高温高压条件下甲烷和二氧化碳溶解度试验

根据不同温度和压力条件下测得的甲烷和二氧化碳两种气体在碳酸氢钠型水中的溶解度数据,对两种气体的溶解度与温度、压力及地层水矿化度之间的关系进行研究。结果表明:在地层水中的溶解机制不同,导致两种气体的溶解度值随温度、压力条件的变化具有不同的演变特征;综合前人低温(小于90℃)测试的溶解度数据,可将甲烷溶解度与温度之间的演变关系划分为缓慢递减(0~80℃)、快速递增(80~150℃)和缓慢递增(大于150℃)3个阶段;二氧化碳溶解度随温度的升高而逐渐降低,随压力升高而逐渐增大,其溶解与析离能力受压力影响更为明显;实际地层中,两种气体间溶解度的差异演变影响了天然气的空间分布。     

Evolution of the CBM reservoir-forming dynamic system with mixed secondary biogenic and thermogenic gases in the Huainan Coalfield,China

The secondary biogenic gas is an important original type of the coalbed methane (CBM) in China. Based on the analyses of sedimentary and burial history of the Permian coal-bearing strata, combined with thermal history and gas generation process of coals, the CBM reservoir-forming dynamic system with mixed secondary biogenic and thermogenic gases in the Huainan Coalfield is subdivided into four evolutionary stages as follows: (i) shallowly-buried peat and early biogenic gas stage; (ii) deeply buried coal seams and thermogenic gas stage; (iii) exhumation of coal-bearing strata and adsorbed gas lost stage; and (iv) re-buried coal-bearing strata and secondary biogenic gas supplement stage. The Huainan CBM reservoir-forming model has the features of the basin-centered gas accumulation. The evolution of the reservoir-forming dynamic system proves that the thermogenic gas is not the main gas source for the Huainan CBM reservoir. Only the secondary biogenic gases as an additional source replenish into the coal bed after basin-uplift, erosional unroofing and subsequent scattering of thermogenic gases. Then this kind of mixed CBM reservoirs can be formed under suitable conditions.     

Study on kinetics of hydrocarbon generation from coals in the Qinshui Basin

Coal-bed gas is a new energy resource and studies on its genetic mechanism, coal source rock and the resource assessment have become the hot points in petroleum ge-ology field[1―3]. A new method for the quantitative as-sessment of hydrocarbon generative potential from coals by means of the chemical reaction kinetics has been de-veloped gradually over the recent years and so far some researchers in the field have been reported[4―13]. These works focused on the application of the kinetic model…     

铀对Ⅰ型低熟烃源岩生烃演化的影响

在Ⅰ型低熟烃源岩中加入砂岩型铀矿石的条件下进行生烃模拟实验,对比无铀-加铀样品生烃模拟实验产物的相关参数,探讨油气生成过程中无机铀所起的作用。结果表明:铀的存在促使长链烃类在400℃后裂解成低相对分子质量短链烃,烃类相对分子质量降低,向干气演化,CO2和H2大量生成,且铀的存在使得这一变化的温度点提前50℃;铀可以促进总油生成高峰的提前到来;350℃为铀使烯烃产量变化的转折温度点,烯烃开始向烷烃转变;铀的存在能提高模拟实验中生成的烯烃的异构化程度,并在整体上使生成的烯烃分子在晶格中排得更加紧密;加铀的烃源岩样品的生烃模拟实验产物在族组成、饱和烃气相色谱、生物标志化合物等方面表现出更加成熟的特征,铀可以使有机质的成熟度提高,有利于低熟烃源岩早期生成低熟油气,使铀的存在成为未熟-低熟油气形成的可能无机促进因素之一,这种提前生成的少量油气可以使所在储层变为亲油性,为后期大规模生成的油气运移成藏提供有利的条件,使得即使是致密的储层,也能形成大规模的工业油气藏。     

Influence of overpressure on coalbed methane reservoir in south Qinshui basin

In theory, from the high temperature and pressure during the coal generating gas to the present low temperature and pressure of coalbed methane reservoir, the accumulation of coalbed methane was from oversaturated to undersaturated. The gas content of the coalbed methane reservoir in the south Qinshui basin was 12-35.7 m3/t. According to the isotherm and measured gas content of No. 3 coal, the adsorbed gas content in some wells was highly saturated and oversaturated, which was hard to theoretically understand. In addition, there were no thermogenic and biogenic gases at the late stage in the south Qinshui basin. This article proposed that the overpressure was the main reason for the present high saturation of the coalbed methane reservoir. In early Cretaceous, the coalbed methane reservoir was characterized by overpressure and high saturation caused by gas generation from coal measure source rocks. In late Cretaceous, the coalbed methane reservoir was rapidly uplifted, and with the temperature and pressure decreasing, the pressure condition of adsorbed gas changed from overpressure to normal-under pressure, which resulted in the high saturation and gas content in the present coalbed methane reservoir.     

Secondary biogenic coalbed gas in some coal fields of China

The secondary biogenic coalbed gas, a new genetic and energy source type of coalbed gas in China, has been found in Xinji, Liyazhuang and Enhong areas. The essential characteristics of this type of gas are: (i) the major component of the gas is methane, with C1/C1-5 value higher than 0.99, indicating that the gas is part of dry gas; (ii) theδ13C1 value is in the range of -61.7‰to -47.9‰, mostly lower than -55‰, which is much lower than the estimatedδ13C1 value of thermogenic methane according to the thermal evolution degree of the coal rocks (with R0 value from 0.87% to 1.43%), showing the characteristics of the secondary biogenic gas; (iii) theδ5D value of methane ranges from -244‰to -196‰; (iv)δ13C 2 value ranges from -26.7‰to -15.9‰andδ13C 3 value ranges from -10.8‰to -25.3‰, indicating that the heavier hydrocarbons have a thermogenic origin; (v) the content of CO2 is very low, andδ13CCO2 value changes greatly, reflecting a characteristic of secondary change; (vi)δ15N2 value ranges mainly from -1‰to +1‰, indicating N2 derived significantly from air. The negative linear correlation between the contents of N2 and CH4 reflects the activity of bacteria bearing surface water infiltrating into coal beds. The comprehensive tracing indices show that the coalbed gas in the studied areas is the mixed gas of primarily secondary biogenic gas and a part of remnant thermogenic gas. The uplift of coal beds and the development of faults in the studied areas create favorable conditions for the formation of the secondary biogenic gas.     

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.     

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.     

褐煤储层含气量计算

因我国褐煤中煤层气赋存特征认知程度较低,影响了较低煤级煤层气的开发,褐煤中含气量的研究显得尤为关键。基于此,文中对采自内蒙古海拉尔盆地4个褐煤H1,H2,H3,H4样品进行煤岩煤质分析,25℃平衡水等温吸附实验。计算埋深在400～2 000 m吸附气含量;模拟在储层温度、压力、矿化度、密度条件进行甲烷溶解度的测定结果表明甲烷溶解度随压力、温度的同时增加而增大(低于80℃),基于实验结果,计算了不同埋深(温度、压力)下褐煤储层的水溶气含量;测定4个褐煤样品孔隙度,根据马略特定律计算游离气含量。由吸附气、水溶气及游离气含量计算褐煤含气量。结果表明,埋深小于1 000 m的褐煤含气量随埋深增加而增大;埋深大于1 000m随埋深增加而减少。H1含气量较低,H2,H3,H4含气量较高,400～2 000 m埋深的褐煤含气量介于2.57～6.99 m3/t之间,且均随埋深增加而增大。含气量中吸附气、水溶气、游离气含量比例分别为78.7%,9.3%,12.0%.     

Oil cracking to gases： Kinetic modeling and geological significance

A Triassic oil sample from LN14 of Tarim Basin was pyrolyzed using the sealed gold tubes at 200-620℃under a constant pressure of 50 MPa. The gaseous and residual soluble hydrocarbons were analyzed. The results show that the cracking of oil to gas can be divided into two distinct stages: the primary generation of total C1-5 gases from liquid oil characterized by the dominance of C2-5 hydrocarbons and the secondary or further cracking of C2-5 gases to methane and carbon-rich matters leading to the progressive dryness of gases. Based on the experimental data, the kinetic parameters were determined for the primary generation and secondary cracking of oil cracking gases and extrapolated to geological conditions to predict the thermal stability and cracking extent of crude oil. Finally, an evolution model for the thermal destruction of crude oil was proposed and its implications to the migration and accumulation of oil cracking gases were discussed.     

Kinetic study of hydrocarbon generation of oil asphaltene from Lunnan area, Tabei uplift

The molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons produced in the hydrocarbon generation of oil asphaltene from Lunnnan area were investigated by pyrolysis of asphaltene sealed in gold tube in a limited system. The experimental results indicated that oil asphaltene from Lunnan area had relatively high generation potential of methane. However, the molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons in the hydrocarbon generation of oil asphaltene exhibited different characteristics from that of gas hydrocarbons by primary cracking of kerogen and secondary cracking of oil. Based on kinetic simulation with paleo-geothermal data of oil reservoir, the methane produced by cracking of oil asphatene was characterized by relatively light carbon isotopic compositions. This result could not explain relatively heavy carbon isotopic compositions of natural gas from Lunnan area. Pyrolysis of kerogen from source rocks under very high temperature probably made remarkable contributions to natural gas from Lunnan area.     

The key stage and moment of coalbed gas reservior evolution in the Qinshui Basin,China

The evolution of coalbed gas reservoir is characterized by coalbed gas geochemistry and gas content. On the basis of burial history and thermal history, the forming process of coalbed gas reservoir and the gas accumulative history in the Qinshui Basin are discussed in this paper. The difference of the thermal history, geochemistry characteristic, and gas accumulative history between Yangcheng and Huozhou areas shows that the formation of coalbed gas reservoir in the Qinshui Basin is controlled by the geological process in the critical stage and the critical moment. The components and isotopes of coalbed methane are determined by the stage at which the coal maturation reaches its maximum rank. The coalbed methane accumulative history is related to the temperature and pressure of the coal burial history, because the coalbed gas is mainly in adsorptive state. It is stated that the gas content in the coal seam is controlled by the moment when the coal seam is uplifted to the shallowest position.     

New research progress on the ultrastructure of tectonically deformed coals

The structure of tectonically deformed coals shows some characteristics and regulations on the ultra-scale when influenced by different factors such as temperature, pressure and directional stress. Deformations of the macromolecular structure may induce changes in the nano-scale pore structure, which are very important for gas adsorption and pervasion. The geological impact of different mechanisms of deformation on different types of ultrastructure of tectonically deformed coals is not only of significance as a topic for scientific research, but also in studying environments of metamorphism-deformation at differing metamorphic stages. This research is also very important in studying the accumulation and occurrence conditions of coalbed methane gas, mechanisms of coal and gas outbursts, predictions of coalbed methane resources and dangers of coal and gas outbursts. This paper analyzes current research, within China and other countries, in the ultrastructure of tectonically deformed coals. The research includes (1) structural models of tectonically deformed coals; (2) the relationship between ultrastructure and stress; (3) the structure of tectonically deformed coals and its strain environment. These results are also based on our own experiments including vitirnite reflectance (R_o,max), X-ray diffraction (XRD) and nuclear magnetic resonance (NMR (CP/MAS + TOSS)). We discuss the important effects of the structure of tectonically deformed coals and their physical properties, and then point out some problems concerning the research progress of tectonically deformed coals.     

贵州盘县晚二叠世煤的生烃潜力与生烃模式

用有机地球化学方法研究贵州中西部地区煤岩的生烃机理和生烃模式。石英小玻管热模拟实验和红外光谱对贵州盘县晚二叠世煤的分析表明, 盘县煤的干酪根类型为Ⅲ型, 主要成分是均质镜质体和丝质半丝质体, 主要生成物是短链烃, 显著生烃的起始温度约为300 ～350 ℃。     

论冀中地区O、C—P凝析气藏的形成条件

据凝析油轻烃组成、甲烷及其同系物碳同位素组成、天然气与源岩吸附气指纹时比、双环倍半萜组合特征及地质结构的综合分析,查明O、C—P大多数提析气藏的油气主要来源于石炭—二叠系煤系腐植型有机质,混入了部分下第三系的油气。对石炭—二叠系成烃特点的分析表明,R。=0.6%～1.3%,以成气为主,生油为辅,原始油气比一般大于1OOCm3/t。成熟期的石炭—二叠系有机质的成烃特点和具备油气富集的良好地质条件是O、C—P凝析气藏形成的基本条件。     

Research progress in studies on the coalbed gas geochemistry

The current situation of geochemical studies on coalbed gas is reviewed in this paper. Generally, coalbed gas is compositionally dominated by methane with δ¹³C₁ values ranging approximately from -80‰ to -10‰. However, few isotopic studies have been carried out on other components of coalbed gas except for hydrogen and carbon dioxide, whose δD_CH4 values available for utilization vary from -333‰ to -117‰, and δ¹³C_CO2 values from -29.4‰ to +18.6‰. Two major types of coalbed gas, thermogenic gas and secondary biogenic gas, have been identified, and there are also some other classification criteria. Compared with conventional natural gases, coalbed gas has a wide distribution range of δ¹³C₁ and δ¹³C_CO2 values, especially possessing some extremely heavy values. Current problems that remain unsolved in the coalbed gas geochemistry include the variation mechanism, controlling factors and application of carbon and hydrogen isotopes of methane, the relation between the values of δ¹³C₁ and Ro, the systematic classification scheme and criterion of genetic types, and the application of the coalbed gas geochemistry in evaluating target districts of the coalbed gas exploration.     

西北地区煤层气藏形成条件剖析

从煤层发育程度、煤相、煤显微组成、煤级、煤变质作用、构造作用、围岩圈闭、地层压力以及水地质条件等方面对西北地区侏罗系及石炭-二叠系煤层气藏形成条件进行了详细剖析。研究结果表明，西北侏罗系及石炭-二叠系在上述条件具备时能够形成煤层气藏。     

气体制备与性质一体化微型实验的研究

介绍了一组能适用于液—固、液—液、固—固反应制取气体的多用途微型气体发生器及应用于气体性质实验的反应管等仪器．利用该仪器能组合成为具有气体发生、净化、吸收、性质反应等功能的装置，使仪器的用途大为扩展，为微型化学实验的一体化提供了可能．并通过该仪器对H2、O2、Cl2、CO等几个有代表性气体的制备与性质一体化微型实验进行了研究。     

固体氧化物电解质膜反应器中甲烷氧化偶合反应动力学

研究了固体氧化物电解质膜反应器 ( Ag| YSZ| Ag)中甲烷氧化偶合动力学和外加电流对反应结果的影响 ,提出了该反应系统中甲烷偶合反应网络。用幂指数拟合实验数据 ,得出甲烷总消耗速率、生成 C2 烃和深度氧化速率的动力学方程式 ,并估算了动力学参数。用固体电解质电势分析法监测了反应过程中 Ag催化剂电极表面氧活度 ,结果表明 ,反应室中气相氧与 Ag催化剂电极上的氧并未形成热力学平衡 ,氧的吸附速率小于或接近催化剂电极上氧消耗速率。本实验条件下 ,外加电流 (电压 )并未显著影响甲烷的氧化偶合反应     

The role of sulfur in the pyrolysis of kerogen

Sulfur plays an important role in the generation and evolution of hydrocarbon from organic matter. Here, a pyrolysis experiment in closed system was performed on Maoming oil shales kerogen (Type Ⅰ), Maoming oil shales kerogen added with sulfur ether and Maoming oil shales kerogen added with sulphur. The results suggest that the existence of sulfur can result in: (i) higher yield of hydrocarbons generated from the kerogen; (ii) decrease of the temperature for the maximum generation of heavy hydrocarbons (the C15+ fraction) by 20℃; (iii) decrease of the temperature for the maximum generation of the aromatics fraction by 40℃, and (iv) acceleration of the aromatization process. The pyrolysates from kerogen added with sulfur are similar to the heating products of the sulfur-rich kerogen as reported in the literatures. It seems that the sulfur catalysis is also an important factor that can make the sulfur-rich kerogen generate low-mature oil at the earlier diagenesis stage, except for the weakness of the C-S and S-S bonds.