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

Chem. J. Chinese Universities ›› 2010, Vol. 31 ›› Issue (6): 1206.

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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.

Abstract

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:

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[J]. Chem. J. Chinese Universities, 2010, 31(6): 1206.

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

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