乙醇胺装置流程模拟与开发研究
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摘要
环氧乙烷氨解法是目前生产乙醇胺的主要方法，产品比例、产品质量及能耗是乙醇胺生产中的三个关键因素。国内乙醇胺生产中普遍存在产品色度高、产品比例不合理的问题，造成产品缺乏竞争力。色度问题主要是由于分离系统存在的问题引起的，如精馏塔内压降大、釜温高、相关设备选型不合理等。本文采用流程模拟软件PRO/Ⅱ对乙醇胺装置进行全流程模拟，针对流程特点提出改进措施，并对精馏系统的设备因素进行考察，以期解决上述问题。
乙醇胺及其原料氨和水均为极性组分，模拟中在不同场合分别选用状态方程SRKM或液体活度系数模型NRTL，可以得到比较准确的模拟结果。在原工艺的基础上，通过将分离出的一乙醇胺（MEA）部分循环回反应部分，可以显著提高二乙醇胺（DEA）和三乙醇胺（TEA）产品的收率，提高了原装置的灵活性，但是需增加设备投资及提高装置能耗。
不同乙醇胺产品之间的沸点差较大，从精馏的角度来说易于分离，利用这一特点，本文开发出了带循环物流、侧线出料的精馏系统新流程。模拟计算表明，采用该流程可以显著降低MEA塔和DEA塔的塔釜温度，防止物料高温热解，为降低产品色度创造了必要条件；同时产品纯度保持在99%（重量百分数）以上，能够满足质量要求。
乙醇胺为热敏物系，对分离设备的要求较高。精馏塔适合采用填料塔，塔顶冷凝器宜采用卧置部分冷凝器，TEA塔也可采用塔顶泵循方式取热，这些措施利于减小压降；再沸器选用降膜蒸发器，可防止液层静压并减少物料在高温区的停留时间。流体力学核算结果表明，选用合适的填料及分布器，能够将全塔压降控制在一定的范围以内，从而保证了塔釜温度不会过高，为产品质量提供了保障。
利用本文的研究成果，可以为乙醇胺生产装置提供完整的工艺包。
Ethanolamines are commonly made by the method of reacting aqueous ammonia and ethylene oxide. Product profile, product quality and energy consumption are three key factors in ethanolamine process. Domestic product is weak in competition because of poor color quality and improper product profile, which are very common in domestic ethanolamine units. The poor color quality is caused primarily by the disadvantage in separating system, such as high pressure drop in distillation tower, high temperature at the bottom of the tower, and unsuitable choice of relative devices. By means of flowsheeting software PRO/Ⅱ, the process for ethanolamine unit was simulated in this paper, then some modification was made according to the feature of the process. The factors relating to devices in distillation system were also discussed to help solve the questions above-mentioned.
As ethanolamines and their crude material ammonia and water are all polar components, the considerably accurate results can be obtained by using equation of state SRKM or liquid activity model NRTL in different units. On the basis of initial process, by recycling some of the monoethanolamine separated to the reaction system, the yield of diethanolamine and triethanolamine was increased greatly, which enhanced the flexibility of the unit, but more cost was needed for some new devices and the energy consumption was increased.
Ethanolamine series are easy to be separated by distillation technology because of their high boiling point difference. According to this feature, an optimized distillation process with recycling streams and sidedraws was presented in this study. The simulating results showed that the temperature at the bottom of monoethanolamine tower and diethanolamine tower was reduced greatly, which helps to prevent the degradation of the solutions, so the color index can be lowered, at the same time the product purity was kept above 99% (by weight).
As heat-sensitive material, ethanolamines have more critical requirement on the separating devices. Packed tower was suitable for the distillation, horizontal partial condenser was used as top condenser, and pumparound may also be used for triethanolamine tower, which helps to reduce the pressure drop; falling-film evaporator was used as reboiler, which eliminates the liquid static pressure and helps to reduce the residence time in high temperature region. The results of hydraulic rating showed that the pressure drop in the towers can be limited to a certain degree by choosing packing and distributor correctly, so the bottom temperature may not be too high, and the product quality can be ensured.
Complete process pack for ethanolamine unit was obtained by this study.
乙醇胺及其原料氨和水均为极性组分，模拟中在不同场合分别选用状态方程SRKM或液体活度系数模型NRTL，可以得到比较准确的模拟结果。在原工艺的基础上，通过将分离出的一乙醇胺（MEA）部分循环回反应部分，可以显著提高二乙醇胺（DEA）和三乙醇胺（TEA）产品的收率，提高了原装置的灵活性，但是需增加设备投资及提高装置能耗。
不同乙醇胺产品之间的沸点差较大，从精馏的角度来说易于分离，利用这一特点，本文开发出了带循环物流、侧线出料的精馏系统新流程。模拟计算表明，采用该流程可以显著降低MEA塔和DEA塔的塔釜温度，防止物料高温热解，为降低产品色度创造了必要条件；同时产品纯度保持在99%（重量百分数）以上，能够满足质量要求。
乙醇胺为热敏物系，对分离设备的要求较高。精馏塔适合采用填料塔，塔顶冷凝器宜采用卧置部分冷凝器，TEA塔也可采用塔顶泵循方式取热，这些措施利于减小压降；再沸器选用降膜蒸发器，可防止液层静压并减少物料在高温区的停留时间。流体力学核算结果表明，选用合适的填料及分布器，能够将全塔压降控制在一定的范围以内，从而保证了塔釜温度不会过高，为产品质量提供了保障。
利用本文的研究成果，可以为乙醇胺生产装置提供完整的工艺包。
Ethanolamines are commonly made by the method of reacting aqueous ammonia and ethylene oxide. Product profile, product quality and energy consumption are three key factors in ethanolamine process. Domestic product is weak in competition because of poor color quality and improper product profile, which are very common in domestic ethanolamine units. The poor color quality is caused primarily by the disadvantage in separating system, such as high pressure drop in distillation tower, high temperature at the bottom of the tower, and unsuitable choice of relative devices. By means of flowsheeting software PRO/Ⅱ, the process for ethanolamine unit was simulated in this paper, then some modification was made according to the feature of the process. The factors relating to devices in distillation system were also discussed to help solve the questions above-mentioned.
As ethanolamines and their crude material ammonia and water are all polar components, the considerably accurate results can be obtained by using equation of state SRKM or liquid activity model NRTL in different units. On the basis of initial process, by recycling some of the monoethanolamine separated to the reaction system, the yield of diethanolamine and triethanolamine was increased greatly, which enhanced the flexibility of the unit, but more cost was needed for some new devices and the energy consumption was increased.
Ethanolamine series are easy to be separated by distillation technology because of their high boiling point difference. According to this feature, an optimized distillation process with recycling streams and sidedraws was presented in this study. The simulating results showed that the temperature at the bottom of monoethanolamine tower and diethanolamine tower was reduced greatly, which helps to prevent the degradation of the solutions, so the color index can be lowered, at the same time the product purity was kept above 99% (by weight).
As heat-sensitive material, ethanolamines have more critical requirement on the separating devices. Packed tower was suitable for the distillation, horizontal partial condenser was used as top condenser, and pumparound may also be used for triethanolamine tower, which helps to reduce the pressure drop; falling-film evaporator was used as reboiler, which eliminates the liquid static pressure and helps to reduce the residence time in high temperature region. The results of hydraulic rating showed that the pressure drop in the towers can be limited to a certain degree by choosing packing and distributor correctly, so the bottom temperature may not be too high, and the product quality can be ensured.
Complete process pack for ethanolamine unit was obtained by this study.
引文
禹茂章 主编. 世界精细化工产品手册，北京：化工部科技情报研究所，1986.
卢焕章等. 石油化工基础数据手册，北京：化学工业出版社，1982.
Hammar, H., et al. Ethanolamines and Propanolamines. In: Gerhartz W., et al. eds. Ullmann’s Encyclopedia of Industrial Chemistry. Weinheim, 1987, Vol Al0. 1~22.
何燕. 乙醇胺生产应用与开发前景，化工物资，1997, (3): 29~31.
徐长卿，杨秀全. 乙醇胺化学和国外生产技术概况，日用化学工业，1992, (6): 20~26.
吴兆立，蔡振云，谢荣锦. 国内外乙醇胺工艺流程评述，日用化学工业，1994, (2): 23~27.
BASF AG (DE). Process and apparatus for preparing or reacting alkanolamines, US patent, US4567303, 1986-01-28.
范竹文. 乙醇胺生产的先进技术，化工设计，1995, (1): 51~53.
柴义. 我国乙醇胺生产现状及发展对策，日用化学工业, 1992, (4): 21~25.
柴义. 乙醇胺技术考察报告，日用化学工业, 1992, (2): 51~54, 46.
Union Carbide Corp (US). Continuous process for preparing alkanolamines, US patent, US4847418, 1989-07-11.
BASF AG (DE). Production of ethanolamines, US patent, US5545757, 1996-08-13.
Nippon Catalytic Chem Ind (JP). Process for preparation for alkanolamine, catalyst used in the process and process for preparation of the catalyst, European patent, EP0652207, 1995-05-10.
Mitsui Toatsu Chemicals (JP). Process for preparing alkanolamines, European patent, EP0690043, 1996-01-03.
Huntsman Spec Chem Corp (US). Production of diethanolamine, US patent, US6063965, 2000-05-16.
Nippon Catalytic Chem Ind (JP). A process for producing dialkanolamines, European patent, EP0941986, 1999-09-15.
Melder Johann-Peter, Schulz Gerhard (DE). Process for the preparation of ethanolamines, US patent, US2002115890, 2002-08-22.
DOW Chemical Co.. Ammonation of trialkanolamines, US patent, US4328370, 1982-05-04.
Mechanism of soap browning uncovered, Chemical & Engineering News, sep.16 1996, 74(38): 42.
Buskens Philip (BE), Gutschoven Frank (BE), Melder Johann-Peter (DE), et al. Process for the preparation of alkanolamines having improved color quality, US patent, US2001031897, 2001-10-18.
BASF AG (DE). Method of purifying triethanolamine, US patent, US6388137, 2002-05-14.
BP Chemicals Inc (FR). Process for manufacturing triethanolamine and product obtained, US patent, US2003100798, 2003-05-29.
吴兆立，谢荣锦. 乙醇胺生产的液液管式反应工艺，中国专利，CN1049653A, 1991-03-06.
魏海国. 乙醇胺的管道化反应工艺，［硕士学位论文］，浙江大学, 1993.
吴兆立，谢荣锦，蔡振云. 乙醇胺生产的无水管式反应方法，中国专利，CN1139101A, 1997-01-01.
字敏，许世学，荆碧. 三乙醇胺合成方法改进，云南化工, 1998, (1): 40~41.
何健. 环氧乙烷和液氨合成乙醇胺新工艺的研究，广东化工, 1997, (5): 35~36.
徐荣福. 乙醇胺产品的生产及应用，高桥石化, 2000, (5): 51~53.
王传林，洪继承，王世学. 吉化乙醇胺装置简介，吉化科技, 1996, (4): 18~20.
黄海，杨秀全，徐长卿. 乙醇胺生产新技术，日用化学工业, 1996, (1): 1~3.
胡玉梅. 乙醇胺市场状况及其装置建设初探，石油化工技术经济, 2000, 16 (5): 37~40.
梁诚. 国内外乙醇胺生产现状与发展趋势，中国石油和化工分析报告,2002,(6):15~19.
朱开宏等. 化工过程流程模拟，北京：中国石化出版社，1993.
雷培德，李端阳，汪静. 化工流程模拟及其应用，节能，1994，（3）：6~8.
张志檩，叶立军，庄芹仙. 流程模拟中分解与切断的计算机处理方法探讨，化学工程，1995, 23(6): 59~61.
杨友麒. 过程流程模拟，计算机与应用化学，1995, 12(1): 1~6.
杨友麒. 化工过程模拟，化工进展，1996, (3): 1~7.
李文波，毛鹏生，王长英等. 化工流程模拟技术的现状与发展，化工时刊, 1998, 12(6): 3~6.
胡克林，罗金生. 化工过程模拟技术进展与趋势，新疆工学院学报，1997, 18(4): 254~257, 261.
天津大学物理化学教研室 编. 物理化学 上册，北京：高等教育出版社，1992
Eastham. A. M., Darwent B. deB., Beaubien. P. E.. Chemistry of ethylene oxide. Ⅱ. Kinetics of the reaction of ethylene oxide with amines in aqueous solution, Can. J. of Chem., 1951, 29: 575-84.
李绍芬 主编. 反应工程，北京：化学工业出版社，1990.
P. Ferrero, F. Berbe, L.R.Flamme. Kinetic study of the synthesis of Ethanolamines, Bull. soc. Chim, 1947, 56: 349-68.
Reich, H., et al. Reaction kinetic investigations of the synthesis of Ethanolamines, Chimia, 1966, 20 (1): 29~31.
Sir Soc Italiana Resine SPA. Process for the separation of monoethanolamine, diethanolamine, and triethanolamine from crude ethanolamine mixtures, US patent, US3849262, 1974-11-19.
Schultz, G., et al. Kinetic investigations on the oxyethylation of ammonia in concentrated aqueous solutions, Chem. lng. tech., 1986, 40: 446-8.
Potter. C., Macdonald. W. C.. The kinetics of consecutive second-order reactions, Can. J. of Research., 1947, 25B: 415-19.
大庆石化总厂信息工艺模拟室编印. PRO/Ⅱ参考手册——组分和热力学性质与单元操作，1997.
张建侯，许锡恩 编著. 化工过程分析与计算机模拟，北京：化学工业出版社，1989.
金克新，赵传钧，马沛生 编. 化工热力学，天津：天津大学出版社，1990.
大庆石化总厂信息中心编译. PRO/Ⅱ关键字输入手册，1994.
DOW Chemical CO.? Process for ethanolamines, US patent, US4355181, 1982-10-19.
Christoph Brodmann, Urs Haller, Arvid K.Eldring. Know-how for Ethanolamine Production, Sulzer technical review, 2000, (2): 32~35.
高峰，诸爱士，沈剑仕. 管式反应器连续法合成乙醇胺反应技术的研究，精细石油化工，1990, (4): 24~28.
杨志才，何盛宝. 热敏物料的真空精馏，化学工程，1992, 20 (4): 19~23.
倪健. 高纯度三乙醇胺的生产，精细石油化工进展，2001, 2 (11): 46~50.
谭国民，杨志才. 热敏物料的蒸馏及常用设备（Ⅰ）——蒸馏过程的特征，化学工程师，2001, (4)：19~21.
姚玉英 主编. 化工原理 上册，天津：天津大学出版社，1999.
陆士庆 主编. 炼油工艺学，北京：中国石化出版社，1998.
王树楹 主编. 现代填料塔技术指南，北京：中国石化出版社，1998.
卢焕章等. 石油化工基础数据手册，北京：化学工业出版社，1982.
Hammar, H., et al. Ethanolamines and Propanolamines. In: Gerhartz W., et al. eds. Ullmann’s Encyclopedia of Industrial Chemistry. Weinheim, 1987, Vol Al0. 1~22.
何燕. 乙醇胺生产应用与开发前景，化工物资，1997, (3): 29~31.
徐长卿，杨秀全. 乙醇胺化学和国外生产技术概况，日用化学工业，1992, (6): 20~26.
吴兆立，蔡振云，谢荣锦. 国内外乙醇胺工艺流程评述，日用化学工业，1994, (2): 23~27.
BASF AG (DE). Process and apparatus for preparing or reacting alkanolamines, US patent, US4567303, 1986-01-28.
范竹文. 乙醇胺生产的先进技术，化工设计，1995, (1): 51~53.
柴义. 我国乙醇胺生产现状及发展对策，日用化学工业, 1992, (4): 21~25.
柴义. 乙醇胺技术考察报告，日用化学工业, 1992, (2): 51~54, 46.
Union Carbide Corp (US). Continuous process for preparing alkanolamines, US patent, US4847418, 1989-07-11.
BASF AG (DE). Production of ethanolamines, US patent, US5545757, 1996-08-13.
Nippon Catalytic Chem Ind (JP). Process for preparation for alkanolamine, catalyst used in the process and process for preparation of the catalyst, European patent, EP0652207, 1995-05-10.
Mitsui Toatsu Chemicals (JP). Process for preparing alkanolamines, European patent, EP0690043, 1996-01-03.
Huntsman Spec Chem Corp (US). Production of diethanolamine, US patent, US6063965, 2000-05-16.
Nippon Catalytic Chem Ind (JP). A process for producing dialkanolamines, European patent, EP0941986, 1999-09-15.
Melder Johann-Peter, Schulz Gerhard (DE). Process for the preparation of ethanolamines, US patent, US2002115890, 2002-08-22.
DOW Chemical Co.. Ammonation of trialkanolamines, US patent, US4328370, 1982-05-04.
Mechanism of soap browning uncovered, Chemical & Engineering News, sep.16 1996, 74(38): 42.
Buskens Philip (BE), Gutschoven Frank (BE), Melder Johann-Peter (DE), et al. Process for the preparation of alkanolamines having improved color quality, US patent, US2001031897, 2001-10-18.
BASF AG (DE). Method of purifying triethanolamine, US patent, US6388137, 2002-05-14.
BP Chemicals Inc (FR). Process for manufacturing triethanolamine and product obtained, US patent, US2003100798, 2003-05-29.
吴兆立，谢荣锦. 乙醇胺生产的液液管式反应工艺，中国专利，CN1049653A, 1991-03-06.
魏海国. 乙醇胺的管道化反应工艺，［硕士学位论文］，浙江大学, 1993.
吴兆立，谢荣锦，蔡振云. 乙醇胺生产的无水管式反应方法，中国专利，CN1139101A, 1997-01-01.
字敏，许世学，荆碧. 三乙醇胺合成方法改进，云南化工, 1998, (1): 40~41.
何健. 环氧乙烷和液氨合成乙醇胺新工艺的研究，广东化工, 1997, (5): 35~36.
徐荣福. 乙醇胺产品的生产及应用，高桥石化, 2000, (5): 51~53.
王传林，洪继承，王世学. 吉化乙醇胺装置简介，吉化科技, 1996, (4): 18~20.
黄海，杨秀全，徐长卿. 乙醇胺生产新技术，日用化学工业, 1996, (1): 1~3.
胡玉梅. 乙醇胺市场状况及其装置建设初探，石油化工技术经济, 2000, 16 (5): 37~40.
梁诚. 国内外乙醇胺生产现状与发展趋势，中国石油和化工分析报告,2002,(6):15~19.
朱开宏等. 化工过程流程模拟，北京：中国石化出版社，1993.
雷培德，李端阳，汪静. 化工流程模拟及其应用，节能，1994，（3）：6~8.
张志檩，叶立军，庄芹仙. 流程模拟中分解与切断的计算机处理方法探讨，化学工程，1995, 23(6): 59~61.
杨友麒. 过程流程模拟，计算机与应用化学，1995, 12(1): 1~6.
杨友麒. 化工过程模拟，化工进展，1996, (3): 1~7.
李文波，毛鹏生，王长英等. 化工流程模拟技术的现状与发展，化工时刊, 1998, 12(6): 3~6.
胡克林，罗金生. 化工过程模拟技术进展与趋势，新疆工学院学报，1997, 18(4): 254~257, 261.
天津大学物理化学教研室 编. 物理化学 上册，北京：高等教育出版社，1992
Eastham. A. M., Darwent B. deB., Beaubien. P. E.. Chemistry of ethylene oxide. Ⅱ. Kinetics of the reaction of ethylene oxide with amines in aqueous solution, Can. J. of Chem., 1951, 29: 575-84.
李绍芬 主编. 反应工程，北京：化学工业出版社，1990.
P. Ferrero, F. Berbe, L.R.Flamme. Kinetic study of the synthesis of Ethanolamines, Bull. soc. Chim, 1947, 56: 349-68.
Reich, H., et al. Reaction kinetic investigations of the synthesis of Ethanolamines, Chimia, 1966, 20 (1): 29~31.
Sir Soc Italiana Resine SPA. Process for the separation of monoethanolamine, diethanolamine, and triethanolamine from crude ethanolamine mixtures, US patent, US3849262, 1974-11-19.
Schultz, G., et al. Kinetic investigations on the oxyethylation of ammonia in concentrated aqueous solutions, Chem. lng. tech., 1986, 40: 446-8.
Potter. C., Macdonald. W. C.. The kinetics of consecutive second-order reactions, Can. J. of Research., 1947, 25B: 415-19.
大庆石化总厂信息工艺模拟室编印. PRO/Ⅱ参考手册——组分和热力学性质与单元操作，1997.
张建侯，许锡恩 编著. 化工过程分析与计算机模拟，北京：化学工业出版社，1989.
金克新，赵传钧，马沛生 编. 化工热力学，天津：天津大学出版社，1990.
大庆石化总厂信息中心编译. PRO/Ⅱ关键字输入手册，1994.
DOW Chemical CO.? Process for ethanolamines, US patent, US4355181, 1982-10-19.
Christoph Brodmann, Urs Haller, Arvid K.Eldring. Know-how for Ethanolamine Production, Sulzer technical review, 2000, (2): 32~35.
高峰，诸爱士，沈剑仕. 管式反应器连续法合成乙醇胺反应技术的研究，精细石油化工，1990, (4): 24~28.
杨志才，何盛宝. 热敏物料的真空精馏，化学工程，1992, 20 (4): 19~23.
倪健. 高纯度三乙醇胺的生产，精细石油化工进展，2001, 2 (11): 46~50.
谭国民，杨志才. 热敏物料的蒸馏及常用设备（Ⅰ）——蒸馏过程的特征，化学工程师，2001, (4)：19~21.
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