直馏柴油中硫化物甲基锍盐合成及电喷雾-高分辨质谱分析  

Synthesis and Characterization of Methylsulfonium Salt in Diesel Fraction Using Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

作　　者：潘娜[1] 史权[1] 徐春明[1] 刘鹏[1] 张亚和[1] 何俊辉[1] 赵锁奇[1] 

机构地区：[1]中国石油大学重质油国家重点实验室,北京102200

出　　处：《分析化学》2010年第3期413-416,共4页Chinese Journal of Analytical Chemistry

基　　金："973"基金(No.2004CB217801)资助项目

摘　　要：在四氟硼酸银的催化作用下,以碘甲烷对直馏柴油进行甲基衍生化反应,使其中的有机硫化物转变成极性较强的锍盐,再用电喷雾-傅立叶变换离子回旋共振质谱仪进行检测。结合气相色谱-脉冲火焰光度检测器(GC-PFPD)分析,研究不同类型的硫化物甲基衍生化反应的选择性和转化率。结果表明:柴油中硫化物在室温条件下容易与碘甲烷发生甲基化反应,大部分硫化物转化为锍盐,总转化率超过80%,苯并噻吩类比二苯并噻吩类更易发生甲基衍生化反应,转化率也相应较高。烷基二苯并噻吩不同取代位异构体间反应选择性存在较大差异,高分辨质谱分析结果表明,直馏柴油中存在环状硫醚类化合物。Sulfur compounds in the diesel were selectively derived into methylsulfonium salts by reacting with iodomethane in the presence of silver tetrafluoroborate,and characterized by positive-ion electrospray ionization （ ESI） fourier transform ion cyclotron resonance （ FT-ICR MS） . The conversion ratios and react selectivities of the methylation for various sulfur compounds were investigated by gas chromatograph coupled with pulse flame photometric detector （ GC-PFPD） . Result shows that the sulfur compounds in the diesel can react with iodomethane easily at room temperature,the most of sulfur compound derived into methylsulfonium salts; the homologue of benzothiophene get the higher conversion ratio and react selectivity than the homologue of dibenzothiophene （ DBT） . It is found that primarily sterically hindered alkylated DBT,for example,4-or 4-, 6-DBT,is recalcitrant to be methylated. Other than benzothiophenes and dibenzothiophenes,one-and tworing sulfides,as well as other sulfur compounds with a double bond equivalent （ DBE） value ranged from 1 to 12 are identified in the diesel.

关 键 词：柴油 硫化物 甲基衍生化 电喷雾 离子回旋共振 质谱 

分 类 号：TE626.24[石油与天然气工程—油气加工工程]