核磁共振芳碳率作为成熟度指标的有效性讨论
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摘要
石油地质学中,寻找油窗范围内较为有效的成熟度指标一直是油气地球化学家致力研究的科学问题之一。随着固体核磁共振技术在干酪根地球化学上的应用及发展,芳碳率被认为是具有潜力的有效成熟度指标。为对该问题进行深入探讨,对茂名盆地油柑窝组油页岩干酪根进行了高温高压黄金管热解实验,对生烃后的干酪根残渣进行了~(13)C DP/MAS核磁共振定量分析,并与美国绿河油页岩干酪根芳碳率的热演化特征进行对比;还调研了Ⅱ型及Ⅲ型干酪根芳碳率的热演化特征。结果显示,干酪根芳碳率均随成熟度的增加而增大,但不同类型干酪根的芳碳率的增长模式不同。未成熟阶段,芳碳率可以用来区分干酪根类型;生烃高峰之前,芳碳率随热成熟度增加而显著增加,可以用来指示成熟度,但与Ro关系要因类型而异;生烃高峰之后,不同干酪根的芳碳率演化趋于一致,若用来指示成熟度对NMR测试精度要求较高。若要得到精确的成熟度数据,最好建立研究区相关类型干酪根的芳碳率热演化曲线。
In petroleum geology, the determination of an effective maturity index for the oil window is a scientific issue that geochemists have committed to solve. As solid-state nuclear magnetic resonance techniques were developed and applied to kerogen studies, aromaticity was generally accepted as the most useful maturity proxy among the NMR structural parameters. In this investigation, artificial maturation of Maoming oil shale kerogen was performed in a closed gold tube system. The insoluble kerogen residue was analyzed using quantitative ~(13)C DP/MAS NMR spectroscopy. The relationship between aromaticity and Easy%Ro for thermally matured Maoming oil shale kerogen was established, and compared with Green river oil shale kerogen. The thermal matured characteristics of kerogen types II and III were also cited from the reported references. No matter which type of kerogen was used, aromaticity increased with maturity, but the actual relationship differed. Aromaticity can be used to classify kerogen types during the immature stage. Before the oil window peak, the kerogen aromaticity could be used to indicate the kerogen maturity since there was an obvious increase in the aromaticity, along with the maturation for each of the kerogen types. However, aromaticity measurement errors could result in the wrong indication of the maturity. Therefore, it would be better to establish the evolution curve between aromaticity and maturity for the kerogen in the investigated region.
In petroleum geology, the determination of an effective maturity index for the oil window is a scientific issue that geochemists have committed to solve. As solid-state nuclear magnetic resonance techniques were developed and applied to kerogen studies, aromaticity was generally accepted as the most useful maturity proxy among the NMR structural parameters. In this investigation, artificial maturation of Maoming oil shale kerogen was performed in a closed gold tube system. The insoluble kerogen residue was analyzed using quantitative ~(13)C DP/MAS NMR spectroscopy. The relationship between aromaticity and Easy%Ro for thermally matured Maoming oil shale kerogen was established, and compared with Green river oil shale kerogen. The thermal matured characteristics of kerogen types II and III were also cited from the reported references. No matter which type of kerogen was used, aromaticity increased with maturity, but the actual relationship differed. Aromaticity can be used to classify kerogen types during the immature stage. Before the oil window peak, the kerogen aromaticity could be used to indicate the kerogen maturity since there was an obvious increase in the aromaticity, along with the maturation for each of the kerogen types. However, aromaticity measurement errors could result in the wrong indication of the maturity. Therefore, it would be better to establish the evolution curve between aromaticity and maturity for the kerogen in the investigated region.
引文
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[4]Price L C,Barker C E.Suppression of vitrinite reflectance in amorphous rich kerogen-A major unrecognized problem[J].J Pet Geol,1985,8(1):59-84.
[5]Hao F,Chen J Y.The cause and mechanism of vitrinite reflectance anomalies[J].J Pet Geol,1992,15(3):419-434.
[6]Carr A D.Suppression and retardation of vitrinite reflectance,Part 1.Formation and significance for hydrocarbon generation[J].J Pet Geol,2000,23(3):313-343.
[7]Carr A D.Suppression and retardation of vitrinite reflectance,Part 2.Derivation and testing of a kinetic model for suppression[J].J Pet Geol,2000,23(4):475-496.
[8]张振苓,邬立言,舒念祖.烃源岩热解分析参数Tmax异常的原因[J].石油勘探与开发,2006,34(5):72-75.Zhang Zhen-ling,Wu Li-yan,Shu Nian-zu.Cause analysis of abnormal Tmax values on Rock-Eval pyrolysis[J].Pet Explor Develop,2006,34(5):72-75(in Chinese with English abstract).
[9]Dewing K,Sanei H.Analysis of large thermal maturity datasets:Examples from the Canadian Arctic Islands[J].Int JCoal Geol,2009,77(3):436-448.
[10]尚慧芸,姜乃煌.关于Tm/Ts指标的意义及应用[J].地球化学,1983,12(3):250-255.Shang Hui-yun,Jiang Nai-huang.The implication and application of Tm/Ts index[J].Geochimica,1983,12(3):250-255(in Chinese with English abstract).
[11]Peters K E,Walters C C,Moldowan J M.The Biomarker Guide,Biomarkers and Isotopes in Petroleum Exploration and Earth History[M].2nd ed.New York:Cambridge University Press,2005:608-640.
[12]王广利,王铁冠,张林晔,张学军.济阳坳陷古近系烃源岩分子成熟度参数的异常分布[J].地球化学,2006,35(5):560-566.Wang Guang-li,Wang Tie-guan,Zhang Lin-ye,Zhang Xue-jun.▌pp.102?110▌Jan.,2018Anomalies of molecular indicators in Jiyang Eogene source rocks[J].Geochimica,2006,35(5):560-566(in Chinese with English abstract).
[13]郭小文,何生,陈红汉.甲基双金刚烷成熟度指标讨论与应用[J].地质科技情报,2007,26(1):71-76.Guo Xiao-wen,He Sheng,Chen Hong-han.Discussion and application of the maturity indicators of methyl double diamantane hydrocarbons[J].Geol Sci Technol Inf,2007,26(1):71-76(in Chinese with English abstract).
[14]张学军,徐兴友,彭平安.车排子凸起轻质油成熟度分析与烃源层再认识[J].地球化学,2013,42(2):180-187.Zhang Xue-jun,Xu Xing-you,Peng Ping-an.Maturity assessment of light oils in Chepaizi Uplift and re-understanding of its source rock[J].Geochimica,2013,42(2):180-187(in Chinese with English abstract).
[15]Carr A D,Williamson J E.The relationship between aromaticity,vitrinite reflectance and maceral composition of coals:Implications for the use of vitrinite reflectance as a maturation parameter[J].Org Geochem,1990,16(1):313-323.
[16]Wei Z B,Gao X X,Zhang D J,Da J.Assessment of thermal evolution of kerogen geopolymers with their structural parameters measured by solid-state 13C NMR spectroscopy[J].Energ Fuel,2005,19(1):240-250.
[17]Bartuska V J,Maciel G E,Schaefer J,Stejskal E O.Prospects for carbon-13 nuclear magnetic resonance analysis of solid fossil-fuel materials[J].Fuel,1977,56(4):354-358.
[18]Wang Z Y,Fan P,Cheng K M.The thermal evolution indicator of carbonate rocks[J].Sci China B,1995:733-740.
[19]Werner-Zwanziger U,Lis G,Mastalerz M,Schimmelmann A.Thermal maturity of typeⅡkerogen from the New Albany Shale assessed by 13C CP/MAS NMR[J].Solid State Nucl Magn Reson,2005,38(6):140-148.
[20]Mao J D,Fang X W,Lan Y Q,Schimmelmann A,Mastalerz M,Xu L,Schmidt-Rohr K.Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13C NMR spectroscopy[J].Geochim Cosmochim Acta,2010,74(7):2110-2127.
[21]van Krevelen D W.Coal:Typology-Chemistry-Physics-Constitution[M].Amsterdam:Elsevier,1961:514p.
[22]Mao J D,Hu W G,Schmidt-Rohr K,Davies G,Ghabbour E A,Xing B.Quantitative characterization of humic substances by solid-state carbon-13 nuclear magnetic resonance[J].Soil Sci Soc Am J,2000,64(3):873-884.
[23]马骁轩,冉勇.茂名油页岩中干酪根的热模拟地球化学演变及表征[J].地球化学,2013,42(4):373-378.Ma Xiao-xuan,Ran Yong.Simulation and characterization of thermal evolution of kerogen in Maoming oil shale[J].Geochimica,2013,42(4):373-378(in Chinese with English abstract).
[24]Fletcher T H,Gillis R,Adams J,Hall T.Characterization of macromolecular structure elements from a Green River oil shale,II.Characterization of pyrolysis products by 13C NMR,GC/MS,and FTIR[J].Energ Fuel,2014,28(5):2959-2970.
[25]Gao Y,Zou Y R,Liang T,Peng P A.Jump in the structure of Type I kerogen revealed from pyrolysis and 13C DP MASNMR[J].Org Geochem,2017,doi:http://dx.doi.org/10.1016/j.orggeochem.2017.07.004.
[26]李殿超,朱建伟,严焕榕,郭敏,郑志文.广东省茂名盆地油页岩的沉积特征及分布规律[J].吉林大学学报(地球科学版),2006,36(6):938-943.Li Dian-chao,Zhu Jian-wei,Yan Huan-rong,Guo Min,Zheng Zhi-wen.Sedimentary characteristics and distribution rule of oil shale in Maoming basin in Guangdong Province[J].J Jilin Univ(Earth Sci),2006,36(6):938-943(in Chinese with English abstract).
[27]Behar F,Kressmann,S,Rudkiewicz J L,Vandenbroucke M.Experimental simulation in a confined system and kinetic modeling of kerogen and oil cracking[J].Org Geochem,1991,19(1/3):173-189.
[28]刘金钟,唐永春.用干酪根生烃动力学方法预测甲烷生成量之一例[J].科学通报,1998,43(11):1187-1191.Liu Jinzhong,Tang Yongchun.Kinetics of early methane generation from Green River shale[J].Chinese Sci Bull,1998,43(22):1908-1912.
[29]熊永强,耿安松,王云鹏,刘德汉,贾蓉芬,申家贵,肖贤明.干酪根二次生烃动力学模拟实验研究[J].中国科学(D辑),2001,31(4):315-320.Xiong Yongqiang,Geng Ansong,Wang Yunpeng,Liu Dehan,Jia Rongfen,Shen Jiagui,Xiao Xianming.Kinetic simulating experiment on the secondary hydrocarbon generation of kerogen[J].Sci China D,2002,45(1):13-20.
[30]杜军艳,程斌,廖泽文.三塘湖盆地二叠系干酪根热模拟气体产物的地球化学特征[J].地球化学,2014,43(5):510-517.Du Jun-yan,Cheng Bin,Liao Ze-wen.Geochemical characterization of gaseous pyrolysates from a Permian kerogen of Santanghu Basin[J].Geochimica,2014,43(5):510-517(in Chinese with English abstract).
[31]Sweeny J J,Burnham A K.Evaluation of a simple model of vitrinite reflectance based on chemical kinetics[J].AAPG Bull,1990,70(10):1559-1570.
[32]Solum M S,Mayne C L,Orendt A M,Pugmire R J.Characterization of macromolecular structure elements from a Green River oil shale,I.Extracts[J].Energ Fuel,2013,28(1):453-465.
[33]傅家谟,徐芬芳,陈德玉,刘德汉,胡成一,贾蓉芬,徐世平,Brassell A S,Eglinton G.茂名油页岩中生物输入的标志化合物[J].地球化学,1985,14(2):99-114.Fu Jia-mo,Xu Fen-fang,Chen De-yu,Liu De-han,Hu Cheng-yi,Jia Rong-fen,Xu Shi-ping,Brassell A S,Eglinton G.Biomarker compounds of biological inputs in Maoming oil shale[J].Geochimica,1985,14(2):99-114(in Chinese with English abstract).
[34]Dennis L W,Maciel G E,Hatcher P G,Simoneit B R T.13Cnuclear magnetic resonance studies of kerogen from Cretaceous black shales thermally altered by basaltic intrusions and laboratory simulations[J].Geochim Cosmochim Acta,1982,46(6):901-907.
[35]Witte E G,Schenk H J,Müller P J,Schwochau K.Structural modifications of kerogen during natural evolution as derived from 13C CP/MAS NMR,IR spectroscopy and Rock-Eval pyrolysis of Toarcianshales[J].Org Geochem,1988,13(4/6):1039-1044.
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