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The Effect of Heating on the Surface Area, Porosity and Surface Acidity of a Bentonite

Published online by Cambridge University Press:  01 January 2024

Hülya Noyan ,
Müşerref Önal  and
Yüksel Sarikaya
Hülya Noyan
Affiliation:
Department of Chemistry, Faculty of Science, Ankara University, Beşevler, 06100 Ankara, Turkey
Müşerref Önal
Affiliation:
Department of Chemistry, Faculty of Science, Ankara University, Beşevler, 06100 Ankara, Turkey
Yüksel Sarikaya*
Affiliation:
Department of Chemistry, Faculty of Science, Ankara University, Beşevler, 06100 Ankara, Turkey
*
*E-mail address of corresponding author: [email protected]
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Abstract

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The Hançılı bentonite from Turkey shows significant changes in surface area, micro- and mesoporosity, surface acidity and acid strength with heating from 100 to 900°C for 2 h. The specific surface area (S) and specific micro-mesopore volume (V) of the original and heated samples were evaluated from N2 adsorption and desorption data, respectively, by standard methods. The adsorption of n-butylamine from the solution in cyclohexane on the samples was used to determine the total surface acidity (nm) and the adsorption equilibrium constant (K) was taken as a measure of the acid strength. S, V and nm having initial values of 98 m2g−1, 0.080 cm3g−1 and 4.8 × 10−4 mol g−1, respectively, stayed approximately constant as the temperature increased to 450°C and then decreased almost in parallel with each other, reaching their minimum or zero at 900°C. The total surface acidity, in general, declines with increasing temperature. The most acidic sites, however, increase with heating, and especially at dehydration and dehydroxylation. Acid strength reaches its maximum during the dehydroxylation phase at ∼600°C. It was concluded that the total surface acidity does not necessarily parallel the strength of the most acid sites.

Keywords

Acid StrengthBentoniteHeatingSurface AciditySurface Area
Type
Research Article
Information
Clays and Clay Minerals , Volume 54 , Issue 3 , June 2006 , pp. 375 - 381
Copyright
Copyright © 2006, The Clay Minerals Society

References

Abu-Zreig, M.M. Al-Akhras, N.M. and Attom, M.F., (2001) Influence of heat treatment on the behaviour of clayey soils Applied Clay Science 20 129–135 10.1016/S0169-1317(01)00066-7.CrossRefGoogle Scholar
Adams, J.M., (1987) Synthetic organic chemistry using pillared cation-exchanged and acid-treated montmorillonite catalysts: a review Applied Clay Science 2 309–342 10.1016/0169-1317(87)90039-1.CrossRefGoogle Scholar
Adams, J.M. Clapp, T.V. and Clement, D.E., (1983) Catalysis by montmorillonites Clay Minerals 18 411–421 10.1180/claymin.1983.018.4.06.CrossRefGoogle Scholar
Alemdaroğlu, T. Akkuş, G. Önal, M. and Sarıkaya, Y., (2003) Investigation of the surface acidity of a bentonite modified by acid activation and thermal treatment Turkish Journal of Chemistry 27 675–681.Google Scholar
Barrer, R.M., (1989) Shape-selective sorbents based on clay minerals: a review Clays and Clay Minerals 37 385–395 10.1346/CCMN.1989.0370501.CrossRefGoogle Scholar
Basila, M.R. Kantner, T.R. and Rhee, K.H., (1964) The nature of the acidic sites on a silica-alumina. Characterization by infrared spectroscopic studies of trimethylamine and pyridine chemisorption The Journal of Physical Chemistry 68 3197–3207 10.1021/j100793a020.CrossRefGoogle Scholar
Benesi, H.A., (1956) Acidity of catalyst surfaces. I. Acid strength from colors of adsorbed indicators Journal of the American Chemical Society 78 5490–5494 10.1021/ja01602a008.CrossRefGoogle Scholar
Benesi, H.A., (1957) Acidity of catalyst surfaces. II. Amine titration using Hammett indicators The Journal of Physical Chemistry 61 970–973 10.1021/j150553a030.CrossRefGoogle Scholar
Blumenfeld, A.L. and Fripiat, J.J., (1997) 27A1-1H Redor NMR and 27A1 Spin-Echo Editing: A new way to characterize Brönsted and Lewis acidity in zeolites Journal of Physical Chemistry B 101 6670–6675 10.1021/jp970564y.CrossRefGoogle Scholar
Bradley, W.F. and Grim, R.E., (1951) High temperature thermal effects of clay and related materials American Mineralogist 36 182–201.Google Scholar
Breen, C. Deane, A.T. and Flynn, J.J., (1987) The acidity of trivalent cation-exchanged montmorillonite. Temperature-programmed desorption and infrared studies of pyridine and n-butylamine Clay Minerals 22 169–178 10.1180/claymin.1987.022.2.05.CrossRefGoogle Scholar
Brindley, G.W., (1978) Thermal reactions of clay and clay minerals Ceramica 24 217–224.Google Scholar
Brown, D.R. and Rhodes, C.N., (1997) Brönsted and Lewis acid catalysis with ion-exchanged clays Catalysis Letters 45 35–40 10.1023/A:1019038806333.CrossRefGoogle Scholar
Brown, D.R. and Rhodes, C.N., (1997) A new technique for measuring surface acidity by ammonia adsorption Thermochimica Acta 294 33–37 10.1016/S0040-6031(96)03139-5.CrossRefGoogle Scholar
Brunauer, S. Emmett, P.H. and Teller, E., (1938) Adsorption of gases in multimolecular layers Journal of the American Chemical Society 60 308–319 10.1021/ja01269a023.CrossRefGoogle Scholar
Brunauer, S. Deming, L.S. Deming, D.M. and Teller, E., (1940) On a theory of the van der Waals adsorption on gases Journal of the American Chemical Society 62 1723–1732 10.1021/ja01864a025.CrossRefGoogle Scholar
Ceylan, H. Yıldız, A. and Sarıkaya, Y., (1993) Investigation of adsorption of fatty acids on two different clays using IR, DTA and TGA techniques Turkish Journal of Chemistry 17 267–272.Google Scholar
Chandrasekhar, S. and Ramaswamy, S., (2002) Influence of mineral impurities on the properties of kaolin and its thermally treated products Applied Clay Science 21 133–142 10.1016/S0169-1317(01)00083-7.CrossRefGoogle Scholar
Chorom, M. and Rengasamy, P., (1996) Effect of heating on swelling and dispersion of different cationic forms of a smectite Clays and Clay Minerals 44 783–790 10.1346/CCMN.1996.0440609.CrossRefGoogle Scholar
Drits, V.A. Besson, G. and Muller, F., (1995) An improved model for structural transformations of heat-treated aluminous dioctahedral 2:1 layer silicates Clays and Clay Minerals 43 718–731 10.1346/CCMN.1995.0430608.CrossRefGoogle Scholar
Emmerich, K. and Kahr, G., (2001) The cis- and trans-vacant variety of a montmorillonite — an attempt to create a model smectite Applied Clay Science 20 119–127 10.1016/S0169-1317(01)00065-5.CrossRefGoogle Scholar
Emmerich, K. Madsen, F.T. and Kahr, G., (1999) Dehydroxylation behavior of heat-treated and steam-treated homoionic cis-vacant montmorillonites Clays and Clay Minerals 47 591–604 10.1346/CCMN.1999.0470506.CrossRefGoogle Scholar
Elzea, J.M. Odom, J.E. and Miles, W.J., (1994) Distinguishing well-ordered opal-CT and opal-C from high temperature α-cristobalite by X-ray diffraction Analytica Chimica Acta 286 107–116 10.1016/0003-2670(94)80182-7.CrossRefGoogle Scholar
Everett, D.H. Parfitt, G.D. Sing, K.S.W. and Wilson, R., (1974) The SCI/IUPAC/NPL project on surface area standards Journal of Applied Chemistry and Biotechnology 24 199–219 10.1002/jctb.5020240404.CrossRefGoogle Scholar
Flessner, U. Jones, D.J. Rozière, J. Zajac, J. Storaro, L. Lenardo, M. Pavan, M. Jimènez-Lòpez, A. Rodrìguez-Castellòn, E. Trombetta, M. and Busca, G., (2001) A study of the surface acidity of acid-treated montmorillonite clay catalysts Journal of Molecular Catalysis A: Chemical 168 247–256 10.1016/S1381-1169(00)00540-9.CrossRefGoogle Scholar
Frenkel, M., (1974) Surface acidity of montmorillonites Clays and Clay Minerals 22 435–441 10.1346/CCMN.1974.0220510.CrossRefGoogle Scholar
Gamiz, E. Linares, J. and Delgado, R., (1992) Assessment of two Spanish bentonites for pharmeceutical uses Applied Clay Science 6 359–368 10.1016/0169-1317(92)90003-6.CrossRefGoogle Scholar
Ge, Z. Li, D. and Pinnavaia, T.J., (1994) Preparation of alumina-pillared montmorillonites with high thermal stability, regular microporosity and Lewis/Brönsted acidity Microporous Materials 3 165–175 10.1016/0927-6513(94)00020-4.CrossRefGoogle Scholar
Gregg, S.J. and Sing, K.S.W., (1982) Adsorption, Surface Area and Porosity 2 London Academic Press.Google Scholar
Grim, R.E., (1968) Clay Mineralogy 2 New York McGraw-Hill.Google Scholar
Grim, R.E. and Güven, N., (1978) Bentonites — Geology, Mineralogy, Properties and Uses New York Elsevier.Google Scholar
Hammett, L.P. and Deyrup, A.J., (1932) A series of simple basic indicators I. The acidity functions of mixtures of sulphuric and perchloric acid with water Journal of the American Chemical Society 54 2721–2739 10.1021/ja01346a015.CrossRefGoogle Scholar
Jacobs, P.A. and Delannay, F., (1984) The measurement of surface acidity Characterization of Heterogeneous Catalysts New York Dekker 1–28.Google Scholar
Joshi, R.C. Achari, G. Horfield, D. and Nagaraj, T.S., (1994) Effect of heat treatment on strength of clays Journal of Geotechnical Engineering-ASCE 120 1080–1088 10.1061/(ASCE)0733-9410(1994)120:6(1080).CrossRefGoogle Scholar
Kahraman, S. Önal, M. Sarıkaya, Y. and Bozdoğan, , (2005) Characterization of silica polymorphs in kaolins by X-ray diffraction before and after phosphoric acid digestion and thermal treatment Analytica Chimica Acta 552 201–206 10.1016/j.aca.2005.07.045.CrossRefGoogle Scholar
Kou, M.R.S. Mendioroz, S. and Munoz, V., (2000) Evaluation of the acidity of pillared montmorillonites by pyridine adsorption Clays and Clay Minerals 48 528–536 10.1346/CCMN.2000.0480505.CrossRefGoogle Scholar
Kumar, P. Jasra, R.V. and Bhat, T.S.G., (1995) Evolution of porosity and surface acidity in montmorillonite clay on acid activation Industrial and Engineering Chemistry Research 34 1440–1448 10.1021/ie00043a053.CrossRefGoogle Scholar
Laidler, K.J. and Meiser, J.H., (1982) Physical Chemistry London Benjamin/Cumnings 772 pp.Google Scholar
Laszlo, P., (1987) Chemical reactions on clay Science 235 1473–1477 10.1126/science.235.4795.1473.CrossRefGoogle Scholar
Linsen, B.G., (1970) Physical and Chemical Aspects of Adsorbents and Catalysts London Academic Press.Google Scholar
Loeppert, R.H. Zelazny, L.W. and Volk, B.G., (1986) Acidic properties of montmorillonite in selected solvents Clays and Clay Minerals 34 87–92 10.1346/CCMN.1986.0340111.CrossRefGoogle Scholar
McClellan, A.L. and Hornsberger, H.F., (1967) Cross-sectional areas of molecules adsorbed on solid surfaces Journal of Colloid and Interface Science 23 577–599 10.1016/0021-9797(67)90204-4.CrossRefGoogle Scholar
Moore, D.M. Reynolds, R.C. Jr., (1997) X-ray Diffraction and the Identification and Analysis of Clay Minerals 2 New York Oxford University Press.Google Scholar
Mortland, M.M. and Raman, K.V., (1968) Surface acidity of smectite in relation to hydration, exchangeable cation, and structure Clays and Clay Minerals 16 393–398 10.1346/CCMN.1968.0160508.CrossRefGoogle Scholar
Mozas, T. Bruque, S. and Rodriquez, A., (1980) Effect of thermal treatment on lanthanide montmorillonites: Dehydration Clay Minerals 15 421–428 10.1180/claymin.1980.015.4.09.CrossRefGoogle Scholar
Murray, H.H., (1991) Overview — clay mineral applications Applied Clay Science 5 379–395 10.1016/0169-1317(91)90014-Z.CrossRefGoogle Scholar
Murray, H.H., (2000) Traditional and new applications for kaolin, smectite and palygorskite. A general overview Applied Clay Science 17 207–221 10.1016/S0169-1317(00)00016-8.CrossRefGoogle Scholar
Neaman, A. Pelletier, M. and Villiéras, F., (2003) The effect of exchanged cation, compression, heating and hydration on textural properties of bulk bentonite and its corresponding purified montmorillonite Applied Clay Science 22 153–168 10.1016/S0169-1317(02)00146-1.CrossRefGoogle Scholar
Occelli, M.L. Landau, S.D. and Pinnavaia, T.J., (1987) Physicochemical properties of a delaminated clay cracking catalyst Journal of Catalysis 104 331–338 10.1016/0021-9517(87)90365-4.CrossRefGoogle Scholar
Önal, M. Sarıkaya, Y. Alemdaroğlu, T. and Bozdoğan, , (2002) The effect of acid activation on some of the physicochemical properties of a bentonite Turkish Journal of Chemistry 26 409–416.Google Scholar
Önal, M. Sarıkaya, Y. Alemdaroğlu, T. and Bozdoğan, , (2003) Isolation and characterization of a smectite as a micro-mesoporous material from a bentonite Turkish Journal of Chemistry 27 683–693.Google Scholar
Parry, E.P., (1963) An infrared study of pyridine adsorbed on acidic solids. Characterization of surface acidity Journal of Catalysis 2 371–379 10.1016/0021-9517(63)90102-7.CrossRefGoogle Scholar
Pinnavaia, T.J., (1983) Intercalated clay catalysis Science 220 365–371 10.1126/science.220.4595.365.CrossRefGoogle Scholar
Ravichandran, J. and Sivasankar, B., (1997) Properties and catalytic activity of acid-modified montmorillonite and vermiculite Clays and Clay Minerals 45 854–858 10.1346/CCMN.1997.0450609.CrossRefGoogle Scholar
Reicle, W.T., (1985) Catalytic reactions by thermally activated, synthetic, anionic clay minerals Journal of Catalysis 94 547–557 10.1016/0021-9517(85)90219-2.CrossRefGoogle Scholar
Ruiz, J.A.C. Melo, D.M.A. Souza, J.R. and Alcazar, L.O., (2002) Determination of total acid in palygorskite chemically modified by n-butylamine thermodesorption Materials Research 5 173–178 10.1590/S1516-14392002000200014.CrossRefGoogle Scholar
Rouquerol, F. Rouquerol, J. and Sing, K., (1999) Adsorption by Powder and Porous Solids London Academic Press.Google Scholar
Sarıkaya, Y. and Aybar, S., (1978) The adsorption of NH3, N2O and CO2 gases on the 5A molecular sieve Communication of the Faculty of Science, University of Ankara B24 33–39.Google Scholar
Sarıkaya, Y. Önal, M. Baran, B. and Alemdaroğlu, T., (2000) The effect of thermal treatment on some of the physicochemical properties of a bentonite Clays and Clay Minerals 48 557–562 10.1346/CCMN.2000.0480508.CrossRefGoogle Scholar
Sarıkaya, Y. Sevinç, and Akınç, M., (2001) The effect of calcination temperature on some of the adsorptive properties of fine alumina powders produced by emulsion evaporation Powder Technology 116 109–114 10.1016/S0032-5910(00)00365-X.CrossRefGoogle Scholar
Sarıkaya, Y. Ada, K. Alemdaroğlu, T. and Bozdoğan, , (2002) The effect of Al3+ concentration on the properties of alumina powders obtained by reaction between aluminium sulphate and urea in boiling aqueous solution Journal of the European Ceramic Society 22 1905–1910 10.1016/S0955-2219(01)00514-3.CrossRefGoogle Scholar
Sarıkaya, Y. Alemdaroğlu, T. and Önal, M., (2002) Determination of the shape, size and porosity of fine α-Al2O3 powders prepared by emulsion evaporation Journal of the European Ceramic Society 22 305–309 10.1016/S0955-2219(01)00294-1.CrossRefGoogle Scholar
Srasra, E. Bergaya, F. van Damme, H. and Ariquib, N.K., (1989) Surface properties of an activated bentonite-decolorisation of rape-seed oils Applied Clay Science 4 411–421 10.1016/0169-1317(89)90019-7.CrossRefGoogle Scholar
Tan, Yilmaz, L. and Zaimoğlu, S., (2004) Variation of some engineering properties of clays with heat treatment Materials Letters 58 1176–1179 10.1016/j.matlet.2003.08.030.CrossRefGoogle Scholar
Tanabe, K. Misono, M. Ono, Y. and Hattori, H., (1989) New Solid Acids and Bases, Their Catalytic Properties Amsterdam Elsevier.Google Scholar
Varma, R.S., (2002) Clay and clay-supported reagents in organic synthesis Tetrahedron 58 1235–1255 10.1016/S0040-4020(01)01216-9.CrossRefGoogle Scholar
Walling, C., (1950) The acid strength of surfaces Journal of the American Chemical Society 72 1164–1168 10.1021/ja01159a025.CrossRefGoogle Scholar
Wang, M.C. Benway, J.M. Arayssi, A.M., Hoodinott, K.B. Lamb, R.O. and Lutenegger, A.J., (1990) The effect of heating on engineering properties of clays Physicochemical Aspects of Soil and Related Materials Philadelphia ASTM STP 1095 1139–1158.Google Scholar