ISSN 1392 1231. CHEMIN TECHNOLOGIJA. 2009. Nr.

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Adsorption properties of modified bentonite clay

A. Mockoviakov, Z. Orolnov
Institute of Geotechnics, Slovak Academy of Sciences, 45 Watsonova STR., 043 53, Koice, Slovak Republic E-mail: mocka@saske.sk Received 2 February 2009; Accepted 17 February 2009
The adsorption ability of natural bentonite of Slovak provenience was compared with that of composite material based on bentonite. The magnetic composite material was prepared using the method of precipitation of magnetic nanoparticles (Matik, 2004) on the surface of a selected support bentonite, at temperatures 20 and 85 C in different weight ratios of bentonite / magnetic particles. The surface and pore properties of natural bentonite as well as the magnetic composite were studied using the low nitrogen adsorption method. It has followed from the adsorption study that the clays under study are mesoporous. The increased values of the specific surface area and total pore volume of the composite material should be attributed to magnetic nanoparticles forming a secondary mesoporous structure. The natural and the modified bentonite have been used in sorption experiments in which the adsorption of toxic metals (zinc, cadmium and nickel) from model solutions were studied. The sorption experiments, evaluated by the Freundlich and the linearized Langmuir sorption model, revealed that the use of magnetic bentonite was more favourable. In case of a lower initial concentration of toxic metals in model solutions, the efficiency of sorption was more than 90%. The magnetic modification of natural bentonite seems to be an interesting way to enhance its sorption ability.

Introduction
Clays are hydrous aluminosilicates composed of mixtures of fines-grained clay minerals, crystals of other minerals and metal oxides. Clays play an important role in the environment by taking up cations and anions through adsorption or ion exchange. They belong to lowcost sorbents [1], as the cost is an important parameter. The good adsorption ability comes from their negative charge which can be neutralised by adsorption of positively charged anions. Clays obtaining montmorillonite are referred to bentonite which belongs to the 2 : 1 clay family composed of two tetrahedrally coordinated sheets of silicon surrounding and an octahedrally coordinated sheet of aluminium ions. Clay can be modified to improve its sorption ability [2, 3]; one of the methods is the use of magnetic modification in which, e.g., bentonite coated with iron can be obtained [4]. The term iron oxide is often used in scientific literature to describe the group of iron compounds with hydroxide, oxyhydroxide and oxide structures. They are widely used in practice as pigments, catalysts, sorbents, in ferrofluids [5], etc., and the route of chemical synthesis has a significant influence on their chemical, structural and physical properties. The aim of this work was to study the sorption properties of magnetic composites while removing heavy metals (Zn, Cd and Ni) from model solutions and to compare their adsorption capacity with that of unmodified bentonite.

Methods
Magnetic bentonite was prepared from a solution containing a mixture of Fe(II) and Fe(III) salts and

bentonite, treated by the sedimentation method. Two different bentonite/iron oxide weight ratios 1 : 1, 5 : 1 denoted as A and E were studied. Magnetic particles were precipitated dropping a solution of NH4OH during a continuous stirring for 30 min in a nitrogen atmosphere at two ambient temperatures and 85 C. The final products were washed with de-ionized water to remove unfixed iron oxide and dried at a temperature of 70 C [6]. For characterization of the surface and pore properties of the prepared composites, nitrogen adsorption experiments were carried out at 77 K with an ASAP 2400 sorption apparatus (Micrometrics). The specific surface area SBET was calculated from the adsorption isotherms according to the BET (Brunauer, Emmett and Teller) method in a relative pressure range 0.030.2 p/p0. The value of the total pore volume Va was determined from the maximum adsorption at a relative pressure of 0.99 p/p0. The micropore volume Vmicro as well as the value of external surface St were obtained from the t-plot analysis. The pore size distribution of the studied samples was calculated using the BJH (BarettJoynerHalenda) method from the desorption isotherms. The sorption of zinc, nickel, and cadmium cations from model aqueous solutions by natural and modified bentonites was carried out using batch-type equilibrium experiments in a rotary shaker for 24 hours at a constant ambient temperature. The measured dependence of adsorption capacity on pH revealed that over pH 6.5 the capacity decreased, and for the sorption processes, pH 5 was chosen. The initial metal ion concentration was changed in the range 1750 mg/l, and the amount of sorbent was 2 g/l. The final metal concentration was determined by atomic absorption spectroscopy (AAS using a Varian Spectr AA-30) and the metal uptake was calculated from the difference. The isotherms at zinc sorption were fitted with the Langmuir equation.

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Results and discussion

The adsorption / desorption isotherms of natural and modified bentonites are shown in Figures 1, 2. Their characteristic features, hysteresis loops are associated with the capillary condensation in mesopores. The arising final parts of the isotherms indicate an occurrence of macropores in the pore structures of the samples [7]. Table summarizes the values of the BET surface area, external surface and total pore volume. The higher values of the specific surface area and the increased values of total pore volumes are related to the agglomerated structure of iron oxide particles, which has been created during the precipitation process. As seen from Figure 2, the pore structure of synthesized pure iron oxides contains mainly mesopores forming an almost symmetrical distribution curve (Fig. 3). The calculated micropore volume Vmicro of the samples has shown that the contribution of small pores to the total pore volume is not significant.
Table. Structural parameters of natural bentonite and composites Sample Bentonite A20 E20 A85 E85 SBET, m2/g 39.4 73.7 90.7 82.8 84.8 Va, cm3/g 0.096 0.216 0.187 0.251 0.183 Vmikro, cm3/g 0.005 0.004 0.002 0.004 0.003 St, m2/g 27.6 64.2 83.9 73.7 77.5 Fractal dimension D 2.72 2.57 2.63 2.52 2.62

Fig. 1. Isotherms of bentonite and bentonite composite

on the synthesis temperature: the distribution curve corresponding to the magnetic composite prepared at an ambient temperature is shifted to the smaller pore diameters, implying out that the size of magnetic particles precipitated on bentonite at the ambient temperature is smaller than in case of the synthesis temperature 85 C. It can explain the value of the highest specific surface of the composite sample E20; the highest total pore volume in sample A85 can be attributed to the content of magnetic particles. These two mentioned samples were selected for the sorption experiments.

Fig. 2. Isotherms of bentonite, composite E and synthesized iron oxides

The pore size distribution of the samples is shown in Figure 3, where an increase in the pore volume of composite materials is also noticeable. A comparison of the modified bentonites A and E shows that a higher pore volume was obtained at sample A where the content of magnetic particles was higher. The effect of synthesis temperature of samples A was not expressive. The porosity of the composite samples E was different, depending

Fig. 3. Pore size distribution in the sample

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The sorption of zinc, nickel and cadmium from aqueous solutions was carried out on natural bentonite and on composites A85 and E20. The amount of metal ions Zn2+ adsorbed on natural and modified bentonite E20 as a function depending on its initial concentration in the range 10100 mg/l was studied. The obtained isotherms were fitted with the linearized Langmuir type model (Fig. 4) according to the equation [8]: synthesis
Ce qe = 1 Qm . K + Ce Qm

Cd/g, 23.7 mg Cd/g and 29.4 mg Cd/g, respectively. It can be seen in Figure 6 that the increase in the amount of the sorbent ions on composites A85 and E20 was most expressive again in a lower concentration range. Another sorption experiment showed that both composite sorbents A85 and E20 were very effective in comparison with natural bentonite at Cd2+ ions sorption in the initial concentration range 110 mg/l.

where Ce is the equilibrium concentration of metal in solution, and qe denotes the amount of sorbed metal ions. The Langmuir maximum sorption capacity Qm of bentonite and E20, calculated from the slopes of the plots, were 22 mg Zn/g and 23 mg Zn/g, respectively.

Fig. 5. Sorption of nickel on bentonite and composite E20

Fig. 4. Adsorption of Zn(II) on natural and modified bentonite E20

Nickel sorption on natural bentonite and composite E20, carried out in dependence on the initial metal concentration range 10750 mg/l, is shown in Figure 5. The isotherms fitted by the Freundlich model show, that in spite of wider range of the initial concentration, the maximum sorption capacity was still not attained. Comparing the sorption isotherms in Figure 5, an increase in Ni sorption on the composite bentonite E20 is observable in the range of lower concentrations. Another sorption experiment, including the concentration range 1 15 mg/l, was carried out (Fig. 5). It followed from the experiment that the magnetic composite E20 showed at a lower concentration range a very good sorption capacity; in comparison to natural bentonite, a more than 90% sorption efficiency of composite material was achieved. The sorption of cadmium was investigated on three sorbents including natural bentonite, as well as composites A85 and E20. The effect of metal ion initial concentration on the amount of sorbed ions was investigated over the concentration range 150 mg/l at a constant ambient temperature. The experimental data on sorption were fitted with the linearized Langmuir type model (Fig. 6). The calculated sorption capacities of natural bentonite, composites A85 and E20 were 27.7 mg

Fig. 6. Sorption of cadmium on bentonite, composites A85 and E20

It can be concluded that the magnetically modified bentonite samples A85 and E20 should be more convenient in removing metals from an aqueous solution when their concentration is very low but still harmful.

Conclusions
The composite sample prepared in bentonite / iron oxide weight ratio 5 : 1 at a temperature of 20 C showed a higher amount of Zn2+ ions sorbed over the whole concentration range (10100 mg/l) in comparison to natural bentonite. The sorption of Ni2+ ions in a lower initial concentration range (115 mg/l) was very

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favourable for the same magnetic composite sorbent. In case of the sorption of Cd2+ ions, the use of magnetic sorbents prepared in two bentonite / iron oxide weight ratios, 1 : 1 and 5 : 1, at a temperature of 85 C and 20 C respectively, was very convenient. The magnetically modified bentonite seems to be a promising candidate for the practical use in the removal of heavy metals.

8.

Kavak D. // Journal of Hazardous Materials. 2009. Vol. 163, N 1. P. 308314.

A. Mockoviakov, Z. Orolnov MODIFIKUOTO BENTONITINIO MOLIO ADSOBCINS SAVYBS Santrauka

Darbe lyginamos gamtinio bentonito (Slovakija) ir kompozicini mediag su bentonitu adsorbcins galimybs. Magnetins kompozicins mediagos buvo ruoiamos pagal magnetini nanodaleli nusdimo ant pasirinkto pagrindo bentonito metod (Matik, 2004) 20 ir 85 oC temperatroje, esant skirtingiems bentonito / magnetini daleli svoriniams santykiams. Gamtinio bentonito paviriaus ir por savybs yra tokios pat kaip ir magnetinio kompozito, kuris buvo tirtas, remiantis azoto adsorbcijos metodu. Taigi, pagal adsorbcijos tyrimus molis yra mezopor mediaga. Kompozicins mediagos didesnis savitojo paviriaus plotas ir suminis por tris turt priklausyti nuo magnetini nanodaleli, susidarant mezoporei struktrai. Sorbcijos darbuose buvo naudojami gamtinis ir modifikuotas bentonitas ir tirta toksik metal (cinko, kadmio ir nikelio) adsorbcija i tirpal. Atlikus sorbcij pagal Freundlio (Freundlich) ir linijin Lengmiuro (Langmuir) sorbcijos modelius, nustatyta, kad mintiems tikslams geriau naudoti magnetin bentonit. Kai tirpaluose yra maesns pradini toksik metal koncentracijos, sorbcijos naumas yra daugiau nei 90 %. Taigi modifikavus gamtin bentonit, padidja jo sorbcins galimybs.

Acknowledgements
The authors are grateful to the Slovak VEGA Grant Agency for financial support of the project G/0119/29.

References
1. 2. 3. 4. 5. 6. 7. Bailey S. E. et al. // Water Research. 1999. Vol. 33, N 11. P. 24692479. Volzone, C. et al. // Cermica. 2002. Vol. 48, N 307. P. 153156. Karahan, S. et al. // J. Colloid Interface Sci. 2006. Vol. 293, N 1. P. 3642. Oliveira, L. et al. // Appl. Clay Sci. 2003. Vol. 22, N 4. P. 169177. Jakabsk . et al. Using of the Ferromagnetic Fluids in Mineral Processing. Koice, 2004. Matik M. et al. // Acta Montanistica. 2004. Vol. 9, N 4. P. 418422. Sing K. S. W. et al. // Pure Appl. Chem. 1985. Vol. 57, N 4. P. 603619.

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