Natural gas geochemistry of low evolutionary stage of medium- and small-sized basins in Yunnan Province, southwestern China

The biogenic gas and premature-low mature associated gases in some medium and small-sized basins of Yannan Province, such as Luliang, Yanglin, Baoshan and Jinggu basins, have beed researched. The results show that the biogenic-gas consists mainly of methane which is more than 99% in gasous hydrocarbons and of lighter carbon isotopic composition with δ13C1 values from -60.0‰ to - 75.4‰. The methane carbon isotopic compositions in the Baoshan Basin is relatively heavy (δ13C1 - 60‰- - 65‰), but those in Luliang and Yanglin basins are lighter (δ13C1, less than -70‰), which implies that the gas field of the Baoshan Basin formed earlier than the others. In the Jinggu Basin, where crude oil is premature-lower mature, the natural gas of associated oil relatively wet and the relative content of methane about 58%-95% in gasous hydrocarbons. Constituently the gas composition is much similar to associated one, but the methane carbon isotopic compositions from - 53.8‰ to - 57.8‰ are obviously richer in 12C than those of general oil fields and similarly characterize the biothermo-catalytic transitional zone gas. Their ethane carbon isotopic compositions from - 34.6‰ to -29.0‰ show that they may be derived from type Ⅰ or Ⅱ source rock. But for the associated gas from lower evolutionary stage, the heavier ethane carbon isotopic composition as well as the reversed order among the carbon isotopic composition of ethane, propylane and butane also implies that some gases from the type Ⅲ organic matter are mixed. The δ13CCo2 of the samples essentially less than - 10‰ may be generated from organic matter.     

A breakthrough of researching reservoir adsorption gas and its significance

GC-C-MS on linear isotope analysis equipment makes it possible to measure the hydrocarbon gases at the level of 10 -3-10 -2 μL- By applying this technique the carbon isotopes of C1-C3 of the adsorbed gas from the Triassic oil sand bed of the Aican-l Well in the Turpan-Hami basin were analysed. The δ13C values of C1-C3, are -55.1‰, -38.6‰ and -35.0‰ respectively. In terms of geochemical characteristics of natural gases and crude oils, in combination with basinal geological backgrounds, it is considered that the reservoir adsorbed gas was formed by crude-oil biodegradation, absorbed by reservoir rocks and its oil-gas source is related with the Permain (perhaps including the Carboniferous). The adsorbed gas is obviously different from the Jurassic coal-generated oil and gas.     

Kinetic study of the hydrocarbon generation from marine carbonate source rocks characterization of products of gas and liquid hydrocarbon

The kinetic parameters of hydrocarbon generation from the marine carbonate source rocks were determined and calibrated through kinetic simulating experiment. The kinetic parameters of hydrocarbon generation then were extrapolated to geological condition by using the relative software. The result shows that gaseous hydrocarbons (C_1, C_2, C_3, C_(4-5)) were generated in condition of 150℃相似文献   

Carbon and hydrogen isotopic compositions and their evolutions of gases generated by herbaceous swamp peat at different thermal maturity stages

Coalbed methane (CBM) accumulation models include continuous gas accumulation and staged gas accumulation.However,studied on the geochemical characteristics and indices to evaluate staged accumulation CBM are lacking.This study for the first time obtained the carbon and hydrogen isotopic compositions of methane and ethane generated at different evolution stages using thermal simulation of samples prepared by treating an herbaceous swamp peat at different temperatures.The results showed that the carbon isotopic compositions of methane and ethane were obviously affected by the thermal evolution level of the starting sample,while the hydrogen isotopic compositions were closely related to the maturity of gases.The carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter with Ro values from 1.2%,1.7%,2.4%,3.2% and 3.7% to 5.2% were determinated.The relationship between Ro values and the carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter at different evolution stages as well as the carbon or hydrogen isotopic relationships between methane and ethane were established.The results provide a scientific basis for studying the genesis of CBM generated at different maturity intervals and understanding the geochemical characteristics of staged accumulation CBM.These results were applied to a case study on CBM from the southern Qinshui basin,and it was found that the CBM accumulated after the Middle Jurassic and was characteristic of staged gas accumulation.This is consistent with the result of geological studies,and further showed that the results of thermal simulation experiments are very important for evaluating the genesis of natural CBM.     

Geochemical characteristics and formation process of natural gas in Kela 2 gas field

 On the basis of a large amount of natural gascomponents and the carbon isotope as well as some otheranalysis data in Kela 2 gas field, the geochemical character-istics, source, origin, and formation process of natural gashave been discussed. The components of gas in the field tendto be "dry", and the drying coefficient is close to 1.0. Thecarbon isotope tends to be heavier, for instance, the averageof δ¹³C₁ is -27.36‰ and that ofδ¹³C₂ is -18.5‰. Compre-hensive analysis shows that humic natural gas in the Kuqapetroleum system comes mainly from Triassic and Jurassicsource rocks, and the contribution of Jurassic source rocks tothe pool maybe is more than that of Triassic rocks. The maincause that the gas tends to be dry and bears heavier isotopecomposition lies in the fact that Kela 2 natural gas is the ac-cumulation of late production of humic source rocks, and itis affected by the abnormal high pressure as well. Consider-ing the hydrocarbon generating and structural history, wecan regard the gas pool formation processes as twice fillingand twice adjusting (destroying), that is, the filling anddestroying process in the early Himalayan movement and thefilling and adjusting in the late Himalayan movement.     

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.     

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.     

Geochemical characteristics and source rock of Ordovician gas reservoir, Changqing Gasfield

Carbon isotopic composition of methane in Ordovician gas reservoir in the Changqing Gasfield can reflect the dominance of Upper Paleozoic coaltype gas despite its high mature degree. The¹²C-rich ethane in the Ordovician reservoir (δ¹³C₂ < −29%), known as a marker as oiltype gas, does not indicate the Ordovician marine carbonate as main source rock, it is because of the relative less ethane content in coaltype gas than in oiltyped gas due to generation and migration. The way of Upper Paleozoic coaltype gas migrating into the Ordovician reservoir is widely through the unconformlty instead of only through the erosion groove in the weathering crust.     

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。     

Constraints on the origins of hydrocarbon gas from compositions of gases at their site of origin

It is widely accepted that natural gas is formed from thermal decomposition of both oil in reservoirs and, to a lesser extent, the organic matter in shales from which the oil was derived. But laboratory pyrolysis experiments on shales do not reproduce the methane-rich composition typical of most gas reservoirs, leading to suggestions that other mechanisms, such as transition-metal catalysis, may be important. The discrepancy might, however, instead arise because gas (and oil) deposits have migrated from their source rocks, so that the reservoir composition might not be representative of the composition in the source rocks where the hydrocarbons were generated. To address this question, we have analysed gas samples coproduced with oils directly from a source rock (the Bakken shales, North Dakota, USA) where the local geology has prevented significant hydrocarbon migration. The methane contents of these Bakken-shale gases are much lower than that of conventional gas reservoirs, but are consistent with that from pyrolysis experiments on these shales. Thus, because these Bakken gases form with (rather than from) oils, we argue that compositional differences between gases from source rocks and conventional gas deposits result from fractionation processes occurring after hydrocarbon expulsion from the source rock.     

The occurrence and significance of C25HBI in Cenozoic saline lacustrine source rocks from the Western Qaidam Basin,NW China

The saline lacustrine deposit of the Oligocene Lower Ganchaigou Formation is the main source rock for the Western Qaidam Basin,NW China.In this study,abundant highly branched isoprenoids with 25 carbon atoms (C25HBI) were detected in the upper section of the Lower Ganchaigou Formation.C25HBI is a biomarker for diatoms,and can provide information regarding biogeochemical processes during production and preservation of sedimentary organic matter.The carbon isotopic values of C25HBI in these source rocks were in the range of-18‰ to-20‰.The relative enrichment in 13C of C25HBI suggests that these isoprenoids were derived from diatom blooms.In this case,the diatoms used HCO3-as an additional carbon source to dissolved CO2 in water column due to their high biological productivity.Conversely,the diatom blooms indicated an abundant nutrient supply to the environment and high primary productivity.Thus,the occurrence of 13C-enriched C25HBI could be an ideal marker for good source rocks.The decreased concentration of CO2(aq) in the water column induced by diatom blooms can result in an enrichment in 13C of organic matter synthesized by primary producers.This may be a possible reason for the occurrence of 13C-enriched organic matter in the Cenozoic source rocks of the Western Qaidam Basin.Previous studies have shown that the high carbon number n-alkanes sourced from diatoms have no carbon preference.Hence,the sources of n-alkanes in regional source rocks are complex,and should be considered when discussing the sources of organic matter in future studies.     

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 specific carbon isotopic compositions of branched and cyclic hydrocarbons from Fushun oil shale

Various branched and cyclic hydrocarbons are isolated from the Fushun oil shale and their carbon isotopes are determined. The analytical results show that the branched and cyclic hydrocarbons are fully separated from n-alkanes by 5 A molecular-sieve adduction using long time and cold solvent. The branched and cyclic hydrocarbon fraction obtained by this method is able to satisfy the analytic requests of GC-IRMS. The carbon isotopic compositions of these branched and cyclic hydrocarbons obtained from the sample indicate that they are derived from photoautotrophic algae, chemoautotrophic bacteria (-33.4‰— -39.0‰) and methanotrophic bacteria (-38.4‰— -46.3‰). However the long-chain 2-methyl-branched alkanes indicate that their carbon isotopic compositions reflect biological origin from higher plants. The carbon isotopic composition of C30 4-methyl sterane (-22.1‰) is the heaviest in all studied steranes, showing that the carbon source or growth condition for its precursor, dinoflageilate, may be different from that of regular steranes. The variation trend of δ^13C ValUes between isomers of hopanes shows that ^13C-enriched precursors take precedence in process of their epimerization. Methanotrophic hopanes presented reveal the processes of strong transformation of organic matter and cycling of organic carbon in the water column and early diagenesis of oil shale.     

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.     

油气组分及同位素组成特征在莺琼盆地油气二次运移研究中的应用

油气不同组分的物理化学特性差异及地层中岩石、矿物选择性吸附造成的色层效应使油气在运移过程中其组分和同位素组成发生一定的变化 ,这为利用油气地化特征探讨油气运移提供了理论基础。利用该原理对莺琼盆地崖 13 1气藏天然气甲烷δ13C1值及凝析油族组分 (烷烃、芳烃、胶质 )、C6化合物 (正构烷烃、异构烷烃、环烷烃、芳烃 )等的相对含量和碳同位素组成进行了研究。结果表明 ,该气藏中天然气甲烷及凝析油族组分的δ13C1值由西到东呈现逐渐变轻的趋势 ;凝析油中极性相对弱的组分含量逐渐增加 ,极性相对强的组分含量逐渐降低。这表明崖13 1气藏中的油气应主要来自一号断层西侧的莺歌海盆地 ,其运移方向是由西以东。对莺琼盆地东方 1 1气藏天然气甲烷δ13C1值的研究表明 ,该气藏主要是由下覆烃源岩生成的天然气向上运移到浅层形成的 ,气藏中大部分天然气的垂向运移距离在 2km以上     

Kinetics of early methane generation from Green River shale

During oil/gas exploration in an area, there is a question as to whether methane in the strata was generatedin situ mainly by thermal degradation of local organic matter. The key to the question is whether the kerogen could produce methane of more than 80 mL/g TOC, when its R_o increased from initial (0.36%) to current value of 0.70% during thermal evolution. The authors have made efforts to answer this question by the kinetics method. First, a series of pyrolysis experiments were carried out to obtain data of methane yield and R_o evolution, from which kinetic parameters of methane and R_o were derived; then these parameters were extrapolated to the geological condition and finally, a methane yield, 96 mL/g TOC, was predicted. The result suggests that from the view of hydrocarbon generation, methane in the seam should be from thermal degradation of local kerogen.     

Vegetation evolution on the central Chinese Loess Plateau since late Quaternary evidenced by elemental carbon isotopic composition

There are many controversial issues in loess studies such as natural vegetation types on the Chinese Loess Plateau during the historical periods and the spatial and temporal evolution of C3/C4 plants. Elemental carbon isotopic composition （δ^13Cec） in the loess section may offer new evidence for these problems. Elemental carbon （EC） is produced by incomplete combustion of vegetation, and its carbon isotopic composition has a very small difference from that of the formal vegetation, then δ^13Cec can be used as a record to recover the changes of vegetation. Elemental carbon was extracted by applying the oxidation method from the Ioess-paleosol sequence in the central Chinese Loess Plateau, and its car- bon isotope composition was analyzed by the isotope mass spectrometer. The results showed that the vegetation in this region was a mixed type of C3 and C4 plants, dominated with C3 plants in most of the time. Since late Quaternary, C3/C4 plants may not follow a simple glacial-interglacial cycle mode on the Chinese Loess Plateau, but showing fluctuations. C3 plants increased gradually in L4 period, and more C3 plants occurred during $3 period, and C4 plants increased again during L3-- L2 periods, after that, Cs plants dominated again during S1 --S0 periods. During periods of paleosol development, C3 plants were abundant in S3 and S1, and there were more Ca plants in S2 and SO. During periods of loess sedimen- tation, there were more C3 plants in L4 and L1, and there were more C4 plants in L3 and L2. On the orbital timescale, the vegetation variations revealed by δ^13Cec record are consistent with the results of pollen data and also similar to the results obtained by organic carbon isotopic composition since the last glacial period.     

Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs

Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons.     

准噶尔盆地乌伦古地区石炭系油气源特征及潜力探讨

目前研究认为乌伦古坳陷油气主要来自石炭系烃源岩的贡献,根据原油产状、原油物性、轻烃指纹、生物标志化合物特征及天然气组分、同位素特征,将乌伦古坳陷原油划分为I、II两类,天然气划分为A、B两类,彼此之间存在显著的差异。通过油源对比,及两类油气饱和烃、生物标志化合物以及碳同位素特征,表明I类原油生物标志物与滴水泉组具有较强的相似性,主要来自下石炭统滴水泉组,II类原油主要来自上石炭统巴塔玛依内山组。气源分析结果表明,A类天然气产自于上石炭统巴塔玛依内山组烃源岩,B类天然气来自于下石炭统姜巴斯套组烃源岩。     

Variations of organic carbon isotopic composition and its environmental significance during the last glacial on western Chinese Loess Plateau

The last glacial period is characterized by a cold and dry climate with low atmospheric CO2 concentration. The relatively arid climate and low CO2 concentration are favorable to the growth of C4 plants, but the low temperature limits the development of th…