Origin of shale gas in the Triassic Yanchang Formation,Ordos Basin,China

The Chang 7 Member shale gas of the Upper Triassic Yanchang Formation, Ordos Basin, is a representative of continental shale gas in China. The Chang 7 shale is currently in the oil window, suggesting it should primarily be producing oil, but an exploratory well found high levels of gas production. In addition, the methane carbon isotopic composition (δ¹³C₁) of Chang 7 shale gas is generally depleted in ¹³C relative to that calculated by Ro, according to the δ¹³C-Ro equation. It is uncertain whether Chang 7 shale gas has mixed with biogenic gas or early thermogenic gas. In this study, over 100 samples of fresh shale cores were collected from the Yanchang Formation, and on-site gas desorption experiments and experimental analysis were carried out. Measured shale gas content was considerable, and was found to be proportional to the abundance of organic matter. Through comprehensive evaluation of the gas composition and δ¹³C₁, it was concluded that there was no biogenic gas contribution to the shale gas in the study area. The negative δ¹³C₁ of shale gas was due to the different formation mechanisms of shale gas and conventional natural gas. Methane in shale gas reservoirs is the result of methane accumulation at all stages, which increases the shale gas content.     

Characteristics and origin of desorption gas of a transitional shale: A case study from the Lower Permian Taiyuan Formation shale,Ordos Basin,northern China

In China, marine shale and terrestrial shale have achieved significant breakthroughs. Comparing with marine shale and terrestrial shale, the research and exploration of transitional shale are still in the preliminary stage, and the content and origin of desorbed gas from transitional shales are poorly documented, thus limiting the understanding of gas generation and potential play elements. Geochemical characteristics of desorbed gas, including content and origin, are analyzed from 9 core samples of the Lower Taiyuan Formation shale from well SSL23 in the Ordos Basin, northern China. The results show that the Taiyuan Formation shale in the study area are characterized by high total organic carbon content of 2.70–9.00%, type III organic matter, and high T_max ranging from 461 to 520°C. The desorbed gas content of the shale samples varies from 0.79 to 2.37 m³/t, with an average of 1.35 m³/t. The gases are dominated by hydrocarbons (83.72–98.62%), with small amounts of non-hydrocarbons (1.38–16.28%) and the methane is the dominant component of the desorbed gases. The carbon isotope δ¹³C₁ ranges from ?43.9 to ?26.3 ‰, the δ¹³C₂ ranges from ?27.2 to ?23.1 ‰ and the δ¹³C₃ ranges from ?25.3 to ?11.6 ‰, respectively. The Whiticar chart and the plot of δ¹³C₁-δ¹³C₂ suggest that gases released from the Taiyuan Formation shale are thermogenic in origin and possibly coal-derived.     

A kinetic model of stable carbon isotope ratios in gaseous hydrocarbons generated from thermal cracking of n-tetracosane and its application to the Tarim Basin

Based on quantitative modeling and experimental data on n-tetracosane cracking to generate gaseous hydrocarbons in a confined system, we calculated the generation kinetics and carbon isotope kinetics of methane, ethane and propane and determined the main controlling factors influencing the variation of δ¹³C₂ and δ¹³C₃. The carbon isotope of gaseous hydrocarbons from n-C₂₄ cracking to gas are comparable to those from crude oil reported recently, and they can be used to investigate the geochemical characteristics of crude oil cracking to gas under geological conditions. The geological model of n-C₂₄ cracking suggests it is stable at 150 – 160 °C and its cracking temperature ranges from 180 to 200 °C, consistent with geological models of crude oil cracking currently reported. With increasing degree of thermal stress, the changes in δ¹³C₂ and δ¹³C₃ are larger than that of δ¹³C₁. It is shown that isotope accumulation controlled by the recharging history of a reservoir has a considerable impact on the carbon isotope distribution of natural gas. Compared to that of cumulative gas, the carbon isotope ratio of partly accumulation gas is heavier and influences the fractionation of the δ¹³C₂ and δ¹³C₃ curves to a greater extent. The geological model of n-C₂₄ cracking to gas has been used to interpret the origin of carbon isotopic variation of natural gas in some reservoirs in the Tarim Basin.     

四川盆地海相页岩气碳同位素特征及指示意义

为明确四川盆地页岩气碳同位素特征及地质意义,采用气相测谱等分析手段,对涪陵、长宁、彭水、威远地区页岩气样品进行分析。结果表明:研究区页岩气成分以甲烷为主,含量为96.10%～99.40%,乙烷、丙烷等含量低;非烃气体中以N₂与CO₂为主;含有微量氦气,含量为0.01%～0.03%,CO₂的碳同位素含量为-12.5‰～8.9‰,表明CO₂的来源包含有机成因与无机成因。目前四川盆地页岩气田均发现碳同位素倒转排序(δ¹³C₃<δ¹³C₂<δ¹³C₁),其机理主要为不同来源的烃类气体混合、气体与矿物反应、烷烃的解吸/扩散过程的分馏作用。页岩气碳同位素倒转程度与页岩层系的封闭性密切相关,因为页岩层系的自封闭性直接影响气体排烃及天然气扩散程度。此外,页岩气产量与倒转程度有良好正相关性,表明页岩气碳同位素特征对页岩气产量预测、保存条件与富集规律评价有重要指示作用。研究结果对四川盆地海相页岩气深入勘探具有一定指导意义。     

Geochemistry and origin of the world's largest gas field from Persian Gulf,Iran

The South Pars field, which is the Iranian part of the world largest non-associated gas accumulation (taking into account its Qatari part, North Field, with 1342 tcf proved reserve), is hosted by Upper Permian Dalan and Lower Triassic Kangan carbonates. Carbon isotopic and molecular composition studies were undertaken to investigate the origin of non-associated gases from this field. In general, evaluation of the δ¹³C values of methane, ethane and propane and gas wetness (C₂–C₅/C₁–C₅) indicates a thermogenic origin. On the other hand, results of the isotopic analyses showed no mixing of biogenic gases in all of the analyzed gas samples. A further evaluation using natural gas plot, carbon isotopic composition of methane to pentane vs. 1 / n, showed δ¹³C₁ < δ¹³C₂ < δ¹³C₃ as normal trend. However, the carbon isotopic compositions of butane and pentane indicate a minor reverse trend in the normal progression of carbon isotopic compositions. This reversal in carbon isotope ratio among butane and pentane is interpreted as a consequence of mixing from multiple sources with different maturities.δ¹³C_CO2 in South Pars field is similar with those of thermogenic origin. The diagram of δ¹³C_CO2 vs. δ¹³C_CH4 indicates that South Pars gases plot into the isotopic compositional field for methane derived from thermogenic origin. The H₂S concentration is much lower than the Khuff Formation and it seems it has originated from different processes. Apparently, the Lower Silurian organic-rich shales, which are the main source for hydrocarbons in the Arabian Plate and southern Iran, including South Pars field, generally contain kerogen type II with some contribution of type III in some areas.Burial history modeling indicates that at the end of the Cretaceous time pre-Permian sediments remained immature in the Qatar Arch, and their present day maturity is lower than values obtained based on isotopic data. Therefore, lateral migration of gas from the nearby Silurian source rock kitchens towards the north and south of the Qatar Arch is the most probable origin for the significant natural gas accumulations in South Pars field.     

中扬子宜昌地区下寒武统水井沱组页岩气地球化学特征及其成因

中扬子宜昌地区下寒武统水井沱组页岩钻遇良好的页岩气显示,区内宜页1井水井沱组页岩经水力压裂后获得了高产工业气流,是四川盆地外下寒武统页岩气新的勘探区。采集压裂产气段的9个页岩气样品,测试气体组分、碳和氢同位素组成以及He同位素组成,分析水井沱组页岩气地球化学特征并探讨了页岩气成因。研究表明,页岩气组成中甲烷含量为87.17%~92.75%,乙烷含量为0.83%~0.94%,含微量的丙烷,页岩气干燥系数为0.99,为典型干气;非烃气体中氮气含量稍高,平均为7.73%,二氧化碳平均含量低于1%,不含H₂S。甲烷碳同位素值为-33.8‰~-33.1‰,乙烷碳同位素值为-39.2‰~-36.0‰,丙烷碳同位素值为-39.4‰~-38.5‰,二氧化碳的碳同位素值为-16.8‰~-14.6‰。甲烷氢同位素值为-133.8‰~-128.5‰,乙烷氢同位素值为-168.0‰~-146.1‰。气态烃稳定同位素分布具有δ¹³C₁ > δ¹³C₂ > δ¹³C₃和δD_CH4 > δD_C2H6的倒转特征。He同位素R/R_a为0.04~0.08,表明He为典型的壳源成因。综合页岩气分子组成和比值、碳氢同位素倒转分布以及页岩现今处于过成熟热演化阶段等特征,认为宜昌地区下寒武统页岩气为油型气,具有二次裂解成因的特点,且与四川盆地筇竹寺组页岩气具有相似的特征。     

油型气乙烷碳同位素演化规律与成因

通过分析四川盆地和北美Appalachian、Fort Worth等盆地页岩气和常规油型气乙烷碳同位素特征和成因,得出随着成熟度的增加,乙烷碳同位素经历3个演化阶段：初次生气阶段正常增加,与甲烷碳同位素具有线性相关;二次裂解阶段同位素值减少,与乙烷含量的倒数具有线性关系,符合二端元气混合模型;湿气裂解阶段碳同位素值增加,与乙烷含量的自然对数呈线性关系,符合瑞利分馏模型。不同阶段页岩气碳同位素倒转的成因不同,瑞利分馏阶段碳同位素分馏速率乙烷>丙烷,并且甲烷碳同位素发生次生变化是造成过成熟阶段页岩气碳同位素反序的原因。富¹²C的乙烷是四川盆地页岩气高产井的重要地球化学特征。对于成熟度R_o>2.2%的天然气,乙烷碳同位素用于气源鉴别需要用瑞利分馏的公式校正。     

焦石坝地区龙马溪组页岩解吸气地球化学特征及地质意义

通过对焦石坝地区龙马溪组页岩岩心进行解吸以分析其气体组分和碳同位素组成,研究了四川盆地志留系龙马溪组页岩气碳同位素倒转现象。结果表明,解吸气相对井口气组分明显偏湿、碳同位素值明显偏重;各组分碳同位素值随解吸时间变重：不同样品δ¹³C₁值最大变重幅度12.3 ‰ ~23.9 ‰ ,而不同样品δ¹³C₂值最大变重幅度仅0.8 ‰ ~2.3 ‰ ,即甲烷碳同位素值相对重烃变化更明显,与前人页岩岩心解吸实验结果一致。研究结果认为：地层状态下页岩气可能并未发生碳同位素倒转,岩心解吸过程中观察到的δ¹³C₁值比δ¹³C₂值变化更明显,不是不同组分扩散速率差异造成,而主要是由于甲烷与乙烷处于不同解吸阶段导致,即乙烷处于其解吸早期阶段而甲烷处于其解吸较晚阶段;生产过程中吸附作用引起的烷烃气不同组分相态差异与所处解吸阶段差异可能是导致四川盆地龙马溪组页岩气碳同位素完全倒转的主要原因,但不能否认干酪根裂解气与原油裂解气的混合对页岩气碳同位素倒转做出的部分甚至大部分贡献。     

东营凹陷沙四段原油裂解热模拟实验及产物特征

对东营凹陷沙四段成熟阶段早期的原油样品(按比例与水、砂混合封入金管) ,采用高压釜封闭连续加热方式进行热压模拟实验。根据11个模拟温度点的烃类裂解气产率分析,原油裂解气累计产率为650～660 m³/t_TOC。原油裂解气R_O值在1.3%～1.5%和2.3%～2.7%区间存在2个明显的高峰。原油裂解气中甲烷含量和C₂/C₃值随模拟温度升高而明显增加,但C₁/C₂值变化较小。原油裂解气碳同位素在成熟阶段相对较轻,高—过成熟阶段不断变重,并且甲烷与乙烷、乙烷与丙烷的碳同位素差值具有逐渐增加的趋势。     

ORGANIC GEOCHEMISTRY OF CRUDE OILS AND UPPER CRETACEOUS SOURCE ROCKS FROM CONCESSION 11, WEST SIRTE BASIN,LIBYA

This paper reports the results of Rock‐Eval pyrolysis and total organic carbon analysis of 46 core and cuttings samples from Upper Cretaceous potential source rocks from wells in the West Sirte Basin (Libya), together with stable carbon isotope (δ¹³C) and biomarker analyses of eight oil samples from the Paleocene – Eocene Farrud/Facha Members and of 14 source rock extracts. Oil samples were analysed for bulk (°API gravity and δ¹³C) properties and elemental (sulphur, nickel and vanadium) contents. Molecular compositions were analysed using liquid and gas chromatography, and quantitative biological marker investigations using gas chromatography – mass spectrometry for saturated hydrocarbon fractions, in order to classify the samples and to establish oil‐source correlations. Core and cuttings samples from the Upper Cretaceous Etel, Rachmat, Sirte and Kalash Formations have variable organic content and hydrocarbon generation potential. Based on organofacies variations, samples from the Sirte and Kalash Formations have the potential to generate oil and gas from Type II/III kerogen, whereas samples from the Etel and Rachmat Formations, and some of the Sirte Formation samples, have the potential to generate gas from the abundant Type III kerogen. Carbon isotope compositions for these samples suggest mixed marine and terrigenous organic matter in varying proportions. Consistent with this, the distribution of n‐alkanes, terpanes and steranes indicates source rock organofacies variations from Type II/III to III kerogen. The petroleum generation potential of these source rocks was controlled by variations in redox conditions during deposition together with variations in terrigenous organic matter input. Geochemical analyses suggest that all of the oil samples are of the same genetic type and originated from the same or similar source rock(s). Based on their bulk geochemical characteristics and biomarker compositions, the oil samples are interpreted to be derived from mixed aquatic algal/microbial and terrigenous organic matter. Weak salinity stratification and suboxic bottom‐water conditions which favoured the preservation of organic matter in the sediments are indicated by low sulphur contents and by low V/Ni and Pr/Ph ratios. The characteristics of the oils, including low Pr/Ph ratio, CPI ～l, similar ratios of C₂₇:C₂₈:C₂₉ ααα‐steranes, medium to high proportions of rearranged steranes, C₂₉ <C₃₀‐hopane, low Ts/Tm hopanes, low sulphur content and low V/Ni ratio, suggest a reducing depositional environment for the source rock, which was likely a marine shale. All of the oil samples show thermal maturity in the early phase of oil generation. Based on hierarchical cluster analysis of 16 source‐related biomarker and isotope ratios, four genetic groups of extracts and oils were defined. The relative concentrations of marine algal/microbial input and reducing conditions decrease in the order Group 4 > Group 3 > Group 2 > Group1. Oil – source rock correlation studies show that some of the Sirte and Kalash Formations extracts correlate with oils based on specific parameters such as DBT/P versus Pr/Ph, δ¹³C_saturates versus δ¹³C_aromatics, and gammacerane/hopane versus sterane/hopane.     

中扬子宜昌地区下寒武统水井沱组页岩现场解吸气特征及地质意义

中扬子宜昌地区下寒武统水井沱组页岩具有良好的气体显示，是四川盆地外页岩气新的勘探区。通过对2口页岩气探井共64块水井沱组页岩的含气性现场解吸，测定了解吸气含量、气体组分、解吸气碳和氢稳定同位素组成，分析了解吸气组分变化、解吸过程中气态烃和二氧化碳同位素的变化，同时探讨了页岩气赋存状态、气体稳定同位素倒转特点及其地质意义。研究结果表明：水井沱组页岩现场解吸气含量为0.32~5.48 m³/t，连续含气量大于2 m³/t的地层厚44.05 m，含气性与TOC有很强的正相关性；解吸气甲烷含量为81.90%~95.48%，乙烷含量为0.78%~3.95%，含微量丙烷，为典型的干气；非烃气体中氮气含量稍高，平均约为6.7%，二氧化碳含量低于1%，不含H₂S；吸附气占50%~60%，游离气占40%~50%。解吸早期吸附性弱的CH₄和N₂先脱附出来，吸附性强的C₂H₆和CO₂后脱附出来，至解吸结束仍有相当量的C₂H₆和CO₂未脱附出来。解吸过程中碳、氢同位素均发生变化，δ¹³C_CH4变化范围为-39.92 ‰~-25.86 ‰，δ¹³C_C2H₆为-41.57 ‰~-39.34 ‰，δ¹³C_C3H₈为-40.89 ‰~-35.46 ‰，δ¹³C_CO2为-23.42 ‰~-19.23 ‰；δD_CH4为-136.90 ‰~-128.00 ‰，δD_C2H₆为-160.45 ‰~-155.30 ‰；由于同位素的质量分馏效应，解吸过程中残留的甲烷碳同位素增大了5.15 ‰~13.33 ‰，甲烷氢同位素增大1.64 ‰~8.90 ‰，乙烷碳、氢同位素和二氧化碳的碳同位素基本不变。气体碳同位素分馏还受页岩物性的影响，大的孔隙体积引起更显著的甲烷碳同位素分馏效果，同时还引起乙烷体积含量的差异。利用解吸半量体积所取气样的同位素值代表全部气体的平均值，δ¹³C_CH4平均值为-33.19 ‰，δ¹³C_C2H₆平均值为-40.04 ‰，δ¹³C_C3H₈平均值为-39.07 ‰，页岩气表现出δ¹³C_CH4 > δ¹³C_C2H₆且δ¹³C_C3H₈ > δ¹³C_C2H₆、δD_CH4 > δD_C2H₆的同位素"倒序"特征。与威远地区下寒武统筇竹寺组类似，宜昌地区水井沱组页岩气同样处于气态烃同位素反转阶段的早期，具有多源复合热成因气的特点。     

MONITORING GAS DISTRIBUTION AND ORIGIN IN THE CULZEAN FIELD,UK CENTRAL NORTH SEA,USING DATA FROM A CONTINUOUS ISOTOPE LOGGING TOOL AND ISOTUBE AND TEST SAMPLES

The high pressure – high temperature Culzean field, UK Central North Sea, contains lean gas condensate in the Triassic Joanne sandstones and the Middle Jurassic Pentland sandstones. A comprehensive gas analysis programme was installed as an integrated part of field development in order to monitor gas composition, distribution and origin in the reservoirs and overburden pre‐ production start‐up. Isotube OUT and isotube IN gas samples were collected. The isotube IN data show that some gas is recycled, including alkenes representing contamination from the degradation of mud additives; but concentrations are minor, and do not seem to affect the isotope values derived from the C₂ and C₃ isotube OUT gases significantly. ¹³C‐enriched methane derived from drill‐bit metamorphism is recorded in the isotube IN gas, but likewise in low concentrations. Gas data were also acquired from a Continuous Isotope Logging Tool (CILT) which measures real‐time gas concentrations and isotope values of C₁–C₃ each foot through the entire drilled section. The CILT thus provides a continuous trend of methane isotope values versus depth, and this trend is useful in identifying changes in gas composition. However, concerns related to CILT include: (i) C₁–C₃ stable carbon isotope detection limits for isotube OUT gas analyses are considerable lower than for CILT; due to the lower isotube gas concentrations required for measurement of C₃ isotopes, isotubes are able to map a shallower vertical thermogenic gas migration front in the overburden. (ii) Discrepancies between isotube OUT and CILT isotope values may be significant and cannot be assigned to analytical uncertainty; by contrast, test gas and isotube OUT isotope values are comparable. Hence, CILT isotope values from specific depths cannot stand in isolation but must be complemented by isotube OUT isotope measurements. Gas in the Pentland reservoir is the most coaly in composition due to self‐sourcing from the Pentland coals. The coals are the primary source rock for the gas encountered in the entire reservoir interval at Culzean, but the underlying Joanne sandstones contain contributions from highly mature marine shales in the Kimmeridge Clay Formation and/or Heather Formation. The Lower Cretaceous seal on top of the Pentland reservoir is relatively tight but some minor migration/leakage of thermogenic gas into the overburden is recorded by the detection of C₃ isotopes. Thermogenic gas also occurs in high porosity intervals in the Upper Cretaceous succession but this gas is interpreted to have migrated laterally in porous carrier beds and did not enter these intervals at the well locations.     

四川盆地东北地区下寒武统海相页岩气成因: 来自气体组分和碳同位素组成的启示

通过对四川盆地东北地区下寒武统海相页岩的现场解吸,获取气样并进行了组分和稳定碳同位素分析。结果表明,页岩气的甲烷含量介于96.39 % ~98.83 % ,其他组分含量较少;各组分相对含量随着解吸时间和累积解吸气量呈现规律性变化,该变化规律可能为泥页岩对不同气体吸附能力的差异所致。页岩气甲烷稳定碳同位素组成(δ¹³C₁)在-32.20 ‰ ~-29.50 ‰ 之间,乙烷稳定碳同位素组成(δ¹³C₂)介于-37.70 ‰ ~-36.60 ‰ ,所有气样均有δ¹³C₁>δ¹³C₂的"逆序"特点,这可能是在高成熟阶段,液态烃裂解气与早期生成的干酪根裂解气混合作用所致。随解吸时间增加,δ¹³C₁约有2.3 ‰ 的分馏,这可能与气体在解吸过程中的扩散作用有关。     

Positive carbon isotope excursions: global correlation and genesis in the Middle–Upper Ordovician in the northern Tarim Basin, Northwest China

Stable carbon isotope ratio(δ~(13) C_(carb)) analysis has been widely applied to the study of the inter-continental or global marine carbonate correlation.Large-scale Cambrian-Ordovician carbonate platforms were developed in the Tarim Basin.But research on fluctuation characteristics and global correlation of(δ~(13) C_(carb)) is still weak.Based on conodont biostratigraphy and whole-rock 8(δ~(13) C_(carb)) data in the Tahe oil-gas field of the northern Tarim Basin,the global correlation and genesis of positive carbon isotope excursions in the Darriwilian—Early Katian was examined.Three positive excursions were identified in the Tahe oil-gas field including the middle Darriwilian carbon isotope excursion(MDICE),the Guttenberg carbon isotope excursion(GICE).and a positive excursion within the Pygodus anserinus conodont zone which is named the Early Sandbian carbon isotope excursion(ESICE) in this paper.Furthermore,these positive excursions had no direct relation with sea level lluctuations.MDICE and GICE could be globally correlated.The Middle-Upper Ordovician Saergan Formation source rocks of the Kalpin outcrops were in accordance with the geological time of MDICE and ESICE.GICE had close relationship with the source rock of the Lianglitag Formation in the basin.Massive organic carbon burial was an important factor controlling the genesis of these positive excursions.     

Assessing shale gas resources of Wufeng-Longmaxi shale (O3w-S1l) in Jiaoshiba area,SE Sichuan (China) using Petromod I: Burial and thermal histories

Burial and thermal histories of Wufeng-Longmaxi shale (O_3w-S_1l) in Jiaoshiba, an important shale gas exploration target in SE Sichuan, were modeled using PetroMod software. Results of Well JY4 show the shale was buried to 2000 m in Silurian, uplifted 1000 m due to a later erosion, subsided again at Permian, and reburied to maximum depth around 6200 m at the end of Cretaceous (K3). Finally, the shale uplifted to the current depth of 2500 m. Thermal history of the shale was reconstructed based on the burial evolution after constrained by measurements. The shale entered oil-window in later Silurian and passed gas generation peak at early Triassic. Thermal maturation accelerated significantly since the Triassic and finalized its maximum maturation (2.0–2.5% Ro) at K3.     

Application of butane geochemistry of natural gas in hydrocarbon exploration

In order to distinguish the source and migration direction of natural gas by geochemical characteristics of butane,the components and carbon isotopes of natural gas from major hydrocarbonbearing basins in China were analyzed.The results showed that:(1) Oil-type gas has i-C 4 /n-C 4 <0.8,δ 13 C butane <-28‰,δ 13 C i-butane <-27‰,δ 13 C n-butane <-28.5‰,whereas coal-type gas has i-C 4 /n-C 4 >0.8,δ 13 C butane >-25.5‰,δ 13 C i-butane >-24‰,δ 13 C n-butane >-26‰.(2) When δ 13 C i-butane-δ 13 C n-butane is greater than 0,the maturity of oil-type gas is generally more than 2.4% and that of coal-type gas is greater than 1.4%,whereas when the difference is less than 0,the maturity of oil-type gas is generally less than 1.1% and that of coal-type gas is less than 0.8%.(3) When natural gas migrates through dense cap rocks,the value of i-C 4 /n-C 4 increases,whereas when it migrates laterally along a reservoir,the value of i-C 4 /n-C 4 decreases.(4) Sapropelic transition zone gas with composition and carbon isotopic signatures similar to those of oil-type gas in the low thermal evolution stage is found to have a relatively high butane content.(5) The values of i-C 4 /n-C 4 and δ 13 C n-butane δ 13 C i-butane of gas which has suffered biological degradation are significantly higher than those obtained from thermogenic and bio-thermocatalytic transition zone gas.Thus,natural gas of different genetic types can be recognized through component analysis and carbon isotopic signatures of butane,the natural gas maturity can be estimated from the difference in carbon isotopic content between isobutane and n-butane,and the migration direction of natural gas can be determined from i-C 4 /n-C 4 ratios and transport conditions,which can also be used to thermogenic and bio-thermocatalytic transition zone gas.     

KINETICS OF HYDROCARBON GAS GENERATION FROM MARINE KEROGEN AND OIL: IMPLICATIONS FOR THE ORIGIN OF NATURAL GASES IN THE HETIANHE GASFIELD, TARIM BASIN, NW CHINA

In this paper we derive kinetic parameters for the generation of gaseous hydrocarbons (C_1‐5) and methane (C₁) from closed‐system laboratory pyrolysis of selected samples of marine kerogen and oil from the SW Tarim Basin. The activation energy distributions for the generation of both C_1‐5 (Ea = 59‐72kcal, A = 1.0×10¹⁴ s^?1) and C₁ (Ea = 61‐78kcal, A = 6.06×10¹⁴ s^?1) hydrocarbons from the marine oil are narrower than those for the generation of these hydrocarbons from marine kerogen (Ea = 50‐74kcal, A = 1.0×10¹⁴ s^?1 for C_1‐5; and Ea = 48‐72kcal, A=3.9×10¹³ s^?1 for C₁, respectively). Using these kinetic parameters, both the yields and timings of C_1‐5 and C₁ hydrocarbons generated from Cambrian source rocks and from in‐reservoir cracking of oil in Ordovician strata were predicted for selected wells along a north‐south profile in the SW of the basin. Thermodynamic conditions for the cracking of oil and kerogen were modelled within the context of the geological framework. It is suggested that marine kerogen began to crack at temperatures of around 120°C (or 0.8 %Ro) and entered the gas window at 138°C (or 1.05 %Ro); whereas the marine oil began to crack at about 140 °C (or 1.1 %Ro) and entered the gas window at 158 °C (or 1.6%Ro). The main geological controls identified for gas accumulations in the Bachu Arch (Southwest Depression, SW Tarim Basin) include the remaining gas potential following Caledonian uplift; oil trapping and preservation in basal Ordovician strata; the extent of breaching of Ordovician reservoirs; and whether reservoir burial depths are sufficiently deep for oil cracking to have occurred. In the Maigaiti Slope and Southwest Depression, the timing of gas generation was later than that in the Bachu Arch, with much higher yields and generation rates, and hence better prospects for gas exploration. It appears from the gas generation kinetics that the primary source for the gases in the Hetianhe gasfield was the Southwest Depression.     

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采用模拟实验方法,考察不同温度(250～480℃)、不同压力(0.1～50MPa)下原油裂解成气的演化特征。证明了高压可以降低油裂解的反应速度,抑制原油裂解;高压条件下比低压条件下的油裂解气更接近天然气的组成。讨论了LnC     

四川盆地页岩气地球化学特征及资源潜力

页岩气是绿色低碳清洁的非常规天然气资源。我国页岩气资源丰富,加快页岩气勘探开发,对于改善中国能源结构、实现中国“2030年碳达峰、2060年碳中和”目标具有重要现实意义。四川盆地奥陶系五峰组—志留系龙马溪组是当前中国页岩气勘探开发的重点层系。通过对四川盆地威远、长宁、昭通、涪陵及威荣等地区五峰组—龙马溪组页岩气实验分析,系统分析了五峰组—龙马溪组页岩气地球化学特征,探讨了页岩气成因、碳氢同位素倒转原因及页岩气来源,展望了盆地页岩气资源勘探前景。结果表明：①五峰组—龙马溪组页岩气为典型干气,碳氢同位素均呈负序列分布,长宁、昭通与涪陵地区烷烃气碳同位素组成相对威远、威荣地区更重、具有更高热演化程度,稀有气体为典型壳源成因。②五峰组—龙马溪组页岩气为高—过成熟阶段热成因油型气,主要为原油裂解气和干酪根裂解气的混合气,烷烃气碳氢同位素倒转主要由高—过成熟阶段原油裂解气与干酪根裂解气的混合、高演化阶段地层水与甲烷交换作用等原因造成。③五峰组—龙马溪组页岩气的甲烷碳同位素值与下志留统龙马溪组泥岩干酪根碳同位素值较为匹配,符合碳同位素分馏规律δ¹³C_干酪根>δ¹³C_油>δ¹³C_烷烃气。④四川盆地海相、海陆过渡相和陆相页岩气资源总量约为41. 5×10¹² m³,资源前景广阔。     

ORGANIC GEOCHEMICAL CHARACTERIZATION AND SHALE GAS POTENTIAL OF THE PERMIAN BARREN MEASURES FORMATION,WEST BOKARO SUB‐BASIN,EASTERN INDIA

This study investigates the shale gas characteristics of the Permian Barren Measures Formation (Gondwana Supergroup) in the West Bokaro sub‐basin of the Damodar Valley Basin, eastern India. A total of 23 core shale samples collected from a borehole located in the western part of the sub‐basin were analysed using organic geochemical techniques and scanning electron microscopy. The samples are black carbonaceous shales composed chiefly of quartz, mica and clay minerals. Rock‐Eval pyrolysis data show that the analysed samples contain a mixture of Type II and Type III kerogen with TOC values of 2.7 to 6.2%. Rock‐Eval T_max values ranging from 443 to 452 °C correspond to calculated vitrinite reflectance of approximately 0.8–0.9%. A cross‐plot of hydrogen index versus T_max indicates that the samples have reached peak oil to wet gas maturities. A pristane/n‐C₁₇ versus phytane/n‐C₁₈ cross‐plot, together with biomarker parameters such as the dominance of C₂₉ over C₂₇ and C₂₈ steranes and high moretane/hopane ratios (0.22–0.51), demonstrate that the shale samples contain terrigenous organic matter deposited in a suboxic environment. Scanning electron microscopy images of shale samples show the presence of a complex, mostly intergranular pore network. Both micropores (>0.75μm) and nanopores (<0.75μm) were observed. Some pores are elongated and are associated with layer‐spaces in sheet silicate minerals; others are non‐elongated and irregular in shape. The organic geochemical parameters and the observed pore attributes suggest that the Barren Measures Formation has good shale gas potential.