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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 H2. 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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Carbon and hydrogen isotopic characteristics of natural gases from the Luliang and Baoshan basins in Yunnan Province, china

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Science china Earth Sciences 2006年第9期49卷 938-946页

作者： XU Yongchang1, LIU Wenhui2. SHEN Ping1, WANG Wanchun1, WANG Xiaofeng1, Tenger1, YAN Yaomin3 & LIU Ruobin3 1. Lanzhou Center of Oil & Gas Resources, institute of Geology and Geophsics, Chinese Academy of Sciences, Lanzhou 730000, china 2. Research institute of petroleum Exploration and Production, SINOPEC, Beijing 100083, china 3. South branch of petroleum Exploration and Production Company, SINOPEC, Kuming 650000, china 1. Lanzhou Center of Oil & Gas Resources Institute of Geology and Geophsics Chinese Academy of Sciences Lanzhou 730000 China 2. Research institute of petroleum Exploration and Production SINOPEC Beijing 100083 China 3. South branch of petroleum Exploration and Production Company SINOPEC Kuming 650000 China

The Luliang and Baoshan basins of Yunnan Province are two small-sizedcontinental oil/gas-bearing sedimentary basins, which were developed at the bases of theCarboniferous and Devonian systems during the Late Tertiary, covering an area of 32. km^2.and 2.4km^2. respectively. Since the 1990s, there have been discovered small-sized natural gas pools inthese two basins. The natural gases are composed mainly of hydrocarbon gases, with nonhydrocarbonsaccounting for less than 2.. Of the hydrocarbon gases, methane accounts for more than 99%, and thecomponents above C_2.account for less than 0.2.. On the basis of previous studies of geologicalbackground, the composition of natural gases and their carbon isotopic composition, it has beendefined that these two gas pools are of bacterial origin. In this work we have comprehensivelymeasured the carbon and hydrogen isotopic composition of natural gases from these two basins andhave gone into the details of the mechanism of gas generation. The δ^(13)C_1 values of naturalgases from the Luliang Basin are within the range of -72.1 per thousand - -73.3 per thousand, andthe δD_(CH_4) values, -2.2.per thousand - -2.4 per thousand, indicating that the bacterial gasgeneration is dominated by the way of CO_2.reduction. It has been evidenced that undercontinental-facies fresh water conditions there did occur the CO_2.reduction as a process ofbacterial gas generation. The δ^(13)C_1 values of natural gases from the Baoshan Basin are withinthe range of - 62.5 per thousand - -63.5 per thousand, and the δD_(CH_4) values, -2.2.per thousand- -2.0 per thousand. These isotopic characteristics are fallen into transitional phase of acetatefermentation and CO_2.reduction as defined by Whiticar et al. (1986). An important discovery in theLuliang Basin is the carbon isotopic composition of ethane of purely biogenetic origin, i.e., itsδ^(13)C_2.values are within the range of - 61.2.per thousand - - 66.0 per thousand. These carbonisotopic values have been r

关键词： bacterial gas, carbon and hydrogen isotope, CO2 reduction, acetate fermentation.

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Application of backflush and micro-flow techniques to the analysis of C5—C13 hydrocarbons in crude oils and its geochemical significance

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Progress in Natural Science:Materials International 2007年第11期17卷 1382-1387页

作者： Wang Peirong1,2. Zhao Hong2.3, Xu Guanjun1,4, Zhu Cuishan2.3, Xiao Tingrong4, Zhang Min2.3 and Zhang Bin1,4(1. Key Laboratory of petroleum Geochemistry, china National petroleum Corporation, Beijing 100083, china 2. Geochemistry Department of Yangtze University, Jingzhou 43402., china 3. Key Laboratory of Exploration Technologies for Oil and Gas Resources, Ministry of Education, Yangtze University, Jingzhou 43402., china 4. petroleum Geology Central Laboratory, Research institute of petroleum Exploration and development, petrochina, Beijing 100083, china) Key Laboratory of petroleum Geochemistry China National Petroleum Corporation Beijing 100083 China Geochemistry Department of Yangtze University Jingzhou 434023 China Key Laboratory of Exploration Technologies for Oil and Gas Resources Ministry of Education Yangtze University Jingzhou 434023 China petroleum Geology Central Laboratory Research Institute of Petroleum Exploration and Development PetroChina Beijing 100083 China

An Agilent 6890N GC equipped with both FID and Agilent 5975 MSD analyzer has been employed to analyze C5—C13 hydrocarbon fractions of crude oils. A technical combination of program temperature volatilizer injection, backflush and micro-flow controller afforded a fine separation of C5—C13 compounds on a PONA column with the heavy part of crude oils being cut off before entering the analytical column. Both GC-FID chromatogram and GC-MS mass chromatograms (MID and full scan) could be obtained at the same time. The retension time differences of nC6—nC13 alkanes between GC and TIC were in the range of 0.02.0.58 minutes. Totally 2.6 peaks have been assigned group compositions. Results on 8 typical oil samples from CNPC Key Laboratory Crude Oil Library showed that the characteristics of C6—C13 hydrocarbon group composition could be used in oil-oil correlation studies.

关键词： GC analysis GC/MS analysis backflush micro-flow controller light fraction in crude oil

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Wave tectono-sedimentary processes in Tarim basin

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Science china Earth Sciences 2005年第11期48卷 1949-1959页

作者： JIN Zhijun1,2. ZHANG Yiwei1 & CHEN Shuping1 1. Key Laboratory for Hydrocarbon Accumulation, Ministry of Education, china University of petroleum, Beijing 102.49, china 2. Exploration and Production Research institute, china petroleum & Chemical Corporation, Beijing 100083, china 1. Key Laboratory for Hydrocarbon Accumulation Ministry of Education China University of Petroleum 102249 Beijing China 2. Exploration and Production Research institute China Petroleum & Chemical Corporation 100083 Beijing China

Based on the unconformities, the formation times of structures, and geological wave filtering applied to basin fills of typical wells around the Manjiaer area in the Tarim basin, the wave tectono-sedimentary processes in the Tarim Basin are discussed. The results of geological wave filtering of basin fills of typical wells show that, in time domain, the evolution of the Tarim basin was controlled by various wave processes with the periods of 740±Ma, 2.0±Ma, 100±Ma and 30±Ma. The analyses of basin fills, basin subsidence and unconformities show that the trends of the sedimentary facies belts, depocenters, and centers of subsidence migrated and interchanged periodically with periods of 2.0±Ma. These show the propagation of wave movements in space domain. The wave evolution of the Tarim basin is of significance to understanding the formation of the oil and gas reservoirs in the basin.

关键词： Tarim basin, tectonics, sedimentation, crustal undation, wave evolution

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Hydrocarbon test in lower-layer atmosphere to predict deep-sea petroleum or hydrate in the Okinawa Trough: an example

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Acta Oceanologica Sinica 2003年第4期22卷 569-576页

作者： Gong Jianming1, Chen Jianwen 1, 2. Li Gang1, Zhang Xunhua1, Li Jipeng3, Huang Fulin1 1. Qingdao institute of Marine Geology, Qingdao 2.6071, china. 2. Ocean University of china, Qingdao 2.6003, china 3. Hefei institute of petroleum Chemical Exploration, china petroleum Exploration and development Research institute, Hefei 2.002.,china Qingdao Inst Marine Geol Qingdao 266071 Peoples R China Ocean Univ china Qingdao 266003 Peoples R China china Petr Explorat & Dev Res Inst Hefei Inst Petr Chem Explorat Hefei 230022 Peoples R China

Light hydrocarbon (methane, ethane, propane, butane and CO2. test and C isotopic analysis of CO are conducted for over 100 lower-layer atmospheric samples from the East china Sea slope and the Okinawa Trough. The results show that the lower-layer atmosphere mainly consists of CO2.and then of CH4, and the CO2.concentrations are calculated to have a high average value of 0.87 omega/10(-2. about three times that of the regional background (0-3 omega/10(-2.). The result also shows that the average value of C isotope - 2..8 x 10(-3) is given to the CO2. inferring that it is inorganic gas. Thus, for the future 's work in the Okinawa Trough, special attention should be paid to CO2.hydrate, which is very possibly an important hydrate type.

关键词： lower-layer atmosphere hydrocarbon test C isotopic analysis deep-sea petroleum gas hydrate

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二氧化碳泡沫压裂技术在低渗透低压气藏中的应用

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石油学报 2004年第3期25卷 66-70页

作者：王振铎王晓泉卢拥军中国石油勘探开发研究院廊坊分院河北廊坊065007

针对低渗透、低压气藏压裂改造中压裂液返排困难的问题 ,研究了CO2.泡沫压裂技术 ,分析了CO2.泡沫压裂过程中井筒和储层温度场变化对CO2.液气转化的影响 ,对提高CO2.泡沫压裂液的流变性、内相恒定与工艺措施等进行了室内研究。现场试验... 详细信息

针对低渗透、低压气藏压裂改造中压裂液返排困难的问题 ,研究了CO2.泡沫压裂技术 ,分析了CO2.泡沫压裂过程中井筒和储层温度场变化对CO2.液气转化的影响 ,对提高CO2.泡沫压裂液的流变性、内相恒定与工艺措施等进行了室内研究。现场试验表明 ,CO2.泡沫压裂技术能减少进入地层的水基压裂液量 ,提供地层液体返排的能量 ,达到了压裂液自喷、快速、多排的目的 ,从而降低了压裂液对储层的二次伤害 ,提高了低渗透。

关键词：二氧化碳泡沫压裂技术低压低渗透气藏储层伤害现场试验

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低渗透油藏基于支撑剂指数的压裂优化设计方法研究

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石油钻采工艺 2008年第3期30卷 87-89页

作者：蒋廷学胥云中国石油勘探开发研究院廊坊分院河北廊坊065007

以最大采油指数为目标函数,应用支撑剂指数的概念,研究了压裂优化设计的新方法。其主要的研究结论是,对低渗、特低渗透油藏而言,在强调长缝的同时,还必须强调相对高的无量纲裂缝导流能力,才能获得最大的压后产量。该方法不仅适用于探井... 详细信息

以最大采油指数为目标函数,应用支撑剂指数的概念,研究了压裂优化设计的新方法。其主要的研究结论是,对低渗、特低渗透油藏而言,在强调长缝的同时,还必须强调相对高的无量纲裂缝导流能力,才能获得最大的压后产量。该方法不仅适用于探井压裂改造,也适用于开发井的压裂增产改造;不仅适用于固定支撑剂量条件下的压裂优化设计,也适用于不同支撑剂量条件下的压裂方案优选。而且,现场应用简便,优化结果科学、合理。该新方法的应用及推广,对今后低渗透、特低渗透油藏的压裂改造具有一定的指导意义。

关键词：特低渗透油藏支撑剂指数压裂优化设计

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Primary migration and secondary alteration of the Upper Paleozoic gas reservoir in Ordos Basin,china―Application of fluid inclusion gases

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Science china Earth Sciences 2008年第S1期51卷 165-173页

作者： GONG Se 1,2.,PENG PingAn 1 ,SHUAI YanHua 3 ,DAI JinXing 3 &ZHANG WenZheng 4 1 Guangzhou institute of Geochemistry,the Chinese Academy of Sciences,Guangzhou 510640,china 2.Common Wealth Scientific and Research Organization,{2. Resources,PO Box 136,North Ryde,New South Wales,1670,Australia 3 Research institute of {2. Exploration and development,petrochina,Beijing 100083,china 4 Research institute of Exploration and development,Changqing {2. Corporation,Xi’an 71002.,china Guangzhou institute of Geochemistry the Chinese Academy of Sciences Guangzhou 510640 China Common Wealth Scientific and Research Organization Petroleum Resources PO Box 136 North Ryde New South Wales 1670 Australia Research institute

The composition of fluid inclusions(FI)often represents the initial geochemical characteristics of palaeo-fluid in reservoir *** on composition and carbon isotopic composition of gas during primary migration,reservoir-forming and subsequent secondary alterations are discussed through comparing fluid inclusion gas with coal-formed gas and natural gas in present gas reservoirs in the Ordos *** results show that primary migration of gas has significant effect on the molecular but not on the carbon isotopic composition of *** and diffusion fractionation took place during the secondary migration of gas in Upper Paleozoic gas reservoir according to carbon isotopic composition of methane in *** and carbon isotopic composition of natural gas were nearly unchanged after the gas reservoir forming through comparing the FI gases with the natural gas in present gas reservoir.

关键词： secondary alteration fluid inclusion carbon isotope Ordos Basin

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Cracking conditions of crude oil under different geological environments

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Science china Earth Sciences 2008年第S1期51卷 77-83页

作者： ZHAO WenZhi,WANG ZhaoYun,ZHANG ShuiChang&WANG HongJun Research institute of petroleum Exploration&{2.,petrochina,Beijing 100083,china petrochina Res Inst Petr Explorat & Dev Beijing 100083 Peoples R China

There are mainly 3 kinds of existing states of oil generating from source rocks,that is,dispersive liquid hydrocarbon inside of source rock,dispersive liquid hydrocarbon outside of source rock and concentrated liquid hydrocarbon outside of source *** of the differences in thermal history and medium conditions around,and the interaction of organic and inorganic matter,the liquid hydrocarbon with 3 kinds of existing state has different cracking *** gas generation dynamics experiments of crude oil matching different mediums indicate that the distribution of activation energy of methane changes a lot according to medium *** carbonate has a main influence on oil cracking conditions and can largely reduce its activation energy,which reflects the lower cracking temperature of crude *** mudstone takes a second place and the sandstone is the *** catalytic cracking function to the oil of the carbonate,of the mudstone and of the sandstone changes weaken in *** corresponding Ro values of main gas generation period in different mediums are as follows:1.5%―3.8%with pure crude oil,1.2.―3.2.with dispersive crude oil in carbonate,1.3%~3.4% with dispersive crude oil in mudstone and 1.4%―3.6%with dispersive crude oil in *** influence of pressure to crude oil cracking is relatively *** the low heating speed condition, pressure restrains the oil cracking and gas generation,but in the high heating speed condition,pressure has an indistinctive influence to the oil cracking and gas *** also makes a different effort in different evolvement *** the middle and lower Cambrian source rocks in the Tarim Basin as an example,primary oil generating quantity is 2.32.2.×10 8 t,residual oil and oil cracking gas quantity is 806.2.×10 8 t and 106.95×10 12.m 3 respectively.

关键词： different existing state oil cracking condition gas source rock kitchen of oil cracking type

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Prediction of petroleum exploration risk and subterranean spatial distribution of hydrocarbon accumulations

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petroleum Science 2011年第1期8卷 17-23页

作者： Xie Hongbing Guo Qiulin Li Feng Li Jianzhong Wu Na Hu Suyun Liang Kun School of Energy Resources China University of GeosciencesBeijing 100083China Research institute of petroleum Exploration ＆ {2. PetroChinaBeijing 100083China Science ＆ Technology Management Department China National Petroleum CorporationBeijing 100007China

Investigation of spatial distribution of oil and gas resource and accurate prediction of the geographic location of its undiscovered resource is significant for reducing exploration risk and improving exploration benefit.A new method for predicting spatial distribution of oil resource is discussed in this *** consists of prediction of risk probability in petroleum exploration and simulation of hydrocarbon abundance. Exploration risk probability is predicted by multivariate statistics,fuzzy mathematics and information processing techniques.A spatial attribute database for sample wells was set up and the Mahalanobis distance and Fuzzy value of given samples were ***,the Bayesian formula was used to calculate the hydrocarbon-bearing probability at the area of exploration ***,a hydrocarbon probability template is formed and used to forecast the probability of the unknown area. The hydrocarbon abundance is simulated based on Fourier integrals,frequency spectrum synthesis and fractal ***,the fast Fourier transformation（FFT） is used to transform the known hydrocarbon abundance from the spatial domain to the frequency domain,then,frequency spectrum synthesis is used to produce the fractal frequency spectrum,and FFT is applied to get the phase information of hydrocarbon-bearing ***,the frequency spectrum simulation is used to calculate the renewed hydrocarbon abundance in the play. This method is used to predict the abundance and possible locations of the undiscovered petroleum accumulations in the Nanpu Sag of the Bohai Bay Basin,*** prediction results for the well-explored onshore area of the northern Nanpu Sag agree well with the actual *** the less-explored offshore areas in the southern Nanpu Sag,the prediction results suggest high hydrocarbon abundance in Nanpu-1 and Nanpu-2.providing a useful guiding for future exploration.

关键词： Hydrocarbon resources abundance risk forecast Nanpu sag frequency spectrum simulation fractal theory

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