张琨,张居和,张璐,陈莹
ZHANG Kun,ZHANG Juhe,ZHANG Lu,CHEN Ying

• 1:大庆油田有限责任公司勘探开发研究院
• 2:大庆油田有限责任公司采气分公司

摘要(Abstract)：

原油中烃类气相色谱分析的传统方法是先对原油进行族分离得到饱和烃和芳烃,然后分别进行气相色谱分析,因此不能反映原油的原始特性和烃类组分的全貌。全二维气相色谱分析方法能直接对原油样品进行分析,同时获得饱和烃和芳烃的地球化学参数,避免原油样品经族分离带来的分析误差,缩短分析时间。通过一维、二维色谱柱及升温速率、柱流量、初始柱温等条件实验,优选出原油中烃类全二维气相色谱分析的最佳实验条件;应用原油的全二维气相色谱/飞行时间质谱分析结果,建立了饱和烃、芳烃、萘系列、菲系列及二苯并噻吩化合物的相对位置定性图版,再利用图版对原油中组分进行定性分析;采用面积归一化法进行定量分析,并计算出了石油天然气行业标准所规定的饱和烃与芳烃地球化学参数;精确度实验结果表明,质量分数大于1%的样品多次重复分析的相对偏差小于5%,符合原油实验测定要求。
The traditional method of analyzing the gas chromatogram for the hydrocarbon in the crude oil is to separate the group of the crude oil and obtain the saturated and aromatic hydrocarbons,and then analyze the gas chromatogram respectively,therefore the close-up of the original characteristics and hydrocarbon components of the crude oil cannot be presented.On the contrary,the analyzing method of GC×GC can not only conduct the sample analyses of the crude oil,but in the meantime collect the geochemical parameters of the saturated and aromatic hydrocarbons,so the analysis errors resulted from the group separation of the oil samples can be avoided,and furthermore the analysis time can be shortened.With the help of the experiments under the conditions of 1D & 2D chromatographic columns,heating rate,column flux and initial column temperature,the optimal experiment conditions of the GC×GC analyses for the crude oil are chosen;by means of the analyzed results of of the GC×GC/TOFMS,the chart boards of the relative locations of the saturated & aromatic hydrocarbons,naphthalene & phenanthrene serieses and dibenzothiophene compounds are built,and then the qualitative analyses of the oil components are engaged by the above boards;the quantitative analysis is conducted by area normalization method,and moreover the geochemical parameters of the saturated and aromatic hydrocarbons are computed according to the standards of oil and gas industry;the result of the precision experiment shows that the relative error of the multiple analysis for the samples with more than 1%mass fraction is less than 5%,thus the test requirements of the crude oil experiment have been met.

关键词(KeyWords)： 原油;烃类;全二维气相色谱;分析方法;实验条件;定性;定量
crude oil;hydrocarbon;GCxGC;analyzing method;experimental condition;qualitative;quantitative

Abstract:

Keywords:

基金项目(Foundation): 中国石油天然气股份公司重大科技专项“大庆探区非常规油气勘探开发关键技术研究与现场试验”(2012E2603)

作者(Author): 张琨,张居和,张璐,陈莹
ZHANG Kun,ZHANG Juhe,ZHANG Lu,CHEN Ying

参考文献(References)：

• [1]冯子辉.大庆油田石油地质实验技术新进展[J].大庆石油地质与开发,2004,23(5):23-25.
• [2]王玉华,冯子辉,方伟,等.大庆油田有机地球化学实验技术进展及应用[J].大庆石油地质与开发,2007,26(3):1-6.
• [3]陈世明,张凤荣,罗琳,等.海塔盆地饱和烃气相色谱资料解释标准的建立及应用[J].大庆石油地质与开发,2010,29(6):55-58.
• [4]冯志强,张晓东,任延广,等.海拉尔盆地油气成藏特征及分布规律[J].大庆石油地质与开发,2004,23(5):16-19.
• [5]吴志峰,李景坤,黄春艳,等.原油中甾萜类化合物的精馏富集分析[J].大庆石油地质与开发,2007,26(3):35-38.
• [6]肖廷荣,李力,张居和,等.SY/T5779—2008石油和沉积有机质烃类气相色谱分析方法[S].中华人民共和国石油天然气行业标准.北京:石油工业出版社,2009:1-9.
• [7]阮春海,叶芬,孔宏伟,等.石油样品全二维气相色谱分析的分离特性[J].分析化学,2002,30(5):548-551.
• [8]花瑞香,阮春海,王京华,等.全二维气相色谱用于不同石油馏分的族组成分布研究[J].化学学报,2002,60(12):2185-2191.
• [9]李艳艳.全二维气相色谱用于轻质石油馏分中芳烃含量的测定[J].色谱,2006,24(4):380-384.
• [10]Beens J,Blomberg J,Schoenmkaers P J.Proper tuning of Comprehensive two-dimensional gas chromatogrpahy(GC×GC)to optimize the separation of complex oil fractions[J].High Resol.Chromatogr,2000,23(3):182-188.
• [11]Ruan Chunhai,Xu Guowang,Lu Xin,et al.Quality evaluation of volatile oils of traditional Chinese medicines by using comprehensive two-dimensional gas chromatography(GC×GC)[J].Chromatographia,2003,57(S2):65-270.
• [12]路鑫,武建芳,吴建华,等.全二维气相色谱/飞行时间质谱用于柴油组成的研究[J].色谱,2004,22(1):5-11.
• [13]蒋启贵,王强,马媛媛,等.全二维气相色谱/飞行时间质谱在石油地质样品分析中的应用[J].石油实验地质,2009,31(6):627-632.
• [14]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.
• [15]王汇彤,翁娜,张水昌,等.全二维气相色谱/飞行时间质谱对原油芳烃分析的图谱识别[J].科学通报,2010,55(21):2124-2130.