質(zhì)譜技術(shù)與石油分子組成2011-12-4北京

昌平2011實(shí)驗(yàn)室學(xué)術(shù)年會(huì)中國(guó)石油大學(xué)(北京)史權(quán)質(zhì)譜技術(shù)與石油分子組成2011-12-4北京昌平21Everythingyoualwayswantedtoknowaboutmassspectrometrybutwereafraidtoask...一臺(tái)稱量分子和分子碎片質(zhì)量的天平質(zhì)譜儀Everythingyoualwayswantedt2質(zhì)譜圖216.0216.5217.0217.5218.0218.5219.0219.5220.0220.5m/z221.0217.088601217.091845219.095082+++高分辨回旋共振質(zhì)譜儀質(zhì)譜圖216.0216.5217.0217.5218.0213苯并咔唑217218219質(zhì)譜圖單位質(zhì)量分辨四極桿質(zhì)譜儀苯并咔唑217218219質(zhì)譜圖單位質(zhì)量分辨4質(zhì)譜圖與色譜圖的區(qū)別m/zRTMS信號(hào)隨質(zhì)量變化分子組成

GC信號(hào)隨時(shí)間變化混合物組成

質(zhì)譜圖與色譜圖的區(qū)別m/zRTMSGC5質(zhì)譜圖50100150200250300350400m/z217216108218107941891909418816382苯并咔唑ProfileCent.質(zhì)譜圖50100150200250300350400m/z26質(zhì)譜圖遼河原油質(zhì)譜圖遼河原油7石油的找、采、用勘探開(kāi)發(fā)儲(chǔ)運(yùn)加工石油的找、采、用勘探開(kāi)發(fā)儲(chǔ)運(yùn)加工8石油勘探----地球化學(xué)分析0102030405060708090100Time(min)s10072001nC20nC30石油勘探----地球化學(xué)分析01020304050607089石油勘探----地球化學(xué)分析0102030405060708090100Time(min)0102030405060708090100Time(min)0102030405060708090100Time(min)石油勘探----地球化學(xué)分析010203040506070810203040506070801060mHP-5MSLD6-2-1m/z191m/z217m/z123m/z85203040506070801060mHP-5MSLD11C30H52Hopane1234567891011121314232425261516171819202122302728C30H52Hopane123456789101112112C2924-乙基膽甾烷1814671211141517192021222324252627282923C2924-乙基膽甾烷18146712111415171913質(zhì)譜技術(shù)與石油分子組成ppt課件1460RT/min46504858525456m/z217甾烷類化合物組成復(fù)雜，無(wú)法實(shí)現(xiàn)單體化合物完全分離m/z21760RT/min46504858525456m/z2115質(zhì)譜技術(shù)與石油分子組成ppt課件16455055601-LD6-2-1372.3>217.2386.3>217.2400.3>217.260mHP-5MS

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20R455055601-LD6-2-1372.3>217.2381760RT/min60mHP-5MSoverlaid372.3>217.2386.3>217.2400.3>217.246504858525456疊加在一起的圖形效果這些峰在色譜上共逸出LD6-2-1Sat.60RT/min60mHP-5MSoverlaid31860RT/min46504858525456372.3>217.2386.3>217.2400.3>217.2217.21-LD21-1-13675-368260mHP-5MS60RT/min46504858525456372.3>19色譜柱：HP-5MS(60m)儀器：BrukerVarain450GC320MSSCIONTQ?GC-MS色譜柱：HP-5MS(60m)儀器：BrukerV20石化應(yīng)用iC4iC52M4C4=2MC5MCYC571.9C3MC52MC690.1C3MC691.9CBZ80.1C1MCYC5nC669CnC5nC798CnC4C6烯烴催化裂化汽油單體烴分析石化應(yīng)用iC4iC52M4C4=2MC5MCYC53MC5221石化應(yīng)用柴油氣相色譜圖石化應(yīng)用柴油氣相色譜圖22石化應(yīng)用潤(rùn)滑油氣相色譜圖石化應(yīng)用潤(rùn)滑油氣相色譜圖23烷烴理論異構(gòu)體數(shù)量石油單體組成分析是一個(gè)永遠(yuǎn)無(wú)法實(shí)現(xiàn)的目標(biāo)類型(族)組成數(shù)據(jù)更有應(yīng)用價(jià)值!烷烴理論異構(gòu)體數(shù)量石油單體組成分析是一個(gè)永遠(yuǎn)無(wú)法實(shí)現(xiàn)的目標(biāo)24石油烴族組成裂片法(矩陣法)基線法母體峰法406080100120140160180200220240260280300320340m/z-->5743718599113127141155183211268239296334烴類含量，％鏈烷烴一環(huán)環(huán)烷二環(huán)環(huán)烷三環(huán)環(huán)烷烷基苯66.719.210.82.60.7石油烴族組成裂片法(矩陣法)基線法母體峰法4060801025氣相色譜按沸點(diǎn)或極性分離樣品飛行時(shí)間高分辨質(zhì)譜區(qū)分相同整數(shù)質(zhì)量分子GC-FITOFMS場(chǎng)電離源軟電離產(chǎn)生分子離子氣相色譜按沸點(diǎn)或極性分離樣品飛行時(shí)間高分辨質(zhì)譜區(qū)分相同整數(shù)質(zhì)26飽和烴芳烴非堿性氮烯烴碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)-4S-6S-8S-10S-12S-14S-16S碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)噻吩硫柴油的類型及碳數(shù)分布飽和烴芳烴非堿性氮烯烴碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳數(shù)碳27加氫前后芳烴類型及碳數(shù)分布變化低碳數(shù)多環(huán)芳烴含量高碳數(shù)碳數(shù)ZZ催化重油加氫催化重油低碳數(shù)單環(huán)芳烴增加烷基苯類環(huán)烷苯類二環(huán)烷苯類萘類苊類芴類菲類環(huán)烷菲類芘類屈類苝類二苯并蒽類－6－8－10－12－14－16－18－20－22－24－26－38Z類型加氫前加氫后催化重油加氫前后芳烴類型及碳數(shù)分布變化低碳數(shù)多環(huán)芳烴含量高碳數(shù)碳數(shù)Z28加氫前后芳烴類型及碳數(shù)分布變化加氫前加氫后催化重油加氫前后芳烴類型及碳數(shù)分布變化加氫前加氫后催化重油29石油分析的主要難題石油極性大分子的組成分析核心問(wèn)題：GC&LCMSNMRC3vsSH43.4mDa>500,000@m/z500石油分析的主要難題石油極性大分子的組成分析核心問(wèn)題：GC&30FT-ICRMS199419961999FT-ICRMS19941996199931FT-ICRMSFT-ICRMS3214.5TFT-ICRMSCOVERSTORYSeptember21,2009|Volume87|Number38|pp.12-17

DiggingIntoAsphaltenes

AlanMarshallFT-ICRMS14.5TFT-ICRMSCOVERSTORYSept33阿美石油公司?？松梨跉づ蒲┓瘕堉袊?guó)石化中國(guó)石油大學(xué)(北京)加拿大Calgary大學(xué)FT-ICRMS2007-20099.4TFT-ICRMS阿美石油公司埃克森美孚殼牌雪佛龍中國(guó)石化中國(guó)石油大學(xué)(北京34渣油裂化液體產(chǎn)物222.1288272.1444320.2383463.0195150200250300350400450500550m/z渣油裂化液體產(chǎn)物222.1288272.1444320.2335337.05337.10337.15337.20337.25337.30337.35m/z337.05337.10337.15337.20337.25337.30337.35m/z*CC24H22N1C22H41O2*CC23H34N1C24H17O2C19H29O5*CC21H26N1S1C23H33N2C24H33O1C20H33O4C22H29N2O1C20H33O2S1C23H29O2C16H33O5S1C22H25O1S1C25H21O1*CC23H18N1O1C23H17N2O1C21H21O2S1*CC22H14N1S1121:C21H21O42:C18H25O4S1337.05337.10337.15337.20337.2536FT-ICRMSFT-ICRMS37石油分析相關(guān)質(zhì)譜技術(shù)離子源質(zhì)量分析器電子轟擊（EI）場(chǎng)致電離（FI）電噴霧（ESI）四極桿三重四級(jí)桿飛行時(shí)間離子回旋亟待解決的問(wèn)題重油及雜原子化合物的定量分析可以解決的問(wèn)題可蒸餾組分（汽油、柴油、VGO）烴類組成