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8th International Conference on Role of Engineering Towards a Better Environment

(Global Environmental Changes & Sustainable Development), Alexandria, Egypt, 20 of December, 2010
th

Removal of Copper Ions by Cementation onto Zinc Powder in an Air Sparged Vessel
Yehia M.S. El-Shazly1; and Eman A. Gohar2 1 Alexandria University; Faculty of Engineering; Chemical Engineering Department; Alexandria 21544; Egypt. 2 Alexandria Sanitary Drainage Company; Alexandria, Egypt. Abstract
In view of the cost effectiveness of the air sparging as a mean of agitation and enhancement of mass transfer compared to other mechanical methods; the rate of removal of copper ions from an industrial waste solution by cementation in an air sparged bed of zinc powder was studied. The rate of cementation was found to increase by increasing the air velocity as well as by decreasing the concentration of copper ions in the solution. The mass transfer data were correlated by the equation:

The experimental results showed a lower mass transfer coefficient than what was predicted from previous models. Keywords: Wastewater treatment; mass transfer; Copper removal; Cementation; Air sparging.

1.

Introduction

Copper is considered a toxic element for human life if exceeded a certain limit. The World Health Organization limit for use of copper in contact with drinking water is 2 mg/liter [1]. Multiple effects are related to the consumption of water contaminated with copper, such as gastrointestinal, hepatic, renal, and an exogenous pigmentation (green hair) [2-4]. Waste solutions containing Copper ions are discharged from industries such as metal finishing, paint industry, printed circuit industries, copper mines drainage solutions, chemical and electrochemical machining of copper and its alloys etc. The recovery and removal of copper from industrial effluent has been carried by many techniques such as liquid membrane and ultra-filtration [5-6], adsorption [7-9], precipitation and flocculation [10-13], electrochemical precipitation [14-15], and the ion exchange technique [16-18]. The purpose of this work is to study the rate of removal of the copper ions from the solution by replacing them with the far less toxic zinc ions [1] from zinc metal powder in an air agitated vessel. The present work is not only important for waste water treatment but also can be important for the refinement of zinc from zinc ores containing copper: Cu ions are removed from the ZnSO4 leach liquor by cementation on zinc powder and replaced by zinc ions. Moreover, the final product will be particles composed of zinc core with a copper coating. This can be further used for the production of composites using the powder metallurgy technique [19].

Table 1 List of symbols a A C C0 d D E0 F g G H K m P n Q R T t V Vs s J St Sc Re Fr Constant Surface area of powder Copper ions concentration Initial Copper ions concentration particle diameter Diffusivity of Copper ions Standard potential difference Faradays constant; 96.485 kJ/volt g. equivalent Gravity acceleration Free energy Height of liquid Mass transfer coefficient Mass of zinc powder Power Number of electron transferred Air volumetric flow rate Gas constant Temperature Time Superficial air velocity Volume of solution Solution viscosity Solution density Zinc density Diffusion layer thickness Mass transfer J factor; Stanton Number Schmidt Number Reynolds Number Froude Number

2.

Cementation

Cementation is the recovery of an ionized metal from its solution by the spontaneous electrochemical reduction to its elemental metallic state, with a consequent oxidation of a sacrificial metal. The process is used for the recovery of the metals as well as for their

purification. The heterogeneous reaction for the cementation can be considered as a multitude of short-circuit galvanic microcells on the surface of the metal M2 as can be seen in the following reaction [20]:

(1) Where M1 and M2 are in this case, the copper and zinc respectively, and the change of the free energy for this reaction is expressed as

(2) G0 can be calculated for this case from the equation: (3) and is found to be -212.3 kJ/mol. This high value indicates that this reaction is spontaneous and diffusion controlled. According to Strickland and Lawson [21], the process will involve the following steps: The diffusion of ions of the depositing metal (M1) to the deposit-solution interface from the bulk of the solution, the conductance of electrons from the dissolving metal (M2) through the deposit, incorporation of the deposited metal atoms into a crystal lattice, release of the M2 ions to the solution, transfer of the M2 ions to the deposit-solution vicinity through the deposit layer, and diffusion of the M2 ions into the bulk of the solution. The process is diffusion controlled [22-26] , and hence can be enhanced by increasing the rate of mass transfer of the more noble ions to the surface of the less noble metal. Various techniques are used to increase the yield of the process depends on increasing the rate of mass transfer; among them is the cementation onto a rotating disc [23, 27], on reciprocating perforated zinc disc [28], in a jet reactor [29], on particles in a stirred tank reactor [30-31], or on a bed of particles of the more noble metal while the solution is flowing [24, 32] and in the presence of suspended ceramic particles [33]. In this research, the rate of mass transfer of copper ions onto zinc powder is studied in an airsparged vessel to induce the stirring required to enhance the rate of mass transfer and the rate of the reaction: Cu2+ + Zn Cu + Zn2+ (4)

Previous studies on the use of gas sparging technique to enhance the mass and heat transport have shown that it is a more simple and economic technique than mechanical stirring [34-36]. Moreover, air sparging is a common technique for water and wastewater aeration treatment [37], and it be conducted inclusively.

3.

Materials and Methods

The apparatus used in the present work (Figure 1) consists of a sintered-glass of 13.5 cm in diameter and 12 cm in height grade G4. The sintered-glass is connected to an air compressor (2 hp) and the flow rate of the air from the compressor is adjusted by a flowmeter located before the sintered-glass. A non-return valve is placed just before the sintered glass to prevent the solution from going into the line and to the compressor. Each experiment consisted of 15 g of zinc powder and 500 ml of freshly prepared copper sulfate solution. The zinc powder was used as received and the particles diameter was determined under the microscope and found to have an average of 8 m. The amount of zinc used is much higher than required according to stoichiometry to ensure the absence of any problem resulting from the deficiency of the required amount. The pH of the solution was found to be 4.8; otherwise it was adjusted using few drops of concentrated HCl. The compressed air is allowed to flow and then the zinc particles were added to the solution. The copper sulfate concentrations varied between 0.025 to 0.1 mol/L, while the superficial air velocity varied between 0.03 to 0.22 cm/s. For each run, samples were drawn and analyzed for copper concentration every 2 min. Each run lasted for 14 minutes. The concentration of copper in the solution was determined using Atomic Absorption Spectroscopy technique (PERKIN-ELMER 2380 Atomic Absorption Spectrometer). The chemicals used were AR grade and the solution was prepared using distilled water. All the experiments were carried out at a constant temperature (25 oC). The physical properties of the solution used (, and D) were taken from the literature [38].

(1) Air compressor (2) Flow meter (3) Non-return valve (4) Holder (5) Porous media (6) Zinc Particles (7) Sintered-glass

Figure 1 Schematic diagram of the experimental set up.

4.

Results and Discussions

The cementation of copper was found to follow the first order kinetics according to the equation:

(5) which upon integration yields;

(6) The concentration-time data plotted as ln(Co/C) Vs. time in Figure 2 shows that the present data fit equation (6) quite well. The mass transfer coefficient was determined from the slope of the straight line.

Figure 2 Plot of concentration-time data for different superficial air velocities at CuSO4 concentration 0.025 mol/L. Figure 3 shows the effect of superficial gas velocity on the mass transfer coefficient of copper cementation on zinc particles at different CuSO4 concentrations, the data was found to fit the equation: (7)

Figure 3 Effect of air superficial velocity on the value of mass transfer coefficient at different copper sulphate concentrations.

The exponent 0.34 is consistent with the value obtained by different authors who used gas sparging to enhance the rate of mass transfer at different geometries [39-41]. The increase in the rate of mass transfer and the rate of cementation with superficial gas velocity may be attributed to the following effects: i. With increasing gas velocity, the fixed bed of zinc particles becomes fluidized; with the higher the gas velocity: the higher the degree of fluidization and turbulence: particles motion and collision of particles decreases the diffusion layer thickness () around each particle with a consequent increase in the mass transfer coefficient ( ) and the rate of cementation. The rising bubbles promote turbulence in their wake and induce radial momentum [39, 42], turbulence and radial momentum contribute to decreasing the diffusion layer thickness () around each particle. Visual observations have shown that the solution entrained with the rising bubbles moves upward to the solution surface and then moves downward at the container wall by continuity where it forms large eddies in the solution bulk. These eddies contribute to enhancing the rate of mass transfer and the rate of cementation on the Zn particles. The present pattern is consistent with the pattern observed by other authors [43].

ii. iii.

Figure 4 shows the effect of the initial copper sulfate concentration on the rate of mass transfer. The decrease in the mass transfer coefficient with the increase of the copper ions concentration is attributed the decrease in the diffusivity of Cu ions with increasing the CuSO4 concentration as a result of the interionic attraction between ions and the increase in the solution viscosity [38].

Figure 4 Plot of concentration-time data for different initial copper sulfate concentrations at superficial air velocity 0.1 cm/s. To correlate the present mass transfer data, the method of dimensional analysis was used. The present data could be correlated by the functional equation [39]: (8) Dimensional analysis leads to writing the equation in the form:

(9) For the conditions 1500< Sc <1900 and 2.5*10-6 < Re.Fr < 0.001, the data fit the equation: (10)

Figure 5 shows the obtained correlation with the experimental results.

Figure 5 Overall mass transfer correlation for the cementation of copper onto zinc powder in an air sparged vessel. It would be of interest to compare the present data with the prediction of the model derived for mass transfer at gas sparged surfaces [44]. The model is based on the surface renewal theory with Kolmogorovs theory of isotropic turbulence. According to this model, the rate of mass transfer is given by: (11) Figure 6 shows that the present data lie below the model prediction, this discrepancy may be attributed to the fact that in the present case, copper deposited on the zinc particles increases the mass transfer resistance. In this case, for Copper ions to reach the zinc surface where it reacts, it has to cross two resistances in series, namely, the liquid phase diffusion layer and the porous copper powder layer surrounding each zinc particle. Another possible reason for the decrease in the present mass transfer coefficient below model prediction is the interference of O2 reduction reaction with copper cementation on Zinc; O2 reduction takes place as a result of the formation of the cell [ Zn | electrolyte | Cu ] and thereby two simultaneous reactions occur: at the Zinc anode, the reaction is

(12) while at the copper cathode, the following two reactions take place:

, (13)

and

(14) with a resultant decrease in the efficiency of the process for the competition between the two cathodic reactions. Such a problem can be resolved by using nitrogen as the sparging gas instead of the air; however, the added cost of using the nitrogen will increase the cost of the process largely. Moreover, the deviation is also attributed to the relatively low superficial air velocity range used in the present work (maximum V < 5 cm/s) which is not favorable for generating isotropic turbulence [45].

K *106; m/s

Superficial air velocity *103; m/s

Copper Sulfate concentration; mol/L

Figure 6 Comparison between the current study results ( [44] .

) and the theoretical model (

5.

Power requirement

It is helpful to examine the required energy to conduct the sparging process. The energy input rate required to drive the process can be estimated from the equation [46]:

(15) Figure 7 shows the values of the mass transfer coefficient; K; at the different power supplied to the air to overcome the static pressure of the solution. As expected; an increase in the energy consumed in the sparging process resulted in an increase in the mass transfer coefficient. Also, upon decreasing the concentration and viscosity of the solution, the mass transfer coefficient increases for the same energy consumption.

Figure 7 The mass transfer coefficient obtained at different power in the sparging process. Calderbank and Moo-Young [47] estimated the mass transfer coefficient, K, obtained from a mass transfer process as a function of the power used as:

(16) Figure 8 shows that again the mass transfer coefficient estimated from this equation is higher than the experimental results. Again, this is due to the formation of the additional resistance of the copper layer on the zinc particles, the presence of a second cathodic reaction which retard the copper reduction, and the absence of isotropic turbulence at this low superficial air velocity.

K *106; m/s

Superficial air velocity *103; m/s

Copper Sulfate concentration; mol/L

Figure 8 Comparison between the mass transfer coefficient obtained from current study ( ) and the mass transfer coefficient estimated from Calderbank and Moo-Young ( ) [47].

6.

Conclusions

In this research, the removal of copper ions from its solution by cementation in an air sparged bed of zinc powder was studied. The possible application of this research in the treatment of water and wastewater containing copper ions which can be conducted in sparged tanks along with the aeration treatment. Also, it can be applied for the purification of zinc leach liquor from copper ions or for the preparation of powder that can be further used in powder metallurgy. The process was found to follow a first order kinetics and diffusion controlled reaction: the rate of cementation increases with the increase of the air velocity while it decreases with the increase of the copper ion concentration and viscosity. A mathematical equation to describe the process was presented based on the dimensional analysis. The resultant data was found to be lower than predicted by other models, which might be the result of the formation of the deposited copper layer on the zinc particles, the use of air which contains oxygen that might interfere with the main cementation reaction, and the low velocity of air used.

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