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gas formation mechanism of marine carbonate source rocks in China

Science China Earth Sciences 2005年第4期48卷 441-453页

作者： ZHAO Wenzhi1, WANG Zhaoyun1, HE Haiqing2, ZHANG Mingjie3, WANG Hongjun1, WANG Yunpeng4 & QIN Yong5 1. Research Institute of Petroleum Exploration & Development, PetroChina, Beijing 100083, China 2. PetroChina Exploration & Production, Beijing 100011, China 3. Department of Geology, Lanzhou University, Lanzhou 730000, China 4. Guangzhou Geochemical Institute, Chinese Academy of Sciences, Guangzhou 510640, China 5. China University of Mining and Technology, Xuzhou 221000, China Research Institute of Petroleum Exploration & Development PetroChinaBeijin China PetroChina Exploration & Production Beijing China Department of Geology Lanzhou University Lanzhou China Guangzhou Geochemical Institute Chinese Academy of Sciences Guangzhou China China University of Mining and Technology Xuzhou China

By breaking through the conventional ideology on the study of gas-formation mechanism of source rocks which focused on merely the characteristics of source rocks them- selves, and based on the development and distribution characteristics of marine carbonate source rocks in the medium-to-bottom parts of the Chinese superimposed sedimentary basins as well as various processes in the course of gas generation and reservoir forming, the complex hydrocarbon-generating model of carbonates is established. Such a model concerns not only the “three-stage” gas formation characteristics of carbonates, but also the gas generation process due to a thermal cracking of oil and the re-generation process of gas from heated secondary organic matters during the gas-generation and reservoir-forming course. The high-quality hy- drocarbon generating matter of marine carbonate source rocks determined a high gas-oil ratio and tended to form paleo-oil-reservoirs, representing an enrichment process of organic matters. The thermal cracking of oil in palaeo-oil-reservoirs is an important means for the effective forma- tion of gas reservoirs. The secondary organic matters in carbonate reservoirs may regenerate gas after a secondary deep burial, thus becoming an effective gas source.

关键词： carbonate, three-stage hydrocarbon generation, inhibitive effect of maturity, oil-cracking gas, second-ary asphalt gas.

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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 Lanzhou Center of Oil & gas Resources Institute of Geology and Geophsics Chinese Academy of Sciences Lanzhou China Research Institute of Petroleum Exploration and Production SINOPEC Beijing China South Branch of Petroleum Exploration and Production Company SINOPEC Kuming 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 325 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 - -234 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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Oil cracking: An important way for highly efficient gen- eration of gas from marine source rock kitchen

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Chinese Science Bulletin 2005年第22期50卷 2628-2635页

作者： ZHAO Wenzhi WANG Zhaoyun ZHANG Shuichang WANG Hongjun WANG Yunpeng Research Institute of Petroleum Exploration & Development Petro- China Beijing 100083 China Guangzhou Institute of Geochemistry Chinese Academy of Sciences Guangzhou 510640. China

The potentials of gas generation by kerogen in the late period and by crude oil cracking are closely related to the origin of natural gas in the high- to over mature ma- rine area and their exploration perspectives. The carbon structure of kerogens, with different types and at different evolution stages, have been experimentally studied using the high magnetic field solid 13C nuclear magnetic resonance technique in order to determine the oil and gas potential of kerogens. Results show that the contents of gas potential carbon(GPC) of types I, II, III kerogens at the high- to over mature stage are very low, indicating their weak gas-generating capacity and limited gas production; however, the content of oil potential carbon(OPC) of the low mature type I kerogen is much higher, implying that a large amount of crude oil generated during the oil-generating period will be the material for later gas generation by oil cracking. The kinetic experiment of gas generation by crude oil cracking shows that, when the temperature is about 160℃(Ro=1.6%), the crude oil will start to produce large amounts of gas; the temperature range for major gas generation of crude oil is higher than that of the kerogens, and the gas production is 2 to 4 times higher than that of kerogens. The natural gas de- rived from oil cracking (called oil-cracked gas) is much abundant in methyl hexamethylene, which is quite different from the natural gas produced by thermal degradation of kerogens (named kerogen degradation gas) at high- to over mature stage.

关键词：石油裂化反应油原退化磁场结构 GPC

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Experimental study on geochemical characteristic of methane hydrate formed in porous media

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Journal of natural gas Chemistry 2009年第2期18卷 217-221页

作者： Qiang Chen Changling Liu Yuguang Ye Qingdao Institute of Marine Geology the Ministry of Land and Resources Qingdao 266071 Shandong China The key Laboratory of Marine Hydrocarbon Resources and Environment Resources the Ministry of Land and Resources Qingdao 266071 Shangdong China

The natural occurrence of methane hydrates in marine sediments has been intensively studied over the past decades, and geochemical charac-teristic of hydrate is one of the most attractive research fields. In this paper, we discussed the geochemical anomaly during hydrate formation in porous media. By doing so, we also investigated the temperature influence on hydrate formation under isobaric condition. It turns out that sub-cooling is an important factor to dominate hydrate formation. Larger subcooling provides more powerful driving force for hydrate formation. During the geochemical anomaly research, six kinds of ions and the total dissolved salt （TDS） were measured before and after the experiment in different porous media. The result is that all kinds of ionic concentration increased after hydrate formation which can be defined as salting out effect mainly affected by gas consumption. But the variation ratio of different ions is not equal. Ca^2＋ seems to be the most significantly influenced one, and its variation ratio is up to 80%. Finally, we theoretically made a model to calculate the TDS variation, the result is in good accordance with measured one, especially when gas consumption is large.

关键词： hydrate formation porous media subcooling salting out effect geochemical anomaly

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Analysis of the flow of non-Newtonian viscoelastic fluids in fractal reservoir with the fractional derivative

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Science China(Physics,Mechanics & Astronomy) 2004年第4期47卷 424-441页

作者： TONG Dengke WANG Ruihe Department of Applied Mathematics Petroleum University Dongying 257061 China Department of Applied Mathematics Petroleum University Dongying 257061 China

In this paper, fractional order derivative, fractal dimension and spectral dimension are introduced into the seepage flow mechanics to establish the relaxation models of non-Newtonian viscoelastic fluids with the fractional derivative in fractal reservoirs. A new type integral transform is introduced, and the flow characteristics of non-Newtonian viscoelastic fluids with the fractional order derivative through a fractal reservoir are studied by using the integral transform, the discrete Laplace transform of sequential fractional derivatives and the generalized Mittag-Leffler functions. Exact solutions are obtained for arbitrary fractional order derivative. The long-time and short-time asymptotic solutions for an infinite formation are also obtained. The pressure transient behavior of non-Newtonian viscoelastic fluids flow through an infinite fractal reservoir is studied by using the Stehfest's inversion method of the numerical Laplace transform. It is shown that the clearer the viscoelastic characteristics of the fluid, the more the fluid is sensitive to the order of the fractional derivative. The new type integral transform provides a new analytical tool for studying the seepage mechanics of fluid in fractal porous media.

关键词： fractional calculus, non-Newtonian viscoelastic fluids, porous media, fractal, exact solution.

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Exact solutions for the flow of non-Newtonian fluid with fractional derivative in an annular pipe

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Science China(Physics,Mechanics & Astronomy) 2005年第4期48卷 485-495页

作者： TONG Dengke WANG Ruihe YANG Heshan Institute of Mathematics and Computional Science University of Petroleum Beijing 102249 China Institute of Mathematics and Computional Science University of Petroleum Beijing 102249 China Institute of Mathematics and Computional Science University of Petroleum Beijing 102249 China

This paper deals with some unsteady unidirectional transient flows of Oldroyd-B fluid in an annular pipe. The fractional calculus approach in the constitutive relationship model Oldroyd-B fluid is introduced and a generalized Jeffreys model with the fractional calculus has been built. Exact solutions of some unsteady flows of Oldroyd-B fluid in an annular pipe are obtained by using Hankel transform and Laplace transform for fractional calculus. The following four problems have been studied: (1) Poiseuille flow due to a constant pressure gradient; (2) axial Couette flow in an annulus; (3) axial Couette flow in an annulus due to a longitudinal constant shear; (4) Poiseuille flow due to a constant pressure gradient and a longitudinal constant shear. The well-known solutions for Navier-Stokes fluid, as well as those corresponding to a Maxwell fluid and a second grade one, appear as limited cases of our solutions.

关键词： fractional calculus, generalized Oldroyd-B fluid, exact solutions, velocity fields.

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Hydrocarbon Enrichment and Main Controlling Factors in Offshore Rift Basins of China:A Case Study in the Beibuwan Basin

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Acta Geologica Sinica(English Edition) 2021年第1期95卷 192-207页

作者： ZHANG Gongcheng WU Aijun LI Hongyi QU Hongjun LI Youchuan XIAO Lingli ZHANG Zhenyu SHEN Jiao Department of Geology Northwest UniversityXi'an 710069China CNOOC Research Institute Co. Ltd.Beijing 100028China

Beibuwan B asin is an important offshore oil and gas bearing basin of ***,the distribution of oil and gas in different sags is uneven,and the rule of hydrocarbon accumulation and main controlling factors have not been clearly understood in this *** on abundant seismic,well and analytical data,the differences and main controlling of tectonic evolution,sedimentary filling and source rock quality in sags are analyzed,and combined with the study of geothermal filed,the main controlling factors of differential hydrocarbon generation in sags of the Beibuwan Basin are *** the basis of the research above,the hydrocarbon enrichment of the basin is clarified through the systematic analysis of reservoir-caprock assemblage and accumulation characteristics of different structural *** results show that there are four NE-trending sag zones in the basin,and under the influence of fault activity,the scale of sags is regularly *** scale of rifts in different sag zones decreases gradually from northwest to southeast and the scale of rifts in the middle of a single sag zone is normally larger than that at two *** the control of the sag-controlling faults activity,paleoproductivity and organic matter preservation conditions,the quality of source rocks in sags of the Beibuwan Basin decreases from northwest to *** hydrocarbon-rich sags in the Beibuwan Basin were formed under the control of source rocks and geothermal field,and the distribution of large-medium scale fields is controlled by the favorable structural traps in the rift strata of inner gentle slope *** understanding of the hydrocarbon enrichment and main controlling factors in the Beibuwan Basin also provides a significant guidance for the oil and gas exploration in other rift basins.

关键词： source rocks sag-controlling fault activity paleoproductivity co-control of source and heat hydrocarbon enrichment Beibuwan Basin

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Characteristics of porosity and permeability layer of fossil Halimeda reef mineral rock of Miocene in the Xisha Islands and its genetic model

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Acta Oceanologica Sinica 2015年第4期34卷 74-83页

作者： XU Hong ZHU Yurui EBERLI G.P. LUO Wei ZHAO Xinwei CAI Ying LIU Xinyu YAN Guijing ZHANG Bolin WEI Kai CUI Ruyong Key Laboratory of Marine Hydrocarbon Resources and Environment Geology Qingdao Institute of Marine GeologyMinistry of Land and Resources Chengdu University of Technology Comparative Sedimentology Laboratory University of Miami Zhanjiang Branch of China national Offshore Oil Corporation (CNOOC) Limited China University of Geosciences

Halimeda is one of the major reef-building algas in the middle Miocene of Xisha, and one of the significant reef-building algas in the algal reef oil and gas field of the South China Sea. However, there have been few reports regarding the characteristics of mineral rocks, reservoir porosity and permeability layers, and sedimentation-diagenetic-evolution of fossil Halimeda systems. The present paper briefly introduces the relevant studies on chlorophyta Halimeda and the research status of oil and gas exploration. Through the 1 043 m core of the Xichen-1 well, we studied the characteristics of the mineral rocks and porosity and permeability of the middle Miocene Halimeda of the Yongle Atoll, identified and described the segments of fossil Halimeda, and pointed out that most of the segment slides are vertical sections in ovular, irregular or long strips. The overwhelming majority of these fossil Halimeda found and studied are vertical sections instead of cross sections. In this paper, knowledge regarding the cross sections of fossil Halimeda is reported and proven to be similar with the microscopic characteristics of modern living Halimeda;fossil Halimeda are buried in superposition;it is shown that there are different structures present, including typical bio-segment structure, and due to its feature of coexisting with red alga, tying structure, twining structure and encrusting structure are all present;and finally, it is suggested to classify the fossil Halimeda into segment algal reef dolomites. In addition, all of the studied intervals are moderately dolomitized. Secondary microcrystalline-dolosparite dominates the original aragonite raphide zones, and aphanitic-micrite dolomite plays the leading role in the cortexes and medullas;in the aragonite raphide zones between medulla and cysts, secondary dissolved pores and intercrystalline pores are formed inside the segments, and algal frame holes are formed between segments;therefore, a pore space network system （dissol

关键词： Xisha Islands Miocene fossil Halimeda segment dolostone reservoir evolution model

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Synthesis and Properties of Novel Polymers Based on PD Electron-withdrawing Unit

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Chinese Journal of Polymer Science 2016年第1期34卷 34-43页

作者： Qing Zhao Jing-yu Qian Ying Liang Zhi-cheng Zhong Song Wang Ke Liu 田文晶李在房 College of Chemical Engineering and Food Science Hubei Key Laboratory of Low Dimensional Optoelectronic Materials and DevicesHubei University of Arts and ScienceXiangyang 441053China State Key Laboratory of Supramolecular Structure and Materials Jilin UniversityChangchun 130012China

In this article, we designed and synthesized a series of 5-（2,6-dimethyl-4H-pyran-4-ylidene）-1,3-diethyl-2-thioxodihydropyrimidine-4,6（1H, 5H）-dione（PD） unit based polymers（PFTDT, CZTDT, PHTDT and THTDT） for the first time. In these polymers, fluorene, 2,7-carbazole, phenothiazine and thiophene are employed as electron-donating groups and PD as electron-withdrawing group. TGA measurements demonstrated that these polymers possess good thermal stability（all above 377 °C）. Very broad absorption spectrum was also obtained from the polymer THTDT（300？850 nm）. CV characterization found that these polymers owned low highest occupied molecular orbital（HOMO） energy levels（？5.39 e V for THTDT, ？5.49 e V for CZTDT and ？5.78 e V for PFTDT） except for PHTDT（？5.17 e V）. The geometry and electronic properties of PFTDT, CZTDT, PHTDT and THTDT were investigated by means of theoretical calculation. All the above advantages demonstrate that PD based polymers could be candidates for electronic devices.

关键词： PD unit Polymer Low bandgap Low HOMO energy level

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A discussion on the upper limit of maturity for gas generation by marine kerogens and the utmost of gas generative potential:Taking the study on the Tarim Basin as an example

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Chinese Science Bulletin 2007年第A1期52卷 125-132页

作者： CHEN JianPing ZHAO WenZhi XIAO ZhongYao ZHANG ShuiChang DENG ChunPing SUN YongGe WANG ZhaoMing Research Institute of Petroleum Exploration & Development PetroChina Beijing 100083 China Key Lab of Petroleum Geochemistry CNPC Beijing 100083 China Research Institute of Petroleum Exploration & Development Tarim Oilfield Company PetroChina Koda 841000 China State Key Lab of Organic Geochemistry Guangzhou Institute of Geochemistry Chinese Academy of Sciences Guangzhou 510640 China

The experimental data yielded by Rock-Eval pyrolysis, kerogen atomic H/C, Py-GC and gold-tube sealing thermal simulation on the marine Cambrian-Ordovician source rock from the Tarim Basin revealed that the upper limit of maturity for natural gas generation or the "deadline of gas generation" for marine types I and II kerogens is equal to 3.0% of vitrinite reflectance (Ro); while the "deadline of gas generation" for type III kerogens typically like coals is as high as 10% Ro. Thus, different organic matter has obviously different utmost maturities for gas generation. The mass-balance calculation by kerogen elements showed that when Ro>1.5%, the utmost amount of gas generation for the marine type II kerogen is less than 185 m3/t TOC, accounting for less than 30% of its total hydrocarbon generative potential; when Ro>2.0%, it becomes 110 m3/t TOC, less than 20% of the total hydrocarbon generative potential. The amount of the gas generative potential obtained by Rock-Eval is only around one tenth of the calculated value by the mass balance of kerogen elements at the same thermal evolutionary stage, while those by Py-GC and gold-tube sealing simulation are intervenient between the above two. The utmost of gas generative potential at the over 1.3% Ro stage is around 60―90 m3/t TOC, therefore, the amount of gas generation obtained by Rock-Eval is the minimum of gas generative potential, while that by the mass-balance calculation of kerogen elements is the maximum that the actual amount of gas generation should not exceed.

关键词：油母岩质海洋源岩石天然气

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