INFLUENCE OF OPERATING CONDITIONS ON THE REJECTION AND FLUX OF COBALT AND NICKEL IONS IN AQUEOUS SOLUTIONS BY NANOFILTRATION MEMBRANE

Abstract Heavy metals are the major sources of environmental pollution and they are non-degradable; therefore continue to exist in water. This paper presents the potential use of nanofiltration membrane for the removal of cobalt and nickel ions from aqueous solution. The influences of pH and pressure are discussed. Permeate flux was higher for both cobalt (39.804L/m/h) and nickel (50.525 L/m/h) at higher pH (4) than at lower pH (pH 3) (38.37 l/m/h and 46.507 l/m/h) respectively. The effect of pH on cobalt and nickel rejection was investigated but the effect of pH on % rejection of former was not significant. The average rejections of 5 mg/L of Co2+ at pH 3 and 4 were 94.37% and 94.36% respectively. The nickel ion rejection increased for both pH especially for pH 4. Higher operating pressure leads to higher permeate flux for both nickel and cobalt. The rejection of both metals ions (nickel and cobalt) is high at the three different pressures. Keywords: acid mine drainage, nanofiltration, nickel removal, nickel rejection, cobalt removal, cobalt rejection, fluxes, solution pH, Pressure 1. Introduction The rate at which industrial activities is increasing has caused more environmental pollution and the detrimental of ecosystems, especially aquatic, with the accumulation of pollutants, such as synthetic compounds, nuclear wastes and heavy metals. The removal of heavy metals from wastewater is of critical importance due to their high toxicity and tendency to accumulate in living organisms [1]. Cobalt and Nickel are common pollutants found in
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various industrial effluents. They constitute a great part in the water pollution and the removal of these metals cations from both industrial and municipal water is of extreme importance. Both in the past decade and recently, extensive research works have focused on the removal of cobalt and nickel ions from waste water by different techniques including solvent extraction [2], adsorption of solids such as metal oxides [3 & 4], ion flotation [5 & 6], electrocoagulation [7 & 8], chemical precipitation [1, 9 & 10] and ion exchange [11]. Membrane separation processes, available in variety of separation capabilities have become promising techniques for separating heavy metals from aqueous solutions. [12-14]. Nanofiltration (NF) is the most recent membrane separation process in liquid phase. It appears as an attractive alternative technique since it allows (i) the removal of multivalent ions without any chemical additives, (ii) continuous separation and (iii) treatment of rather large feed water flowrates [15]. There are successful investigations using NF as tools for the removal of heavy metal ions [15-19]. NF membranes have pores of nano-scale dimensions to meet industrial needs in the area of small molecules and ion separations; thus solute rejection by NF is usually influenced by membrane charge and membrane pore size. The objective of this study was to investigate the potential of nanofiltration in the treatment nickel and cobalt aqueous solution.

2 Experimental 2.1 Nanofiltration membrane characteristics A composite nanofiltration membrane (Nano-Pro A 3012) was chosen for this research as representative of a class of membranes which are acid stable in water treatment applications. According to the manufacturer, the maximum operating pressure is 40 bar (580 psi),

maximum operating temperature 50C (122F), allowable pH Continuous Operation: 0 -12, Recirculation Flow Rate: Minimum 90L/min (24gpm), Maximum 280L/min (74 gpm). 2.2 Analytical method Nickel ion concentration was analysed by using inductively coupled plasma optical emission. Measurements of solution pH and temperature were made using a pH meter (Mettler Toledo FG20) purchased from Microsep and thermometer, respectively. 2.3 Flux decline experiments The experiments were carried out with one litre of single solution of (CoSO 4.7H2O and NiSO4.6H2O) in varied concentration of 5mgL, 10mg/L while varying solution pH from 3 to 4 and pressure (30bar, 20bar and 10bar). The solution pH was varied from 3 and 4 at constant pressure of 30bar. Flux decline experiments were conducted by using a 1 000-ml dead-end membrane filtration apparatus (Memcon South Africa) with magnetic stirrer. A membrane sheet was fitted to the cell. The membrane active area is about 0.01075m 2. The operating pressure was employed via high-pressure regulator and a nitrogen gas cylinder. The permeate flux was collected in a beaker on the electrical balance and the permeate mass was determined.

2.4 Filtration Experiments Membrane sheet stored in 0.7% w/w benzalkonium chloride at 2-30C was used for the study. The membrane sheet was initially rinsed in clean distilled water and was used to measure the clean water flux (CWF) using distilled water before each nickel solution was used with the system. The clean water flux experiments were done to see if membrane did not foul. The clean water flux was done at stirring velocity rate of 500 rpm and a pressure of 30
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bar. Feed single nickel solutions and cobalt solutions were prepared for each test condition. The pH of the feed was controlled by addition of NaOH. 0.0208g of NaOH was used to raise the pH of cobalt sulphate solution to 4 and 0.082g of NaOH was used to raise the pH of nickel sulphate solution to 4. After filtration was terminated, the membrane was cleaned with deionized water, followed by a clean water flux measurement. The water fluxes at different operating conditions were measured to determine water flux recovery. 2.5 Laboratory Dead-End Test Cell The investigation was done using a Memcon Laboratory Stirring Cell as shown in fig. 1. The membrane tested was placed in the cell. A litre of sample was then placed in the cell at the product inlet. Pressure was then applied with nitrogen gas and the permeate collected and its mass determined. 2.6 Analysis of Results The permeate flux and rejection were investigated as a function of working parameters such as operating time and water recovery. The permeate flux Jv (l/m2/h) was determined by measuring the volume of permeate collected in a given time interval divided with membrane area by the relation:
Jv = Q A

(1)

Where, Q and A represents flow rate of permeate and the membrane area, respectively. The observed rejection which is the measure of how well a membrane retains a solute was calculated by the following relation:
Cp Ci

% R = (1

) 100

(2)

Where Cp and Ci are the solution concentrations in the permeate and in the initial feed solution, respectively.

Feed Reservoir

Stirring Rod Membrane Magnetic Stirrer

Compressed Nitrogen Gas Scale

Figure 1: Schematic diagram of laboratory dead-end filtration system.

3. Results and Discussions 3.1 Clean water flux as a function of pressure Clean water flux as a function of pressure was done for three different pressures (30, 20, and 10 bar) before nickel was added to the feed solutions to establish initial conditions and to determine the effect of pressure on flux. The fluxes as a function of time and water recovery are shown in figure 2. The feed pressure had a significant effect on nanofiltration membrane performance. A relatively high flux (46.94 l/m/h) was obtained at 30 bar and the flux decreased significantly at 20 bar (28.10 l/m/h) and 10 bar (16.29 l/m/h). It is also intresting to note that the flux declined a little bit with increasing water recovery as a result of the higher osmotic pressure of the feed solution. However, the decline on the flux was not very much. These fluxes are low for a nanofiltration membrane and it was decided to conduct all subsequent runs at a pressure of 30 bar.

(a)

(b)

Figure 2: Flux of deionized water as function of time and water recovery (30 bar). 3.2 Effect of solution pH on flux In several studies on pH effects, it was found that pH of the feed solutions has a significant effect on solute flux and rejection. The effect of solution pH on flux is shown in figures 3a and 3b for a solution pH of 3 and 4 at the concentration of 10mg/l nickel and 5mg/L cobalt. A higher permeate flux was experienced at the higher pH (pH 4) for both nickel and cobalt (50.525 l/m/h and 39.804 l/m/h) respectively than at lower pH (pH 3) (46.507 l/m/h and 38.37 l/m/h) respectively. The solution flux increased at higher pH (pH 4), as a result of increases in membrane permeability. Such an increase is probably consistent with increased fixed charge, increased electrical double layer thickness within membrane pores, or both [20].

(a)

(b)

Figure: 3 Effect of pH on flux (a) as function of time (b) as function of water recovery at two different pH for Ni2+ and Co2+ 3.3 Effect of solution pH on ions rejection The effect of solution pH on nickel and cobalt ion rejections is shown in figures 4a and 4b of 10mg/l nickel and 5mg/L cobalt. It is well known that pH plays a major role in the

performance of nanofiltration membrane but the effect of pH on % rejection of cobalt was not significant. Never the less it must be noticed that the pH effect is different for different salts. The average rejections of 5 mg/L of Co2+ at pH 3 and 4 were 94.37% and 94.36% respectively. The nickel ion rejection increased for both pH especially for pH 4. The result could be the effect of increase in the negative charge of the membrane. Increased ion concentration could cause a reduction in the electrical double layer thickness in membrane pores and thus increase the solute partition coefficient, causing a reduction in the rejection of ionic species.

(a)

(b)

Figure 4: Effect of pH on the ion rejection (a) as function of time (b) as function of water recovery at two different pH for Ni2+ and Co2+ 3.4 Effect of pressure on flux The results of flux of water recovery and time are shown in figures 5a and 5b. Pressure difference is the driving force responsible for a nanofiltration process. At increase effective feed pressure, the permeate flux increased for the both metal ions (nickel and cobalt). At higher pressure, the compressing effect of the pressure on the membrane is little thus more water passes through the membrane and thus leads to higher flux and increase in water recovery. At lower pressure, the average pore size of the separation layer of the membrane reduced because the compressing effect of the pressure on the membrane is high. At pressure of 10bar, the water recovery for nickel and cobalt was 38% and 23% respectively; that is the lower the pressure the lower water recovery for the period of filtration.

(a)

(b)

Figure 5: Effect of pressure on flux decline (a) as time (b) as function of function of water recovery at two different pH for Ni2+ and Co2+ 3.5 Effect of pressure on ion rejection The results of ion rejection as a function of water recovery and time are shown in figures 6a and 6b. It is clear that the rejection of both metals (nickel and cobalt) is high at the three different pressures.. From the result below, it can be concluded that the three different pressures will obtain the best selectivity during nanofiltration.

Figure 6: Effect of pressure on ion rejection (a) as function of water recovery (b) as function of time at two different pH for Ni2+ and Co2+ Conclusion The performance of a nanofiltration membrane for the removal of nickel and cobalt ions from an aqueous solution was investigated using a dead-end test cell. The following conclusions can be made as a result of the investigation:
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 The pH has a significant effect on permeate flux for both cobalt and nickel. The flux at pH 4 is higher the flux at pH 3 for both nickel and cobalt. The result shows that the pH effect is different for different salts. The effect of pH on % rejection of cobalt was not much. The average rejections of 5 mg/L of Co2+ at pH 3 and 4 were 94.37% and 94.36% respectively. The nickel ion rejection increased for both pH (3 and 4) especially for pH 4. The average rejection for pH 3 and pH 4 are 83.063% and 86.155% respectively. Operating pressure is an important parameter for the running of the membrane equipment. High operating pressure (30bar) led to high permeation flux for both nickel and cobalt. But high pressure means high consumption, and therefore high power equipment should be used. Higher nickel ion and cobalt ion rejection were experienced at the three different pressures.

References 1. Gonzalez-Munoz M.J, Rodrguez M.A, Luque S and A` lvarez J.R, Recovery of heavy metals from metal industry wastewaters chemical precipitation and nanofiltration. Desalination 2006, 200(1-3): 742744. 2. Drew M.G.B., Foreman M.R.St.J., Geist A., Hudson M.J., Marken F., Norman V. and Weigl M., Synthesis, structure, and redox states of homoleptic d-block metal complexes with bis-1,2,4-triazin-3-yl-pyridine and 1,2,4-triazin-3-yl-bipyridine extractants, Polyhedron 2006, 25: 888-900.

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3. Wang W., Shao Z., Liu Y. and Wang G, Removal of multi-heavy metals using biogenic manganese oxides generated by a deep-sea sedimentary bacteriumBrachybacterium sp. Strain Mn32, Microbiology 2009, 155(Pt 6): 1989-1996. 4. Dong D., Liu L., Hua X and Lu Y, Comparison of lead, cadmium, copper and cobalt adsorption onto metal oxides and organic materials in natural surface coatings, Microchemical Journal 2007, 85: 270-275. 5. Polat H and Erdogan, Heavy metals removal from wastewaters by ion flotation, Journal of Hazardous Materials 2002, 92: 21-32. 6. Karimi H., Ghaedi M., Shokrollahi A., Rajabi H. R., Soylak M. and Karimi B, Development of a selective and sensitive flotation method for determination of trace amounts of cobalt, nickel, copper and iron in environmental samples, Journal of Hazardous Materials 2008, 151(1): 26-32. 7. Dermentzis K., Christoforidis A. and Valsamidou E, Removal of nickel, copper, zinc and chromium from synthetic and industrial wastewater by electrocoagulation, International Journal of Environmental Sciences 2011, 1(5): 697-710. 8. Mansour S.E. and Hasieb I.H, Removal of Ni(11) and Co(11) mixtures from synthetic drinking water by electrocoagulation technique using alternating current,

International Journal of Chemical Technology 2012, 4(2): 31-44. 9. Oustadakis P., Agatzini-Leonardou S. and Tsakiridis P.E., Nickel and cobalt precipitation from sulphate leach liquor using MgO pulp as neutralizing agent, Minerals Engineering 2006, 19(11): 1204-1211.

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10. Karbanee N., Van Hille R.P and Lewis A.E, Controlled nickel sulphide precipitation using gaseous hydrogen sulphide, Industrial & Engineering Chemistry Research 2008, 47(5): 1596-1602. 11. Roque-Malherbe RM., Duconge Hzernande J.J Del Valle W. and Teledo E, Lead, copper, cobalt and nickel removal from water solutions by dynamic ionic exchange in LECA zeolite beds, International Journal of Environment and Pollution , 2007 31(3/4): 292-302. 12. Urgun-Demirtas M., Benda P.L., Gillenwater P.S., Negri M.N. and Xiong H., Achieving very low mercury levels in refinery wastewater by membrane filtration, Journal of Hazardous Materials 2012, 215: 98-107. 13. Bazinet L. and Firdaous L. Membrane Processes and Devices for Separation of Bioactive Peptides, Recent Patent on Biotechnology 2009, 3: 61-72 14. Huang Y., Barker R.W. and Vane L.M., Low-energy distillation-membrane separation process, Industrial & Engineering Chemistry Research 2010, 49(8): 3760-3768. 15. Bouranene S., Fievet P., Szymczyk A., Samar M.E-H. and Vidonne A., Influence of operating conditions on the rejection of cobalt and lead ions in aqueous solutions by a nanofiltration polyamide membrane, Journal of Membrane Science, 2008, 325: 150157. 16. Anthati V.A.K and Marathe K.V., Selective separation of copper (11) and Cobalt (11) from wastewater by using continuous cross-flow micellar-enhanced ultrafiltration and surfactant recovery from metal micellar solutions, The Canadian Journal of Chemical Engineering 2011, 89: 292-298.

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17. Lin S-H., Wang T-Y and Juang R-S, Metal rejection by nanofiltration by diluted solutions in the presence of complexing agents, Separation Science and Technology 2004, 39(2): 363-376. 18. Mohammad A.W., Othaman R. and Hilal N, Potential use of nanofiltration membranes in treatment of industrial wastewater from Ni-P electroless plating, Desalination 2004, 168: 241-252. 19. Escoda A., Fievet P., Lakard S., Szymczyk A. and Deon S., Influence of salts on the rejection of polyethyleneglycol by an NF organic membrane: Pore swelling and salting-out effects, Journal of Membrane Science 2010, 347: 174-182. 20. Dahmani, B. & Chabene, M. Effect of solution chemistry on nanofiltration membranes of nickel removal from aqueous solution. Chemical Engineering and Process Technology, 2(1), pp103-107, 2011.

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