Modification of non-template synthesized ferrierite/ZSM-35 for n-butene skeletal isomerization to isobutylene

被引:79
作者
Xu, WQ
Yin, YG
Suib, SL
Edwards, JC
OYoung, CL
机构
[1] UNIV CONNECTICUT,DEPT CHEM,STORRS,CT 06269
[2] UNIV CONNECTICUT,DEPT CHEM ENGN,STORRS,CT 06269
[3] UNIV CONNECTICUT,INST MAT SCI,STORRS,CT 06269
[4] TEXACO USA INC,CTR RES & DEV,BEACON,NY 12508
关键词
D O I
10.1006/jcat.1996.0324
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
Non-template synthesized ferrierite/ZSM-35 has been successfully modified by removal of non-shape selective acid sites and lowering of the number of acid sites. Modified materials were extensively studied by XRD, FT-IR, NMR, XPS, ammonia TPD, and kinetic evaluations for skeletal isomerization of n-butene to isobutylene. Removal of non-shape selective acid sites from non-template synthesized ferrierite/ZSM-35 greatly suppresses butene dimerization reactions. These non-shape selective acid sites are located inside larger internal pores (as compared to the zeolitic pores) and on the surface of non-template synthesized ferrierite/ZSM-35 materials due to their lower crystallinity. Such non-shape selective acid sites were removed via framework dealumination of the surface with acid treatment. Lowering of the number of acid sites of non-template synthesized ferrierite/ZSM-35 decreases interactions of butene intermediates on adjacent acid sites and was achieved via framework dealumination by steaming. Steaming of non-template synthesized ferrierite/ZSM-35 at higher temperatures or higher steam pressures produces more dealumination and, accordingly, further lowering of the number of acid sites. The presence of Na+/K+ ions gives more resistance to framework dealumination during steaming and the same potential for removing strong and weak acid sites, However, steaming of ferrierite/ZSM-35 of hydrogen form leads to removal of greater amounts of strong acid sites than weak acid sites, Studies have shown that steaming of non-template synthesized ferrierite/ZSM-35 of Na+/K+ forms followed by NH4+ ion exchange and acid washing is an effective modification procedure, Catalytic performances for such modified materials are very similar to those for template-synthesized materials, with respects to yields, selectivities, and catalytic stability. (C) 1996 Academic Press, Inc.
引用
收藏
页码:232 / 244
页数:13
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