环己烯水合法生产己二酸中微量杂质剖析  

Analysis of trace impurities in cyclohexene hydration into adipic acid

作　　者：王红专[1,2] 董建勋 陈聚良[1,2] 

机构地区：[1]河南神马尼龙化工有限责任公司,河南平顶山467013 [2]河南省聚酰胺中间体重点实验室,河南平顶山467013 [3]中国平煤神马集团能源化工研究院,河南平顶山467000

出　　处：《合成纤维工业》2016年第5期70-73,共4页China Synthetic Fiber Industry

摘　　要：为了探究己二酸生产过程中影响己二酸产品质量的微量杂质并加以控制,采用GC/MS-TQ8030气相色谱-质谱联用仪分析了环己烯水合法生产己二酸时中间产物环己醇中的杂质,采用酯化萃取与中和萃取的方法,分别对环己烯和环己醇重组分氧化产物以及己二酸结晶母液和己二酸产品进行了考察。结果表明:环己醇中的主要杂质为环己烯和环己醇重组分,环己烯硝酸氧化产物能够确定的有12种,影响己二酸的纯度,且氧化液颜色为深褐色,给后续吸附脱色造成困难,实际生产中应控制环己醇中环己烯含量低于100mg/kg;环己醇重组分硝酸氧化产物能够确定的有36种,且多为不溶于水的化合物,影响己二酸的色度,实际生产中应控制环己醇重组分含量低于500 mg/kg;己二酸结晶母液和己二酸产品中均检测到苯酚,反应器散热效率低,微量苯酚难从己二酸体系中分离是导致己二酸中微量苯酚存在的原因,实际生产中采用6台反应器串联,当1#,2#,3#反应器投料量占总投料量的70%,且3个反应器温度控制在80℃以下时,己二酸产品中苯酚等杂质明显下降。The trace impurities in cyclohexanol , an intermediate of cyclohexene hydration into adipic acid , were analyzed with a GC/MS-TQ8030 gas chromatography-mass spectrometer .The cyclohexene , oxidation products of cyclohexanol heavies , adipic acid crystallization mother liquor and adipic acid product were studied by esterification -extraction or neutralization-extraction.The results showed that the dominant impurities in cyclohexanol comprised cyclohexene and cyclohexanol heavies ;12 kinds of nitric acid oxidation products of cyclohexene were determined bearing upon the purity of adipic acid , and the oxidation solution was dark brown , resulting in the difficulties in adsorption decoloration;the cyclohexene content in cyclohexanol should be controlled lower than 100 mg/kg in the practical production;36 kinds of nitric acid oxidation products of cyclohexnol heavies , dominantly insoluble in water , were determined bearing upon the chromaticity of adipic acid , and the cyclohexanol heavies should be con-trolled lower than 500 mg/kg;trace phenol was detected in adipic acid and adipic acid crystallization mother liquor due to the low heat emission efficiency of reactors resulting in the difficult separation of phenol from adipic acid system ;the impurities like phe-nol in adipic acid product were obviously decreased when the feeding amount of reactors 1#, 2#and 3#accounted for 70%in the total feeding amount of six series reactors and the temperature was controlled below 80 ℃ for the three reactors in the practical production.

关 键 词：环己醇 环己烯 环己醇重组分 己二酸 杂质 剖析 

分 类 号：TQ225.146[化学工程—有机化工]