氯丙烯直接环氧化合成环氧氯丙烷（ECH）工艺研究
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摘要
环氧氯丙烷是氯醇橡胶、合成环氧树脂、甘油及缩水甘油醚等重要原料,属于有机化工原料和精细化工产品的重要品种之一。目前,环氧树脂用量和用途的不断扩大,环氧氯丙烷的需求强劲,但面对环境保护的日益增强的需求,使得坏氧氯丙烷的环保、绿色合成成为重要的发展方向。
与传统的丙烯高温氯化法、乙酸丙烯酯法和近年来发展的甘油法合成环氧氯丙烷工艺相比,H2O2/钛-硅分子筛催化氯丙烯直接环氧化合成环氧氯丙烷的方法,因为无污染、高转化率、高选择性以及反应条件温和等优势,故已成为环氧氯丙烷绿色环保合成工艺的发展趋势。
本论文根据国内外文献资料的报道及走访调查,以钛-硅分子筛作催化剂,以50wt%H2O2为氧化剂,甲醇为溶剂,研究了用氯丙烯直接环氧化合成环氧氯丙烷的工艺体系和钛-硅分子筛催化剂再生方法。在小试基础上,设计了一套不等容二釜串联连续合成中试路线,对小试实验进行了验证,并结合既有工程经验,设计了一种催化剂连续过滤回收方式。
另外,对该工艺的“三废”情况进行了简要说明,对原料的消耗及成本进行了计算、比较和分析。
Epichlorohydrin is a raw material and fine chemical product, especially for the preparation of epoxide resins, glycerine, pichlorohydrin rubber and glycerin ether. Recently, the demand of epichlorohydrin has been increased sharply with the expanding market of epoxide resins. As a consequence, the ecological protection in the manufacture of epichlorohydrin becomes quite critical, resulting in a hot and urgent research topic to develop green chemical process of epichlorohydrin.
Compared with the traditional processes of high temperature chlorination of propylene and ally acetate method, and recently developed glycerin method, the chemical process of epichlorohydrin (ECH) via direct epoxidation of 3-chloroprop-1-ene using H2O2/titanium-silicon zeloite as a catalyst has become a widely-accepted green technology due to several distinct advantages such as no pollution, high yield, good selectivity and mild reaction conditions.
According to the domestic and international literatures, the dissertation mainly focused on the chemical process of epichlorohydrin (ECH) via direct epoxidation of chloropropene and the regerenation technology of the catalyst, using titanium-silicon molecular sieve as catalyst,50wt% H2O2 as oxidizer, and methyl alcohol as solvent. Based on the parameters from lab experiments, a set of continuous pilot-scale line as well as a continuous filtration for catalyst were proposed.
In addition, the process of "three wastes", the calculation of raw material consumption and cost were briefly discussed and analyzed.
与传统的丙烯高温氯化法、乙酸丙烯酯法和近年来发展的甘油法合成环氧氯丙烷工艺相比,H2O2/钛-硅分子筛催化氯丙烯直接环氧化合成环氧氯丙烷的方法,因为无污染、高转化率、高选择性以及反应条件温和等优势,故已成为环氧氯丙烷绿色环保合成工艺的发展趋势。
本论文根据国内外文献资料的报道及走访调查,以钛-硅分子筛作催化剂,以50wt%H2O2为氧化剂,甲醇为溶剂,研究了用氯丙烯直接环氧化合成环氧氯丙烷的工艺体系和钛-硅分子筛催化剂再生方法。在小试基础上,设计了一套不等容二釜串联连续合成中试路线,对小试实验进行了验证,并结合既有工程经验,设计了一种催化剂连续过滤回收方式。
另外,对该工艺的“三废”情况进行了简要说明,对原料的消耗及成本进行了计算、比较和分析。
Epichlorohydrin is a raw material and fine chemical product, especially for the preparation of epoxide resins, glycerine, pichlorohydrin rubber and glycerin ether. Recently, the demand of epichlorohydrin has been increased sharply with the expanding market of epoxide resins. As a consequence, the ecological protection in the manufacture of epichlorohydrin becomes quite critical, resulting in a hot and urgent research topic to develop green chemical process of epichlorohydrin.
Compared with the traditional processes of high temperature chlorination of propylene and ally acetate method, and recently developed glycerin method, the chemical process of epichlorohydrin (ECH) via direct epoxidation of 3-chloroprop-1-ene using H2O2/titanium-silicon zeloite as a catalyst has become a widely-accepted green technology due to several distinct advantages such as no pollution, high yield, good selectivity and mild reaction conditions.
According to the domestic and international literatures, the dissertation mainly focused on the chemical process of epichlorohydrin (ECH) via direct epoxidation of chloropropene and the regerenation technology of the catalyst, using titanium-silicon molecular sieve as catalyst,50wt% H2O2 as oxidizer, and methyl alcohol as solvent. Based on the parameters from lab experiments, a set of continuous pilot-scale line as well as a continuous filtration for catalyst were proposed.
In addition, the process of "three wastes", the calculation of raw material consumption and cost were briefly discussed and analyzed.
引文
[1]《化工百科全书》编辑委员会.化工百科全书.化学工业出版社,1994,7：551.
[2]戴祖贵,张永强,刘易,杜泽学.环氧氯丙烷合成的研究进展.石油化工,2008,37(7)：738-742.
[3]薛祖源.环氧氯丙烷生产技术和发展意见.中国氯碱,2007,(6)：1-4.
[4]何燕.环氧氯丙烷的技术进展和市场展望.精细化工原料及中间体,2007,(10)：23-26.
[5]王新龙.环氧氯丙烷生产技术进展及发展建议.化学工业与工程技术,2006,27(1)：46-48.
[6]陈康庄.硕士学位论文.氯丙烯环氧化制环氧丙烷催化剂性能研究,湖南大学,2006.
[7]吕楠.环氧氯丙烷市场分析与发展战略.中国化工信息(周刊),2002,7：29.
[8]张旭之主编.丙烯衍生物工学,北京,化工出版社,1995.5：437-449.
[9]孙渝,奚祖威,曹国英.氯丙烯直接环氧化制取环氧氯丙烷研究进展.石油与天然气化工,1999,28(4)：246-249.
[10]崔小明.环氧氯丙烷的生产及市场前景.石油化工技术经济,2001,5(17)：27-31.
[11]王荫培.利用一氯醋酸生产过程中发生的氯化氢气体制造二氯丙醇.化学世界,1959，4：153-154.
[12]王荫培.一氯醋酸和二氯丙醇生产过程中过量氯的利用.化学世界,1959,7：338-339.
[13]G. Freddy. Solvay will make epichlorohydrin from glycerol. J. Ind. Bioprocess,2006, 28:8-9
[14]S. Chemickou, H. Vyrobu, A. Spolecnost. Method of preparing dichloropropanols from glycerine. PCT Int Appl. WO 2005021476,2005.
[15]Solvay. Process for producing dichloropropanol from the glycerol, the glycerol coming eventually the conversion of animal fats in the manufacture of biodiesel. PCT Int Appl. WO 2005054167,2005.
[16]Dow Chemical Corp. Glycerol dichlorohydrin. US Pat Appl. US 2198600,1940.
[17]Dow Chemical Corp. Prepartion of glycerol dichlorohydrin. US Pat Appl. US 2144612, 1939.
[18]R. Tesser, E. Santancesaria, M. Di Serio, et al. Kinetics of glycerol chlorination with hydrochloric acid:a new route to α,γ-dichlorohydrin. American Chemcal Society, 2007-09-05.
[19]江苏扬农化工集团有限公司.一种甘油催化氯化制备二氯内醇的方法.中国,CN 101029000，2007.
[20]舒云.我国环氧氯内烷市场发展分析.中国石油和化工经济分析,2007,1：22-25
[21]Solvay公司决定在泰国新建环氧氯丙烷装置.石油化工,2007,36(12：1-219.
[22]B. V. Comprimo. Preparation of oxiranes by oxidation of unisaturated comounds with organic peracids or salts, anhydrides or esters thereof. Neth Appl. NL 7609148,1977.
[23]Hoechst Aktiengesellschaft. Process for improving the activity of used supported silver catalysts. US Pat Appl. US 4177169,1979.
[24]W. Rene, L. Luc. Process for the manufature of olefine oxides. Eur. Pat. Appl. EP 19322,1980.
[25]Mitsui Toasu Chemicals, Incorporated. Preparation of epichlorohydrins by epoxidation of allyl chlorides with cunene hydroperoxide. Jpn Kokai Tokyo Koho, JP 6304573, 1988.
[26]Mitsui Toasu Chemicals, Incorporated. Preparation of epichlorohydrins by epoxidation of allyl chlorides with cunene hydroperoxide. Jpn Kokai Tokyo Koho, JP 6304574, 1988.
[27]Mitsui Toasu Chemicals, Incorporated. Method for preparing epichlorohydrin. US Pat Appl. US 4876372,1989.
[28]C. Venturello, E. Alneri, M. Ricci. A new, effective catalytic system for eporidation of olefins by hydrogen peroxide under phase-transfer conditions. J. Org. Chem.,1983, 48(21):3831-3833.
[29]阳国军.硕士学位论文.氯丙烯环氧化新型催化材料的探索研究,北京：石油化工科学研究院,2003.
[30]曹国英,李宏愿.TS分子筛催化剂上丙烯基氯的环氧化性能.催化学报,1995,16(3)：217-221.
[31]M. G. Clerici, P. Ingallina. Eppxidation of lower olefine with hydrogen peroxide and titanium silicalite. J. Catal.,1993,140(1):71-83.
[32]李钢,郭新闻,王祥生.水热法合成的钛硅分子筛催化剂性能研究.石油学报(石油加工),1999,15(5)：73-76.
[33]门海主,刘靖,王祥生.钛硅分子筛催化剂的酸碱改性处理.大连理工大学学报,2002,42(1)：42-46.
[34]汪玲玲,刘月明,张海娇等.Ti-MWW催化烯丙基氯环氧化高效合成环氧氯内烷.催化学报,2006,31(4)：245-249.
[35]徐成华,吕绍洁,邓桂英等.ri-ZSM-5分筛催化氯丙烯环氧化制环氧氯丙烷.石油化工,2002,31(4)：245-249.
[36]王庆法,学位论文.氢氧直接合成过氧化氢与氯丙烯环氧化反应的集成过程研究.天津大学化工学院,2004.
[37]华东师范大学,一种生产环氧氯丙烷的方法,中国,CN 101]72970A,2008.
[38]陈艳凤,学位论文.TS-1催化剂成型及其催化氯丙烯环氧化反应的研究.北京：石油化工科学研究院,2007.
[39]Solvay. Epoxidation catalyst, its use and epoxidation method in the presence of said catalyst. PCT Int Appl, WO 9928029.1999.
[40]Solvay. Epoxidation catalyst, its use and epoxidation method in the presence of said catalyst. PCT Int Appl, WO 9928030.1999.
[41]Solvay. Epoxidation catalyst, its use and epoxidation method in the presence of said catalyst. US Pat Appl, US 6699812.2004.
[42]张宇,学位论文.氯丙烯直接环氧化催化剂稳定性及其再生方法研究,北京：石油化工科学研究院,2006.
[43]张宇,熊勇,刘易,杜泽学.TS-1催化氯丙烯直接环氧化反应的失活研究.石油炼制与化工,2006,37(7)：21-24.
[44]J. S. Reddy, A. Sayari. A New and simple method for the preparation of acive Ti-β zeolite catalysts. J. Chem. Soc., Chem Commnu,1995,1:23.
[45]徐大伟,郜广玲,李玮等.环氧氯丙烷的洁净生产.石油化工,2000,10(29)：794-797.
[2]戴祖贵,张永强,刘易,杜泽学.环氧氯丙烷合成的研究进展.石油化工,2008,37(7)：738-742.
[3]薛祖源.环氧氯丙烷生产技术和发展意见.中国氯碱,2007,(6)：1-4.
[4]何燕.环氧氯丙烷的技术进展和市场展望.精细化工原料及中间体,2007,(10)：23-26.
[5]王新龙.环氧氯丙烷生产技术进展及发展建议.化学工业与工程技术,2006,27(1)：46-48.
[6]陈康庄.硕士学位论文.氯丙烯环氧化制环氧丙烷催化剂性能研究,湖南大学,2006.
[7]吕楠.环氧氯丙烷市场分析与发展战略.中国化工信息(周刊),2002,7：29.
[8]张旭之主编.丙烯衍生物工学,北京,化工出版社,1995.5：437-449.
[9]孙渝,奚祖威,曹国英.氯丙烯直接环氧化制取环氧氯丙烷研究进展.石油与天然气化工,1999,28(4)：246-249.
[10]崔小明.环氧氯丙烷的生产及市场前景.石油化工技术经济,2001,5(17)：27-31.
[11]王荫培.利用一氯醋酸生产过程中发生的氯化氢气体制造二氯丙醇.化学世界,1959，4：153-154.
[12]王荫培.一氯醋酸和二氯丙醇生产过程中过量氯的利用.化学世界,1959,7：338-339.
[13]G. Freddy. Solvay will make epichlorohydrin from glycerol. J. Ind. Bioprocess,2006, 28:8-9
[14]S. Chemickou, H. Vyrobu, A. Spolecnost. Method of preparing dichloropropanols from glycerine. PCT Int Appl. WO 2005021476,2005.
[15]Solvay. Process for producing dichloropropanol from the glycerol, the glycerol coming eventually the conversion of animal fats in the manufacture of biodiesel. PCT Int Appl. WO 2005054167,2005.
[16]Dow Chemical Corp. Glycerol dichlorohydrin. US Pat Appl. US 2198600,1940.
[17]Dow Chemical Corp. Prepartion of glycerol dichlorohydrin. US Pat Appl. US 2144612, 1939.
[18]R. Tesser, E. Santancesaria, M. Di Serio, et al. Kinetics of glycerol chlorination with hydrochloric acid:a new route to α,γ-dichlorohydrin. American Chemcal Society, 2007-09-05.
[19]江苏扬农化工集团有限公司.一种甘油催化氯化制备二氯内醇的方法.中国,CN 101029000，2007.
[20]舒云.我国环氧氯内烷市场发展分析.中国石油和化工经济分析,2007,1：22-25
[21]Solvay公司决定在泰国新建环氧氯丙烷装置.石油化工,2007,36(12：1-219.
[22]B. V. Comprimo. Preparation of oxiranes by oxidation of unisaturated comounds with organic peracids or salts, anhydrides or esters thereof. Neth Appl. NL 7609148,1977.
[23]Hoechst Aktiengesellschaft. Process for improving the activity of used supported silver catalysts. US Pat Appl. US 4177169,1979.
[24]W. Rene, L. Luc. Process for the manufature of olefine oxides. Eur. Pat. Appl. EP 19322,1980.
[25]Mitsui Toasu Chemicals, Incorporated. Preparation of epichlorohydrins by epoxidation of allyl chlorides with cunene hydroperoxide. Jpn Kokai Tokyo Koho, JP 6304573, 1988.
[26]Mitsui Toasu Chemicals, Incorporated. Preparation of epichlorohydrins by epoxidation of allyl chlorides with cunene hydroperoxide. Jpn Kokai Tokyo Koho, JP 6304574, 1988.
[27]Mitsui Toasu Chemicals, Incorporated. Method for preparing epichlorohydrin. US Pat Appl. US 4876372,1989.
[28]C. Venturello, E. Alneri, M. Ricci. A new, effective catalytic system for eporidation of olefins by hydrogen peroxide under phase-transfer conditions. J. Org. Chem.,1983, 48(21):3831-3833.
[29]阳国军.硕士学位论文.氯丙烯环氧化新型催化材料的探索研究,北京：石油化工科学研究院,2003.
[30]曹国英,李宏愿.TS分子筛催化剂上丙烯基氯的环氧化性能.催化学报,1995,16(3)：217-221.
[31]M. G. Clerici, P. Ingallina. Eppxidation of lower olefine with hydrogen peroxide and titanium silicalite. J. Catal.,1993,140(1):71-83.
[32]李钢,郭新闻,王祥生.水热法合成的钛硅分子筛催化剂性能研究.石油学报(石油加工),1999,15(5)：73-76.
[33]门海主,刘靖,王祥生.钛硅分子筛催化剂的酸碱改性处理.大连理工大学学报,2002,42(1)：42-46.
[34]汪玲玲,刘月明,张海娇等.Ti-MWW催化烯丙基氯环氧化高效合成环氧氯内烷.催化学报,2006,31(4)：245-249.
[35]徐成华,吕绍洁,邓桂英等.ri-ZSM-5分筛催化氯丙烯环氧化制环氧氯丙烷.石油化工,2002,31(4)：245-249.
[36]王庆法,学位论文.氢氧直接合成过氧化氢与氯丙烯环氧化反应的集成过程研究.天津大学化工学院,2004.
[37]华东师范大学,一种生产环氧氯丙烷的方法,中国,CN 101]72970A,2008.
[38]陈艳凤,学位论文.TS-1催化剂成型及其催化氯丙烯环氧化反应的研究.北京：石油化工科学研究院,2007.
[39]Solvay. Epoxidation catalyst, its use and epoxidation method in the presence of said catalyst. PCT Int Appl, WO 9928029.1999.
[40]Solvay. Epoxidation catalyst, its use and epoxidation method in the presence of said catalyst. PCT Int Appl, WO 9928030.1999.
[41]Solvay. Epoxidation catalyst, its use and epoxidation method in the presence of said catalyst. US Pat Appl, US 6699812.2004.
[42]张宇,学位论文.氯丙烯直接环氧化催化剂稳定性及其再生方法研究,北京：石油化工科学研究院,2006.
[43]张宇,熊勇,刘易,杜泽学.TS-1催化氯丙烯直接环氧化反应的失活研究.石油炼制与化工,2006,37(7)：21-24.
[44]J. S. Reddy, A. Sayari. A New and simple method for the preparation of acive Ti-β zeolite catalysts. J. Chem. Soc., Chem Commnu,1995,1:23.
[45]徐大伟,郜广玲,李玮等.环氧氯丙烷的洁净生产.石油化工,2000,10(29)：794-797.