Mechanisms of Brönsted and Lewis acids of zeolite on pentenes conversion by in situ DRIFTS
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摘要: 本研究基于原位水热合成和气相浸渍的方法分别合成了含有Brönsted/Lewis酸的Beta分子筛和只含有Lewis酸的AlCl3@Si-Beta样品,并通过原位漫反射红外技术对比研究了Brönsted酸和Lewis酸催化直链和侧链戊烯同分异构体转化作用机理的差异。结果表明,同时含有Brönsted/Lewis酸的Beta分子筛中,Brönsted酸起主要的活化作用,催化戊烯进行异构和叠合反应时均遵循经典的碳正离子机理;而AlCl3@Si-Beta中的Lewis酸不含氢质子或羟基,催化α-戊烯进行双键迁移和2-戊烯的顺反异构反应时遵循AB-AD机理,以类烯丙基物种作为中间体,无法催化戊烯进行骨架异构和叠合反应。Abstract: Zeolites have been extensively used in the chemical and petrochemical industries owing to their tunable acidities and unique pore structures. Beta zeolite with Brönsted and Lewis acids and AlCl3@Si-Beta with only Lewis acid were prepared by hydrothermal synthesis and gas-phase impregnation methods, respectively. Mechanisms differences of Brönsted and Lewis acids on four pentene isomers transformation were investigated by in situ diffraction infrared Fourier transform spectrum (DRIFTS). The results suggested that Brönsted in Beta played a main role in isomerization and oligomerization reactions which all followed classical carbenium ion mechanisms. On the contrary, Lewis acid in AlCl3@Si-Beta without hydrogen proton or hydroxyl catalyzed α-pentene double-bond migration to produce β-pentene and cis-trans isomerization reaction of 2-pentene by AB-AD mechanism with allyl-like species as intermediates, and could not catalyze pentenes skeletal isomerization and oligomerization reactions.
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Key words:
- zeolite /
- Brönsted acid /
- lewis acid /
- pentene isomers /
- mechanism
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表 1 不同样品的织构性质
Table 1 Textual properties of two samples.
Sample Surface area/(m2·g−1) Volume b/
(cm3·g−1)SBET a Smic b Sext c Beta 592.1 335.1 256.9 0.13 AlCl3@Si-Beta 465.7 432.9 32.8 0.17 a: SBET obtained by the BET method, b: Calculated from the t-plot method, c: Calculated from difference value of SBET and Smic 表 2 不同样品的酸性质
Table 2 Acidic properties of samples
Sample Acid types/(μmol Py·g−1) a Brönsted acid b Lewis acid c 30 ℃ 200 ℃ 350 ℃ 30 ℃ 200 ℃ 350 ℃ Beta 160.4 156.1 82.7 445.8 124.9 120.1 AlCl3@Si-Beta 0.0 0.0 0.0 160.9 32.4 12.7 a: Calculated from the band areas of the FT-IR spectra obtained by pyridine desorption at 30, 200, and 350 ℃, b: SBrönsted acid =1.88*A*0.65*0.65/M (A represents peak area at about 1540 cm−1; M represents mass of catalyst), c: SLewis acid = 1.42*A*0.65*0.65/M (A represents peak area at about 1450 cm−1; M represents mass of catalyst) 表 3 不同酸性分子筛催化戊烯反应的产物分布[29]
Table 3 Product distribution of pentene isomers reactions on two zeolites with different acids[29]
Sample Reactant Product distribution n-pentene cis-2-pentene trans-2-pentene 2-methyl-1-butene 2-methyl-2-butene C6 + Beta n-pentene × √ √ − − √ cis-2-pentene √ × √ − − − 2-methyl-1-butene − − √ × √ √ 2-methyl-2-butene − − − √ × √ AlCl3@Si-Beta n-pentene × √ √ × × × cis-2-pentene √ × √ × × × 2-methyl-1-butene × × × × √ × 2-methyl-2-butene × × × √ × × Reaction condition: 10% pentenes in helium and reaction temperature 100 ℃, “√” represents a large amount of product, “×” represents none, “−” represents a very small amount of product which can be ignored -
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