三乙烯二胺分离工艺的设计与模拟
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摘要
三乙烯二胺是聚氨酯工业中应用最广,用量最大聚氨类催化剂。近年来聚氨酯泡沫塑料发展十分迅速,其产量已在聚氨酯中占到80%,随着应用范围的日渐广泛,对催化剂三乙烯二胺的需求亦会大幅度增加。工业催化教研室研究出制备三乙烯二胺新方法,具有较高的选择性,研究其产物的分离设计与模拟,进行可行性分析,有助于将其投入工业生产,实现工业化。
ASPEN PLUS是美国ASPEN技术公司的先进流程模拟软件,采用此软件进行流程模拟,为企业提供准确的单元操作模型,可以大大提高模拟效率,还可以进行已有装置的优化操作或新建、改建装置的优化设计。
本文以ASPEN PLUS软件为工作平台,采用严格精馏塔操作单元,并以NRTL和ELECNRTL热力学方程物性计算方法对三乙烯二胺的分离纯化工艺流程进行了模拟,用ASPEN PLUS的Property Estimation(性质估计)对两种未知物质的物性做了有效准确的估计,给出了相应的工艺参数。通过直观推断法和调优法得出要研究的四个精馏序列,以能耗和设备费用为目标函数对它们进行了研究。在模拟过程中重点考察了模拟过程中塔板数、进料位置和塔顶采出量等参数的变化对整个模拟计算结果所产生的影响。经过分析得出最优的分离序列,可以得到97.86%质量浓度的哌嗪和哌嗪衍生物的混合产品及96.57%质量浓度的三乙烯二胺。
一些工艺物流需要加热,而另一些工艺物流则需要冷却,把这些物流匹配在一起,充分利用热物流去加热冷物流,提高过程的热回收率,对分离序列进行热集成研究。采用夹点分析法和问题表格法对分离序列进行换热网络综合,获得更加节省能量的热集成分离工艺流程,节省能量达48.29%。
Triethylenediamine is not only the most widely used but also the largest demanded polyammonia catalyst in the area of polyurethane industry. Recently, polyurethane foam develops quite rapidly, which occupies approximately 80% in the overall polyurethane products. With the application area becoming larger, the demand for catalyst triethylenediamine increases drastically. Industry catalysis research institute develops a new method of making triethylenediamine, which has a relatively higher selectivity. The researches on the design, simulation of the separation process of the reaction products and the analysis of the feasibility, are quite helpful to put this method into industrial production and realize industrialization.Software-ASPEN PLUS is an advanced software for process simulation which is produced by ASPEN Co. in America. Using this software to simulate the process, accurate unit operation models can be provided for enterprises . It can not only increase simulation efficiency but also can evaluate the operation of the original equipment and reconstruct, remodify the original equipment to reach a most excellent design.Software ASPEN PLUS is chosen as the working platform in this article, strict distillation tower operation unit is adopted. The NRTL and ELECNRTL thermod ynamic equations are used to simulate the process of separating and purifying triethylenediamine.The function of property estimation within software Aspen Plus is used to estimate the physical property of two unknown substances effectively and accurately. Consequently, reasonable technological parameters are obtained. Choosing energy consumption and equipment consumption as the objective functions, four distillation separation sequences are chosen based on the methods of direct deduction and optimization. Some important parameters such as the number of the plates, feed stage and flow rate of overhead product are studied during the simulation process. The effect of the changing of those parameters on the whole simulation process is also studied. The best separation sequence is chosen through analysis. The mass fraction of Piperazine, 2MP, NEP is 97.86% and triethylenediamine's mass fractionis 96.57% through the treatment of it.Some technical streams need to be heated while others need to be cooled. Mixing those streams together and completely using hot streams to heat cool streams to enhance the heat
recycling rate. At the same time, the separation sequence's heat integration is studied. Pinch technology and Problem Table are adopted to study heat exchange network of the separation sequence. More energy saving separation technical process is obtained. Energy saving can be reached 48.29%.
ASPEN PLUS是美国ASPEN技术公司的先进流程模拟软件,采用此软件进行流程模拟,为企业提供准确的单元操作模型,可以大大提高模拟效率,还可以进行已有装置的优化操作或新建、改建装置的优化设计。
本文以ASPEN PLUS软件为工作平台,采用严格精馏塔操作单元,并以NRTL和ELECNRTL热力学方程物性计算方法对三乙烯二胺的分离纯化工艺流程进行了模拟,用ASPEN PLUS的Property Estimation(性质估计)对两种未知物质的物性做了有效准确的估计,给出了相应的工艺参数。通过直观推断法和调优法得出要研究的四个精馏序列,以能耗和设备费用为目标函数对它们进行了研究。在模拟过程中重点考察了模拟过程中塔板数、进料位置和塔顶采出量等参数的变化对整个模拟计算结果所产生的影响。经过分析得出最优的分离序列,可以得到97.86%质量浓度的哌嗪和哌嗪衍生物的混合产品及96.57%质量浓度的三乙烯二胺。
一些工艺物流需要加热,而另一些工艺物流则需要冷却,把这些物流匹配在一起,充分利用热物流去加热冷物流,提高过程的热回收率,对分离序列进行热集成研究。采用夹点分析法和问题表格法对分离序列进行换热网络综合,获得更加节省能量的热集成分离工艺流程,节省能量达48.29%。
Triethylenediamine is not only the most widely used but also the largest demanded polyammonia catalyst in the area of polyurethane industry. Recently, polyurethane foam develops quite rapidly, which occupies approximately 80% in the overall polyurethane products. With the application area becoming larger, the demand for catalyst triethylenediamine increases drastically. Industry catalysis research institute develops a new method of making triethylenediamine, which has a relatively higher selectivity. The researches on the design, simulation of the separation process of the reaction products and the analysis of the feasibility, are quite helpful to put this method into industrial production and realize industrialization.Software-ASPEN PLUS is an advanced software for process simulation which is produced by ASPEN Co. in America. Using this software to simulate the process, accurate unit operation models can be provided for enterprises . It can not only increase simulation efficiency but also can evaluate the operation of the original equipment and reconstruct, remodify the original equipment to reach a most excellent design.Software ASPEN PLUS is chosen as the working platform in this article, strict distillation tower operation unit is adopted. The NRTL and ELECNRTL thermod ynamic equations are used to simulate the process of separating and purifying triethylenediamine.The function of property estimation within software Aspen Plus is used to estimate the physical property of two unknown substances effectively and accurately. Consequently, reasonable technological parameters are obtained. Choosing energy consumption and equipment consumption as the objective functions, four distillation separation sequences are chosen based on the methods of direct deduction and optimization. Some important parameters such as the number of the plates, feed stage and flow rate of overhead product are studied during the simulation process. The effect of the changing of those parameters on the whole simulation process is also studied. The best separation sequence is chosen through analysis. The mass fraction of Piperazine, 2MP, NEP is 97.86% and triethylenediamine's mass fractionis 96.57% through the treatment of it.Some technical streams need to be heated while others need to be cooled. Mixing those streams together and completely using hot streams to heat cool streams to enhance the heat
recycling rate. At the same time, the separation sequence's heat integration is studied. Pinch technology and Problem Table are adopted to study heat exchange network of the separation sequence. More energy saving separation technical process is obtained. Energy saving can be reached 48.29%.
引文
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[2] 张瑞生,王弘轼,宋宏宇.过程系统工程概论.北京:科学出版社,2001.
[3] Rudd D.F., Watson C.C..Strategy of Process Engineering. USA:John Wiley and Sons, 1968.
[4] Himmelblau D.M., Bischoff K.B..Process Analysis and Simulation. USA: John Wiley and Sons, 1968.
[5] 矢木荣,西村肇.化学学.日本:丸善株式会社,1969.
[6] 陈丙珍译.控制论方法在化学和化工中的应用.北京:化学工业出版社,1983.
[7] 张瑞生,沈才大.化工系统工程基础.上海:华东化工学院出版社,1991.
[8] 格隆等著,陆震维译.过程系统工程(上册).北京:化学工业出版社,1983.
[9] 曲平,俞裕国.化工过程模拟与优化.大连:大连理工大学化工学院内部教材,1998.
[10] 姚平经.过程系统分析与综合(第二版).大连:大连理工大学出版社,2004.
[11] Westerberg A W, Hutchison H P, Motard R L, and Winter P. Process Flowsheeting. England: Cambridge University Press, 1979.
[12] 雷培德,李端阳,汪静,陈献忠.化工过程模拟技术及HYSIM模拟系统在化工生产中的应用.湖北化工,2002,(6):4-6.
[13] 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.
[14] 冯权莉.通用化工流程模拟技术进展与应用.云南工业大学学报,1996,12(1):52-57.
[15] 唐宏青.合成氨流程模拟与分析系统SAPROSS(Ⅱ)(上).化工设计,1995,(1):29-32.
[16] 陆恩锡,张慧娟,尹清华.化工过程模拟及相关高新技术(Ⅰ)化工过程稳态模拟.化工进展,1999,(4):63-64.
[17] 麻德贤,李成岳,张卫东.化工过程分析与合成.北京:化学工业出版社,2002.
[18] 杨友麒.化工过程系统模拟新进展.化学工程.1992,20(2):72-79.
[19] 荣本光,利海,韩方煜等.用序贯模块法模拟多组分完全复杂的精馏流程(Ⅰ)模型与算法策略.计算机与应用化学,1996,13(3):161-166.
[20] 陆恩锡,张慧娟.化工过程模拟及相关高新技术(Ⅱ)化工过程动态模拟.化工进展,2000,(1):76-78.
[21] 陈晓春,马桂荣.动态模拟技术与化学工程.现代化工.2002,22(3):14-17.
[22] 姚平经.化工过程系统工程.大连:大连理工大学出版社,1992.
[23] 张述伟,陆明亮,徐志武.低温甲醇洗系统模拟与分析.化肥设计,1994,(32):25-31.
[24] 周传光,李玉刚,韩方煜.尿素装置解析塔的模拟.计算机与应用化学,1995,(2):109-113.
[25] 周传光,金思毅,张青瑞,崔波,赵文.中型合成氨装置在线数据校正与模拟优化软件的设计与实现.青岛化工学院学报,1998,19(1):70-74.
[26] 郭建锐,张述伟,王长英,俞裕国,湿式冷却塔评估软件的开发,2003,4:283-285.
[27] 原璐,吕海霞,项曙光.Aspen Plus功能扩展方法探讨.青岛科技大学学报,2005,26(2):128-132.
[28] 谢扬,沈庆扬.ASPEN PLUS化工模拟系统在精馏过程中的应用.化工生产与技术,1996,6(3):17-22.
[29] 徐亦方,邬亚男,陈志奎等.ASPEN PLUS/Model Manager操作100例.北京:石油化工出版社,1994.
[30] ASPEN Technology Inc. ASPEN PLUS 10.0 USER GUIDE. US: Aspen Technology Inc, 1994.
[31] Luyben, W.L. etc. Process Modeling Simulation and Control for Chemical Engineers. 2nd Ed. New York: Mcgraw-Hill, 1990.
[32] 吴冠京等.ASPEN PLUS物性方法和模型.大庆:大庆石化总厂计算机开发公司,1999.
[33] 谢安俊,刘世华,张华岩,陈斌.大型化工流程模拟软件—ASPEN PLUS.石油与天然气化工,1995,24(4):247-251.
[34] 王文庆,李延辉.Aspen软件在大型聚乙烯装置上的应用.合成树脂及塑料,2004,21(3):43-47.
[35] 中国化工品大全[M].北京:中国物资出版社,1995.
[36] 王志刚,翟封振,卫慧凯,王向容,葛晓东.三乙烯二胺合成工艺研究[J].精细化工,1994,11(6):57-60.
[37] 李海涛,王旭,高峰,董维佳.三乙烯二胺合成技术述评[J].化学工业与工程技术,2001,22(6):35.
[38] 巴斯福股份公司.在高纯度三亚乙基二胺(TEDA)制备中所得母液的处理.中国,CN1385430A,2002.12.18.
[39] Josef D, Process and catalysts for manufacture of 1, 4-diazabicyclo [2.2.2] octane from piperazine. Germany, DE3735214.1989.
[40] Wolfgang H. Preparation of 1, 4-diazabicyclo [2.2.2] octane from piperazine. Germany, DE3823160.1990.
[41] Katsuyoshi S. 1, 4-diazabicyclo [2.2.2] octane. Japan, JP141895.1976.
[42] Hans Josef B. Preparation of triethylenediamine and piperazine. Germany, DE3934459. 1991.
[43] Harubito S. Crystalline silicate catalysts for the manufacture of triethylenediamines. Japan, JP122654. 1988.
[44] Horst H. 1, 4-diazabicyclo [2.2.2] octane. Germany, DE206896.1984.
[45] 董宏光,王涛,秦立民,姚平经,袁一.精馏分离序列综合邻域结构的研究.华东理工大学学报,2004,30(1):29-33.
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