Discussion of gas enrichment mechanism and natural gas origin in marine sedimentary basin,China

There are abundant natural gas resources in Chinese marine sedimentary basin. The exploration hot shots of natural gas are the Palaeozoic marine strata here in recent years, and several large scale gas fields have been discovered. Chinese Palaeozoic high-post matured and coal measure hydrocarbon source rocks are mainly prone to gas generation in the present. This research considered that gas source rocks and TSR are the key cause of gas enrichment of marine strata. High-quality argillaceous and coal measure hydrocarbon rocks are distributed widely in the Palaeozoic marine strata, which have been in highly matured phase in the present. The argillaceous source rock generally contains various sulfates that could accelerate crude oil cracking to gas for TSR occurrence, and coal measure source rock mainly generates gas, so Chinese marine basin gives priority to accumulating gas. Marine strata have not founded oil reservoirs in the Sichuan Basin and Ordos Basin, and they consist mainly of dry gas. Marine natural gases are the mixed gases of oil cracking gas and coal-formed gas in a general way, oil cracking gases contain usually some H2S and CO2. Hydrocarbon carbon isotopes are very complicated, and methane and ethane isotopic values bear apparent reversal caused by thermal evolution and mixing among different genetic types of natural gas. Coal-formed gases are the main component of Chinese marine natural gas. The Upper Permian of the Sichuan Basin and the Carboniferous-Permian of the Ordos Basin coal measure hydrocarbon source rock present large hydrocarbon generation potential, which are the prospecting highlight of marine natural gas hereafter. Oil cracking gas exploration will be paid much attention to in the Tarim Basin because of the lack of coal measure hydrocarbon source rock.     

Oil cracking： An important way for highly efficient generation of gas from marine source rock kitchen

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 marine 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℃（R0=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 derived 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.     

Fundamental geological elements for the occurrence of Chinese marine oil and gas accumulations

The Paleozoic strata in the Tarim Basin, Sichuan Basin and Ordos Basin are the major targets for marine petroleum exploration, with developed high quality hydrocarbon, mainly argillite. The deep burial of these source rocks suggests that they mainly develop gas instead of oil. But different maturities of organic matter may lead to different hydrocarbon facies. Through thermochemical sulfate reduction （TSR）, the hydrocarbon in the carbonate rocks may undergo a process of pyrolytic cracking and be catalyzed into gases. The marine reservoirs mainly consist of carbonate and clastic rocks, and the former is controlled by sedimentary facies, dolomitization, solution, TSR and cracking. The multiphase tectonic cycling develops multiple source-reservoir-cap combinations and diversified types of traps and reservoirs, featuring multiphase reservoir formation, mainly late-phase formation or consolidation. Palaeo-uplifts play a controlling role in hydrocarbon accumulation. Differences in major source rocks in the three basins lead to different locations of oil-gas accumulation layers, different types and patterns of reservoirs and different features of reservoir formation.     

Pyrolysis of oil at high temperatures: Gas potentials, chemical and carbon isotopic signatures

Although the gas cracked from oil has been believed to be one of the important sources in highly ma-tured marine basins, there are still some debates on its resource potentials and chemical and isotopic compositions. In this study a Cambrian-sourced marine oil sample from the Silurian reservoir of well TZ62 in the central Tarim basin was pyrolyzed using sealed gold tubes with two different pyrolysis schemes: continuous pyrolysis in a closed system and stepwise semi-open pyrolysis. The results show that the maximum weight yield of C_1–5 gases occurs at EasyRo=2.3% and the residual gas poten-tial after this maturity is only 43.4 mL/g, about 12% of the yield of 361 mL/g at EasyRo=2.3%. Combined with the results of kinetic modeling, the main stage of gas generation from oil cracking is believed within the EasyRo=1.6%―2.3%. The increase in the volume yield of C_1–5 gases at EasyRo>2.3% in a closed system is mainly related to the re-cracking of previously formed C_2–5 wet gases, not the direct cracking of oil. The stepwise pyrolysis experiments show that the gas from the cracking of residual oil at EasyRo>2.3% is characterized by very high dryness index (higher than 92%) and heavy methane carbon isotopes ranging from -28.7‰ to -26.7‰, which is quite different from the gases from the con-tinuous pyrolysis in a closed system. The kinetic modeling of methane carbon isotope fractionation shows that the carbon isotopes of methane within the main stage of gas generation (EasyRo<2.3%) are far lighter than the carbon isotopes of the precursor oils under a geological heating rate of 2 ℃/Ma. The above observations and results provide some new clues to the accurate recognition and objective re-source evaluation of oil cracking gas in highly mature marine basins.     

Thermal cracking of n-octodecane and its geochemical significance

The mechanism of carbon isotopic fractionation for gaseous hydrocarbons is revealed by investigating the residual liquid hydrocarbons in laboratory pyrolysates of n-octodecane. The results indicate that cracking and polymerization in the relatively low temperatures and dispropor-tionation reactions leading to light hydrocarbons and pol-yaromatic hydrocarbons at high temperatures are probably causes for the carbon isotope reversal of gaseous hydrocarbons that is commonly observed in pyrolysis experiments. This study provides significant insight for quantitative modeling of natural gas δ13C values and aid in the identification and assessment of natural gases derived from oil cracking.     

Experimental evidence for formation water promoting crude oil cracking to gas

Crude oil cracking to gas is the key to determining the exploration potential and strategy for deep hydrocarbon resources.Identifying the factors that affect the threshold and potential of crude oil cracking to gas as well as other possible influencing factors will provide the scientific basis for deep hydrocarbon exploration.A comparison of pyrolysis simulation experiments of crude oil,hydrous crude oil,and various water media under a constant temperature(350℃) and pressure(50 MPa) shows that water plays a large role in crude oil cracking to gas.(1) When water is added,the gas yields increase significantly,including those of alkane gases and non-hydrocarbon gases:the yield of alkane gases increases 1.8-3 times;the yields of H2 and CO2 also increase significantly.This means that water takes part in the process of crude oil cracking to gas,and supplies hydrogen.Therefore,the presence of water will dramatically enhance the potential of crude oil cracking to gas.(2) Mg2+ ions in the formation water promote the crude oil + water reaction to some extent and increase the total yield of alkane gases and the yields of both H2 and CO2 ;more interestingly,the i-C4/n-C4 and i-C5/n-C5 ratios increase significantly.This indicates that Mg2+ ions in formation water act as a catalyst,and a disproportionation reaction is involved in the crude oil + water reaction.This study helps us to understand the factors influencing crude oil cracked gas and to evaluate the hydrocarbon resources in deep sedimentary basins.     

Characteristics of hydrocarbon accumulation and exploration potential of the northern South China Sea deepwater basins

Although the huge potential of the northern South China Sea deepwater basins has been proven by a series of discoveries that followed the exploration breakthrough of well LW 3-1-1, recent drilling and other studies have demonstrated the uniqueness and complicated nature of hydrocarbon accumulations of the deepwater basins there. Based on a review of previous work and the latest exploration activities and studies, the purpose of this paper is to discuss the critical controls for hydrocarbon accumulations in the deepwater basins of the northern South China Sea. A terrestrial-marine transitional coal-bearing source rock is proposed to be the primary source rock for the deepwater basins. A marine source rock, which was first identified as contributing to hydro-carbon generation in this region, probably plays a significant role in the deep-and ultra-deep water basins south to the Pearl River Mouth and Qingdongnan basins. The shelf margin delta depositional systems in the Baiyun Sag, sourced from the Pearl River, are currently primary exploration targets in the deepwater part of the Pearl River Mouth Basin, whereas the western Red River delta-ic-submarine fan depositional systems, initially proven by drilling, are the possible major exploration reservoirs in the Qing-dongnan deepwater areas. Current deepwater exploration targets at the large-sized structural traps and deep and ultra-deep areas in the south of the Pearl River Mouth and Qingdongnan basins will be the future exploration focus. Deepwater exploration activities and relevant fundamental studies, supporting and promoting each other, are of great importance to the national energy supply of China, the basic regional studies of the South China Sea, advancements in technology, and development of related deepwater industries, and will safeguard national sovereignty and territorial integrity.     

A discussion on gas sources of the Feixiansuan Formation H2S-rich giant gas fields in the northeastern Sichuan Basin

In recent years several H2S-rich oolite giant gas pools have been discovered in the Lower Triassic Feixianguan Formation of the northeastern Sichuan basin, and their explored gas reserves have been over 5000×10^8 m^3. However, gas sources remain unsolved due to multiple source horizons with high maturity in this area and TSR alterations. By integrating analytical data of natural gas samples with conprehensive investigations on many factors, such as oil-gas geology, distribution and evolution of source rocks, charging and adjustment of gas pools, mixture of natural gases and secondery alterations, the present study concluded that the dominant source for the Feixianguan Fr. gas pools is the Permian Longtan Fr. source rock and secondly the Silurian Longmaxi Fr. source rock. Natural gases from the various gas pools differ genetically due to the matching diversity of seal configurations with phases of hydrocarbon generation and expulsion by different source rocks, among which natural gases in Puguang Gasfield are dominated by the trapped gas generated from the Longtan Fr. source rock and commingled with the gas cracked from the Silurian crude oil, while those in Dukouhe, Tieshangpo and Luojiazhai Gasfields are composed mainly of the Silurian oil-cracking gas and commingled with the natural gas derived from the Longtan Fr. source rock.     

Study of CNG／diesel dual fuel engine＇s emissions by means of RBF neural network

Great efforts have been made to resolve the serious environmental pollution and inevitable declining of energy resources. A review of Chinese fuel reserves and engine technology showed that compressed natural gas (CNG)/diesel dual fuel engine (DFE) was one of the best solutions for the above problems at present. In order to study and improve the emission performance of CNG/diesel DFE, an emission model for DFE based on radial basis function (RBF) neural network was developed which was a black-box input-output training data model not require priori knowledge. The RBF centers and the connected weights could be selected automatically according to the distribution of the training data in input-output space and the given approximating error. Studies showed that the predicted results accorded well with the experimental data over a large range of operating conditions from low load to high load. The developed emissions model based on the RBF neural network could be used to successfully predict and optimize the emissions performance of DFE. And the effect of the DFE main performance parameters, such as rotation speed, load, pilot quantity and injection timing, were also predicted by means of this model. In resum6, an emission prediction model for CNG/diesel DFE based on RBF neural network was built for analyzing the effect of the main performance parameters on the CO, NOx emissions of DFE. The predicted results agreed quite well with the traditional emissions model, which indicated that the model had certain application value, although it still has some limitations, because of its high dependence on the quantity of the experimental sample data.     

Analysis on forming conditions of deep marine reservoirs and their concentration belts in superimposed basins in China

By taking the Tarim Basin, Sichuan Basin and Ordos Basin as examples, the conditions for deep marine reservoir formation were illustrated in three aspects listed below： late-stage superimposition style, burial history and structural deformation of the marine stratigraphic system. The burial history of marine source rocks can be divided into three types, i.e., type I, type II and type III, which are obviously different from the case with present hydrocarbon phases in terms of hydrocarbon generation and pe- troleum-reservoir formation. Based on evolution history, the structural belts in the marine stratigraphic sequence can also be divided into four types, i.e. earlier normal fault-later fault-fold type, earlier uplift-later fault-fold type, earlier uplift-later flattened slope type, and earlier depression-later thrust type. In this paper, a successive gas generation model was proposed, and it was particularly pointed out that coupling of geothermal field annealing evolution and tectonic subsidence and late gas generation from dispersed liquid hydrocarbon in highly matured to over-matured source rocks are key factors for formation of marine petroleum reservoirs. The geological conditions for formation of high-grade reservoirs in deep marine system, covering early hydrocarbon injection, deep denudation and buried dolo- mitization, were summarized. It was finally concluded that three major structural belts, i.e. paleo-uplift belt characterized by composite hydrocarbon accumulation, paleo-fault belt and high-energy sedimentary facies belt, were involved in marine hydrocarbon accumulation.     

南美地区油气地质特征及常规油气资源潜力

在分析南美油气地质特征的基础上,进行南美主要含油气盆地待发现常规油气资源评价,总结待发现油气资源分布规律,探讨其勘探前景。结果表明,受4大板块碰撞影响,南美沉积盆地可分成弧前、弧后、前陆、内克拉通和被动陆缘盆地5种类型。南美油气成藏条件优越,烃源岩以中新生界海相-陆相泥岩为主,生烃潜力大。储层以白垩系和第三系碎屑岩和碳酸盐岩为主,分布广泛。盖层中新生界区域性泥岩和盐岩为主,封堵能力强。采用以成藏组合为基础评价单元的资源评价方法,将南美65个盆地共划分出152个成藏组合,并进行了资源评价。预测南美65个主要含油气盆地的待发现石油可采资源量为263716MMB,待发现凝析油可采资源量为7405MMB,待发现天然气可采资源量为559020BCF。待发现油气资源在平面上呈“两带”展布、“两中心”富集特征;在纵向上主要富集于白垩系和第三系。被动陆缘盆地和前陆盆地是南美未来油气勘探的两个重点领域,其中深海和前陆冲断带是主要勘探方向,巴西、委内瑞拉是重点关注国家。     

Discussion of gas enrichment mechanism and natural gas origin in marine sedimentary basin, China

There are abundant natural gas resources in Chinese marine sedimentary basin. The exploration hot shots of natural gas are the Palaeozoic marine strata here in recent years, and several large scale gas fields have been discovered. Chinese Palaeozoic high-post matured and coal measure hydrocarbon source rocks are mainly prone to gas generation in the present. This research considered that gas source rocks and TSR are the key cause of gas enrichment of marine strata. High-quality argillaceous and coal measure hydrocarbon rocks are distributed widely in the Palaeozoic marine strata, which have been in highly matured phase in the present. The argillaceous source rock generally contains various sulfates that could accelerate crude oil cracking to gas for TSR occurrence, and coal measure source rock mainly generates gas, so Chinese marine basin gives priority to accumulating gas. Marine strata have not founded oil reservoirs in the Sichuan Basin and Ordos Basin, and they consist mainly of dry gas. Marine natural gases are the mixed gases of oil cracking gas and coal-formed gas in a general way, oil cracking gases contain usually some H2S and CO2. Hydrocarbon carbon isotopes are very complicated, and methane and ethane isotopic values bear apparent reversal caused by thermal evolution and mixing among different genetic types of natural gas. Coal-formed gases are the main component of Chinese marine natural gas. The Upper Permian of the Sichuan Basin and the Carboniferous-Permian of the Ordos Basin coal measure hydrocarbon source rock present large hydrocarbon generation po- tential, which are the prospecting highlight of marine natural gas hereafter. Oil cracking gas exploration will be paid much attention to in the Tarim Basin because of the lack of coal measure hydrocarbon source rock.     

中国低渗透油气的现状与未来

中国低渗透油气资源丰富,具有很大的勘探开发潜力。近20年来,在低渗透砂岩、海相碳酸盐岩、火山岩勘探方面取得了很大发现,形成了国际一流的开发配套技术,实现了低渗透油气藏的规模有效开发,低渗透油气产量持续上升,其在产量构成中所占比例逐年增加。无论从近几年新增探明储量还是从剩余油气资源量看,低渗透油气都是今后勘探开发的主要对象,低渗透油气是中国未来油气工业的勘探开发主流,对保障国家能源安全具有重要的战略意义。     

原油裂解成气研究进展

原油裂解气可以作为重要的天然气来源,将是未来重要的勘探方向之一。对原油裂解成气研究方法、产物特征、识别标志、原油裂解程度定量表征、原油裂解成气门限、主成气期、影响因素以及中国原油裂解气区的主要勘探及研究态势进行了总结和评述。认为原油裂解成气的门限和主生气期是原油裂解气形成中的关键科学问题,尤其是在超压条件下,原油裂解成气的主生气门限、化学动力学问题及原油裂解成气定量预测等研究需要加强;盐岩及其体系中的不同矿物对原油裂解成气的影响及机理尚不明确;中国东部湖相原油裂解气研究仍显薄弱,为加强对湖相裂解气形成与分布规律的正确认识,丰富原油裂解气形成理论,缓解中国东部天然气资源短缺问题,针对中国东部陆相断陷湖盆应进一步开展原油裂解气的相关研究。     

Two accumulation modes of marine-origin natural gas in the Tarim Basin

HeUanhe gas field, Lungudong gas field and Tazhong gas field are marine marine-origin natural gas reservoirs in the craton area in the Tarim Basin. The natural gas is generated from Cambrian source rocks. The simulation experiment indicated that the cracking of the dispersedly dissoluble organic matter remaining in the source rocks is the main origin of marine natural gas. There are two modes to form gas reservoirs, one is the dry gas reservoir such as HeUanhe gas field, in which gas accumulated on the fault belt with violent tectonic movement, the other is condensate gas reservoir formed on the inheriting uplift such as Lunnan and Tazhong gas fields. The hybrid simulation experiment of cracking gas and crude oil indicated that crude oil accumulated on a large scale in those uplift belts at the early stage, and natural gas filled the ancient oil reservoir at the late stage, and the gas reservoirs were formed after the gas mixed with the crude oil.     

东濮凹陷北部地区古近系油型气成因类型及分布特征

以热压模拟实验模拟东濮凹陷干酪根热裂解和原油热裂解过程,分析干酪根热裂解气和原油裂解气组分特征的差异,以此建立干酪根热裂解成因气和原油裂解成因气的判识方法;结合东濮凹陷北部地区天然气碳同位素及天然气组分数据,对研究区油型气进行划分,进而探讨干酪根热裂解气与原油裂解气的分布特征。结果表明,研究区古近系油型气分为干酪根热裂解气与原油裂解气,干酪根热裂解气具有相对较高的C1/C2值和较低的C2/C3值特征,而原油裂解气则与之相反。干酪根热裂解气和原油裂解气的分布存在明显差异:前者分布范围更广,后者更近于洼陷中心分布,两者分布的差异性与其生成及成藏条件差异有关。根据干酪根热裂解气与原油裂解气分布特点,推测在邻近洼陷中心区具有良好的干酪根裂解成气及原油裂解成气的条件和油型气勘探前景。     

吐哈盆地北部山前带下侏罗统天然气气源与成藏模式

为了明确山前带柯柯亚下侏罗统气藏,对于这套位于中上侏罗统油气藏之下的天然气性质、来源及成藏模式,运用地球化学分析和天然气气藏解剖方法进行研究.研究结果表明:本区天然气甲烷碳同位素分布在-44.0‰～－38.7‰,乙烷碳同位分布在-29.0‰～－27.5‰,属于偏腐泥型的腐殖气,伴生原油的物理性质和生物标志物呈现出典型的成熟煤系油特征,并与中上侏罗统油气来源不同,即地质条件和地球化学数据都证明天然气母质处于成熟演化阶段,垂向运移距离短,来自八道湾组煤系泥岩;天然气大量充注前大面积致密储层的形成、下侏罗统异常超压的发育以及源储的紧密叠置,都是形成致密砂岩气藏的地质条件.