碳基固体酸在硝基苯加氢制备对氨基苯酚中的应用  

Application of carbon-based solid acid in hydrogenation of nitrobenzene to p-aminophenol

作　　者：黄伟 储政 任磊 李珊 HUANG Wei;CHU Zheng;REN Lei;LI Shan(Sinopec Nanjing Research Institute of Chemical Industry Co.,Ltd.,Nanjing 210048,Jiangsu,China)

机构地区：[1]中石化南京化工研究院有限公司,江苏南京210048

出　　处：《化工进展》2023年第1期272-281,共10页Chemical Industry and Engineering Progress

摘　　要：考察了以马铃薯淀粉为碳源制备的碳基固体酸催化剂和质量分数3%的Pt/C为加氢催化剂作用下硝基苯加氢制备对氨基苯酚的反应条件,在以酸度为2.316mmol/g的固体酸为酸性催化剂时,优化的反应条件下硝基苯的转化率100%,对氨基苯酚的选择性67.6%。总结了硝基苯加氢制备对氨基苯酚的反应机理:①硝基苯在Pt/C催化剂上发生加氢反应生成中间产物苯基羟胺;②苯基羟胺在固体酸催化剂上发生Bamberger重排反应生成对氨基苯酚;③主要的副反应包括:苯基羟胺进一步加氢生成苯胺,苯基羟胺歧化反应生成苯胺和亚硝基苯,苯基羟胺与亚硝基苯发生缩合反应生成副产物氧化偶氮苯。通过机理分析和实验验证,提出要提高对氨基苯酚的收率,需综合考虑硝基苯加氢过程和Bamberger重排反应过程。Using carbon-based solid acid from potato starch as carbon source,and 3%(mass)Pt/C as catalyst,we explored the reaction conditions of hydrogenation of nitrobenzene to p-aminophenol.Under the optimized reaction conditions,when solid acid with acidity of 2.316mmol/g was used as acid catalyst,the conversion of nitrobenzene was 100% and the selectivity of p-aminophenol was 67.6%.The reaction mechanism of hydrogenation of nitrobenzene to p-aminophenol was summarized:①nitrobenzene was hydrogenated on Pt/C catalyst to produce phenylhydroxylamine intermediate;②p-aminophenol was produced by Bamberger rearrangement of phenylhydroxylamine on solid acid catalyst;③the main side reactions include further hydrogenation of phenylhydroxylamine to aniline,disproportionation of phenylhydroxylamine to aniline and nitrosobenzene,condensation of phenylhydroxylamine with nitrosobenzene to produce by-product azobenzene oxide.Through mechanism analysis and experimental verification,it is proposed that in order to improve the yield of p-aminophenol,the hydrogenation of nitrobenzene and the Bamberger rearrangement process should be comprehensively considered.

关 键 词：催化剂 碳基固体酸 加氢 机理研究 合成 

分 类 号：TH3[机械工程—机械制造及自动化]