催化蒸馏生产醋酸丁酯新工艺模拟优化
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摘要
醋酸丁酯是一种性能优良的有机溶剂，广泛用于制药，涂料等行业。醋酸酯化传统上一般使用浓硫酸作催化剂，虽然转化率高，但存在着副反应多，腐蚀严重，后处理复杂和污染等问题。研究采用以固体酸为催化剂的连续反应精馏技术生产醋酸丁酯新工艺，该工艺通过反应精馏塔将化学反应过程与精馏分离过程耦合为一体，具有转化率高、选择性好、能耗低、操作容易、投资省、生产效率高、设备腐蚀轻及副反应少等一系列优点，并应用于企业的生产中，取得了一定的经济效益。
但是实践发现反应精馏工艺仍有需要改进之处，如从反应精馏塔出来的粗酯酸值高需要中和，精馏塔顶的返回料较多降低了生产效率。因此本文结合前人的研究工作在模拟优化的基础上，对该工艺流程做出了两处改进。一是反应精馏塔以前全是装填催化反应填料，一边反应一边分离，现在的反应精馏塔该由三部分组成，上部为具有部分冷凝作用的精馏段，装填普通填料；中部为反应精馏段，如同以前装有催化反应填料；下部为提馏段，装填普通的精馏。其中塔上部的精馏
广西大学硕士学位论文催化蒸馏生产醋酸丁醋新工艺模拟优化
段，具有回流量内部自动调节、控制响应速度快、操作能耗低等优点，
在间歇精馏、共沸精馏中有着良好的应用前景。二是在反应塔和精馏
塔间省去了中和工序，采用直接精馏粗醋以除去其中的少量醋酸。
本文用VisualC++编程，在分别对精馏塔和改进后反应精馏塔进
行模拟计算后，进一步对改进后的整个工艺流程进行了模拟和优化，
得到了该流程的操作规律和最佳工作状况，模拟结果表明采用改进后
的流程后，不仅得到质量更优的醋酸丁醋，而且简化了原工艺流程，
提高了生产效益，从理论上证明了本工艺流程的可行性和优越性，为
下一步的实验研究提供了方向和指导。
N-butyl acetate is of excellent performance as an organic, which is widely used in the pharmacy and the painting. Conventionally, sulfuric acid is often used as catalyst in the esterification of acetic acid. Although the rate of conversion is high in the process, many problems exists, such as too much secondary reaction, serious corrosion, complicated final treatment and pollution. The new technology to produce n-butyl acetate by continuously catalytic distillation technique with solid acid catalyst was combined with chemical reaction and separation process by reaction distillation tower. It had many advantages to produce n-butyl acetate by continuously catalytic distillation technique with solid acid catalyst, such as higher conversion, better selectivity, lower energy consumption, more simple operation, less investment, higher efficiency, less corrosion and side-reaction, and so on. It has been applied in industry and yielded a good economic returns.
However, the technology still need to be improved, ie. the concentration of acid in crude ester is quite high, which needs neutralization, and the more out-feed decreases the efficiency. So on the basis of previous simulation and optimization, two parts of the technology were modified. Firstly, the previous single reaction section was changed
into three parts, the upper part is distillation section with partial condensation, the middle the reaction section and the below the stripping section. The upper distillation section has many advantages, such as the inner automatic adjustment of reflux, faster responding speed controlled by reflux and lower energy consumption. It has good applying prospective in the batch distillation and the azeotropic distillation. Secondly, the neutralization process was removed between the reaction tower and distillation tower, and the direct distillation can also remove small quantity of acetic acid.
By use of Visual C++, the whole modified process after calculating the distillation tower and reaction tower was simulated respectively, and the operation rule and optimum operation condition was obtained. The results showed that the quality of n-butyl acetate was satisfactory, the old process reduced, and the efficiency was quite higher after being modified. Therefore the feasibility and superiority of new technology was proved in theory, and the direction and instruction for the next research was put forward.
但是实践发现反应精馏工艺仍有需要改进之处，如从反应精馏塔出来的粗酯酸值高需要中和，精馏塔顶的返回料较多降低了生产效率。因此本文结合前人的研究工作在模拟优化的基础上，对该工艺流程做出了两处改进。一是反应精馏塔以前全是装填催化反应填料，一边反应一边分离，现在的反应精馏塔该由三部分组成，上部为具有部分冷凝作用的精馏段，装填普通填料；中部为反应精馏段，如同以前装有催化反应填料；下部为提馏段，装填普通的精馏。其中塔上部的精馏
广西大学硕士学位论文催化蒸馏生产醋酸丁醋新工艺模拟优化
段，具有回流量内部自动调节、控制响应速度快、操作能耗低等优点，
在间歇精馏、共沸精馏中有着良好的应用前景。二是在反应塔和精馏
塔间省去了中和工序，采用直接精馏粗醋以除去其中的少量醋酸。
本文用VisualC++编程，在分别对精馏塔和改进后反应精馏塔进
行模拟计算后，进一步对改进后的整个工艺流程进行了模拟和优化，
得到了该流程的操作规律和最佳工作状况，模拟结果表明采用改进后
的流程后，不仅得到质量更优的醋酸丁醋，而且简化了原工艺流程，
提高了生产效益，从理论上证明了本工艺流程的可行性和优越性，为
下一步的实验研究提供了方向和指导。
N-butyl acetate is of excellent performance as an organic, which is widely used in the pharmacy and the painting. Conventionally, sulfuric acid is often used as catalyst in the esterification of acetic acid. Although the rate of conversion is high in the process, many problems exists, such as too much secondary reaction, serious corrosion, complicated final treatment and pollution. The new technology to produce n-butyl acetate by continuously catalytic distillation technique with solid acid catalyst was combined with chemical reaction and separation process by reaction distillation tower. It had many advantages to produce n-butyl acetate by continuously catalytic distillation technique with solid acid catalyst, such as higher conversion, better selectivity, lower energy consumption, more simple operation, less investment, higher efficiency, less corrosion and side-reaction, and so on. It has been applied in industry and yielded a good economic returns.
However, the technology still need to be improved, ie. the concentration of acid in crude ester is quite high, which needs neutralization, and the more out-feed decreases the efficiency. So on the basis of previous simulation and optimization, two parts of the technology were modified. Firstly, the previous single reaction section was changed
into three parts, the upper part is distillation section with partial condensation, the middle the reaction section and the below the stripping section. The upper distillation section has many advantages, such as the inner automatic adjustment of reflux, faster responding speed controlled by reflux and lower energy consumption. It has good applying prospective in the batch distillation and the azeotropic distillation. Secondly, the neutralization process was removed between the reaction tower and distillation tower, and the direct distillation can also remove small quantity of acetic acid.
By use of Visual C++, the whole modified process after calculating the distillation tower and reaction tower was simulated respectively, and the operation rule and optimum operation condition was obtained. The results showed that the quality of n-butyl acetate was satisfactory, the old process reduced, and the efficiency was quite higher after being modified. Therefore the feasibility and superiority of new technology was proved in theory, and the direction and instruction for the next research was put forward.
引文
[1] 济南市轻工研究所编译．合成食用香料手册．北京：轻工业出版社，1985：227～234
[2] 段长强等．现代化学试剂手册．第一分册．化学工业出版社，1988：198
[3] 童张法，韦藤幼，廖安平等．连续催化反应精馏生产醋酸丁酯的方法及设备．中国专利，ZL 94108405．1．1997
[4] 姚蒙正，王家儒等．精细化工产品合成原理．北京：中国石化出版社，1993：452
[5] 李鹏飞，庞先桑．在离子交换树脂上负载的固体超强酸催化剂的研制．精细石油化工，1993，(1)：17
[6] 文华．醋酸和正丁醇催化酯化反应精馏的研究[学位论文]．北京：北京化工大学，1995，7～28
[7] 杨志才，崔现宝，高静．乙酸与丁醇酯化反应精馏过程．化工学报，1998，49(1)：39
[8] 廖安平，童张法．连续催化反应精馏制备醋酸正丁酯．见：第七届全国化学工程论文报告会论文集．北京，1994，576～578
[9] 龙云飞，童张法，韦藤幼等．连续反应精馏制备醋酸正丁酯中试研究．化工研究进展：第五届全国高校化工工艺学术会论文集．北京化学工业出版社，北京，1996，421
[10] Backhaus A A. Us Patent 1400849, 1921
[11] 王龙延．催化蒸馏技术．现代化工，1990，4(2)：43～47．
[12] 许锡恩，朱宝福，陈洪钫等．反应精馏．石油化工，1985，14(8)：480～486
[13] Vankataramah S, Chan W K, Boston J F. Reactillation Using ASPEN PLUS, Chem Eng Progr, 1992, 88(3): 43
[14] Zhang Jirui, et al. Process and apparatus for preparation of ethylbenzene with dilute ethylene contained in dry gas by catalytic distillation[P]. US Patent Application:2001001845. 2001
[15] 宋少光．催化精馏合成乙二醇乙醚的研究．天津大学学位论文，1992，15～32
[16] Dorbon M, Chodorge J A, Cosyns J, et al. Process for the production of high purity isobutene combing reactive distillation with hydroisomedsation and skeletal isomerisation. US: 6 137 023, 2000
[17] Lawson K Ⅱ, Nkosi B. Production of MIBK using catalytic distillation technology.
US: 5 969 203, 1999.
[18] Barbosa D, Doherty D F. the influence of Equilibrium Chemical Reactions on Vapour_liquid Phase Diagrams, Chem. Eng. Sci., 1998, 43(3): 529
[19] Schaerfl Jr, Robert A, Day M J, et al. Preparation of substituted hydroxyhydrocinnamate esters by continuous transesterification using reactive distillation. US: 6 291 703, 2001
[20] Krishnamurthy R, Taylor R. A Nonequlibriun Stage Model of Nulticomponent Separation Process, Part Ⅰ: Model Description and method od Solution, AIChE J, 1985, 31(3): 449
[21] Suzuki I, Yagi H, Komatsu H, et al. Caluculation of Multicomponent Distillation Accompanied by a Chemical Reaction, J. Chem. Eng. Japan., 1971, 41(1): 26
[22] Piero B, et al. Ind. Chem. Ital., 1974, 10(1): 1
[23] Jelinek J, Hlavcek V, Chem. Eng. Commun., 1976, 2: 79
[24] 钱伯章．催化蒸馏技术及其应用．精细石油化工，1990，18(4)：3-10．
[25] Neson P. Countercurrent Equilibrium Stage Separation with Reaction. AIchE J, 1971, 17(5): 103
[26] Kaibel G, et al. Chem. Eng. Tech., 1978, 50(8): 586
[27] 刘训峰，张瑞生，袁渭康．伴有平衡反应的分离过程的数学模拟(Ⅰ)-板式反应精馏塔的模拟计算．化学反应工程与工艺，1993，9(3)：279～286．
[28] Broyden C G. Math. Comp., 1965, 19: 577
[29] Broyden C G. ibid, 1971, 25: 285
[30] Schubert L K. Modification of a Quasi-Newton Method for Nonlinear Equations with a sperse Jacobian, Math. Comp, 1970, 24: 27
[31] Leye L De, Froment G F, Comput. Chem. Eng., 1986, 10(5): 493
[32] 朱建华，沈复，反应精馏过程的非平衡级模型初探．计算机与应用化学，1995，11(3)：167
[33] 方永成，江桂秀，万爱媛，王怡敏．催化蒸馏数学模型的研究．石油炼制，1989，(2)：22～28．
[34] Sundamacher K, Hoffmann U. Development of a New Catalytic Distillation Process for fuel Ethers via a Detailed Nonequilibrium Model. Chem. Eng. Sci., 1996, 51(10): 2359～2368
[35] 吴燕翔 王良恩 赵之山，谭天恩．乙酸甲酯水解催化精馏过程催化剂包内的传质模型(Ⅰ)．化工学报，2002，52(5)：18～19
[36] 韩英，张瑞生．全回流催化精馏塔的模拟计算．华东化工学院学报，1989，15(3)：331～338．
[37] 唐正姣．催化酯化反应精馏过程模拟计算[硕士学位论文]．广西大学，1998，5～43
[38] 韦藤幼，袁海宽，童张法．无流量控制的间歇精馏方法及设备．中国专利，CN 1404896A．2003
[39] 华东理工大学计算中心热力学教研室．华东化工学院大型气液平衡数据库．上海，1988
[40] 陈中亮．化工计算机计算．化学工业出版社，2000：208～221
[41] 康金章．计算机数值方法．厦门：厦门大学出版社，1996，61～78
[42] Zhen Yuxiang, Xu xien. Study on Catalytic distillation Processes. Part Ⅰ: Mass Transfer Characteristics in Catalytic Bed within the Column. Trans. IChemE, 1992, 70(9): 459
[43] 许锡恩等．反应精馏．石油化工，1985，14(9)：550
[44] 韦圆红，李艳琳，童张法等．醋酸丁酯合成催化动力学研究．广西科学，1996，3(1)：32
[45] 马德坪，顾树珍，用分子筛催化剂液相合成乙酸乙酯．石油化工，1989，18(7)：431
[46] 张瑞生．板式反应精馏塔的模拟计算—修正的Newton-Raphson法．华东化工学院学报，1989，15(1)：25～314
[47] 盖旭东．反应蒸馏分离技术进展．现代化工，1995，15(5)：17～20
[48] 许锡恩，李家玲，刘铁涌．反应精馏过程的模拟．石油化工，1989，18：642～648．
[49] 韦藤幼，童张法．连续催化反应精馏生产醋酸丁酯新工艺．化工设计，2003，13(3)：14～16
[50] 将维钧，雷良恒，刘茂林．化工原理(下册)．北京：清华大学出版社，1993，34～67
[2] 段长强等．现代化学试剂手册．第一分册．化学工业出版社，1988：198
[3] 童张法，韦藤幼，廖安平等．连续催化反应精馏生产醋酸丁酯的方法及设备．中国专利，ZL 94108405．1．1997
[4] 姚蒙正，王家儒等．精细化工产品合成原理．北京：中国石化出版社，1993：452
[5] 李鹏飞，庞先桑．在离子交换树脂上负载的固体超强酸催化剂的研制．精细石油化工，1993，(1)：17
[6] 文华．醋酸和正丁醇催化酯化反应精馏的研究[学位论文]．北京：北京化工大学，1995，7～28
[7] 杨志才，崔现宝，高静．乙酸与丁醇酯化反应精馏过程．化工学报，1998，49(1)：39
[8] 廖安平，童张法．连续催化反应精馏制备醋酸正丁酯．见：第七届全国化学工程论文报告会论文集．北京，1994，576～578
[9] 龙云飞，童张法，韦藤幼等．连续反应精馏制备醋酸正丁酯中试研究．化工研究进展：第五届全国高校化工工艺学术会论文集．北京化学工业出版社，北京，1996，421
[10] Backhaus A A. Us Patent 1400849, 1921
[11] 王龙延．催化蒸馏技术．现代化工，1990，4(2)：43～47．
[12] 许锡恩，朱宝福，陈洪钫等．反应精馏．石油化工，1985，14(8)：480～486
[13] Vankataramah S, Chan W K, Boston J F. Reactillation Using ASPEN PLUS, Chem Eng Progr, 1992, 88(3): 43
[14] Zhang Jirui, et al. Process and apparatus for preparation of ethylbenzene with dilute ethylene contained in dry gas by catalytic distillation[P]. US Patent Application:2001001845. 2001
[15] 宋少光．催化精馏合成乙二醇乙醚的研究．天津大学学位论文，1992，15～32
[16] Dorbon M, Chodorge J A, Cosyns J, et al. Process for the production of high purity isobutene combing reactive distillation with hydroisomedsation and skeletal isomerisation. US: 6 137 023, 2000
[17] Lawson K Ⅱ, Nkosi B. Production of MIBK using catalytic distillation technology.
US: 5 969 203, 1999.
[18] Barbosa D, Doherty D F. the influence of Equilibrium Chemical Reactions on Vapour_liquid Phase Diagrams, Chem. Eng. Sci., 1998, 43(3): 529
[19] Schaerfl Jr, Robert A, Day M J, et al. Preparation of substituted hydroxyhydrocinnamate esters by continuous transesterification using reactive distillation. US: 6 291 703, 2001
[20] Krishnamurthy R, Taylor R. A Nonequlibriun Stage Model of Nulticomponent Separation Process, Part Ⅰ: Model Description and method od Solution, AIChE J, 1985, 31(3): 449
[21] Suzuki I, Yagi H, Komatsu H, et al. Caluculation of Multicomponent Distillation Accompanied by a Chemical Reaction, J. Chem. Eng. Japan., 1971, 41(1): 26
[22] Piero B, et al. Ind. Chem. Ital., 1974, 10(1): 1
[23] Jelinek J, Hlavcek V, Chem. Eng. Commun., 1976, 2: 79
[24] 钱伯章．催化蒸馏技术及其应用．精细石油化工，1990，18(4)：3-10．
[25] Neson P. Countercurrent Equilibrium Stage Separation with Reaction. AIchE J, 1971, 17(5): 103
[26] Kaibel G, et al. Chem. Eng. Tech., 1978, 50(8): 586
[27] 刘训峰，张瑞生，袁渭康．伴有平衡反应的分离过程的数学模拟(Ⅰ)-板式反应精馏塔的模拟计算．化学反应工程与工艺，1993，9(3)：279～286．
[28] Broyden C G. Math. Comp., 1965, 19: 577
[29] Broyden C G. ibid, 1971, 25: 285
[30] Schubert L K. Modification of a Quasi-Newton Method for Nonlinear Equations with a sperse Jacobian, Math. Comp, 1970, 24: 27
[31] Leye L De, Froment G F, Comput. Chem. Eng., 1986, 10(5): 493
[32] 朱建华，沈复，反应精馏过程的非平衡级模型初探．计算机与应用化学，1995，11(3)：167
[33] 方永成，江桂秀，万爱媛，王怡敏．催化蒸馏数学模型的研究．石油炼制，1989，(2)：22～28．
[34] Sundamacher K, Hoffmann U. Development of a New Catalytic Distillation Process for fuel Ethers via a Detailed Nonequilibrium Model. Chem. Eng. Sci., 1996, 51(10): 2359～2368
[35] 吴燕翔 王良恩 赵之山，谭天恩．乙酸甲酯水解催化精馏过程催化剂包内的传质模型(Ⅰ)．化工学报，2002，52(5)：18～19
[36] 韩英，张瑞生．全回流催化精馏塔的模拟计算．华东化工学院学报，1989，15(3)：331～338．
[37] 唐正姣．催化酯化反应精馏过程模拟计算[硕士学位论文]．广西大学，1998，5～43
[38] 韦藤幼，袁海宽，童张法．无流量控制的间歇精馏方法及设备．中国专利，CN 1404896A．2003
[39] 华东理工大学计算中心热力学教研室．华东化工学院大型气液平衡数据库．上海，1988
[40] 陈中亮．化工计算机计算．化学工业出版社，2000：208～221
[41] 康金章．计算机数值方法．厦门：厦门大学出版社，1996，61～78
[42] Zhen Yuxiang, Xu xien. Study on Catalytic distillation Processes. Part Ⅰ: Mass Transfer Characteristics in Catalytic Bed within the Column. Trans. IChemE, 1992, 70(9): 459
[43] 许锡恩等．反应精馏．石油化工，1985，14(9)：550
[44] 韦圆红，李艳琳，童张法等．醋酸丁酯合成催化动力学研究．广西科学，1996，3(1)：32
[45] 马德坪，顾树珍，用分子筛催化剂液相合成乙酸乙酯．石油化工，1989，18(7)：431
[46] 张瑞生．板式反应精馏塔的模拟计算—修正的Newton-Raphson法．华东化工学院学报，1989，15(1)：25～314
[47] 盖旭东．反应蒸馏分离技术进展．现代化工，1995，15(5)：17～20
[48] 许锡恩，李家玲，刘铁涌．反应精馏过程的模拟．石油化工，1989，18：642～648．
[49] 韦藤幼，童张法．连续催化反应精馏生产醋酸丁酯新工艺．化工设计，2003，13(3)：14～16
[50] 将维钧，雷良恒，刘茂林．化工原理(下册)．北京：清华大学出版社，1993，34～67