螺旋微通道反应器贝克曼重排制备己内酰胺

doi:10.11949/0438-1157.20230820

化工学报 ›› 2023, Vol. 74 ›› Issue (10): 4182-4190.DOI: 10.11949/0438-1157.20230820

• 催化、动力学与反应器 • 上一篇下一篇

螺旋微通道反应器贝克曼重排制备己内酰胺

李晨亚¹(), 刘捷¹, 王建芝¹, 刘艳萍², 林笑¹, 喻发全¹()

^1.武汉工程大学化工与制药学院，湖北武汉 430205
^2.武汉工程大学环境生态与生物工程学院，绿色化工过程教育部重点实验室，新型反应器与绿色化学工艺湖北省重点实验室，湖北省高端精细化学品工程技术研究中心，湖北武汉 430205

收稿日期:2023-08-09 修回日期:2023-09-27 出版日期:2023-10-25 发布日期:2023-12-22
通讯作者: 喻发全
作者简介:李晨亚（1991—），男，硕士研究生，2262659737@qq.com
基金资助:
国家自然科学基金项目(22078251);武汉工程大学研究生教育创新基金项目(CX2022032)

Preparation of caprolactam by Beckmann rearrangement in spiral microchannel reactor

Chenya LI¹(), Jie LIU¹, Jianzhi WANG¹, Yanping LIU², Xiao LIN¹, Faquan YU¹()

^1.School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, Hubei, China
^2.School of Environmental Ecology and Biological Engineering, Key Laboratory of Green Chemical Engineering Process of Ministry of Education, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, Hubei Engineering Research Center for Advanced Fine Chemicals, Wuhan Institute of Technology, Wuhan 430205, Hubei, China

Received:2023-08-09 Revised:2023-09-27 Online:2023-10-25 Published:2023-12-22
Contact: Faquan YU

摘要/Abstract

摘要：

利用螺旋微通道反应器实现贝克曼重排制备己内酰胺。通过原位溶剂气化与二次流技术，克服了该高黏度反应体系在微反应器内流动阻力大、易造成局部热点、产能小等问题。探究了反应温度、溶剂气化、螺旋直径、管道内径、原料浓度、流量等因素对反应的转化率和选择性的影响。实验结果表明，在2 mm内径螺旋管道中，二氯乙烷为溶剂，酸肟摩尔比1.1前提下，预热温度80℃、重排温度90℃、环己酮肟溶液10%~20 %（质量分数），停留时间15 s、螺旋直径20 mm时，转化率可达100%，选择性达99%以上。同时实现了单管20.2 g/min的产能，按每年8000 h计算将达到9.7 t/a。本研究结果可为高通量、高效率的微通道反应器设计与开发提供理论指导，为高黏体系的微反应器提供解决方案。

关键词: 贝克曼重排, 己内酰胺制备, 微反应器, 多相反应, 界面

Abstract:

Caprolactam was prepared by Beckmann rearrangement using a spiral microchannel reactor. Through in-situ solvent vaporization and secondary flow technology, it overcomes the problems of high flow resistance in the microreactor of the high-viscosity reaction system, easy to cause local hot spots, and low production capacity. The effect of reaction temperature, solvent vaporization, helical size, pipe inner diameter, feedstock concentration, and flow rate on the conversion and selectivity of the reaction was investigated. The experimental results showed that the conversion rate could reach 100% and the selectivity was more than 99% with a 2 mm inner diameter spiral pipe, dichloroethane as solvent and an acid-oxime molar ratio at 1.1, a preheating temperature at 80℃, a rearrangement temperature at 90℃, a cyclohexanone oxime solution concentration at 10%—20%(mass), a retention time at 15 s, and a spiral diameter at 20 mm.20.2 g/min capacity for a single tube was realized, which corresponds to 9.7 t/a based on 8000 h per year. The results would provide theoretical guidance in the design and development of high-throughput and high-efficiency microchannel reactors. This study presents a solution for microreactors for highly viscous systems.

Key words: Beckman rearrangement, caprolactam preparation, microreactor, multiphase reaction, interface

中图分类号:

TQ 236

李晨亚, 刘捷, 王建芝, 刘艳萍, 林笑, 喻发全. 螺旋微通道反应器贝克曼重排制备己内酰胺[J]. 化工学报, 2023, 74(10): 4182-4190.

Chenya LI, Jie LIU, Jianzhi WANG, Yanping LIU, Xiao LIN, Faquan YU. Preparation of caprolactam by Beckmann rearrangement in spiral microchannel reactor[J]. CIESC Journal, 2023, 74(10): 4182-4190.

图/表 11

图1 实验装置

Fig.1 The schematic overview of the experimental setup

图2 螺旋微通道反应器示意图

Fig.2 Schematic diagram of spiral microchannel reactor

图3 预热温度(TW)和重排温度(TR)对环己酮肟转化率(C)和己内酰胺选择性(S)的影响[10%(质量分数)环己酮肟-DCE溶液，20 %(质量分数)发烟硫酸，Q = 25 ml/min，MA/O = 1.1，t = 15 s，D = 20 mm，d = 2 mm]

Fig.3 Effect of preheating temperature (TW) and rearrangement temperature (TR) on cyclohexanone oxime conversion (C) and caprolactam selectivity (S)

图4 不同TR时在拍摄点C处的流型图

Fig.4 Flow patterns at shooting point C with different TR

图5 不同沸点溶剂和停留时间对环己酮肟转化率(C)和己内酰胺选择性(S)的影响[10%(质量分数)环己酮肟, 20%(质量分数)发烟硫酸, Q = 25~75 ml/min, MA/O = 1.1, TW = 80℃, TR = 90℃, D = 20 mm, d = 2 mm]

Fig.5 Effects of solvents with different boiling points and retention time on cyclohexanone oxime conversion and caprolactam selectivity

图6 DCE溶剂体系[(a)~(h)]和正辛烷溶剂体系(i)在拍摄点A处的流型图

Fig.6 Flow patterns of DCE solvent system [(a)—(h)] and n-octane solvent system (i) at shooting point A

图7 不同溶剂体系在拍摄点B处的流型图

Fig.7 Flow patterns of different solvent systems at shooting point B

图8 螺旋直径和停留时间对环己酮肟转化率和己内酰胺选择性的影响[10%(质量分数)环己酮肟-DCE溶液, 20%(质量分数)发烟硫酸, Q = 15~75 ml/min, MA/O = 1.1, TW = 80℃, TR = 90℃, d = 2 mm]

Fig.8 Effect of helix diameter and retention time on cyclohexanone oxime conversion and caprolactam selectivity

图9 管内径对环己酮肟转化率和己内酰胺选择性的影响[10%(质量分数)环己酮肟-DCE溶液,20%(质量分数)发烟硫酸,Q=25、56、100 ml/min, MA/O=1.1, TW=80℃, TR=90℃, t=20 s, D=20 mm]

Fig.9 Effect of tube inner diameter on cyclohexanone oxime conversion and caprolactam selectivity

图10 环己酮肟溶液浓度(ωCHO)对环己酮肟转化率、己内酰胺选择性和物料温度的影响[20%(质量分数)发烟硫酸,Q = 25 ml/min,MA/O = 1.1,TW = 80℃,TR = 90℃,t = 15 s,D = 20 mm,d = 2 mm]

Fig.10 Effect of mass fraction of cyclohexanone oxime solution(ωCHO) on cyclohexanone oxime conversion, caprolactam selectivity and material temperature

图11 环己酮肟溶液的流量对环己酮肟转化率和己内酰胺选择性的影响[20%(质量分数)环己酮肟-DCE溶液,20%(质量分数)发烟硫酸, MA/O = 1.1, TW = 80℃, TR = 90℃, t = 20 s, D = 20 mm, d = 2 mm]

Fig.11 Effect of cyclohexanone oxime solution flow rate on cyclohexanone oxime conversion and caprolactam selectivity

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螺旋微通道反应器贝克曼重排制备己内酰胺

Preparation of caprolactam by Beckmann rearrangement in spiral microchannel reactor

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