren et al. / Journal of Hazardous Materials 181 (2010) 908915 Table 2 and EH+ /H2 for the evolution of hydrogen at different cathode current densities. CCD (A m2 ) EH+ /H2 300 1.0076 1.4808 400 1.0221 1.4954 500 1.0331 1.5064 600 1.04254 1.5158

911

Table 3 The effect of Zn2+ concentration on cathode current efciency and power consumption. Zinc concentration (g L1 ) 36.68 40.20 53.58 59.53 78.79 CCE (%) 99.16 99.18 99.50 99.53 99.82 W (kWh t1 ) 1179.31 1136.97 1029.43 1029.17 1002.76

When the cathodic current density increased to 500 A m2 , the current efciency was almost unchanged, meanwhile, the higher the current density, the more the ohmic drop and the higher the power consumption, so favorable result was achieved with a current density of 500 A m2 . The electrochemical deposition of zinc metal at a cathode occurs in an electrolyte containing Zn2+ , NH3 H2 O, NH4 Cl and H2 O. Zn2+ is mainly existence as Zn(NH3 )4 2+ , with the main reactions as follows:
+ Zn(NH3 )2 4 + 2e Zn + 4NH3

3.2. Effect of zinc concentration The effect of zinc concentration on cathodic current efciency and power consumption was investigated under the conditions as follows: NH4 Cl concentration of 50 g L1 , cathodic current density of 500 A m2 , zinc concentration varying from 30 to 80 g L1 , other factors as mentioned above. Table 3 illustrates that high cathodic current efciencies were obtained in zinc concentrations range of 3680 g L1 , substantially higher than 99%, and specic power consumptions were much lower than that in conventional zinc electrowinning (32003400 kWh t1 Zn) [13]. The cathodic polarization curves obtained from solutions with different concentrations of Zn2+ are shown in Fig. 4. The cathodic linear polarization curves are the same shape for the solutions with different concentrations of Zn2+ . An increase in the cathodic polarization was recorded when concentration of Zn2+ decreases in the electrolyte, in accordance with results shown in Table 4. This is because the increase in the hydrogen evolution reaction rate attributed to the decrease of Zn2+ concentrations, followed by the decrease in the partial current densities for the electrodeposition of zinc. Comparison of Table 3 with Fig. 4 indicates that the greater the polarizing effect of Zn2+ concentration is, the lower the cathode current efciency and the higher the power consumption. 3.3. Effect of NH4 Cl concentration To study the effect of NH4 Cl concentration on the cathodic current efciency, several experiments were carried out by varying NH4 Cl concentrations from 40 to 80 g L1 , the results were shown in Fig. 5. Fig. 5 reveals that the cathode current efciency decreases slightly when NH4 Cl concentration is below 60 g L1 . When NH4 Cl concentration is over 60 g L1 , current efciency drops sharply. From experimental results, the maximum NH4 Cl concentration is

(3) (4)

2H2 O + 2e H2 + 2OH By the Nernst Equation:

EZn2+ /Zn = EZn 2+ /Zn +

RT ln[Zn2+ ] = 0.7626 + 0.02958 lg[Zn2+ ] nF (5)

EH+ /H2 = 0.05916 lg[H+ ] = 0.05916 pH In Zn2+ NH3 NH4 ClH2 O system, equilibriums occur: Zn2+ + 4NH3 [Zn2+ ] =
+ Zn(NH3 )2 4

(6)

(7) (8)

+ [Zn(NH3 )2 4 ]

4 [NH3 ]4

1 g 4 is 9.46 for Zn(NH3 )4 2+ . In this electrolyte, NH3 H2 O and NH4 + forms buffer solution, the equilibrium equation is as follow: NH3 H2 O NH+ + OH 4 (9)

The pH in this buffer solution is calculated as follow: pH = pKa + lg [NH3 ] [NH+ ] 4 (10)

Kb = 1.8 105 for NH3 H2 O, and Ka = Kw /Kb = 5.6 1010 . As pH 8, [NH4 + ] = 5 mol L1 , the free concentration of NH3 is 0.2748 mol L1 , [Zn(NH3 )4 2+ ] = 0.8191 mol L1 , from Eq. (5), we obtain EZn2+ /Zn = 0.7651 V. Tafel formula for the evolution of H2 on zinc cathode is as follow: = 0.72 + 0.116 lg ic (11)

At room temperature (298 K), cathode current densities ic was 300, 400, 500 and 600 A m2 , pH 8, the corresponding and the potential value for evolution hydrogen (EH+ /H2 ) are listed in Table 2. It can be seen from Table 2 that the potential for the evolution of hydrogen decreases with the increase in cathode current density. As the potential for deposition of zinc is more positive than that of hydrogen, the increase in cathode current density inhibits the evolution of hydrogen, therefore, the CCE for zinc deposition increases with the increase in current density. The EH+ /H2 for the evolution of hydrogen shifts to a more negative value as the increase in cathode current density, the partial cathode current for the evolution of hydrogen decreases. In the electrodeposition process, much more bubbles were formed at the cathode surface at lower current density than that of higher current density. This phenomenon is consistent with the calculation.

Fig. 4. The cathodic polarization curves under different concentrations of Zn2+ : (a) Zn2+ 35.64 g L1 , (b) Zn2+ 61.67 g L1 , (c) Zn2+ 74.43 g L1 , (d) Zn2+ 100.2 g L1 .

912 Table 4 The effect of temperature (a) and initial pH (b)on (a) Temperature ( C) 20 CZn (g L1 ) m (g) CCE (%) CV (V) 1.047 2.0452 99.23 1.36 30 1.454 2.0585 99.88 1.32

X. Ren et al. / Journal of Hazardous Materials 181 (2010) 908915

CZn , m, CCE and CV. (b) Initial pH 40 1.511 2.0585 99.88 1.28 50 1.534 2.0604 99.95 1.25 4 1.481 1.9197 93.14 1.56 5 1.193 1.9703 95.60 1.43 8 1.126 2.0585 99.87 1.35 9 1.132 2.0342 98.68 1.36 10 1.148 1.9973 96.90 1.68

of 60 g L1 . As pH = 8, [Zn(NH3 )4 2+ ] = 0.8191 mol L1 , Ka = Kw /Kb = 5.6 1010 , from Eq. (10), we obtained lg [NH3 ] [NH+ ] 4 = 1.2518 (12)

and [NH3 ] = 0.056[NH+ ] 4 Combining Eqs. (5), (8) and (13), we obtain: EZn2+ /Zn = 1.015 0.1183 lg[NH+ ] 4 (14) (13)

Eq. (14) shows that when [NH4 + ] is greater than 1.0 mol L1 (53.46 g L1 ), the potential for deposition zinc shifts to more negative value, which results in the reduction of H+ more easily and when [NH4 + ] is less than 1.0 mol L1 (53.46 g L1 ), it begins to shift to more positive value. This thermodynamic calculation results are in accord with the results shown in Fig. 5. The concentration of NH4 Cl higher than 53.46 g L1 has no additional benet to increase CCE. The electrochemical dissolution of hot galvanizing slag at an anode in an electrolyte containing Zn2+ , NH3 H2 O, NH4 Cl, H2 O ions occurs as follows: Al(OH)3 + 3NH+ + 3e = Al + 3NH3 H2 O 4 Zn(OH)2 + 2NH+ + 2e = Zn + 2NH3 H2 O 4 Zn(OH)2 + nNH3 H2 O = NH+ 4 + OH = NH3 H2 O
+ Zn(NH3 )2 n

(15) (16)

+ 2OH

(17) (18) (19) (20)

2H2 O + O2 + 4e = 4OH

EO2 /H2 O = 1.229 0.0591 pH EAl(OH)3 /Al = 2.572 + 0.05916 lg

[NH+ ] 4 [NH3 H2 O]

1.000, 1.012, 1.021, 1.023, and 1.036 Vcorresponding to NH4 Cl concentration of 40, 50, 60, 70 and 80 g L1 , respectively. These calculation results show that the dissolution of Al will occur rstly, and then the dissolution of Zn. The oxygen evolution reaction is difcult to happen, and, there was no bubble adhering to anode surface observed in the electrolysis procedure. The current passed through the anode is used to dissolve of aluminum, zinc and iron. According to Table 1, the highest anode current efciency for dissolving Zn is 16.73%, this value is much lower than that obtained from experiments as shown in Fig. 5. As current passing through the anode, Al and Zn are oxidized as Al(OH)3 and Zn(OH)2 adhering to anodic surface in alkali electrolyte containing NH4 Cl and NH3 H2 O. Subsequently, Zn(OH)2 reacts with NH3 H2 O to form complex Zn(NH3 )n 2+ as shown in reaction (17) and (18). The formation of Al(OH)3 inhibits dissolution of aluminum. The Al(OH)3 detached from the electrode surface into electrolyte and formed Al(OH)3 precipitation with the dissolution of Zn(OH)2 . The dissolution of Zn(OH)2 and detachment of Al(OH)3 keep the electrolysis process going on. Fig. 5 demonstrates that the NH4 Cl concentration has the signicant impact on the anode dissolution process. The current efciency for dissolving zinc increases with the addition of NH4 Cl up to 60 g L1 ; above this value, the current efciency decreases. This phenomenon is in accordance with calculation results obtained from Eq. (14). Fig. 6 is the anodic polarization curves obtained from solutions with different concentrations of NH4 Cl. An increase in the anodic polarization was recorded when concentration of NH4 Cl increases in the electrolyte. But the anodic polarization curves are two types of the shape as concentrations of NH4 Cl is lower and higher than 60 g L1 . As concentration of NH4 Cl is lower than 60 g L1 , the more positive anodic polarization improves the dissolution of Zn. On the contrary, the negative anodic polarization benets the dissolution of Al.

(21)

From Eqs. (12), (14), (20), (21), and conditions: pH = 8, [Zn(NH3 )4 2+ ] = 0.8191 mol L1 , Ka = Kw /Kb = 5.6 1010 , Ksp(Al(OH)3 ) = 5.5 1046 and room temperature (25 C), we obtain: EO2 /H2 O = 0.7557 V, EAl(OH)3 /Al = 2.099 and EZn2+ /Zn =

Fig. 5. The effect of NH4 Cl concentration on anode current efciency for dissolving Zn (ACE) and cathode current efciency (CCE).

Fig. 6. The anodic polarization curves under different concentrations of NH4 Cl. (a) NH4 Cl 40 g L1 , (b) NH4 Cl 50 g L1 , (c) NH4 Cl 60 g L1 , (d) NH4 Cl 70 g L1 , (e) NH4 Cl 80 g L1 .

X. Ren et al. / Journal of Hazardous Materials 181 (2010) 908915

913

2 ct =0 x2 ct = constant x
s ct = c t + b cs ct t x

(29) (30) (31)

where, ct (mol L1 ) is the concentration of Zn2+ species with diss (mol L1 ) is the tance, x [mm], from an electrode, at a time t (s), ct concentration adhering to electrode surface for the Zn2+ species b (mol L1 ) is the bulk concentration for the Zn2+ at a time t (s), ct species at a time t (s). We can re-write the mass-balance equations for Zn(NH3 )n 2+ and Zn(NH3 )nm 2+ as following
+ 1 Kb b 2 c (Zn(NH3 )2 + m ) s s = 2 c (Zn(NH3 )2 )x (c ct m )Kb ct t x2

(32)

Fig. 7. The effect of stirring rate on cathode current efciency.

3.4. Effect of stirring rate The effect of stirring rate was studied under the conditions as follows: zinc concentration of 53.58 g L1 , NH4 Cl concentration of 60 g L1 , current density of 500 A m2 , pH of 8, room temperature. The effect of stirring rate on the cathode current efciency is plotted in Fig. 7. Fig. 7 indicates that stirring rate plays the important impact on the cathode current efciency. As the stirring rate increases, the CCE increases sharply from 0 to 400 r min1 , and then the CCE increases with the increase in the stirring rate slightly from 400 to 500 r min1 . This can be explained as following: In an electrolyte containing Zn2+ , NH3 H2 O, NH4 Cl and H2 O, the electrodeposition of Zn may follow mechanism in which the interfacial electron transfer does not occur directly between the electrode and the Zn(NH3 )n 2+ . Instead, the charge transfer processes directly involve some reaction intermediates that form from initial reactants through pure chemical reactions in the electrolyte solution.
+ Zn(NH3 )2 n (n m)NH3 kcf kcb + Zn(NH3 )2 m + 2e kef keb

+ 2 c (Zn(NH3 )2 1 Kb b + n ) s s = 2 c (Zn(NH3 )2 )x (c ct n )Kb ct 2 t x

(33)

where
2

D , kcf + kcb

Kf =

kcf , kcf + kcb

Kb =

kcb kcf + kcb

(34)

The above two equations can be solved with boundary conditions: x=0:
+ 2+ s c (Zn(NH3 )2 n ) = c (Zn(NH3 )n );

+ 2+ s c (Zn(NH3 )2 m ) = c (Zn(NH3 )m );

(35)

x>:

+ 2+ b b c (Zn(NH3 )2 n ) = c (Zn(NH3 )n ) = Kf ct ;

+ 2+ b b c (Zn(NH3 )2 m ) = c (Zn(NH3 )m ) = Kb ct

(36)

The resultant solutions are:

+ s c (Zn(NH3 )2 n )=Kb ct +

Kb b s + s (1/ (c ct )x + (c s (Zn(NH3 )2 n ) Kb ct )e t

)x

Zn + mNH3

(22)

(0 x )

(37) Kf b + s s (1/ )x + (c s (Zn(NH3 )2 (c ct m ) Kf ct )e t

General equations under unsteady-state diffusion:

+ c (Zn(NH3 )2 m )

2+ 2 + c (Zn(NH3 )m ) + D(Zn(NH3 )2 +kcf c (Zn(NH3 )2 m ) n ) 2 x

+ s c (Zn(NH3 )2 m )=Kf ct +

)x

(0 x )

(38)

(nm)

+ (NH3 ) kcb c (Zn(NH3 )2 m )

=0

(23) If there is concentration polarization of Zn(NH3 )n 2+ , we have to use the general solutions about the concentration proles. ic = nFD
2 c (Zn(NH3 )+ m ) x 2 c (Zn(NH3 )+ m ) x b ct s ct

+ 2+ 2 c (Zn(NH3 )2 + c (Zn(NH3 )n ) + n ) kcf c (Zn(NH3 )2 = D(Zn(NH3 )2 n ) n ) t x2

+(
x=0

chem )x=0 2 c (Zn(NH3 )+ n ) x

c Zn(NH3 )

(nm)

+ + kcb c (Zn(NH3 )2 m )

=0

(24) = nFD

+ nFD
x=0

+ D(Zn(NH3 )2 n )

+ 2+ 2 2 c (Zn(NH3 )2 + c (Zn(NH3 )m ) n ) +D(Zn(NH3 )2 =0 m ) 2 2 x x (25)

x =0

= nFD

1/6 1/2 1/2 y uo s ct )

(39)

If we assume that
+ D(Zn(NH3 )2 n )

= D1/3 =D (26) ic =

(40) (41) (42)

+ D(Zn(NH3 )2 m )

1/2 b nFD2/3 1/6 y1/2 uo (ct

Then,
+ 2+ 2 (c (Zn(NH3 )2 n ) + c (Zn(NH3 )m )) 2 x + 2+ ct = c (Zn(NH3 )2 n ) + c (Zn(NH3 )m )

uo = 2 r =0 (27) (28) ic = 21/2 nF

1/2 1/2

D2/3

1/6 1/2

b s 1/2 (ct ct )

(43)

From the above equation, ic for electrodeposition of Zn has liner relationship with 1/2 . The result was plotted in Fig. 8.

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X. Ren et al. / Journal of Hazardous Materials 181 (2010) 908915

Fig. 8. The plot of ic vs. 1/2 . Fig. 10. The plot of increase in Zn2+ concentration vs. 1/2 .

Fig. 8 shows that the electrodeposition reaction was determined by mass transfer rate at lower stirring rate. In the stirring rate region of 0400 r min1 , the increase in agitation is favor of mass transfer. At higher stirring rate than 400 r min1 , the electrodeposition reaction was determined by the surface transformation rate, the stirring rate has no much more effect on current efciency [16]. The effect of stirring rate on increase in zinc concentration in anolyte was plotted in Fig. 9. Fig. 9 shows that the dissolution of Zn from the anode is accelerated by increasing stirring rate in region of 0300 r min1 . When stirring rate is higher than 300 r min1 , the increase in Zn2+ concentration declines sharply, the reason can be explained that the detachment of Al(OH)3 from anode surface improves the dissolution of Al. With the increase of stirring speed, aluminum hydroxide attached at the surface of anode peeled off gradually, which speed up the diffusions of aluminum ions from anode surface to boundary layer, and thus increases the dissolving rate of aluminum ions. The anodic dissolution of zinc in chloride solutions including NH3 H2 O, NH4 Cl can be considered as the reverse reaction of (22). Similarly, we can obtain the linear relationship between increase of zinc concentration in anolyte (ia ) (ia , the current for dissolution of Zn) with the stirring rate as following: ia = 21/2
1/2 1/2

3.5. Effect of temperature In order to evaluate the effect of temperature on the cathodic current efciency, power consumption and the dissolution of anode, the experiments were conducted in the temperature range of 2050 C with NH4 Cl concentration of 60 g L1 , zinc concentration of 40 g L1 , current density of 500 A m2 , pH of 8, stirring rate of 300 r min1 . The anode dissolution enhances with the increase of temperature, but not sharply, as it can be seen from the increase of zinc concentration in anode compartment in Table 4(a), while the cathode current efciency increases slightly in Table 4(a). Although the temperature plays a signicant role in reducing the power consumption by increasing solution conductivity and mass transferring, increasing temperature also increase volatilization of the ammonia making a waste of ammonia. It is reasonably to take the electrolysis under room temperature. 3.6. Effect of initial pH To examining the effect of initial pH on m, CCE, CV and CZn , the experiments were conducted under the temperature of 25 C with NH4 Cl concentration of 60 g L1 , zinc concentration of 60 g L1 , cathode current density of 500 A m2 and stirring rate of 300 r min1 . When the initial pH value ranges from 5.45 to 7.88, white precipitates can be observed, so initial pH of 4, 5, 8, 9 and 10 were selected for experiments. The results were listed in Table 4(b). The result of Table 4(b) shows that the initial pH of aqueous solution usually plays an important role in the process. In the Zn2+ NH3 NH4 ClH2 O system, when initial pH was 8, the highest current efciency and the lowest cell voltage requirements were achieved for deposition of Zn at the cathode. Increasing the initial pH need to add more ammonia, the volatilization of the ammonia makes a waste of ammonia and the pollution of the production environment, so pH value should not be higher than 8.
Table 5 The long-period electrowinning results. Time (h) 0 1.0 2.0 3.0 4.0 CV (V) 0.70 1.48 1.49 1.49 1.51 CZn (g L1 ) 1.123 1.123 1.122 1.123 CCE (%) 99.85 99.88 99.86 99.85

DZn

2/3 1/6 1/2

o s 1/2 (cZn cZn )c

(44)

In the stirring rate region of 0300 r min1 , we can obtain the plot of ia vs. 1/2 as shown in Fig. 10. Fig. 10 shows that the anodic dissolution of zinc was determined by mass transfer rate at stirring rate of 0300 r min1 .

Fig. 9. The effect of stirring rate on increase in zinc concentration in anolyte ( CZn ).

Note:

CZn , increase in concentration of zinc in anolyte.

X. Ren et al. / Journal of Hazardous Materials 181 (2010) 908915 Table 6 Chemical composition of deposition (103 ). Element Content Zn (%) 99.99 Pb 0.05 Fe 0.05 Cd 0.36 Ni 0.38 Co 0.21 Cu 0.75 Sb 0.04 As 0.03

915

Mn 0.35

were investigated. The results revealed that current density, NH4 Cl concentration and agitation had the signicant impact on the cathodic current efciency and anodic dissolution rate, while zinc concentration, temperature and pH had less affect. The optimized conditions were as follows: the current density of 500 A m2 , zinc concentration of no less than 30 g L1 , ammonium chloride concentration of 60 g L1 , pH of 8, temperature of room temperature, stirring rate of 300 and 400 r min1 for anode and cathode compartments, respectively. The partial current for deposition and has liner relationship with 1/2 , and the dissolution reaction of zinc at anode is determined by mass transfer rate at stirring rate 0300 r min1 . Acknowledgements The authors would like to thank the department of science & technology of Shandong province of the Republic of China for nancially supporting this research under Contract No. 2007GG20004001. Moreover, the authors would also like to thank Wei Lan in Jinan University, PRC, for her efforts in developing a grammatical and cohesive manuscript. References
[1] M.K. Jha, V. Kumar, R.J. Singh, Review of hydrometallurgical recovery of zinc from industrial wastes, Resour. Conserv. Recy. 33 (2001) 122. [2] M.A. Rabah, A.S. EI-Sayed, Recovery of zinc and some of its valuable salts from secondary resources and wastes, Hydrometallurgy 37 (1995) 2332. [3] M.A. Barakat, Recovery of metal values from zinc solder slag, Waste Manage. 19 (1999) 503507. [4] L.R. Gouvea, C.A. Morais, Recovery of zinc and cadmium from industrial waste by leaching/cementation, Miner. Eng. 20 (2007) 956958. [5] P. Dvo rak, J. Jandov, Hydrometallurgical recovery of zinc from hot dip galvanizing ash, Hydrometallurgy 77 (2005) 2933. [6] M.S. Safarzadeh, D. Moradkhani, P. Ashtari, Recovery of zinc from CdNi zinc plant residues, Hydrometallurgy 97 (2009) 6772. [7] M.N. Babu, K.K. Sahu, B.D. Pandey, Zinc recovery from sphalerite concentrate by direct oxidative leaching with ammonium, sodium and potassium persulphates, Hydrometallurgy 64 (2002) 119129. [8] J.L Limpo, A. Luis, M.C. Cristina, Hydrolysis of zinc chloride in aqueous ammoniacal ammonium chloride solutions, Hydrometallurgy 38 (1995) 235 243. [9] M.B. Mansur, S.D.F. Rocha, F.S. Magalhaes, J.S. Benedetto, Selective extraction of zinc(II) over iron(II) from spent hydrochloric acid pickling efuents by liquidliquid extraction, J. Hazard. Mater. 150 (2008) 669678. [10] G. Csicsovszki, T. Kkesi, T.I. Trk, Selective recovery of Zn and Fe from spent pickling solutions by the combination of anion exchange and membrane electrowinning techniques, Hydrometallurgy 77 (2005) 1928. [11] P. Guillaume, N. Leclerc, F. Lapicque, C. Boulanger, Electroleaching and electrodeposition of zinc in a single-cell process for the treatment of solid waste, J. Hazard. Mater. 152 (2008) 8592. [12] T. Mukongo, K. Maweja, B. wa Ngalu, I. Mutombo, K. Tshilombo, Zinc recovery from the water-jacket furnace ue dusts by leaching and electrowinning in a SEC-CCS cell, Hydrometallurgy 97 (2009) 5360. [13] H.J. Zheng, Zh.H. Gu, Y.P. Zheng, Electrorening zinc slag in ammoniacal ammonium chloride system, Hydrometallurgy 90 (2008) 812. [14] S. Savari, S. Sachdeva, A. Kumar, Electrolysis of sodium chloride using composit poly(styrene-co-divinylbenzene) cation exchange membranes, J. Membrane Sci. 310 (2008) 246261. [15] F. Faverjon, M. Rakib, G. Durand, Electrochemical study of a hydrogen diffusion anode-membrane assembly for membrane electrolysis, Electrochim. Acta 51 (2005) 386394. [16] C.H. Bamford, R.G. Compton, Electrode Kinetics: Principles and Methodology, Elsevier Science Publishers B.V., 1986.

Fig. 11. X-ray diffraction pattern of the product zinc.

Table 4(b) also shows the effect of initial pH on increase in concentration of zinc in anolyte ( CZn ). The results illustrates that higher or lower initial pH is conducive to the dissolution of zinc. At lower initial pH, zinc may be improved to dissolute by chemical reaction, and at higher initial pH, the dissolution of zinc may be improved by the formation of Zn(NH3 )n 2+ complex more easily. 3.7. The product zinc of long-period electrowinning A long-period electrowinning, using a xed volume, and with a starting composition as Section 3.5 and temperature of 25 C, was performed to determine the cell voltage, cathode current efciency, surface morphology and chemical composition of deposition. The electrolyte composition of Zn and cell voltage was analyzed, at different intervals, during the experiment. The results obtained are summarized in Table 5. The metal produced in the long-period electrolysis was of satisfactory quality according to the standard ISO 752-2004, as it is shown in Table 6. The coating layer was bright and dendrite-free and high purity. The results listed in Table 6 show that with the increase of electrolysis time, cell voltage increases gradually. However, the increase in concentration of zinc in the anolyte is mainly the same during the same period with a slightly decrease of cathode current efciency. Under optimum conditions, the rate of anodic dissolution of zinc is basically the same, but the depletion of zinc due to electrodeposition reduces the concentration of zinc ions and results in the increase in cell voltage and decrease in cathode current efciency. The X-ray diffraction pattern of the product zinc was shown in Fig. 11. The gure showed that the metal zinc produced by this method was ne crystal according to the Scherrer equation. 4. Conclusions In this study, the conditions for deposition of zinc and dissolution of zinc in the anion-exchange membrane electrolysis reactor