有序介孔氧化铝的制备及其在丁烯歧化中的应用.pdf

第40卷第7期
燃料化学学报
Vol 40 No. 7
012年7月
Journal of Fuel Chemistry and Technol
Jul,2012
文章编号:0253-2409(2012)07-0855-06
有序介孔氧化铝的制备及其在丁烯歧化中的应用
李睿,袁桂梅,陈胜利,华德润,周政,桑磊,陈爱城
(中国石油大学重质油国家重点实验室,北京10249)
摘要:采用有机铝源及阴离子模板剂制备了高比表面积、大孔容、窄孔径分布的有序介孔氧化铝(Al2O3)载体,研究了铝源
水解速率、模板剂碳链长度以及洗涤介质等因索对有序介孔氧化铝载体合成的颩响。实验结果表明,提高铝源水解速率和用
乙醇溶剂洗涤Al2O,前躯体都有利于Al203载体形成有序介孔结构,所得Al2O3载体的孔径和孔体积随着模板剂碳链长度的
增加而増大。分别用有序介孔Al2O3和普通介孔Al2O3为载体,采用浸渍法负载氧化铼(Rc2O,)制备了铼基催化剂,并用于
评价丁烯歧化合成丙烯的反应性能。实验结果表明,铼基有序介孔催化剂(Re/OMA)的丁烯歧化性能显著优于普通铼基介
孔催化剂(Re/MA),丁烯转化率高于50%,丙烯选择性约60%,丙烯收率达30%,催化剂寿命明显延长。
关键词;有序介孔氧化铝;铼基催化剂;丁烯歧化;丙烯
中图分类号:TQ424文献标识码:A
Preparation of ordered mesoporous alumina
and its catalytic application in metathesis of butene
LI Rui, YUAN Gui-mei, CHEN Sheng-li, HUA De-run, ZHOU Zheng, SANG Lei, CHEN Ai-cheng
(State Key Laboratory of Heavy Oil Processing, China University of Petroleum( Beijin), Beijing 102249, Chin
Abstract Ordered mesoporous alumina(OMA )with high surface area, large pore volume, and narrow pore
size distribution was synthesized from organic aluminum precursors and anionic templates; the influence of
various preparation parameters such as hydrolysis speed of the aluminum precursor, chain length of the carboxylic
templates and washin medium on the properties of as-synthesized OMA was investigated. With OMA as
support, trhenium-based catalyst was prepared by incipient-wetness impregnation method and used in the
metathesis of butene to propene. The results showed that increasing hydrolysis speed of the aluminum precursor
as well as using ethanol as the washing medium are beneficial to the formation of the organized pore structure;
the pore volume and pore diameter of as-synthesized OMA increase with an increase of the chain length of the
carboxylic templates used here Compared with the rhenium catalyst supported on conventional mesoporous
alumina, the mhenium-based catalyst prepared with OMA as the support exhibits better performance in the
metathesis of butane, i. e. higher selectivity to propene and longer catalytic life; the conversion of butane and
selectivity to propene reach 50% and 60%, respectively
Key words: ordered mesoporous alumina; rhenium catalyst; butene metathesis; propene
有序介孔材料具有高度规整的孔道、高比表面高于以普通Al203作载体的催化剂的催化性能。因
积、窄孔径分布等优点,在催化及其他工业领域都有此,研究制备以有序介孔Al203为载体的催化剂及
着巨大的应用价值和广泛的应用前景。而Al203材其烯烃歧化性能,具有非常重要的意义
料以其独特的吸附性能、催化特性等引起了研究者
本实验用模板法制备了有序介孔A203载体,
广泛的亲睐,制备有序介孔Al203材料和拓展其应并考察了不同铝源、模板剂和后处理方式等对制备
用领域已经成为研究者的重要研究课题。
有序介孔Al203孔结构性质的影响。分别以制备的
目前,人们已经研究出多种合成有序介孔有序介孔A203和普通介孔Al203为载体,采用浸
A2O2材料的方法,但对合成过程中影响有序介孔渍法负载Re2O1制备了Re20,/Al203催化剂,并用
Al203孔结构性质的因素仍不明确。因此,研于评价丁烯岐化生产丙烯的反应性能。
究优化合成过程中影响有序介孔Al20。孔结构的因1实验部分
素是十分必要的。同时,研究者发现在烯烃歧1.1催化剂的制备
化反应中,以有序介孔Al20,作载体的催化剂明显1.1.1有序介孔氧化铝载体的制备
收稿日期:2011-10-15;修回日期:2011-1203。
基金项目:中国石油天然气集团公司科技创新基金(2009D-5006-0542)。
联系作者:袁桂梅,E-mail: mayuan(@cup.edu.ca