乙醇胺缩合胺化反应合成乙二胺研究进展

doi:10.16085/j.issn.1000-6613.2020-0767

摘要/Abstract

摘要：

乙醇胺（MEA）缩合胺化反应是一种绿色、高效的乙二胺（EDA）催化合成技术。本文综述了MEA缩合胺化反应合成EDA的催化反应过程、缩合胺化催化剂及胺化产物分离纯化技术的最新研究进展和动向，重点探讨了缩合胺化反应机理、反应热力学及动力学、催化剂酸性及孔道结构对反应性能的影响、催化剂失活、胺化产物分离纯化技术等，总结了缩合胺化反应合成EDA工艺过程中存在的技术问题。提出通过制备多级孔道沸石分子筛催化剂实现择形催化与高效扩散之间的协调统一；通过强化分子筛催化剂改性方法研究，实现催化剂表面酸性的精确调控。在择形催化和酸催化的协同作用下，有望从根本上解决缩合胺化反应中存在的技术问题，加快缩合胺化反应工艺技术的工业化应用普及。

关键词: 乙二胺, 选择性, 化学反应, 制备, 催化剂, 分离

Abstract:

Condensation amination of monoethanolamine (MEA) is a green and efficient method in selective synthesis of ethylenediamine (EDA). Progresses and trends in reaction process, catalyst, separation and purification are reviewed in this work. Reaction mechanism, thermodynamics and kinetics, effect of catalysts including acidity, pore properties and deactivation, separation and purification are discussed in detail. Furthermore, the core issues in the industrialization of this reaction are analyzed and it's pointed out that fabrication of hierarchical zeolite with tunable surface acidity is an effective way to overcome the diffusion limitation in selective synthesis of EDA. Via the synergism between shape selective catalysis and acid catalysis, it is expected to overcome the problems and promote the application in selective synthesis of EDA via condensation amination of MEA in industry.

Key words: ethylenediamine, selectivity, chemical reaction, preparation, catalyst, separation

中图分类号:

TQ217

赵锋伟, 惠丰, 袁俊, 张前, 梅苏宁, 余秦伟, 杨建明, 刘昭铁, 吕剑. 乙醇胺缩合胺化反应合成乙二胺研究进展[J]. 化工进展, 2020, 39(S2): 212-220.

Fengwei ZHAO, Feng HUI, Jun YUAN, Qian ZHANG, Sunning MEI, Qinwei YU, Jianming YANG, Zhaotie LIU, Jian LYU. Progress in selective synthesis of ethylenediamine via condensation amination of monoethanolamine[J]. Chemical Industry and Engineering Progress, 2020, 39(S2): 212-220.

图/表 1

参考文献 50

1	梁淑东, 黄科林, 彭小玉, 等. 乙二胺的性质及应用[J]. 企业科技与发展, 2010(10): 16-18.
	LIANG S D, HUANG K L, PENG X Y, et al. The nature and applications of ethylenediamine[J]. Enterprise Science and Technology & Development, 2010(10): 16-18.
2	MICHEL D, FORD M F, JOHNSON T A, et al. Production of ethylenediamine from monerthanolamine and ammonia: EP 0252424[P]. 1988-01-13.
3	杨溢, 兰昭洪, 田保亮, 等. 乙二胺合成工艺进展[J]. 石油化工, 2012, 41(5): 603-608.
	YANG Y, LAN Z H, TIAN B L, et al. Progress in research of ethylenediamine synthesis[J]. Petrochemical Technology, 2012, 41(5): 603-608.
4	CHEN X Z, ZHOU S D, ZHANG H J. Synthesis of ethylenediamine in a tubular reactor: experimental and theoretical kinetics[J]. Progress in Reaction Kinetics & Mechanism, 2012, 37: 411-422.
5	张华良, 杨师, 洪超, 等. 乙二醇催化合成乙二胺[J]. 应用化学, 2017, 34(5): 557-562.
	ZHANG H L, YANG S, XU C, et al. Synthesis of ethylenediamine by catalytic ammoniation of ethylene glycol[J]. Chinese Journal of Applied Chemistry, 2017, 34(5): 557-562.
6	符丽, 郭瓦力, 刘喜兴, 等. 静态混合管式变温反应连续合成乙二胺[J]. 过程工程学报, 2014, 14(5): 802-808.
	FU L, GUO W L, LIU X X, et al. Continuous synthesis of ethylenediamine by tubular non-isothermal reaction with a static mixer[J]. The Chinese Journal of Process Engineering, 2014, 14(5): 802-808.
7	邓信忠, 裴世红, 程怡, 等. 二氯乙烷连续催化氨化合成乙二胺[J]. 精细石油化工, 2013, 30(1): 8-12.
	DENG X Z, PEI S H, CHENG Y, et al. Continuous catalytic synthesis of ethylenedlamine from dichloroethane and ammonia[J]. Speciality Petrochemicals, 2013, 30(1): 8-12.
8	ZHANG Y C, BAI G Y, YAN X L. Amination of ethanolamine over cobalt modified H-ZSM-5 catalysts[J]. Catalysis Communications, 2007, 8: 1102-1106.
9	丁云杰, 吕元, 严丽, 等. 一种在临氢条件下一乙醇胺和氨转化为乙二胺的催化剂: CN200910237770.7[P]. 2010-11-03.
	DING Y J, LYU Y, YAN L, et al. A catalyst for the conversion of monoethanolamine and ammonia to ethylenediamine in the presence of hydrogen: CN200910237770.7[P]. 2010-11-03.
10	丁云杰, 吕元, 严丽, 等. 以乙醇胺和氨为原料在临氢条件下制备乙二胺的方法: CN10704753A[P]. 2010-05-12.
	DING Y J, LYU Y, YAN L, et al. Preparation of ethylenediamine from ethanolamine and ammonia under hydrogenation: CN10704753A[P]. 2010-05-12.
11	SEGAWA K, MIZUNO S, SUGIURA S, et al. Selective synthesis of ethylenediamine from ethanolamine over modified H-mordenite catalyst[J]. Studies in Surface Science & Catalysis, 1996, 101: 267-276.
12	DEEBA M, FORD M F, JOHNSON T A. Production of ethylenediamine from monoethanol- amine and ammonia: US 4918233[P]. 1990-04-17.
13	SEGAWA K, SHIMURA T. Effect of dealumination of mordenite by acid leaching for selective synthesis of ethylenediamine from ethanolamine[J]. Applied Catalysis A: General, 2000, 194/195: 309-317.
14	ZHAO F W, ZHANG Q, HUI F. Catalytic behavior of alkali treated H-MOR in selective synthesis of ethylenediamine via condensation amination of monoethanolamine[J]. Catalyst, 2020(10): 1-15.
15	白义国, 陈立功. 双官能团醇类化合物催化胺化反应的研究进展[J]. 化学进展, 2005, 17(2): 293-298.
	BAI Y G, CHEN L G. Progress in the catalytic amination of bifunctional alcohols[J]. Progress in Chemistry, 2005, 17(2): 293-298.
16	REDDY B N, KULKAMI S J, SUBRAHMANYAM M. Zeolite catalysed intramolecular cyclization of 5-amino-1-pentanol to piperidine bases[J]. Applied Catalysis A: General, 1994, 119(1): 23-32.
17	DUME C, HŐLDERICH W F. Amination of 1-octanol[J]. Applied Catalysis A: General, 1999, 183(1): 167-176.
18	VEEFKIND V A, LERCHER J A. On the elementary steps of acid zeolite catalyzed amination of light alcohols[J]. Applied Catalysis A: General, 1999, 181: 245-255.
19	LATHA B M, SADASIVAM V, SIVASANKAR B. A highly selective synthesis of pyrazine from ethylenediamine on copper oxide/copper chromite catalysts[J]. Catalysis Communications, 2007(8): 1070-1073.
20	SELVARAJ M, MIN B R, SHUL Y G, et al. Comparison of mesoporous solid acid catalysts in the production of DABCO by cyclization of ethanolamine II. Synthesis of DABCO over mesoporous solid acid catalysts[J]. Microporous and Mesoporous Materials, 2004, 74: 157-162.
21	陈涛. 乙醇胺气固相催化合成乙二胺研究[D]. 西安: 长安大学, 2012.
	CHEN T. Study on catalytic synthesis of ethylenediamine from ethanolamine in gas-solid phase[D]. Xi’an: Chang’an University, 2012.
22	HUA Y M, HU W M. Rapid synthesis of ZSM-5 zeolite catalyst for amination of ethanolamine[J]. Journal of Zhejiang University-Science A (Applied Physics & Engineering), 2004, 5(6):705-708.
23	华月明, 胡望明. 改性ZSM-5分子筛上乙醇胺催化胺化合成乙撑胺[J]. 高校化学工程学报, 2005, 19(1): 88-92.
	HUA Y M, HU W M. Catalytic amination of ethanolamine on modified ZSM-5 zeolites[J]. Journal of Chemical Engineering of Chinese Universities, 2005, 19(1): 88-92.
24	魏阿宝, 李春荣, 吕剑. 乙醇胺气固相催化合成乙撑胺[D]. 西安: 长安大学, 2012.
	WEI A B, LI C R, LYU J. Synthesis of ethylene polyamine from ethanolamine by gas-solid catalytic reaction[D]. Xi’an: Chang’an University, 2012.
25	黄科林, 王则奋, 孙果宋, 等. 乙二胺合成的研究进展[J]. 化工技术与开发, 2010, 39(8): 36-40.
	HUANG K L, WANG Z F, SUN G S, et al. Synthesis progress of ethylenediamine[J]. Technology & Development of Chemical Industry, 2010, 39(8): 36-40.
26	杨建明, 赵锋伟, 吕剑. 乙醇胺及其下游产品的研究现状[J]. 化工进展, 2007, 26(7): 940-943.
	YANG J M, ZHAO F W, LYU J. Research advances in production of ethanol amine and its downstream products[J]. Chemical Industry and Engineeing Progress, 2007, 26(7): 940-943.
27	赵锋伟, 杨建明, 吕剑. 胺化反应合成乙二胺催化剂的研究[J]. 工业催化, 2008, 16(2): 70-72.
	YANG J M, ZHAO F W, LYU J. Study on synthesis of ethylenediamine ovr modified mordenite catalyst[J]. Industrial Catalysis, 2008, 16(2): 70-72.
28	REDDY P R, SUBRAHMANYAM M, KULKAMI S J. Vapour phase acylation of furan and pyrrole over zeolites[J]. Catalysis Letters, 1998, 54: 95-100.
29	ANAND R, JYOTHI T M, RAO B S. A comparative study on the catalytic activity of ZnO modified zeolites in the synthesis of alkylpyrazines[J]. Applied Catalysis A: General, 2008, 208: 203-211.
30	FAN L S, CHENG D G, CHEN F Q, et al. Preparation of highly dispersed iron species over ZSM-5 with enhanced metal-support interaction through freeze-drying impregnation[J]. Chinese Journal of Catalysis, 2019, 40(7): 1109-1115.
31	VENUGOPAL A, SARKARI R, ANJANEYULU C, et al. Influence of acid-base sites on ZnO-ZnCr₂O₄ catalyst during dehydrocyclization of aqueous glycerol and ethylenediamine for the synthesis of 2-methylpyrazine: kinetic and mechanism studies[J]. Applied Catalysis A: General, 2014, 469: 398-409.
32	SACHIN B, KAKODKAR, SAJO P,et al. Selective synthesis of dibutylamine over Naβ zeolite catalyst[J]. Bulletin of the Catalysis Society of India, 2005, 4: 101-108.
33	杨建明, 赵锋伟, 吕剑. 丝光沸石晶相结构对乙醇胺催化胺化反应的影响[J]. 现代化工, 2007, 27(2): 188-190.
	YANG J M, ZHAO F W, LYU J. Effect of crystal-phase structure of H-mordenite on cataltic amination of monotthanolamine[J]. Modern Chemical Industry, 2007, 27(2): 188-190.
34	NUNES M H O, TEIXEIRA V, SCHMAL M, et al. The effect of copper loading on the acidity of Cu/HZSM-5 catalysts: IR of ammonia and methanol for methylamines synthesis[J]. Applied Catalysis A: General, 2005, 294: 148-155.
35	GROEN J C, ZHU W D, BROUWER S, et al. Direct demonstration of enhanced diffusion in mesoporous ZSM-5 zeolite obtained via controlled desiliacation[J]. Journal of the American Chemical Society, 2007, 129: 355-360.
36	HAO K, SHEN B J, WANY Y D. Influence of combined alkaline treatment and Fe-Ti-loading modification on ZSM-5 zeolite and its catalytic performance in light olefin production[J]. Journal of Industrial & Engineering Chemistry, 2012, 18: 1736-1740.
37	KULKAMI S J, SUBRAHMANYAM M, RAMA A V. Catalytic synthesis of 2-methyl pyrazine over Zn-modified zeolites[J]. Indian Institute of Chemical Technology, 1993, 49: 455-459.
38	HOLM M S, TAAMING E, EGEBLAD K, et al. Catalysis with hierarchical zeolites[J]. Catalysis Today, 2011, 168(1): 3-16.
39	LIU Z P, FAN W M, MA J H. Adsorption, diffusion and catalysis of mesostructured zeolite HZSM-5[J]. Adsorption, 2012, 18: 493-501.
40	CHOI M, NA K, KIM J, et al. Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts[J]. Nature, 2009, 461: 246-250.
41	郝妙莉, 刘弓, 杨伯伦, 等. 基于Aspen模拟的乙醇胺催化胺化产物的精馏分离[J]. 现代化工, 2008, 28(8): 79-83.
	HAO M L, LIU G, YANG B L, et al. Simulation of distillation based on Aspen Plus for products from catalytic amination of ethanolamine[J]. Modern Chemical Industry, 2008, 28(8): 79-83.
42	王伟, 毛伟, 吕婧, 等. 萃取精馏法分离乙二胺和H₂O的共沸物[J]. 化学工程, 2014, 42(10): 25-28.
	WANG W, MAO W, LYU J, et al. Separation of EDA and H₂O azeotrope by extractive distiuation[J]. Chemical Engineering, 2014, 42(10): 25-28.
43	田忠社, 梁建国, 韦雄雄, 等. 乙二胺直接环化产物的分离与模拟[J]. 化学工程, 2012, 40(3): 67-70.
	TIAN Z S, LIANG J G, WEI X X, et al. Separation and simulation of products from direct cyclization of ethylenediamine[J]. Chemical Engineering (China), 2012, 40(3): 67-70.
44	WANG W W, JIA Q, DUAN J H, et al. Simulation and optimization for separation of ethylenediamine-waterazeotropic mixture[C]//International Conference on Materials, Environmental and Biological Engineering. France: Atlantis Press, 2015: 371-374.
45	袁俊, 杨建明, 赵锋伟, 等. 热泵变压精馏分离乙二胺水溶液的模拟[J]. 化学工程, 2015, 43(4): 75-78.
	YUAN J, YANG J M, ZHAO F W, et al. Simulation on separation of ethylenediamine and water by heat-pump pressure swing distillation[J]. Chemical Engineering, 2015, 43(4): 75-78.
46	袁俊, 杨建明, 赵锋伟, 等. 热集成变压精馏分离乙二胺水溶液的模拟[J]. 计算机与应用化学, 2015(2): 235-238.
	YUAN J, YANG J M, ZHAO F W, et al. Simulation on separation of ethylenediamine and water by heat-integrated pressure swing distillation[J]. Computers and Applied Chemistry, 2015(2): 235-238.
47	LI R, YE Q, SUO X, et al. Heat-integrated pressure-swing distillation process for separation of a maximum-boiling azeotrope ethylenediamine/water[J]. Chemical Engineering Research & Design, 2016, 105: 1-15.
48	何晓旭, 钱欣瑞, 鄢烈祥, 等. 热集成变压精馏分离乙二胺-水共沸体系的模拟优化[J]. 化工进展, 2018, 37(6): 2426-2431.
	HE X X, QIAN X R, YAN L X, et al. Simulation and optimization for azeotrope of ethylenediamine-water based on heat-integrated pressure-swing distillation[J]. Chemical Industry and Engineering Progress, 2018, 37(6): 2426-2431.
49	TREJBAL J. Vapor-liquid equilibrium for binary mixtures of 1,4-diazabicyclo [2.2.2] octane with ethylenediamine, ethanolamine, and ethylene glycol[J]. International Journal of Thermophysics, 2009, 30: 490-498.
50	杨建明, 袁俊, 赵锋伟, 等. 常规和双效变压精馏工艺分离乙醇胺和三乙烯二胺的模拟[J]. 石油化工, 2014, 43(8): 924-928.
	YANG J M, YUAN J, ZHAO F W, et al. Simulation of separation of monoethanolamine and triethylenediamine by common and double effect pressure swing distillation[J]. Petrochemical Technology, 2014, 43(8): 924-928.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.
[6]	李世霖, 胡景泽, 王毅霖, 王庆吉, 邵磊. 电渗析分离提取高值组分的研究进展[J]. 化工进展, 2023, 42(S1): 420-429.
[7]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[8]	李化全, 王明华, 邱贵宝. 硫酸酸解钙钛矿相精矿的行为[J]. 化工进展, 2023, 42(S1): 536-541.
[9]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[10]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[11]	徐晨阳, 都健, 张磊. 基于图神经网络的化学反应优劣评价[J]. 化工进展, 2023, 42(S1): 205-212.
[12]	贺美晋. 分子管理在炼油领域分离技术中的应用和发展趋势[J]. 化工进展, 2023, 42(S1): 260-266.
[13]	廖志新, 罗涛, 王红, 孔佳骏, 申海平, 管翠诗, 王翠红, 佘玉成. 溶剂脱沥青技术应用与进展[J]. 化工进展, 2023, 42(9): 4573-4586.
[14]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[15]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.