松辽盆地南部浅层天然气地球化学特征及其成因分析

由于松辽盆地南部浅层天然气成因研究比较薄弱,通过采集伏龙泉地区泉头组天然气样品,对天然气组分、碳同位素、轻烃组分进行了分析。结果表明该地区天然气有油型气和生物降解气2种成因。第一类天然气甲烷碳同位素值在-35‰左右,甲烷及其同系物碳同位素呈正碳分布;甲基环己烷指数在20%左右、环己烷指数略高于10%,符合油型气的特征。由甲烷碳同位素计算的R₀值,以及轻烃中的庚烷值和异庚烷值均在高-过成熟的范围,因此是高成熟的油型气。第二类天然气甲烷碳同位素偏轻,丙烷碳同位素偏重;轻烃色谱图中以环烷烃为主峰,轻烃内组成中支链烷烃和环烷烃含量高,各项轻烃参数(甲基环己烷指数、庚烷值、K1值等)都在较大范围内波动,为生物降解气。这一研究对于今后该区天然气勘探与资源评价及其成藏机理研究具有重要意义。     

四川八角场油气田大安寨组凝析气藏的地质-地球化学研究

本文在综合论述大安寨组凝析气藏地质特征的基础上,讨论了储层高度致密化的原因,并根据凝析油轻烃C_4—C_7的族组成、庚烷值与异庚烷值、轻烃指纹化合物对比,结合天然气碳同位素资料,分析了本组气藏的气源及其受外源影响的可能性。认为,油气不仅来自本组的源岩,而且有其深部香溪群油气的明显混入。此外,本文还初步分析了某些气井在开采过程中,凝析油轻烃含量与组成的变化。     

渤海湾盆地渤中19- 6凝析气田凝析油成熟度判定及成因意义

关于渤海湾盆地渤中19- 6凝析气田凝析油成熟度存在成熟与高成熟两种截然不同观点,尚未达到统一定论。本文综合利用轻烃、饱和烃和芳烃成熟度参数对凝析油成熟度进行了综合判定,并深入分析了凝析油和天然气的成因关系及凝析气藏形成机制。结果表明：异庚烷值与庚烷值、Ts/（Ts+Tm）与C29Ts/（C29Ts+C29H）、甲基单金刚烷指数与甲基双金刚烷指数、甲基菲指数、二苯并噻吩类成熟度参数和TNR2显示渤中19- 6凝析气田凝析油处于成熟阶段。结合天然气成熟度和储层流体包裹体特征,可知渤中19- 6凝析气田的原油成藏期早于天然气,随着晚期大量天然气的充注,油气会发生相控混溶作用形成含液态烃的气流体,当温度和压力达到混溶后烃类体系的露点以上,则形成凝析气藏。     

煤成气轻烃地球化学特征及其影响因素——以四川盆地须家河组为例

轻烃在天然气中含量虽低,但因其含有丰富的地球化学信息,在天然气成因等研究方面引起了关注。作者以四川盆地须家河组煤成气和雷三段油型气为例,采用GC和GC-IR-MS技术对煤成气轻烃的地球化学分布特征及其影响因素进行了系统分析。煤成气C₇轻烃组成具有甲基环己烷分布优势,在甲基环己烷、正庚烷和二甲基环戊烷相对组成中,甲基环己烷含量最高,分布在48%~73%,平均为63.9%,煤成气轻烃单体烃碳同位素重,δ¹³C分布在-25.1‰~-20.0‰之间,大部分分布在-23.0‰~-21.0‰。轻烃的分布受到多种因素影响,天然气成熟度对轻烃中芳烃含量变化影响复杂,在成熟和高成熟阶段,天然气轻烃中芳烃含量低,成熟度对芳烃的含量影响较小,而在过成熟阶段,芳烃含量高,成熟度对芳烃含量影响大。通过凝析油和天然气轻烃组成对比,蒸发分馏作用对热演化参数Ctemp和庚烷值、甲苯/正庚烷等影响较大,但对成因类型参数如(2-MH+2,3-DMP)/C₇与(3-MH+2,4-DMP)/C₇,P2/C₇与N2/P3,正庚烷、甲基环己烷和二甲基环戊烷相对含量关系等影响小。天然气成因类型对轻烃Mango参数K1值、正庚烷、甲基环己烷和二甲基环戊烷相对含量关系以及轻烃单体烃碳同位素影响大,因此,可以利用这些参数进行天然气成因类型判识。     

轻烃指纹分析及其应用

轻烃指纹分析包括对天然气、原油以及岩石轻烃的分析.利用轻烃分析技术获得的指纹特征参数,不仅可以反映油气的成因类型、演化程度,用于气-油-源岩的对比,而且还可用于同源油气形成后经水洗、生物降解、热蚀变等的影响而造成的细微化学差异的判别,反映油气的保存条件.在对天然气和原油轻烃分析先进技术进行概述的基础上,着重论述了岩石轻烃低沸点溶剂密封快速抽提分析技术,并对轻烃指纹分析方法的应用发展作了探讨.     

渤中19-6潜山构造带凝析油中轻烃地球化学特征及意义

为了明确渤海湾盆地渤中19-6大气田的地化特征和成因,选取研究区潜山凝析气藏7个凝析油样品进行全油色谱分析,剖析其轻烃组成特征,探讨轻烃参数在该区的地质应用.结果表明:渤中19-6凝析油的Mango轻烃参数K₁和K₂值相对稳定,表明研究区原油成因类型基本一致.C₆~C₈组成中正构烷烃具显著优势,甲基环己烷指数平均为39%;庚烷值与异庚烷值,正庚烷/甲基环己烷（F）比值较高,反映它们较高成熟度;轻烃参数计算原油生成温度为125.8~128.1 ℃,其相对偏低,可能与取样过程中凝析油的相态变化有关;2-甲基戊烷/3-甲基戊烷,2-甲基己烷/3-甲基己烷比值高,K₂值低;凝析油正构烷烃摩尔浓度呈三段式分布,甲苯/正庚烷和原油蜡含量随深度而增加.结合饱和烃参数以及金刚烷参数揭示渤中19-6潜山油气为湖相腐泥Ⅱ₁型母质在高成熟阶段（Ro=1.05%~1.30%）的产物,气藏形成后发生一定程度分馏造成油气组分调整.      

陆域冻土区天然气水合物地球化学勘查中顶空气轻烃应用模式试验

为探索顶空气轻烃技术在陆域冻土区天然气水合物地球化学勘查中的应用,选择祁连山木里已知天然气水合物矿区和哈拉湖未知区作为方法技术的试验区.试验指标包括土壤顶空气、土壤酸解烃、岩芯顶空气轻烃测井、甲烷碳同位素.研究表明:祁连山木里已知天然气水合物矿藏上方,土壤顶空气轻烃组分以甲烷为主,甲烷所占比例非常高,90.6％的样品C1含量都在78％以上,甲烷含量显著高于常规油气盆地;未发现天然气水合物的哈拉湖试验区,无明显的土壤顶空气轻烃异常现象.顶空气轻烃异常模式为:平面上,矿藏上方近地表土壤中存在明显的顶空气甲烷强异常;剖面上,在天然气水合物稳定带上方呈现"前缘晕"异常特征;其空间分布与祁连山水合物矿藏展布空间具有套合关系.甲烷碳同位素和烃类组成判断地表油气化探异常为热解成因,与祁连山冻土区天然气水合物的气体为同一成因来源.陆域冻土区天然气水合物顶空气轻烃地球化学勘查技术试验结果表明:顶空气轻烃地球化学方法既可以判断水合物成因类型,也可以圈出水合物矿藏范围.     

生物降解作用对大宛齐油田库车组原油轻烃参数的影响

塔里木盆地大宛齐油田的部分原油经受了不同程度的微生物降解作用,通过对该油田原油中轻烃分布特征的研究, 能更深入地认识微生物降解作用对轻烃的影响。结果表明,微生物优先消耗正构烷烃,其次为异构烷烃和环烷烃;从而导致 C6、C7轻烃三角图发生相应变化。在大宛齐原油中,随微生物降解程度的增加,正庚烷值和异庚烷值逐渐减小;当庚烷值 为0~21,异庚烷值为0~2.6时,为“微生物降解”原油。微生物降解作用亦能使苯/正己烷、甲苯/正庚烷两个比值增大,而 使正庚烷/甲基环己烷比值减小;基于甲苯/正庚烷、正庚烷/甲基环己烷两个比值建立的判别次生蚀变作用的模板,当原油 处于轻微微生物降解作用时,该模板易与蒸发分馏趋势混淆,需谨慎使用。     

准噶尔盆地南缘煤成油的地球化学特征

齐古油田的原油来源于准噶尔盆地南缘中、下侏罗统的煤系地层.具有饱和烃与芳烃含量高,Pr/Ph>2.5的特征.原油与母岩的碳同位素组成有较好的一致性,都富集重组分.色质分析结果表明,离子特征峰具有典型陆源高等植物输入的标志.泥岩有机质的显微富氢组分占20%以上,它们富集于河流三角洲和水下冲积扇等地.在弱还原-还原环境的低演化阶段形成天然气,也能形成石油,在该盆地沿边缘呈带状分布。     

鄂尔多斯盆地伊陕斜坡中南部高热演化地区古生界天然气地球化学研究

苏里格南部和高桥高热演化地区古生界天然气具有乙烷等重烃组分含量低,大多数样品的湿气系数小于2%,天然气甲烷碳同位素组成显著偏重,乙烷等重烃组分碳同位素组成变化大等特征。热演化程度更高、甲烷碳同位素更重、湿气系数更低的东南部地区,古生界天然气均显示乙烷等重烃组分碳同位素异常偏轻、碳同位素倒转的特征。通常,当乙烷等重烃组分含量极低的高演化天然气混入少量乙烷等重烃组分含量高、碳同位素组成显著偏轻的天然气就可形成天然气的乙烷等重烃组分碳同位素异常偏轻、碳同位素倒转。早白垩世末盆地抬升阶段初期古地温降至相当于高-过成熟阶段的温度区间时,气源岩和储层中残余的少量液态烃的热裂解生成的天然气混入导致了乙烷等重烃组分碳同位素异常偏轻与碳同位素的倒转。因此,应以甲烷碳同位素组成作为主要指标、乙烷等重烃组分碳同位素组成作为参考指标,结合成藏地质条件进行高演化天然气的成因判识。提出了研究区古生界天然气以煤成气为主,并有一定数量油型气混入的认识。     

Low-temperature gas from marine shales: wet gas to dry gas over experimental time

Marine shales exhibit unusual behavior at low temperatures under anoxic gas flow. They generate catalytic gas 300° below thermal cracking temperatures, discontinuously in aperiodic episodes, and lose these properties on exposure to trace amounts of oxygen. Here we report a surprising reversal in hydrocarbon generation. Heavy hydrocarbons are formed before light hydrocarbons resulting in wet gas at the onset of generation grading to dryer gas over time. The effect is moderate under gas flow and substantial in closed reactions. In sequential closed reactions at 100°C, gas from a Cretaceous Mowry shale progresses from predominately heavy hydrocarbons (66% C₅, 2% C₁) to predominantly light hydrocarbons (56% C₁, 8% C₅), the opposite of that expected from desorption of preexisting hydrocarbons. Differences in catalyst substrate composition explain these dynamics. Gas flow should carry heavier hydrocarbons to catalytic sites, in contrast to static conditions where catalytic sites are limited to in-place hydrocarbons. In-place hydrocarbons and their products should become lighter with conversion thus generating lighter hydrocarbon over time, consistent with our experimental results.     

Origin and Source of Deep Natural Gas in Nanpu sag,Bohai Bay Basin,China

Natural gas exploration in Nanpu sag, Bohai Bay Basin, has achieved breakthroughs in recent years, and a number of natural gas and condensate wells with high yield have been found in several structures in the beach area. Daily gas production of single wells is up to 170,000 m3, and high-yield wells are mainly distributed in?the Nanpu No. 1 structural belt.?Studies have shown that these natural gases are mainly hydrocarbon gases, with methane content about 80% to 90% and ethane 6%-9%, so they are mainly wet gas; and non-hydrocarbons are at a low level.?Carbon isotopes of methane range from -42‰ to -36‰, and ethane from -28‰ to -26‰. Calculated maturity based on the relationship between δ13C and Ro of natural gas, the gases are equivalent to those generated from organic matter when Ro is 1.0%-1.7% (mainly 1.25%-1.32%). The natural gas is oil-type gas generated from the source rocks at mature to high mature stage, associated with condensate, so carbon isotopes of the gases are heavier. Natural gas in the Nanpu No.1 structural belt is mainly associated gas with condensate. The analysis of the origin and source of natural gas and condensate, combined with the monomer hydrocarbon carbon isotopes and biomarker, indicated that the main source rocks in the Nanpu No.1 structural belt were Es3 (the lower member of the Shahejie Formation), followed by Es1 (the upper member of the Shahejie Formation).?The high-mature hydrocarbons from source rocks in the deep sag mainly migrated through deep inherited faults into shallow traps and accumulated to form oil and gas pools. Therefore, there is a great potential for exploring gas in deep layers.     

Composition of Volatile Components in Mineral-Hosted Fluid Inclusions at Hydrothermal Deposits. Water–Rock–Gas Systems in Ore-Forming Processes

The paper presents data on the average analyzed concentrations of volatile components (CO₂, CH₄ and other hydrocarbons, N₂, and H₂S) in natural fluids producing hydrothermal Au, Sn, W, Mo, Cu, Pb, and Zn mineral deposits. Characteristics of the gas regime at these deposits are determined. Thermodynamic simulations are carried out to model how compounds with volatile components are formed when water interacts with silicic and mafic rocks within wide P–T ranges. The speciation of volatile components determined by direct analysis is in good agreement with numerical simulations of water–rock systems (for silicic and mafic rocks). More reduced species with volatile components are formed in mafic rocks.     

Stable carbon isotopes of alkane gases from the Xujiahe coal measures and implication for gas-source correlation in the Sichuan Basin,SW China

The Upper Triassic Xujiahe Formation in the Sichuan Basin, SW China consists of a series of coal measures. The first, third and fifth members of this formation are dominated by gas prone dark mudstones and coals. The mudstones contain Type II and III kerogens with average organic carbon contents around 1.96%. These source rocks are mature in the central Sichuan and highly mature in the western Sichuan Basin, characterized by gas generation with subordinate amounts of light oil or condensate oils. The source rocks are intercalated with the sandstone dominated second, fourth and sixth members of the Xujiahe Formation, thus leading to three separate self contained petroleum systems in the region. The proven gas reserves in the Xujiahe Formation are only less than that of the Triassic Feixianguan Formation and the Xujiahe Formation has the second largest gas field (Guang’an gas field) in the basin. Gases derived from the Xujiahe Formation coals generally show a normal stable carbon isotopic trend for C₁–C₄ n-alkanes, with the highest δ¹³C₂ values among the nine gas pay zones in the basin (?20.7‰ to ?28.3‰), and δ¹³C₁ values as low as ?43.0‰ in the central Sichuan. Gas accumulations with an oil leg have also been found in the eastern and southern Sichuan where the thickness of the Xujiahe Formation is significantly reduced. Gases in these accumulations tend to show low δ¹³C₂ values (?30.0‰ to ?36.3‰), characteristic of oil prone source rocks.     

Bitumen from Coalport tar tunnel

The Coalport (Shropshire, U.K.) Tar Tunnel bitumen has been known since 1787 and the first geochemical data are reported here. The bitumen was analyzed for molecular markers useful for correlational studies. Gas chromatographic analysis of aliphatic and aromatic hydrocarbons failed to detect any specific major components normally used for genetic correlational and maturational studies. A search for minor and trace components by gas chromatographic-mass fragmentographic analysis showed the presence of triterpenoid hydrocarbons primarily of the 17α (H)-hopane series (C₂₇ to C₃₅, ex. C₂₈) and a C₂₆ to C₃₁ series of ring A/B demethylated hopanes. Two homologous sterane series (C₂₇ to C₂₉) of the 5α, 14β, 17β (H)-sterane and 13β, 17α (H)-diasterane type were also detected. Pophyrins of the DPEP and etio series (C₂₇ to C₄₁, DPEP/etio > 1) were also found. Characterization of their alkyl substitution pattern demonstrated C₁, C₂ and C₃ substituents on the pyrole moieties of the parent petroporphyrins.The molecular markers detected in this bitumen indicate its biogenic origin and show evidence of diagenetic and geothermal maturation processes. The overall geochemical characteristics of the Coalport Tar Tunnel bitumen suggest that it corresponds to a well matured crude oil, which was heavily altered by in-reservoir biodegradation or close to surface exposure.     

Laboratory methods for evaluating migrated high molecular weight hydrocarbons in marine sediments at naturally occurring oil seeps

A laboratory study has been conducted to determine the best methods for the detection of C₁₀–C₄₀ hydrocarbons at naturally occurring oil seeps in marine sediments. The results indicate that a commercially available method using n-C₆ to extract sediments and gas chromatography–flame ionization detection (GC–FID) to screen the resulting extract is effective at recognizing the presence of migrated hydrocarbons at concentrations from 50 to 5000 ppm. When non-biodegraded, the amount of oil charge is effectively tracked by the sum of n-alkanes in the gas chromatogram. However, once the charge oil becomes biodegraded, with the loss of n-alkanes and isoprenoids, the amount of oil is tracked by the quantification of the unresolved complex mixture (UCM). Gas chromatography–mass spectrometry (GC–MS) was also found to be very effective for the recognition of petroleum related hydrocarbons and results indicate that GC–MS would be a very effective tool for screening samples at concentrations below 50 ppm oil charge.     

Determination of isotope ratios in the natural gas components CH4 and N2 separated by gas chromatography

To determine stable-isotope ratios of natural gas components a system is constructed to separate CH₄ and N₂ from milliliter quantities of natural gas by gas chromatography. Having passed through the separation column and a catharometer detector the gas flow is distributed consecutively into two lines, one in which N₂ is trapped in a helium cryostat at 4.2 K and one in which CH₄ is immediately combusted by CuO to CO₂ and H₂O which are trapped separately.The δ ²H-, δ ¹³C- and δ ¹⁵N-values are determined by conventional isotope mass spectrometry.     

Microbial alteration of natural gas in Xinglongtai field of the Bohai Bay Basin, China

Xinglongtai field has been an important petroleum-producing area of Liaohe Depression for 30 years. Oil exploration and production were the focus of this field, but the gas was ignored. This study examined twenty five gas samples with the purpose of determining the gas genetic types and their geochemical characteristics. Molecular components, stable carbon isotopic compositions and light hydrocarbons were also measured, and they proved that microbial activity has attacked some of the gas components which resulted in unusual carbon isotopic distributions. Propane seems to be selectively attacked during the initial stage of microbial alteration, with abnormally lower con-tent compared to that of butane as well as anomalously heavy carbon isotope. As a consequence, the carbon isotopic distribution among the gas components is partially reverse, as δ13C1<δ13C2<δ13C3>δ13C4. Besides, n-alkanes of C3+ gas components are preferentially attacked during the process of microbial alteration. This is manifested that n-alkanes are more enriched in 13C than corresponding iso-alkanes. As a result, the concentrations of n-alkanes be-come very low, which may be misleading in indentifying the gas genetic types. As to four gas samples, light hydro-carbon compositions display evidence for microbial alteration. The sequence of hexane isomers varies obviously with high content of 2,3-DMC4, which indicates that they have been in the fourth level of extensively bacterial al-teration. So the geochemical characteristics can be affected by microbial alteration, and recognition of microbial alteration in gas accumulations is very important for interpreting the natural gas genetic types.     

辽河盆地烃类气体组分及同位素组成

辽河盆地是一新生代断陷盆地,盆地内天然气资源丰富,天然气成因复杂.本文通过对该盆地80个天然气样中烃类气体组分组成及同位素组成的分析研究,探讨了该盆地烃类气体的成因,为盆地天然气勘探提供了地球化学方面的信息.     

Geochemical characterization of adsorbed light gaseous alkanes in near surface soils of the eastern Ganga basin for hydrocarbon prospecting

This study aims to assess the hydrocarbon potential of Ganga basin utilizing the near surface geochemical prospecting techniques. It is based on the concept that the light gaseous hydrocarbons from the oil and gas reservoirs reach the surface through micro seepage, gets adsorbed to soil matrix and leave their signatures in soils and sediments, which can be quantified. The study showed an increased occurrence of methane (C₁), ethane (C₂) and propane (C₃) in the soil samples. The concentrations of light gaseous hydrocarbons determined by Gas Chromatograph ranged (in ppb) as follows, C₁: 0–519, C₂: 0–7 and C₃: 0–2. The carbon isotopic (VPDB) values of methane varied between ?52.2 to ?27.1‰, indicating thermogenic origin of the desorbed hydrocarbons. High concentrations of hydrocarbon were found to be characteristic of the Muzaffarpur region and the Gandak depression in the basin, signifying the migration of light hydrocarbon gases from subsurface to the surface and the area’s potential for hydrocarbon resources.