海洋天然气水合物氢氧同位素分馏初探

天然气水合物的形成会造成氢、氧同位素的分馏.在实验室合成研究中,利用天然海水 [(含 0.03%十二烷基硫酸钠 (SDS)]与甲烷气体反应,通过对水合物生成前后溶液中的 Cl-的质量浓度和氢、氧同位素组成的测定,研究了天然气水合物生成过程中氢、氧同位素的分馏情况.实验证明氢、氧的重同位素易于富集在水合物中,其在天然海水-甲烷体系中的分馏系数分别为 1.018～ 1.036和 1.003 4～ 1.006 3,这一分馏系数稍大于前人在纯水和 NaCl溶液中所测得的分馏系数.     

天然气成因碳同位素指标评述

地球排气过程和费-托合成反应中碳同位素分馏作用使其具有非常大的变化范围,覆盖了目前所说的有机成因气和无机成因气,要求人们重新审视目前判别无机成因气的碳同位素指标。天然气水合物中甲烷和二氧化碳较轻碳同位素值表明,无机成因天然气可以有更宽的同位素分布范围．碳同位素不是天然气成因唯一的判别方法,利用甲烷伴生气体的组分含量、天然气运移方式、赋存特征、与构造作用的关系都可以判断天然气的无机成因．     

祁连山冻土区天然气水合物分解气碳氢同位素组成特征

开展祁连山冻土区天然气水合物气体同位素研究,是解决其气体成因、来源等科学问题的一个重要手段。本研究采集祁连山南麓多年冻土区水合物科学钻探DK2和DK3孔共8个含水合物的岩芯样品,采用真空顶空法收集样品中水合物的分解气,分别用气相色谱(GC)、气相色谱同位素比值质谱(GC-IRMS)测定其气体成分和同位素组成,测试结果表明:祁连山冻土区天然气水合物样品的气体碳氢同位素变化较大,甲烷、乙烷和丙烷的碳同位素(δ13C)变化范围分别为-52.6‰～-48.1‰、-38.6‰～-30.7‰和-34.7‰～-21.2‰,而二氧化碳的碳同位素(δ13C)最低为-27.9‰,最高为16.7‰;甲烷、乙烷和丙烷的氢同位素(δD)变化范围分别为-285‰～-227‰、-276‰～-236‰和-247‰～-198‰。通过对这些碳氢同位素进行综合研究,包括气体分子组成与同位素的关系分析、甲烷的碳氢同位素之间的关系判断等,结果表明研究区天然气水合物的气体主要来源于热解气,而且是在淡水环境中形成的有机成因气。     

南海北部天然气水合物钻探区烃类气体成因类型研究

南海北部天然气水合物钻探区水合物气、顶空气样品和沉积物样品烃类气体组分和甲烷同位素特征测试结果表明,气体样品中烃类气体以甲烷为主,含微量乙烷和丙烷,C1/(C2+C3)值均大于或接近1 000。甲烷的碳同位素值为-54.1‰~-62.2‰,氢同位素值为-180‰~-255‰,属于微生物气或是以微生物气为主的混合气,甲烷由CO2还原生成,由原地提供或侧向运移而来。沉积物样品酸解烃分析显示多数样品甲烷丰度大于90%,含一定量的乙烷、丙烷及少量的丁烷,C1/(C2+C3)值均小于50。甲烷的碳同位素值为-29.8‰~-48.2‰,呈现典型的热解气特征,显示由深部运移而来。     

东北漠河盆地甲烷碳氢稳定同位素异常及形成机制

东北漠河盆地是我国陆域多年冻土区天然气水合物聚集成藏及勘探的潜在区域。近几年,在漠河盆地实施天然气水合物钻探实验井和气源探井的过程中发现,该区甲烷碳、氢同位素δ^13 CCH4、δDCH4值明显偏低,负向偏移特征明显:碳同位素δ^13 CCH4 值多数小于-60‰,最低达-82.9‰;氢同位素δDCH4 值绝大多数低于-350‰,最低达-450‰。通常,埋深小于1 500m的范围,甲烷碳同位素δ^13 CCH4 值随深度增大,氢同位素δDCH4 值随深度减小;深度大于1 500m,甲烷碳、氢同位素δ^13CCH4 、δDCH4 值随深度同步增大。研究表明:漠河盆地的甲烷碳稳定同位素负向偏移,主要与甲烷的微生物成因有关;甲烷氢稳定同位素负向偏移,则是盆地所处较高纬度独特气候引起的地表水蒸发或大气冷凝降水过程的瑞利蒸馏和乙酸发酵的甲烷生成方式共同作用的结果。     

青海祁连山冻土区天然气水合物的气体成因研究

在祁连山冻土区发现天然气水合物之后,其气体成因或来源便成为一个重要的科学问题。开展了气体组成和同位素特征及δ13C1-1/n、C1/(C2+C3)-δ13C1、δDCH4-δ13CCH4、(δ13C2-δ13C3)-ln(C2/C3)、ln(C2/C3)-ln(C1/C2)等关系图解的综合研究,结果显示:祁连山冻土区天然气水合物的气体以轻烃为主,具湿气特征,其同位素表现为正碳同位素系列特征。研究区天然气水合物的气体为有机成因,且以热解成因为主,夹少量微生物成因(醋酸根发酵),其中,热解成因气主要与原油裂解气、原油伴生气有关,少部分与凝析油伴生气、煤成气、干酪根裂解气有关。这一分析结果可能意味着研究区天然气水合物的气体来源与油型气密切相关,而与煤型气关系不大。     

海底天然气渗漏系统微生物作用及冷泉碳酸盐岩的特征

海底天然气渗漏系统是全球海洋环境中广泛分布的自然现象。部分渗漏天然气通过细菌作用转变为二氧化碳,同时海水硫酸盐被还原为硫化氢, 与孔隙水中的钙和铁结合而沉淀冷泉碳酸盐岩。冷泉碳酸盐岩的常见矿物有微晶方解石、文石、白云石和黄铁矿。冷泉碳酸盐岩常发育一些特殊的组构, 如黄铁矿环带结核、溶蚀面、平底晶洞、凝块和向下生长的叠层石组构等。碳酸盐岩特别负的δ13C值指示碳来源于生物成因的甲烷, 而18O富集可能与天然气水合物的分解有关。冷泉碳酸盐岩中黄铁矿的δ34S值低于海水的, 这指示硫来源于微生物还原的海水硫。冷泉碳酸盐岩中的生物标志化合物及其极负的δ13C值指示微生物的生命代谢活动。     

川东北飞仙关组鲕滩天然气地球化学特征与成因

四川盆地东北部下三叠统飞仙关组鲕滩气藏天然气烃类气体以甲烷为主,含量主要分布在75%～90%之间,C2 含量很少,为0%～0.15%,干燥系数为0.997 0～0.999 8,是典型的干气;非烃气体以H2S和CO2为主,含量分别为4.21%～16.24%和0.97%～10.41%.天然气δ13C1值为-29.0‰～-31.5‰,δ13C2值为-29.4‰～-32.4‰.多参数表明鲕滩气藏天然气是以腐泥型为主的高过成熟天然气.高含H2S的天然气分布区域与含石膏地层分布基本一致,这些H2S为飞仙关组气藏附近的石膏经热化学硫酸盐还原作用(TSR)而生成,CO2是其主要的副产物.在TSR过程中,C2 重烃气体比甲烷更容易与硫酸盐发生反应,也就是C2 重烃气体的消耗速率大于甲烷,从而导致发生TSR反应的天然气C2 含量低、H2S和CO2含量高.天然气δ13C1值与甲烷含量之间具有很好的负相关关系,而与天然气酸性系数[H2S/(H2S CnH2n 2)]具有正相关关系.根据同位素动力学的分馏效应,随着TSR的进行,烃类分子中的12C损耗速率大于13C,残留下来的烃类分子中则更加富集13C,也就是TSR反应使天然气碳同位素变重.     

祁连山冻土区天然气水合物DK-8孔岩心顶空气地球化学特征及其指示意义

通过对祁连山木里冻土区天然气水合物DK-8孔不同深度岩芯中气体组分和甲烷碳同位素分析测试,对比分析其变化特征与天然气水合物及异常现象产出层段、断层或破碎带分布之间的空间关系,指出它们对天然气水合物及烃类运移作用的地球化学指示意义。岩芯中气体含量(μL/kg)在149～167m、228～299m、321～338m、360～380m等深度段具异常值特征,它们与天然气水合物及主要异常现象产出层段基本一致,表明岩芯中烃类含量的异常值特征主要是天然气水合物及异常现象的反映。根据离断层或破碎带不同距离岩芯烃类总体积百分比(vol%)、甲烷碳同位素δ13C1值(‰PDB)及C1/C1-5、C1/ΣC2-5、C1/ΣC2-3、C1/C2、C2/C3、C2/ΣC3-4、iC4/nC4、iC5/nC5等特征,代表天然气水合物及其异常的具异常值特征的岩芯中烃类主要由运移而来,它们与断层或破碎带关系密切,下部断层或破碎带是主要烃类运移通道,中上部断层或破碎带可成为天然气水合物赋存空间。     

祁连山冻土区天然气水合物DK-8孔岩芯顶空气地球化学特征及其运移指示意义

通过对祁连山木里冻土区天然气水合物DK-8孔不同深度岩芯中气体组分和甲烷碳同位素分析测试,对比分析其变化特征与天然气水合物及异常现象产出层段、断层或破碎带分布之间的空间关系,指出它们对天然气水合物及烃类运移作用的地球化学指示意义.岩芯中气体含量(μL/kg)在149～167m、228～299m、321～338m、360～380m等深度段具异常值特征,它们与天然气水合物及主要异常现象产出层段基本一致,表明岩芯中烃类含量的异常值特征主要是天然气水合物及异常现象的反映.根据离断层或破碎带不同距离岩芯烃类总体积百分比(vol％)、甲烷碳同位素δ13C1值(‰PDB)及C1/∑C1-5、C1/∑C2-5、C1/∑C2-3、C1/C2、C2/C3、C2/∑C3-4、iC4/nC4、iC5/nC5等特征,代表天然气水合物及其异常的具异常值特征的岩芯中烃类主要由运移而来,它们与断层或破碎带关系密切,下部断层或破碎带是主要烃类运移通道,中上部断层或破碎带可成为天然气水合物赋存空间.     

海底天然气水合物分解与甲烷归宿研究进展

综述了近年来天然气水合物分解与甲烷归宿等方面的研究成果。天然气水合物的汇聚与地质构造或地层圈闭有关，其溶解受物质转换控制，分解则受热转换控制。水合物释放甲烷的运移方式包括分散式、中心式和大规模排放式。缺氧氧化和耗氧氧化是甲烷在海洋环境中的2种主要转化方式。天然气水合物释放甲烷的最终归宿主要为：①重新形成天然气水合物；②形成化能自养生物群落和沉淀出碳酸盐沉积；③与氧发生氧化后转变为CO2；④直接排放进入到大气中。沉积物中的微构造、化能自养生物群落、自生碳酸盐矿物及其碳氧同位素组成是水合物释放事件的指纹记录。     

祁连山冻土区天然气水合物烃类气体成因及其意义

对祁连山冻土区天然气水合物钻井岩心游离气样品开展研究,测试烃类气体的组分和碳氢同位素,判断天然气水合物的气体成因类型及成藏模式。结果显示烃类气体组分复杂,除甲烷外,还含有较高的乙烷、丙烷等重烃组分。甲烷碳同位素分布范围最广,气体成因来源相对简单,没有明显受到次生改造作用的影响。该区天然气水合物属于热解成因,判断来自深部的三叠统尕勒得寺组烃源岩。本研究可为我国高原冻土天然气水合物勘探和开发提供理论依据。     

天然气水合物成因探讨

天然气水合物是未来的能源资源。其分布于极地地区、深海地区及深水湖泊中。在海洋里,天然气水合物主要分布于外大陆边缘和洋岛的周围,其分布与近代火山的分布范围具有一致性。同位素组成表明天然气水合物甲烷主要是由自养产甲烷菌还原CO₂形成的。典型的大陆边缘沉积物有机碳含量低（＜0．5％～1．0％）,不足以产生天然气水合物带高含量的甲烷。赋存天然气水合物的沉积物时代主要为晚中新世-晚上新世,具有一定的时限性,并且天然气水合物与火山灰或火山砂共存,表明其形成与火山-热液体系有一定联系。火山与天然气水合物空间上的一致性表明,天然气水合物甲烷的底物可能主要是由洋底火山喷发带来的CO2。由前人研究结果推断 HCO^－₃在脱去两个O原子的同时,可能发生了亲核重排,羟基 H原子迁移到 C原子上,形成了甲酰基（HCO^－）,使甲烷的第一个 H原子来源于水。探讨了甲烷及其水合物的形成机制,提出了天然气水合物成因模型。     

Progress in Global Gas Hydrate Development and Production as a New Energy Resource

Natural gas hydrates have been hailed as a new and promising unconventional alternative energy, especially as fossil fuels approach depletion, energy consumption soars, and fossil fuel prices rise, owing to their extensive distribution, abundance, and high fuel efficiency. Gas hydrate reservoirs are similar to a storage cupboard in the global carbon cycle, containing most of the world’s methane and accounting for a third of Earth’s mobile organic carbon. We investigated gas hydrate stability zone burial depths from the viewpoint of conditions associated with stable existence of gas hydrates, such as temperature, pressure, and heat flow, based on related data collected by the global drilling programs. Hydrate-related areas are estimated using various biological, geochemical and geophysical tools. Based on a series of previous investigations, we cover the history and status of gas hydrate exploration in the USA, Japan, South Korea, India, Germany, the polar areas, and China. Then, we review the current techniques for hydrate exploration in a global scale. Additionally, we briefly review existing techniques for recovering methane from gas hydrates, including thermal stimulation, depressurization, chemical injection, and CH4–CO2 exchange, as well as corresponding global field trials in Russia, Japan, United States, Canada and China. In particular, unlike diagenetic gas hydrates in coarse sandy sediments in Japan and gravel sediments in the United States and Canada, most gas hydrates in the northern South China Sea are non-diagenetic and exist in fine-grained sediments with a vein-like morphology. Therefore, especially in terms of the offshore production test in gas hydrate reservoirs in the Shenhu area in the north slope of the South China Sea, Chinese scientists have proposed two unprecedented techniques that have been verified during the field trials: solid fluidization and formation fluid extraction. Herein, we introduce the two production techniques, as well as the so-called “four-in-one” environmental monitoring system employed during the Shenhu production test. Methane is not currently commercially produced from gas hydrates anywhere in the world; therefore, the objective of field trials is to prove whether existing techniques could be applied as feasible and economic production methods for gas hydrates in deep-water sediments and permafrost zones. Before achieving commercial methane recovery from gas hydrates, it should be necessary to measure the geologic properties of gas hydrate reservoirs to optimize and improve existing production techniques. Herein, we propose horizontal wells, multilateral wells, and cluster wells improved by the vertical and individual wells applied during existing field trials. It is noteworthy that relatively pure gas hydrates occur in seafloor mounds, within near-surface sediments, and in gas migration conduits. Their extensive distribution, high saturation, and easy access mean that these types of gas hydrate may attract considerable attention from academia and industry in the future. Herein, we also review the occurrence and development of concentrated shallow hydrate accumulations and briefly introduce exploration and production techniques. In the closing section, we discuss future research needs, key issues, and major challenges related to gas hydrate exploration and production. We believe this review article provides insight on past, present, and future gas hydrate exploration and production to provide guidelines and stimulate new work into the field of gas hydrates.     

祁连山冻土区含天然气水合物层段岩心热模拟实验研究

以热模拟实验为手段,对祁连山冻土区DK-2和DK-3孔含天然气水合物层段岩心(泥岩、油页岩和煤)热模拟烃类气体的组分、碳同位素组成与天然气水合物进行对比,以探寻这些气源岩与天然气水合物气源之间的可能联系。实验结果显示：低温(300 ℃以下)条件下,产生的气体以非烃CO₂为主,烃类气体含量少,且泥岩产生烃类气体量<油页岩产生烃类气体量<煤产生烃类气体量,表现出不同岩石吸附气体的差异性特征;随着热模拟温度增加,产生的烃类气体量明显增加,至500 ℃时达到最高,相反CO₂产气量变化不大;随热模拟温度增加,泥岩、油页岩、煤所产生烃类气体的碳同位素值呈现先变轻后变重的演化趋势和δ¹³C₁ ＜δ¹³C₂＜δ¹³C₃的正碳同位素序列特征;泥岩在350~400 ℃条件下或油页岩在380~400 ℃条件下所产生的烃类气体在组成和同位素特征上与天然气水合物中烃类气体较为相似,推测天然气水合物气源与深部泥岩或油页岩具有地球化学成生联系,相反煤产生的烃类气体虽然在组成上与天然气水合物中烃类气体较为相近,但两者同位素值相差较远,推测煤与天然气水合物气源关系不大。     

Carbon Geochemistry of Gas Hydrate‐associated Sediments in the Southwestern Taiwan Basin

Marine gas hydrates, one of the largest methane reservoirs on Earth, may greatly affect the deep sea sedimentary environment and biogeochemistry; however, the carbon geochemistry in gas hydrate-bearing sediments is poorly understood. In this study, we investigated the carbon variables in sediment core 973-3 from the southwestern Taiwan Basin in the South China Sea to understand the effect of environmental factors and archaeal communities on carbon geochemistry. The carbon profiles suggest the methanogenesis with the incerase of dissolved inorganic carbon(DIC) and high total organic carbon(TOC)(mean = 0.46%) originated from terrigenous organic matter(mean δ~(13)C_(TOC) value of-23.6‰) driven by the abundant methanogen ‘Methanosaeta and Methanomicrobiales'. The active anaerobic oxidation of methane is characterized by the increase of DIC and inorganic carbon(IC), and the depleted δ~(13)C_(IC), coupled with the increase of TOC and the decrease of δ~(13)C_(TOC) values owing to the methanotroph ‘Methanosarcinales/ANME' in 430–840 cm. Environmental factors and archaeal communities in core 973-3 are significantly correlated to carbon variables owing to methane production and oxidation. Our results indicate that the carbon geochemical characteristics are obviously responding to the formation and decomposition of gas hydrates. Furthermore, pH, Eh and grain size, and Methanosaeta greatly affect the carbon geochemistry in gas hydrate-associated sediments.     

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。     

多孔介质中天然气水合物稳定性的实验研究进展

勘探表明天然气水合物多产出于细碎屑沉积物中,其分布和赋存形式受温度、压力、水化学条件等多种物理化学因素的影响。前人的实验研究表明不同孔径尺度中的甲烷水合物稳定性有别于块状、层状水合物,同时孔隙表面的润湿性也是影响因素之一。在综合分析前人研究成果的基础上,系统阐述了孔隙的孔径、孔隙内表面润湿性对所含天然气水合物稳定性的影响规律,总结了可能的内在机理;并指出了当前应当尽快建立包括空间效应、温度、压力和组分等因素的综合天然气水合物相图,查明含天然气水合物沉积物的孔隙结构和表界面特征,建立天然气水合物的稳定性模型,将有助于精确预测天然气水合物的分布和规模,对于水合物开发和甲烷存储技术的研发也有着重要的意义。