Carbon isotope geochemistry of Paleozoic oils from Big Horn Basin

Twenty crude oils from Paleozoic reservoirs in the Big Horn Basin. Wyoming were fractionated into light hydrocarbons, saturates, monoaromatics. diaromatics, polyaromatics-and-polars. and asphaltenes. Amounts and isotopic composition of each fraction were found to be internally consistent with the degree of maturation of the oil. confirming the established single source origin for these oils. A variation of approximately three per mil in the carbon isotopic composition of the whole oil and individual fraction was explained as being caused by maturation. The isotope-type-curves for these oils, the variations in isotopic composition as a function of compound group-type, were not found to be as simple as commonly believed. Other alteration processes, such as migration and deasphalting, might have influenced the pattern of the isotope distributions among fractions. The conservative nature of mass balance and subsequent isotope flows among various fractions of crude oil showed that the maturation of crude oil consists of consecutive processes leading from larger and more polar components into smaller and less polar components culminating in natural gas. Calculations were made to project the amount of condensates associated with the crude oils, and the amount of natural gas which had been generated from crude oils of a given maturity.     

青海聚乎更钻探区天然气水合物拉曼光谱特征

了解天然气水合物的微观结构特征对水合物资源勘探和评价具有重要意义。采用显微激光拉曼光谱技术,对青海聚乎更钻探区内DK8-19、DK11-14 和DK12-13等3个站位共9个天然气水合物岩心样品进行了分析测试,探讨了钻探区天然气水合物的拉曼光谱特征。结果表明,青海聚乎更钻探区天然气水合物广泛分布,垂直方向在126.1~322.2 m范围内不连续分布,不同钻孔、不同埋深水合物样品的拉曼光谱特征基本一致,初步判断为Ⅱ型结构水合物,且为多元气体水合物。水合物客体除甲烷、乙烷、丙烷及丁烷等 烷烃外,普遍含有氮气组分。此外,在DK8-19站位埋深为126.1 m样品中发现水合物相中硫化氢组分的拉曼信号,这说明特定区域内可能存在硫化氢气体且形成了水合物。聚乎更钻探区水合 物样品拉曼光谱特征为冻土区天然气水合物成藏与分布规律研究提供了新的启示。     

祁连山木里冻土区天然气水合物矿区稀有气体氦、氖地球化学特征及其指示意义

稀有气体氦(He)、氖(Ne)是天然气水合物中的痕量组分,其化学性质稳定,在地质作用过程中其丰度变化几乎不受复杂化学反应和近地表微生物的影响。顶空气He、Ne地球化学勘查方法可以排除沼泽区微生物的强烈干扰,提高包括天然气水合物在内的油气近地表地球化学勘查的效用及精度。选择祁连山木里冻土区天然气水合物矿区进行试验研究,获得近地表土壤顶空气He平均含量为799×10-6,Ne平均含量208×10-6,均高于其在大气中的丰度。稀有气体He、Ne具有很强的穿透能力,平面上,在已知水合物矿藏和水合物远景区上方具有明显的地球化学顶部异常特征;钻井地球化学垂向剖面上,水合物富集层位上方具有明显的上置气异常特征。顶空气He、Ne近地表平面异常和钻井岩屑剖面异常特征证实,祁连山水合物形成过程中烃类气体发生了分异和垂向微渗漏,其携带笼中的稀有气体He、Ne以“类气相”地气流形式垂向迁移。试验证明,顶空气He、Ne异常对木里天然气水合物矿藏具有良好的指示作用。顶空气He、Ne勘查方法是冻土区水合物地球化学勘查技术的有效补充。     

水合物生成过程中碳同位素组成变化的实验研究

天然气水合物是一种新型的洁净能源。甲烷天然气水合物是储量最丰富的一种类型,常出现在深海中或极地大陆上,其生成的过程中会发生同位素的分馏效应。通过实验室模拟水合物生成的过程,利用天然海水与甲烷或二氧化碳气体反应,以及更接近实际生成环境的甲烷-海水-沉积物动态聚散实验,对甲烷水合物和二氧化碳水合物生成前后δ13C值进行测定,研究水合物生成过程中δ13C的变化情况。实验证明,水合物反应中碳同位素分馏是存在的,其变化程度明显小于氧同位素和氢同位素。甲烷水合物碳同位素的分馏系数αC的值为1000 3~1000 9。二氧化碳水合物生成反应后气相的碳、氧同位素变轻,重同位素趋向于进入水合物中,二氧化碳水合物碳同位素的分馏系数αC的值为1000 7~1001 2。海水中溶解的CO2气体在甲烷水合物形成过程中会被水合物捕获,从而使得δ13CDIC值变小,重的碳同位素趋于进入水合物中,而较轻的碳同位素留在海水中。但由于海水中含有的溶解CO2气体有限,经过多轮水合物动态聚散后δ13CDIC值的变化幅度会越来越小。     

Formation of gas hydrate deposits in the Siberian Arctic shelf

Natural gas hydrate deposits have been estimated to store about 10% of gas in hydrate form (even with regard to a higher concentration of gas in hydrates), proceeding from the known ratio of dissolved-to-deposited gas. This high percentage is largely due to the fact that the buffer factor in natural gas hydrate deposits is lower than that for free gas because of less diverse structural conditions for gas accumulation. Therefore, the available appraisal of world resources of hydrated gas needs a revision.Hydrates in rocks are either syngenetic or epigenetic. Syngenetic hydrates originate from free or dissolved gas which was present in rocks in situ at the time when PT-conditions became favorable for gas hydrate formation. Epigenetic hydrates are derived from gas which came by migration into rocks with their PT-conditions corresponding to formation of gas hydrates.In addition to the optimum PT-conditions and water salinity, economic gas hydrate accumulation requires sustained supply of natural gas into a specific zone of gas hydrate formation. This condition is feasible only in the case of vertical migration of natural gas along faults, fractured zones, and lithologic windows, or, less often, as a result of lateral migration.Of practical importance are only the gas hydrate deposits produced by vertical or lateral gas migration.     

Indirect Indicators of Gas HydrateOccurrence within Submarine Sediments

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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.     

海底天然气水合物赋存的间接识别标志

天然气水合物是近十多年来发现的一种新型超级洁净能源, 因其在能源勘探、海底灾害环境和全球气候变化研究中的重要性而日益引起世界各国的高度重视.尽管此种化合物通常分布于大陆边缘沉积物和极地永冻层内, 但前者的水合物赋存量占据全球天然气水合物总量的90 %以上.鉴于此, 拟就该种化合物在海底沉积物中赋存的简接标志进行详细讨论, 以使人们在不进行沉积物取样或没有采集到水合物样品的情况下, 也能快速准确地确定此种化合物的分布.      

Use of comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry for the characterization of biodegradation and unresolved complex mixtures in petroleum

A comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) method has been developed for separation of a series of petroleum samples using a polar/non-polar column set configuration. Groups of oils were selected to provide samples from the same oil family to assist in comparison of compositional changes during biodegradation. The groups also represented different sources and ages to allow an assessment of the application of GC × GC for the differentiation of oil source, as well as fluid history. The increased resolution and separation afforded by the GC × GC technique provides more complete compositional information on complex biodegraded oil samples than one-dimensional GC, and improves the ability to study biodegradation trends. Among the components identified, it is proposed that alkyl-decahydronaphthalenes constitute a significant contribution to the UCM.     

最新国际天然气水合物研究现状与资源潜力评估(上)

地层骨架孔隙中水合物的高质量形成是开展水合物实验研究的前提和物质基础,可为我国深水油气及水合物资源开发提供理论指导。依据南海GMGS2-07井水合物层地质条件,利用TOUGH+HYDRATE数值模拟软件和自主研制的水合物反应生成装置开展数值模拟和实验研究,在验证数值模拟方法准确性和可靠性的基础上,通过控制变量法分别开展不同地层导热系数和含水饱和度条件下水合物生成质量的影响研究。结果表明：(1) 数值模拟与室内实验过程中,水合物形成时温度、压力与三相物质变化趋势一致且特征值十分接近,验证了数值模拟方法的准确性和可靠性。(2) 导热系数越大,水合物生成越快,最终形成的水合物饱和度越大,分布也更加均匀。但导热系数与最终形成水合物的饱和度的正负相关性,存在临界边界。本次所选用的反应釜尺寸,临界边界距上、右边界距离为1.8 cm,临界边界内导热系数与水合物饱和度呈正相关性,临界边界外呈负相关性。临界边界随着反应釜尺寸的增大而增大,但临界边界位置不受地层渗透率的影响。(3) 随地层含水饱和度增加,最终形成的水合物饱和度先增大后减小,峰值处含水饱和度小于初始压力条件下的理论气水比。当初始压力为7.8 MPa,含水饱和度约22.23%时,所形成的水合物饱和度最大且分布最不均匀。由此可知,选用高导热系数材料制备地层骨架、使初始含水饱和度低于气水理论比以及调整初始温压条件使之偏向相平衡曲线左方有利于形成分布均匀的高饱和水合物。研究认为深水油气含水合物固井和水合物资源钻采提供依据,为水合物商业化开采提供技术储备。

     

甲烷水合物在AlCl3溶液中的相平衡条件

利用可视法测定了甲烷水合物在AlCl₃溶液中的三相平衡(甲烷水合物-AlCl₃液相-甲烷气相)条件.AlCl₃溶液中甲烷水合物的生成压力为4.040～8.382 MPa,温度为272.15～278.15 MPa.对相同摩尔浓度的AlCl₃和KCl溶液中甲烷水合物生成条件的抑制作用进行了讨论.并将实验结果与前人的研究数据进行了对比,通过统计分析得到一计算甲烷水合物相平衡压力与温度的经验公式,经计算所得结果与实验数据一致.研究认为AlCl₃溶液可以作为一种良好的抑制剂用于油气工业的输送管道中。     

天然气水合物研究现状与未来挑战

人类在21世纪后期面临着油气资源枯渴,寻求洁净高效的新能源成为科学界追求的目标。为此,近三十年来,世界各国相继投入了大量的资金和人力开展新能源研究。目前,人们在一种重要的新能源---气水合物的基础研究、地质调查、勘探开发等领域取得了较大的进展;但尚存在许多急待解决的重大理论问题,如天然气水合物形成与分解的动力学过程和地质条件,气水合物资源量计算办法,经济型天然气水合物开采、开发模式,气水合物对全球气候的影响等。天然气水合物作为化石燃料,具有巨大潜力;作为甲烷碳库,是海底地质灾害的诱因;作为温室气体,对全球气候变化有着重要的影响作用。天然气水合物研究未来面临挑战。     

Molecular simulation studies on natural gas hydrates nucleation and growth: A review

How natural gas hydrates nucleate and grow is a crucial scientific question. The research on it will help solve practical problems encountered in hydrate accumulation, development, and utilization of hydrate related technology. Due to its limitations on both spatial and temporal dimensions, experiment cannot fully explain this issue on a micro-scale. With the development of computer technology, molecular simulation has been widely used in the study of hydrate formation because it can observe the...     

晚期泥底辟控制作用导致神狐海域SH5钻位未获水合物的分析

海底泥底辟构造与天然气水合物成藏关系密切,泥底辟既能为水合物提供充分的气源物质,同时又能促使地层温度场改变进而影响水合物成藏稳定性。南海北部神狐海域SH5站位虽然BSR明显,但钻探证实不存在天然气水合物。该钻位温度剖面异常高,温度场上移,同时在其下伏地层中发现泥底辟构造和裂隙通道。根据上述事实并结合泥底辟发育各个阶段中的特点,认为泥底辟构造对天然气水合物成藏具有控制作用。泥底辟发育早期和中期阶段,低热导率和低热量有机气体有利于天然气水合物生成;而在晚期阶段,高热量液体上侵稳定带底界,导致水合物分解迁移。SH5站位很可能由于受到处于晚期阶段的泥底辟上侵而未能获取天然气水合物。     

非活动大陆边缘的天然气水合物及其成藏过程述评

非活动陆缘是板块活动相对较弱的地区，也是水合物发育的有利地区。通过对世界各地非活动陆缘地区水合物富集情况的系统分析，发现断褶组合构造、底辟构造以及“麻坑”地貌（Pockmark)与水合物的关系密切。尽管模拟海底反射层（Bottom Simulating Reflector,简称BSR，下同）是最重要的水合物识别标志，但水合物与BSR之间并不存在严格的一一对应关系。非活动陆缘具有丰富的烃类物质来源和适宜的温压条件，而断裂－褶皱组合构造、垒堑式构造和底辟构造等则为烃类气体的运移、富集和成藏提供了有利的构造环境，便于最终形成水合物。非活动陆缘的深水区往往发育有多期叠合盆地，因其物源、温压、构造和沉积条件的内在关联性，常常形成深部石油、中部天然气、浅部水合物的“三位一体”烃类能源结构模式。     

基于天然气水合物地震数据计算南海北部陆坡海底热流

天然气水合物是一种由水的冰晶格架及其间吸附的气体分子（以甲烷为主）组成的固态化合物,地震剖面上的似海底反射BSR是天然气水合物赋存的重要地球物理标志。相同气体成分水合物的相对稳定的温压关系是根据BSR的赋存深度计算海底热流的理论基础。选择南海北部陆坡有典型BSR反射的地震剖面,计算了南海北部陆坡天然气水合物发育区的压力、温度、地温梯度、热导率及热流等地热参数。通过计算热流值与实测热流值的对比可以大致推测,在南海北部陆坡海底运用该方法计算的热流值误差可能在12％以内。本研究不仅可以为海底热流等理论研究提供一定信度的数据资料,而且通过实测热流值校正后的热流数据以及经验公式,可以反过来用于BSR深度的计算以及天然气水合物稳定域的预测,具有重要的实践意义。     

国际天然气水合物勘查开发研究新进展——第七届爱丁堡国际天然气水合物大会特邀报告综述

简要介绍了2011年7月在英国爱丁堡召开的第七届国际天然气水合物大会概况。对会议中5个大会特邀主题报告给予介绍或评述。Thomas介绍了亨弗利·戴维对科学发现的追求和应用,后者在实验室发现了气水合物。Ripmeeste总结了实验模拟中对气水合物客体与载体相互作用、水合物形成和分解过程的认识和成果。Suess指出过去25年间人们对海洋天然气水合物的研究经历了从“避免策略到旨在获取”、“能源开发和二氧化碳储存兼顾”、“追求储量到记录环境变化”3个阶段。Kurihara总结了日本多年的研发结果,包括数字模拟研究、对甲烷储层的分类和产气能力的评估、天然气生产方法等,讨论了商业发展甲烷水合物的可行性和挑战。Sloan介绍了管道安全复杂体系的4种概念性端元类型,并指出风险管理策略比防治更为经济,是未来防止水合物堵塞的重要工具。     

天然气水合物孔底冷冻取样方法的室内试验研究

本研究提出的天然气水合物孔底冷冻取样方法是利用外部冷源在孔底降低水合物岩心温度,采用主动式降温的方法降低水合物的临界分解压力,达到被动式降压来抑制水合物分解,获得水合物岩心的方法。首先,通过分析天然气水合物温压特性得出了孔底冷冻取样方法的可行性;然后,借助室内冷冻模拟试验确定了干冰为冷冻剂,酒精作为助冷催化剂和载冷剂的冷冻方式;最后,依据冷冻模拟试验得出的干冰法冷冻方式研制了FCS型天然气水合物孔底冷冻取样器样机,并进行了土层钻进冷冻取样试验,取得冷冻黄土岩心。本研究提出天然气水合物孔底冷冻取样思想,为天然气水合物取样器的设计提供了新的思路。     

The experience of mapping of Baikal subsurface gas hydrates and gas recovery

Lake Baikal is the only fresh-water lake where natural gas hydrate accumulations were found in sediments. For the recent decade, Baikal has become a natural laboratory for investigation of the properties of gas hydrates, their indicators, and recovery of gas from subsurface (subbottom) gas hydrates. We present the main results of subsurface gas hydrate mapping and gas recovery test near the delta of the Goloustnaya River.     

天然气水合物勘探-开发-储运-环境响应研究新进展--第五届天然气水合物国际会议简介

主要根据第五届天然气水合物国际会议(ICGH5)的资料,介绍了天然气水合物勘探、开发、储运和环境响应研究的新进展.在勘探、开发方面,主要使用多维地震和核磁共振等方法来研究天然气水合物的分布情况,并根据天然气水合物声阻抗与沉积物孔隙度之间的关系来估算天然气水合物的资源量;在储运方面,与传统的液化天然气方法相比,以天然气水合物丸粒形式储运天然气所需的费用和所消耗的总能量以及所释放出的CO2相对较少;在环境响应方面,对深海储存CO2以及CH4流体对海洋和大气影响的研究,为解决天然气水合物可能引起的环境问题提供了新的思路.最后,介绍了各国天然气水合物的研究情况,并对天然气水合物研究中尚需解决的问题进行了展望.