复杂油样中硫化氢的直接质谱分析研究  

Direct Mass Spectrometric Analysis of Hydrogen Sulfide in Complex Oil Samples

作　　者：张源 郑亚君[1] 路芳芳 张智平[1] ZHANG Yuan;ZHENG Ya-jun;LU Fang-fang;ZHANG Zhi-ping(School of Chemistry and Chemical Engineering,Xi’an Shiyou University,Xi’an 710065,China)

机构地区：[1]西安石油大学化学化工学院,陕西西安710065

出　　处：《质谱学报》2023年第1期46-54,共9页Journal of Chinese Mass Spectrometry Society

基　　金：国家自然科学基金(21777128);陕西省自然科学基础研究计划项目(2019JC-33);陕西高校青年创新团队项目(Z19257)。

摘　　要：复杂油样黏度高、本体复杂,不利于其中硫化氢(H_(2)S)的分析评价,虽然已发展了多种用于复杂样品中H_(2)S检测的方法,但是存在分析过程繁琐、误差大、灵敏度低等问题。本文基于三嗪与H_(2)S反应可生成噻二嗪的原理,将含有H_(2)S的复杂原油样品直接加入含有三嗪的乙腈溶液进行反应,通过对反应过程中实验参数的优化,建立了复杂油样中H_(2)S的纸喷雾电离源-质谱分析方法。根据产物噻二嗪的质谱信号强度与H_(2)S浓度之间的关系,构建H_(2)S定量分析标准曲线用于分析多种实际原油样品。结果表明,该方法的线性范围为0.1~1000μg/L,检出限为0.041μg/L,日内和日间精密度分别为3.04%、3.18%;对采自不同地域的6种原油样品中H_(2)S进行快速质谱分析,加标回收率为91.7%~103.5%,相对标准偏差为1.2%~4.5%。该方法具有操作简单、价格低廉、精密度高、准确性好、对仪器污染小等优点,可为原油中H_(2)S的直接分析提供方法参考。Due to the high viscosity and bulk complexity of crude oil samples,it poses a grand challenge to determine hydrogen sulfide(H_(2)S)in them.Although many methods have been developed for the analysis of H_(2)S in complex systems,these methods generally have complex processes,large analysis error and low sensitivity.In the study,based on the reaction between triazine and H_(2)S by generating thiadiazine,a small volume of complex crude oil sample was introduced directly into a triazine solution using acetonitrile as solvent for transferring H_(2)S into detectable species by organic mass spectrometry.The experimental parameters of solution composition,acetic acid content,reaction time and reaction temperature were optimized,and the method of paper spray ionization-mass spectrometry(PSI-MS)was established for rapid analysis of H_(2)S in complex crude oil samples.An optimal performance was achieved when the reaction of triazine and H_(2)S was carried out at 30℃for 2 h with acetonitrile containing 0.1%acetic acid as solvent.The standard curve for the quantitative analysis of H_(2)S was constructed according to the linear relationship between MS signal intensity of resulting thiadiazine and the concentration of H_(2)S,which was applied for actual crude oil samples from different sources.The results showed that the linear range and the limit of detection(LOD)were 0.1-1000μg/L and 0.041μg/L with intra-day precision of 3.04%and inter-day precision of 3.18%,respectively.The PSI-MS was also employed to determine H_(2)S in different actual crude oil samples,and the spiked recovery was 91.7%-103.5%with relative standard deviation(RSD)of 1.2%-4.5%.This method has the advantages of easy operation,low cost,high sensitivity and less contamination to mass spectrometer,which is promising for the direct and fast analysis of H_(2)S in complex crude oil samples.

关 键 词：质谱 纸喷雾 硫化氢 三嗪 油样 

分 类 号：O657.63[理学—分析化学]