钛硅分子筛催化环己酮液相氨肟化固定床工艺

doi:10.3724/SP.J.1088.2013.20939

催化学报 ›› 2013, Vol. 34 ›› Issue (3): 604-611.DOI: 10.3724/SP.J.1088.2013.20939

钛硅分子筛催化环己酮液相氨肟化固定床工艺

卓佐西, 林龙飞, 邓秀娟, 王钰宁, 刘月明

华东师范大学化学系上海市绿色化学与化工过程绿色化重点实验室, 上海 200062

收稿日期:2012-09-30 修回日期:2012-10-30 出版日期:2013-04-02 发布日期:2013-04-03
通讯作者: 刘月明
基金资助:
国家自然科学基金(20973064); 国家科技支撑计划(2012BAE05B02); 上海市科委基础研究重点项目(12JC14030600); 上海市重点学科建设项目基金(B409).

Fixed-bed process of liquid-phase ammoximation of cyclohexanone over titanosilicates

ZHUO Zuoxi, LIN Longfei, DENG Xiujuan, WANG Yuning, LIU Yueming

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, EastChinaNormalUniversity, Shanghai 200062, China

Received:2012-09-30 Revised:2012-10-30 Online:2013-04-02 Published:2013-04-03
Supported by:
This work was supported by the National Natural Science Foundation of China (20973064), the National Key Technology R&D Program (2012BAE05B02), the Science and Technology Commission of Shanghai Municipality (12JC1403600), and the Shanghai Leading Academic Discipline Project (B409).

摘要/Abstract

摘要：

采用固定床模式,研究了钛硅分子筛催化环己酮制环己酮肟液相氨肟化反应.结果表明,该工艺模式具有可行性与普适性.优化的反应条件为:温度333K,体系氨浓度>2%,酮/H₂O₂摩尔比=5,H₂O₂空速0.083h^-1.此时环己酮转化率、环己酮肟选择性、H₂O₂转化率及其有效利用率分别达18.7%,99.5%,94.7%和98.7%.进一步研究了H₂O₂在该过程中的反应行为,发现固定床工艺模式能有效提高H₂O₂的有效利用率,其主要原因是该模式有利于羟胺的生成及其进一步与酮反应生成肟.适当的空速与氨和酮的浓度是实现H₂O₂高效利用的关键因素.

关键词: 环己酮, 肟化, 钛硅分子筛, 固定床, 过氧化氢

Abstract:

Liquid-phase ammoximation of cyclohexanone to the corresponding oxime was conducted in a fixed-bed reactor over titanium silicalite (TS-1), which was proved to be a feasible and universal process. The primary rules of ammoximation were explored in the fixed-bed reactor system.The initial results indicated that the utilization of H₂O₂ was enhanced obviously through this mode, which is attributed to successful hydroxylamine generation and smooth contact with ketones. Further investigations of H₂O₂ reaction behavior showed that the proper weight hourly space velocity of H₂O₂ and the concentrations of ammonia and ketone both play a key role in highly efficient utilization of H₂O₂. The cyclohexanone and H₂O₂ conversion, cyclohexanone-oxime selectivity, and H₂O₂ efficiency reached 18.7%, 94.7%, 99.5%, and 98.7%, respectively, under the optimum reaction conditions of temperature of 333 K, ammonia concentration higher than 2%, cyclohexanone/H₂O₂ molar ratio of 5, and WHSV (H₂O₂)of 0.083h^-¹ with 85% t-BuOH as solvent.

Key words: cyclohexanone, ammoximation, titanium silicalite, fixed bed, hydrogen peroxide

卓佐西, 林龙飞, 邓秀娟, 王钰宁, 刘月明. 钛硅分子筛催化环己酮液相氨肟化固定床工艺[J]. 催化学报, 2013, 34(3): 604-611.

ZHUO Zuoxi, LIN Longfei, DENG Xiujuan, WANG Yuning, LIU Yueming. Fixed-bed process of liquid-phase ammoximation of cyclohexanone over titanosilicates[J]. Chinese Journal of Catalysis, 2013, 34(3): 604-611.

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钛硅分子筛催化环己酮液相氨肟化固定床工艺

Fixed-bed process of liquid-phase ammoximation of cyclohexanone over titanosilicates

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