石油样品中金刚烷类化合物的定量分析新方法
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摘要
在用全二维气相色谱—飞行时间质谱定性石油样品中的金刚烷系列化合物基础上,建立了一套包括前处理方法在内的用全二维气相色谱—氢火焰离子化检测器定量分析石油样品中金刚烷类化合物的新方法。该方法利用全二维气相色谱正交分离的特点,使得常规的金刚烷系列化合物在色谱条件下就能很好地分离,实现了该类化合物的色谱定量分析。为减少前处理过程中低碳数金刚烷类化合物的挥发损失,新方法中对现有的石油样品饱和烃馏分的分离方法进行改进,建立了用小柱法分离收集饱和烃前馏分的方法,具有所需样品量少、分析时间短、实验耗材少的特点,金刚烷回收率满足色谱定量分析的需要。与传统的色谱—质谱定量方法相比,全二维色谱定量方法分离度高,重复性好,对内标物质要求低,7次实验的相对标准偏差小于5%,满足复杂体系的分析要求。
A new method for the quantitative analysis of diamondoid hydrocarbons in petroleum geological samples was established using comprehensive two-dimensional gas chromatography-flame ionization detector(GC×GC-FID). The process included the pretreatment of sample followed by the qualitative analysis of diamondoid hydrocarbons using two-dimensional gas chromatography with time-of-flight mass spectrometry(GC×GC-TOFMS). The diamondoid hydrocarbons could be well separated using the orthogonal separation characteristics of GC×GC, The original separation method of saturated hydrocarbon fraction in petroleum samples was improved in this study in order to reduce the loss of low-carbon diamondoid hydrocarbons in the pretreatment process. A new pretreatment method for saturated hydrocarbon by small column chromatography was established. There were many advantages such as lower sample costs, short analysis time and little consumption of reagents. The recovery of diamondoid hydrocarbons was satisfied for chromatography quantitative analysis. Compared to the traditional internal standard semi-quantitative method by gas chromatography-mass spectrometry(GC-MS), this method had high resolution and lower requirements for internal standards. The quantitative results of diamondoids could be obtained using only one certified reference material of deuterated adamantane. Moreover, the repeatability was good. The relative standard deviation(RSD, n=7) was less than 5%, which could meet the analytical requirements of a complicated system.
A new method for the quantitative analysis of diamondoid hydrocarbons in petroleum geological samples was established using comprehensive two-dimensional gas chromatography-flame ionization detector(GC×GC-FID). The process included the pretreatment of sample followed by the qualitative analysis of diamondoid hydrocarbons using two-dimensional gas chromatography with time-of-flight mass spectrometry(GC×GC-TOFMS). The diamondoid hydrocarbons could be well separated using the orthogonal separation characteristics of GC×GC, The original separation method of saturated hydrocarbon fraction in petroleum samples was improved in this study in order to reduce the loss of low-carbon diamondoid hydrocarbons in the pretreatment process. A new pretreatment method for saturated hydrocarbon by small column chromatography was established. There were many advantages such as lower sample costs, short analysis time and little consumption of reagents. The recovery of diamondoid hydrocarbons was satisfied for chromatography quantitative analysis. Compared to the traditional internal standard semi-quantitative method by gas chromatography-mass spectrometry(GC-MS), this method had high resolution and lower requirements for internal standards. The quantitative results of diamondoids could be obtained using only one certified reference material of deuterated adamantane. Moreover, the repeatability was good. The relative standard deviation(RSD, n=7) was less than 5%, which could meet the analytical requirements of a complicated system.
引文
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[16] WANG Huitong,ZHANG Shuichang,WENG Na,et al.A new analytical method for quantifying of sterane and hopane biomarkers[J].Science China Earth Sciences,2014,57(8):1713-1722.
[17] WANG Guangli,SHI Shengbao,WANG Peirong,et al.Analysis of diamondoids in crude oils using comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry[J].Fuel,2013,107:706-714.
[18] 国家能源局.SY/T 5119-2016,岩石中可溶有机物及原油族组分分析[S].北京:石油工业出版社,2016.National Energy Administration.SY/T 5119-2016,Analytical method of soluble organic matters in rocks and crude oil group composition column chromatography[S].Beijing:Petroleum Industry Press,2016.
[19] 王汇彤,魏彩云,宋孚庆,等.细硅胶层析柱对饱和烃和芳烃的分离[J].石油实验地质,2009,31(3):312-314.WANG Huitong,WEI Caiyun,SONG Fuqing,et al.Separation of saturated and aromatic hydrocarbon using fine silica gel[J].Petroleum Geology & Experiment,2009,31(3):312-314.
[20] GRICE K,ALEXANDER R,KAGI R I.Diamondoid hydrocarbon ratios as indicators of biodegradation in Australian crude oils[J].Organic Geochemistry,2000,31(1):67-73.
[2] WEI Zhibin,MOLDOWAN J M,PAYTAN A.Diamondoids and molecular biomarkers generated from modern sediments in the absence and presence of minerals during hydrous pyrolysis[J].Organic Geochemistry,2006,37(8):891-911.
[3] WEI Zhibin,MOLDOWAN J M,PETER K E,et al.The abundance and distribution of diamondoids in biodegraded oils from the San Joaquin Valley:implications for biodegradation of diamondoids in petroleum reservoirs[J].Organic Geochemistry,2007,38(11):1910-1926.
[4] CHEN Junhong,FU Jiamo,SHENG Guoying,et al.Diamondoid hydrocarbon ratios:novel maturity indices for highly mature crude oils[J].Organic Geochemistry,1996,25(3/4):179-190.
[5] 张坤,唐友军,胡森清,等.平湖斜坡带原油中金刚烷的检出及其地球化学意义[J].石油天然气学报(江汉石油学院学报),2014,36(10):30-34.ZHANG Kun,TANG Youjun,HU Senqing,et al.Detection of diamantine hydrocarbons in the oil of Pinghu Slope Belt and its geochemical significance[J].Journal of Oil and Gas Technology (Journal of Jianghan Petroleum Institute),2014,36(10):30-34.
[6] PYTLAK ?,KOWALSKI A,GROSS D,et al.Composition of diamondoids in oil samples from the Alpine Foreland Basin,Austria:potential as indices of source rock facies,maturity and biodegradation[J].Journal of Petroleum Geology,2017,40(2):153-171.
[7] SCHULZ L K,WILHELMS A,REIN E,et al.Application of diamondoids to distinguish source rock facies[J].Organic Geochemistry,2001,32(3):365-375.
[8] 任康绪,黄光辉,肖中尧,等.大宛齐原油金刚烷类化合物及其在油气运移中的应用[J].中国石油勘探,2012,17(2):27-31.REN Kangxu,HUANG Guanghui,XIAO Zhongyao,et al.Application of diamondoids to hydrocarbon migration in Dawanqi Oilfield,Tarim Basin[J].Petroleum Geology,2012,17(2):27-31.
[9] DAHL J E,MOLDOWAN J M,PETERS K E,et al.Diamondoid hydrocarbons as indicators of natural oil cracking[J].Nature,1999,399(6731):54-57.
[10] WEI Zhibin,MOLDOWAN J M,ZHANG Shuichang,et al.Diamondoid hydrocarbons as a molecular proxy for thermal maturity and oil cracking:geochemical models from hydrous pyrolysis[J].Organic Geochemistry,2007,38(2):227-249.
[11] 马安来,金之钧,朱翠山,等.塔河油田原油中金刚烷化合物绝对定量分析[J].石油学报,2009,30(2):214-218.MA Anlai,JIN Zhijun,ZHU Cuishan,et al.Quantitative analysis on absolute concentration of diamondoids in oils from Tahe Oilfield[J].Acta Petrolei Sinica,2009,30(2):214-218.
[12] MAO D,VAN DE WEGHE H,LOOKMAN R,et al.Resolving the unresolved complex mixture in motor oils using high-performance liquid chromatography followed by comprehensive two-dimensional gas chromatography[J].Fuel,2009,88(2):312-318.
[13] REDDY C M,NELSON R K,SYLVA S P,et al.Identification and quantification of alkene-based drilling fluids in crude oils by comprehensive two-dimensional gas chromatography with flame ionization detection[J].Journal of Chromatography A,2007,1148(1):100-107.
[14] WANG Huitong,ZHANG Shuichang,WENG Na,et al.Analysis of condensate oil by comprehensive two-dimensional gas chromatography[J].Petroleum Exploration and Development,2012,39(1):132-138.
[15] 王汇彤,翁娜,张水昌,等.全二维气相色谱/飞行时间质谱对饱和烃分析的图谱识别及特征[J].质谱学报,2010,31(1):18-27.WANG Huitong,WENG Na,ZHANG Shuichang,et al.Characteristics and identification of saturated hydrocarbons by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry[J].Journal of Chinese Mass Spectrometry Society,2010,31(1):18-27.
[16] WANG Huitong,ZHANG Shuichang,WENG Na,et al.A new analytical method for quantifying of sterane and hopane biomarkers[J].Science China Earth Sciences,2014,57(8):1713-1722.
[17] WANG Guangli,SHI Shengbao,WANG Peirong,et al.Analysis of diamondoids in crude oils using comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry[J].Fuel,2013,107:706-714.
[18] 国家能源局.SY/T 5119-2016,岩石中可溶有机物及原油族组分分析[S].北京:石油工业出版社,2016.National Energy Administration.SY/T 5119-2016,Analytical method of soluble organic matters in rocks and crude oil group composition column chromatography[S].Beijing:Petroleum Industry Press,2016.
[19] 王汇彤,魏彩云,宋孚庆,等.细硅胶层析柱对饱和烃和芳烃的分离[J].石油实验地质,2009,31(3):312-314.WANG Huitong,WEI Caiyun,SONG Fuqing,et al.Separation of saturated and aromatic hydrocarbon using fine silica gel[J].Petroleum Geology & Experiment,2009,31(3):312-314.
[20] GRICE K,ALEXANDER R,KAGI R I.Diamondoid hydrocarbon ratios as indicators of biodegradation in Australian crude oils[J].Organic Geochemistry,2000,31(1):67-73.