氰乙酸乙酯在微反应器中合成工艺研究
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摘要
以氯乙酸为原料,在微反应器中经酯化和氰化两步合成了氰乙酸乙酯,氯乙酸与乙醇经浓硫酸催化条件下在微反应器中酯化得到氯乙酸乙酯,氯乙酸乙酯进一步与氰化钠溶液在微反应器中发生氰化反应制备了氰乙酸乙酯,考察了两步反应过程中停留时间、反应温度、物质的量比例对氰乙酸乙酯收率的影响,优化反应条件为:酯化反应停留时间为167s,氯乙酸与乙醇物质的量比为1∶5,反应温度75℃,氰化反应停留时间为124s,反应温度为70℃。制备过程总收率为84.9%,实现了先氰化后酯化连续反应,解决了工业化生产固废量大,成本较高问题。
Using chloroacetic acid as raw materials,ethyl cyanoacetate was synthesized through esterification and cyanide reaction in microreactor,first,ethyl chloroacetate was synthesized by chloroacetic acid and ethanol in micro reactor under the condition of the sulfuric acid catalysis,ethyl chloroacetate further reacted with sodium cyanide solution in the micro reactor to prepare ethyl cyanoacetate,the conditions of residence time,reaction temperature,proportion of substance in the process of two step reaction influenced the yield of ethyl cyanoacetate was examined,the optimizing reaction conditions as follows:esterification reaction residence time 167 s,mole ratio of chloroacetic acid and ethanol 1∶5,reaction temperature 75℃,cyanide reaction residence time 124 s,reaction temperature 70℃.The total yield of the preparation process was 84.9%.the continuous reaction of cyanation and esterification is realized in the microreactor,and the problem of high solid waste and high cost in industrial production is solved.
Using chloroacetic acid as raw materials,ethyl cyanoacetate was synthesized through esterification and cyanide reaction in microreactor,first,ethyl chloroacetate was synthesized by chloroacetic acid and ethanol in micro reactor under the condition of the sulfuric acid catalysis,ethyl chloroacetate further reacted with sodium cyanide solution in the micro reactor to prepare ethyl cyanoacetate,the conditions of residence time,reaction temperature,proportion of substance in the process of two step reaction influenced the yield of ethyl cyanoacetate was examined,the optimizing reaction conditions as follows:esterification reaction residence time 167 s,mole ratio of chloroacetic acid and ethanol 1∶5,reaction temperature 75℃,cyanide reaction residence time 124 s,reaction temperature 70℃.The total yield of the preparation process was 84.9%.the continuous reaction of cyanation and esterification is realized in the microreactor,and the problem of high solid waste and high cost in industrial production is solved.
引文
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[2]杨英,李德臣.α-氰基丙烯酸酯生产新工艺[J].中国胶粘剂,2004,13(5):46-47.
[3]王克钦,徐阵,林卿云,等.α-氰基丙烯酸酯生产新工艺[J].辽宁化工,1984(6):46-47.
[4]尚会建,康丽娜,赵叶,等.杂多酸催化合成氰乙酸乙酯的研究[J].精细石油化工,2012,29(3):48-51.
[5]刘旭,尹国华,王金花,等.一种氰乙酸乙酯合成的新方法[J].精细与专用化学品,2016,24(1):35-37.
[6]周学永.氯乙酸基础研究与应用[M].中国科学技术出版社,2006,211.
[7]司航.化工产品手册,有机化工原料[M].化学工业出版社,2001,498-499.
[8]Zhao Y,Chen G,Yuan Q.Liquid-liquid two-phase mass transfer in the T-junction microchannels[J].AIChE journal,2007,53(12):3042-3053.
[9]Chen Y,Su Y,Jiao F,et al.A simple and efficient synthesis protocol for sulfonation of nitrobenzene under solventfree conditions via a microreactor[J].RSC Advances,2012,2(13):5637-5644.
[10]Shen J,Zhao Y,Chen G,et al.Investigation of nitration processes of iso-octanol with mixed acid in a microreactor[J].Chinese Journal of Chemical Engineering,2009,17(3):412-418.
[11]张恭孝,王者辉.微反应器技术及其研究进展[J].现代化工,2015,35(2):52-56.
[12]骆广生,王凯,吕阳成,等.微反应器研究最新进展[J].现代化工,2009,29(5):27-31.