Application of Diamondoids in Geochemical Research of Deep Oil and Gas

doi:10.19657/j.geoscience.1000-8527.2020.04.16

Abstract

Abstract:

In recent years, oil and gas exploration in China has expanded to ultra-deep formations, and oil and gas maturity and reservoir preservation have become the focus of research. Because of their unique cage molecular structure, strong thermal stability and biodegradability, diamondoids have broad application potential in deep oil and gas exploration. In this paper, laboratory sample pretreatment and detection methods of diamondoids are described, and their genesis and geological evolution are summarized. New advancement in maturity, oil-cracking, biodegradation, thermochemical sulfate reduction (TSR), evaporative fractionation, and other identification methods with diamondoids are reviewed. Applications of diamondoids in the petroleum geochemistry are limited due to its unknown origin. It is proposed that comparative studies on the evolution process of diamondoids in different sedimentary environments, different types of source rocks and crude oils should be performed, in order to study the methyl-diamantane baseline of crude oils in different sedimentary basins. This can supplement and improve the applications of diamondoids, and can greatly enhance our understanding in deep hydrocarbon accumulation processes and guide deep hydrocarbon exploration.

Key words: diamondoids, maturity, oil-cracking, biodegradation, thermochemical sulfate reduction (TSR), evaporative fractionation

CLC Number:

TE122

YAN Jifa, MA Anlai, LI Xianqing, CONG Gangshi, HE Yukai, ZHANG Yachao. Application of Diamondoids in Geochemical Research of Deep Oil and Gas[J]. Geoscience, 2020, 34(04): 812-820.

Figures/Tables 8

References 52

[1]	冯佳睿, 高志勇, 崔京钢, 等. 深层、超深层碎屑岩储层勘探现状与研究进展[J]. 地球科学进展, 2016,31(7):718-736.
[2]	LANDA S, MACHACEK V. Adamantane, a new hydrocarbon extracted from petroleum[J]. Collection of Czechoslovak Chemical Communications, 1933,5(1):1-5.
[3]	米镇涛, 郭建维, 邱立勤. 笼状烃金刚烷的新合成方法[J]. 燃料化学学报, 1998,26(1):89-92.
[4]	WINGERT W S. GC-MS analysis of diamondoid hydrocarbons in Smackover petroleums[J]. Fuel, 1992,71(1):37-43.
[5]	WEI Z B, 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, 2006,37:891-911. DOI URL
[6]	WEI Z B, MOLDOWAN J M, JARVIE D M, et al. The fate of diamondoids in coals and sedimentary rocks[J]. Geology, 2006,34(12):1013-1016. DOI URL
[7]	WEI Z B, MOLDOWAN J M, ZHANG S C, et al. Diamondoid hydrocarbons as a molecular proxy for thermal maturity and oil cracking: geochemical models from hydrous pyrolysis[J]. Organic Geochemistry, 2007,38, 227-249. DOI URL
[8]	LI J G, PAUL P, CUI M Z. Methyl diamantane index ( MDI) as a maturity parameter for Lower Palaeozoic carbonate rocks at high maturity and overmaturity[J]. Organic Geochemistry, 2000,31(4):267-272. DOI URL
[9]	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. DOI URL
[10]	CHEN J H, FU J M, SHENG G Y, et al. Diamondoid hydrocarbon ratios: Novel maturity indices for highly mature crude oils[J]. Organic Geochemistry, 1996,25(3/4):179-190. DOI URL
[11]	SILVA R C, SILVA R S F, DE CASTRO E V R, et al. Extended diamondoid assessment in crude oil using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry[J]. Fuel, 2013,112:125-133. DOI URL
[12]	LI S F, HU S Z, CAO J, et al. Diamondoid characterization in condensate by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry: the Junggar basin of Northwest China[J]. International Journal of Molecular Sciences, 2012,13(9):11399-11410. DOI URL PMID
[13]	LIANG Q Y, XIONG Y Q, FANG C C, et al. Quantitative analysis of diamondoids in crude oils using gas chromatography-triple quadrupole mass spectrometry[J]. Organic Geochemistry, 2012,43:83-91. DOI URL
[14]	WANG G L, SHI S B, WANG P R, et al. Analysis of diamondoids in crude oils using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry[J]. Fuel, 2013,107:706-714. DOI URL
[15]	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.
[16]	张万峰, 童婷, 李东浩, 等. 原油中金刚烷化合物的高效分析方法[J]. 石油实验地质, 2015,37(6):796-808. DOI URL
[17]	陈军红, 傅家谟, 盛国英, 等. 金刚烷化合物在石油中的分布特征研究[J]. 自然科学进展, 1997,7(3):363-367.
[18]	FANG C C, XIONG Y Q, LIANG Q Y, et al. Variation in abundance and distribution of diamondoids during oil cracking[J]. Organic Geochemistry, 2012,43(1):1-8. DOI URL
[19]	FANG C C, XIONG Y Q, LI Y, et al. The origin and evolution of adamantanes and diamantanes in petroleum[J]. Geochimica et Cosmochimica Acta, 2013,120(11):109-120. DOI URL
[20]	梁前勇, 熊永强, 房忱琛, 等. 两种测定原油中金刚烷化合物方法的对比研究[J]. 地球化学, 2012,41(5):433-441.
[21]	DAHL J E, MOLDOWAN J M, PETERS K E, et al. Diamondoid hydrocarbons as indicators of natural oil cracking[J]. Nature, 1999,399(5):54-57. DOI URL
[22]	SPRINGER M V, GARCIA D F, GONCALVES F T T, et al. Diamondoid and biomarker characterization of oils from the Llanos Orientales Basin, Colombia[J]. Organic Geochemistry, 2010,41(9):1013-1018. DOI URL
[23]	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. DOI URL
[24]	李素梅, 庞雄奇, 杨海军, 等. 塔中I号坡折带高熟油气地球化学特征及其意义[J]. 石油与天然气地质, 2008,29(2):210-216. DOI URL
[25]	BERWICK L, ALEXANDER R, PIERCE K. Formation and reactions of alkyl adamantanes in sediments: carbon surface reactions[J]. Organic Geochemistry, 2011,42:752-761. DOI URL
[26]	GIRUTS M V, RUSINOVA G V, GORDADZE G N. Generation of adamantanes and diamantanes by thermal cracking of high-molecular-mass saturated fractions of crude oils of different genotypes[J]. Petroleum Chemistry, 2006,46(4):225-236. DOI URL
[27]	GIRUTS M V, GORDADZE G N. Generation of adamantanes and diamantanes by thermal cracking of polar components of crude oils of different genotypes[J]. Petroleum Chemistry, 2007,47(1):12-22. DOI URL
[28]	GORDADZE G N, GIRUTS M V. Synjournal of adamantane and diamantane hydrocarbons by high-temperature cracking of higher n-alkanes[J]. Petroleum Chemistry, 2008,48(6):414-419. DOI URL
[29]	FANG C C, XIONG Y Q, LI Y, et al. Generation and evolution of diamondoids in source rock[J]. Marine and Petroleum Geology, 2015,67:197-203. DOI URL
[30]	房忱琛, 吴伟, 刘丹, 等. 煤系中金刚烷化合物演化特征及应用[J]. 天然气地球科学, 2015,26(1):110-117. DOI URL
[31]	LI Y, CHEN Y, XIONG Y Q, et al. Origin of adamantanes and diamantanes in marine source rock[J]. Energy Fuels, 2015,29:8188-8194. DOI URL
[32]	JIANG W M, LI Y, XIONG Y Q. The effect of organic matter type on formation and evolution of diamondoids[J]. Marine and Petroleum Geology, 2018,89:714-720. DOI URL
[33]	陈军红, 傅家谟, 盛国英, 等. 金刚烷化合物的结构特征及其地球化学意义[J]. 科学通报, 1996,41(6):524-527.
[34]	郑伦举, 曹建平, 薛建华, 等. 原油及烃源岩成熟度的新指标—甲基双金刚烷指数[J]. 石油实验地质, 1998,20(4):411-416. DOI URL
[35]	ZHANG S C, HUANG H P, XIAO Z Y, et al. Geochemistry of Palaeozoic marine petroleum from the Tarim Basin, NW China. Part 2: Maturity assessment[J]. Organic Geochemistry, 2005,36:1215-1225. DOI URL
[36]	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.
[37]	LI Y, XIONG Y Q, LIANG Q Y, et al. The application of diamondoid indices in the Tarim oils[J]. AAPG Bulletin, 2018,102(2):267-291. DOI URL
[38]	张水昌, 赵文智, 王飞宇, 等. 塔里木盆地东部地区古生界原油裂解气成藏历史分析——以英南2气藏为例[J]. 天然气地球科学, 2004,15(5):441-451.
[39]	马安来, 金之钧, 朱翠山. 塔里木盆地塔河油田奥陶系原油成熟度及裂解程度研究[J]. 天然气地球科学, 2017,28(2):313-323.
[40]	WILLIAMS J A, BJORϕY M, DOLCATER D L, et al. Biodegradation in South Texas Eocene oils—Effects on aromatics and biomarkers[J]. Organic Geochemistry, 1986,10(3/4):451-461. DOI URL
[41]	WEI Z B, MOLDOWAN J M, PETERS 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. DOI URL
[42]	CHENG X, HOU D J, XU C G. The effect of biodegradation on adamantanes in reservoired crude oils from the Bohai Bay Basin, China[J]. Organic Geochemistry, 2018,123:38-43. DOI URL
[43]	HANIN S, ADAM P, KOWALEWSKI I, et al. Bridgehead alkylated 2-thiaadamantanes: novel markers for sulfurisation occurring under high thermal stress in deep petroleum reservoirs[J]. Chemical Communications, 2002,16:1750-1751.
[44]	姜乃煌, 朱光有, 张水昌, 等. 塔里木盆地塔中83井原油中检测出2-硫代金刚烷及其地质意义[J]. 科学通报, 2007,52(24):2871-2875.
[45]	WEI Z B, WALTERS C C, MOLDOWAN J M, et al. Thiadiamondoids as proxies for the extent of thermochemical sulfate reduction[J]. Organic Geochemistry, 2012,44:53-70. DOI URL
[46]	CAI C F, AMRANI A, WORDEN R H, et al. Sulfur isotopic compositions of individual organosulfur compounds and their genetic links in the Lower Paleozoic petroleum pools of the Tarim Basin, NW China[J]. Geochimica et Cosmochimica Acta, 2016,182:88-108. DOI URL
[47]	CAI C F, XIAO Q L, FANG C C, et al. The effect of thermochemical sulfate reduction on formation and isomerization of thiadiamondoids and diamondoids in the Lower Paleozoic petroleum pools of the Tarim Basin, NW China[J]. Organic Geochemistry, 2016,101:49-62. DOI URL
[48]	马安来, 金之钧, 朱翠山. 塔里木盆地顺南1井原油硫代金刚烷系列的检出及意义[J]. 石油学报, 2018,39(1):313-323.
[49]	MOLDOWAN J M, DAHL J, ZINNIKER D, et al. Underutilized advanced geochemical technologies for oil and gas exploration and production-1: The diamondoids[J]. Journal of Petroleum Science and Engineering, 2015,126:87-96. DOI URL
[50]	PETERSEN H I, CUMMING D, DUJONCQUOY E. Geochemical composition of oils in the Dunga Field, western Kazakhstan: Evidence for a lacustrine source and a complex filling history[J]. Organic Geochemistry, 2018,115:174-187. DOI URL
[51]	吴楠, 蔡忠贤. 轮南低凸起原油中金刚烷化合物的相分馏响应[J]. 断块油气田, 2012,19(4):458-461.
[52]	CHAKHMAKHCHEV A, SANDERSON J, PEARSON C, et al. Compositional changes of diamondoid distributions caused by simulated evaporative fractionation[J]. Organic Geochemistry, 2017,113:224-228. DOI URL

学者	时间	样品	主要认识
Fang等^[18]	2012	原油	金刚烷在Easy R_o=1.0%~2.1%时生成,Easy R_o>2.1%时开始分解
Fang等^[19]	2013	原油	单金刚烷在Easy R_o=1.0%~2.3%时生成,Easy R_o>2.3%时开始分解;双金刚烷在Easy R_o=1.6%~2.7%时生成,Easy R_o>2.7%时开始分解
Fang等^[29]	2015	海相页岩	金刚烷在Easy R_o=0.8%~1.7%时生成,Easy R_o>1.7%时开始分解直至Easy R_o=3.0%时基本完全消失
房忱琛等^[30]	2015	煤系泥岩	金刚烷在Easy R_o=1.0%~1.5%时生成,Easy R_o>1.5%时开始分解
Li等^[31]	2015	干酪根	单金刚烷在Easy R_o=0.8%~1.8%时生成,Easy R_o>1.8%时开始分解;双金刚烷在Easy R_o=1.0%~2.2%时生成,Easy R_o>2.2%时开始分解
Jiang等^[32]	2018	干酪根	金刚烷在Easy R_o=0.6%~2.1%时生成,Easy R_o>2.1%时开始分解

学者	时间	样品	主要认识
Fang等^[18]	2012	原油	金刚烷在Easy R_o=1.0%~2.1%时生成,Easy R_o>2.1%时开始分解
Fang等^[19]	2013	原油	单金刚烷在Easy R_o=1.0%~2.3%时生成,Easy R_o>2.3%时开始分解;双金刚烷在Easy R_o=1.6%~2.7%时生成,Easy R_o>2.7%时开始分解
Fang等^[29]	2015	海相页岩	金刚烷在Easy R_o=0.8%~1.7%时生成,Easy R_o>1.7%时开始分解直至Easy R_o=3.0%时基本完全消失
房忱琛等^[30]	2015	煤系泥岩	金刚烷在Easy R_o=1.0%~1.5%时生成,Easy R_o>1.5%时开始分解
Li等^[31]	2015	干酪根	单金刚烷在Easy R_o=0.8%~1.8%时生成,Easy R_o>1.8%时开始分解;双金刚烷在Easy R_o=1.0%~2.2%时生成,Easy R_o>2.2%时开始分解
Jiang等^[32]	2018	干酪根	金刚烷在Easy R_o=0.6%~2.1%时生成,Easy R_o>2.1%时开始分解

	缩写	公式	资料来源
同系物指标	MAI	1-MA/(1-MA+2-MA)	Chen等^[10];Zhang等^[35]
	MDI	4-MD/(4-MD+1-MD+3-MD)	Chen等^[10];Zhang等^[35]
	DMAI-1	1,3-DMA/(1,3-DMA+1,2-DMA)	Wei等^[7];
	DMAI-2	1,3-DMA/(1,3-DMA+1,4-DMA)	Wei等^[7];
	EAI	1-EA/(1-EA+2-EA)	Schulz等^[23]
	TMAI-1	1,3,5-TMA/(1,3,5-TMA+1,3,4-TMA)	Wei等^[7];Fang等^[18]
	TMAI-2	1,3,5-TMA/(1,3,5-TMA+1,3,6-TMA)	Wei等^[7];Fang等^[18]
	DMDI-1	4,9-DMD/(4,9-DMD+3,4-DMD)	Chen等^[10];Zhang等^[35]
	DMDI-2	4,9-DMD/(4,9-DMD+4,8-DMD)	Chen等^[10];Zhang等^[35]
产率指标	A/D	单金刚烷/双金刚烷	Fang等^[18,19]
	MA/MD	甲基单金刚烷/甲基双金刚烷
	DMA/DMD	双甲基单金刚烷/双甲基双金刚烷
	TMA/DMD	三甲基单金刚烷/三甲基双金刚烷
	As/Ds	总单金刚烷/总双金刚烷

	缩写	公式	资料来源
同系物指标	MAI	1-MA/(1-MA+2-MA)	Chen等^[10];Zhang等^[35]
	MDI	4-MD/(4-MD+1-MD+3-MD)	Chen等^[10];Zhang等^[35]
	DMAI-1	1,3-DMA/(1,3-DMA+1,2-DMA)	Wei等^[7];
	DMAI-2	1,3-DMA/(1,3-DMA+1,4-DMA)	Wei等^[7];
	EAI	1-EA/(1-EA+2-EA)	Schulz等^[23]
	TMAI-1	1,3,5-TMA/(1,3,5-TMA+1,3,4-TMA)	Wei等^[7];Fang等^[18]
	TMAI-2	1,3,5-TMA/(1,3,5-TMA+1,3,6-TMA)	Wei等^[7];Fang等^[18]
	DMDI-1	4,9-DMD/(4,9-DMD+3,4-DMD)	Chen等^[10];Zhang等^[35]
	DMDI-2	4,9-DMD/(4,9-DMD+4,8-DMD)	Chen等^[10];Zhang等^[35]
产率指标	A/D	单金刚烷/双金刚烷	Fang等^[18,19]
	MA/MD	甲基单金刚烷/甲基双金刚烷
	DMA/DMD	双甲基单金刚烷/双甲基双金刚烷
	TMA/DMD	三甲基单金刚烷/三甲基双金刚烷
	As/Ds	总单金刚烷/总双金刚烷