预浓缩与GC-SCD/MS联用测定燃料电池车用氢气中超痕量多形态硫化物和甲醛  

Determination of Ultra-Trace Sulfide and Formaldehyde Components in Hydrogen Fuel for Fuel Cell Vehicles by Pre-Concentration Integrated With GC-SCD/MS

作　　者：徐聪[1] 王亚敏[1] 张祎玮 徐广通[1] 宗保宁[1] 谢在库[2] XU Cong;WANG Yamin;ZHANG Yiwei;XU Guangtong;ZONG Baoning;XIE Zaiku(Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China;Ministry of Science and Technology, SINOPEC, Beijing 100728, China)

机构地区：[1]中国石化石油化工科学研究院,北京100083 [2]中国石化科技部,北京100728

出　　处：《石油学报（石油加工）》2021年第6期1440-1451,共12页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点研发计划课题(2019YFB1505004)基金资助。

摘　　要：为更准确高效地实现氢气中多种超痕量杂质的测定,将预浓缩技术、气相色谱(GC)搭载硫化学发光检测器(SCD)和质谱仪(MS)集成联用,同时测定氢燃料中的超痕量形态硫和甲醛。采用特制冷阱预浓缩捕集并排空样品基体,单毛细柱分离后经微流切割分流,实现了一次进样,分别在SCD和MS上同时测定氢气中的超痕量形态硫和甲醛。参照ISO 21087—2019的规范完成方法验证。结果表明:进样500 mL时,硫化氢和甲醛的检出限分别低达0.011 nmol/mol和0.208 nmol/mol,均优于目前已报道的灵敏度水平。各化合物线性关系良好,相关系数r^(2)均达0.995以上;重复精密度为1.60%~8.24%,加标回收率为92.96%~103.40%。该方法灵敏度及准确度高,集成高效,对中国燃料电池车用氢气质量标准体系的建立和优化具有重要的理论和现实意义。To realize the simultaneous determination of various impurities accurately and efficiently,the combined use of pre-concentration,GC coupled with two detectors of sulfide luminescence detector(SCD)and mass spectrometer(MS)were established to determine ultra-trace sulfur species and formaldehyde in hydrogen fuel.Sulfur species and formaldehyde in hydrogen were analyzed simultaneously over SCD and MS via a single injection across microflow cutting and shunting technology,before which the target compounds were enriched by custom-built two-stage cold traps,and the exhaust matrix were evacuated based on trapping parameters and pro-long with a single capillary column.The method was also successfully developed and validated in accordance with ISO 21087—2019.The results show that the detection limits of hydrogen sulfide and formaldehyde are 0.011 nmol/mol and 0.208 nmol/mol in the volume of 500 mL,which are lower than the existing analytical techniques and fully meet the limit requirements specified by ISO 14687:2019(total sulfur compounds of 0.004μmol/mol)and GB/T 37244—2018(formaldehyde of 0.01μmol/mol).Possible presence of sulfur species in hydrogen fuel and formaldehyde(HCHO)shows a good linear relationship with correlation coefficient r^(2) of above 0.995.The precision RSD(relative standard deviation)of all compounds is between 1.60%—8.24%and the recoveries are between 92.96%—103.40%.The established method is highly sensitive,reliable,efficient,technical economy and practical valuable.It has important theoretical and practical guiding significance for the establishment and optimization of hydrogen quality standard system for fuel cell vehicles(FCVs)of China.

关 键 词：氢燃料 预浓缩 硫化学发光检测法 硫化物测定 甲醛测定 

分 类 号：O657.7[理学—分析化学]