质谱技术与石油分子组成.ppt

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,216.0,216.5,217.0,217.5,218.0,218.5,219.0,219.5,220.0,220.5,m/z,221.0,217.088601,217.091845,219.095082,+,+,+,高分辨回旋共振质谱仪,苯并咔唑,217,218,219,质谱图,单位质量分辨四极杆质谱仪,质谱图与色谱图的区别,m/z,RT,MS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,苯并咔唑,Profile,Cent.,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,0,10,20,30,40,50,60,70,80,90,100,Time(min),s10072001,nC20,nC30,石油勘探-地球化学分析,0,10,20,30,40,50,60,70,80,90,100,Time(min),0,10,20,30,40,50,60,70,80,90,100,Time(min),0,10,20,30,40,50,60,70,80,90,100,Time(min),20,30,40,50,60,70,80,10,60mHP-5MS,LD6-2-1,m/z191,m/z217,m/z123,m/z85,C30H52Hopane,C2924-乙基胆甾烷,60,RT/min,46,50,48,58,52,54,56,m/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/z217,45,50,55,60,1-LD6-2-1,372.3217.2,386.3217.2,400.3217.2,60mHP-5MS,20R,20S,20R,20S,20R,20S,20S,20R,20S,20R,20S,20R,20R,20S,20R,20S,20R,20S,20R,60,RT/min,60mHP-5MS,overlaid,372.3217.2,386.3217.2,400.3217.2,46,50,48,58,52,54,56,叠加在一起的图形效果,这些峰在色谱上共逸出,LD6-2-1Sat.,60,RT/min,46,50,48,58,52,54,56,372.3217.2,386.3217.2,400.3217.2,217.2,1-LD21-1-13675-3682,60mHP-5MS,色谱柱：HP-5MS(60m),仪器：BrukerVarain450GC320MS,SCIONTQGC-MS,石化应用,iC4,iC5,2M4C4=,2MC5,MCYC571.9C,3MC5,2MC690.1C,3MC691.9C,BZ80.1C,1MCYC5,nC669C,nC5,nC798C,nC4,C6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,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,40,60,80,100,120,140,160,180,200,220,240,260,280,300,320,340,m/z-,57,43,71,85,99,113,127,141,155,183,211,268,239,296,334,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,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,碳数,碳数,Z,Z,催化重油,加氢催化重油,Z,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&LC,MS,NMR,C3vsSH43.4mDa500,000m/z500,FT-ICRMS,1994,1996,1999,FT-ICRMS,14.5TFT-ICRMS,COVERSTORY,September21,2009|Volume87|Number38|pp.12-17DiggingIntoAsphaltenes,AlanMarshall,FT-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-ICRMS,2007-2009,9.4TFT-ICRMS,渣油裂化液体产物,222.1288,272.1444,320.2383,463.0195,150,200,250,300,350,400,450,500,550,m/z,337.05,337.10,337.15,337.20,337.25,337.30,337.35,m/z,337.05,337.10,337.15,337.20,337.25,337.30,337.35,m/z,*CC24H22N1,FT-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