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1、摘要环己酮又名尼龙酸,是己二酸生产过程产生的副产物,仅国内己二酸生产企业每年就副产混合二元酸40-60万吨。由于其含杂质、水分多,颜色呈绿色或黄褐色,难以利用。国外一般将其送进污水处理装置作焚烧或填埋处理;国内有采用重结晶法回收,但回收率低于60%,废水量较大,不仅对环境造成污染,而且也造成资源的浪费。为了物尽其用,本文开展了应用基础研究以C4-C6混合二元酸为原料、对甲苯磺酸为催化剂,制备混合二元酸二甲酯,并利用减压精馏得到纯净的二甲酯。实验中考查了各种反应的影响因素,并利用制备的混合二甲酸二甲酯与异辛醇进行酯交换制备
2、混合二元酸二异辛酯。根据实验数据表明,通过酯化法分离混合二元酸的工艺路线是可行的。酯化的适宜反应条件为:反应时间5.0h,醇酸物质的量比6:1,催化剂用量1.0%混合酸,以此条件,二元酸二甲酯的收率可达89%。酯化所得粗酯可以在压力为40mmHg下进行减压精馏,截取95~105℃下的馏分,为丁二酸二甲酯,截取110~120℃下的馏分,为戊二酸二甲酯,截取145~155℃下的馏分,为己二酸二甲酯。利用精馏所得的二元酸二甲酯,通过酯交换法制得的二元酸二异辛酯的颜色很浅,说明通过酯化法可以有效地分离混合二元酸。关键词:环己酮;
3、环己烷;酯交换;混合二元酸二甲酯IIAbstractMixeddibasicacid(DBA),alsoknownasnylonacid,adipicacidproductionprocessby-products,onlydomesticproducersofadipicacidby-productmixtureineachofdicarboxylicacid40-60milliontons.Becauseofitsimpurities,watercontent,thecolorgreenorbrown,itisdif
4、ficulttouse.Foreigngeneraltobesenttosewagetreatmentplantforincinerationorlandfilling;domesticuserecrystallizationrecovery,butrecoverywaslessthan60%,largeamountofwastewater,notonlypollutetheenvironment,butalsoawasteofresources.Inordertomakethebestuse,thisapplicati
5、onofbasicresearchcarriedouttoC4-C6dicarboxylicacidasrawmaterialmixture,p-toluenesulfonicacidascatalyst,preparedbymixingtwoyuanacidester,andtheuseofvacuumdistillationtogetpuredimethylester.Experimentexaminedtheresponseofvariousfactors,anduseamixtureofdimethylester
6、preparedwithdifferentoctanolpreparedbymixingtwoyuanfortransesterificationethylhexylsebacate.Accordingtotheexperimentaldatashowthat,byesterificationofdicarboxylicacidmixtureseparationprocessrouteisfeasible.Esterificationoftheappropriatereactionconditions:reactiont
7、ime5.0h,alkydmolarratioof6:1,1.0%mixedacidcatalyst,inthiscondition,binaryacidesteryieldof89%.Estersderivedfromcrudeesterificationcanbecarriedoutunderthepressureof40mmHgvacuumdistillation,theinterceptionof95~105℃underthedistillate,asdimethylsuccinate,theintercepti
8、onof110~120℃underthefractionsforDimethylglutarate,theinterceptionof145~155℃underthedistillate,isdimethyladipate.Theuseofbinarydistillationfromacidesterbytranse