Characterization of Various Cation Exchanged and Pillared Artvin Bentonites and Their Use as a Catalyst in a Selected Organic Reaction

Abstract

In this study, the catalytic activities of raw, some metal cations exchanged (Fe³⁺ and Cu²⁺) and Fe- and Al-pillared Artvin bentonite samples as a catalyst for acetalization reaction of benzaldehyde with 2, 3-butanediol were investigated. The structural and physicochemical properties of clay samples were examined by using X-Ray powder diffraction (XRD), scanning electron microscope (SEM), Fourier Transform infrared (FTIR) and surface area measurement techniques. The yield of this organic reaction in the presence of Cu-bentonite and Al-pillared bentonites were found as very low whereas Fe-bentonite and Fe-pillared bentonite catalysts showed 60 and 63% yield in acetalization under same conditions, respectively. This study showed that modified Artvin bentonite samples which is the one member of Turkey’s important local and natural sources can be used as catalyst in the selected organic reaction and their utilization in industrial process reactions in small scale. 

Keywords

• Artvin Bentonite,Catalysis,Characterization,illared clays

Çeşitli Katyon Değiştirilmiş ve Sütunlanmış Artvin Bentonitlerinin Karakterizasyonu ve Seçilmiş Bir Organik Reaksiyonda Katalizör Olarak Kullanılmaları

Abstract

Bu çalışmada Artvin ham bentonitinin,  bazı metal katyonları (Fe³⁺ ve Cu²⁺) değiştirilmiş ve Fe- ve Al-sütunlanmış türevlerinin benzaldehitin 2,3-bütandiol ile asetalleşme reaksiyonundaki katalitik aktiviteleri araştırıldı. Bu katalizörlerin yapısal ve fizikokimyasal özellikleri X–ışınları toz kırınım (XRD), taramalı elektron mikroskobu (SEM), Fourier transform infrared (FTIR),  ve yüzey alanı ölçüm teknikleri yardımıyla aydınlatılmıştır. Cu-bentonit ve Al sütunlu-bentonit katalizörlü reaksiyonlarda verimin çok az olduğu buna karşın Fe-bentonit ve Fe-sütunlu bentonit katalizörlerinin kullanıldığı tepkimelerde ise sırasıyla % 60 ve % 63 verimle asetalleşme reaksiyonu gerçekleştiği tespit edilmiştir. Bu çalışma ülkemizin önemli yerli kaynaklarından birini teşkil eden Artvin bentonitinin modifiye edilmesiyle organik reaksiyonları katalizleyebildiğini ve bu ürünlerin küçük ölçekte ve endüstriyel proseslerdeki reaksiyonlar için kullanılabileceğini ortaya koymuştur.

Keywords

• Artvin Bentonit,, Kataliz,Karakterizasyon,Sütunlanmış killer

References

1. [1] Carrado K. A., Suib S. L., Skoularikis N. D. and Coughlin R.W. Chromium(III)-Doped Pillared Clays (PILCs). Inorg. Chem., 25; 4217-4221, 1986. [2] Barrault J., Bouchoule C., Echachoui K., Frini-Srasra N., Trablesi M., and Bergaya F., Catalytic Wet Peroxide Oxidation (CWPO) of Phenol Over Mixed (Al-Cu)-Pillared Clays. App. Catal. B: Environ.15 ; 269-274, 1998. [3] Barrault J., Tatibouët J. M. and Papayannakos N. Catalytic Wet Peroxide Oxidation of Phenol Over Pillared Clays Containing Iron or Copper Species. Surface Chemistry and Catalysis, 3; 777-783, 2000. [4] Tomul F. Adsorption and catalytic properties of Fe/Cr-pillared bentonites. Chem. Engin.J. 186; 380-390, 2012. [5] Balogh M. ve Laszlo P. Organic Chemistry Using Clays. Springer, New York, 1992. [6] Vaccari A. Clays and catalysis: a promising future.Appl. Clay Sci. 14; 161-198, 1999. [7] Tabak, A. Çeşitli Kaolin Yüzeyleri Üzerinde Adsorplanmış Amonyak ve Piridin Türleri. Yüksek Lisans Tezi, Ondokuz Mayıs Üniversitesi Fen-Bilimleri Enstitüsü, Samsun, 1998. [8] Tabak A. Çeşitli Organo- ve Anorgano-Killerin Ara-Yüzey Özelliklerinin FTIR, XRD, BET, UV-Gör, HPLC ve Termik Analiz Teknikleriyle İncelenmesi. Doktora Tezi, Ondokuz Mayıs Üniversitesi Fen-Bilimleri Enstitüsü, Samsun, 2003. [9] Izumi Y., Urabe K. and Onaka M. Zeolite, Clay, and Heteropoly Acid in Organic Reactions. Kodansha Ltd., Tokyo, 1992. [10] Vaccari A. Preparation and catalytic properties of cationic and anionic clays.Catalysis Today 41; 53-71, 1998. [11] Varma, R. S. 2002. Clay and Clay-Supported Reagents in Organic Synthesis. Tetrahedron 58; 1235-1255. [12] Carriazo J.G. Effect of Fe and Ce on Al-pillared bentonite and their performance in catalytic oxidation reactions. Appl. Catalysis A. 317; 120-128, 2007. [13] Devendrapratap U. S, Pankajkumar R. S, Shriniwas D. S. Fe-pillared bentonite—an efficient catalyst for sulfonylation of arenes using aryl and alkyl sulfonyl chlorides, Tetrahedron Letters. 45; 9079–9082, 2004. [14] Bahranowski K., Włodarczyk W., Wisła-Walsh E., Gaweł, A. et al. [Ti,Zr]-pillared montmorillonite – A new quality with respect to Ti- and Zr-pillared clays. Microporous and Mesoporous Materials 202; 155–164, 2015. [15] Mnasri S., Hamdi N., Frini-Srasra N. and Srasra E. Acid–base properties of pillared interlayered clays with single and mixed Zr–Al oxide pillars prepared from Tunisian- interstratified illite–smectite. Arabian Journal of Chemistry, 10; 1175-1183, 2017. [16] Belkhadem F., Clacens J. M., Bengueddach A., and Figueras F. Acidity and catalytic properties for the alkylation of aromatics of PILCs with mixed oxide pillars prepared from two different bentonites. Applied Catalysis A: General 298; 188–193, 2006. [17] Steudel A., Batenburg L.F., Fischer H.R., Weidler, P.G. and Emmerich K. Alteration of swelling clay minerals by acid activation. Appl. Clay Sci. 44; 105-115, 2009. [18] Jozefaciuk G. and Bowanko G. Effect Of Acid And Alkali Treatments On Surface Areas And Adsorption Energies Of Selected Minerals. Clays and Clay Minerals, 50; 771-783, 2002. [19] Vaughan D.E.W. Pillared Clays. Catalysis Today, 2; 187-198, 1988. [20] Nagendrappa, G. Organic Synthesis Using Clay and Clay-Supported Catalysts. Appl. Clay Sci. 53; 106-138, 2011. [21] Zhou C.H. An overview on strategies towards clay-based designer catalysts for green and sustainable catalysis Applied Clay Science 53; 87–96, 2011, [22] Anastas P.T., Kirchhoff M.M. and Williamson, T.C. Catalysis as a foundational pillar of green chemistry Applied Catalysis A: General 221; 3–13, 2001. [23] Tabak A., Afsin B., Caglar B., and Koksal E., “Characterization and Pillaring of a Turkish Bentonite (Resadiye)”, Journal of Colloid and Interface Science. 313; 5-11, 2007. [24] Hutson N. D., Hoekstra M. J. and Yang R. T. Control of Microporosity of Al2O3-Pillared Clays: Effect of pH, Calcination Temperature and Clay Cation Exchange Capacity. Microporous and Mesoporous Materials, 28; 447-459, 1999.