The roles of acid strength and pore diffusion in the enhanced cracking activity of steamed Y zeolites

被引:156
作者
Williams, BA
Babitz, SM
Miller, JT
Snurr, RQ
Kung, HH
机构
[1] Northwestern Univ, Dept Chem Engn, Evanston, IL 60208 USA
[2] Northwestern Univ, VN Ipatieff Lab, Evanston, IL 60208 USA
[3] Amoco Chem, Naperville, IL 60566 USA
基金
美国国家科学基金会;
关键词
zeolite Y; hydrocarbon cracking; cracking mechanism on zeolites; cracking; effect of steaming; diffusion effect on cracking; effect of acid strength; effect of diffusion;
D O I
10.1016/S0926-860X(98)00264-6
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
Steamed HY or ultrastable Y (H-USY) zeolites are active hydrocarbon cracking catalysts. The high activity of H-USY compared to HY zeolite has been previously explained by the generation of unusually strong and active Bronsted acid sites, or an increase in the number of accessible sites in a micropore diffusion-controlled reaction. However, neither model explains the accumulated literature observations. A model is proposed that incorporates a change in the predominant cracking reaction mechanism as a function of alkane conversion and the very different rates of these mechanisms. Additionally, an oligomeric cracking mechanism is introduced to explicitly account for coking and deactivation of the catalyst. The model is capable of accounting for most literature results. It concludes that the large enhancement in cracking activity by steaming is due to a proportionally smaller increase in external surface area of the zeolite crystals and possibly a small increase in the specific initiation activity of each site. These small changes lead to a much larger overall effect because of the sensitive dependence of oligomeric cracking acid, to a lesser extent, bimolecular cracking on the alkene partial pressure. (C) 1999 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:161 / 175
页数:15
相关论文
共 80 条
[1]   ROLE OF BRONSTED AND LEWIS ACID SITES DURING CRACKING REACTIONS OF ALKANES [J].
ABBOT, J .
APPLIED CATALYSIS, 1989, 47 (01) :33-44
[2]   CALORIMETRIC INVESTIGATION OF THE EFFECT OF DEALUMINATION ON THE ACIDITY OF ZEOLITES [J].
AUROUX, A ;
BENTAARIT, Y .
THERMOCHIMICA ACTA, 1987, 122 (01) :63-70
[3]   Surface equilibration in adsorption microcalorimetry of bases on H-USY [J].
Babitz, SM ;
Williams, BA ;
Kuehne, MA ;
Kung, HH ;
Miller, JT .
THERMOCHIMICA ACTA, 1998, 312 (1-2) :17-25
[4]   Role of Lewis acidity in the deactivation of USY zeolites during 2-methylpentane cracking [J].
Babitz, SM ;
Kuehne, MA ;
Kung, HH ;
Miller, JT .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 1997, 36 (08) :3027-3031
[5]  
BABITZ SM, IN PRESS APPL CATAL
[6]   THE INACTIVITY OF EXTRA FRAMEWORK ALUMINUM IN THE CRACKING OF 2,3-DIMETHYLBUTANE ON USHY [J].
BAMWENDA, GR ;
ZHAO, YX ;
WOJCIECHOWSKI, BW .
JOURNAL OF CATALYSIS, 1994, 150 (02) :243-253
[7]   THE EFFECTS OF EFAL EXTRACTION ON 2-METHYLPENTANE CRACKING OVER STEAMED HY [J].
BAMWENDA, GR ;
ZHAO, YX ;
GROTEN, WA ;
WOJCIECHOWSKI, BW .
JOURNAL OF CATALYSIS, 1995, 157 (01) :209-221
[8]   X, Y, ALUMINUM-DEFICIENT, AND ULTRASTABLE FAUJASITE-TYPE ZEOLITES .3. CATALYTIC ACTIVITY [J].
BARTHOMEUF, D ;
BEAUMONT, R .
JOURNAL OF CATALYSIS, 1973, 30 (02) :288-297
[9]   INFLUENCE OF FRAMEWORK AND NONFRAMEWORK ALUMINUM ON THE ACIDITY OF HIGH-SILICA, PROTON-EXCHANGED FAU-FRAMEWORK ZEOLITES [J].
BEYERLEIN, RA ;
MCVICKER, GB ;
YACULLO, LN ;
ZIEMIAK, JJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (07) :1967-1970
[10]  
BEYERLEIN RA, 1986, ACS M DIV PETROL CHE, V31, P190