质谱技术与石油分子组成

质谱技术与石油分子组成2011-12-4北京昌平2011实验室学术年会中国石油大学(北京)史权Everythingyoualwayswantedtoknowaboutmassspectrometrybutwereafraidtoask...一台称量分子和分子碎片质量的天平质谱仪质谱图216.0216.5217.0217.5218.0218.5219.0219.5220.0220.5m/z221.0217.088601217.091845219.095082NN13CN13C13C+++高分辨回旋共振质谱仪N苯并咔唑217218219质谱图N13CN13C13C单位质量分辨四极杆质谱仪质谱图与色谱图的区别m/zRTMS信号随质量变化分子组成GC信号随时间变化混合物组成质谱图50100150200250300350400m/z217216108218107941891909418816382N苯并咔唑ProfileCent.质谱图辽河原油石油的找、采、用勘探开发储运加工石油勘探----地球化学分析0102030405060708090100Time(min)s10072001nC20nC30石油勘探----地球化学分析0102030405060708090100Time(min)0102030405060708090100Time(min)0102030405060708090100Time(min)203040506070801060mHP-5MSLD6-2-1m/z191m/z217m/z123m/z85C30H52Hopane1234567891011121314232425261516171819202122302728C2924-乙基胆甾烷181467121114151719202122232425262728292360RT/min46504858525456m/z217甾烷类化合物组成复杂，无法实现单体化合物完全分离m/z217455055601-LD6-2-1372.3217.2386.3217.2400.3217.260mHP-5MS20R20S20R20S20R20S20S20R20S20R20S20R20R20S20R20S20R20S20R60RT/min60mHP-5MSoverlaid372.3217.2386.3217.2400.3217.246504858525456叠加在一起的图形效果这些峰在色谱上共逸出LD6-2-1Sat.60RT/min46504858525456372.3217.2386.3217.2400.3217.2217.21-LD21-1-13675-368260mHP-5MS色谱柱：HP-5MS(60m)仪器：BrukerVarain450GC320MSSCIONTQ™GC-MS石化应用iC4iC52M4C4=2MC5MCYC571.9C3MC52MC690.1C3MC691.9CBZ80.1C1MCYC5nC669CnC5nC798CnC4C6烯烃催化裂化汽油单体烃分析石化应用柴油气相色谱图石化应用润滑油气相色谱图烷烃理论异构体数量碳数异构体数量馏分538181075123551583472036.6×1042536.7×1063041.1×1083549.3×10104062.4×10124582.2×101460221.5×1020801056.4×10281005920×1038汽油柴油、中间馏分VGOVR汽油柴油、中间馏分VGOVR碳数异构体数量馏分538181075123551583472036.6×1042536.7×1063041.1×1083549.3×10104062.4×10124582.2×101460221.5×1020801056.4×10281005920×1038汽油柴油、中间馏分VGOVR汽油柴油、中间馏分VGOVR石油单体组成分析是一个永远无法实现的目标类型(族)组成数据更有应用价值!石油烃族组成裂片法(矩阵法)基线法母体峰法406080100120140160180200220240260280300320340m/z--5743718599113127141155183211268239296334烃类含量，％链烷烃一环环烷二环环烷三环环烷烷基苯66.719.210.82.60.7气相色谱按沸点或极性分离样品飞行时间高分辨质谱区分相同整数质量分子GC-FITOFMS场电离源软电离产生分子离子饱和烃芳烃非碱性氮烯烃81012141618202224262830碳数碳数8101214161820222426283081012141618202224262830碳数81012141618202224262830碳数81012141618202224262830碳数81012141618202224262830碳数碳数810121416182022242628308101214161820222426283081012141618202224262830810121416182022242628308101214161820222426283081012141618202224262830碳数碳数碳数碳数碳数8101214161820222426283081012141618202224262830NHNH碳数碳数碳数碳数81012141618202224262830810121416182022242628308101214161820222426283081012141618202224262830SS81012141618202224262830碳数碳数碳数8101214161820222426283081012141618202224262830S-4S-6S-8S-10S-12S-14S-16S碳数碳数碳数810121416182022242628308101214161820222426283081012141618202224262830碳数碳数81012141618202224262830碳数噻吩硫柴油的类型及碳数分布加氢前后芳烃类型及碳数分布变化低碳数多环芳烃含量高碳数碳数ZZ催化重油加氢催化重油低碳数单环芳烃增加烷基苯类环烷苯类二环烷苯类萘类苊类芴类菲类环烷菲类芘类屈类苝类二苯并蒽类－6－8－10－12－14－16－18－20－22－24－26－38Z类型加氢前加氢后催化重油加氢前后芳烃类型及碳数分布变化加氢前加氢后催化重油石油分析的主要难题石油极性大分子的组成分析核心问题：GC&LCMSNMRC3vsSH43.4mDa500,000@m/z500FT-ICRMS199419961999FT-ICRMS14.5TFT-ICRMSCOVERSTORYSeptember21,2009|Volume87|Number38|pp.12-17DiggingIntoAsphaltenesAlanMarshallFT-ICRMS阿美石油公司埃克森美孚壳牌雪佛龙中国石化中国石油大学(北京)加拿大Calgary大学FT-ICRMS2007-20099.4TFT-ICRMS渣油裂化液体产物222.1288272.1444320.2383463.0195150200250300350400450500550m/z337.05337.10337.15337.20337.25337.30337.35m/z337.05337.10337.15337.20337.25337.30337.35m/z*CC24H22N1C22H41O2*CC23H34N1C24H17O2C19H29O5*CC21H26N1S1C23H33N2C24H33O1C20H33O4C22H29N2O1C20H33O2S1C23H29O2C16H33O5S1C22H25O1S1C25H21O1*CC23H18N1O1C23H17N2O1C21H21O2S1*CC22H14N1S1121:C21H21O42:C18H25O4S1FT-ICRMS石油分析相关质谱技术离子源质量分析器电子轰击（EI）场致电离（FI）电喷雾（ESI）四极杆三重四级杆飞行时间离子回旋亟待解决的问题重油及杂原子化合物的定量分析可以解决的问题可蒸馏组分（汽油、柴油、VGO）烃类组成定量分析大分子杂原子化合物的定性认识2012年重质油国家重点实验室学术年会中国青岛2012年重质油国家重点实验室学术年会中国厦门2012年重质油国家重点实验室学术年会中国????