基于TMC路径尿素法合成甲苯-2,4-二氨基甲酸甲酯的热力学计算和路径考察  

Thermodynamic Analysis and Path Investigation on Synthesis of Dimethyl Toluene-2,4-Dicarbamate by Urea Route via TMC Intermediate

作　　者：李群[1] 王盟[1] 安华良[1] 赵新强[1] 王延吉[1] 

机构地区：[1]河北工业大学化工学院绿色化工与高效节能河北省重点实验室,天津300130

出　　处：《石油学报（石油加工）》2014年第6期1093-1099,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(21076059);天津市自然科学基金项目(12JCYBJC12800);河北省应用基础研究计划重点基础研究项目(12965642D)资助

摘　　要：以2,4-二氨基甲苯(TDA)、尿素和甲醇(MeOH)为原料,合成了甲苯-2,4-二氨基甲酸甲酯(TDC)。在对以3-氨基-4-甲基苯氨基甲酸甲酯(TMC)为中间产物的反应路径进行热力学分析的基础上,考察了催化剂及反应条件对基于TMC合成TDC反应的影响,筛选出活性较高的碱式碳酸铜催化剂,确定了适宜的反应条件。结果表明,由TDA、尿素和甲醇经TMC合成TDC的反应在热力学上可行。在TDA与碱式碳酸铜、尿素和甲醇的摩尔比为1∶0.07∶5∶80,反应温度463.15K,反应压力3.0 MPa,反应时间6h条件下,TDA的转化率为97.3%,TDC的收率和选择性分别为48.0%和49.3%。Dimethyl toluene-2,4-dicarbamate（TDC）was synthesized with 2,4-toluene diamine（TDA）,urea and methanol（MeOH）as raw materials.The reactions of TDC synthesis via 3-amino-4-methyl-N-phenylcarbamate（TMC）intermediate were thermodynamically studied first,and then the catalyst was selected and the effects of reaction conditions on TDC synthesis via TMC intermediate were investigated.The results showed that the reaction of TDC synthesis via TMC intermediate was thermodynamically feasible.CuCO3·Cu（OH）2·H2O was found to be a favorite catalyst for the synthesis of TDC.TDA conversion,TDC yield and selectivity were 97.3%,48.0%and 49.3%,respectively,under the conditions of n（TDA）∶n（CuCO3·Cu（OH）2· H2O）∶n（Urea）∶n（MeOH）=1∶0.07∶5∶80,463.15 K,3.0MPa and 6h.

关 键 词：尿素 2 4-二氨基甲苯(TDA) 甲醇 3-氨基-4-甲基苯氨基甲酸甲酯(TMC) 甲苯-2 4-二氨基甲酸甲酯(TDC) 

分 类 号：TQ246.3[化学工程—有机化工]