一氯丙酮生产工艺开发研究
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摘要
本文采用管式反应器，以丙酮和氯气为原料合成一氯丙酮，考察了反应物料相态、反应管尺寸、反应物料配比等因素对反应结果的影响；研究了共沸精馏分离沸点及其相近的氯丙酮混合物；进行了100t/a一氯丙酮中试的研究和设计。中试产品经过数家制药企业使用，产品符合制药企业的质量要求。
丙酮与氯气反应制取一氯丙酮，是一个快速的连锁反应。采用管式反应器，可有效抑制二氯和多氯丙酮的生成，提高反应的选择性。丙酮气化后与氯气反应，较之液态丙酮与氯气反应，物料易于混合，可通过控制反应物配比和单程转化率来提高反应的选择性，抑制二氯及多氯产物的生成。气相停留时间直接影响反应转化率和选择性。本研究课题没有花费大量时间进行动力学测定，直接采用尺寸不等的反应管考察反应结果，确定优选的工艺条件。经过实验，选定Φ20*600mm的反应管进行氯化反应，物料配比为：丙酮/氯气=4：1-5：1(摩尔比)。
丙酮氯化制备一氯丙酮时，难免会有少量的1、1-二氯丙酮产生，由于二者沸点仅相差0.3℃，常规分离方法不能将两者分开。通过实验研究，确定采用水作共沸剂，恒沸蒸馏分离氯丙酮混合物。实验确定共沸剂水的加入量与氯丙酮混合液的比例为1：1(体积比)时，能达到良好的分离效果，可得到纯度99％以上的一氯丙酮。
反应过程的放大是过程放大的核心和关键。参照小试反应管参数和工艺参数，采用多根同尺寸反应管并联的列管式反应器作为中试反应器，有效减小了“放大效应”的影响。在综合考虑产品质量、生产成本、环境保护等因素的前提下，进行工艺流程设计，在生产一氯丙酮的同时，副产染料级氯丙酮和盐酸，既减少环境污染，又降低了生产成本。
该生产工艺流程简单，过程易于控制。中试装置经过正常运转和成本核算，证明该生产工艺技术可行，投资少，污染小，具有较好的经济效益和社会效益。
This thesis focuses on developing a novel technology to produce Monochloroacetone in high degree of purity and less environmental pollution.
Monochloroacetone is prepared by the reaction of acetone vapor with chlorine in a pipe reactor. The influence of several factors on the reaction, such as the states
of acetone in the reaction, sizes of the pipe reactor, ratios of acetone to chlorine, has been investigated experimentally and theoretically. The reaction of acetone
with chlorine gas is a rapid chain reaction. Using a pipe reactor can diminish formation of polychlorinated products. Comparing with liquid acetone ,acetone vapor is
easier to mix with chlorine gas and this will befits to the results of the reaction. Selectivity of the reaction can be increased by controlling ratio of acetone to chlorine
and conversion per pass of acetone. Residence time of reactants in the pipe reactor is a main factor to influence the conversion of acetone and selectivity of the reaction.
We didn't spend much more time on establishment of dynamics equation of the reaction, but carry out the reaction in a series of different sizes pipe reactors to get the
best technological parameters. That is the size of reactor is 20·600mm and the ratio of acetone to chlorine is 4: 1-5: 1 (mole ratio).
The mixture of Monochloroacetone and 1,1-dichloroacetone ,which have very similar boiling points, the difference of boiling points of theses two compounds is only 0.3℃, is
separated by azeotropic distillation using water as azeotropic former. The purity of Monochloroacetone can be reached to 99% by azeotropic distillation in the ratio of water
to the mixture of Monochloroacetone and 1,1-dichloroacetone 1:1(volume ration).
The amplification of reactor is the core of scaling process. We designed a tubular reactor with one hundred tubes that have same sizes with the pipe reactor in laboratory research and operate under the same
technological condition with laboratory experiments. This way minimize the "scaling effects" in scaling process. Based on the consideration of purity and cost of the products and environmental protection, the process is designed to produce Monochloroacetone as well as by products of choloroacetone for dyestuff manufacture and hydrochloric acid to reduce cost and avoid pollution.
The pilot plant research in the scale of 100t/a Monochloroacetone and the design of the producing process have been done. And the products of Monochloroacetone of this pilot apparatus have been tested and used by several pharmaceutical factories. The quality of Monochloroacetone meets the quality requirement of pharmaceutical industry. And the apparatus has been running more than two years profitably.
丙酮与氯气反应制取一氯丙酮，是一个快速的连锁反应。采用管式反应器，可有效抑制二氯和多氯丙酮的生成，提高反应的选择性。丙酮气化后与氯气反应，较之液态丙酮与氯气反应，物料易于混合，可通过控制反应物配比和单程转化率来提高反应的选择性，抑制二氯及多氯产物的生成。气相停留时间直接影响反应转化率和选择性。本研究课题没有花费大量时间进行动力学测定，直接采用尺寸不等的反应管考察反应结果，确定优选的工艺条件。经过实验，选定Φ20*600mm的反应管进行氯化反应，物料配比为：丙酮/氯气=4：1-5：1(摩尔比)。
丙酮氯化制备一氯丙酮时，难免会有少量的1、1-二氯丙酮产生，由于二者沸点仅相差0.3℃，常规分离方法不能将两者分开。通过实验研究，确定采用水作共沸剂，恒沸蒸馏分离氯丙酮混合物。实验确定共沸剂水的加入量与氯丙酮混合液的比例为1：1(体积比)时，能达到良好的分离效果，可得到纯度99％以上的一氯丙酮。
反应过程的放大是过程放大的核心和关键。参照小试反应管参数和工艺参数，采用多根同尺寸反应管并联的列管式反应器作为中试反应器，有效减小了“放大效应”的影响。在综合考虑产品质量、生产成本、环境保护等因素的前提下，进行工艺流程设计，在生产一氯丙酮的同时，副产染料级氯丙酮和盐酸，既减少环境污染，又降低了生产成本。
该生产工艺流程简单，过程易于控制。中试装置经过正常运转和成本核算，证明该生产工艺技术可行，投资少，污染小，具有较好的经济效益和社会效益。
This thesis focuses on developing a novel technology to produce Monochloroacetone in high degree of purity and less environmental pollution.
Monochloroacetone is prepared by the reaction of acetone vapor with chlorine in a pipe reactor. The influence of several factors on the reaction, such as the states
of acetone in the reaction, sizes of the pipe reactor, ratios of acetone to chlorine, has been investigated experimentally and theoretically. The reaction of acetone
with chlorine gas is a rapid chain reaction. Using a pipe reactor can diminish formation of polychlorinated products. Comparing with liquid acetone ,acetone vapor is
easier to mix with chlorine gas and this will befits to the results of the reaction. Selectivity of the reaction can be increased by controlling ratio of acetone to chlorine
and conversion per pass of acetone. Residence time of reactants in the pipe reactor is a main factor to influence the conversion of acetone and selectivity of the reaction.
We didn't spend much more time on establishment of dynamics equation of the reaction, but carry out the reaction in a series of different sizes pipe reactors to get the
best technological parameters. That is the size of reactor is 20·600mm and the ratio of acetone to chlorine is 4: 1-5: 1 (mole ratio).
The mixture of Monochloroacetone and 1,1-dichloroacetone ,which have very similar boiling points, the difference of boiling points of theses two compounds is only 0.3℃, is
separated by azeotropic distillation using water as azeotropic former. The purity of Monochloroacetone can be reached to 99% by azeotropic distillation in the ratio of water
to the mixture of Monochloroacetone and 1,1-dichloroacetone 1:1(volume ration).
The amplification of reactor is the core of scaling process. We designed a tubular reactor with one hundred tubes that have same sizes with the pipe reactor in laboratory research and operate under the same
technological condition with laboratory experiments. This way minimize the "scaling effects" in scaling process. Based on the consideration of purity and cost of the products and environmental protection, the process is designed to produce Monochloroacetone as well as by products of choloroacetone for dyestuff manufacture and hydrochloric acid to reduce cost and avoid pollution.
The pilot plant research in the scale of 100t/a Monochloroacetone and the design of the producing process have been done. And the products of Monochloroacetone of this pilot apparatus have been tested and used by several pharmaceutical factories. The quality of Monochloroacetone meets the quality requirement of pharmaceutical industry. And the apparatus has been running more than two years profitably.
引文
[1]郭惠元，中国医药工业杂志，1994；25(10)：465
[2]王而华等，中国医药工业杂志，1991；22(9)：385
[3]戚建军等，中国医药工业杂志，1998；29(6)：243
[4]周伟澄等，中国医药工业杂志，1997；28(2)：59
[5]上海染料，1997；1：20
[6]张思规等，精细有机化学品技术手册，科学出版社，1991
[7]周伟澄，中国医药工业杂志，1997；28(3)：154
[8]郝素娥，精细有机合成单元反应与合成设计，哈尔滨工业大学出版社，2001
[9]张铸勇，精细有机合成单元反应，华东化工学院出版社，1995
[10]王积涛等，有机化学，南开大学出版社，1993
[11]李述文等，实用有机化学手册，上海科技出版社，1981
[12]段长强等，现代化学试剂手册，化学工业出版社，1986
[13]Methoden der organischen Chemie,Brand V/3: 615
[14]雷国明，四川化工，1992；(1)：18
[15]J.Peter Guthrie et. CAN.J.Chem 1986,64:1250
[16]Clamens, Serge, et. Fr. Demande FR 2,633,614,(1990)
[17]Hiegel, Gene A. et. Synth.Comun.,1985; 15 (5): 385
[18]J. Org. Chem. 1960;29:1956
[19] 周桑其，化学通报，1994；6，36
[20]Dolidze, S.V. et. Soobshch. Akad. Nauk Gruz. SSR, 1987;128(1):69(RUSS)
[21]Distler, et. Ger. off. 1971,2018972
[22]Akamatsu,et. Japan Kokai Tokkyo Koho:JP 97255614(1997)
[23]大本典彦等，特许公报，昭50-37650(1975)
[24]Arnold Kanfman, et.U.S.Pat. 1968; 3397240
[25]Schubart, Ger. off. 1977;2716895
[26]Egawa Akio,et. Japan Kokai Tokkyo Koho :JP55002647 (1980)
[27]Kaminakai, et. Japan Kokai Tokkyo Koho:JP88162646 (1988)
[28]Akamatsu, et. Japan Kokai Tokkyo Koho:JP 63297337(1963)
[29]曲正等，新技术新工艺，1994(3)：38
[30]Krieger, Kenneth H.et.U.S.Pat.4439623(1984
[31]陈甘棠等，化学反应工程，化学工业出版社，1979
[32]Brill. W.F.J. Org. Chem. 26,2969(1961)
[33]I. Jame,et. J. Chromatogr. 70,151(1972)
[34]A. A. Casselman,et. J. Chromatogr. 80,155(1973)
[35]覃泰群等，染料工业，1983；(4)：26
[36]夏朝彬，精细石油化工，1992，(5)：53
[37]夏朝彬，染料工业，1992，29(2)：34
[38]高全昌等，化学世界，1988，29(10)：446
[39]陈培榕等，现代仪器分析实验技术，清华大学出版社，1999
[40]陈立功，精细化学品的现代分离与分析，化学工业出版社，2000
[41]达世禄，色谱学导论，武汉大学出版社，1999
[42]戴金水，化学试剂，1995，17(3)：181
[43]Victor P.Kurkov, et. U.S. Pat. 4251467(1982)
[44]罗绩深等，化学反应工程与工艺，1991，7(2)：198
[45]高占先等，大连化工，1993，(3)：26
[46]马恒寿等，化学与粘合，1992，3：155
[47]神原周，日本特许公报，昭47-42815(1972)
[48]板喜一郎，日本公开特许公报，昭49-124012(1974)
[49]岸本英隆，日本公开特许公报，昭50-37714(1975)
[50]冯伯华等，化学工业手册，V/1，V/3，化学工业出版社，1991
[51]L．M．罗斯，实用精馏设计，化学工业出版社，1993
[52]陈洪钫等，化工分离过程，化学工业出版社，1995
[53]谢端绶等，化工工艺算图，化学工业出版社，1985
[54]卢焕章等，石油化工基础数据手册，化学工业出版社，1992
[55]陈敏恒等，工业反应过程的开发方法，化学工业出版社，1985
[56]朱炳辰等，化学反应工程，化学工业出版社，2001
[57]卓震等，化工容器及设备，中国石化出版社，1998
[58]杨春晖等，精细化工过程及设备，哈尔滨工业大学出版社，2000
[59]无，换热器设计，上海科学技术出版社，1988
[60]吕绍杰等，化工标准化，化学工业出版社，1998
[2]王而华等，中国医药工业杂志，1991；22(9)：385
[3]戚建军等，中国医药工业杂志，1998；29(6)：243
[4]周伟澄等，中国医药工业杂志，1997；28(2)：59
[5]上海染料，1997；1：20
[6]张思规等，精细有机化学品技术手册，科学出版社，1991
[7]周伟澄，中国医药工业杂志，1997；28(3)：154
[8]郝素娥，精细有机合成单元反应与合成设计，哈尔滨工业大学出版社，2001
[9]张铸勇，精细有机合成单元反应，华东化工学院出版社，1995
[10]王积涛等，有机化学，南开大学出版社，1993
[11]李述文等，实用有机化学手册，上海科技出版社，1981
[12]段长强等，现代化学试剂手册，化学工业出版社，1986
[13]Methoden der organischen Chemie,Brand V/3: 615
[14]雷国明，四川化工，1992；(1)：18
[15]J.Peter Guthrie et. CAN.J.Chem 1986,64:1250
[16]Clamens, Serge, et. Fr. Demande FR 2,633,614,(1990)
[17]Hiegel, Gene A. et. Synth.Comun.,1985; 15 (5): 385
[18]J. Org. Chem. 1960;29:1956
[19] 周桑其，化学通报，1994；6，36
[20]Dolidze, S.V. et. Soobshch. Akad. Nauk Gruz. SSR, 1987;128(1):69(RUSS)
[21]Distler, et. Ger. off. 1971,2018972
[22]Akamatsu,et. Japan Kokai Tokkyo Koho:JP 97255614(1997)
[23]大本典彦等，特许公报，昭50-37650(1975)
[24]Arnold Kanfman, et.U.S.Pat. 1968; 3397240
[25]Schubart, Ger. off. 1977;2716895
[26]Egawa Akio,et. Japan Kokai Tokkyo Koho :JP55002647 (1980)
[27]Kaminakai, et. Japan Kokai Tokkyo Koho:JP88162646 (1988)
[28]Akamatsu, et. Japan Kokai Tokkyo Koho:JP 63297337(1963)
[29]曲正等，新技术新工艺，1994(3)：38
[30]Krieger, Kenneth H.et.U.S.Pat.4439623(1984
[31]陈甘棠等，化学反应工程，化学工业出版社，1979
[32]Brill. W.F.J. Org. Chem. 26,2969(1961)
[33]I. Jame,et. J. Chromatogr. 70,151(1972)
[34]A. A. Casselman,et. J. Chromatogr. 80,155(1973)
[35]覃泰群等，染料工业，1983；(4)：26
[36]夏朝彬，精细石油化工，1992，(5)：53
[37]夏朝彬，染料工业，1992，29(2)：34
[38]高全昌等，化学世界，1988，29(10)：446
[39]陈培榕等，现代仪器分析实验技术，清华大学出版社，1999
[40]陈立功，精细化学品的现代分离与分析，化学工业出版社，2000
[41]达世禄，色谱学导论，武汉大学出版社，1999
[42]戴金水，化学试剂，1995，17(3)：181
[43]Victor P.Kurkov, et. U.S. Pat. 4251467(1982)
[44]罗绩深等，化学反应工程与工艺，1991，7(2)：198
[45]高占先等，大连化工，1993，(3)：26
[46]马恒寿等，化学与粘合，1992，3：155
[47]神原周，日本特许公报，昭47-42815(1972)
[48]板喜一郎，日本公开特许公报，昭49-124012(1974)
[49]岸本英隆，日本公开特许公报，昭50-37714(1975)
[50]冯伯华等，化学工业手册，V/1，V/3，化学工业出版社，1991
[51]L．M．罗斯，实用精馏设计，化学工业出版社，1993
[52]陈洪钫等，化工分离过程，化学工业出版社，1995
[53]谢端绶等，化工工艺算图，化学工业出版社，1985
[54]卢焕章等，石油化工基础数据手册，化学工业出版社，1992
[55]陈敏恒等，工业反应过程的开发方法，化学工业出版社，1985
[56]朱炳辰等，化学反应工程，化学工业出版社，2001
[57]卓震等，化工容器及设备，中国石化出版社，1998
[58]杨春晖等，精细化工过程及设备，哈尔滨工业大学出版社，2000
[59]无，换热器设计，上海科学技术出版社，1988
[60]吕绍杰等，化工标准化，化学工业出版社，1998