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Mechanism of catalytic hydropyrolysis of sedimentary organic matter with MoS_2

petroleum Science 2011年第2期8卷 134-142页

作者： He Kun Zhang Shuichang Mi Jingkui Chen Jianping Cheng Lei petroleum Geology research and Central Laboratory Research Institute of Petroleum Exploration and Development （RIPED） PetroChina Beijing 100083 China CNPC Key Laboratories for petroleum Geochemistry Beijing 100083 China

MoS2 was used as an efficient catalyst for hydropyrolysis （Hypy） of three samples of sedimentary organic matter with different maturities. Through comparison with Soxhlet extraction （SE）, it was found that MoS2 catalytic Hypy can remarkably promote the yields of total chloroform extracts, saturates, aromatics, hopanes and steranes. In addition, the difference of biomarker parameters indicated that isomerization of covalently-bound biomarkers is much more difficult than their free counterparts. Meanwhile, the high conversion of total organic carbon （TOC） in MoS2 catalytic Hypy of organic matter proved that the presence of dispersed molybdenum sulfide accelerated the breaking of C-C bonds and the release of hydrocarbons. To address the catalytic mechanism, a series of control experiments based on free Hypy and catalytic Hypy were conducted. The results showed that the calculated atomic ratio of carbon conversion/hydrogen conversion for catalytic Hypy was much larger than the presumed value of 1/2, indicating that intensive hydrogenation took place and significantly influenced the distribution of liquid products. Analysis of stable hydrogen isotope data, infrared spectra and m/z 83 ion chromatograph of the saturate fraction further confirmed this hypothesis. The difference of S content changing （AS） between catalyst-free Hypy and catalytic Hypy, and the thermal characteristics of the catalyst, indicated that active H2S was definitely generated and it probably initiated free radical reactions in the early stage of hydropyrolysis of organic matter.

关键词： Catalytic hydropyrolysis molybdenum disulfide kerogen coal Soxhlet extraction,biomarkers

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Physical simulation of fluid flow and production performance in extra-low permeability porous media

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petroleum Science 2009年第4期6卷 415-420页

作者： You Yuan Yue Xiang’an Li Mingyi Zhao Chunpeng Zhang Tao Key Laboratory of petroleum Engineering Ministry of EducationChina University of PetroleumBeijing 102249China Enhanced Oil Recovery research Center China University of PetroleumBeijing 102249China Jilin Oil Field PetroChinaSongyuanJilin 138000China exploration&Production research institute SinopecBeijing 100083China exploration Department Changqing Oil FieldPetroChinaXi’anShaanxi 710018China

For extra-low permeability reservoirs, with a permeability of about 0.3×10?3 μm2, fluid flow and production performance in cores were studied. A long core holder with a multi-location piezometric measurement was specially designed. An artificial long core, about 700 mm long and with a cross section of 45mm×45mm, was used. In the experiment, pressure distribution along the core can be measured in real time. Single phase flow in the core was investigated. Different modes of production in long cores were also simulated including natural depletion, water flooding, and advanced water flooding. Through physical simulation, flow parameters were collected and production characteristics in extra-low permeability cores were studied. From experimental results, it can be seen that fluid flow in extra-low permeability cores is different from that in high permeability cores. Transmission of pressure in extra-low permeability cores is very slow, and it needs a long time for the pressure to become stable. The distribution curve of pressure along the core is nonlinear and the production rate in extra-low permeability reservoirs decreases sharply. The development effects of different production modes in extra-low permeability cores were compared with one another. Among the production modes, advanced water flooding has much potential for effective development of extra-low permeability reservoirs. Natural depletion and conventional water flooding can also be used in early production periods. In addition, the countermeasures and some ideas especially for the potential development of extra-low permeability reservoirs are suggested.

关键词： Extra-low permeability reservoirs physical simulation fluid flow production performance

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含蜡原油石蜡沉积模拟方法研究

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石油学报 2003年第2期24卷 105-108页

作者：刘敏中国石油勘探开发研究院北京100083

对从苏丹Unity油田现场取得有代表性的原油样品进行了原油组分分析和析蜡点测试。并针对油田的生产状况 ,利用与美国德士古石油公司合作建立的自动化高压石蜡沉积循环管道模拟系统 ,采用冷却实验步骤测试了苏丹原油从高于原油析蜡点温... 详细信息

对从苏丹Unity油田现场取得有代表性的原油样品进行了原油组分分析和析蜡点测试。并针对油田的生产状况 ,利用与美国德士古石油公司合作建立的自动化高压石蜡沉积循环管道模拟系统 ,采用冷却实验步骤测试了苏丹原油从高于原油析蜡点温度到较低环境温度范围内在现场流速、油温和环境温度下的石蜡沉积速率 ,定量研究了流速和油温对石蜡沉积速率的影响 ,并采用分子扩散和剪切效应的总效应来描述石蜡沉积机理。利用临界蜡张力作为模拟放大因子 ,采用半经验的石蜡沉积数学模型 ,预测了Unity油田 2 1井的生产井筒在现场生产条件下的石蜡沉积情况 ,模拟了不同产量和不同时间的蜡沉积剖面。结果表明 ,该油井在目前高产条件下 ,未发生石蜡沉积问题 ;在低产时 ,须考虑清蜡和防蜡措施。

关键词：石蜡沉积临界蜡张力模拟研究生产工况井筒石蜡沉积机理含蜡原油

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Formation　of　the　Central－Asia　Coal－Formed　Gas　Accumulation　Domain　and　its 　Source　Rocks──Series　Study　Ⅰ　on　the　Central－Asia　Coal－formed　Gas　Accumulation　Domain

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石油勘探与开发 1995年第3期 117-124页

作者： Dai Jin-xing He Bin Sun Yong-xiang Li Peng-ju Li Xian-qi(research institute of petroleum exploration and development, CNPC, beijing, 100083)

ＦｏｒｍａｔｉｏｎｏｆｔｈｅＣｅｎｔｒａｌ－ＡｓｉａＣｏａｌ－ＦｏｒｍｅｄＧａｓＡｃｃｕｍｕｌａｔｉｏｎＤｏｍａｉｎａｎｄｉｔ８ＳｏｕｒｃｅＲｏｃｋｓ──ＳｅｒｉｅｓＳｔｕｄｙⅠｏｎｔｈｅＣｅｎｔｒａｌ－ＡｓｉａＣｏ... 详细信息

ＦｏｒｍａｔｉｏｎｏｆｔｈｅＣｅｎｔｒａｌ－ＡｓｉａＣｏａｌ－ＦｏｒｍｅｄＧａｓＡｃｃｕｍｕｌａｔｉｏｎＤｏｍａｉｎａｎｄｉｔ８ＳｏｕｒｃｅＲｏｃｋｓ──ＳｅｒｉｅｓＳｔｕｄｙⅠｏｎｔｈｅＣｅｎｔｒａｌ－ＡｓｉａＣｏａｌ－ｆｏｒｍｅｄＧａｓＡｃｃｕｍ...

关键词： Central-Asia Gas accumulation domain Coal-measure Gas source rocks

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Total alkyl dibenzothiophenes content tracing the filling pathway of condensate reservoir in the Fushan Depression,South china Sea

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Science china Earth Sciences 2008年第S2期51卷 138-145页

作者： LI MeiJun1,WANG TieGuan1,LIU Ju2,ZHANG MeiZhu2,LU Hong3,MA QinLin2 & GAO LiHui2 1 State Key Laboratory of petroleum Resources and Prospecting,Earth Sciences and Geoinformatics School,china University of petroleum,beijing 102249,china 2 Southern Oil exploration and development Company,petrochina,Guangzhou 510640,china 3 Guangzhou institute of Geochemistry,Chinese Academy of Sciences,Guangzhou 510240,china State Key Laboratory of petroleum Resources and Prospecting Earth Sciences and Geoinformatics School China University of Petroleum Beijing China Southern Oil exploration and development Company PetroChina Guangzhou China Guangzhou institute of Geochemistry Chinese Academy of Sciences Guangzhou China

The condensates are generally characterized by high maturity,low concentration of steranes and ter-panes biomarkers and low content of non-hydrocarbon fraction. In this case commonly used steranes,terpanes and carbazoles parameters cannot be effectively applied in the reservoir-filling tracing. The hydrogen bond formed by sulfur atom in the dibenzothiophenes (DBTs) results in molecule adsorption and fractionation during oil migration in reservoir. Like carbazoles,total DBTs content decreases with the increasing of oil migration distance. Therefore,a new parameter——total DBTs content is proposed to be used to trace the oil migration orientation and filling pathway. In present study,total DBTs con-tents of condensates and light oils are obtained by adding internal standard——eight deuterium atoms substituted DBT during Gas Chromatography-Mass Spectrometry analysis of aromatic fraction. Except for a few samples with much lower content of non-hydrocarbon fraction,the total DBTs content shows a fine positive correlation with that of carbazoles. Large errors can be caused in the process of pyrrolic nitrogen compounds separation. The application of this new parameter in the Fushan Depression of Beibu Gulf Basin,South china Sea indicates that this parameter is a reliable one to trace filling pathway in condensate reservoirs. Combined with other DBTs-related parameters,such as 4-/1-methydibenzo-thiophene and 2,4-/1,4-dimethyldibenzothiophene,oil migration orientation and filling pathway of the Fushan Depression was determined. The accumulations of Huachang oil field in the Fushan Depres-sion are mainly migrated and charged from northeast to southeast along the Huachang uplift. It can be predicated that the light oil and condensates in the Huachang oil field should be sourced from the source kitchen at the Bailian Sag. It shows that total DBTs content is an effective parameter to tracing oil migration orientation and filling pathway.

关键词： dibenzothiophene alkyl dibenzothiophene condensate reservoir filling pathway molecular markers the Fushan Depression

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A NEW METHOD FOR PREDICTION OF PRODUCTIVITY OF FRACTURED HORIZONTAL WELLS BASED ON NON-STEADY FLOW

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Journal of Hydrodynamics 2007年第4期19卷 494-500页

作者： LEI Zheng-dong CHENG Shi-qing LI Xiang-fang XIAO Hua-ping research institute of petroleum exploration and development Beijing 100083 China CMOE Key Laboratory of petroleum Engineering China University of Petroleum Beijing 102249China beijing Huayou Natural Gas Co. Itd Beijing 100100 China

Hydraulic fracturing technologies of horizontal well are important ways to develop oil-gas field with low permeability. Productivity forecast of fractured horizontal wells is a difficult problem of hydraulic fracturing technologies. Basing on non-steady flow of fractures fluid during production, applying potential function principles, superposition principle and mathematical method for solving, coupling of seepage flow in the formation and pipe flow in the well bore, a new model on multi-fracture interference productivity forecast of fractured horizofltal well is established in this article. The results indicate the coincidence rate between this model and practice is high. The pressure loss in the horizontal well bore has definite influence on the production status of fractured horizontal wells. The productions of different fractures in horizontal well bore are unequal, the productions of outer fractures are higher than middle fractures; the pressure in the well bore shows an uneven distribution, the pressure declines gradually from finger tip to heel end. Asymmetry of fractures may make productivity of fractured horizontal wells decline. The conclusions are instructive in designing fractured horizontal well for low permeability reservoir.

关键词： horizontal well fracturing productivity couple non-steady flow

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Effects of Light Olefins Formation during Catalytic Pyrolysis of n-Heptane

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china petroleum Processing & Petrochemical Technology 2011年第4期13卷 8-14页

作者： Cheng Xiaojie Xie Chaogang Wei Xiaoli (SINOPEC research institute of petroleum Processing, beijing 100083) SINOPEC research institute of petroleum Processing Beijing 100083 China

The influence of zeolite structure and process parameters (including reaction temperature and catalyst/oil ratio) on rules for formation of ethylene and propylene in the course of catalytic pyrolysis of n-heptane was studied in a small- scale fixed fluid catalytic cracking unit. Test results have revealed that compared to the USY zeolite and Beta zeolite, the catalytic pyrolysis of n-heptane in the presence of the ZRP zeolite catalyst can result in higher yield and selectivity of ethyl- ene and propylene, while a higher reaction temperature and a higher catalyst/oil ratio can promote the formation of ethylene and propylene during catalytic pyrolysis of n-heptane. The ethylene formation reaction is more sensitive to the changes in reaction temperature, whereas the changes in catalyst/oil ratio are more influential to the propylene formation reaction. This paper has made a preliminary exploration into the different reaction pathways for formation of ethylene and propylene on zeolites with different structures.

关键词： n-heptane catalytic pyrolysis light olefins reaction pathway

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烃源岩压实渗流排油模型

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石油学报 2004年第5期25卷 34-37页

作者：石广仁张庆春中国石油勘探开发研究院北京100083

提出了烃源岩油水两相系统相对渗透率计算公式 ,与逐次沉积压实排液的原理相结合 ,建立了新的排油模型 (简称压实渗流模型 )。该模型与原有纯压实模型相比 ,主要优点是 :①取消了纯压实模型中基于排液前的油水之比与排液量中的油水之比... 详细信息

提出了烃源岩油水两相系统相对渗透率计算公式 ,与逐次沉积压实排液的原理相结合 ,建立了新的排油模型 (简称压实渗流模型 )。该模型与原有纯压实模型相比 ,主要优点是 :①取消了纯压实模型中基于排液前的油水之比与排液量中的油水之比相等的粗略假设 ,使排液量中的油水之比由油水两相的相对渗透率和粘度来确定 ,从本质上改善了地质模型的合理性 ;②克服了纯压实模型因前期排油过早、过大及后期偏小的缺点 ,大大提高了排油史的模拟精度 ,从而确保随后对油运、聚史的模拟真实性。两种模型在库车坳陷进行了对比应用。

关键词：盆地模拟油水系统烃源岩相对渗透率排油模型压实渗流模型库车坳陷

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Hydrogen isotopic compositions, distributions and source signals of individual n-alkanes for some typical crude oils in Lunnan Oilfield, Tarim Basin, NW china

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Science china Earth Sciences 2005年第8期48卷 1220-1226页

作者： LU Hong1, LI Chao1, SUN Yongge1, PENG Ping’an1 & XIAO Zhongyao2 1. State Key Laboratory of Organic Geochemistry, Guangzhou institute of Geochemistry, Chinese Academy of Sciences, Guangzhou510640, china 2. Tarim research institute of exploration and development of petroleum, china petroleum, Korla 841000, china State Key Laboratory of Organic Geochemistry Guangzhou Institute of Geochemistry Chinese Academy of Sciences Guangzhou China Tarim research institute of exploration and development of petroleum China Petroleum Korla China

Isotopic compositions of carbon-bound hydrogen in individual n-alkanes from sev-eral typical crude oil samples from Lunnan Oilfield, Tarim Basin, NW china, were firstly measured using newly developed gas chromatography-thermal conversion-isotope ratio mass spectrometry. The similar range of δ D of individual n-alkanes of crude oils among reservoirs of different geo-logical times reflects that hydrocarbons are all derived from the same marine depositional envi-ronment. Compared to the theoretic value (?150‰) and the reported δ D values (nC13―nC27, ?160‰―?90‰) of individual n-alkanes for Ordovician-sourced crude oils in the Canadian Wil-liston Basin, the hydrogen isotopic composition of individual n-alkanes in crude oils from Lunnan Oilfield is characterized by heavy hydrogen isotopic values (nC12―nC27, ?120‰―?60‰). In terms of the factors that control the fractionation of hydrogen isotopes, relatively saline deposi-tional environment and higher thermal maturation were attributed to the heavy δ D values of in-dividual n-alkanes in crude oils from Lunnan Oilfield.

关键词： hydrogen isotopes, individual n-alkanes, distribution, hydrocarbon source, Lunnan Oilfield.

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考虑断层发育史并适用于欠压实的地史模型

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石油学报 2002年第1期23卷 24-26页

作者：石广仁中国石油勘探开发研究院北京100083

在盆地模拟系统中 ,地史模型的功能是重建油气盆地的沉积史和构造史。其模拟方法分为正演和反演两种类型。正演是指从古到今恢复地史 ,如超压技术 ,适用于欠压实带 ;反演是指由今溯古恢复地史 ,如回剥技术 ,适用于正常压实带。回剥技术... 详细信息

在盆地模拟系统中 ,地史模型的功能是重建油气盆地的沉积史和构造史。其模拟方法分为正演和反演两种类型。正演是指从古到今恢复地史 ,如超压技术 ,适用于欠压实带 ;反演是指由今溯古恢复地史 ,如回剥技术 ,适用于正常压实带。回剥技术的优点是精度高 ,缺点是因未考虑超压而不适用于欠压实带。相反 ,超压技术的优点是适用于欠压实带 ,缺点是精度低。作者首先提出的回剥与超压相结合的技术 ,既考虑超压又确保精度 ,其主要思路是 :从已知的盆地现状出发 ,先采用回剥技术 ,由今溯古重建各地层的地史 ;然后对各地层进行超压计算 ,从古到今修正回剥技术所得的地史。为确保重建精度 ,地史模型应考虑尽可能多的地质现象 ,如沉积间断、沉积压实、欠压实 (超压 )、单层剥蚀、多层连续剥蚀、断层及古水深等 ,其中断层发育史的模拟最难实现。

关键词：油气盆地盆地模拟地史模型断层发育史超压史回剥超压

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