间苯二胺水解制备间氨基苯酚的工艺研究_杨秀芬

摘要间氨基苯酚是一种重要的精细化工原料和有机中间体，在石油化学工业、农药、医药、染料等领域的应用非常广泛。到目前为止，开发出了多种合成间氨基苯酚的工艺，主要有硝基苯法、间苯二酚氨解法、间硝基苯酚电解法、苯胺羟基化法和间苯二胺盐酸水解法等，但它们大都分别存在着工艺落后、污染严重、成本较高、收率和选择性不高和对设备要求较高的问题。本文提出了间苯二胺硫酸水解制备间氨基苯酚的新工艺，并对此进行了系统的研究，着重探讨了水解产物的分离和间苯二胺水解反应两大部分，研究内容和结果如下：鉴于间苯二胺硫酸水解制备间氨基苯酚工艺的水解产物主要包含间苯二胺、间氨基苯酚和间苯二酚三种组分的情况，本文对三组分的混合水溶液进行了萃取分离研究，通过对比，筛选出较好的萃取剂乙酸异戊酯和乙酸正丁酯，并确定了相应萃取分离条件。分别以乙酸异戊酯和乙酸正丁酯为萃取剂，对间氨基苯酚、间苯二酚和间苯二胺的单组分溶液进行了溶剂萃取的液液相平衡研究。结果表明，乙酸正丁酯优于乙酸异戊酯，对三组分的萃取分离更有利。在以乙酸正丁酯为萃取剂的条件下，分别得到了间苯二酚酸水物系、间苯二胺碱水物系和间氨基苯酚盐水物系的相平衡数据关联式。通过单因素实验和正交实验，考察了反应时间、温度、物料配比和酸的浓度对间苯二胺水解反应的影响，确定了优化的工艺条件为：酸的浓度为22%，反应温度为200℃，间苯二胺与浓硫酸的摩尔比为1：1.98，反应时间为6h。在此条件下间苯二胺的转化率达到了81.19%，间氨基苯酚的收率为56.34%，选择性达到69.38%，副产物间苯二酚的收率是24.13%。通过动力学实验，分别得到了在190℃、200℃、210℃温度条件下间苯二胺水解反应的速率方程。本文提出了硫酸法水解制备间氨基苯酚的新工艺，对溶剂萃取法分离水解产物进行了系统的相平衡研究，优化了水解工艺条件，得出不同温度条件下的间苯二胺水解反应的速率方程，对此未见国内外文献报导，为该工艺的深入研究打下了基础。关键词：间氨基苯酚；间苯二胺；间苯二酚；水解Abstractm-Aminophenol(MAP),animportantchemicalrawmaterialandorganicintermediate,hasbeenwidelyusedformanyfieldssuchas,petrochemicalindustry,agriculturalchemicals,dyestuff,andpharmacy.NowsomanysolutionshadbeenfoundtoprepareMAP,whichincludednitrobenzenesulfonatedakkalifusion,resorcinolliquidammonolysissolution,m-nitrophenolelectrolysis,hydroxylationofaniline,andm-phenylenediaminehydrolysiswithHCl,butthosetechnicshavemanylimitationssuchas,outdatedtechnics,seriouspollution,highcosts,lowyieldandselectivity,highequipmentrequirementandsoon.SothistechnicsforMAPbym-phenylenediaminehydrolysiswithH2SO4wasreportedandsystematicallystudiedinthispaper.Theseparationofhydrolyzateandthehydrolysisofm-phenylenediamineweretwopointsthearticlefocuson,andtheresultswerereportedasfollow.TheextractionforseparatingMAP,m-aminophenolandresorcinolwasresearched,andtheresultsshowedthatthebetterextractantwereisopentylacetateandBuAc,andtheoptimaloperationconditionwasalsodetetmined.Theliquid-liquidequilibriumofMAP,orm-phenylenediamine,orresorcinolwithdifferentsolventasextractionwerestudied,respectively,andtheresultsshowedthatBuAcwasbetterthanisopentylacetatefortheseparation.TheequilibriumdatawererelatedwithHandequation,andthepraticalformulasofthesystemresorcinol,thesystemm-phenylenediamine,andthesystemMAPwithBuAcasextractantwerefoundout.ThesyntheticprocessofMAPwasexplored,andtheoptimalreactionconditionswereconfirmedasfollow:theconcentrationofacid22%,reactiontemperature200,themole℃ratioofm-phenylenediaminetoacid1:1.98,reactiontime6h.Undertheseconditionstheconversionofm-phenylenediamineacidcanreachupto81.19%,andtheyieldandselectivityofMAPwas56.34%and69.38%,respectively,andtheyieldofby-productresorcinolwas24.13%.Inaddition,therateequationsofm-phenylenediaminehydrolysisatdifferenttemperatureof190℃,200℃,and210℃werealsoobtainedthroughkineticexperiment,whichcangivetheactualoperationtheoreticalguidance.Inthisacticle,thenewtechnicsforMAPbym-phenylenediaminehydrolysiswithH2SO4wasrecored,theseparationofhydrolyzatewiththemethodofsolventextractionwasstudied,thereactionconditionwasoptimized,andrateequationunderdifferenttemperaturewasobtained.Thoseresultshadnotbeenreportedwithanyliterature,andlayfoundationforthein-depthresearchonthisprocess.Keywords:m-Aminophenol,m-Phenylenediamine,Resorcinol,Hydrolysis-i-目录第一章绪论..............................................................................................................................11.1间氨基苯酚的用途及市场消费前景.............................................................................11.1.1用途...........................................................................................................................11.1.2市场消费情况...........................................................................................................21.1.3发展前景...................................................................................................................41.2间氨基苯酚的生产发展及合成技术现状.....................................................................51.2.1间氨基苯酚的生产发展史.......................................................................................51.2.2间氨基苯酚的生产现状...........................................................................................51.2.3间氨基苯酚的合成方法...........................................................................................61.3课题的提出及研究的目的和意义...............................................................................121.3.1课题的提出.............................................................................................................121.3.2间苯二胺水解合成间氨基苯酚的可行性.............................................................131.3.3课题研究的目的和意义.........................................................................................14第二章间苯二胺、间氨基苯酚与间苯二酚萃取分离的研究...........................................152.1引言...............................................................................................................................152.2间氨基苯酚、间苯二酚和间苯二胺的萃取分离原理...............................................162.3萃取剂的选择[73，74]......................................................................................................162.4实验药品和仪器.............................