Thermal and chemical modification of a halloysite and application to the adsorption of a cationic dye

F. Bessaha, N. Mahrez, D. Merouani, S. Sadouki, K. Marouf-Khelifa, A. Khelifa


Abstract: Algerian halloysite was treated at 600 °C and with hydrochloric acid solutions of various concentrations. The resulting materials were characterised by elemental analysis, TG, TDA, TEM, XRD and nitrogen adsorption at 77 K. The modied halloysites were employed as malachite green (MG+) adsorbents from aqueous solutions. Thermal treatment at 600 °C results in the formation of dehydroxylated halloysite, due to –OH release from the structure. Acid treatment involves a relative increase in SiO2 content. The ratio of SiO2/Al2O3 increased from 1.92 to 27.75, consequence of the leaching of Al ions from the octahedral layer. This phenomenon is accompanied by the progressive amorphisation of the structure with increasing HCl concentration. Thermo-chemical treatments preserve the tubular morphology, though the obtained tubes are somewhat damaged. Specific surface area increased significantly from 60.5 to a maximum of 503 m2/g. Total volume is mainly represented by mesopores. Microporosity grows progressively with HCl treatment, reaching a maximum of 21 %. The MG+ adsorption onto the modified halloysites is rapid in the rst 10 min. The adsorbed quantity decreased with increasing temperature. The afnity follows the sequence: H600-0.5N > H600-3N > H600-5N > H600.

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Crini, G.; Non-conventional low-cost adsorbents for dye removal: a review. Bioresour Technol, 97 (2006)1061-85.

Marouf-Khelifa, K.; Abdelmalek, F.; Khelifa, A.; Addou, A.; TiO2-assisted degradation of a perfluorinated surfactant in aqueous solutions treated by gliding arc discharge. Chemosphere 70 (2008) 1995-2001.

Tekin, N.; Kadıncı, E.; Demirbas, Ö.; Alkan, M.; Kara, A.; Adsorption of Polyvinylimidazole onto Kaolinite. J, Colloid Interface Sci, 296 (2006) 472-479.

Unuabonah, E.I.; Olu-Owolabi,B.I.; Adebowale, K.O.; Ofomaja, A.E.; Adsorption of lead and cadmium ions from aqueous solutions by tripolyphosphate-impregnated Kaolinite clay. Colloids Surf,, A 292 (2007) 202-211.

Castellini, E.; Andreoli, R.; Malavasi,G.; Pedone, A.; Deflocculant effects on thesurface properties of kaolinite investigated through malachite green adsorption. Colloids Surf, A 329 (2008) 31-37.

Tehrani-Bagha, A.R.; Nikkar, H.; Mahmoodi, N.M.; Markazi, M.F.; Menger, M.; The sorption of cationic dyes onto kaolin: Kinetic, isotherm and thermodynamic studies. Desalination 266 (2011) 274-280.

Errais, E.; Duplay, J.; Elhabiri, M.; Khodja, M.; Ocampo, R.; Baltenweck-Guyot, R.; Darragi, F.; Anionic RR120 dye adsorption onto raw clay: Surface properties and adsorption mechanism. Colloids Surf, A, 403(2012)69-78.

Lin, Y.; Ng, KM.; Chan, CM.; Sun, G.; Wu, J.; High-impact polystyrene/halloysite nanocomposites prepared by emulsion polymerization using sodium dodecyl sulfate as surfactant. J, Colloid Interface Sci, 358 (2011) 423-9.

Mellouk, S.; Cherifi, S.; Sassi, M.; Marouf-Khelifa, K.; Bengueddach, A.; Schott, J.; Khelifa, A.; Intercalation of halloysite from Djebel Debagh (Algeria) and adsorption of copper ions. Appl, Clay Sci, 44 (2009) 230-236.

Kadi, S.; Lellou, S.; Marouf-Khelifa, K.; Schott, J.; Gener-Batonneau, I.; Khelifa, A.; Preparation, characterisation and application of thermally treated Algerian halloysite. Microporous Mesoporous Mater, 158(2012) 47–54.

Marouf, R.; Khelifa, N.; Marouf-Khelifa, K.; Schott, J.; Khelifa, A.; Removal

of pentachlorophenol from aqueous solutions by dolomitic sorbents. J, Colloid Interface Sci, 297 (2006) 45-53.

Marouf-Khelifa, K.; Khelifa, A.; Belhakem, A.; Marouf, R.; Abdelmalek, F.;

Addou, A.; The adsorption of pentachlorophenol from aqueous solutions onto exchanged Al-MCM-41 materials. Sci, Technol, 22 (2004) 1.

Qiu, G.; Jiang, T.; Li, G.; Fan, X.; Huang Z.; Activation and removal of silicon

in kaolinite by thermochemical process. Scand. J, Metall, 33 (2004) 121-128.

Liu, M.; Guo, B.; Du, M.; Chen, F.; Jia, D.; Halloysite nanotubes as a novel β-nucleating agent for isotactic polypropylene. Polymer 50 (2009) 3022-3030.

Lee, S.; Y. Kim, S.; Adsorption of naphthalene by HDTMA modified kaolinite

and halloysite. J, Appl, Clay Sci, 22 (2002) 55-63.

Giles, H.H. ; MacEwan, C. T, S. N.; Makhwa, D.; Smith, J.; 786. Studies in

adsorption. Part XI. A system of classification of solution adsorption isotherms, and its use in diagnosis of adsorption mechanisms and in measurement ofspecific surface areas of solids. J, Chem, Soc, 93(1960) 3973-3993.

Bendenia,S.; Batonneau-Gener,I.; Comparot, J.D.; Marouf-Khelifa, K.; Hammoudi, H.; Khelifa, A.; Acidity study of X zeolites modified by nickel and/or chromium cations in the case of binary and ternary exchanges. Microporous Mesoporous Mater, 159 (2012) 111-118.

Bulut,E. ; Ozacar,M.; Sengil,I.A.; Adsorption of malachite green onto bentonite:

Equilibrium and kinetic studies and process design. Microporous Mesoporous

Mater, 115 (2008) 234-246

Kumar,K.V.; Sivanesan, S.V.; Ramamurthi S.; Adsorption of malachite green onto Pithophorasp., a fresh water algae: Equilibrium and kinetic modeling. Process Biochem, 40 (2005) 2865-2872.

Gupta, V.K.; Srivastava, S.; Mohan,K.D.; Equilibrium uptake, sorption dynamics, process optimization, and column operations for the removal and recovery of malachite green from wastewater using activated carbon and activated slagInd.Eng, Chem, Res, 36 (1997) 2207-2218.


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