天然气运移的气体组分的地球化学示踪

本文通过我国不同含油气盆地典型地区岩石酸解气、罐顶气和天然气中化学组分分析,结合天然气的形成和盆地的地质演化,研究了天然气运移时组分的变化。结果表明,天然气通过地层孔隙系统运移时,组分会发生明显分馏,表现在甲烷相对重烃、异构丁烷相对正构丁烷的优先迁移。酸解气、罐顶气和成藏天然气中C₁/C₂+、iC₄/nC₄及总烃/非烃等比值,是天然气运移示踪的有效指标。     

桂北376铀矿床烃气地球化学研究

烃气测量法在锡、金、铜、铅锌等金属矿床找矿中得到了广泛应用,而该技术在花岗岩型铀矿找矿中的应用鲜有报道。本文对桂北376铀矿床已知矿体开展了烃气测量试验,结果显示：相较于其他金属矿,该铀矿区花岗岩和土壤中总烃含量极低,而且花岗岩总烃含量(平均19.42μL/kg)高于上覆土壤(平均6.32μL/kg)。花岗岩中U与多数烃气组分呈负相关,与重烃呈正相关,重烃在U迁移过程中作用强于轻烃;花岗岩烃气标准化配分模式以C₁、iC₄和C₂^-正异常为特征;铀矿化程度与iC₄/nC₄、(C₁+iC₄+C₂^-)/(C₂+C₃+nC₄)及C₂^-/C₃^-比值呈正相关,与C₂₊/∑C比值呈负相关等可为寻找铀矿提供依据。3...     

松辽盆地西部斜坡区四方台组砂岩中烃类流体特征与铀成矿关系

通过对松辽盆地西部斜坡区四方台组33个砂岩样品的酸解烃分析,探讨了酸解烃中烃类气体组成特征、成因及来源,并结合该地区铀矿化地质特征初步分析了烃类流体与砂岩型铀成矿关系.酸解烃中气体组成特征参数C₁/ΣC、C₁/C₂₊、C₂/iC₄、C₂/C₃、iC₄/nC₄、iC₅/nC₅特征表明,四方台组底部砂岩中烃类气体为有机成因的油气型,烃类气主要处于成熟-高成熟阶段,是原油裂解气和原油伴生的混合气,它们主要沿盖层断裂运移到四方台组底部砂岩中.西部斜坡区四方台组含铀砂岩中烃类流体含量普遍增高,表明该区四方台组铀矿化与烃类气体关系密切.四方台组底部靠近沟通油气田的盖层断裂附近是西部斜坡区砂岩型铀矿找矿的重点地区.     

羌塘盆地QK-1孔烃类气体分布特征与成因来源

青藏高原冻土区面积约150×104 km²,是中国最大的冻土区,具备良好的天然气水合物形成条件和找矿前景,而羌塘盆地是形成条件和找矿前景最好的地区。南羌塘盆地毕洛错地区QK-1科学钻探试验井顶空气样品的烃类气体组分和碳同位素分析测试结果表明,其烃类气体组分复杂,CH₄含量为3.0×10^-6~4 526.8×10^-6,平均为209.0×10^-6;δ¹³C₁值为-55.9‰~-37.8‰,平均为-43.2‰,C₁/(C₂+C₃)值小于10,显示出明显的热解气特征。结合钻探区的地质背景和岩性特征,推断QK-1孔烃类气体可能来源于深部迁移上来的热解气,浅部可能有生物成因气的混入。     

不同成因类型煤型气地球化学特征及其判识意义

通过数理统计前人公开发表的国内外21个盆地或地区的324组煤型气地化数据, 分析不同成因类型煤型气地层分布和稳定碳、氢同位素组成及空间分布特征, 提出多个煤型气成因类型判识图版, 并以实例论证这些图版的可行性.研究结果表明: 与煤层相关的生物成因气不同于常规生物气, 最显著区别在于前者δ13C(CH₄)上限值低, 即生物成因气δ13C(CH₄)＜-60‰, 热成因气δ13C(CH₄)＞-40‰, 混合成因气δ13C(CH₄)介于二者之间.随着有机质演化程度增强, 从生物成因气至热成因气, δ13C(CH₄)、δ13C(CO₂-CH₄)、δ13C(C₂H₆-CH₄)及CH₄/(C₂H₆+C₃H₈)具有变重趋势且相关性明显, δ13C(CH₄)与δ13C(CO₂-CH₄)、δ13C(CH₄)与δ13C(C₂H₆-CH₄)及δ13C(CH₄)与CH₄/(C₂H₆+C₃H₈)是划分煤型气成因类型最可靠的图版.      

松辽盆地庆深气田天然气成因类型鉴别

通过对松辽盆地徐家围子烃源岩和原油热模拟实验、烷烃气碳同位素组成分析, 认为在高演化阶段单一热力作用可以引起重烃气(δ13C₂ > δ13C₃ > δ13C₄) 碳同位素组成倒转, 但CH₄与C₂H₆(δ13C₁ > δ13C₂) 却很难发生倒转.庆深气田天然气重甲烷碳同位素组成、烷烃气碳同位素完全倒转、高稀有气体同位素组成(R/Ra > 1.0), 说明该气田天然气来源具有多样性.利用R/Ra与CO₂/3He和R/Ra与CH₄/3He关系对庆深气田天然气成因类型进行识别, 认为该气田烷烃气中甲烷有部分为无机成因, 重烃气则为有机成因.该地区高地温梯度导致有机成因重烃气碳同位素组成发生倒转, 而CH₄与C₂H₆碳同位素组成倒转主要与重碳同位素的无机甲烷混入有关.      

湘鄂西龙马溪组页岩解析气同位素组成特征及应用

湘鄂西地区位于中扬子板块,研究区龙马溪组富有机质页岩的有机质类型以Ⅱ₁型为主,Ⅱ₂型次之,TOC含量高,有机质热成熟度高,页岩矿物以脆性矿物为主,黏土矿物次之。通过分析三个实验阶段(20 ℃、65 ℃、90 ℃)解析气样发现,气体中CH₄含量较高(90.34%~99.64%),含有少量非烃气体。龙马溪组页岩气CH₄碳同位素值为-41.9‰~-30.8‰,C₂H₆碳同位素值为-42.3‰~-36.2‰,δ²H_CH4为-193.4‰~-156.0‰,随着成熟度的增加,CH₄碳同位素、C₂H₆碳同位素以及CH₄氢同位素都有升高的趋势。烃类气体碳同位素具有明显的倒转现象,即δ¹³C₁>δ¹³C₂。根据解析实验三个阶段的气体同位素特征和测得的各阶段含气特征建立游离气与吸附气所占比例的计算公式,进一步推算出解析过程总含气量中所含有的游离气量以及吸附气量。     

川西地区有机流体包裹体产状、组分及成因序次分析

川西地区三叠-侏罗系地层中的有机流体包裹体有6种赋存形式,3种主要相态。激光拉曼探针测试分析表明,包裹体的有机组分包括CH₄、C₂H₂、C₂H₄、C₂H₆、C₃H₈、C₃H₆、C₄H₆、C₆H₆等8种组分,非烃组分主要包括CO₂、H₂、H₂S、CO等4种。综合均一温度、盐度以及埋藏史、热史分析,有机流体包裹体可分为4个期次,是该地区油气生成、运移、演化以及不同成岩作用阶段共同作用的结果,对油气成藏规律有重要的指示作用。     

青海木里煤田天然气水合物特征与成因

青海木里煤田成功钻获天然气水合物实物样品,使我国成为世界上首次在中低纬度冻土区发现天然气水合物的国家。通过对钻获天然气水合物样品的分析,以及对以往异常可燃气体涌出钻孔的测井曲线的重新解释和对比分析,初步确定天然气水合物赋存于中侏罗统江仓组油页岩段的细粉砂岩夹层内的孔隙和裂隙中。研究结果显示,天然气水合物中的气体以重烃类为主,甲烷达52%~68%;其δ13C值为-50.5‰(PDB标准),并具有δl3C_l<δ13C₂<δ13C₃<δ13iC₄<δl3nC₄的特征,其δD值分别为-266‰和-262‰(VSMOW标准),显示出明显的深部热解气特征。结合木里煤田煤层气地质特征,认为煤层气是木里煤田天然气水合物的主要来源,并将其命名为“煤型气源”天然气水合物。      

页岩气析出过程中的H同位素分馏及地质意义

通过长时间储层温度下页岩气现场解吸实验,揭示页岩气析出过程中气体赋存状态变换与气体组分及甲烷H、C稳定同位素的关联性。结果表明,与解吸气甲烷C同位素(δ¹³C₁)早期变化幅度较小、后期持续变重的现象不同,甲烷H同位素(δD(CH₄))具有先变轻后变重的规律,且在解吸至40%～50%阶段后与δ¹³C₁变重同步。依据δD(CH₄)变化规律及页岩含气性、气体渗流特征,可将页岩气析出过程划分为游离气压差渗流、游离气渗流–吸附气解吸扩散共存和吸附气解吸扩散3个阶段:阶段Ⅰ裂隙及基质孔隙中的游离气在压差作用下渗流,产出页岩气的δD(CH₄)和δ¹³C₁基本不变;阶段Ⅱ游离气渗流与吸附气解吸扩散共存,质量较轻的12CH₄优先脱附,吸附气的补给使产出气体的δD(CH₄)显著变轻(变轻4‰～10‰),而δ¹³C₁变轻的现象...     

Gas Sources of Natural Gas Hydrates in the Shenhu Drilling Area, South China Sea: Geochemical Evidence and Geological Analysis

The Shenhu gas hydrate drilling area is located in the central Baiyun sag, Zhu Ⅱ depression, Pearl River Mouth basin, northern South China Sea. The gas compositions contained in the hydrate-bearing zones is dominated by methane with content up to 99.89% and 99.91%. The carbon isotope of the methane (δ13C1 ) are 56.7‰ and 60.9‰, and its hydrogen isotope (δD) are 199‰ and 180‰, respectively, indicating the methane from the microbial reduction of CO2 . Based on the data of measured seafloor temperature and geothermal gradient, the gas formed hydrate reservoirs are from depths 24-1699 m below the seafloor, and main gas-generation zone is present at the depth interval of 416-1165 m. Gas-bearing zones include the Hanjiang Formation, Yuehai Formation, Wanshan Formation and Quaternary sediments. We infer that the microbial gas migrated laterally or vertically along faults (especially interlayer faults), slump structures, small-scale diapiric structures, regional sand beds and sedimentary boundaries to the hydrate stability zone, and formed natural gas hydrates in the upper Yuehai Formation and lower Wanshan Formation, probably with contribution of a little thermogenic gas from the deep sedments during this process.     

Origin of the Gas Hydrate and Free Gas in the Qilian Permafrost,Northwest China: Evidence from Molecular Composition and Carbon Isotopes

The Qilian permafrost of the South Qilian Basin (SQB) has become a research focus since gas hydrates were discovered in 2009.Although many works from different perspectives have been conducted in this area,the origin of gas from gas hydrate is still controversial.Molecular composition and carbon isotope of 190 samples related to gas hydrates collected from 11 boreholes allowed exploration of genetic type,thermal maturity, biodegradation,as well as gas-source correlation of alkane gases from gas hydrates and free gases.Results indicate that alkane gases biodegraded after the formation of natural gas.According to differences in carbon isotopes of methane and their congeners (CH4,C2H6,C3H8),the thermal maturity (vitrinite reflectance,VRo) of most alkane gases ranges from 0.6% to 1.5%,indicating a mature to high mature stage.The thermal maturity VRo of a small part of alkane gas (in boreholes DK5 and DK6) is higher than 1.3%,indicating a high mature stage.Alkane gases were mainly produced by secondary cracking,consisting of crude oil-cracking gases and wet gases cracking to dry gases.Genetic types of alkane gases are primarily oil-type gases generated from shales and mudstones in the upper Yaojie Formation of Jurassic,with less coal-type gases originated from the mudstones in the Triassic Galedesi Formation and the lower Yaojie Formation of Jurassic.Carbon dioxides associated with alkanes from gas hydrates and free gases indicate the thermal decomposition and biodegradation of organic matter.The origins of natural gases from gas hydrates and free gases shed light on the evaluation of petroleum resource potential,deeply buried sediments,and petroleum resource exploration in the SQB.     

陆域天然气水合物取样关键因素探讨

温度和压力是保持天然气水合物不分解的2个重要参数。依据热物理力学理论和理想气体特性,通过计算机模拟0℃以上甲烷水合物和二氧化碳水合物在不同温度-压力条件下的分解,得到甲烷水合物分解P-T平衡相图,探讨了钻探获取陆域天然气水合物取样温压关系。     

冲绳海槽中段西陆坡下缘天然气水合物存在的可能性分析

海洋中的天然气水合物主要发育在有机质供应充分、沉积速率快、热流值较高、水深大于300m的大陆斜坡和活动边缘的增生楔发育区;沉积物类型主要以泥质砂岩、砂质泥岩和浊积岩为主。似海底反射层(BSR)和极性反转是识别天然气水合物层的关键标志。冲绳海槽中段西陆坡下缘水深大于1000m;沉积物类型主要为粉砂质泥和泥质粉砂,在部分层位见浊积层。与东海陆架相比,西陆坡下缘的有机质含量、沉积速率的热流值都较高,其范围分别为0.75%～1.25%、10～40cm/ka和70～437mw/m2;单道地震剖面具有明显的似海底反射层(BSR)和极性反转特征,因此,推断冲绳海槽中段西陆坡下缘可能存在天然气水合物层。     

The methane hydrate formation and the resource estimate resulting from free gas migration in seeping seafloor hydrate stability zone

It is a typical multiphase flow process for hydrate formation in seeping seafloor sediments. Free gas can not only be present but also take part in formation of hydrate. The volume fraction of free gas in local pore of hydrate stable zone (HSZ) influences the formation of hydrate in seeping seafloor area, and methane flux determines the abundance and resource of hydrate-bearing reservoirs. In this paper, a multiphase flow model including water (dissolved methane and salt)-free gas hydrate has been established to describe this kind of flow-transfer-reaction process where there exists a large scale of free gas migration and transform in seafloor pore. In the order of three different scenarios, the conversions among permeability, capillary pressure, phase saturations and salinity along with the formation of hydrate have been deducted. Furthermore, the influence of four sorts of free gas saturations and three classes of methane fluxes on hydrate formation and the resource has also been analyzed and compared. Based on the rules drawn from the simulation, and combined information gotten from drills in field, the methane hydrate(MH) formation in Shenhu area of South China Sea has been forecasted. It has been speculated that there may breed a moderate methane flux below this seafloor HSZ. If the flux is about 0.5 kg m⁻² a⁻¹, then it will go on to evolve about 2700 ka until the hydrate saturation in pore will arrive its peak (about 75%). Approximately 1.47 × 10⁹ m³ MH has been reckoned in this marine basin finally, is about 13 times over preliminary estimate.     

祁连山冻土区天然气水合物伴生碳酸盐C、O同位素特征及其地质意义

伴生碳酸盐矿物在海底与天然气水合物伴生是一种普遍现象,但在陆上冻土区中报道较少。以近两年在祁连山冻土区发现天然气水合物伴生的碳酸盐矿物为研究对象,根据对含碳酸盐样品的显微镜观察及矿物分析,确定了伴生碳酸盐的矿物种属及赋存状态。按碳酸盐矿物组成及地质产状的不同,其赋存状态分成4种类型,即白色薄层状、烟灰色菱形晶簇状、深灰色薄壳状、微细浸染状。根据不同赋存形态碳酸盐的C、O同位素特征,认为烟灰色菱形晶簇状方解石或呈(云烟状)微晶方解石可能与天然气水合物分解有关。碳酸盐C、O同位素随深度变化特征表明在一定深度处可能存在着烃类物质的活动,即天然气水合物分解,导致碳酸盐的矿物生成。     

南海天然气水合物稳定带厚度及资源量估算

中国的南海一直被人们认为蕴藏着丰富的天然气水合物资源,综合中国南海的水深、地热梯度及底部水温等地质资料,运用VisualBasic.Net编程分析在该海域范围内天然气水合物稳定带厚度,讨论其分布特征,并以此来评估该区域的水合物资源量.结果表明当地热梯度为0.06℃/m,在区域1中可能存在天然气水合物,其稳定带的最大厚度可达400 m,天然气水合物分布较为规则,从外向内逐渐增厚.但在区域2中由于受到水深和地热等因素的影响不存在天然气水合物,此时天然气水合物的资源量约为0.55×104 km3;当地热梯度随机取值时,该区的天然气水合物资源量约为0.57×104 km3.通过对地热梯度取不同的值,估算得到在该研究区天然气水合物的资源量约为0.6×104 km3.      

盐类对甲烷水合物稳定性影响研究进展

甲烷水合物稳定性主要控制着甲烷水合物稳定带的厚度,温度、压力、孔隙水盐度和气体组分等因素影响着水合物稳定带的厚度。甲烷水合物的形成与地层水关系密切,而地层水中的各种盐离子(Cl~-、Na~+、Mg~(2+)、SO_4(~2-)、Ca~(2+))以及过渡金属(Fe、Mn、Cu、Co、Ni等)会影响天然气水合物的形成和分解条件。因此,研究盐类对甲烷水合物的稳定性认识有助于更加深入了解天然气水合物的成藏条件。本文分析了氯化物、硫酸盐、碳酸盐三大盐类对甲烷水合物稳定性的影响:同一盐类不同盐度条件下,随着盐度的增加,甲烷水合物相平衡曲线向低温高压偏移。总结了不同盐类和阴阳离子对甲烷水合物的抑制作用大小:在相同浓度、不同盐类条件下,盐类浓度在1.0~1.5 mol/L时盐类对甲烷水合物的抑制作用大小为MgCl_2CaCl_2Na ClKCl,盐类浓度大于1.5 mol/L时CaCl_2的抑制作用较强;阴离子对甲烷水合物的抑制作用大小争议较大,阳离子中Mg~(2+)对甲烷水合物的抑制作用最强。从目前的研究成果来看,已有数据与实际地质条件还存在一定差距,需要在真实实验条件下加强氯化物-硫酸盐-碳酸盐-甲烷-水体系的详细研究。本文提出,将高压可视反应腔与显微激光拉曼技术相结合,有望准确获取天然气水合物稳定形成时的温压条件,明确盐类和阴阳离子的抑制作用大小,以及盐类和离子特性如何影响水合物的形成和稳定,以便为未来的水合物勘探开发提供参考。     

The Geochemical Context of Gas Hydrate in the Eastern Nankai Trough

Abstract. Geochemical studies for gas hydrate, gas and organic matter collected from gas hydrate research wells drilled at the landward side of the eastern Nankai Trough, offshore Tokai, Japan, are reported. Organic matter in the 2355 m marine sediments drilled to Eocene is mainly composed of Type III kerogen with both marine and terrigenous organic input. The gas hydrate-bearing shallow sediments are immature for hydrocarbon generation, whereas the sediments below 2100 mbsf are thermally mature. The origins of gases change from microbial to thermogenic at around 1500 mbsf.
Carbon isotope compositions of CH₄ and CO₂, and hydrocarbon compositions consistently suggest that the CH₄ in the gas hydrate-bearing sediments is generated by microbial reduction of CO₂. The δ¹³C depth-profiles of CH₄ and CO₂ suggest that the microbial methanogenesis is less active in the Nankai Trough sediments compared with other gas hydrate-bearing sediments where solid gas hydrate samples of microbial origin were recovered. Since in situ generative-potential of microbial methane in the Nankai Trough sediments is interpreted to be low due to the low total organic carbon content (0.5 % on the average) in the gas hydrate-bearing shallow sediments, upward migration of microbial methane and selective accumulation into permeable sands should be necessary for the high concentration of gas hydrate in discrete sand layers.