The influence of ZSM-5 zeolite composition and crystal size on the in situ conversion of Fischer-Tropsch products over hybrid catalysts

被引:102
作者
Martínez, A [1 ]
López, C [1 ]
机构
[1] Univ Politecn Valencia, CSIC, Inst Tecnol Quim, Valencia 46022, Spain
关键词
Fischer-Tropsch synthesis; gasoline octane; isoparaffins; aromatics; hybrid catalysts; iron catalyst; ZSM-5; zeolite; crystal size; addition of Ga and Pd;
D O I
10.1016/j.apcata.2005.07.038
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
The influence of the composition (Si/Al ratio, addition of Ga and Pd) and crystal size of ZSM-5 zeolite for the direct conversion of syngas to high-octane gasoline products over hybrid catalysts comprising a physical mixture of an iron-based FTS catalyst (KFeCo) and the zeolite has been studied at 310 degrees C, 20 bar, and H-2:CO = 1:1. The presence of the zeolite altered the product distribution towards the formation of gasoline-range isoparaffins and aromatics through the cracking, skeletal isomerization, hydrogen transfer, and aromatization reactions occurring on the zeolite acid sites. The extent of these reactions increased with the density of Bronsted acid sites. A progressive loss of the zeolite activity for the acid-catalyzed reactions occurred with TOS. The stability of the zeolite with TOS was Substantially improved by decreasing its crystallite size, probably by favoring the diffusion of aromatics preventing their further transformation into coke. The incorporation of Ga to the ZSM-5 zeolite enhanced the initial formation of aromatics but increased the deactivation rate of the zeolite by promoting dehydrogenation reactions leading to coke. By contrast, the addition of small amounts of Pd to the ZSM-5 zeolite appeared a good strategy, together with decreasing crystallite size, for improving the useful lifetime of the zeolite. (c) 2005 Elsevier B.V. All rights reserved.
引用
收藏
页码:251 / 259
页数:9
相关论文
共 26 条
[1]   The effect of a higher operating temperature on the Fischer-Tropsch/HZSM-5 bifunctional process [J].
Botes, FG .
APPLIED CATALYSIS A-GENERAL, 2005, 284 (1-2) :21-29
[2]   The addition of HZSM-5 to the Fischer-Tropsch process for improved gasoline production [J].
Botes, FG ;
Böhringer, W .
APPLIED CATALYSIS A-GENERAL, 2004, 267 (1-2) :217-225
[3]   ADVANCES IN FISCHER-TROPSCH CHEMISTRY [J].
CAESAR, PD ;
BRENNAN, JA ;
GARWOOD, WE ;
CIRIC, J .
JOURNAL OF CATALYSIS, 1979, 56 (02) :274-278
[4]   CATALYTIC CRACKING OF GAS-OIL - BENEFITS IN ACTIVITY AND SELECTIVITY OF SMALL Y-ZEOLITE CRYSTALLITES STABILIZED BY A HIGHER SILICON-TO-ALUMINIUM RATIO BY SYNTHESIS [J].
CAMBLOR, MA ;
CORMA, A ;
MARTINEZ, A ;
MOCHOLI, FA ;
PARIENTE, JP .
APPLIED CATALYSIS, 1989, 55 (01) :65-74
[5]   SYNTHESIS GAS CONVERSION TO AROMATIC-HYDROCARBONS [J].
CHANG, CD ;
LANG, WH ;
SILVESTRI, AJ .
JOURNAL OF CATALYSIS, 1979, 56 (02) :268-273
[6]   CONVERSION OF CYCLOHEXENE OVER Y-ZEOLITES - A MODEL REACTION FOR HYDROGEN TRANSFER [J].
CHENG, WC ;
RAJAGOPALAN, K .
JOURNAL OF CATALYSIS, 1989, 119 (02) :354-358
[7]  
CORMA A, 1988, ACS SYM SER, V368, P542
[8]   SYNTHESIS OF MOTOR FUELS FROM HY-ZEOLITE SUPPORTED FISCHER-TROPSCH IRON CATALYSTS [J].
EGIEBOR, NO ;
COOPER, WC ;
WOJCIECHOWSKI, BW .
APPLIED CATALYSIS, 1989, 55 (01) :47-64
[9]   DETERMINATION OF INTEGRATED MOLAR EXTINCTION COEFFICIENTS FOR INFRARED-ABSORPTION BANDS OF PYRIDINE ADSORBED ON SOLID ACID CATALYSTS [J].
EMEIS, CA .
JOURNAL OF CATALYSIS, 1993, 141 (02) :347-354
[10]  
FIATO RA, 1985, Patent No. 4518707