S-1催化环己酮肟气相Beckmann重排反应动力学

doi:10.3969/j.issn.0438-1157.2013.03.019

化工学报 ›› 2013, Vol. 64 ›› Issue (3): 924-930.DOI: 10.3969/j.issn.0438-1157.2013.03.019

• 催化、动力学与反应器 • 上一篇下一篇

S-1催化环己酮肟气相Beckmann重排反应动力学

金星, 孟凡会, 王书海, 王亚权

天津大学化工学院,绿色合成与转化教育部重点实验室,天津 300072

收稿日期:2012-05-15 修回日期:2012-07-18 出版日期:2013-03-05 发布日期:2013-03-05
通讯作者: 王亚权
作者简介:金星(1988—),女,硕士研究生。
基金资助:
国家自然科学基金项目(21276183)。

Kinetics of S-1 catalyzed vapor phase Beckmann rearrangement of cyclohexanone oxime to caprolactam

JIN Xing, MENG Fanhui, WANG Shuhai, WANG Yaquan

Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300072, China

Received:2012-05-15 Revised:2012-07-18 Online:2013-03-05 Published:2013-03-05
Supported by:
supported by the National Natural Science Foundation of China(21276183).

摘要/Abstract

摘要： 目前尼龙6生产中主要采用发烟硫酸催化环己酮肟液相Beckmann重排制己内酰胺,副产大量硫酸铵,而且存在设备腐蚀等问题。采用气相重排法可以克服上述缺点。本工作在以前得到的优化反应条件下,根据实验并采用催化剂失活的Wojciechowski模型获得了S-1催化环己酮肟气相Beckmann重排制己内酰胺反应动力学方程及参数。该模型将催化剂的活性与在线反应时间相关联,进而可以计算任何在线反应时间时催化剂的失活速率,或者根据要求的转化率最低允许值计算催化剂能在线反应的时间。

关键词: 环己酮肟, Beckmann重排, 己内酰胺, S-1

Abstract: Caprolactam,the intermediate for the production of Nylon-6,is mainly produced through sulfuric acid catalyzed liquid phase Beckmann rearrangement of cyclohexanone oxime.This process has several disadvantages,such as the corrosion of reactors and by-production of a large amount of ammonium sulfate.These shortcomings can be prevented by vapor phase Beckmann rearrangement.In this work,the kinetics of vapor phase Beckmann rearrangement of cyclohexanone oxime to caprolactam was studied by both experiments and modeling.The results showed that the changes of catalyst activity with online reaction time could be correlated with the catalyst deactivation model developed by Wojciechowski,from which the kinetic equation and the corresponding parameters of the reaction were obtained.The results could be used to calculate deactivation rates at any online reaction time or catalyst life at the permissible lower conversion.

Key words: cyclohexanone oxime, Beckmann rearrangement, caprolactam, S-1

中图分类号:

TQ013.2

金星, 孟凡会, 王书海, 王亚权. S-1催化环己酮肟气相Beckmann重排反应动力学[J]. 化工学报, 2013, 64(3): 924-930.

JIN Xing, MENG Fanhui, WANG Shuhai, WANG Yaquan. Kinetics of S-1 catalyzed vapor phase Beckmann rearrangement of cyclohexanone oxime to caprolactam[J]. CIESC Journal, 2013, 64(3): 924-930.

参考文献 24

[1]	Cheng Liquan(程立泉).Technologies for the production of caprolactam[J].Chemical Industry and Engineering Progress(化工进展),2005,24 (5):565-567
[2]	Tao Weichuan(陶伟川),Mao Dongsen(毛东森),Xia Jianchao(夏建超),Chen Qingling(陈庆龄),Hu Ying(胡英).Effect of hydrofluoric acid post-treatments on catalytic performance of silicalite-1 for vapor-phase Beckmann rearrangement of cyclohexanone oxime[J].Chinese Journal of Catalysis(催化学报),2006,27(3):245-249
[3]	Ichihashi H,Ishida M,Shiga A,Kitamura M,Suzuki T,Suenobu K,Sugita K.The catalysis of vapor-phase Beckmann rearrangement for the production of ε-caprolactam[J].Catalysis Surveys From Asia,2003,7(4):261-270
[4]	Meng F H,Wang Y Q,Wang L N,Yang R M,Zhang T.Influence of Br- and Na+ in synthesis of silicalite-1 on catalytic performance in vapor phase Beckmann rearrangement of cyclohexanone oxime[J].Journal of Molecular Catalysis A:Chemical,2011,335 (1/2):105-111
[5]	Sato H,Hirose K I,Nakamura Y.FT-IR study of the Beckmann rearrangement over pentasil-type zeolite[J].Chemistry Letters,1993,22(12):1987-1990
[6]	Tao W,Mao D,Xia J,Chen Q,Hu Y.A novel modification for silicalite-1 with high stability and selectivity in vapor phase Beckmann rearrangement of cyclohexanone oxime[J].Chemistry Letters,2005,34(4):472-473
[7]	Costa A,Deyá P M,Sinisterra J V,Marinas J M.Vapor phase Beckmann rearrangement of the cyclohexanone oxime catalyzed by AlPO4-γAl2O3 systems[J].Canadian Journal of Chemistry,1980,58:1266-1270
[8]	Burguet M C,Aucejo A,Corma A.Kinetics of and catalyst decay accompanying the gas phase rearrangement of cyclohexanone-oxime over a hy ultrastable zeolite[J].Canadian Journal of Chemical Engineering,1987,65(6):944-949
[9]	Takahashi T,Nishi M,Tagawa Y,Kai T.Catalyst deactivation of high-silica HZSM-5 in the Beckmann rearrangement reaction of cyclohexanone oxime[J].Microporous Materials,1995,3(4/5):467-471
[10]	Takahashi T,Nasution M N A,Kai T.Effects of acid strength and micro pore size on ε-caprolactam selectivity and catalyst deactivation in vapor phase Beckmann rearrangement over acid solid catalysts[J].Applied Catalysis,A:General,2001,210(1/2):339-344
[11]	Takahashi T,Kai T,Nakao E.Catalyst deactivation in the Beckmann rearrangement of cyclohexanone oxime over HZSM-5 zeolite and silica-alumina catalysts[J].Applied Catalysis,A:General,2004,262(2):137-142
[12]	Takahashi T,Nakanishi M,Kai T.Effect of micropore size on catalyst deactivation in vapor phase Beckmann rearrangement over zeolites[J].Journal of the Japan Petroleum Institute,2006,49(6):301-307
[13]	Yamaguchi Y,Yasutake N,Nagaoka M.Ab initio study of noncatalytic Beckmann rearrangement and hydrolysis of cyclohexanone-oxime in subcritical and supercritical water using the polarizable continuum model[J].Journal of Molecular Structure:Theochem.,2003,639(1/2/3):137-150
[14]	Bucko T,Hafner J,Benco L.Active sites for the vapor phase Beckmann rearrangement over mordenite:an Ab initio study[J].Journal of Physical Chemistry A,2004,108(51):11388-11397
[15]	Cesana A,Palmery S,Buzzoni R,Spanò G,Rivetti F,Carnelli L.Silicalite-1 deactivation in vapour phase Beckmann rearrangement of cyclohexanone oxime to caprolactam[J].Catalysis Today,2010,154(3/4):264-270
[16]	Zhang Y J,Wang Y Q,Bu Y F.Vapor phase Beckmann rearrangement of cyclohexanone oxime on Hβ-zeolites treated by ammonia[J].Microporous and Mesoporous Materials,2008,107(3):247-251
[17]	Zhang Yongjie(章永洁),Wang Yaquan(王亚权),Bu Yifeng(卜亿峰),Wang Li(王莅),Mi Zhentao(米镇涛),He Fei(何菲),Wu Wei(吴魏),Min Enze(闵恩泽),Fu Songbao(傅送保),Zhu Zehua(朱泽华).Hβ and modified Hβ zeolites as catalysts for the Beckmann rearrangement of cyclohexanone oxime[J].Journal of Chemical Industry and Engineering(China)(化工学报),2004,55(12):2103-2105
[18]	Meng Fanhui(孟凡会).Modification and catalytic performance of silicalite-1 in vapor phase Beckmann rearrangement of cyclohexanone oxime .Tianjin:Tianjin University,2011
[19]	Wojciechowski B W.A theoretical treatment of catalyst decay[J].Canadian Journal of Chemical Engineering,1968,46(1):48-52
[20]	Wojciechowski B W.The kinetic foundations and the practical application of the time on stream theory of catalyst decay[J].Catalysis Reviews—Science and Engineering,1974,9(1):79-113
[21]	Ryland L B,Tamele M W,Wilson J N.Cracking Catalysts [M].New York:Reinhold Publishing Corp.,1960
[22]	Flego C,Dalloro L.Beckmann rearrangement of cyclohexanone oxime over silicalite-1:an FT-IR spectroscopic study[J].Microporous and Mesoporous Materials,2003,60(1/2/3):263-271
[23]	Samarin K L,Pomilenko R I,Tyurgaev I Y.Kinetics of the rearrangement of the oxime of cyclohexanone in the gas phase over a solid catalyst under nonstationary conditions[J].Kinetikai Kataliz,1975,16:896-901
[24]	Fois G A,Ricchiardi G,Bordiga S,Busco C,Dalloro L,Spanò G,Zecchina A.The Beckmann rearrangement catalyzed by silicalite:a spectroscopic and computational study[J].Studies in Surface Science and Catalysis,2001,135:149

S-1催化环己酮肟气相Beckmann重排反应动力学

Kinetics of S-1 catalyzed vapor phase Beckmann rearrangement of cyclohexanone oxime to caprolactam

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 24

相关文章 15

编辑推荐

Metrics

本文评价

[1]	万丽, 梁德青. 一种可生物降解水合物动力学抑制剂的研究[J]. 化工学报, 2022, 73(2): 894-903.
[2]	彭超, 王榆元, 邓昌爱, 赵方方, 游奎一. 连续反应-萃取耦合技术制备硫酸羟胺[J]. 化工学报, 2019, 70(5): 1842-1847.
[3]	晋东洋, 张峰, 陈日志, 仲兆祥, 邢卫红. 陶瓷膜反应器中环己酮氨肟化的催化剂失活机制与再生[J]. 化工学报, 2017, 68(5): 1874-1881.
[4]	冯利利, 卢书培, 齐兴义, 韩晓. Me-OMS-1s分子筛催化叔丁基过氧化氢分解制备叔丁醇[J]. 化工学报, 2015, 66(10): 3965-3970.
[5]	任文杰1，周向葵1，贾会敏2，李识寒1，张卫峰1. 应用于环己酮氨肟化反应的TS-1研究进展[J]. 化工进展, 2014, 33(07): 1748-1752.
[6]	史雪芳，丁克鸿. 环己酮肟气相重排制备己内酰胺工艺[J]. 化工进展, 2013, 32(03): 584-587.
[7]	刘国清, 吴剑, 罗和安. 三相体系中TS-1分子筛催化环己酮氨肟化制环己酮肟[J]. Chinese Journal of Chemical Engineering, 2012, 20(5): 889-894.
[8]	谢艳新, 侯丽丽, 杨倩, 蒋登高. AB-8树脂吸附反式1,2-环己二醇热力学和动力学[J]. CIESC Journal, 2012, 20(2): 277-283.
[9]	谭维一，张致慧，陈群，何明阳. 己内酰胺类离子液体催化合成N-单烷基苯胺[J]. 化工进展, 2012, 31(04 ): 896-900.
[10]	刘国清，袁霞，吴剑，罗和安. 环己酮肟Beckmann 重排反应微观混合的数值模拟 [J]. CIESC Journal, 2011, 62(3): 658-663.
[11]	戚行时1，毛丽秋1，尹笃林1，游奎一2，罗和安2. VPO复合物催化环己烷亚硝化一步合成ε-己内酰胺 [J]. CIESC Journal, 2011, 30(2): 314-.
[12]	邢小霞，桑欣欣，谢慧. 刮板薄膜蒸发器在己内酰胺生产中的应用 [J]. CIESC Journal, 2010, 29(6): 1164-.
[13]	赵基钢1，王雷1,2，沈本贤1，肖卫国2. 两种体系合成的TS-1分子筛表征及其丙烯直接环氧化反应性能比较 [J]. CIESC Journal, 2010, 29(2): 264-.
[14]	顾耀明1,2，刘春平2，程立泉1,2，朱泽华3. HTS-1钛硅分子筛催化环己酮氨肟化工业试验 [J]. CIESC Journal, 2010, 29(1): 187-.
[15]	刘绚艳，尹笃林. 钛硅分子筛TS-1的合成改性及其催化功能 [J]. CIESC Journal, 2009, 28(9): 1568-.