TiO2柱层状HTiNbO5的合成及在环己酮肟气相Beckmann重排反应中的催化性能

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (6): 1206.

TiO₂柱层状HTiNbO₅的合成及在环己酮肟气相Beckmann重排反应中的催化性能

郭宪吉¹, 侯文华², 刘淑敏¹, 李利民¹

1. 郑州大学化学系, 郑州 450001;
2. 南京大学介观化学教育部重点实验室, 南京 210093

收稿日期:2009-11-18 出版日期:2010-06-10 发布日期:2010-06-10
通讯作者: 郭宪吉, 男, 博士, 教授, 主要从事层柱材料和有序孔材料等催化新材料、催化反应以及燃料电池方面的研究. E-mail: guoxj@zzu.edu.cn
基金资助:
河南省教育厅自然科学基础研究基金(批准号: 2008A150024)资助.

Preparation of TiO₂-pillared HTiNbO₅ and Catalytic Performance in Vapor Phase Beckmann Rearrangement Reaction of Cyclohexanone Oxime

GUO Xian-Ji^1*, HOU Wen-Hua², LIU Shu-Min¹, LI Li-Min¹

1. Department of Chemistry, Zhengzhou University, Zhengzhou 450001, China;
2. Key Laboratory of Mesoscopic Chemistry, Ministry of Education, Nanjing University, Nanjing 210093, China

Received:2009-11-18 Online:2010-06-10 Published:2010-06-10
Contact: GUO Xian-Ji. E-mail: guoxj@zzu.edu.cn
Supported by:
河南省教育厅自然科学基础研究基金(批准号: 2008A150024)资助.

摘要/Abstract

摘要：

钛酸异丙酯(TIP)、CH₃COOH和H₂O按体积比1∶16∶40混合后得到Ti(Ⅳ)多聚阳离子柱化液, 与正癸胺插层钛铌酸盐进行交换反应后制得钛(Ⅳ)多聚阳离子插层钛铌酸盐, 其层间距为1.70 nm. 在空气气氛中于623 K焙烧处理后, 所得产品能保持良好的层柱结构. 在空气气氛中于723 K焙烧后所得的TiO₂柱层状钛铌酸(TiO₂-HTiNbO₅), 其层间距为0.97 nm, 比表面积为89 m²/g. 以TiO₂-HTiNbO₅为载体, 用浸渍法制备了一系列B₂O₃负载量不同的负载型样品B₂O₃/TiO₂-HTiNbO₅, 考察了它们在环己酮肟气相Beckmann重排反应中的催化性能并测试了它们的红外光谱. B₂O₃/TiO₂-HTiNbO₅的催化性能优于TiO₂-HTiNbO₅. 在B₂O₃负载质量分数为7.31%的催化剂上, 环己酮肟转化率接近100%且在4.5 h内无明显改变, 己内酰胺选择性接近90%. 红外光谱分析结果表明, 当B₂O₃负载量很低时, 硼组分高度分散于载体TiO₂-HTiNbO₅表面, 并主要以BO₄结构形式存在; 当B₂O₃负载质量分数高于7.31%时, BO₃结构形式在数量上占优势. 将催化性能与红外光谱结果关联后可知, 对于负载型样品B₂O₃/TiO₂-HTiNbO₅, 表面的BO₃和BO₄两种结构形式在环己酮肟气相Beckmann重排反应中具有协同促进作用.

关键词: TiO2柱层状钛铌酸; 逐步离子交换; 己内酰胺; 环己酮肟气相Beckmann重排反应

Abstract:

A mixture of titanium isopropoxide, acetic acid and deionized water in a volume ratio of 1∶16∶40 generated a solution containing Ti(Ⅳ) polycation species, which was allowed to exchange with alkylammo-nium ions in the interlayers of the n-decylamine-preswelled titanoniobate. This exchange reaction led to the formation of Ti(Ⅳ) polycation-intercalated layered titanoniobate with an interlayer distance of 1.70 nm. The ordered layered structure of the novel material was still retained upon calcination at 623 K. Characterizations of XRD and N₂ adsorption-desorption isotherms indicated that the TiO₂-pillared HTiNbO₅ (abbreviated to TiO₂-HTiNbO₅) obtained by calcination at 723 K in air environment was a porous layered materials with an interlayer distance of 0.97 nm and a BET specific surface area of 89 m²/g. The vapor phase Beckmann rearrangement reaction of cyclohexanone oxime was studied with TiO₂-HTiNbO₅ and B₂O₃/TiO₂-HTiNbO₅ as catalysts. The cyclohexanone oxime conversion and the selectivity for the formation of ε-caprolactam on B₂O₃/TiO₂-HTiNbO₅ were higher than those on TiO₂-HTiNbO₅. The B₂O₃/TiO₂-HTiNbO₅ catalyst with B₂O₃ loading mass fraction of 7.31% exhibited a near-100% conversion of the oxime within 4.5 h and a near 90% selectivity for ε-caprolactam. FTIR spectra indicated that highly dispersed BO₄ species were present in the surface of B₂O₃/TiO₂-HTiNbO₅ with a low B₂O₃ loading; for the B₂O₃/TiO₂-HTiNbO₅ samples with a B₂O₃ loading higher than 7.31%, BO₃ species were dominant. BO₄ and BO₃ species on the surface of TiO₂-HTiNbO₅ showed synergistic promotion effect for vapor-phase Beckmann rea-rrangement reaction of cyclohexanone oxime.

Key words: TiO2-pillared HTiNbO5; Step-wise ion exchange; ε-Caprolactam; Vapor-phase Beckmann rearrangement reaction of cyclohexanone oxime

TrendMD:

郭宪吉, 侯文华, 刘淑敏, 李利民. TiO₂柱层状HTiNbO₅的合成及在环己酮肟气相Beckmann重排反应中的催化性能. 高等学校化学学报, 2010, 31(6): 1206.

GUO Xian-Ji*, HOU Wen-Hua, LIU Shu-Min, LI Li-Min. Preparation of TiO₂-pillared HTiNbO₅ and Catalytic Performance in Vapor Phase Beckmann Rearrangement Reaction of Cyclohexanone Oxime. Chem. J. Chinese Universities, 2010, 31(6): 1206.

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TiO₂柱层状HTiNbO₅的合成及在环己酮肟气相Beckmann重排反应中的催化性能

Preparation of TiO₂-pillared HTiNbO₅ and Catalytic Performance in Vapor Phase Beckmann Rearrangement Reaction of Cyclohexanone Oxime

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