应用高温甲烷吸附实验研究川东北地区五峰组页岩甲烷吸附能力

页岩甲烷吸附能力是决定页岩气井开采方案的重要参数,对评估页岩气藏潜力意义重大。干酪根类型、总有机碳含量、矿物组成、成熟度和孔径等是影响页岩吸附性能的因素,但针对高温高压下过剩吸附现象对页岩甲烷吸附能力影响的研究还需开展进一步的探索。为揭示四川盆地东北地区五峰组页岩甲烷吸附能力,本文通过场发射扫描电镜、低温氮气吸附和高压甲烷吸附实验,研究了高温高压下页岩的甲烷吸附能力,并分析了页岩孔隙结构等对页岩吸附能力的影响。结果表明:①五峰组页岩孔隙结构非均质性强,发育有机孔隙、粒(晶)间孔隙、粒(晶)内孔隙和粒(晶)间溶孔等多种孔隙;②比表面积平均为19.1282m^2/g;孔体积平均为0.0195cm^3/g;孔径平均为5.2226nm;③修正后的饱和吸附气量为2.56m^3/t;④五峰组页岩甲烷吸附性能受控于比表面积、孔体积;有机质含量越大、有机质热演化程度越低,其甲烷吸附性能越强;⑤孔隙结构是影响页岩甲烷吸附能力的重要内因。同时指出低压条件下的实验吸附曲线不适合直接评价页岩甲烷吸附能力。     

Analysis of geological effects on methane adsorption capacity of continental shale: a case study of the Jurassic shale in the Tarim Basin,northwestern China

The Jurassic shale is an important source rock for the found gas reservoirs in the Tarim Basin, northwestern China, but has never been researched for shale gas potential. The geological effects on methane adsorption capacity for the gas shale have been investigated in this paper through the geochemical, mineralogical and adsorption analyses on samples from wells and sections. The methane adsorption capacity ranges from 0.58 to 16.57 cm³/g, and the total organic carbon (TOC) content is between 0.5 and 13.5 wt%. The organic maturity measured by T_max is between 410 °C (immature) and 499 °C (overmature). The methane adsorption capacity of the Jurassic continental shale in the Tarim Basin is affected by many geological factors, including the TOC content, organic matter maturity, mineral composition, surface area and pore size distribution. The TOC content is the most significant factor with a positive effect on the adsorption capacity of the Jurassic shale, and the influence varies piecewise according to the TOC content. The TOC content contributes much more to the methane adsorption capacity of organic‐rich shale samples (TOC content > 0.7 wt%) than to the organic‐lean samples (TOC content < 0.7 wt%). The mineral composition is a secondary factor, and the abundance of clay content has a positive effect on the methane adsorption capacity despite its relatively weaker adsorption ability compared to TOC. The pore size distribution has different effects on surface area and pore volume. Mesopores and micropores provide the major surface area and are mainly derived from TOC and illite, which has a positive influence on the adsorption capacity. Mesopores and macropores offer the major pore volume and are mainly formed by illite, which is the major contributor for pore volume rather than surface area. In addition, the TOC and illite contents of the Jurassic shale in the Tarim Basin are closely related to the origin, maturity and diagenesis evolution of the shale: (1) both TOC and illite content variations are related to the different provenances and depositional environments of shale; (2) the decrease of TOC content with increasing maturity is also partly attributed to hydrocarbon generation; and (3) the increase of illite content with increasing maturity is due to illitization in the diagenesis of shale. Copyright © 2015 John Wiley & Sons, Ltd.     

Methane adsorption comparison of different thermal maturity kerogens in shale gas system

To determine the effect of thermal maturity on the methane sorption in shale gas system, two different thermal maturity kerogens of type II isolated from Barnett shale of Fort Worth Basin were used to measure the methane adsorption amount under the pressure ranging from 0 to 14 MPa at constant temperatures. One kerogen was called Lee C-5-1 with 0.58% of vitrinite reflectance; the other was called Blakely#1 kerogen with 2.01% of vitrinite reflectance. The results suggested that the methane sorption capacity of kerogen Blakely#1 was higher than the immature kerogen Lee C-5-1, and its Langmuir constant and Langmuir maximum sorption amount, which were reached by fitting the measured data for at least square method, greater than the immature kerogen Lee C-5-1. This may be associated with that nanopores opened up during the degradation of organic matter, and which increased the specific surface area of kerogen. Therefore, the over mature kerogen has greater methane adsorption capacity.     

Reservoir characteristics and methane adsorption capacity of the Upper Triassic continental shale in Western Sichuan Depression,China

The well-developed continental shale sequences in the Western Sichuan Depression are characterised by extremely low porosity and permeability, complex lithologies and strong lateral facies changes. The overall lack of proper characterisation of the shale properties has restricted gas exploration and development in the region. In this study, shales from the fifth member of the Xujiahe Formation of the Upper Triassic (T₃x⁵) are comprehensively characterised in terms of their organic geochemistry, mineral composition, microscopic pore structure and gas content. In addition, the influence of various geological factors on the adsorbed gas content is investigated. We proposed a new model for predicting the adsorption gas content of continental shale. The T₃x⁵ shale sequence is found to be rich in organic matter but with variable mineral compositions, pore types and reservoir physical properties. The porosity and permeability of shales are better than those of siltstones and fine sandstones interbedded with the shale under an overall densification background. Mesopores (2–50 nm) are common in the shale sequence, followed by micropores and then macropores. The gas-adsorption capacity of organic-rich shales increases with increasing TOC and clay-mineral contents, maturity and pressure, but decreases with increasing quartz content, carbonate minerals and temperature. The gas-adsorption capacity can thus be expressed as a function of organic matter, clay-mineral content, temperature and pressure. The calculated results are in good agreement with the experiment results and indicate that adsorption gas in the studied shales accounts for 78.9% of the total gas content.     

Kinetic Modeling the Formation of Low-mature Gases and Analysis of the Possibility to Be Accumulated

At present, shallow gases have received much attention due to low cost in exploration and production. Low-mature gases, as one significant origin to shallow gas, turns to be an important research topic. The present understanding of low-mature gases is confined within some geological cases, and few laboratory studies have been reported. Therefore, the potential and characters of low- mature gases are not clear up to now. Here, two premature samples （one coal and the other shale） were pyrolyzed in a gold confined system. The gaseous components including hydrocarbon gases and non-hydrocarbon gases were analyzed. Based on kinetic modeling, the formation of low-mature gases was modeled. The results showed that during low mature stage, about 178 mL/gTOC gas was generated from the shale and 100 mL/gTOC from the coal. Two third to three fourth of the generated gases are non-hydrocarbon gases such as H2S and CO2. The total yields of C1-5 for the two samples are almost the same, 30-40 mL/gTOC, but individual gaseous hydrocarbon is different. The shale has much lower C1 but higher C2-5, whereas the coal has higher C1 but lower C2-5. Hydrocarbon gases formed during low-mature stage are very wet. The stable carbon isotope ratios of methane range from -40‰ to -50‰ （PDB）, in good consistence with empiric criterion for low-mature gases summed up by the previous researchers. The generation characters suggest that the low-mature gases could be accumulated to form an economic gas reservoir, but most of them occur only as associated gases.     

皖南地区二叠系孤峰组页岩中高密度含甲烷包裹体特征及其地质意义

对皖南地区泾县昌桥剖面的二叠系孤峰组硅质页岩裂缝石英脉中流体包裹体进行了显微激光拉曼光谱测试、热力学温度测定及拉曼光谱图谱解析,观测到了高密度甲烷包裹体。利用甲烷包裹体的拉曼散射峰v₁位移2910.6~2911.2 cm-1,计算得到甲烷包裹体密度为0.2295~0.2618 g/cm3,具有高密度甲烷包裹体特征。含甲烷组分的气液两相盐水包裹体均一温度分布在216.8~242.3℃。由于气液两相盐水包裹体与甲烷包裹体是共生的,通过状态方程热力学计算高密度甲烷包裹体在共生气液两相盐水包裹体最小温度216.8℃的捕获压力为76~95 MPa。对甲烷流体包裹体密度和捕获压力的计算,揭示了区域内二叠系孤峰组高演化程度的硅质页岩在地史演化过程中存在高压甲烷流体产出的证据,为开展皖南地区二叠系页岩气勘探评价提供了科学依据。      

辽东湾断陷金县1-1低凸起东斜波沙三段泥岩古地层压力恢复及应用

烃源岩生烃过程中欠压实作用形成的异常高压是油气成藏的主要动力,而泥岩孔隙度演化记录了其地层压力的变化过程。根据现今泥岩压实剖面特征建立欠压实泥岩孔隙度计算模型,利用"回归反推"方法恢复成藏期沙三段欠压实泥岩古孔隙度增量,然后根据泥岩孔隙度压实模型恢复欠压实泥岩在成藏期的总古孔隙度,最后通过改进的Phillip-pone公式计算成藏期古地层压力并恢复其演化过程。研究表明,金县1-1低凸起东斜坡成藏期沙三段烃源岩普遍发育异常高压,古流体动力由南向北逐渐增强,压力系数分布呈现东南部低西北部高的特点,古流体压力的强弱变化规律对油气运移及有利目标的优选具有重要的意义。     

Source identification of methane in groundwater in shale gas development areas: A critical review of the state of the art,prospects, and future challenges

Shale gas exploration and development carry the risk of causing groundwater contamination and enhancing the greenhouse effect through methane leakage. Identifying the source of abnormal methane in groundwater of shale gas development areas is becoming a research hotspot in the fields of groundwater and climate change. This paper reviews the traditional methodology in identifying sources of methane and its deficiency in groundwater application. Then potential and advantages of using noble gases were discussed on how to overcome these limitations of the traditional method. Finally, based on noble gas, the current application status and future challenges of methane source identification in groundwater were analyzed. It can be summarized as:(1) due to chemical and/or microbial processes in the aquifer system, the traditional methodology for methane source identification, which utilizes molecular and isotopic compositions of hydrocarbon gas, has multiple interpretationsand large uncertainties;(2) the non-reactive nature and well-characterized isotopic compositions of noble gases in the atmosphere, hydrosphere, and crust, make noble gases ideal indicators of the sources of methane in groundwater. Moreover, the mechanism of formation and release of crustal noble gas prevent shale gas signatures from being interfered with by natural gas;(3) the key scientific tasks surrounding the use of noble gases for methane source identification include quantitatively separating the components of atmosphere-derived, mantle-derived, and crust-derived noble gases from the bulk noble gases in groundwater. It quantifies the solubility fractionation of noble gases induced by water-gas interaction during methane migration to the aquifer. The application of noble gases can bring a new perspective to tracing the source of methane in groundwater and is of great significance to the protection of groundwater quality in shale gas development areas and mitigation of climate change.     

南襄盆地泌阳凹陷陆相页岩油地质特征与评价

南襄盆地泌阳凹陷中部深凹区发育有淡水环境及咸水环境沉积的深湖—半深湖相页岩。该套页岩岩相复杂、类型多、变化快, 可分为泥质粉砂岩、粉砂质页岩、隐晶灰质页岩、重结晶灰质页岩及白云质页岩, 总体富含有机质, 这为陆相页岩油的形成提供了充分的物质基础。研究区页岩具有纵向厚度大、横向分布广、有机质丰度高及类型好、热演化程度适中、脆性矿物含量高及含油气性好等特征, 具备良好的陆相页岩油形成条件。在明确泌阳凹陷具备良好的陆相页岩油形成条件基础上, 进一步开展了陆相页岩油地质评价方法的研究, 提出了一套包含岩石学分析、地质多参数综合评价、有利区带评价等8项关键技术的地质评价方法, 并明确了泌阳凹陷陆相页岩油富集的主控因素及有利目标区, 进而优化部署页岩油水平井, 取得了中国陆相页岩油勘探的重大突破, 展示了中国陆相页岩油良好的勘探开发前景。     

松辽及外围盆地油页岩资源潜力与政策建议

油页岩是一种重要的替代能源,我国东北地区的松辽及外围盆地油页岩资源非常丰富。根据最新研究结果,松辽盆地的油页岩资源折算成页岩油约为578.4亿t。目前,东北地区油页岩开发生产基本仍局限在老油页岩基地,采用露天或井下挖掘开采,成本高、生产规模小,产量尚未达到历史上的最高水平,与丰富的资源很不匹配。同时,巨大的油页岩资源及其可能带来的丰厚回报,驱使国内外投资者在松辽及外围盆地开始争夺油页岩资源,由此可能引起油页岩资源无序竞争及资源浪费等诸多严重问题。国家应立足长远,加强油页岩资源的科学管理,促进油页岩资源的合理开发和利用。     

海陆过渡相页岩气层系沉积研究进展与页岩气新发现

四川盆地海相页岩气成功规模效益开发,使我国页岩气跨入了高速发展的快车道,确立了页岩气在我国能源安全保障中的重要战略地位。我国海陆过渡相页岩气资源丰富,有望成为我国页岩气增储上产的现实领域。目前海陆过渡相页岩气勘探开发和地质评价还处在初期阶段,海陆过渡相富有机质页岩发育特征与分布、沉积模式、有机质富集机理等非常规油气沉积学相关研究有待深入。通过系统厘定海陆过渡相相关概念与特征,明确了国内外典型海陆过渡相页岩气层系;系统总结海陆过渡相页岩沉积研究现状与新进展,揭示了海陆过渡相中富有机质页岩有利发育环境、主要沉积模式和页岩气储层基本特征。系统梳理鄂尔多斯、四川、渤海湾等盆地海陆过渡相页岩气勘探开发新发现,指出了我国海陆过渡相页岩气具有良好勘探开发前景。海陆过渡相页岩层系常伴有煤层,可进行页岩气、煤层气等联合开采,实现“体积开发”,以期有效推动我国天然气产业高质量大发展。     

中国陆相盆地油页岩成因类型及矿床特征*

针对油页岩成因类型,国内外学者做过一些有益的探讨,但尚不存在统一的分类方案。鉴于中国油页岩以陆相成因为主,作者从油页岩的沉积环境出发,总结出从深湖-半深湖到湖沼环境,油页岩中湖泊生物来源的有机质所占比例逐渐减少,陆源有机质影响变大,并以此把中国陆相盆地油页岩分为深湖腐泥型油页岩、半深湖腐殖腐泥型油页岩和湖沼腐泥腐殖型油页岩3种成因类型。通过系统梳理中国29个陆相含油页岩盆地矿床特征,发现深湖腐泥型油页岩主要赋存于大中型坳陷盆地,往往具有分布范围广、空间展布稳定、品质和厚度中等的特点;发育在小型断陷盆地中的深湖腐泥型油页岩矿床具有分布范围小、横向差异大、品质良好和厚度巨大的特点。半深湖腐殖腐泥型油页岩在断陷盆地和坳陷盆地都有分布,具有分布范围小、空间上品质和厚度差异明显。湖沼腐泥腐殖型油页岩主要沉积于断陷盆地中,具有分布局限、品质好、厚度薄的特点。     

页岩储层可压裂性影响因素及评价方法

可压裂性是页岩在水力压裂中具有能够被有效压裂的能力的性质,是页岩开发中最关键的评价参数,影响因素包括页岩脆性、天然裂缝、石英含量、成岩作用及其他因素,目前常利用页岩矿物组成或岩石力学参数来表征,难以全面反映页岩在水力压裂过程中的综合性质。采用极差变换和经验赋值方法将参数标准化,使用层次分析法确定不同因数对可压裂性影响的权重,使用标准化值与权重系数加权得到可压裂系数的数学模型可对页岩可压裂性进行定量评价。可压裂系数越大,页岩可压裂性越强。采用该模型计算渝东南地区渝页1井龙马溪组页岩可压裂系数为0.485 5,Barnett页岩可压裂系数为0.484 4,总体处于同一水平;同时,使用该模型将页岩可压裂性分为3个级别,可压裂系数在0.132 0~0.282 0的页岩可压裂性低,水力压裂效果不佳;可压裂系数在0.282 0~0.456 7的页岩可压裂性中等,水力压裂能够取得较好的效果;可压裂系数在0.456 7~0.784 0的页岩可压裂性高,是优质的可压裂层。水力压裂应选择可压裂系数大于0.360 7的页岩。     

甘肃省新能源——油页岩特征及开发利用条件分析

非常规油气资源的勘查和开发利用目前已被提到议事日程。油页岩就是首先要考虑开发利用的、现实的、有可能部分代替常规油气资源的非常规能源之一,并已经成为新能源领域里研究的热点。甘肃省的中生代盆地里不仅赋存有良好的煤炭、石油资源,而且蕴藏着较为丰富的油页岩资源。现已查明,省内油页岩预测资源量至少约2 000亿t,折合页岩油约1...     

PPTS-1压力传递型泥页岩渗透性测试系统

井壁失稳一直是困扰油气勘探开发的难题,而泥页岩渗透性是评价泥页岩井壁稳定性的重要指标之一。介绍了一套基于LabVIEW软件平台的PPTS-1压力传递实验系统平台,采用岩心分析法和压力传递测试技术精确测试泥页岩的渗透率。实验结果表明,该实验平台操作简单,性能稳定,测试精度高,为井壁稳定性深入研究提供了支撑。      

非常规油气地质调查工程进展与主要成果

中国地质调查局油气资源调查中心牵头组织实施的“非常规油气地质调查工程”,开展了黑龙江省鸡西地区煤系气地质调查、松辽盆地及外围油页岩地质调查、松辽盆地西斜坡油砂原位试采工程、陆域天然气水合物地质调查与祁连山木里天然气水合物野外长期观测站建设、陕西关中地区氦气地质调查和非常规油气资源国情调研等工作,获取了大量基础数据,取得了黑鸡地1井、黑鸡地3井、黑鸡地4井等一系列突破性成果和重要进展,初步掌握了我国油页岩、油砂、陆域天然气水合物、氦气以及鸡西盆地煤系气等非常规油气资源潜力。该工程在煤系气、油页岩、氦气等领域产生重要影响,提振了非常规油气勘探开发信心,推动了科技创新与地质调查深度融合,促进了非常规油气学科发展。     

基于微孔充填模型的页岩储层吸附动力学特征分析

微孔填充是吸附质分子在吸附剂纳微孔隙中、较高平衡压力下表现出来的一种吸附特征,以此为基础发展起来的热
力学理论在确定吸附剂微观结构及吸附性能研究方面起到了巨大推动作用。基于此,该文重点探讨了甲烷在页岩中吸附时
填充率θ、特征能量E、特征系数n、微分吸附功A 、吸附热Q、吸附焓ΔH 及吸附熵ΔS 的变化关系。结果表明：特征系数n
取1较为适当;温度升高特征能量E 值略降,3组样品E 值范围4.14~5.63 kJ/mol;随着θ 的不断增加,A ,Q ,｜ΔH ｜及｜
ΔS ｜等参数值逐渐降低,各能量参数随吸附进行而发生较为规律的变化,无突变。结果认为,热力学参数一定程度上代表
了TOC 及Ro 等参数的综合效应,受单一因素干扰性不强。将计算的Q 及ΔS 等热力学参数与四川盆地志留系龙马溪组页岩的
相应参数进行了对比,进一步表明四川盆地该套龙马溪组页岩具有巨大的页岩气勘探和开发潜力。     

页岩气开发水力压裂技术综述

世界页岩气资源丰富,但由于页岩地层渗透率很低,目前还没有广泛开发。水力压裂技术是页岩气开发的核心技术之一,广泛用于页岩储层的改造。介绍了水力压裂作业的压裂设计、裂缝监测、压裂液配制和添加剂选择,以及常用的压裂技术,包括多级压裂、清水压裂、同步压裂、水力喷射压裂和重复压裂。结合国外页岩气开发的实例和国内压裂技术的应用情况,分析了各种压裂技术的适用性。研究认为,清水压裂是现阶段中国页岩气开发储层改造的适用技术,开采长度(厚度)大的页岩气井,可以使用多级分段清水压裂技术。同步压裂技术是规模化的页岩气开发的客观需要。     

油页岩成矿作用研究中的关键方法和技术

油页岩作为一种重要的非常规油气资源,如何有效地利用油页岩成矿作用研究中的关键方法和技术实现油页岩的综合识别与评价极其重要。油页岩识别的关键技术主要包括基于岩石学的地质识别、精确的地球化学指标识别、测井技术的垂向高分辨率快速识别和地震技术的三维空间定量刻画。先进的测试技术、创新的理论方法以及高品质地球物理资料的二次开发利用将不断提升油页岩从定性到定量预测识别的精度。油页岩成矿作用研究的关键方法是从古构造条件、古气候条件、古地理条件以及古湖泊环境等地质因素入手,探讨其综合作用下有机质来源、保存条件及成岩作用的变化,由定性向半定量—定量地精细刻画油页岩中有机质聚集过程,从而有效地预测油页岩的展布及其富集规律。由于文中材料以中国陆相含油页岩盆地的研究成果为主,而陆相成因油页岩的识别特征及成因机制可能与海相等成因存在差异,因此,仍需油页岩地质学家不断深入研究与总结。希望此文对页岩油、页岩气及烃源岩研究也具有一定的借鉴意义。     

改性煤系高岭土矿粉填充橡胶的结构与性能

以煤系高岭土为主要原料通过相对富集,超细粉碎、表面改性处理等方法,得到一种橡胶填充剂MUCKP。用它代替通用炭黑作为橡胶的补充填充剂,制备了胶片,对填充后的橡胶进行了应用性能研究。结果表明:用于天然橡胶时,当填充剂粒度小于400目时,已有较好的补强作用,其主要性能指标类似于通用炭黑,可以部分等量替换碳黑作为橡胶的补强填充剂。取代量在20%~25%之间。