Modeling the effects of completion techniques and formation heterogeneity on CO2 sequestration in shallow and deep saline aquifers

This work studied the effect of completion techniques and reservoir heterogeneity on CO₂ storage and injectivity in saline aquifers using a compositional reservoir simulator, CMG-GEM. Two reservoir models were built based on the published data to represent a deep saline aquifer and a shallow aquifer. The effect of various completion conditions on CO₂ storage was then discussed, including partial perforation of the reservoir net pay (partial completion), well geometry, orientation, location, and length. The heterogeneity effect was addressed by considering three parameters: mean permeability, the vertical to horizontal permeability ratio, and permeability variation. Sensitivity analysis was carried out using iSIGHT software (design of experiments) to determine the dominant factors affecting CO₂ storage capacity and injectivity. Simulation results show that the most favorable option is the perforation of all layers with horizontal wells 250–300 m long set in the upper layers. Mean permeability has the most effect on CO₂ storage capacity and injectivity; k _v/k _h affects CO₂ injectivity storage capacity more than permeability variation, V _k. More CO₂ can be stored in the heterogeneous reservoirs with low mean permeability; however, high injectivity can be achieved in the uniform reservoirs with high mean permeability.     

Geochemical effects of CO2 sequestration in sandstones under simulated in situ conditions of deep saline aquifers

The geochemical effects of brine and supercritical CO₂ (SCCO₂) on reservoir rocks from deep (1500–2000 m) saline aquifers were examined via experimental simulation at in situ conditions. Dry sandstone samples were mounted in a triaxial cell and autoclave system, evacuated, and saturated with 1 M NaCl solution. The brine-rock system was allowed to react at 30 MPa confining pressure, 15 MPa pore fluid pressure, and 60 °C while SCCO₂ was injected at a pressure gradient of 1–2 MPa. The experiment was conducted for a period of 1496 h, during which fluids were periodically sampled and analyzed. The pH measured in partially degassed fluid samples at 25 °C decreased from a starting value of 7.0–4.3 (9 days) and finally 5.1 after saturation with SCCO₂.     

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<...     

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.     

The role of CO2 in the chemical modification of deep continental crust

Compositional differences between granulite facies rocks and equivalent amphibolite facies rocks and the observation of CO₂-rich fluid inclusions in granulites, have led to the suggestion that CO₂ must play a role in modifying the composition of deep continental crust. How CO₂ effects this change has remained unclear. Using the thermodynamic properties of aqueous ions in a fluid of evolving $\text{CO}{}_2\text{H}{}_2\text{O}$ ratio, it is possible to model the incongruent dissolution of feldspars under conditions appropriate for granulite facies metamorphism. The results demonstrate that dissolution will be strongly enhanced at high $\text{CO}{}_2\text{H}{}_2\text{O}$ ratios, with ion solubilities being Na⁺ >K⁺ ? Ca⁺⁺. This enhancement is compatible with the reported compositional contrasts between granulite and amphibolite facies rock, but requires large fluid volumes.To test the dissolution model, a detailed field and petrologic study was conducted in a well exposed granulite facies terrane in West Greenland. Strong correlation between fluid composition and bulk rock chemistry can be documented; CO₂-rich regions contain rocks which consistently have low ratios, while H₂O-rich regions consistently have high ratios. Magnetite rims on sulfide grains are ubiquitous in high regions and are absent in high regions, and they provide evidence that CO₂ was introduced into the region. These correlations and observations are predictable from the properties of the dissolution process. These considerations, along with observations regarding graphite petrogenesis, provide strong arguments that the total fluid volume interacting with the rock during metamorphism was very large, in some cases equaling or exceeding total rock volume. Such large fluid volumes can lead to significant compositional modification of the crust, and will mask the original protolith chemistry. Such processes should lead to Ca- and Al-enriched, Na-, K-, S- and Si-depleted residues in the deep crust.     

The hydromagnesite playas of Atlin, British Columbia, Canada: A biogeochemical model for CO2 sequestration

Anthropogenic greenhouse gas emissions may be offset by sequestering carbon dioxide (CO₂) through the carbonation of magnesium silicate minerals to form magnesium carbonate minerals. The hydromagnesite [Mg₅(CO₃)₄(OH)₂·4H₂O] playas of Atlin, British Columbia, Canada provide a natural model to examine mineral carbonation on a watershed scale. At near surface conditions, CO₂ is biogeochemically sequestered by microorganisms that are involved in weathering of bedrock and precipitation of carbonate minerals. The purpose of this study was to characterize the weathering regime in a groundwater recharge zone and the depositional environments in the playas in the context of a biogeochemical model for CO₂ sequestration with emphasis on microbial processes that accelerate mineral carbonation.Regions with ultramafic bedrock, such as Atlin, represent the best potential sources of feedstocks for mineral carbonation. Elemental compositions of a soil profile show significant depletion of MgO and enrichment of SiO₂ in comparison to underlying ultramafic parent material. Polished serpentinite cubes were placed in the organic horizon of a coniferous forest soil in a groundwater recharge zone for three years. Upon retrieval, the cube surfaces, as seen using scanning electron microscopy, had been colonized by bacteria that were associated with surface pitting. Degradation of organic matter in the soil produced chelating agents and acids that contributed to the chemical weathering of the serpentinite and would be expected to have a similar effect on the magnesium-rich bedrock at Atlin. Stable carbon isotopes of groundwater from a well, situated near a wetland in the southeastern playa, indicate that  12% of the dissolved inorganic carbon has a modern origin from soil CO₂.The mineralogy and isotope geochemistry of the hydromagnesite playas suggest that there are three distinct depositional environments: (1) the wetland, characterized by biologically-aided precipitation of carbonate minerals from waters concentrated by evaporation, (2) isolated wetland sections that lead to the formation of consolidated aragonite sediments, and (3) the emerged grassland environment where evaporation produces mounds of hydromagnesite. Examination of sediments within the southeastern playa–wetland suggests that cyanobacteria, sulphate reducing bacteria, and diatoms aid in producing favourable geochemical conditions for precipitation of carbonate minerals.The Atlin site, as a biogeochemical model, has implications for creating carbon sinks that utilize passive microbial, geochemical and physical processes that aid in mineral carbonation of magnesium silicates. These processes could be exploited for the purposes of CO₂ sequestration by creating conditions similar to those of the Atlin site in environments, artificial or natural, where the precipitation of magnesium carbonates would be suitable. Given the vast quantities of Mg-rich bedrock that exist throughout the world, this study has significant implications for reducing atmospheric CO₂ concentrations and combating global climate change.     

Gas geochemistry of natural analogues for the studies of geological CO2 sequestration

Geological sequestration of anthropogenic CO₂ appears to be a promising method for reducing the amount of greenhouse gases released to the atmosphere. Geochemical modelling of the storage capacity for CO₂ in saline aquifers, sandstones and/or carbonates should be based on natural analogues both in situ and in the laboratory. The main focus of this paper has been to study natural gas emissions representing extremely attractive surrogates for the study and prediction of the possible consequences of leakage from geological sequestration sites of anthropogenic CO₂ (i.e., the return to surface, potentially causing localised environmental problems). These include a comparison among three different Italian case histories: (i) the Solfatara crater (Phlegraean Fields caldera, southern Italy) is an ancient Roman spa. The area is characterised by intense and diffuse hydrothermal activity, testified by hot acidic mud pools, thermal springs and a large fumarolic field. Soil gas flux measurements show that the entire area discharges between 1200 and 1500 tons of CO₂ per day; (ii) the Panarea Island (Aeolian Islands, southern Italy) where a huge submarine volcanic-hydrothermal gas burst occurred in November, 2002. The submarine gas emissions chemically modified seawater causing a strong modification of the marine ecosystem. All of the collected gases are CO₂-dominant (maximum value: 98.43 vol.%); (iii) the Tor Caldara area (Central Italy), located in a peripheral sector of the quiescent Alban Hills volcano, along the faults of the Ardea Basin transfer structure. The area is characterised by huge CO₂ degassing both from water and soil. Although the above mentioned areas do not represent a storage scenario, these sites do provide many opportunities to study near-surface processes and to test monitoring methodologies.     

Experiments and geochemical modelling of CO2 sequestration by olivine: Potential,quantification

Aqueous solutions equilibrated with supercritical CO₂ (150 °C and total pressure of 150 bar) were investigated in order to characterize their respective conditions of carbonation. Dissolution of olivine and subsequent precipitation of magnesite with a net consumption of CO₂ were expected. A quantified pure mineral phase (powders with different olivine grain diameter [20–80 μm], [80–125 μm], [125–200 μm] and [>200 μm]), and CO₂ (as dried ice) were placed in closed-batch reactors (soft Au tubes) in the presence of solutions. Different salinities (from 0 to 3400 mM) and different ratios of solution/solid (mineral phase) (from 0.1 to 10) were investigated. Experiments were performed over periods from 2 to 8 weeks. Final solid products were quantified by the Rock-Eval 6 technique, and identified using X-ray diffraction, Raman spectroscopy, electron microprobe and scanning electron microscopy. Gaseous compounds were quantified by a vacuum line equipped with a Toepler pump and identified and measured by gas chromatography (GC). Carbon mass balances were calculated.     

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。     

塔里木盆地奥陶系礁灰岩CO2毛细残余封存能力实验研究

实施CO2地质封存是目前公认的减少温室气体排放的有效方法。在可能进行封存的场所中,咸水含水层封存潜力最大,机理也最为复杂。其中毛细残余封存机理在封存量和封存安全性方面均具有十分重要的意义。在评价毛细残余封存量时,残余气饱和度是一个十分重要的参数。文中提出了测定残余气饱和度的实验方法,并实际应用于中国塔里木盆地奥陶系礁灰...     

渤海湾盆地形成与华北克拉通破坏

渤海湾盆地是一个中、新生代盆地,位于华北克拉通的东部地块上,是华北克拉通破坏的中心区域。渤海湾盆地的结构、构造记录了华北克拉通破坏的构造过程。文章综合10a来据三维地震资料揭示的渤海湾盆地构造,和20a来渤海湾盆地周边华北克拉通区域中、新生代构造和地球化学研究成果,系统提出华北克拉通破坏期间,渤海湾盆地深、浅部的构造机制分别为:中生代浅部构造机制是挤出构造成因,深部构造机制为局部有限的拆沉+底侵模式;新生代构造机制是北西向壳内伸展机制,与印度和欧亚板块碰撞激发的软流圈的东扩远程效应和太平洋俯冲带的跃迁式东撤的联合效应——区域性"西进东退"的深部机制有关。     

基于灰色关联分析法的松辽盆地CO_2地质储存适宜性评价

松辽盆地是中国主要的能源基地,随着中国振兴东北老工业基地政策的实施,如何应对工业和经济发展带来的CO_2排放量的增加,将成为亟需解决的问题。在盆地内进行CO_2地质储存将成为盆地内解决该问题的主要技术选择之一。以松辽盆地为研究对象,在深入分析松辽盆地CO_2地质储存条件的基础上,从储存规模、储存安全性和社会环境风险及经济适宜性4个方面综合考虑,构建了由16个指标组成的松辽盆地CO_2地质储存适宜性评价指标体系,利用灰色关联分析法对松辽盆地33个二级构造单元进行了盆地级适宜性评价工作,评价结果为进一步场地级目标靶区的筛选提供了科技支撑。     

Identification of C24 and C25 lanostanes in Tertiary sulfur rich crude oils from the Jinxian Sag, Bohai Bay Basin, Northern China

Unusual short chain lanostanes (C₂₄ and C₂₅) and C₃₀ lanostane were identified in sulfur rich crude oils from the Jinxian Sag, Bohai Bay Basin, northern China. Besides the regular steranes (C_27-30), a series of 4-methyl steranes (C₂₂₋₂₃, C₂₇₋₃₀), 4,4-dimethyl steranes (C₂₂₋₂₄, C₂₈₋₃₀), short chain steranes (C₂₃₋₂₆), abundant pregnanes (C₂₁₋₂₂) and androstanes (C₁₉₋₂₀), together with sulfur containing steroids (20-thienylpregnanes and thienylandrostanes) were detected in the aliphatic and branched-cyclic hydrocarbon fraction of these crude oils. A literature survey of some long chain sterane analogues (e.g., A-nor-steranes, norcholestanes, C₃₀ steranes, lanostanes) and pregnanes seems to point to a sponge and/or dinoflagellate source. 4-Methyl, 4,4-dimethyl steroids and lanosterols (4,4,14-trimethyl steroids as the basic skeleton of lanostanes) can be derived from methanotrophic bacteria. Thus, a biological origin from a prokaryotic methylotroph can be used to explain the common source of abundant short chain steranes (C_23-26), 4-methyl (C_22-23) and 4,4-dimethyl steranes (C_22-24), as well as lanostanes (C_24-25 and C₃₀ analogues) in our oil samples. Generally, the steroids appear to have been extensively sulfurized with sulfur substitution at the C-22 position in the side chain during the early stage of diagenesis, which was readily subject to attack by bacterial degradation (enzymatic cleavage) and/or abiotic oxidation. As a consequence, short chain sterane analogues (e.g., abundant pregnanes and androstanes in this study) and short chain lanostanes (C₂₄−C₂₅) might later be released through cleavage of weak C-S bonds at the C-22 carbon in the sulfurized steroids and lanostane sulfides. Finally, the formation of the short chain C₂₄−C₂₅ lanostanes and distinctive occurrence of short chain steranes in this study can be well explained by microbial biodegradation of sulfurized lanostanoids and steroids in the reservoir.     

深部咸含水层CO2注入的流体迁移模拟研究 ——以松辽盆地三肇凹陷为例

CO2地质封存是减少温室气体向大气排放的有效措施之一,而深部咸含水层CO2地质封存是目前可行的最有潜力的封存技术。先前研究表明,松辽盆地是一个潜在的封存场地。基于对松辽盆地地质资料的初步分析,选取三肇凹陷的姚家组1段和青山口组2、3段地层作为CO2的注入层,建立一个典型二维模型,研究CO2注入后的迁移规律。结果表明,CO2注入后会向上和侧向迁移,后期可能出现的对流作用能促进CO2的溶解。残留气体饱和度、注入层水平和垂直渗透率的比值对模拟结果影响最大。此外,储层中的薄页岩夹层有利于CO2的溶解,因此,在保证注入性和封存量的情况下,储层中低渗透性夹层是允许的。     

渤海湾盆地东营凹陷北带油包裹体成分特征

油包裹体成分在油源对比和流体包裹体PVT热动力学模拟具有至关重要的作用。本文采用常规荧光光谱、定量荧光技术和在线压碎群体包裹体成分分析方法对东营凹陷北带沙三段和沙四段砂岩储层样品中的油包裹体成分进行分析。荧光光谱分析结果表明油包裹体荧光颜色从黄色-黄白色-白色-蓝白色到蓝色呈现连续变化特征,主波长范围在445nm至550nm之间,指示了东营凹陷北带捕获的包裹体中油的成熟度从低到高呈连续变化。观察到的发蓝白色荧光的油包裹体荧光光谱主波长均小于500nm,黄色荧光的油包裹体荧光光谱主波长大于500nm。油包裹体荧光光谱参数主波长和Q值反映发蓝白色和黄色荧光的油包裹体中饱和烃、芳烃、非烃含量和API明显不同,发蓝白色荧光的油包裹体中的烃类具有密度相对较小、成熟度较高的特征。定量荧光和群体包裹体成分结果也表明由于发蓝白色和黄色荧光的油包裹体成分不同导致QGF光谱以及TSF参数都具有明显的区别,发蓝白色荧光的油包裹体甲烷含量偏高,而发黄色荧光的油包裹体C₇-C₉含量相对偏高。     

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.     

深部咸含水层CO2注入下压力抬升与流体迁移的大尺度模拟研究:以松辽盆地为例

地下深部封存CO2已经被公认是人类削减温室气体排放的一条有效而又科学的途径。深部咸含水层CO2地质封存因封存潜力巨大,技术可行,且已有实际的工程运行,因而备受关注。松辽盆地是中国潜在的CO2储存场地之一,选择松辽盆地为大尺度模拟研究对象,选取姚家组砂岩层为储层,选取嫩江组泥岩为盖层,运用TOUGH-MP并行计算代码建立了覆盖整个松辽盆地的三维地质模型,在中央凹陷区开展大尺度CO2注入模拟研究,包括CO2运移、储存、地层压力提升以及储存安全性等问题。模拟结果表明:持续注入100a后形成的CO2羽远小于产生的压力积聚区影响范围。注入产生的压力抬升将在注入停止后迅速消散,不会对区域地层压力和浅层地下水系统产生显著影响。在千年之内注入的CO2将随着时间持续,逐渐溶解于水中,而不会因盖层微弱的渗透性而逃逸。