氢氰酸法合成高品质原甲酸三甲酯  

Synthesis of High Quality Trimethyl Orthoformate from HCN

作　　者：雷洪[1] 

机构地区：[1]西南大学化学化工学院,重庆400715

出　　处：《精细化工》2008年第1期94-97,共4页Fine Chemicals

基　　金：致谢：感谢北京清华紫光英力化工技术有限责任公司陈小平女士和重庆清华紫光英力天然气公司对本研究的指导和支持.

摘　　要：以氢氰酸、甲醇、无水氯化氢为原料,在溶剂R1存在下经成盐、醇解、精馏制备原甲酸三甲酯,总收率可达80%。成盐反应的最佳工艺为：投料配比n（HCN）∶n（CH3OH）∶n（HCl）=1∶1.05∶1.15,反应温度-15-5℃,反应时间10 h,体系w（H2O）〈0.2%,在该工艺下,HCOCH3NH.HCl的收率达87.1%,残留氰根ρ（HCN）〈0.1 g/L;醇解反应的最佳反应温度是30-35℃,反应时间8 h。两步合成有效地控制了产品的主要杂质三嗪,产品中w（三嗪）〈0.1%,w（原甲酸三甲酯）≥99.80%。工业化中试在100 L搪瓷釜中进行,最好收率达81.1%,w（原甲酸三甲酯）=99.85%,w（三嗪）=0.07%。In the presence of solvent R1, trimethyl orthoformate was synthesized from the starting materials HCN, methanol and hydrogen chloride gas through methyl formimidate hydrochloride formation,alcoholysis and rectification. The total yield was up to 80%. The optimized conditions of formation of methyl formimidate hydrochloride are as follows. Mole ratio of starting materials is n （ HCN）：n（ CH3OH） ：n （HCl） = 1 ： 1.05： 1.15, the reaction temperature is - 15 - 5 ℃, the reaction time is 10 h and the moisture in the reaction system is kept 〈 0.2%. Yield of/nethyl formimidate hydrochloride reaches 87.1% ,and the residual HCN is lower than 0. 1 g/L. The proper temperature of the alcoholysis reaction was 30 -35℃ and the reaction time was 8 h. The main impurity triazine in the product was effectively minimized in this two-step synthetic method. In the product, the content of triazine is below 0. 1% and purity of trimethyl orthoformate is higher than 99.80%. The reaction was scaled-up and proceeded in 100 L reactor. The best yield was up to 81.1% , purity of trimethyl orthoformate was 99.85% and the content of triazine was 0.07%.

关 键 词：氢氰酸 原甲酸三甲酯 三嗪 高品质 精细化工中间体 

分 类 号：TQ612[化学工程—精细化工]