Methane adsorption in the low–middle-matured Neoproterozoic Xiamaling marine shale in Zhangjiakou,Hebei

The adsorption capacity of high–over-matured shale has been widely investigated, but the adsorption capacity and the main factors influencing low–middle-matured, type II kerogen-containing, and organic-rich marine shale have been rarely explored. This research conducts organic geochemistry, mineralogical composition, adsorption isotherm tests to reveal the adsorption and main influencing factors of the different geochemistry characteristics, mineralogical compositions, temperature and pressure conditions of the low–middle-matured Neoproterozoic Xiamaling marine shale in Zhangjiakou, Hebei. The investigated shale is in a low–middle maturity stage, contains type II kerogen and is rich in organic matter. The results show that the total organic carbon (TOC) content of the Xiamaling shale is positively correlated with the methane adsorption capacity, which is the most important influencing factor on the adsorptive property of shale. The methane adsorption capacity first decreases to the minimum value as the temperature reaches 360°C equivalent Ro (EqRo = 1.0%), then increases and reaches the maximum value at 620°C (EqRo = 3.28%) and finally decreases again as the temperature rises at the last simulation stage. The mineral components exhibit an insignificant influence on the methane absorbability because of organic-matter coatings. The TOC-normalised methane adsorption capacity is positively correlated with the illite–smectite and clay-mineral contents but shows no significant correlation with brittle minerals, such as quartz. Soluble organic matter and kerogen caused the methane dissolution and adsorbtion, respectively. The strong dissolution property of the soluble organic matter is the most important cause of the larger adsorption capacity of the original shale compared with that of the residual samples. Moreover, the methane adsorption capacity of the Xiamaling shale decreases with increasing temperature, and increases with pressure below the critical pressure but decreases exceeding the critical pressure.     

基于Ono-Kondo格子模型的页岩气超临界吸附机理探讨

页岩气吸附机理的研究对于页岩气成藏和储量评价具有重要意义.甲烷在地层温度和压力条件下处于超临界状态,页岩气的吸附实际上为超临界吸附,但其机理目前尚不明确.在建立Ono-Kondo格子模型的基础上,结合低温氮气吸附和高压甲烷等温吸附实验,对龙马溪组页岩的微观孔隙结构和超临界吸附曲线进行了分析.结果表明,页岩中发育的孔隙尺度较小,比表面积较大,吸附气主要赋存于微孔和中孔中;页岩的等温吸附曲线在压力较大时,必然存在下降的趋势,这并非异常现象,而是超临界甲烷过剩吸附量的本质特征.Ono-Kondo格子模型对页岩高压等温吸附曲线的拟合效果很好,相关系数均在0.99以上,说明该模型可以表征页岩纳米孔隙中超临界甲烷的吸附特征.基于拟合得到的吸附相密度可将过剩吸附量转换为绝对吸附量,并直接计算地层温度和压力下甲烷的吸附分子层数,计算层数均小于1,表明甲烷分子并没有铺满整个孔隙壁面.因此受流体性质、吸附剂吸附能力和孔隙结构3个方面的影响,页岩气的吸附机理为单层吸附,不可能为双层甚至多层吸附.      

柴达木盆地东部石炭系页岩吸附特性实验研究

柴达木盆地东部石炭系页岩是一套待开发的优质烃源岩,吸附是页岩气最主要的储集状态,但针对该区页岩吸附特征的研究较少。依据物质守恒与热力学平衡原理,运用自主设计的气固双相等温吸附实验仪,参考煤的高压等温吸附测定行业标准,对取自柴达木盆地东部石浅1井的页岩样品进行了不同温度(30 ℃、40 ℃、50 ℃和60 ℃)的甲烷等温吸附实验研究,并运用LangmuirFreundlich(L F)模型对吸附量实验值进行非线性回归分析;根据ClausiusClapeyron方程计算得到页岩对甲烷的等量吸附热方程。研究结果表明：压力一定时,页岩对甲烷的吸附量随着温度升高而降低;温度一定时,随压力升高,甲烷吸附量出现先增大后降低的现象,具有典型的超临界吸附特征;L F模型对等温吸附过程拟合效果良好,实验结果将模型中4个参数确定,且各参数物理意义明确;计算得到等量吸附热与吸附量之间的关系为：q=-3 679.7n+9 779.5,等量吸附热随吸附量增大而降低。等量吸附热结合L F模型可以预测任意温度、压力下页岩对甲烷的吸附量,且预测值与实验所得数据结果吻合较好,对页岩气储量评估与开发利用具有实际意义。     

页岩中气体的超临界等温吸附研究

页岩气等温吸附实验多为临界温度以上的吸附实验,其得到的吸附量为过剩吸附量。为了研究页岩气超临界等温吸附机理,运用重力法,在临界温度以上,分别进行了甲烷和二氧化碳在页岩中的高压等温吸附实验。在分析经典型吸附和超临界吸附区别的基础上,通过修改的超临界等温吸附模型(Langmuir方程和微孔充填(Dubinin Radushkevich,D-R))对实验数据进行了拟合。结果表明:简单的Langmuir方程可近似拟合甲烷吸附实验数据,但精度不高,且无法拟合二氧化碳的吸附数据;将吸附相密度作为可优化参数,修改的微孔充填模型和Langmuir模型能很好地拟合甲烷和二氧化碳的吸附数据,其中修改的微孔充填模型拟合效果最好,且回归得到的超临界甲烷吸附相密度同文献报道的一致,表明吸附气可能以微孔充填的形式存在。      

构造抬升过程中煤储层吸附能力的耦合效应及控制因素

煤层气盆地在地史演化过程中几乎都经历了多次抬升作用,构造抬升作用对煤储层吸附能力有着直接的影响。文中通过物理模拟实验和数值模拟对构造抬升过程中煤储层吸附能力的耦合效应和控制因素进行探讨。研究选取高、低煤阶煤储层样品进行等温吸附实验,并假定地温梯度分别为2、4和6 ℃/hm,压力梯度分别为0.3、0.5和1.0 MPa/hm模拟抬升过程中吸附量的变化。研究结果表明,煤储层在构造抬升过程中的吸附能力的变化主要受温压综合作用、煤储层热演化程度和构造抬升强度的控制。构造抬升时,温度作用效果占主导地位,煤储层吸附量增加;反之,压力作用效果占主导地位,煤储层吸附量减少。高煤阶煤层吸附量的变化量大于低煤阶变化量。抬升强度较大时煤层吸附量持续降低,较小时会使吸附量增加。煤层气在抬升过程中可能会出现吸附或解吸,与以往只是解吸的认识不同。当温度作用效果大于压力作用效果,即煤储层吸附量增加时,抬升作用易导致煤储层的含气欠饱和。     

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.     

超临界状态下煤岩吸附/解吸二氧化碳的实验

查明超临界状态下煤岩对CO₂的吸附/解吸特征,能为煤层气开采现场注CO₂的注入参数选取提供理论依据。以山西屯留矿的瘦煤和寺河矿的无烟煤为研究对象,借助ISO-300型等温吸附实验仪分别进行了不同温度(35℃、45℃、55℃)、最高压力达到CO₂临界压力以上时的吸附/解吸实验。结果表明:超临界状态下,随着压力升高,容量法测得的吸附量存在最大值,不代表煤样的绝对吸附量,而是Gibbs吸附量;根据煤岩在高压下吸附CO₂的本质,计算出超临界状态下煤岩吸附/解吸CO₂的真实量。超临界状态下煤岩吸附CO₂的真实量与压力之间符合langmuir吸附曲线,随着吸附压力的升高,Gibbs吸附量与绝对吸附量之间的差值越来越大;随着温度的升高,煤样的饱和吸附量降低;同样条件下,高变质程度的无烟煤对CO₂的饱和吸附量大于瘦煤;超临界状态下煤样对CO₂的绝对吸附等温线和绝对解吸等温线是可逆的。      

较高温度下煤吸附甲烷实验及其意义

报道了3个煤样在30℃、5 0℃、70℃条件下的等温吸附实验结果,认为饱和吸附量与温度存在相关关系;据此,可以预测深部煤层的吸附甲烷含量。      

Differential Characteristics of the Upper Ordovician-Lower Silurian Wufeng-Longmaxi Shale Reservoir and its Implications for Exploration and Development of Shale Gas in/around the Sichuan Basin

The Upper Ordovician Wufeng-Lower Silurian Longmaxi shale is widely distributed in the Sichuan Basin and its periphery, which is the key stratum for marine shale gas exploration and development(ED) in China. Based on sedimentary environment, material basis, storage space, fracability and reservoir evolution data, the reservoir characteristics of the Wufeng-Longmaxi shale and their significance for shale gas ED are systematically compared and analyzed in this paper. The results show that(1) the depocenter of the Wufeng(WF)-Longmaxi(LM) shale gradually migrates from east to west. The high-quality shale reservoirs in the eastern Sichuan Basin are mainly siliceous shales, which are primarily distributed in the graptolite shale interval of WF2-LM5. The high-quality reservoirs in the southern Sichuan Basin are mainly calcareous-siliceous and organic-rich argillaceous shales, which are distributed in the graptolite shale interval of WF2-LM7.(2) Deep shale gas(the burial depth 3500 m) in the Sichuan Basin has high-ultrahigh pressure and superior physical properties. The organic-rich siliceous, calcareous-siliceous and organic-rich argillaceous shales have suitable reservoir properties. The marginal area of the Sichuan Basin has a higher degree of pressure relief, which leads to the argillaceous and silty shales evolving into direct cap rocks with poor reservoir/good sealing capacity.(3) Combining shale gas exploration practices and impacts of lithofacies, depth, pressure coefficient and brittle-ductile transition on the reservoir properties, it is concluded that the favorable depth interval of the Wufeng-Longmaxi shale gas is 2200～4000 m under current technical conditions.(4) Aiming at the differential reservoir properties of the Wufeng-Longmaxi shale in the Sichuan Basin and its periphery, several suggestions for future research directions and ED of shale gas are formulated.     

准噶尔盆地彩南地区深层低阶煤吸附特征及其影响因素

现有数据表明我国1 000 m以浅低阶煤层含气量普遍偏低,而深层低阶煤试采效果显示较好。基于Langmuir方程开展了低阶煤高温高压环境下等温吸附模拟实验,结果表明:褐煤吸附量约占长焰煤、气煤吸附量的1/3,吸附能力最弱,随着煤阶的升高,吸附量逐渐增大;实验发现低阶煤在55℃、12 MPa以下吸附量随温度、压力增大而增加较快,并建立了基于煤阶-温度-压力条件下的深层低阶煤饱和吸附模型;煤层随着埋藏深度的增加,吸附量呈现出快速增加-缓慢增加-缓慢递减的过程,即深层煤层吸附量存在吸附临界深度带,为1 400~1 700 m。1 400 m以浅吸附量受压力正效应大于温度负效应,吸附量随埋深增加而增加,临界深度带内吸附量达到极限,不再增加,1 700 m以深温度负效应大于压力正效应,吸附量随深度增加而减小。实验结果为深层低阶煤层气资源评价及开发潜力提供理论依据。      

煤层气吸附量动态变化模型研究

基于吸附势理论、气体状态方程,建立了煤储层压力与煤体吸附半径、孔隙半径与煤体吸附量、储层压力与煤体吸附量之间的关系模型,得出储层压力、吸附量、孔隙半径等多参数耦合的煤层气吸附量动态变化模型,利用潘庄区块煤体结构测试数据以及等温吸附试验结果对模型进行了验证。结果表明:潘庄区块以孔径小于7.7 nm的微孔为主,以孔径7.7 nm为临界点孔容呈先减小后增大趋势;模型计算的吸附量动态变化结果与煤体空气干燥基等温吸附变化结果在趋势上具有较高的一致性,模型的起始点为枯竭压力以及枯竭吸附量,得出潘庄区块枯竭吸附量为3 m3/t。模型不仅能够计算地层条件下不同温度和压力共同作用下煤体对甲烷气体的吸附量,且能够预测煤层气排采过程煤层气吸附量的动态变化,有助于确定煤层气排采工作制度以及提高煤层气采收率。      

不同煤阶深煤层含气量差异及其变化规律

基于Langmuir 等温吸附方程式,开展不同煤阶不同温压条件下等温吸附模拟实验,实验结果表明：在煤岩镜质组反 射率Ro<3.0%时,Langmuir 等温吸附曲线随煤阶、温度、压力升高表现出明显的分带性。随着煤阶的升高,煤吸附能力逐 渐增强。温度小于55℃时不同煤阶Langmuir 体积受温度影响较小,之后影响逐渐增大。低煤阶在12 MPa、中高煤阶在 15 MPa以前随压力增加Langmuir 体积增大明显。根据实测含气量外推法结合高温高压等温吸附实验建立了深煤层含气量数 学模型,显示煤层含气量随埋深呈现快速增加—缓慢增加—不增加—缓慢减小的变化规律,其中低煤阶临界深度介 于1400~1700 m,中高煤阶临界深度介于1500~1800 m。该含气量数学模型对预测深部煤层含气量变化规律及煤层气资源评 价提供基础依据。     

Microscopic Pore characteristics and methane sorption capacity of the lower cambrian shales in yangtze platform北大核心CSCD

The lower Cambrian develops a set of organic-rich black shales in Yangtze Platform and is regarded as one of the key layers of shale gas exploration. The microscope pore structure characteristics and methane sorption capacity were investigated using scanning electron microscope, nitrogen adsorption and methane sorption experiments, and then their controlling factors combining with organic matter, mineral compositions were discussed for Niutitang shales in Zunyi area, Mufushan shales in Nanjing area and Huangboling shales in Chizhou area. The results show as below; ( I ) The pores in lower Cambrian shales are mainly dominated by organic pores, interlayer pores in clay minerals and micro-fractures, as well as containing some intergranular pores between brittle mineral grains, honeycomb poies formed by pyrite crystals falling out, and dissolution molds in fossils; ( 2) DKT pore size distributions show the pores is mainly concentrated in the range of less than 4 nm in lower Cambrian shales and kerogens, while a certain amount of pores are above 4 nm are also existed in lower Cambrian shales, which may be contributed by smectite; ( 3)The specific surface area, pore volume and Langmuir methane sorption capacity of the lower Cambrian shales are ranging from 5.58 to 31. 96 inVg, 0.026 to 0.088 mL/g and 1.36 to 5. 3 mL/g, respectively, which are mainly controlled by TOC and smectite contents, but the effect of TOC and smectite on physical properties are quite different for the lower Cambrian shales in different regions; ( 4)The specific surface area of two Niutitang kerogens are 7. 08 and 7. 92 times than that of the shales and methane sorp-Tion capacity of kerogens arc 5.81 and 7.09 times than that of the shales, suggesting that kerogen is a main carrier of methane gas occurrence in.     

适用于中深层-深层页岩气的高压吸附模型

我国目前开发的中深层-深层页岩气藏储层压力高.低压下的吸附实验和理论难以满足勘探开发的需要.针对这一问题,对Uniform Langmuir模型进行了修正,发展了一个适用于中深层-深层页岩气的高压吸附模型,即修正的Uniform Langmuir（Unilan）模型.然后,利用文献发表的高压吸附实验数据对修正的Unilan模型进行了验证,并与其他高压吸附模型进行了对比,发现:相对于其他高压吸附模型,修正的Unilan模型具有拟合参数少和精度高的优点.最后,基于拟合得到的Unilan模型参数,结合页岩样品矿物组成,开展了模型参数分析,发现:有机质和黏土矿物对页岩气吸附均有贡献;吸附达到饱和时的吸附相体积大于微孔体积且小于总孔体积;吸附熵变主要与吸附态甲烷分子-页岩的相互作用强度有关.      

温度对煤吸附甲烷的影响实验

为了研究温度对煤吸附甲烷的影响,实验测定了不同温度下煤对甲烷的吸附等温线,并对实验数据进行了拟合,同时对覆盖度与压力、温度、吸附量以及孔隙类型的关系进行了分析。结果表明:随着温度的增高,饱和吸附量和吸附速率明显降低,并且含气量与覆盖度呈正相关关系;同一压力下,随着温度升高,覆盖度降低;相对覆盖度概念可以解释高温覆盖度高而吸附量小于低温阶段的现象;结合孔隙度和液氮分析结果发现,随着温度的增高,小孔和微孔的吸附能力强于中孔和大孔;甲烷在煤上的等量吸附热随吸附量的增大而增大,但无规律可循,且由Clausius-Clapeyron方程预测出的等温吸附曲线与实测值有偏差,表明煤表面能量的不均匀性和表面离子的复杂性。      

陆相页岩微观孔隙结构特征及对甲烷吸附性能的影响

页岩的微观孔隙结构对其甲烷吸附性能及页岩油气潜力具有重要影响,前人研究主要集中在海相页岩。该文以四川 盆地川西坳陷上三叠统须家河组五段为例,开展了陆相页岩的探索研究。首先通过低温氮气吸附实验对页岩样品的微观孔 隙结构特征进行了研究,计算了页岩的比表面积、孔径分布、孔体积和平均孔径等孔隙结构参数;然后通过高压甲烷等温 吸附实验,研究了页岩样品的甲烷吸附特征;最后探讨了页岩微观孔隙结构特征对甲烷吸附性能的影响。结果表明,须五 段页岩平均孔径为7.81~9.49 nm,主体孔隙为中孔,也含有一定量的微孔和大孔,孔隙形状以平行板状孔为主,含有少量 墨水瓶形孔。页岩比表面积高出常规储层岩石许多,有利于气体在页岩表面吸附存储,孔径在2~50 nm的中孔提供了主要 的孔体积,构成了页岩中气体赋存的主要空间。在85℃条件下,页岩甲烷吸附的兰氏体积为1.21~4.99 m3/t,不同页岩样品 之间的吸附性能差异明显。页岩的兰氏体积与比表面积之间呈现良好的正相关关系,比表面积与黏土矿物含量呈正相关, 而与总有机碳含量关系不明显。页岩的兰氏体积与微孔和中孔体积之间都具有良好的正相关关系,微孔体积和中孔体积与 总有机碳含量之间存在一定的正相关关系,但是正相关性的程度没有微孔体积和中孔体积与黏土矿物含量之间的关系强 烈。陆相页岩有机质热演化程度相对较低,因此有机孔发育有限：但另一方面同时黏土矿物含量较高,所以其内部发育大 量微孔和中孔,从而构成可观的比表面,影响甲烷吸附能力。     

渝东北地区WX2井页岩气赋存特征及其勘探指示意义

为了深入研究渝东北地区龙马溪组页岩气赋存特征,该文以WX2井页岩高温高压等温吸附及覆压孔隙度实验数据为 基础,通过误差最小原则挑选了适合研究区的吸附模型,并基于孔隙度随有效应力变化关系建立游离气模型,综合分析了 吸附气、游离气及总含气随埋藏深度的变化特征。研究结果表明：WX2井页岩不同温度下过剩吸附量随着压力增大,均呈 现先增大后减小的趋势,随着温度的升高,最大吸附量逐渐减小,而校正后的绝对吸附量随压力增加,先迅速增大后增速 放缓,且用D-A模型拟合绝对吸附量数据平均误差最小,基本可以反应研究区页岩真实吸附过程。页岩样品在加压过程中 孔隙及微裂隙会逐渐闭合,卸压时绝大部分会重新打开,存在部分塑性变形造成的不可逆损伤,但不可逆损伤所占比重较 轻。不同方向样品孔隙度与有效应力之间具有负指数关系,富含层理页岩平行样品较垂直样品具有更大的初始孔隙度以及 更强的孔隙应力敏感性。页岩气赋存特征综合受控于储集层特征、吸附能力、温度及压力等因素,其中温度对吸附气和游 离气含量为负效应,储层压力为正效应;吸附气、游离气及总含气量均遵循先增大后减小的总体趋势,其中吸附气及游离 气含量分别主要受控于温度及储层压力。此外,临界深度上下,页岩吸附态与游离态相对含量发生变化,其对页岩气富集 评价具有重要意义。     

郑州市东区深层地热特征及合理开发利用

介绍了郑州市东区深层地热的特征,把深层地热资源划分为三层：埋藏深度320～850 m的第一地热储层,热储岩性为新近系中细砂层,热储平均厚度1553 m。热储温度33°C,地温梯度2.5～3.5°C/100 m。埋藏深度850～1 200m的第二热储层储岩性为新近系细砂、中细砂层,热储总厚度86～187m,热储温度45°...     

A Preliminary Study of the Gas Hydrate Stability Zone in the South China Sea

Based on the analysis of sea-bottom temperature and geothermal gradient, and by means of the phase boundary curve of gas hydrate and the sea-bottom temperature versus water depth curve in the South China Sea, this paper studies the temperature and pressure conditions for gas hydrate to keep stable. In a marine environment, methane hydrate keeps stable at water depths greater than 550 m in the South China Sea. Further, the thickness of the gas hydrate stability zone in the South China Sea was calculated by using the phase boundary curve and temperature-depth equations. The result shows that gas hydrate have a better perspective in the southeast of the Dongsha Islands, the northeast of the Xisha Islands and the north of the Nansha Islands for thicker stability zones.     

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。