模拟储层条件下突出煤的导电性质研究

研究了模拟储层条件瓦斯突出煤的导电性质,得到了瓦斯突出煤在不同储层条件下的电阻率变化特征,为研究瓦斯突出地球物理场的电磁波响应特征提供了基础.     

CO2分压条件下煤中矿物质溶解度数值模拟

查明煤中矿物质在不同温度和CO₂分压条件下溶解度变化规律,能为注入CO₂过程中煤储层渗透率分析提供重要依据。借助水文地球化学模拟软件PHREEQC对在不同温度和CO₂分压条件下煤中各矿物的溶解度进行了水化学模拟,得出不同温度和CO₂分压条件下矿物质溶解度的变化规律。结果表明：在无CO₂分压时,随着温度的升高各矿物的溶解度增加;当溶液中CO₂分压增加到一定程度时,随着温度的升高各矿物的溶解度降低（石英除外）;在温度相同时,随着CO₂分压的增加,所有矿物（石英除外）溶解度均增加,方解石的溶解度随着CO₂分压的升高呈现出迅速增加的趋势,其他矿物随着CO₂分压的升高,溶解度增加的速率较为缓慢。     

CO2/N2二元气体对甲烷在煤中吸附影响的分子模拟研究

二元气驱技术(CO₂/N₂-ECBM)已成为煤层气增产的重要手段,明确CO₂/N₂在煤层中的竞争吸附规律以及对煤层物性的影响具有重大意义。利用分子模拟软件Materials Studio建立延川南煤层气实际区块温度、压力条件下的煤分子模型。基于巨正则蒙特卡洛(GCMC)方法研究CO₂/N₂交替驱替煤层气技术中各注入阶段对CH₄吸附的影响,明确CO₂、N₂对煤层孔渗物性的影响规律。结果表明:在CO₂注入阶段,煤层中甲烷迅速解吸;煤中气体吸附总量上升,煤基质膨胀效应增强,导致煤的孔隙体积降低。而转N₂注入后,由于N₂分压作用使得CH₄、CO₂吸附量呈现出不同程度的降低;当ω_N2/ω_CO2≤0.6时煤分子中气体总吸附量迅速降低,而当N₂饱和吸附后气体总吸附量保持稳定。煤层孔渗物性随着气体吸附总量呈现出迅速增大后趋于平缓的趋势。此外,ω_N2/ω_CO2>0.6后N₂吸附率迅速降低,这会使得产出气中CH₄纯度较低,导致后期提纯成本大大增加。因此,当ω_N2/ω_CO2=0.6左右时,CH₄解吸量为最大值,煤孔隙率较高,最有利于煤层气的开发。      

煤与瓦斯突出物理模拟试验中甲烷相似气体的探索

当前煤与瓦斯突出物理模拟试验多采用二氧化碳代替甲烷,导致试验结果偏差较大。为了保证模拟试验相似性并规避甲烷气体带来的安全风险,提出了甲烷相似气体的概念。基于瓦斯在突出过程中的作用机制和相似准则,结合煤与瓦斯突出防治规定,建立了以瓦斯含量、瓦斯放散初速度、初始瓦斯膨胀能和含瓦斯煤力学性质为参数的相似指标。初步采用二氧化碳体积分数为20%、40%、60%、80%的二氧化碳和氮气二元混合气体作为甲烷相似气体的筛选气体。按照相关规范,分别测定了甲烷和筛选气体的相似指标参数值,确定了与瓦斯含量、瓦斯放散初速度、初始瓦斯膨胀能和含瓦斯煤力学性质接近的混合气体组分分别是二氧化碳体积分数为60%、35%、45%和54%。相关性分析结果表明,上述4种配比气体与甲烷性质相关性高,可以作为相似气体的待定气体。采用待定气体和甲烷进行了模拟试验,结果表明,二氧化碳体积分数为45%的混合气体的突出现象和突出临界值与甲烷接近,与甲烷相似性高。     

中煤级煤吸附甲烷的物理模拟与数值模拟研究

基于184个中煤级（镜质组最大反射率Ro,max介于0.65%~2.50%）煤在平衡水条件下的等温吸附实验成果,模拟了中煤级煤的朗格缪尔体积和压力与煤级的关系,建立了不同埋深（温度、压力）条件下不同煤级煤饱和吸附气量量板,探讨了压力和温度对中煤级煤吸附甲烷能力的综合效应,对比分析了中煤级煤吸附特征与低、高煤级煤的差异,提出了中煤级煤吸附气量预测的方法。     

江苏省及近海区域CO2地质封存储层条件分析

对江苏省及近海区域地质进行了分析表明,下扬子地块发育的苏北—南黄海南部盆地为该省CO₂地质封存潜在目标场所。文章通过地层及岩性资料分析了CO₂封存适宜地层,在此基础上,根据钻井与地震测量剖面资料,阐述了各构造单元的800～3500 m深度范围存在的CO₂封存适宜地层的厚度,探讨CO₂封存空间适宜性。结果表明：盐城组下段、三垛组、戴南组、阜宁组一段与三段、赤山组砂岩具有较好CO₂储存空间;苏北—南黄海盆地的赤山组分布较少,盐城组、三垛组、戴南组、阜宁组地层分布范围较广;金湖凹陷、高邮凹陷、溱潼凹陷、海安凹陷、白驹凹陷、阜宁凹陷、盐城凹陷、南二凹陷、南四凹陷、南五凹陷、南七凹陷、南二低凸起具有较好的CO₂封存储层潜力;洪泽凹陷、临泽凹陷、涟南凹陷、涟北凹陷、南三凹陷、南六凹陷CO₂封存储层潜力较差。     

超临界CO2温变对低渗透煤层孔渗变化的实验研究

为解决我国高瓦斯煤层渗透性差导致瓦斯抽采率低的难题,利用超临界二氧化碳强扩散和溶解增透等独特优点,采用自制三轴渗透实验装置,开展不同温度下超临界二氧化碳作用后煤的宏观增透实验,在宏观增透实验基础上进行煤微观扫描成像实验。结果表明：恒定体积应力和孔隙压力条件下,不同温度超临界二氧化碳作用后,煤的渗透率较增透前提高一个数量级,但在二氧化碳的超临界温度范围内,煤的渗透率随温度增加呈负指数变化规律。超临界二氧化碳作用后,煤微观孔隙率较增透前提高两个数量级,随着温度增加,煤微观孔裂隙的演化速率减慢,孔隙率随温度增加呈负指数变化规律。宏微观实验数据同时表明,煤宏观渗透率随微观孔隙率增加而增大。超临界二氧化碳增透过程中,孔隙压力对低渗透煤层的增透效果起主控作用。     

CO2注入对煤储层应力应变与渗透率影响的实验研究

以沁水盆地成庄矿煤样为研究对象,利用实验室自主研发的CO₂注入与煤层气强化开采实验模拟装置进行不同有效应力和CO₂吸附压力下的煤岩渗透率测试。实验结果表明,煤岩的裂隙压缩系数受到CO₂吸附的影响,初始状态下、亚临界CO₂吸附和超临界CO₂吸附煤样裂隙压缩系数分别为0.066、0.086和0.089。引起裂隙压缩系数改变的原因主要有两方面：CO₂和煤中矿物反应提高了煤基质的不连续性;CO₂软化了煤基质同时降低了煤岩的力学性质。利用考虑吸附应变以及内部膨胀系数的渗透率模型对实测渗透率进行拟合,发现有效应力和内部膨胀系数成正比。CO₂吸附压力和有效应力的增大均提高了煤岩的内部膨胀系数,这影响了煤岩孔裂隙的开度,降低了煤储层的渗透率,并最终降低CO₂在煤储层中的可注性。     

热力耦合条件下超临界CO2驱替煤层CH4实验

为提高煤层CH₄抽采效率,利用自主研发的实验系统,模拟超临界CO₂在深部煤层中驱替CH₄的过程,开展了不同温度和注入压力条件下原煤试样中超临界CO₂渗流、吸附及驱替CH₄实验。结果表明：在恒定温度条件下,随着超临界CO₂注入压力逐渐增大,煤体渗透率提高,CO₂吸附量增加。超临界CO₂注入压力和温度对驱替效果影响显著。不同温度条件下,当超临界CO₂注入压力从8 MPa增至12 MPa,CH₄驱替量平均增长了0.076 cm³/g,CH₄驱替效率增加了17%~23%,超临界CO₂置换体积比呈线性递减趋势;相同注入压力条件下,温度每升高10℃,驱替效率平均增加8%,置换体积比平均下降0.5。研究结果为高效抽采煤层CH₄和实现CO₂封存提供理论依据。     

煤层CO2地质封存的微观机理研究

煤层CO₂地质封存可实现CO₂减排和增产煤层气双重目标,是一种极具发展前景的碳封存技术。相对于其他封存地质体而言,煤的微孔极其发育,煤层CO₂封存机制与煤中气、水微观作用关系密切,其内在影响机理尚不清楚。以2个烟煤样品的系统煤岩学分析测试为基础,构建了煤的大分子结构及板状孔隙空间模型,进一步采用分子动力学方法模拟了不同温、压条件下、不同煤基质类型表面的CO₂和水的润湿行为,揭示煤层CO₂注入后引起的水润湿性变化规律,初步阐明煤层CO₂封存的可注性、封存潜力、封存有效性等影响因素及微观作用机理。结果表明：(1)影响煤润湿性的主要因素是煤中极性含氧官能团,其含量越高煤的润湿性越强;(2)煤中注入CO₂后,CO₂通过溶解作用穿透水分子层与水分子发生竞争吸附,从而减小水在煤表面润湿性;(3)随注入压力增大和温度降低,煤表面CO₂吸附量增多,对氢键破坏作用增强,润湿性减弱越明显;(4)亲水性煤层CO<...     

Caprock interaction with CO2: A laboratory study of reactivity of shale with supercritical CO2 and brine

Crushed rock from two caprock samples, a carbonate-rich shale and a clay-rich shale, were reacted with a mixture of brine and supercritical CO₂ (CO₂–brine) in a laboratory batch reactor, at different temperature and pressure conditions. The samples were cored from a proposed underground CO₂ storage site near the town of Longyearbyen in Svalbard. The reacting fluid was a mixture of 1 M NaCl solution and CO₂ (110 bar) and the water/rock ratio was 20:1. Carbon dioxide was injected into the reactors after the solution had been bubbled with N₂, in order to mimic O₂-depleted natural storage conditions. A control reaction was also run on the clay-rich shale sample, where the crushed rock was reacted with brine (CO₂-free brine) at the same experimental conditions. A total of 8 batch reaction experiments were run at temperatures ranging from 80 to 250 °C and total pressures of 110 bar (∼40 bar for the control experiment). The experiments lasted 1–5 weeks.Fluid analysis showed that the aqueous concentration of major elements (i.e. Ca, Mg, Fe, K, Al) and SiO₂ increased in all experiments. Release rates of Fe and SiO₂ were more pronounced in solutions reacted with CO₂–brine as compared to those reacted with CO₂-free brine. For samples reacted with the CO₂–brine, lower temperature reactions (80 °C) released much more Fe and SiO₂ than higher temperature reactions (150–250 °C). Analysis by SEM and XRD of reacted solids also revealed changes in mineralogical compositions. The carbonate-rich shale was more reactive at 250 °C, as revealed by the dissolution of plagioclase and clay minerals (illite and chlorite), dissolution and re-precipitation of carbonates, and the formation of smectite. Carbon dioxide was also permanently sequestered as calcite in the same sample. The clay-rich shale reacted with CO₂–brine did not show major mineralogical alteration. However, a significant amount of analcime was formed in the clay-rich shale reacted with CO₂-free brine; while no trace of analcime was observed in either of the samples reacted with CO₂–brine.     

超临界CO2对烟煤和无烟煤化学结构的影响

超临界CO₂对煤化学结构的改造对煤层CO₂封存能力极为关键。论文开展了模拟埋深1500m （62.5℃、15 MPa）条件下4组不同变质程度煤的ScCO₂-H₂O体系与煤岩地球化学反应实验。通过傅里叶变换红外光谱和X射线粉末衍射实验获得了反应前后煤化学结构演化特征,探讨了煤化学结构演化的机理。结果表明：ScCO₂作用后,煤中脂肪烃链长度普遍增加,仅肥煤的芳香烃丰度增大,肥煤、瘦煤和贫煤含氧基团丰度的增大主要由氢键基团含量的增加贡献,无烟煤含氧基团丰度则主要受低分子化合物溶出的影响。ScCO₂引起的溶胀作用造成肥煤和瘦煤芳香层面之间交联键断裂,芳香微晶内部结构疏松,而芳香层面内C_Ar-C_Ar交联的形成提高了肥煤和瘦煤芳香性和芳香环缩合度;贫煤和无烟煤中非稠合多苯结构脱落使芳香微晶内部更紧凑,脂肪烃链长度的增加则降低了贫煤和无烟煤芳香性和芳香环缩合度。     

火山岩吸附CO2气的成藏潜力及实例分析

火山岩的脱气实验和对昌德东CO2气藏气源的分析结果表明加热火山岩到250℃时,脱出挥发分总量为0.0299～0.0790mL/g,其中CO2脱出量为0.0218～0.0706mL/g(0.429～1.387wt%);挥发组分以CO2为主,还含有H2、CO、CH4等还原性气体,以及少量低碳烷烃,CO2含量和总烃呈现反比关系;基性岩的CO2脱出量、脱出率高于中、酸性岩;CO2脱出量与岩石碱质含量正相关.松辽盆地北部昌德东CO2气藏成藏模式为"自生自储",成藏CO2气主要来自深部被火山岩吸附的气.随岩浆上升,在岩浆冷凝成火山岩的过程中被吸附于火山岩的节理、劈理和晶体位错之中的CO2气,连同火山岩包体中的残留气,成为高纯CO2气藏的主要补给源,并非地幔气体沿大断裂上来直接充注成藏.     

超临界CO2注入煤层对顶板岩石纵波速度及力学响应特征研究

深部煤层CO₂地质封存与CH₄强化开采(CO₂–ECBM)技术在提高煤层气采收率的同时可实现碳减排,具有能源和环境双重效益。超临界CO₂(ScCO₂)、水和煤层顶板之间的地球化学反应可改变其物理力学性质,增加CO₂泄漏的风险。以沁水盆地胡底煤矿3号煤层顶板岩石为研究对象,开展“ScCO₂–水–岩”地球化学反应模拟实验,探讨CO₂煤层封存条件下ScCO₂–水–顶板岩样地球化学反应过程及其对岩石纵波速度和力学性质的影响。结果表明:ScCO₂–水–岩之间化学溶蚀反应造成岩样Ca、Mg元素显著降低,促使岩样表面形成孤立状溶蚀孔,并随着反应时间的持续,进而形成大量的“溶蚀坑”和“溶蚀缝”;增加了岩样结构不连续性,使得声波传播路径增大、能量损失加剧,导致纵波波速降低;ScCO₂–水–岩反应后岩样的峰值强度和弹性模量降低,泊松比升高,且三者之间的变化率与反应时间之间呈现Logistic函数的变化关系。对于胡底煤矿而言,ScCO₂–水–岩反应过程中顶板力学性质的弱化不足以造成盖层的破裂和CO₂泄漏,但在评价煤层CO₂封存安全性时,还应考虑煤层吸附膨胀应力对顶板的影响。      

含裂隙碳酸盐岩酸化中超临界CO2对虫孔生长的影响初探

酸化是一种广泛应用于碳酸盐岩储层的增渗改造技术,其基本原理是将酸液注入储层裂隙,通过溶蚀反应使矿物溶解形成虫孔等通道,从而提高储层的渗透性和生产效率。以往的研究主要聚焦于优化注酸条件以提高成孔效率,忽略了碳酸盐岩酸化副产物CO2的影响。本研究针对三个含单裂隙的碳酸盐岩试样,开展不同浓度盐酸溶液的酸化实验,监测试样渗透率的变化;并在试验前后分别进行裂隙表面形貌激光扫描和内部空隙CT扫描,基于扫描结果对比分析了注酸条件对溶蚀效果的影响。研究结果表明：在流速、酸液浓度与种类等条件相同的条件下,CO2是否进入超临界态对虫孔形态有重要影响;超临界CO2可有效促进虫孔的生长,生成窄而长的虫孔,并显著提高溶蚀效果,试样的渗透率可提高3~9倍;而在CO2未进入超临界态的条件下,溶蚀形态接近面溶蚀或锥形虫孔,未贯通试样,试验前后渗透率没有显著变化,这是因为酸化反应产生的气态CO2会阻碍酸液的流动,从而降低酸化效果。本文结果揭示了在酸化中正面利用副产物CO2的可能性,有助于对现有酸化工程方案的优化和提升。     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.