微反应器中乙炔法合成N-乙烯基吡咯烷酮的过程研究

doi:10.16085/j.issn.1000-6613.2021-1518

摘要/Abstract

摘要：

搭建了以商用微反应器为核心的气液微反应系统，成功实现了加压乙炔法合成N-乙烯基吡咯烷酮（NVP）的产品过程，采用液相循环方式完成反应物2-吡咯烷酮的高效转化，全面考察了反应温度、KOH含量、内构件数量和原料乙炔纯化对液相反应的影响。结果表明，反应温度和KOH含量对选择性有显著影响，高温和高含量催化剂会严重降低产物NVP的选择性，综合调控反应温度和KOH含量，可保证产物选择性在95%以上；微反应器中内构件的存在有利于促进气液传质过程；反应体系水分的脱除有助于循环反应中转化率和选择性的提高；与高压釜相比，产物NVP收率提高了28.7%（无助剂），反应时间有适当缩短。

关键词: 微反应器, 乙烯化反应, 气液反应, 乙炔, N-乙烯基吡咯烷酮

Abstract:

Vinylation reaction of 2-pyrrolidone with acetylene to synthesize N-vinyl pyrrolidone was successfully implemented in a microreactor, which had the advantages of the intrinsic safety of acetylene and intensified gas-liquid mass transfer. To realize the efficient transformation of the reactants, the liquid phase was recycled to obtain the sufficient gas-liquid contact time. The effects of reaction temperature, KOH content, internals in the microreactor and acetylene purifier on vinylation reaction with the recycled liquid phase were investigated in detail. The results showed that both reaction temperature and KOH content had significant effects on the selectivity to N-vinyl pyrrolidone. The higher reaction temperature and higher catalyst content caused the reduction of the selectivity seriously, among which a better result of >95% selectivity to NVP can be achieved by comprehensive control of these two operation conditions. The application of internals improved the mixing efficiency and promoted the gas-liquid mass transfer rate evidently. As a comparison, the yield of NVP was increased by 28.7% (without promoters) against the semi-continuous process in autoclaves, and the reaction time was shortened as well.

Key words: microreactor, vinylation reaction, gas-liquid reaction, acetylene, N-vinyl pyrrolidone (NVP)

中图分类号:

TQ236

阎丽芳, 储博钊, 钟思青, 程易. 微反应器中乙炔法合成N-乙烯基吡咯烷酮的过程研究[J]. 化工进展, 2022, 41(6): 2902-2909.

YAN Lifang, CHU Bozhao, ZHONG Siqing, CHENG Yi. Synthesis of N-vinyl pyrrolidone by acetylene process in a microreactor[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 2902-2909.

图/表 13

图1 催化剂的失活反应

图2 催化剂的除水反应

图3 减压蒸馏装置示意图

图4 基于微反应器的乙烯基化反应流程图

图5 单通道内的内构件示意图

图6 反应物和产物在GC中定量分析的标准曲线

图7 2-P的乙烯化反应

图8 反应温度对循环反应的影响（反应条件为1MPa，C2H2∶N2=1∶1，KOH质量分数为5%，气液比为200∶1，3层内构件）

图9 液相循环反应中反应物和产物浓度变化示意图

图10 KOH含量对循环反应的影响（反应条件为1MPa，C2H2∶N2=1∶1，气液比为200∶1，3层内构件）

图11 内构件数量对循环反应的影响（反应条件为180℃，1MPa，C2H2∶N2=1∶1，气液比为200∶1，KOH质量分数为4%）

图12 反应体系水分控制对循环反应的影响（反应条件为180℃，1MPa，C2H2∶N2=1∶1，气液比为200∶1，KOH质量分数为5%，3层内构件）

表1 不同反应器反应性能的比较

反应器类型	关键反应条件			反应指标	参考文献
反应器类型	反应时间 /h	助剂	反应温度 /℃	Y_NVP/%	参考文献
微反应器	1.3	无	160	68.4	本工作
膜分散式反应器^①	3~4	无	180	57.8	［19］
高压釜	3	无	150	39.7	［10］
高压釜^②	3	1,4-丁二醇	150	62.7
高压釜^②	2	聚四氢呋喃	150	50.7

参考文献 30

1	REPPE Walter, KRZIKALLA Heidelberg, DORNHEIM Otto. Method of production of N-vinyl compounds: DE877757[P]. 1953-04-09.
2	BAPTISTA Robert J. Walter Reppe: pioneer in acetylene chemistry[EB/OL]. [2009-06-21]. .
3	崔英德, 易国斌, 廖列文. 聚乙烯吡咯烷酮的合成与应用[M]. 北京: 科学出版社, 2001: 156-195.
	CUI Yingde, YI Guobin, LIAO Liewen. Synthesis ans application of polyvinyl pyrrolidone[M]. Beijing: Science Press, 2001: 156-195.
4	秦振宝, 张军. N-乙烯基吡咯烷酮的合成研究进展[J]. 合成技术及应用, 2012, 27(2): 23-27.
	QIN Zhenbao, ZHANG Jun. Study on processes for the synthesis of N-vinyl pyrrolidone[J]. Synthetic Technology & Application, 2012, 27(2): 23-27.
5	FOGG Peter G T, BLIGH Sim wan Annie, Elizabeth DERRICK M, et al. IUPAC-NIST solubility data series. 76. solubility of ethyne in liquids[J]. Journal of Physical and Chemical Reference Data, 2001, 30(6): 1693-1875.
6	SCHMIDT-RADDE MARTIN DR, HEIDER MARC DR, DAMS ALBRECHT DR, et al. Process for the preparation of N-vinyllactams: EP0732324[P]. 1999-10-13.
7	MUTAFFISThomas D, CARLUCCIO Frank, CHIDDIX Max E. Method for preparing alkali metal pyrrolidones: US3185706[P]. 1965-05-25.
8	LIU K C, TAYLOR P D. Process for the preparation of N-vinyllactams: US4873336[P]. 1989-10-10.
9	PARTHASARATHY R, HORT Eugene V, CHAKRABARTI Paritosh M. Vinylation reaction: US4410726[P]. 1983-10-18.
10	CHU Shiao-jung, Pine-sci KUO, DAI Chu-chang, et al. Method for the producing of N-vinyl-2-pyrrolidone by vinylation: US5665889[P]. 1997-09-09.
11	赵铁, 段为. 一种生产乙烯基吡咯烷酮的方法: CN103102298A[P]. 2013-05-15.
	ZHAO Tie, DUAN Wei. Method for producing n-vinyl pyrrolidone: CN103102298A[P]. 2013-05-15.
12	HANFORD W E, FULLER D L. Acetylene chemistry[J]. Industrial & Engineering Chemistry, 1948, 40(7): 1171-1177.
13	Ioan-Teodor TROTUŞ, ZIMMERMANN Tobias, Ferdi SCHÜTH. Catalytic reactions of acetylene: a feedstock for the chemical industry revisited[J]. Chemical Reviews, 2014, 114(3): 1761-1782.
14	NEDWICK J J. Liquid phase process for acetylene reactions[J]. Industrial & Engineering Chemistry Process Design and Development, 1962, 1(2): 137-141.
15	SCHOBERT Harold. Production of acetylene and acetylene-based chemicals from coal[J]. Chemical Reviews, 2014, 114(3): 1743-1760.
16	SCHNIZER Arthur W, CHRISTI Corpus. Production of N-vinyl pyrrolidone: US2669570[P]. 1954-02-16.
17	SHIMASAKI Yuuji, YANO Hitoshi, ARIYOSHI Kimio. Catalyst for production of tertiary N-alkenyl carboxylic acid amide, and process for production of tertiary N-alkenyl carboxylic acid amide using said catalyst: US5625076[P]. 1997-04-29.
18	易国斌, 崔英德, 康正, 等. γ-丁内酯催化合成聚乙烯吡咯烷酮(PVP)单体的研究[J]. 化学世界, 2001, 42(5): 256-258.
	YI Guobin, CUI Yingde, KANG Zheng, et al. Studies on catalytic synthesis of monomer for polyvinylpyrrolidone (PVP) from γ-butyrolactone[J]. Huaxue Shijie (Chemical World), 2001, 42(5): 256-258.
19	黎四芳. N-乙烯基吡咯烷酮的制备方法: CN101391974B[P]. 2012-07-04.
	LI Sifang. Process for production of N-vinyl pyrrolidone: CN101391974B[P]. 2012-07-04.
20	方立贵, 谢中平, 杜鹃, 等. 一种N-乙烯基吡咯烷酮NVP合成的新工艺: CN103319391A[P]. 2013-09-25.
	FANG Ligui, XIE Zhongping, DU Juan, et al. Novel process for synthesizing N-vinyl pyrrolidone (NVP): CN103319391A[P]. 2013-09-25.
21	张世林. 一种乙烯基吡咯烷酮合成反应器: CN105214570B[P]. 2016-08-24.
	ZHANG Shilin. Vinyl pyrrolidone synthesis reactor: CN105214570B[P]. 2016-08-24.
22	JENSEN Klavs F. Flow chemistry—Microreaction technology comes of age[J]. AIChE Journal, 2017, 63(3): 858-869.
23	WILES Charlotte, WATTS Paul. Recent advances in micro reaction technology[J]. Chemical Communications, 2011, 47(23): 6512-6535.
24	HESSEL Volker, ANGELI Panagiota, GAVRIILIDIS Asterios, et al. Gas–liquid and gas–liquid–solid microstructured reactors: contacting principles and applications[J]. Industrial & Engineering Chemistry Research, 2005, 44(25): 9750-9769.
25	YOSHIDA Jun ichi, KIM Heejin, NAGAKI Aiichiro. Green and sustainable chemical synthesis using flow microreactors[J]. ChemSusChem, 2011, 4(3): 331-340.
26	WEGNER Jens, CEYLAN Sascha, KIRSCHNING Andreas. Flow chemistry–A key enabling technology for (multistep) organic synthesis[J]. Advanced Synthesis & Catalysis, 2012, 354(1): 17-57.
27	XUE Fei, DENG Hongping, XUE Chengwen, et al. Reaction discovery using acetylene gas as the chemical feedstock accelerated by the “stop-flow” micro-tubing reactor system[J]. Chemical Science, 2017, 8(5): 3623-3627.
28	VORONIN Vladimir V, LEDOVSKAYA Maria S, BOGACHENKOV Alexander S, et al. Acetylene in organic synthesis: recent progress and new uses[J]. Molecules, 2018, 23(10): 2442.
29	E Yu SHMIDT, PROTSUK N I, VASIL’TSOV A M, et al. Improved method for the synthesis of 1-vinylindole[J]. Chemistry of Heterocyclic Compounds, 2013, 49(3): 404-407.
30	YAN Lifang, CHU Bozhao, ZHONG Siqing, et al. Synthesis of N-vinyl pyrrolidone by acetylene process in a microreactor[J]. Chemical Engineering Journal Advances, 2020, 2: 100018.

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