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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, {3. 100083, china 2. Geochemistry Department of Yangtze University, Jingzhou 43.023. china 3. Key Laboratory of exploration Technologies for Oil and Gas Resources, Ministry of Education, Yangtze University, Jingzhou 43.023. china 4. petroleum Geology Central Laboratory, research Institute of petroleum exploration and {13., Petrochina, {3. 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 286 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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Natural gas origins of large and medium-scale gas fields in china sedimentary basins

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Science china Earth Sciences 2008年第S1期51卷 1-13页

作者： ZHANG ShuiChang &ZHU GuangYou research Center of research Institutes of Petrochina {3. and development,beijing 100083.china research Center of research Institutes of Petrochina {3. and development Beijing 100083 China

china sedimentary basins present abundant natural gas resource thanks to its unique geological *** highly-matured hydrocarbon source rocks,widespread coal-measure strata and low temperature Quaternary saline strata,etc.,indicate the wide foreground of china natural gas resources. Up to now,most of the petroliferous basins have been discovered to have wholesale natural gas accumulation from Precambrian,Paleozoic,Mesozoic to Cenozoic in the east,the central,the west and the coast of *** large and medium-scale gas reservoirs are mainly composed of hydrocarbon gas with big dry coefficient,tiny non-hydrocarbon,wide carbon isotope distribution and varying origin types,the hydrocarbon gas includes coal-formed gas,oil-formed gas,biogenic gas and inorganic gas, ***-formed gas is the main type of china natural gas resources,in particular several explored large-scale gas fields(>100 billion cubic meter)of Kela 2,Sulige and Daniudi,etc.,they all belong to coal-formed gas fields or the gas fields consisting mostly of coal-formed ***-formed gas is also abundant in china marine basins,for example marine natural gas of Sichuan Basin generated from crude oil cracking *** and secondary biogenic gas fields were discovered respectively in the Qaidam Basin and Western Slope of Songliao *** addition,inorganic gases are mainly distributed in the eastern china,in particular the Songliao Basin with abundant carbon dioxide accumulation,indicating that the eastern china present large exploration potential of inorganic gas.

关键词： natural gas origin sedimentary basin large and medium-scale gas field

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Mn content of reservoir calcite cement: A novel inorganic geotracer of secondary petroleum migration in the tectonically complex Junggar Basin (NW china)

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Science china Earth Sciences 2007年第12期50卷 1796-1809页

作者： CAO Jian1,HU WenXuan1,YAO SuPing1,ZHANG YiJie2,WANG XuLong3.ZHANG YueQian3.TANG Yong3.& SHI XinPu3.1 State Key Laboratory for Mineral Deposit research,Department of Earth Sciences,Nanjing University,Nanjing 210093.china 2 research Institute of {3. and development,Petrochina,beijing 100083.china 3.research Institute of {3. and development,Petrochina Xinjiang Oilfield Company,Karamay 83.000,china 1. State Key Laboratory for Mineral Deposit research Department of Earth Sciences Nanjing University Nanjing 210093 China 2. research Institute of exploration and development PetroChina Beijing 100083 China 3. research Institute of exploration and development PetroChina Xinjiang Oilfield Company Karamay 834000 China

Electronic probe microanalysis(EPMA) results of reservoir calcite cement from fourteen core samples in the Junggar Basin show that Mn-content varies largely between different samples from below the detect limitation to 4.14%,while it displays a generally good correlation with oil-gas ***,therefore,likely indicates that concentration of the Mn-content of the calcite cement has a close rela-tion to the intensity of petroleum fluid charging during hydrocarbon secondary *** order to assess this hypothesis,oxygen and strontium isotopic measurements on sixteen calcite veins host in source sequences were carried out to investigate the feature of the oil-source petroleum *** results imply that during hydrocarbon generation and migration,deep hot fluid has dissolved volcanic minerals interlined between mudstone source *** Mn is a kind of typical trace element enriched in volcanic rocks,it is reasonable to conclude that the petroleum fluid formed in the source sequences would be ***,calcite cements precipitated from such Mn-rich petroleum fluid would be Mn-rich *** to the geologic chromatographic effect during migration along reservoir rocks,the decreasing of the Mn-content of the reservoir calcite cements indicates the migration ***,this novel geotracer was further successfully applied in the study of hydrocarbon migration in the Junggar Basin in combination with organic geochemical analyses during the hydrocarbon *** Mn content of the reservoir calcite cement appears promising as a novel inorganic geotracer for the petroleum *** paper represents a search for novel indicators of secondary petroleum migration in tectonically complex basins based on fundamentals of the reservoir fluid-rock interactions.

关键词： petroleum migration, inorganic geochemistry, water-rock interaction, reservoir calcite cement, the Junggar Basin

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Formation mechanism of carbonate cemented zones adjacent to the top overpressured surface in the central Junggar Basin,NW china

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Science china Earth Sciences 2010年第4期53卷 529-540页

作者： YANG Zhi1,2,ZOU CaiNeng1,3.HE Sheng2,LI QiYan1,HE ZhiLiang3.WU HengZhi5,CAO Feng1,MENG XianLong4,WANG FuRong2 & XIAO Qilin21 State Key Laboratory of EOR,research Institute of petroleum exploration & {3.,Petrochina,beijing 100083.china 2 Key Laboratory of Tectonics and petroleum Resources of Ministry of Education,china University of Geosciences,Wuhan 43.074,china 3.State Key Laboratory of EOR,research Institute of petroleum exploration & {3.,Petrochina,beijing 100083.china 4 research Institute of petroleum exploration and Production,SINOPEC,beijing 100083.china 5 Southwest Branch Company,SINOPEC,Chengdu 610051,china 1. State Key Laboratory of EOR Research Institute of Petroleum Exploration & Development PetroChina Beijing 100083 China2. Key Laboratory of Tectonics and Petroleum Resources of Ministry of Education China University of Geosciences Wuhan 430074 China3. State Key Laboratory of EOR Research Institute of Petroleum Exploration & Development Petrochina Beijing 100083 China5. Southwest Branch Company SINOPEC Chengdu 610051 China4. Research Institute of Petroleum Exploration and Production SINOPEC Beijing 100083 China

Carbonate cemented zones are normally adjacent to the top overpressured surface in the central Junggar Basin,NW *** carbon and oxygen isotopic compositions and petrological investigations of carbonate cements in the carbonate cemented zones indicate that:(1) carbonate cements are composed dominantly of ferrocalcite,ferroan dolomite,and ankerite;(2) carbonate cements are formed under a high temperature circumstance in the subsurface,and organic fluid migration has an important effect on the formation of them;and(3. carbon and oxygen ions in the carbonate cements migrate from the underlying overpressured *** suggests that the occurrence of carbonate cemented zones in this region results from multiple phases of organic fluid expulsion out of the overpressure compartment through geological *** study provides a plausible mechanism of the formation of carbonate cemented zones adjacent to the top overpressured surface in the clastic sedimentary basins,and has an important implication for understanding the internal correlation between the formation of carbonate cemented zones adjacent to top overpressured surface and geofluids expulsion out of overpressured system.

关键词： carbonate cemented zones formation mechanism stable carbon and oxygen isotopic top overpressured surface central Junggar Basin coal-bearing strata

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Geochemical characteristics and origin of gases from the Upper,Lower Paleozoic and the Mesozoic reservoirs in the Ordos Basin,china

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Science china Earth Sciences 2008年第S1期51卷 183-194页

作者： HU AnPing 1 ,Li Jian 2 ,ZHANG WenZheng 3.,LI ZhiSheng 2 ,HOU Lu 4 &LIU QuanYou 5 1 Department of Earth Sciences,Zhejiang University,Hangzhou 3.0027,china 2 Langfang Branch,Reasearch Institute of petroleum exploration and {3.,Petrochina,Langfang 065007,china 3.Institute of exploration and {3.,Petrochina Changqing Oilfield Company,Xi’an 710021,china 4 University of petroleum,beijing102249,china 5 Petrochina research Institute of petroleum exploration and {3.,beijing 100083.china 1. Department of Earth Sciences Zhejiang University Hangzhou 310027 China2. Langfang Branch Reasearch Institute of Petroleum Exploration and Development PetroChina Langfang 065007 China3. Institute of Exploration and Development PetroChina Changqing Oilfield Company Xi’an 710021 China4. University of Petroleum Beijing 102249 China5. PetroChina Research Institute of Petroleum Exploration and Development Beijing 100083 China

The Ordos Basin,the second largest sedimentary basin in china,contains the broad distribution of natural gas *** far,several giant gas fields have been discovered in the Upper and Lower Paleozoic in this basin,each having over 1000×10 8 m 3.of proven gas reserves,and several gas pools have also been discovered in the *** paper collected the data of natural gases and elucidated the geochemical characteristics of gases from different reservoirs,and then discussed their *** hydrocarbons preserved in the Upper Paleozoic,the elevatedδ13. values of methane,ethane and propane indicate that the gases would be mainly coal-formed gases;the singular reversal in the stable carbon isotopes of gaseous alkanes suggests the mixed gases from humic sources with different *** the Lower Paleozoic,theδ13. 1 values are mostly similar with those in the Upper Paleozoic,but theδ13. 2 andδ13. 3.values are slightly lighter,suggesting that the gases would be mixing of coal-type gases as a main member and oil-type *** are multiple reversals in carbon isotopes for gaseous alkanes,especially abnormal reversal for methane and ethane(i.e.δ13. 1 >δ13. 2 ),inferring that gases would be mixed between high-mature coal-formed gases and oil-type *** the Mesozoic,the δ13.values for gaseous alkanes are enriched in 12C,indicating that the gases are mainly derived from sapropelic sources;the carbon isotopic reversal for propane and butane in the Mesozoic is caused by microbial oxidation and mixing of gases from sapropelic sources with different *** contrast to the Upper Paleozoic gases,the Mesozoic gases are characterized by heavier carbon isotopes of iso-butane than normal butane,which may be caused by gases generated from different kerogen types. Finally,according toδ13. 1 -Ro relationship and extremely low total organic carbon contents,the Low Paleozoic gases would not be generated from the Ordovician source as a main gas source,bycontrast, the Upper Pale

关键词： Ordos Basin natural gas chemical composition carbon isotope genesis

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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 73.000, china 2. research Institute of petroleum {3. and Production, SINOPEC, beijing 100083, china 3. South Branch of petroleum {3. 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 3.5 km^2 and 254km^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, -242 per thousand - -23. 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, -252 per thousand- -260 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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Characteristics,genesis and accumulation history of natural gas in Hetianhe gasfield,Tarim Basin,china

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Science china Earth Sciences 2008年第S1期51卷 84-95页

作者： WANG ZhaoMing 1 ,WANG QingHua 1 ,ZHAO MengJun 2 ,LI Yong 1 &XU ZhiMing 3.1 Tarim Oilfield Company,Petrochina,Kuerle 841000,china 2 research Institute of {3. exploration&development,Petrochina,beijing 100083.china 3.Southwest {3. Institute,Nanchong 63.001,china Petrochina Res Inst Petr Explorat & Dev Beijing 100083 Peoples R China Petrochina Tarim Oilfield Co Kuerle 841000 Peoples R China SW Petr Inst Nanchong 637001 Peoples R China

Hetianhe gasfield in Bachu region of the Tarim Basin is mainly composed of three reservoir-caprock assembly,namely regional caprock of upper mudstone,middle mudstone and lower mudstone of the Carboniferous and reservoir of Bachu bioclastic limestone,glutenite and the Ordovician carbonate buried *** gas in Hetianhe gasfield sourced from the Cambrian source *** is thought that gases in Ma4 well block in the east of Hetianhe gasfield are mainly crude-oil cracked gases,while those in Ma3.and Ma8 well blocks in the west are the mixture gases of kerogen cracked gases and crude-oil cracked *** gas is rich in H2S and accumulated in multiply stages as the result of *** accumulation history is divided into three stages,namely accumulation and breakage in the late Caledonian-early Hercynian,migration and dissipation in the late Hercynian and accumulation in Himalayan. The main accumulation of reformed gas reservoir is in Himalayan.

关键词： gas characteristics gas genesis accumulation history Hetianhe gasfield Tarim 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&{3.,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 223..24×10 8 t,residual oil and oil cracking gas quantity is 806.21×10 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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Free Radicals in Organic Matter for Thermal History Reconstruction of Carbonate Succession

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Acta Geologica Sinica(English Edition) 2007年第4期81卷 605-613页

作者： QIU Nansheng LI Huili JIN Zhijun and ZHU Yinkang 1 State Key Laboratory of petroleum Resource and Prospecting,china University of petroleum,{3. 102249 2 Basin and Reservoir research Center,china University of petroleum,{3. 102249 3.Institute of petroleum exploration and development,SINOPEC,{3. 100083 State Key Laboratory of petroleum Resource and Prospecting China Universityof Petroleum Beijing 102249

Geothermometer is one of the most useful methods to reconstruct the thermal history of sedimentary basins. This paper introduces the application of free radicals concentration of organic matter as a thermal indicator in the thermal history reconstruction of carbonate succession, based on anhydrous thermal simulation results of type I and H1 kerogen. A series of free radicals data are obtained under thermal simulation of different heating temperatures and times, and quantitative modds between free radical concentration （Ng） of organic matter and time-temperature index （TTI） for types I and type H1 kerogen are also obtained. This *** relation was used to model the Ordovician thermal gradients of Well TZ12 in the Tarim Basin. The modeling result is corresponding to the results obtained by apatite fission track data and published data. This new method of thermal history reconstruction will be benefit to the hydrocarbon generation and accumulation study and resource assessment of carbonate succession.

关键词： carbonate succession geothermometer free radicals of organic matter apatite fission track thermal history

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High-Resolution Transgressive-Regressive Sequence Stratigraphy of Chang 8 Member of Yanchang Formation in Southwestern Ordos Basin,Northern china

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Journal of Earth Science 2010年第4期21卷 423-438页

作者：吕明胜陈开远薛良清衣丽萍朱红涛 research Institute of petroleum exploration & {3. PetroChina School of Energy Resources China University of Geosciences china National Oil and Gas exploration and development Corporation Faculty of Earth Resources China University of Geosciences

The reservoirs within the Chang 8 Member of Yanchang(延长) Formation in the southwestern Ordos basin are characterized by low *** is significant to build a high-resolution sequence stratigraphic framework for the exploration and development of these *** on an integrated investigation of well logs,seismic data,cores and outcrops,the Chang 8 Member is interpreted as a 3.d-order transgressive-regressive(T-R) sequence,which consists of six 4th-order T-R sequences,namely,K1,K2,K3.K4,K5 and K6,respectively,from base to *** 4th-order sequence comprises a transgressive systems tract overlain by a regressive systems *** K1 to transgressive systems tract of K4,it is characterized by the landward shifts of facies and overall retrogradational sequence stacking pattern due to accommodation increase more than sediment supply during the 3.d-order base-level *** distributary channels are mainly deposited in the transgressive systems tracts,and the interdistributary bays,sheet sands,and small-scale mouth bars are primarily developed in the regressive systems tracts in response to the 4th-order base-level *** the regressive systems tracts of K4 to K6,it is characterized by the basinward shifts of facies and overall progradational sequence stacking pattern because of accommodation increase less than sediment supply during a fall in 3.d-order base *** distributary channels are mainly accumulated in the transgressive systems tracts,and distributary channels and mouth bars are deposited in the regressive systems tracts as a result of the 4th-order base-level *** stratigraphic and sedimentological analyses indicate that sequences K1,K2,K5 and K6,as well as the basin edge of K3.and K4,remain potential for exploration and development due to their high reservoir quality in response to the low accommodation and more sediment supply.

关键词： transgressive-regressive sequence base level sediment supply sequence stratigraphic framework Ordos basin.

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