CO2地质埋藏深度对高阶煤孔隙结构的影响

高阶煤中的CO₂地质埋藏具有存储CO₂和提高煤层气采收率的双重意义。通过压汞测试和低温液氮吸附实验对经过CO₂地质埋藏模拟实验处理前后的煤样品进行分析测试,探讨了不同埋藏深度下煤中孔隙演化的特征与机理。研究表明：煤的真密度、视密度、孔隙体积、煤基质体积变化、有机质膨胀与收缩等参数均表现出不同的演化特征;埋藏过程中温度压力的增大对H₂O–CO₂–煤的地球化学反应效应的影响并非线性,而是存在一个对孔隙特别是微孔孔容和比表面积改造最大的深度范围,该深度将使得高阶煤孔隙结构得到最佳的改造效果,从而进一步更有利CO₂的地质埋藏和提高煤层气的采收率。     

CO2地质储存的地震监测

主要阐述了CO2隔离技术的基本思路和CO2地中隔离的主要方式,在此基础上提出了CO2煤层中隔离的可行性和隔离机制的分析方法,分析了CO2地质储存的重点研究问题及研究思路,评价了地震监测方法在CO2地质储存检测中的有效性。     

云贵高原湖泊CO2的地球化学变化及其大气CO2源汇效应

湖泊是大气CO₂的源还是汇,长期以来一直都存有争议。云贵高原地区的湖泊由于受流域碳酸盐岩风化作用的影响,使这一问题就显得更特殊,也更复杂。本次研究通过化学平衡计算和气相色谱测定两种方法得到了比较一致的湖水CO₂浓度结果。研究发现,在夏季强烈的光合作用消耗了湖水CO₂,致使湖水中CO₂浓度降低。在贵州草海、百花湖以及云南的泸沽湖、杞麓湖,表层湖水CO₂分压(为便于与大气CO₂比较,文中湖水CO2用分压单位表示)小于200μatm,远低于大气CO₂分压,湖泊正不断地从大气中吸收CO₂,从而构成大气CO₂的汇。     

CO2矿化研究现状及应用潜力

CO₂浓度急剧上升成为一个很严峻的问题,因此,降低大气CO₂浓度成为当务之急.目前涉及的方案中的海洋封存、地质封存,虽封存潜力巨大,但带来的负面影响也不容小觑.CO₂矿化利用实质是模拟自然界岩石化学风化,作为一种新兴的减排方案,既能固定大气CO₂,生成具有工业附加值的碳酸盐产品,又能实现环境友好.能够矿化利用的原材料包括天然富钙、镁硅酸盐矿物,工业碱性废固、液,盐湖中的氯化镁资源等,矿化利用的方法也不尽相同.虽然硅酸盐岩的风化是如何控制长时间尺度的气候变化的机制还没有定论,但风化过程中具有固定大量CO₂的潜力这一认识已达成共识.对含有大量硅酸盐矿物的尾矿矿化CO₂的研究是目前的热点,介绍了尾矿矿化CO₂的研究现状及几种重要尾矿矿物的矿化应用潜力.      

胜利油田富CO2含金流体及有关成因问题

本文分析了胜利油田火山岩中的Au含量，发现CO2气藏区火山岩和非CO2气藏区火山岩中Au含量有明显区别前者含Au很高，平均327×10-9,最高2150×10-9;而后者含Au很低,平均只有2.5×10-9。这一基本事实提供了CO2与金矿化间联系的直接地质证据,指出了在中国东部郯庐断裂两侧找寻新的金矿资源的方向与可能性。研究表明，地幔及其岩浆去气对形成富CO2含Au热液系统有重要的贡献，而一个由深部稳定热源驱动、富含地幔及其岩浆去气带入的CO2和Au并与地壳浅部流体混合的热液环流系统是形成重要金矿化的必要条件。     

1985年国际评价CO2问题专门会议声明

1985年10月9日至15日,在奥地利Villach,由联合国环境署(UNEP)、世界气象组织(WMO)、国家科学联盟理事会(ICSU)联合召开会议。与会的科学家来自29个发达国家和发展中国家,目的是评价不断增加的二氧化碳和大气中具有辐射作用的其它成分(温室气体)对气候变化和由此而引起的其它影响。二氧化碳和其它温室气体浓度的增长,将对下世纪上半期发生重大影响,导致气候变暖,使全     

融水对CO2激光融冰的影响

激光钻探具有高能性、高度方向性、清洁性、非接触式切割钻进等优势,在激光热融穿透冰的过程中,融水对激光的穿透效率有很大影响。为探究融水对激光穿透效率的影响程度,本文选用冰吸收效率更高的CO₂激光,在不同辐照角度、不同激光功率作用下对模拟极地冰心制备的冰样品进行定点穿透实验。结果表明：在负入射角-90°～-15°时,穿透速度为0.67～2.20 mm/s,仅为理论速度的21%～40%,孔径达到了光斑直径的3～5倍;而在正入射角15°～45°时,融水因重力作用及时排除,穿透速度为13.19～36.50 mm/s,是理论速度的2.2～6.5倍。     

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。     

海上CO2地质封存监测现状及建议

海上二氧化碳(CO₂)地质封存是中国应对滨海地区温室气体排放的重要举措,是实现“碳达峰、碳中和”目标不可或缺的关键技术。中国沿海地区工业发达、碳源丰富,近海盆地具有良好的储盖层物性和圈闭特征,封存潜力巨大,目前中国首个海上CO₂地质封存示范工程已在南海珠江口盆地正式启动。CO₂监测作为CCUS技术的重要组成部分,贯穿CO₂地质封存的全生命周期,是确保封存工程安全性和合理性的必要手段。然而,中国海上CO₂地质封存技术处于起步阶段,海上监测任务颇具挑战。文章回顾了国际上海上CO₂地质封存的相关代表性研究工作以及示范项目案例,对监测指标、技术、监测方案等进行分析,提出海上CO₂地质封存监测技术筛选优化方法和监测建议,旨在为中国海上CO₂地质封存示范项目的开展提供参考依据。     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

全国二氧化碳地质储存适宜性评价编图技术方法研究

将全国CO2地质储存潜力与适宜性评价工作划分为5个阶段,依次为区域级预测潜力(E级)评价、盆地级推定潜力(D级)评价、目标区级控制潜力(C级)评价、场地级基础储存量(B级)评价和灌注级工程储存量(A级)评价阶段.第一阶段编制的成果图件主要为全国1∶500万CO2地质储存成果图系;第二、三阶段主要编制沉积盆地CO2地质储存成果图集;第四、五阶段主要编制CO2地质储存示范工程成果图册.提出中国CO2地质储存潜力与适宜性评价和编图是一项有步骤、分阶段逐步完成的工程,评价及编图方法有待通过潜力与适宜性评价和编图的实践不断完善.     

基于数值模拟探讨提高咸水层CO2 封存注入率的途径

咸水层CO2地质封存是减少大气中CO2排放量的有效途径。CO2注入率是衡量咸水层中CO2注入能力的有效因素,因此,研究注入速率的变化规律及提高的措施是很有工程价值的。在很多区域,地层的低渗透性限制了CO2的注入率。针对鄂尔多斯盆地的水文地质条件,通过数值模拟,探讨在低渗透性咸水层中提高CO2注入率的途径,包括改变储层中的盐度、采用水平井注入、增加注入井段的长度以及采取水力压裂等工程措施。其中改变储层中的盐度可通过在注入CO2前向储层中注入一定量的水来实现。模拟结果表明,这些方式可以有效地提高CO2注入率,其中水平井改造方式和水力压裂工程措施效果显著,盐度改造措施在地层初始含盐度较高时,会有更好的效果。研究结果可为鄂尔多斯盆地和类似地区的咸水层CO2地质封存项目提供参考。     

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

Geologic factors controlling CO2 storage capacity and permanence: case studies based on experience with heterogeneity in oil and gas reservoirs applied to CO2 storage

A variety of structural and stratigraphic factors control geological heterogeneity, inferred to influence both sequestration capacity and effectiveness, as well as seal capacity. Structural heterogeneity factors include faults, folds, and fracture intensity. Stratigraphic heterogeneity is primarily controlled by the geometry of depositional facies and sandbody continuity, which controls permeability structure. The permeability structure, in turn, has implications for CO₂ injectivity and near-term migration pathways, whereas the long-term sequestration capacity can be inferred from the production history. Examples of Gulf Coast oil and gas reservoirs with differing styles of stratigraphic heterogeneity demonstrate the impact of facies variability on fluid flow and CO₂ sequestration potential. Beach and barrier-island deposits in West Ranch field in southeast Texas are homogeneous and continuous. In contrast, Seeligson and Stratton fields in south Texas, examples of major heterogeneity in fluvial systems, are composed of discontinuous, channel-fill sandstones confined to narrow, sinuous belts. These heterogeneous deposits contain limited compartments for potential CO₂ storage, although CO₂ sequestration effectiveness may be enhanced by the high number of intraformational shale beds. These field examples demonstrate that areas for CO₂ storage can be optimized by assessing sites for enhanced oil and gas recovery in mature hydrocarbon provinces.     

二氧化碳羽流地热系统的碳封存经济分析

【研究目的】 二氧化碳羽流地热系统（CPGS）在取热的同时可实现CO₂地质封存，在碳达峰与碳中和背景下，CPGS碳封存的经济性是众多学者关注的要点。【研究方法】 以松辽盆地泉头组为例，采用数值模拟方法对比分析了注入压力、井间距与回注温度对热提取率的影响，在供暖情景下，计算了CPGS供暖效益与碳封存成本，并与常规水热型地热系统供暖效益进行了对比。【研究结果】 受携热介质转变与热突破影响，CPGS开采井温度呈现“降低-稳定-降低”的趋势，其中井间距对开采井温降影响显著，井间距越小开采井温降越明显；热提取率与回注压力呈现正相关性，与回注温度呈现负相关性，井间距对热提取率影响不显著；CPGS与常规水热型地热系统相比，采热量呈现“高-低-高”三个阶段，其中回注压力越小、回注温度与储层温度越接近，实现CPGS较水介质多采热能所需的时间越短。【结论】 仅考虑CO₂价格与取热效益，供暖收益抵消部分碳封存成本后，井间距对CO₂封存单位成本影响最为显著，井间距越小，CO₂封存单位成本降低越迅速，在注采井间距300 m条件下，持续开采30 a后CO₂封存单位成本可降至160元/t。     

玄武岩封存CO2技术方法及其进展

玄武岩封存CO₂为碳捕集与封存（CCS）提供了一种新的具有潜在意义的选择。当今世界上已有三个示范工程案例,即日本Nagaoka、美国Wallula和冰岛Carbfix,这些实例初步证实了CO₂玄武岩封存的技术和经济可行性。玄武岩封存CO₂相关技术研究进展包括:（1）Carbfix项目采用水溶液替代胺溶剂来捕集烟气中的CO₂气体,以便同时对CO₂和其他可溶于水的气体进行捕获,而在排放点源只需简单加装水洗塔等设备作为气体分离装置;（2）冰岛提出了适用于CO₂饱和溶液注入与封存的Carbfix方法,设计出能分别注入气体和水溶液的专用系统;（3）Carbfix在注入与封存CO₂过程中首次采用示踪元素监测方法,并通过质量平衡方法定量估算注入CO₂发生碳酸盐化的百分比,发现往玄武岩里注入CO₂不到2年就有95%被完全矿化。今后仍需进一步研究的技术问题包括:（1）CO₂饱和溶液与超临界CO₂两种注入形式如何选择;（2）能否用海水替代淡水溶解CO₂;（3）如何提高地球化学模拟的准确性;（4）如何降低碳捕集、分离和运输环节成本。相关探讨对我国利用基性超基性岩进行CO₂封存具有一定借鉴意义。     

不同含水性无烟煤CO2吸附行为及其对地质封存的启示

深部煤层CO₂地质封存是助力“碳达峰碳中和”战略的重要途径,煤层含水性对以CO₂吸附封存为主的深部煤层CO₂地质封存能力影响显著。以无烟煤为例,开展了45℃下干燥、平衡水、饱和水煤样高压CO₂等温吸附实验,校正了饱和水煤样过剩吸附曲线,利用改进的D-R吸附模型拟合得到三者吸附能力与吸附热,对比了不同含水条件下CO₂绝对吸附曲线,阐释了饱和水增强无烟煤吸附能力的微观作用机理。结果表明:(1)干燥、平衡水、饱和水煤样CO₂吸附能力分别为56.72、45.19和48.36 cm3/g,吸附热分别为29.42、26.23和27.24 kJ/mol。(2) CO₂密度小于0.16 g/cm3(6.48 MPa)时,无烟煤CO₂绝对吸附量大小顺序为干燥煤样、饱和水煤样和平衡水煤样,而CO₂进入超临界状态后,顺序变为饱和水煤样、干燥煤样和平衡水煤样。(3)水分子优先占据高能吸附位是平衡水煤样吸附能力减弱的主要原因,而煤?水体系与CO₂相互作用强于CO₂与H₂O竞争吸附下的煤?CO₂相互作用是饱和水煤样在CO₂超临界阶段吸附能力高于干燥煤样的根本原因。(4)吸附封存是煤层CO₂地质封存的主要形式,深部煤储层条件下,煤层饱和水对超临界CO₂增储作用更为明显,高压注水是提高深部煤层CO₂地质封存潜力,改善煤储层渗透性的有效手段。      

GEOCARBSULF: A combined model for Phanerozoic atmospheric O2 and CO2

A model for the combined long-term cycles of carbon and sulfur has been constructed which combines all the factors modifying weathering and degassing of the GEOCARB III model [Berner R.A., Kothavala Z., 2001. GEOCARB III: a revised model of atmospheric CO₂ over Phanerozoic time. Am. J. Sci. 301, 182-204] for CO₂ with rapid recycling and oxygen dependent carbon and sulfur isotope fractionation of an isotope mass balance model for O₂ [Berner R.A., 2001. Modeling atmospheric O₂ over Phanerozoic time. Geochim. Cosmochim. Acta65, 685-694]. New isotopic data for both carbon and sulfur are used and new feedbacks are created by combining the models. Sensitivity analysis is done by determining (1) the effect on weathering rates of using rapid recycling (rapid recycling treats carbon and sulfur weathering in terms of young rapidly weathering rocks and older more slowly weathering rocks); (2) the effect on O₂ of using different initial starting conditions; (3) the effect on O₂ of using different data for carbon isotope fractionation during photosynthesis and alternative values of oceanic δ¹³C for the past 200 million years; (4) the effect on sulfur isotope fractionation and on O₂ of varying the size of O₂ feedback during sedimentary pyrite formation; (5) the effect on O₂ of varying the dependence of organic matter and pyrite weathering on tectonic uplift plus erosion, and the degree of exposure of coastal lands by sea level change; (6) the effect on CO₂ of adding the variability of volcanic rock weathering over time [Berner, R.A., 2006. Inclusion of the weathering of volcanic rocks in the GEOCARBSULF model. Am. J. Sci.306 (in press)]. Results show a similar trend of atmospheric CO₂ over the Phanerozoic to the results of GEOCARB III, but with some differences during the early Paleozoic and, for variable volcanic rock weathering, lower CO₂ values during the Mesozoic. Atmospheric oxygen shows a major broad late Paleozoic peak with a maximum value of about 30% O₂ in the Permian, a secondary less-broad peak centered near the Silurian/Devonian boundary, variation between 15% and 20% O₂ during the Cambrian and Ordovician, a very sharp drop from 30% to 15% O₂ at the Permo-Triassic boundary, and a more-or less continuous rise in O₂ from the late Triassic to the present.     

CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.