柱上甲基化-碘化钾改性硅胶还原法分离石油样品中芳香类含硫化合物  

Separation of Aromatic Sulfur Compounds in Petroleum Samples by on-Column MethylationCombined With Potassium Iodide Modified Silica Gel Reduction

作　　者：吴建勋 李硕凡 程海洋 张未来 张亚和 史权[1] WU Jianxun;LI Shuofan;CHENG Haiyang;ZHANG Weilai;ZHANG Yahe;SHI Quan(Petroleum Molecular Engineering Center,State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing 102249,China)

机构地区：[1]中国石油大学(北京)重质油国家重点实验室石油分子工程中心,北京102249

出　　处：《石油学报（石油加工）》2024年第3期784-790,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点研发计划项目(2018YFA0702400);中国石油大学(北京)科研基金项目(2462023QNXZ017)资助。

摘　　要：研究开发了一种通过层析柱上甲基化-碘化钾改性硅胶还原法分离石油芳香类含硫化合物的新方法。通过填充担载了六氟锑酸银的硅藻土制备固相萃取柱,实现含硫化合物的快速甲基化和对甲基锍盐的富集;再通过碘化钾改性硅胶对芳香类甲基锍盐进行快速还原,最终得到高纯度的芳香类含硫化合物。利用模型化合物对该方法进行验证,同时将该方法应用于柴油和原油样品,并结合气相色谱串联硫化学发光检测器和气相色谱串联质谱对分离组分进行分析。模型化合物分析结果表明,该方法对包含屏蔽型结构在内的二苯并噻吩类化合物回收率可达95%以上。石油样品的分析结果表明,该方法可实现对不同类型芳香类含硫化合物的高纯度分离,且操作简单、快捷。A novel approach was developed for separating petroleum aromatic sulfur-containing compounds(ASCs)using a new technique of on-column methylation combined with potassium iodide modified silica gel reduction.A solid-phase extraction column was prepared by packing diatomaceous earth loaded with silver hexafluoroantimonate,which facilitated rapid methylation of sulfur-containing compounds and enrichment of methylsulfonium salts.Subsequently,the aromatic methylsulfonium salts were efficiently reduced by potassium iodide-modified silica gel,thus obtaining ASCs of high purity.The method was validated by model compounds,and applied to treat diesel and crude oil samples.The separated fractions were analyzed by gas chromatography coupled with a sulfur chemiluminescence detector(GC-SCD)and gas chromatography-mass spectrometry(GC-MS).The analysis of model compounds demonstrates that the recovery rate of this method for dibenzothiophene compounds including shielded structures can reach 95%.Moreover,the analytical results from the petroleum samples have confirmed that the method can realize high-purity separation of various types of ASCs,and this operation is simple and quick.

关 键 词：含硫化合物 分离 柱上甲基化 改性硅胶 气相色谱-质谱 

分 类 号：TE622[石油与天然气工程—油气加工工程]