石油学报(石油加工) ›› 2021, Vol. 37 ›› Issue (1): 44-54.doi: 10.3969/j.issn.1001-8719.2021.01.005

• 研究报告 • 上一篇    下一篇

Michael加成衍生化结合气相色谱-质谱法测定汽油馏分中的硫醇化合物

张文青,王乃鑫,王威,刘泽龙,蔡新恒   

  1. 中国石化 石油化工科学研究院, 北京 100083
  • 收稿日期:2019-12-26 修回日期:2020-10-10 出版日期:2021-01-25 发布日期:2021-01-12
  • 通讯作者: 刘泽龙,男,教授级高级工程师,从事石油化学质谱分析方面的研究,Tel: 010-82368298, E-mail:liuzl1.ripp@sinopec.com E-mail:liuzl1.ripp@sinopec.com
  • 作者简介:第一作者: 张文青,女,硕士,从事石油化学质谱分析方面的研究
  • 基金资助:

    中国石油化工股份有限公司课题项目(119025)资助

Analysis of Thiols in Naphtha With Michael Addition Derivatization Followed by Gas Chromatography-Mass Spectrometry

ZHANG Wenqing, WANG Naixin, WANG Wei, LIU Zelong, CAI Xinheng   

  1. Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
  • Received:2019-12-26 Revised:2020-10-10 Online:2021-01-25 Published:2021-01-12

摘要: 建立了基于Michael加成反应结合气相色谱-质谱测定汽油中硫醇化合物的方法。以苯基乙烯基砜(PVS)为衍生化试剂,4-二甲氨基吡啶(DMAP)为催化剂,甲醇为溶剂,反应迅速且各硫醇单体转化率均在99%以上。采用气相色谱质谱(GC-MS)测定汽油中硫醇化合物单体,并对C1~C8烷基硫醇进行定量分析,同时对焦化汽油、催化裂化汽油中的烷基硫醇化合物进行定量分析。结果表明:该测定方法对于13种烷基硫醇的定量标准方程在其质量浓度为1~200 mg/L范围内呈现良好的线性关系,相关系数在0.9985~0.9997 之间,加标回收率处在74.1%~124.6%,相对标准偏差(RSD)均小于5%。汽油中硫醇化合物集中分布在C2~C3的低碳数硫醇中,占总硫醇化合物的60%以上。焦化汽油中硫醇化合物含量较高,含较多的正构硫醇;而催化裂化汽油硫醇化合物含量相对较低,同碳数异构硫醇的相对含量多大于正构硫醇含量。

关键词: Michael加成, 硫醇, 汽油, 气相色谱-质谱(GC-MS)

Abstract: An analysis method based on Michael addition reaction for analyzing thiols in naphtha by gas chromatography-mass spectrometry was established. Phenyl vinyl sulfone (PVS) was selected as derivatization reagent, 4-dimethylaminopyridine (DMAP) was used as catalyst, and methanol was used as solvent. The conversions of thiols are all above 99%. Quantitative analysis of 13 types alkyl thiol monomers of C1-C8 shows a good linear correlation in the range of 1-200 mg/L by GC-MS. The correlation coefficients are between 0.9985-0.9997, and the recoveries reach 74.1%-124.6%. The relative standard deviation (RSD) is less than 5%. Quantitative analysis of thiols in coker and FCC naphtha shows that the thiols of naphtha concentrate in C2-C3 of low carbon number thiols, accounting for more than 60%. Coker naphtha has a high content of the total thiols and contains more normal-alkyl thiols. Meanwhile, FCC naphtha has a lower content of thiols than that of coker naphtha. The relative content of isomeric thiols at the same carbon number is much higher than that of normal-alkyl thiols in the FCC naphtha.

Key words: Michael addition, thiols, naphtha, gas chromatography-mass spectrometry (GC-MS)