Korean Journal of Chemical Engineering, Vol.26, No.3, 666-672, May, 2009
Reactivity of Bronsted acid ionic liquids as dual solvent and catalyst for Fischer esterifications
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Abstract.Several water-stable ionic liquids with different acidity and affinity were synthesized and applied as both solvents and acid catalysts for Fischer esterification of ethanol reacting with four aliphatic carboxylic acids (acetic acid, n-hexanoic acid, lauric acid, and stearic acid). Among the studied ionic liquids, [(n-bu-SO3H) MIM][HSO4] (3-butyl-1-(butyl-4-sulfonyl) imidazolium sulfate) and [(n-bu-SO3H) MIM][p-TSO] (3-butyl-1-(butyl-4-sulfonyl) imidazolium toluenesulfonate) show higher reactivity for the production of ethyl esters. The catalytic activities of these ionic liquids are strongly dependent on the acidity of their anions and cations, as well as their hydrophilicity and affinity with the reactants. Water refluxing through the condenser may be another important reason for obtaining high conversion of esterification, indicating a water-sequester process is still needed in order to obtain a higher yield of ester in the ionic liquid catalyzed esterification system. Kinetics studies show the conversions of the acids increase with reaction temperature and time, and reach equilibrium within about two hours. The apparent activation energies are 39.1±2.0, 49.7±2.5, 51.4±2.5 and 59.3±3.0 kJ·mol^(-1) for the formation of ethyl acetate, ethyl n-hexanoate, ethyl laurate and ethyl stearate, respectively.
- Gandhi NN, Patil NS, Sawant SB, Joshi JB, Wangikar PP, Mukesh D, Catal. Rev.-Sci. Eng., 42(4), 439 (2000)
- Hoydonckx HE, De Vos DE, Chavan SA, Jacobs PA, Top. Catal., 27, 83 (2004)
- Otera J, Angew. Chem. Int. Ed., 40, 2044 (2001)
- Dragoi B, Dumitriu E, Prog. Catal., 12, 1 (2003)
- Kulesza K, Bartoszewicz P, In modern polymeric materials for environmental applications, 2 ed., Krakow, Poland, 93 (2006)
- Lanman HE, Nguyen RV, Yao XQ, Chan TH, Li CJ, J. Mol. Catal. A: Chem., 279, 218 (2008)
- Ju HY, Ahn JY, Manju MD, Kim KH, Park DW, Korean J. Chem. Eng., 25(3), 471 (2008)
- Duan ZY, Gu YL, Deng YQ, J. Mol. Catal. A-Chem., 246(1-2), 70 (2006)
- Sugimura R, Qiao K, Tomida D, Yokoyama C, Catal. Commun., 8, 770 (2007)
- Deng YQ, Shi F, Beng JJ, Qiao K, J. Mol. Catal. A-Chem., 165(1-2), 33 (2001)
- Zhu HP, Yang F, Tang J, He MY, Green Chemistry, 5, 38 (2003)
- Welton T, Chem. Rev., 99(8), 2071 (1999)
- Fraga-Dubreuil J, Bourahla K, Rahmouni M, Bazureau JP, Hamelin J, Catal. Commun., 3, 185 (2002)
- Wasserscheid P, Sesing M, Korth W, Green Chemistry, 4, 134 (2002)
- Wasserscheid P, van Hal R, Bosmann A, Green Chemistry, 4, 400 (2002)
- Garcia MT, Gathergood N, Scammells PJ, Green Chemistry, 7, 9 (2005)
- Cole AC, Jensen JL, Ntai I, Tran KLT, Weaver KJ, Forbes DC, Davis JH, J. Am. Chem. Soc., 124(21), 5962 (2002)
- Forbes DC, Davis JH, Morrison DW, Tran KLT, Weaver KJ, Abstr. Pap. Am. Chem. Soc., 225, U416 (2003)
- Forbes DC, Weaver KJ, J. Mol. Catal. A-Chem., 214(1), 129 (2004)
- Xing HB, Wang T, Zhou ZH, Dai YY, Ind. Eng. Chem. Res., 44(11), 4147 (2005)
- Xing HB, Wang T, Zhou ZH, Dai YY, J. Mol. Catal. A-Chem., 264(1-2), 53 (2007)
- Ganeshpure PA, Das J, React. Kinet. Catal. Lett., 92(1), 69 (2007)
- Fang D, Zhou XL, Ye ZW, Liu ZL, Ind. Eng. Chem. Res., 45(24), 7982 (2006)
- Gu YL, Shi F, Deng YQ, J. Mol. Catal. A-Chem., 212(1-2), 71 (2004)
- Ganeshpure PA, George G, Das J, ARKIVOC, 273 (2007)
- Ganeshpure PA, George G, Das J, J. Mol. Catal. A: Chem., 279, 182 (2008)
- Zhang HB, Xu F, Zhou XH, Zhang GY, Wang CX, Green Chemistry, 9, 1208 (2007)
- Wei ZJ, Huang Y, Deng SG, Saha D, Liu YX, Ren QL, React. Kinet. Catal. Lett., 95, 257 (2008)
- Yang QW, Wei ZJ, Xing HB, Ren QL, Catal. Commun., 9, 1308 (2008)
- Wang CM, Guo LP, Li HR, Wang Y, Weng JY, Wu LH, Green Chemistry, 8, 603 (2006)
- Animal and vegetable fats and oils-analysis by gas chromatography of methyl ester of fatty acids. In National Standard of China, GB/T 17377 (1998)
- Nguyen HP, Znifeche S, Baboulene M, Synth. Commun., 34, 2085 (2004)
- Joseph T, Sahoo S, Halligudi SB, J. Mol. Catal. A-Chem., 234(1-2), 107 (2005)
- Izak P, Mateus NMM, Afonso CAM, Crespo JG, Sep. Purif. Technol., 41(2), 141 (2005)
- Belafi-Bako K, Dormo N, Ulbert O, Gubicza L, Desalination, 149(1-3), 267 (2002)
- Pera-Titus M, Fite C, Sebastian V, Lorente E, Llorens J, Cunill F, Ind. Eng. Chem. Res., 47, 3213 (2008)
- Al-Asheh S, Banat F, Al-Lagtah N, Chem. Eng. Res. Des., 82(7), 855 (2004)
- Jiang T, Chang YH, Zhao GY, Han BX, Yang GY, Synth. Commun., 34, 225 (2004)
- Li XZ, Eli WJ, J. Mol. Catal. A: Chem., 279, 159 (2008)