Methylbenzene chemistry on zeolite HBeta: Multiple insights into methanol-to-olefin catalysis

被引:182
作者
Sassi, A
Wildman, MA
Ahn, HJ
Prasad, P
Nicholas, JB
Haw, JF
机构
[1] Univ So Calif, Locker Hydrocarbon Res Inst, Los Angeles, CA 90089 USA
[2] Univ So Calif, Dept Chem, Los Angeles, CA 90089 USA
关键词
D O I
10.1021/jp013392k
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 reactions of 1,2,4-trimethylbenzene, 1,2,4,5-tetramethylbenzene (durene), pentamethylbenzene, hexamethylbenzene (HMB), ethylbenzene, and cumene were studied on large-pore zeolite HBeta catalysts, either alone or with co-injection of methanol-C-13. The reactivity of the methylbenzenes alone increased with increasing methyl substitution, as did selectivity for propene over ethylene. Disproportionation occurred for all methylbenzenes studied, in the case of HMB, pentamethylbenzene was a major volatile product, and we inferred that the heptamethylbenzenium cation also formed and remained in the catalyst. Substantially higher yields of olefins were obtained when methylbenzenes were co-reacted with methanol-C-13. Ethylbenzene alone was unreactive at 350 degreesC. but when injected with five equivalents of methanol-13C, ethylbenzene formed ethylene-C-12(2) with very high selectivity. These and other experiments led to a detailed description of the hydrocarbon pool mechanism for MTO chemistry with side-chain methylation as the predominant route to olefins and the paring reaction as a possible minor pathway.
引用
收藏
页码:2294 / 2303
页数:10
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