醋酸裂解制乙烯酮工业过程数学模拟
摘要
醋酸裂解法制醋酐在国际上是一种非常成熟的工艺路线。尽管较之成本更低的羰基合成法路线已经工业化20年了，但是这种路线仍然在全球被广泛采用。根据1998年的资料统计，在美国和西欧72％的醋酐仍然是醋酸裂解法生产出来的，而羰基合成法的产量仅为25％。
醋酸裂解法继续存在的另一个原因是，醋酸裂解制醋酐的中间产物—乙烯酮是一种非常活泼和有价值的中间体，它是由醋酸裂解产生的，所以醋酸裂解炉一直都备受关注。作者所在的吉化电石厂拥有10台这样的裂解炉。虽然自1965年投产以来，一直都在不断的挖潜改造，但是无论从产量还是从消耗来比较，都与国际先进水平存在很大的差距。从产量看，吉化电石厂一台裂解炉的能力相当于Celanese公司一台炉子的50％；从醋酸消耗来看，每生产一吨醋酐，吉化的装置要比国际先进水平多消耗45kg醋酸。产生上述差距的原因除了管理方面的因素外，更主要的是在理论方面缺乏深入的研究。
本文所采用的数学模型，是从生产实践出发，通过分析反应过程以及对反应动力学的研究而建立起来的，经过模拟实际条件下的反应过程证明，模拟的结果与实际生产过程中相对应的数据吻合的比较好，检验了模型的可靠性。在此基础上，用这个数学模型模拟了改造后的裂解炉，核定了反应器的生产能力。此外还利用模型对不同负荷的生产过程进行了模拟，找到了反应器的极限负荷以及不同负荷下的主要工艺条件，为下一步的开车工作提供了基准操作参数，避免了试车初始阶段操作的盲目性，也提高了此次改造的层次，从这一点来说意义是比较深远的。
The ketene route to acetic anhydride is a mature and widely used way in the production of acetic anhydride in the world, although the oxo synthesis process which owns a cheaper cost than the process of cracking acetic acid has been used for 20 years since it was developed in 1983 by Eastman Company. .According to the statistical data of 1998, 72% acetic anhydride is produced in the process of ketene route in America and West Europe, and the production in the oxo synthesis process is only about a quarter of the total production in the world in 1998.Another reason for the running of the cracking acetic acid route is that the ketene which is an intermediate product in manufacturing acetic anhydride by cracking acetic acid is a very active and valuable intermediate product. The cracking furnace of acetic acid has always been paid attention to. There are 10 such furnaces in the Calcium Carbide Factory of Jilin Chemical Industry Company Ltd. There is evident gap between the world most advanced level and our Factory, not only in the production capacity but also in the consumption of materials, although we have been tapping the potential since our Factory went into operation in 1965. The production capacity of a furnace in our Factory is only half of a furnace in the Celanese Company, and for the consumption of acetic acid in producing 1000kg acetic anhydride, the world most advanced level is 45kg less than our consumption. One of the reasons to which lead the gap mainly lies in lacking deep fundamental research and theoretical analysis to the industrial process.The mathematical model used in this paper proceeds from actual conditions and is set up by analyzing the course of reaction and studying the reaction kinetics. It is proved by simulating the course of reaction under actual conditions that the simulated result tallies
with the corresponding data in actual course of production and the reliability of the model is tested. On the basis of the simulation, this mathematical model is used for simulating the reformed cracking furnace and its capacity is checked. In addition, this mathematical model is used for simulating the course of production under the conditions of several loads. The limited load and the main technological conditions under the conditions of several loads are defined, and then the datum operation parameters are provided. This simulated result avoids the blindness at the beginning of the breaking-in period and improves the grade of the reformation. From this point of view this simulation has profound significance.
醋酸裂解法继续存在的另一个原因是，醋酸裂解制醋酐的中间产物—乙烯酮是一种非常活泼和有价值的中间体，它是由醋酸裂解产生的，所以醋酸裂解炉一直都备受关注。作者所在的吉化电石厂拥有10台这样的裂解炉。虽然自1965年投产以来，一直都在不断的挖潜改造，但是无论从产量还是从消耗来比较，都与国际先进水平存在很大的差距。从产量看，吉化电石厂一台裂解炉的能力相当于Celanese公司一台炉子的50％；从醋酸消耗来看，每生产一吨醋酐，吉化的装置要比国际先进水平多消耗45kg醋酸。产生上述差距的原因除了管理方面的因素外，更主要的是在理论方面缺乏深入的研究。
本文所采用的数学模型，是从生产实践出发，通过分析反应过程以及对反应动力学的研究而建立起来的，经过模拟实际条件下的反应过程证明，模拟的结果与实际生产过程中相对应的数据吻合的比较好，检验了模型的可靠性。在此基础上，用这个数学模型模拟了改造后的裂解炉，核定了反应器的生产能力。此外还利用模型对不同负荷的生产过程进行了模拟，找到了反应器的极限负荷以及不同负荷下的主要工艺条件，为下一步的开车工作提供了基准操作参数，避免了试车初始阶段操作的盲目性，也提高了此次改造的层次，从这一点来说意义是比较深远的。
The ketene route to acetic anhydride is a mature and widely used way in the production of acetic anhydride in the world, although the oxo synthesis process which owns a cheaper cost than the process of cracking acetic acid has been used for 20 years since it was developed in 1983 by Eastman Company. .According to the statistical data of 1998, 72% acetic anhydride is produced in the process of ketene route in America and West Europe, and the production in the oxo synthesis process is only about a quarter of the total production in the world in 1998.Another reason for the running of the cracking acetic acid route is that the ketene which is an intermediate product in manufacturing acetic anhydride by cracking acetic acid is a very active and valuable intermediate product. The cracking furnace of acetic acid has always been paid attention to. There are 10 such furnaces in the Calcium Carbide Factory of Jilin Chemical Industry Company Ltd. There is evident gap between the world most advanced level and our Factory, not only in the production capacity but also in the consumption of materials, although we have been tapping the potential since our Factory went into operation in 1965. The production capacity of a furnace in our Factory is only half of a furnace in the Celanese Company, and for the consumption of acetic acid in producing 1000kg acetic anhydride, the world most advanced level is 45kg less than our consumption. One of the reasons to which lead the gap mainly lies in lacking deep fundamental research and theoretical analysis to the industrial process.The mathematical model used in this paper proceeds from actual conditions and is set up by analyzing the course of reaction and studying the reaction kinetics. It is proved by simulating the course of reaction under actual conditions that the simulated result tallies
with the corresponding data in actual course of production and the reliability of the model is tested. On the basis of the simulation, this mathematical model is used for simulating the reformed cracking furnace and its capacity is checked. In addition, this mathematical model is used for simulating the course of production under the conditions of several loads. The limited load and the main technological conditions under the conditions of several loads are defined, and then the datum operation parameters are provided. This simulated result avoids the blindness at the beginning of the breaking-in period and improves the grade of the reformation. From this point of view this simulation has profound significance.
引文
[1] 高春红，《乙醛醋酸及其衍生物》，全国醋酸醋酐行业协作组，[4]，11～13，(1999)
[2] 《醋酸酐生产工艺规程》，吉化公司电石厂，1998．7
[3] 《Acetic Acid/Acetic Anhydride》 , 97/98-1, PREP [1], 1999
[4] G.V. Jeffreys M. Sc., F. R. I. C., A. M. I. Chem. E. 《A Problem in Chemical Engineering Design—The Manufacture of Acetic Anhydride》, Department of Chemical Engineering, University of Birmingham Member of the Board of Examiners of The Institution of Chemical Engineer, 1961
[5] Howard, M. J. et al. Catalysis Today,18(1993), pp. 325-354
[6] Gauss M. et al. Appl. Homogen. Catal. Organ. Compd., 1 (1996), pp. 104-138
[7] Chem Systems Chem Systems' PERP Report 91-1, July 1993
[8] 柴国梁，《乙醛醋酸及其衍生物》，全国醋酸醋酐行业协作组，[1]，20～24(2000)
[9] 《第三次全国醋酸醋酐生产经营情况调查报告》，全国醋酸醋酐行业协作组，[6](1997)
[10] 罗忠禹，《计算机与应用化学》，[4]，139(1987)
[11] 《乙醛醋酸及其衍生物》，全国醋酸醋酐行业协作组，[3]，37～49(1994)
[12] 卢焕章等编著，《石油化工基础数据手册》，化学工业出版社，1982．2
[13] 马沛生等编著，《石油化工基础数据手册》续编，化学工业出版社，1993．3
[14] 冯伯华等编，《化工工程手册》，第2卷，8-237～8-247，化学工业出版社，1989．10
[15] 洪钱林，《石油化工》，[11]，361(1982)
[16] C. H. Bamford et al. ,J. Chem. Soc. ,2877(1949)
[17] P. G. Blake et al. ,J. Chem. Soc. ,(B), 1153(1968)
[18] P. G. Blake et al. ,J. Chem. Soc. ,(B),94(1969)
[19] P. K. Dehpande et al. ,I& EC Pro. Des. and Dev. ,7[4],511(1968)
[20] 《Acetic Acid and Its Derivatives》, 161-171 (1993)
[21] 李绍芬主编，《反应工程》，化学工业出版社，1990．6
[22] 《Acetic Acid/Acetic Anhydride》 ,PREP [7] ,1993
[23] 《Acetic Anhydride by Carbonylation: Base Metal Catalysts》 PREP [12] 1989
[24] 《Acetic Anhydride by Vapor Phase Carbonylation -Hoechst》PREP [9] 1989
[25] 《Acetyls: Vinyl Acetate, AceticAcid and Anhydride》PREP [06] (1989)
[2] 《醋酸酐生产工艺规程》，吉化公司电石厂，1998．7
[3] 《Acetic Acid/Acetic Anhydride》 , 97/98-1, PREP [1], 1999
[4] G.V. Jeffreys M. Sc., F. R. I. C., A. M. I. Chem. E. 《A Problem in Chemical Engineering Design—The Manufacture of Acetic Anhydride》, Department of Chemical Engineering, University of Birmingham Member of the Board of Examiners of The Institution of Chemical Engineer, 1961
[5] Howard, M. J. et al. Catalysis Today,18(1993), pp. 325-354
[6] Gauss M. et al. Appl. Homogen. Catal. Organ. Compd., 1 (1996), pp. 104-138
[7] Chem Systems Chem Systems' PERP Report 91-1, July 1993
[8] 柴国梁，《乙醛醋酸及其衍生物》，全国醋酸醋酐行业协作组，[1]，20～24(2000)
[9] 《第三次全国醋酸醋酐生产经营情况调查报告》，全国醋酸醋酐行业协作组，[6](1997)
[10] 罗忠禹，《计算机与应用化学》，[4]，139(1987)
[11] 《乙醛醋酸及其衍生物》，全国醋酸醋酐行业协作组，[3]，37～49(1994)
[12] 卢焕章等编著，《石油化工基础数据手册》，化学工业出版社，1982．2
[13] 马沛生等编著，《石油化工基础数据手册》续编，化学工业出版社，1993．3
[14] 冯伯华等编，《化工工程手册》，第2卷，8-237～8-247，化学工业出版社，1989．10
[15] 洪钱林，《石油化工》，[11]，361(1982)
[16] C. H. Bamford et al. ,J. Chem. Soc. ,2877(1949)
[17] P. G. Blake et al. ,J. Chem. Soc. ,(B), 1153(1968)
[18] P. G. Blake et al. ,J. Chem. Soc. ,(B),94(1969)
[19] P. K. Dehpande et al. ,I& EC Pro. Des. and Dev. ,7[4],511(1968)
[20] 《Acetic Acid and Its Derivatives》, 161-171 (1993)
[21] 李绍芬主编，《反应工程》，化学工业出版社，1990．6
[22] 《Acetic Acid/Acetic Anhydride》 ,PREP [7] ,1993
[23] 《Acetic Anhydride by Carbonylation: Base Metal Catalysts》 PREP [12] 1989
[24] 《Acetic Anhydride by Vapor Phase Carbonylation -Hoechst》PREP [9] 1989
[25] 《Acetyls: Vinyl Acetate, AceticAcid and Anhydride》PREP [06] (1989)