Beckmann rearrangement over phosphotungstic acid/SiMCM-41 cyclohexanone oxime to ε-caprolactam

被引:53
作者
Maheswari, R
Shanthi, K
Sivakumar, T
Narayanan, S [1 ]
机构
[1] Indian Inst Chem Technol, Inorgan & Phys Chem Div, Hyderabad 500007, Andhra Pradesh, India
[2] Anna Univ, Dept Chem, Madras 600025, Tamil Nadu, India
关键词
beckmann rearrangement; cyclohexanone oxime; epsilon-caprolactam; SiMCM-41; phosphotungstic acid;
D O I
10.1016/S0926-860X(03)00182-0
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Vapor-phase Beckmann rearrangement of cyclohexanone oxime to epsilon-caprolactam is reported for the first time on phosphotungstic acid (MA)-supported SiMCM-41 catalyst. The catalyst was prepared in the laboratory following standard procedures and was characterised by XRD and FT-IR. By N-2 adsorption, BET surface area, pore size and pore diameter were measured. The conversion of cyclohexanone oxime over the catalyst was studied in the temperature region of 250-400 degreesC using mainly acetonitrile as a solvent at different contact times. Increase in the reaction temperature to 325 degreesC enhances oxime conversion and the selectivity of epsilon-caprolactam. An impressive catalytic performance of cyclohexanone oxime conversion >99% and epsilon-caprolactam selectivity of 75% was observed on 30 wt.% PWA/SiMCM-41 at 325 degreesC using a feed containing10 wt.% oxime in acetonitrile at WHSV = 3.24 h(-1). The catalytic efficiency for this rearrangement reaction was studied, varying the PWA content from 10 to 50 wt.% on SiMCM-41 and also using benzene and ethanol as alternate solvents in place of acetonitrile. The rearrangement reaction and epsilon-caprolactam selectivity with respect to catalyst physical characteristics, PWA content and type of solvent are discussed. (C) 2003 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:291 / 301
页数:11
相关论文
共 45 条
[1]   BECKMAN REARRANGEMENT OF CYCLOHEXANONE-OXIME ON HNAY ZEOLITES - KINETIC AND SPECTROSCOPIC STUDIES [J].
AUCEJO, A ;
BURGUET, MC ;
CORMA, A ;
FORNES, V .
APPLIED CATALYSIS, 1986, 22 (02) :187-200
[2]   A NEW FAMILY OF MESOPOROUS MOLECULAR-SIEVES PREPARED WITH LIQUID-CRYSTAL TEMPLATES [J].
BECK, JS ;
VARTULI, JC ;
ROTH, WJ ;
LEONOWICZ, ME ;
KRESGE, CT ;
SCHMITT, KD ;
CHU, CTW ;
OLSON, DH ;
SHEPPARD, EW ;
MCCULLEN, SB ;
HIGGINS, JB ;
SCHLENKER, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (27) :10834-10843
[3]   Aluminum incorporation in MCM-41 mesoporous molecular sieves [J].
Busio, M ;
Janchen, J ;
vanHooff, JHC .
MICROPOROUS MATERIALS, 1995, 5 (04) :211-218
[4]   Beckmann rearrangement of cyclohexanone oxime over mesoporous Si-MCM-41 and Al-MCM-41 molecular sieves [J].
Chaudhari, K ;
Bal, R ;
Chandwadkar, AJ ;
Sivasanker, S .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2002, 177 (02) :247-253
[5]   STUDIES ON MESOPOROUS MATERIALS .1. SYNTHESIS AND CHARACTERIZATION OF MCM-41 [J].
CHEN, CY ;
LI, HX ;
DAVIS, ME .
MICROPOROUS MATERIALS, 1993, 2 (01) :17-26
[6]   Solvent effects in the liquid phase Beckmann rearrangement of 4-hydroxyacetophenone oxime over H-Beta catalyst [J].
Chung, YM ;
Rhee, HK .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2000, 159 (02) :389-396
[7]   BECKMANN REARRANGEMENT OF CYCLOHEXANONE OXIME ON ZEOLITES [J].
CORMA, A ;
GARCIA, H ;
PRIMO, J ;
SASTRE, E .
ZEOLITES, 1991, 11 (06) :593-597
[8]   ACIDITY AND STABILITY OF MCM-41 CRYSTALLINE ALUMINOSILICATES [J].
CORMA, A ;
FORNES, V ;
NAVARRO, MT ;
PEREZPARIENTE, J .
JOURNAL OF CATALYSIS, 1994, 148 (02) :569-574
[9]   VAPOR-PHASE BECKMANN REARRANGEMENT OF THE CYCLOHEXANONE OXIME CATALYZED BY AIPO4-GAMMA-AL2O3 SYSTEMS [J].
COSTA, A ;
DEYA, PM ;
SINISTERRA, JV ;
MARINAS, JM .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1980, 58 (12) :1266-1270
[10]   THE RELATIONSHIP BETWEEN ACIDITY OF ALUMINAS AND THEIR SELECTIVITY IN THE CONVERSION OF CYCLOHEXANONE OXIME INTO CAPROLACTAM [J].
CURTIN, T ;
MCMONAGLE, JB ;
HODNETT, BK .
CATALYSIS LETTERS, 1993, 17 (1-2) :145-150