Heteropoly acids as catalysts for liquid-phase esterification and transesterification

被引:162
作者
Alsalme, Ali [1 ]
Kozhevnikova, Elena F. [1 ]
Kozhevnikov, Ivan V. [1 ]
机构
[1] Univ Liverpool, Dept Chem, Liverpool L69 7ZD, Merseyside, England
基金
英国工程与自然科学研究理事会;
关键词
Biodiesel; Esterification; Transesterification; Heteropoly acid; Catalysis;
D O I
10.1016/j.apcata.2008.07.027
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Esterification of hexanoic acid and transesterification of ethyl propanoate and ethyl hexanoate with excess methanol (1:20 molar ratio) are tested at 60 degrees C and ambient pressure with a range of HPA catalysts in homogeneous and heterogeneous systems in comparison with conventional homogeneous and solid acid tic activity catalysts such as H2SO4, Amberlyst-15 and zeolites HY and H-Beta. The intrinsic catalyst activity (turnover frequency, TOF) of HPA catalysts is significantly higher than that of the conventional acid catalysts in these reactions. The TOF values decrease with decreasing catalyst acid strength in the order: H3PW12O40 approximate to Cs2,5H0,5PW12O40 > H4SiW12O40 > 15%H3PW12O40/Nb2O5, 15%H3PW12O40/ZrO2, 15%H3PW12O40/TiO2 > H2SO4 > HY, H-Beta > Amberlyst-15. The activity per unit catalyst weight falls in a different order: H2SO4 > H3PW12O40 approximate to H4SiW12O40 > Amberlyst-15 >= Cs2.5H0.5PW12O40 > supported H3PW12O40 > HY, H-Beta. Bulk cesium salt Cs2.5H0.5PW12O40 exhibits high catalytic activity as well as high stability to leaching. Supported HPA catalysts suffer from leaching and exhibit significant contribution of homogeneous catalysis by the leached HPA. (c) 2008 Elsevier B.V. All rights reserved.
引用
收藏
页码:170 / 176
页数:7
相关论文
共 24 条
[1]   Esterification of free fatty acids with methanol using heteropolyacids immobilized on silica [J].
Caetano, C. S. ;
Fonseca, I. M. ;
Ramos, A. M. ;
Vital, J. ;
Castanheiro, J. E. .
CATALYSIS COMMUNICATIONS, 2008, 9 (10) :1996-1999
[2]   Investigation on the esterification of fatty acids catalyzed by the H3PW12O40 heteropolyacid [J].
Cardoso, Abiney L. ;
Augusti, Rodinei ;
Da Silva, Marcio J. .
JOURNAL OF THE AMERICAN OIL CHEMISTS SOCIETY, 2008, 85 (06) :555-560
[3]   Transesterification of vegetable oil to biodiesel using a heteropolyacid solid catalyst [J].
Chai, Fang ;
Cao, Fenghua ;
Zhai, Fengying ;
Chen, Yang ;
Wang, Xiaohong ;
Su, Zhongmin .
ADVANCED SYNTHESIS & CATALYSIS, 2007, 349 (07) :1057-1065
[4]   Chemical routes for the transformation of biomass into chemicals [J].
Corma, Avelino ;
Iborra, Sara ;
Velty, Alexandra .
CHEMICAL REVIEWS, 2007, 107 (06) :2411-2502
[5]   Zirconia-supported 12-tungstophosphoric acid as a solid catalyst for the synthesis of linear alkyl benzenes [J].
Devassy, BM ;
Lefebvre, F ;
Halligudi, SB .
JOURNAL OF CATALYSIS, 2005, 231 (01) :1-10
[6]   Esterification of palmitic acid on the ammonium salt of 12-tungstophosphoric acid: The influence of partial proton exchange on the activity of the catalyst [J].
Giri, BY ;
Rao, KN ;
Devi, BLAP ;
Lingaiah, N ;
Suryanarayana, I ;
Prasad, RBN ;
Prasad, PSS .
CATALYSIS COMMUNICATIONS, 2005, 6 (12) :788-792
[7]   Solid acid catalysis using ion-exchange resins [J].
Harmer, MA ;
Sun, Q .
APPLIED CATALYSIS A-GENERAL, 2001, 221 (1-2) :45-62
[8]   Silica-included heteropoly compounds as solid acid catalysts [J].
Izumi, Y ;
Ono, M ;
Kitagawa, M ;
Yoshida, M ;
Urabe, K .
MICROPOROUS MATERIALS, 1995, 5 (04) :255-262
[9]  
Kozhevnikov I., 2002, CATALYSIS POLYOXOMET, V2
[10]   Catalysis by heteropoly acids and multicomponent polyoxometalates in liquid-phase reactions [J].
Kozhevnikov, IV .
CHEMICAL REVIEWS, 1998, 98 (01) :171-198