Kinetic study on the effect of solvent in 'vapor-phase' Beckmann rearrangement of cyclohexanone oxime on silicalite-1

被引：42

作者：

Komatsu, T ^{[1
]}

Maeda, T ^{[1
]}

Yashima, T ^{[1
]}

机构：

[1] Tokyo Inst Technol, Dept Chem, Meguro Ku, Tokyo 1528550, Japan

来源：

MICROPOROUS AND MESOPOROUS MATERIALS | 2000年 / 35-6卷

关键词：

Beckmann rearrangement; epsilon-caprolactam; cyclohexanone oxime; kinetic; silicalite; solvent; zeolite;

D O I：

10.1016/S1387-1811(99)00218-8

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The effect of solvents in the 'vapor-phase' Beckmann rearrangement of cyclohexanone oxime was studied on silicalite-1 catalyst through kinetic measurements. Solvents with various polarities were examined for the reaction. It was found that ethanol, which has medium polarity, was effective in the formation of epsilon-caprolactam. The rate of epsilon-caprolactam formation fitted the Langmuir-type rate equation for the various solvents. This experimental rate equation was explained by the reaction scheme where the desorption of epsilon-caprolactam caused by the attack of a solvent molecule was the rate-determining step. IR measurements confirmed the desorption of epsilon-caprolactam induced by the attack of the ethanol molecule. Ethanol and methanol gave specific improvements in the yield of epsilon-caprolactam probably due to the effect of OH groups. However, alcohols with higher carbon numbers lowered the yield owing to their hydrophobic nature. Therefore, ethanol and methanol are the most effective solvents for the 'vapor-phase' Beckmann rearrangement of cyclohexanone oxime on silicalite-1. (C) 2000 Elsevier Science B.V. All rights reserved.

引用

页码：173 / 180

页数：8

共 12 条

[1] SIMS/XPS study on the deactivation and reactivation of B-MFI catalysts used in the vapour-phase Beckmann rearrangement [J].

Albers, P ;

Seibold, K ;

Haas, T ;

Prescher, G ;

Holderich, WF .

JOURNAL OF CATALYSIS, 1998, 176 (02) :561-568

[2] Development of advanced zeolite catalysts for the vapor phase Beckmann rearrangement of cyclohexanone oxime [J].

Dai, LX ;

Iwaki, Y ;

Koyama, K ;

Tatsumi, T .

APPLIED SURFACE SCIENCE, 1997, 121 :335-338

[3]

DAI LX, 1996, J CHEM SOC CHEM COMM, P1071

[4] VAPOR-PHASE BECKMANN REARRANGEMENT OF CYCLOHEXANONE OXIME OVER MEL TYPE ZEOLITES [J].

REDDY, JS ;

RAVISHANKAR, R ;

SIVASANKER, S ;

RATNASAMY, P .

CATALYSIS LETTERS, 1993, 17 (1-2) :139-140

[5] Vapour-phase Beckmann rearrangement using B-MFI zeolites [J].

Roseler, J ;

Heitmann, G ;

Holderich, WF .

APPLIED CATALYSIS A-GENERAL, 1996, 144 (1-2) :319-333

[6] Acidity control and catalysis of pentasil zeolites [J].

Sato, H .

CATALYSIS REVIEWS-SCIENCE AND ENGINEERING, 1997, 39 (04) :395-424

[7] FT-IR STUDY OF THE BECKMANN REARRANGEMENT OVER PENTASIL-TYPE ZEOLITE [J].

SATO, H ;

HIROSE, K ;

NAKAMURA, Y .

CHEMISTRY LETTERS, 1993, (12) :1987-1990

[8]

SATO H, 1986, NEW DEV ZEOLITE SCI, P755

[9] CATALYST DEACTIVATION OF HIGH-SILICA HZSM-5 IN THE BECKMANN REARRANGEMENT REACTION OF CYCLOHEXANONE OXIME [J].

TAKAHASHI, T ;

NISHI, M ;

TAGAWA, Y ;

KAI, T .

MICROPOROUS MATERIALS, 1995, 3 (4-5) :467-471

[10] CATALYTIC PROPERTIES OF TITANIUM SILICALITES .4. VAPOR-PHASE BECKMANN REARRANGEMENT OF CYCLOHEXANONE OXIME [J].

THANGARAJ, A ;

SIVASANKER, S ;

RATNASAMY, P .

JOURNAL OF CATALYSIS, 1992, 137 (01) :252-256

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