新场地区上三叠统须五段陆相页岩层系非常规天然气特征与成因

除下古生界海相页岩具有页岩气开采的价值外,四川盆地陆相领域页岩层序也非常发育;其中川西坳陷须五段获得突破,但其非常规天然气地球化学特征十分复杂、成因类型多样,开展非常规天然气特征和成因的研究对于有效的认识四川盆地陆相页岩的勘探开发前景具有重要意义。在对川西坳陷上三叠统须五段陆相页岩层序天然气组分和同位素特征分析的基础上,结合该区实际地质条件的分析,研究了天然气的成因类型、天然气成熟度和天然气的赋存状态。结果表明:须五段天然气主要为烃类气体,甲烷含量、干燥系数变化大;但平均值较低,烷烃同位素具有δ13C1δ13C2δ13C3δ13C4的正常序列分布特点;但甲烷碳同位素值(δ13C1)变化大,在-44.4‰~-27.1‰之间;乙烷碳同位素值明显偏轻,介于-28.1‰~-22.9‰之间。须五段天然气为典型煤型气,具有成熟-中等成熟阶段热成因气的特征;天然气为吸附气与游离气的混合气体,但以吸附气为主,在生产过程中,由于同位素的分馏效应,导致天然气甲烷碳同位素偏重。     

鄂尔多斯盆地延长探区页岩气

通过对中生界页岩气、中生界浅层气、上古生界天然气和周边盆地的生物成因气等多种成因气的地球化学特征(包括组分和碳同位素)对比,探讨鄂尔多斯盆地中生界页岩气的成因.鄂尔多斯盆地中生界页岩气甲烷体积分数为46.08%~94.56%,重烃体积分数为2.86%~37.61%,甲烷碳同位素为-52.0‰~-46.4‰.通过天然气组分及碳同位素对比分析,确定鄂尔多斯盆地延长组页岩气的成因既不是来自上古生界煤型气,也不是生物成因气,而是和盆地浅层气地球化学特征相似,属于偏腐泥型源岩热解形成的原油伴生气,源岩为延长组腐泥型烃源岩.考虑到热演化成熟度特征,认为吴旗—庆阳—富县一带中生界烃源岩热演化程度高,为页岩气勘探有利区.     

伊陕斜坡东南部延长组页岩气地球化学特征分析

鄂尔多斯盆地陆相页岩气勘探潜力巨大,但对于陆相页岩气成因类型的研究相对滞后,限制了对页岩气的进一步勘探和开发。通过综合化学组分分析和碳、氢同位素分析的手段对伊陕斜坡东南部延长组页岩气和原油伴生气的地球化学特征及成因进行研究。研究结果表明延长组页岩气(生产气和真空解吸气)和原油伴生气都以烷烃类气体为主,其中甲烷含量都小于95%,非烃气体含量比较低。页岩解吸气中,非烃气体比例相对较高,且氧气含量异常高,这与解吸装置密封性不好或者装置本身残留空气清除不彻底有关。页岩气和原油伴生气的甲烷含量低、干燥系数(C_1/C_(1~5))主要集中在0.6~0.9之间、C_2/C_3都小于3,δ~(13)C_1值分布于-52.0‰~-44.9‰之间、δ~(13)C_2值都小于-29‰,δ~(13)C_3值都小于-25.5‰和δD_1都小于-150‰,指示研究区页岩气和原油伴生气以陆相环境热成因的热解湿气(油型气)为主。页岩气和原油伴生气样品有相对高的正庚烷含量和正构烷烃(nC_(5-7))含量,δ~(13)C_2值分布于-41.1‰~-31.1‰之间,说明延长组页岩气与原油伴生气都属于偏腐泥型天然气。此外,延长组页岩气和原油伴生气碳同位素系列基本都属正碳同位素系列,且δ~(13)C_1与δ~(13)C_2值,δ~(13)C_2值与δ~(13)C_3值有较好的正相关关系,这也表明页岩气和原油伴生气具有相同或相似的母质来源。     

鄂尔多斯盆地富县地区天然气地球化学特征及其成因

在对鄂尔多斯盆地富县地区奥陶系天然气地球化学特征研究的基础上,将其组分、烷烃气碳同位素、氦同位素、氩同位素等与盆地中部主要气田进行了对比,并结合区域地质背景综合分析了天然气的成因类型.指出该地区奥陶系天然气具有"干燥系数大、二氧化碳含量高、烷烃气碳同位素组成轻、热演化程度高"的特点,与靖边气田奥陶系天然气地球化学特征非常接近.应用国内学者建立的甲烷碳同位素与镜质体反射率关系方程式计算了富县地区奥陶系天然气的Ro约为3.33%,处于过成熟演化阶段.利用天然气成因判别图版综合分析,认为富县地区奥陶系天然气为油型气和煤成气的混合气体,且以油型气为主.     

松南营城组火山岩气藏成藏模式

松南气田营城组火山岩天然气的δ13C1值大于-30‰,具有δ13C1＞δ13C2＞δ13C3负序列或同位素倒转,甲烷同位素偏重,表明松南气田营城组火山岩天然气不仅具有煤型气与油型气混合特性,还具有多期次成藏特征,煤型气充注早,为89～83 Ma;油型气和幔源气充注晚,为78～68 Ma.松南气田营城组天然气中无机气体主...     

低成熟海相黑色页岩生烃特征的热模拟实验

页岩气是黑色富有机质页岩生烃演化完成后滞留在页岩中的烃类气体,为了查明海相黑色页岩生排烃过程中产物的变化规律及影响因素,揭示海相富有机质页岩的生烃潜力,采用地层孔隙热压生烃模拟仪对四川盆地广元地区上寺剖面大隆组黑色页岩进行热压模拟实验.结果表明:①黑色页岩具有极高的生烃潜力,最高产烃量达452.43 mg/gTOC(总有机碳),其中气态烃总产率195.45 mL/gTOC,液态烃最高产率为377.8 mg/gTOC;②油的产率随热模拟温度升高表现为先升后降的特征,生油演化成峰型尖锐的单峰特征,生油高峰在360℃,甲烷随成熟度升高而增加,而重烃气C2-5则表现为先升后降的特征,甲烷主要由油裂解形成,其次是干酪根热解和重烃气裂解;③气态烷烃呈现δ13 C1<δ13 C2<δ13 C3<δ13 C4,且随热模拟温度增加,气态烃的碳同位素值均表现为逐渐富集13 C,说明了热模拟过程中只发生了碳同位素的动力学分馏.基于本次热模拟产物产率随热成熟度变化特征,建立了黑色富有机质页岩的生烃模式,分为两个主要阶段:热催化生油气阶段和热裂解生湿气阶段,特别是在很高热模拟温度下仍未进入生干气阶段,表明在过成熟阶段黑色页岩仍具有一定的生烃潜力.研究结果对拓展高过成熟页岩气勘探领域具有较好的参考意义.     

四川盆地高石梯—磨溪地区震旦系—寒武系天然气的地球化学特征及成因

根据天然气组分、稳定碳同位素和氢同位素等地球化学资料,对四川盆地高石梯—磨溪气田震旦系—寒武系天然气地球化学特征进行分析。结果表明:1震旦系、寒武系天然气均以甲烷为主,重烃含量偏低而非烃含量较高,为典型的干气;2研究区天然气热演化程度较高,震旦系天然气中部分乙烷发生裂解,导致残余天然气的δ13C2变重;3研究区天然气以正碳同位素序列为主,仅部分寒武系天然气的碳同位素序列发生局部倒转,可能是高热演化阶段下同源不同期气或同型不同源气混合所致;4氢同位素显示,震旦系沉积环境的水介质盐度高于寒武系,且震旦系天然气为震旦系烃源岩和寒武系烃源岩的混源气,而寒武系天然气母质来源为寒武系烃源岩。     

元坝地区雷口坡组气源与碳同位素倒转成因

探讨四川盆地元坝地区雷口坡组气源与碳同位素倒转成因.通过雷口坡组烃源岩与天然气地化参数分析,其烃源岩以泥晶灰岩、含泥灰岩为主,TOC质量分数平均为0.37％,生烃能力较差.天然气中非烃气的体积分数多数＜10％,烷烃气组分较干,CH4相对体积分数平均为99.0％,碳同位素较轻,其中δ13C1均值为-34.19‰,δ13 C2均值为-33.31‰,且多数样品发生δ13C1,δ13C2倒转;甲烷氧同位素较轻,均值为-156.3‰.与相邻层位烷烃气对比并结合烃源背景,综合分析认为其气源主要为须家河组媒型气,其甲烷、乙烷碳同位素倒转为水溶分馏作用导致气层中乙烷变轻程度超过甲烷一定幅度引起.     

川东飞仙关组烷烃气碳同位素特征与成因分析

飞仙关组作为川东主力气层,陆续已经发现了普光、毛坝、东岳寨、渡口河等一系列大中型气藏,展示了极其重要的战略地位。目前常规的组成分析方法已经不能满足该层天然气类型及成因的判别要求。通过分析烷烃气碳同位素特征,判识天然气类型、分析其成因机制。实验分析显示部分样品C_1~C_3烷烃气的碳同位素比值呈δ~(13)C_1δ~(13)C_2δ~(13)C_3分布(倒转),显示为多源、多期天然气混入。同时根据C_1/C_2+C_3与δ~(13)C_1及ln(C_1/C_2)与In(C_2/C_3)的值域变化特征,最终判断川东大多气藏以原油裂解气为主,混入一定的煤型气。川东飞仙关组古油藏于晚侏罗世沉积期,其埋藏深度介于5 300~8 200 m之间,油藏温度普遍超过150℃,油发生热裂解,生成烷烃气及沥青,持续时间大于30 Ma。     

川中地区侏罗系天然气成因类型及气源

针对川中地区侏罗系天然气成因类型及气源的认识存在不同的观点,作者综合天然气组分特征、碳同位素特征、轻烃特征对该问题进行了探讨。组分分析结果表明,侏罗系天然气主要为干酪根裂解气;碳同位素分析结果表明,侏罗系天然气主要为油型气,部分为煤型气;轻烃分析结果表明,侏罗系天然气以油型气为主。综合上述成因类型分析结果认为:川中地区侏罗系天然气以干酪根裂解成因油型气为主,同时存在少量的煤型气。川中地区侏罗系油型气来自侏罗系烃源岩,煤型气来自上三叠统烃源岩。     

三种端元气δ13C1-Ro模型建立与应用

端元气δ¹³C₁-R_o模型是天然气成因判识、气源对比及混源气定量判识的重要工具。为了满足Ⅱ型有机质生成天然气识别及评价的需要,根据母质类型将有机热成因天然气划分为I、Ⅱ和Ⅲ型等3种端元气,并利用126组实测天然气数据得到3种端元气的δ¹³C₁-R_o模型。I型,δ¹³C₁=27.55 lg R_o-47.20;Ⅱ型,δ¹³C₁=25.55 lg R_o-40.76;Ⅲ型,δ¹³C₁=48.77 lg R_o-34.10（R_o < 0.9%）,δ¹³C₁=22.42 lg R_o-34.80（R_o ≥ 0.9%）。为了方便模型应利用建模样品的δ¹³C₁、δ¹³C₂数据,绘制了三端元气及其混源气的别图版。根据该图版,济阳拗陷坨165、车571与孤东9井天然气分别为I和Ⅱ型端元气混源、Ⅱ型端元气与I型端元气。     

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.     

The carbon isotope study of biomarkers in the Maoming and the Jianghan tertiary oil shale

In terms of the individual carbon isotope data of biomarkers present in the typical freshwater lake sediment (Maoming oil shale) and saline lake sediment lake (Jianghan oil shale) of China, this paper discusses their precursors and depositional environments of biomarkers in both sediment samples. Our studies showed that phytane and pristane of the Maoming oil shale were derived from the phytol side chain of chlorophyll a. By comparing the isotopic composition of 4-methyl sterane with that of sterane and hopane, it is suggested that 4-methyl sterane which has a higher abundance in the Maoming oil shale come from bacteria. The isotopic composition of biomarkers from the Jianghan rock sample (saline lake sediment ) is significantly different from that of the Maoming oil shale (freshwater lake sediment). Gammacerane was derived from haloprotozoan, with δ13C being about -25.8‰, just in consistency with the value reported in previous studies. The isotopic composition of phytane and pristane in the Jianghan rock is similar to that of sterane and 4-methyl sterane derived from phytoplanktons, illustrating their commonprecursors were algae. This paper reported for the first time the carbon isotope data of porphyrin obtained by GC-IRMS techniques. The approximate δ13C of C32DPEP and C31DPEP porphyrin from the Jianghan Basin indicated that the porphyrin was derived from chlorophyll. In the Maomingoil shale C32DPEP was enriched in 13C relative to C32etio and C31DPEP, implying that C32DPEP came from chlorophyll, and C32etio and C31DPEP are of other origins.     

Kinetic modeling the effects of primary migration, diffusion and waterwashing on Upper Paleozoic coal-derived gas at the center of Ordos Basin

Gold reactor pyrolysis system is used to model the gas formation from the Upper Paleozoic coal measures and the results show coal-derived gas characterized with δ13C1 of-33.46‰, δ13C2 of-23.1‰, dryness(C1/C1-4) 85.6%. And then, effects of the post-genetic processes on coal- derived gas are analyzed in turn: (i) About 27% coal-derived gases constituted with more methane are calculated to be lost during diffusion. The residual in reservoir are characterized with almost the same compositions as the original, which suggests faint influence by diffusion (the residual, δ13C1 of -32.78‰, δ13C2 of-23.1‰, C1/C1-4 83%); (ii) Water washing made about 8% coal-formed gases lost and their components and stable carbon isotopes are stable; (iii) In the final, it is speculated that primary migration makes much more wet gas (C2-4) leave in coal measures. The variance of gas dryness induced by this factor is estimated to be about 10%.     

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.     

Variation of δ13C in karst soil in Yaji Karst Experiment Site,Guilin

This study deals with δ13C variation in karst soil system of Yaji Karst Experiment Site, Guilin, a typical region of humid subtropical karst formations. Samples of near ground air, plant tissue, soil and water (soil solution and karst spring) were respectively collected on site in different seasons during 1996-1999. Considerable variation of δ13C values are not only found with different carbon pools of soil organic carbon, soil air CO2 and soil water HCO-3, but also with the soil depths and with different seasons during a year.The δ13C values of CO2 both of near ground air and soil air are lower in July than those in April by 1%-4‰ PDB. Our results indicate that the δ13C values of carbon in the water and air are essentially dependent on interface carbon interaction of air-plant--soil-rock--water governed by soil organic carbon and soil CO2 in the system.     

Geochemical characteristics of light hydrocarbons in natural gases from the Turpan-Hami Basin and identification of low-mature gas

Theoretical and practical knowledge regarding low-mature gasses is of significant importance to identifying potential natural gas resources. Light hydrocarbon parameters and C and H isotopes are useful tools to identify low-mature gas. Twenty gas samples were collected from the Turpan-Hami Basin for light hydrocarbon analyses. The results showed that the light hydrocarbon components of natural gases contain high methylcycloxane, high isoparaffin and low benzene. This implies that the gas-generating parent materials are of typical humus type and the paleoenvironment is a fresh water sedimentary environment. These features are consistent with the geological setting of the basin. Comparative studies of isoheptane, heptane, and the carbon isotopic compositions of methane in natural gases, and other maturity indices indicated that natural gases in the Turpan-Hami Basin are dominated by low-mature gas formed during the low evolution stage of Jurassic coal seams. The parent materials are of type III, and the maturation degree was in the low evolution stage. These are the fundamental characteristics of low-mature gas. Results of light hydrocarbon research provided further evidence to suggest that the Turpan-Hami Basin is a large-scale gas producer of low-mature gas in China. It is likely that this resource will play an important role in future exploration and development of low-mature gas in China.     

海拉尔-塔木查格盆地中部断陷带CO2气藏中CO2成因分析

以海拉尔-塔木察格盆地中部断陷带CO2气藏中的CO2为研究对象,通过组分分析、碳同位素及氦、氩同位素分析,结合研究区CO2含量和同位素数据及他人研究成果,利用排除法探讨研究区CO2的成因及来源。结果表明:研究区CO2平均含量大于85%,CO2稳定碳同位素偏轻,δ13CCO2为-13.1‰～-8.8‰,为目前已发现的具有较为特殊碳同位素组成特征的CO2气藏;尽管CO2稳定碳同位素偏轻,但通过排除法可以证明该区CO2为无机成因气的结论最为合理,且CO2应来源于上地幔岩浆脱气。     

商都坳陷浅层CO_2气藏成因与典型气藏分析

商都地区CO2气藏的气体组分主要为CO2,体积分数为87.0%～99.9%,碳同位素δ13C值分布在-5.2‰～-6.5‰之间,氦同位素3He/4He体积比分布在(1.69～3.35)×10-6之间,为典型幔源CO2气.乌兰哈达-高勿素断裂是一条长期活动的超深断裂,不仅控制着盆地沉积和演化,而且输导了多期次岩浆活动,提供了幔源CO2运移通道.商都坳陷新生代沉积演化有利于储盖组合的发育,具有良好的CO2气藏形成条件.通过对典型CO2气藏解剖,其具有气藏浅、产量高的特点.SZ5井累计产气量是容积法计算储量的2.23倍,认为存在幔源CO2的不断补充.