基于反应气混合物的ICP-MS/MS测定原油中的钒和镍  

Determination of Vanadium and Nickel in Crude Oil by ICP-MS/MS Based on Reaction Gas Mixture

作　　者：蔡松韬 黄莹秀 袁亮 代宇宣 莫垚坤 黄建华 CAI Song-tao;HUANG Ying-xiu;YUAN Liang;DAI Yu-xuan;MO Yao-kun;HUANG Jian-hua(College of Materials Science and Engineering,Hunan Institute of Technology,Hengyang 421002,China;Institute of Chinese Materia Medica,Hunan Academy of Traditional Chinese Medicine,Changsha 410013,China)

机构地区：[1]湖南工学院材料科学与工程学院,湖南衡阳421002 [2]湖南省中医药研究院中药研究所,湖南长沙410013

出　　处：《光谱学与光谱分析》2025年第1期101-106,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(21975289);湖南省自然科学基金项目(2023JJ50100);湖南省“十四五”应用特色学科材料科学与工程学科(湘教通[2022]351号);国家级大学生创新创业训练计划项目(202211528012,202211528035X);湖南省大学生创新创业训练计划项目(S202311528021);湖南省衡阳市指导性计划项目(202222015692)资助。

摘　　要：原油中金属元素钒和镍(V和Ni)的含量和比值可为深入了解原油的沉积环境特征和有机质类型发挥重要作用。在原油炼制过程中,V和Ni作为原油催化裂化过程中的有害金属元素,会降低催化剂的活性,严重时会导致催化剂中毒,会严重腐蚀设备,在精炼之前必须对原油中的V和Ni进行脱除处理。V和Ni具有致突变性和致癌性,识别或监测原油中V和Ni进入环境的潜在危险变得越来越重要,对原油中V和Ni的含量进行高灵敏精准测定具有重要意义。采用电感耦合等离子体串联质谱(ICP-MS/MS)测定原油中V和Ni的新策略。原油样品经航空煤油简单稀释后直接采用ICP-MS/MS进行分析,针对V和Ni受到的质谱干扰,在MS/MS模式下,采用由NH_(3)/He(He为缓冲气)和H_(2)组成的反应气混合物(NH_(3)/He/H_(2))作为反应气,基于V^(+)与NH_(3)/He/H_(2)不发生反应,而V^(+)的干扰离子与NH_(3)/He/H_(2)发生反应,采用原位质量法消除干扰,选择V^(+)进行测定;基于Ni^(+)与NH_(3)/He/H_(2)发生反应,采用质量转移法消除干扰,选择无干扰团簇离子Ni(NH_(3))_(3)^(+)进行测定。通过与NH_(3)/He反应模式进行对比研究发现,对于V的测定,加入H_(2)为反应气能快速去除氩基离子的干扰,并能协同NH_(3)消除氧化物离子的干扰;对于Ni的测定,加入H_(2)为反应气能促进全氢加合物(-NH_(3))的形成,从而提高生成Ni(NH_(3))_(3)^(+)的产率。在NH_(3)/He/H_(2)反应模式下,V和Ni的背景等效浓度(BEC)更低,Ni的灵敏度更高,V和Ni的检出限(LOD)分别低至0.83和3.76 ng·kg^(-1),定量限(LOQ)分别为2.77和12.5 ng·kg^(-1)。通过分析标准参考物质NIST SRM 1634c并进行加标回收实验评价方法的准确度和精密度,结果显示,方法的测定结果与标准参考物质的认证值基本一致,V和Ni的加标回收率分别为97.7%和103%,相对标准偏差(RSD)分别为1.8%和1.9%。所建立的分析方法避免了繁琐的样品预处理过程,具有操作The content and ratio of metal elements V and Ni in crude oil play an important role in understanding the characterizing depositional environment and organic matter types of crude oil.However,in the process of crude oil refining,V and Ni,as harmful metal elements in the catalytic cracking process of crude oil,will reduce the activity of the catalyst,and even lead to poisoning of the catalyst and serious corrosion of equipment.Before refining,V and Ni must be removed from the crude oil.In addition,V and Ni are mutagenic and carcinogenic,and it is becoming increasingly important to identify or monitor the potential danger of V and Ni in crude oil entering the environment.Therefore,conducting highly sensitive and accurate determination of V and Ni content in crude oil is of great significance.This paper proposes a new strategy for determining V and Ni in crude oil by inductively coupled plasma tandem mass spectrometry(ICP-MS/MS).ICP-MS/MS directly analyzes the crude oil sample after diluting aviation kerosene.For the spectral interferences of V and Ni,in the MS/MS mode,the reaction gas mixture NH_(3)/He/H_(2)is composed of NH_(3)/He(He is the buffer gas),and H_(2)is used as the reaction gas.Based on the fact that V^(+)does not react with NH_(3)/He/H_(2),but the interfering ions of V^(+)react with NH_(3)/He/H_(2),the on-mass method was used to eliminate the interference,and V^(+)was selected for determination.Based on the mass shift reaction between Ni^(+)and NH_(3)/He/H_(2),the interference was eliminated by the mass shift method,and the interference-free cluster ion Ni(NH_(3))_(3)^(+)was selected for determination.By comparing it with the NH_(3)/He reaction mode,it is found that for the determination of V,adding H_(2)as a reaction gas can quickly remove the interference of large ions and cooperate with NH_(3)to eliminate the interference of oxide ions.For the determination of Ni,adding H_(2)as reaction gas can promote the formation of fully hydrogenated adducts(-NH_(3)),thus increasing the yield of Ni(NH_(3))_(3)^(

关 键 词：原油 电感耦合等离子体串联质谱 钒(V) 镍(Ni) 氨气/氦气/氢气(NH_(3)/He/H_(2)) 

分 类 号：O657.3[理学—分析化学]