MCM-41催化苯甲醚酰化反应.pdf

石油化
2013年第42卷第7期
PETROCHEMICAL TECHNOLOGY
787
Siw/Zro2MCM-41催化苯甲醚酰化反应
汤明慧,张波,吴磊
浙江工业大学化学工程与材料学院工业催化研究所,浙江杭州310014
[摘要]采用逐层浸渍法制备了MCM-41介孔分子筛负载zrO2及硅钨酸(SiW)催化剂,考察了催化剂在以苯甲醚为原料、乙
酸酐为酰化试剂的 Friedel- Crafts酰化反应中的催化活性,同时对催化剂进行XRD、N吸-脱附测试、DSC、FTIR、NH1-TPD
等表征,研究了ZrO2与SiW及载体之间的相互作用对催化剂活性的影响。实验结果表明,SiW直接负载到MCM-41后,SiW与
载体发生相互作用使 Keggins结构发生畸变,导致活性下降;但SiW通过ZrO2接枝负载到MCM-41后,SiW较好地分散在载体
表面且保持了完整的 Keggin结构,SiW与zrO2』间的相互作用增加了催化剂上强酸中心的数目,显著提高了催化活性。催化剂
的最佳制备条件为:ZrO2负载量20%(w),SiW负载量60%(w),焙烧温度200℃;最住反应条件为:反应时间4h,反应温度
110℃,催化剂用量为02g(基于10mmol乙較酐),苯甲醚与乙酸酐的摩尔比10
[关键词]砗钨酸/化锆MCM-41介孔分子筛催化剂;苯甲醚; Friedel- Crafts酰化反应
[文章编号]1000-8144(2013)07-0787-08
[中图分类号]」TQ426
文献标志码]A
Friedel-crafts Acylation of Anisole over Siw/ Zro /MCM-41
Tang Minghui, Zhang Bo, Wu Le
Institute of Industrial Catalysis, College of Chemical Engineering and Materials, Zhejiang University of Technology
Hangzhou Zhejiang 310014, China)
I Abstract J MCM-41 molecular sieve supported tungstosilicic acid(Siw)zirconia catalysts(iw/
Zro /M)were prepared through impregnation and characterized by means of XRD, N2 adsorption-
desorption, DSC, FTIR and NH -TPD. Their catalytic activities in the Friedel-crafts acylation of
anisole with acetic anhydride were investigated and compared to those of Siw directly supported on
Mcm-41(Siw/M)and bulk Siw. The effects of the interactions between Zro2, Siw and the support
on their catalytic activities were studied. The results showed that the catalytic activity of Siw/M was
lower than that of bulk Siw, due to the distortion of Siw Keggin structure caused by the interaction
between Siw and the support. However, when Siw was supported on Zro2-grafted MCM-41, an
obvious increase in catalytic activity was observed, which could be attributed to the increase of stron
acidic sites on the catalyst surface due to the fine dispersion of Siw on the support and the interaction
between Siw and Zro The optimal preparation conditions for the Si W/Zro /M catalyst were: Zro
loading of 20%(w), Siw loading of 60%(w)and calcination temperature of 200 C. The optimal
acylation reaction conditions were: reaction temperature of 110 C, reaction time of 4 h, catalyst
dosage of 0. 2 g(based on 10 mmol acetic anhydride), and mole ratio of anisole to acetic anhydride of 10.
L Keywords tungstosilicic acid/ zirconia/mcm-41 mesopore molecular sieve catalyst; anisole
Friedel-crafts acylation
对甲氧基苯乙酮是一种重要的香料和医药中间新型催化剂(固体超强酸58]、分子筛
杂多
体。日前主要以苯甲醚为原料,乙酰氯或乙酸酐为酸31等)可以克服上述缺点。杂多酸是一类具
酰化试剂,采用催化剂经 Friedel- Crafts化反应制
得2)。常用的催化剂为均相催化剂,包括金属氯
[收稿日期」2012-12-17;[修改稿日期」2013-03-18
[作者简介」汤明慧(1990-),女,河南省信阳市人,硕土生,
化物或强无机酸,此类催化剂存在使用量大、与产
电话0571-88320417,电邮sweethourl214C163.com。联系人
物难分离、严重腐蚀设备、污染环境等缺点34」。张波,电话0571-89047,电郎210000 zjut. edu. cn