全二维气相色谱-飞行时间质谱分析有机氯化物形态

SPECIATION ANALYSIS OF ORGANIC CHLORIDES BY COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY COUPLED WITH TIME-OF-FLIGHT MASS SPECTROMETRY

基于全二维气相色谱-飞行时间质谱仪建立有机氯化物形态的定性分析方法,考察了不同高氯原油常压馏分中有机氯化物的分子形态及分布,结果表明常压石油馏分中有机氯化物形态主要有小分子(多)氯代烷烃/烯烃、氯苯酚、烷基氯苯、烷基氯苯胺、烷基氯代硝基苯等类型。综合分析了石油中有机氯化物的来源途径,并对部分途径进行初步实验考察,结果表明油田降黏剂中含有较多有机氯化物,主要以小分子(多)氯代烷烃/烯烃为主,还含有较多的氯代醇、酮、醚等,所考察的有机涂料中有机氯化物以1,2,3-三氯丙烷为主,其次含有较多的多氯取代醚。石油中有机氯化物存在形态的分子表征可为石油中氯来源排查,开发选择性吸附脱氯、加氢脱氯等工艺,以及设计吸附剂、氯转移剂和加氢脱氯催化剂等提供分子信息。

A qualitative and speciation analysis method for organic chlorides was developed basing on comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry,and the method was applied to investigate the molecular form and distribution of organic chlorides in different atmospheric distillates from high-chlorine crude oils.Analysis results showed that organic chlorides in atmospheric petroleum distillates were mainly in forms of(poly-)chloral alkane/olefin,chlorophenol,alkylchlorobenzene,alkylchloroaniline,alkylchloronitrobenzene and their homologues.Moreover,the origin of organic chlorides in crude oil was reviewed and comprehensively analyzed,and some routes for chlorine source were inspected preliminarily by the above-mentioned GC×GC-TOF MS method.The results indicated that in the oilfield viscosity reducer there were lots of organic chlorides such as(poly-)chloral alkane/olefin,chlorhydrin,chlorinated ketone and ether,and organic chlorides in the chosen organic coatings were mainly 1,2,3-trichloropropane and polychloroethers.Consequently,molecular characterization of organic chlorides in petroleum can provide information to trace chlorine sources for developing selective chlorine removal processes,such as adsorption dechlorination,hydrodechlorination,and for designing chlorine adsorbents,chlorine transfer agents and hydrodechlorination catalysts.