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.     

Navajo Sandstone–brine–CO<Subscript>2</Subscript> interaction: implications for geological carbon sequestration

The injection of CO₂ into deep saline aquifers is being considered as an option for greenhouse gas mitigation. However, the response of an aquifer to the injected CO₂ is largely unknown. Experiments involving the reaction of Navajo Sandstone with acidic brine were conducted at 200°C and 25 or 30 MPa to evaluate the extent of fluid–rock interactions. The first experiment examined sandstone interaction with CO₂-impregnated brine; the second experiment examined sandstone dissolution in CO₂-free acidic brine; the third one is carried out in a mixed-flow reactor and designed to measure sandstone dissolution rates based on time-series Si concentrations. The solution chemistry data indicate that the SiO₂(aq) increases gradually and pH increases slowly with reaction progress. Silicate minerals in the sandstone display textures (dissolution features, secondary mineralization), indicating that these phases are reacting strongly with the fluid. Dissolution of feldspars and conversion of smectite to illite are likely to be the two reactions that contribute to the release of SiO₂(aq). The product minerals present at the end of the experiments are illite, illite/smectite, allophane, and carbonate minerals (for the CO₂-charged system). Dissolved CO₂ is likely to acidify the brine and to provide a source of carbon for the precipitation of carbonate minerals. Mineral trapping through the precipitation of carbonate minerals is favored thermodynamically and was observed in the experiments. The chemical reactions likely increase the bulk porosity of the sandstone due to dissolution of silicate minerals. However, allophane and illite/smectite fill voids in sandstone grains. There is no evidence for the removal of clay coatings due to chemical reactions. It is uncertain whether the mechanical forces near an injection well would mobilize the smectite and allophane and clog pore throats. Trace amounts of metals, including Cu, Zn, and Ba, were mobilized.     

Experimental study of potential wellbore cement carbonation by various phases of carbon dioxide during geologic carbon sequestration

Hydrated Portland cement was reacted with CO₂ in supercritical, gaseous and aqueous phases to understand the potential cement alteration processes along the length of a wellbore, extending from a deep CO₂ storage reservoir to the shallow subsurface during geologic carbon sequestration. The 3-D X-ray microtomography (XMT) images showed that the cement alteration was significantly more extensive with CO₂-saturated synthetic groundwater than dry or wet supercritical CO₂ at high P (10 MPa)-T (50 °C) conditions. Scanning electron microscopy with energy dispersive spectroscopy (SEM–EDS) analysis also exhibited a systematic Ca depletion and C enrichment in cement matrix exposed to CO₂-saturated groundwater. Integrated XMT, XRD and SEM–EDS analyses identified the formation of an extensive carbonated zone filled with CaCO₃(s), as well as a porous degradation front and an outermost silica-rich zone in cement after exposure to CO₂-saturated groundwater. Cement alteration by CO₂-saturated groundwater for 2–8 months overall decreased the porosity from 31% to 22% and the permeability by an order of magnitude. Cement alteration by dry or wet supercritical CO₂ was slow and minor compared to CO₂-saturated groundwater. A thin single carbonation zone was formed in cement after exposure to wet supercritical CO₂ for 8 months or dry supercritical CO₂ for 15 months. An extensive calcite coating was formed on the outside surface of a cement sample after exposure to wet gaseous CO₂ for 1–3 months. The chemical–physical characterization of hydrated Portland cement after exposure to various phases of CO₂ indicates that the extent of cement carbonation can be significantly heterogeneous depending on the CO₂ phase present in the wellbore environment. Both experimental and geochemical modeling results suggest that wellbore cement exposure to supercritical, gaseous and aqueous phases of CO₂ during geologic C sequestration is unlikely to damage the wellbore integrity because cement alteration by all phases of CO₂ is dominated by carbonation reactions. This is consistent with previous field studies of wellbore cement with extensive carbonation after exposure to CO₂ for three decades. However, XMT imaging indicates that preferential cement alteration by supercritical CO₂ or CO₂-saturated groundwater can occur along the cement–steel or cement–rock interfaces. This highlights the importance of further investigation of cement degradation along the interfaces of wellbore materials to ensure permanent geologic carbon storage.     

鄂尔多斯盆地伊金霍洛旗附近二叠系石千峰组岩石学、地球化学特征及其固碳能力分析

鄂尔多斯盆地是我国CO2地下埋藏的潜在目标区,位于伊金霍洛旗附近的中神监X井与CO2地下注入井中神注1井相邻,两者钻遇地层系统和岩石组合一致。为对示范区储层的固碳潜力和泥岩改造状况做出预测,为CO2地质储存的数值模拟研究提供基础地质信息和相关数据,通过偏光显微镜、扫描电镜、X射线衍射、X射线荧光等多种技术手段,开展了中神监X井石千峰组的岩石学和地球化学特征研究。结果表明石千峰组的砂岩岩石类型主要为长石岩屑砂岩和岩屑长石砂岩;泥岩主要由石英、粘土矿物和长石组成,其中,粘土矿物主要为伊利石,其次为蒙皂石、高岭石和绿泥石。预测在CO2注入后的流体-砂岩长期相互作用过程中,石千峰组砂岩可以通过形成片钠铝石、方解石、铁白云石和菱铁矿等固碳矿物,形成对CO2泄露而言的矿物圈闭,进而实现CO2的长期和安全封存;红色泥岩夹层将发生金属离子活化,导致泥岩褪色。     

Effect of injected CO2 on geochemical alteration of the Altmark gas reservoir in Germany

Capturing CO₂ from point sources and storing it in geologic formations is a potential option for allaying the CO₂ level in the atmosphere. In order to evaluate the effect of geological storage of CO₂ on rock-water interaction, batch experiments were performed on sandstone samples taken from the Altmark reservoir, Germany, under in situ conditions of 125 °C and 50 bar CO₂ partial pressure. Two sets of experiments were performed on pulverized sample material placed inside a closed batch reactor in (a) CO₂ saturated and (b) CO₂ free environment for 5, 9 and 14 days. A 3M NaCl brine was used in both cases to mimic the reservoir formation water. For the “CO₂ free” environment, Ar was used as a pressure medium. The sandstone was mainly composed of quartz, feldspars, anhydrite, calcite, illite and chlorite minerals. Chemical analyses of the liquid phase suggested dissolution of both calcite and anhydrite in both cases. However, dissolution of calcite was more pronounced in the presence of CO₂. In addition, the presence of CO₂ enhanced dissolution of feldspar minerals. Solid phase analysis by X-ray diffraction and Mössbauer spectroscopy did not show any secondary mineral precipitation. Moreover, Mössbauer analysis did not show any evidence of significant changes in redox conditions. Calculations of total dissolved solids’ concentrations indicated that the extent of mineral dissolution was enhanced by a factor of approximately 1.5 during the injection of CO₂, which might improve the injectivity and storage capacity of the targeted reservoir. The experimental data provide a basis for numerical simulations to evaluate the effect of injected CO₂ on long-term geochemical alteration at reservoir scale.     

Experimental and numerical investigations on CO2 injection and enhanced gas recovery effects in Altmark gas field (Central Germany)

The feasibility of CO₂ storage and enhanced gas recovery (EGR) effects in the mature Altmark natural gas field in Central Germany has been studied in this paper. The investigations were comprehensive and comprise the characterization of the litho- and diagenetic facies, mineral content, geochemical composition, the petrophysical properties of the reservoir rocks with respect to their potential reactivity to CO₂ as well as reservoir simulation studies to evaluate the CO₂ wellbore injectivity and displacement efficiency of the residual gas by the injected CO₂. The Rotliegend sediments of the Altmark pilot injection area exhibit distinct mineralogical, geochemical, and petrophysical features related to litho- and diagenetic facies types. The reservoir rock reactivity to CO₂ has been studied in autoclave experiments and associated effects on two-phase transport properties have been examined by means of routine and special core analysis before and after the laboratory runs. Dissolution of calcite and anhydrite during the short-term treatments leading to the enhancements of permeability and porosity as well as stabilization of the water saturation relevant for CO₂ injection have been observed. Numerical simulation of the injection process and EGR effects in a sector of the Altmark field coupled with a wellbore model revealed the possibility of injecting the CO₂ gas at temperatures as low as 10 °C and pressures around 40 bar achieving effective inflow in the reservoir without phase transition in the wellbore. The small ratio of injected CO₂ volume versus reservoir volume indicated no significant EGR effects. However, the retention and storage capacity of CO₂ will be maximized. The migration/extension of CO₂ varies as a function of heterogeneity both in the layers and in the reservoir. The investigation of CO₂ extension and pressure propagation suggested no breakthrough of CO₂ at the prospective production well during the 3-year injection period studied.     

Mineralogical controls on porosity and water chemistry during O2-SO2-CO2 reaction of CO2 storage reservoir and cap-rock core

Reservoir and cap-rock core samples with variable lithology's representative of siliciclastic reservoirs used for CO₂ storage have been characterized and reacted at reservoir conditions with an impure CO₂ stream and low salinity brine. Cores from a target CO₂ storage site in Queensland, Australia were tested. Mineralogical controls on the resulting changes to porosity and water chemistry have been identified. The tested siliciclastic reservoir core samples can be grouped generally into three responses to impure CO₂-brine reaction, dependent on mineralogy. The mineralogically clean quartzose reservoir cores had high porosities, with negligible change after reaction, in resolvable porosity or mineralogy, calculated using X-ray micro computed tomography and QEMSCAN. However, strong brine acidification and a high concentration of dissolved sulphate were generated in experiments owing to minimal mineral buffering. Also, the movement of kaolin has the potential to block pore throats and reduce permeability. The reaction of the impure CO₂-brine with calcite-cemented cap-rock core samples caused the largest porosity changes after reaction through calcite dissolution; to the extent that one sample developed a connection of open pores that extended into the core sub-plug. This has the potential to both favor injectivity but also affect CO₂ migration. The dissolution of calcite caused the buffering of acidity resulting in no significant observable silicate dissolution. Clay-rich cap-rock core samples with minor amounts of carbonate minerals had only small changes after reaction. Created porosity appeared mainly disconnected. Changes were instead associated with decreases in density from Fe-leaching of chlorite or dissolution of minor amounts of carbonates and plagioclase. The interbedded sandstone and shale core also developed increased porosity parallel to bedding through dissolution of carbonates and reactive silicates in the sandy layers. Tight interbedded cap-rocks could be expected to act as baffles to fluids preventing vertical fluid migration. Concentrations of dissolved elements including Ca, Fe, Mn, and Ni increased during reactions of several core samples, with Mn, Mg, Co, and Zn correlated with Ca from cap-rock cores. Precipitation of gypsum, Fe-oxides and clays on seal core samples sequestered dissolved elements including Fe through co-precipitation or adsorption. A conceptual model of impure CO₂-water-rock interactions for a siliciclastic reservoir is discussed.     

Chemical changes in fluid composition due to CO2 injection in the Altmark gas field: preliminary results from batch experiments

Dissolution?Cprecipitation phenomena induced by CO₂ injection to Altmark Permian sandstone were observed through laboratory experiments carried out under simulated reservoir conditions (125?°C and 50 bars of pressure). The rock sample was collected from the Altmark gas reservoir, which is being considered for enhanced gas recovery. Two sets of experiments were performed with pulverized rock samples in a closed batch reactor with either pure water (run 1) or 3?M aqueous NaCl solution (run 2) and reacted with injected CO₂ for 3, 5, and 9?days. The liquid samples were analyzed by inductively coupled plasma optical emission spectroscopy and total reflection X-ray fluorescence, where the latter proved to be a feasible alternative to conventional analytical techniques, especially since only small sample volumes (about 10???l) are needed. Chemical analysis for both fluids (water and NaCl brine) indicated a significant dissolution of calcite and anhydrite in the solution, which might be a crucial process during CO₂ injection. The brine solution enhanced the dissolution of calcite and anhydrite compared to pure water at the beginning of the reaction. Moreover, the progressive higher Si⁴⁺/Al³⁺ molar ratios (in average by a factor of 3) in the brine experiments indicated quartz dissolution. Thermodynamic calculations of mineral saturation indices highlighted the dissolution of the Ca-bearing minerals, which was in agreement with experimental results. Modeling enabled an evaluation of the dissolution processes of minerals in a low-salinity region, yet hindrances to model more saline conditions emphasize the need for further laboratory studies in order to parameterize models for deep aquifer conditions.     

Carbonate dissolution in Mesozoic sand- and claystones as a response to CO2 exposure at 70 °C and 20 MPa

The response to CO₂ exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO₂ injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO₂ injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO₂ and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO₂; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO₂, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions.     

Gas–water–rock interactions in sedimentary basins: CO2 sequestration in the Frio Formation, Texas, USA

To investigate the potential for the geologic storage of CO₂ in saline sedimentary aquifers, 1600 ton of CO₂ were injected at 1500 m depth into a 24-m sandstone section of the Frio Formation — a regional reservoir in the US Gulf Coast. Fluid samples obtained from the injection and observation wells before, during and after CO₂ injection show a Na–Ca–Cl type brine with 93,000 mg/L TDS and near saturation of CH₄ at reservoir conditions. As injected CO₂ gas reached the observation well, results showed sharp drops in pH (6.5 to 5.7), pronounced increases in alkalinity (100 to 3000 mg/L as HCO₃) and Fe (30 to 1100 mg/L), and significant shifts in the isotopic compositions of H₂O and DIC. Geochemical modeling indicates that brine pH would have dropped lower, but for buffering by dissolution of calcite and Fe oxyhydroxides. Post-injection results show the brine gradually returning to its pre-injection composition.     

Reaction and diffusion at the reservoir/shale interface during CO2 storage: Impact of geochemical kinetics

We use a reactive diffusion model to investigate what happens to CO₂ injected into a subsurface sandstone reservoir capped by a chlorite- and illite-containing shale seal. The calculations simulate reaction and transport of supercritical (SC) CO₂ at 348.15 K and 30 MPa up to 20,000 a. Given the low shale porosity (5%), chemical reactions mostly occurred in the sandstone for the first 2000 a with some precipitation at the ss/sh interface. From 2000 to 4000 a, ankerite, dolomite and illite began replacing Mg–Fe chlorite at the sandstone/shale interface. Transformation of chlorite to ankerite is the dominant reaction occluding the shale porosity in most simulations: from 4000 to 7500 a, this carbonation seals the reservoir and terminates reaction. Overall, the carbonates (calcite, ankerite, dolomite), chlorite and goethite all remain close to local chemical equilibrium with brine. Quartz is almost inert from the point of its dissolution/precipitation. However, the rate of quartz reaction controls the long-term decline in aqueous silica activity and its evolution toward equilibrium. The reactions of feldspars and clays depend strongly on their reaction rate constants (microcline is closer to local equilibrium than albite). The timing of porosity occlusion mostly therefore depends on the kinetic constants of kaolinite and illite. For example, an increase in the kaolinite kinetic constant by 0.25 logarithmic units hastened porosity closure by 4300 a. The earliest simulated closure of porosity occurred at approximately 108 a for simulations designed as sensitivity tests for the rate constants.These simulations also emphasize that the rate of CO₂ immobilization as aqueous bicarbonate (solubility trapping) or as carbonate minerals (mineral trapping) in sandstone reservoirs depends upon reaction kinetics – but the relative fraction of each trapped CO₂ species only depends upon the initial chemical composition of the host sandstone. For example, at the point of porosity occlusion the fraction of bicarbonate remaining in solution depends upon the initial Na and K content in the host rock but the fraction of carbonate mineralization depends only on the Ca, Mg, Fe content. Since ankerite is the dominant mineral that occludes porosity, the dissolved concentration of ferrous iron is also an important parameter. Future efforts should focus on cross-comparisons and ground-truthing of simulations made for standard case studies as well as laboratory measurements of the reactivities of clay minerals.     

Geomechanical and geochemical effects on sandstones caused by the reaction with supercritical CO2: an experimental approach to in situ conditions in deep geological reservoirs

The geochemical and geomechanical behaviour of reservoir rocks from deep saline aquifers during the injection and geological storage of CO₂ is studied in laboratory experiments. A combination of geochemical and geomechanical studies was carried out on various sandstones from the North German Basin. After the mineralogical, geochemical and petrophysical characterization, a set of sandstone samples was exposed to supercritical (sc)CO₂ and brine for 2–4 weeks in an autoclave system. One sample was mineralogically and geochemically characterised and then loaded in a triaxial cell under in situ pressure and temperature conditions to study the changes of the geomechanical rock properties. After treatment in the autoclaves, geochemical alterations mainly in the carbonate, but also in the sheet silicate cements as well as in single minerals of the sandstones were observed, affecting the rocks granular structure. In addition to partial solution effects during the geochemical experiments, small grains of secondary carbonate and other mineral precipitations were observed within the pore space of the treated sandstones. Results of additional geomechanical experiments with untreated samples show that the rock strength is influenced by the saturation degree, the confining pressure, the pore fluid pressure and temperature. The exposure to pure scCO₂ in the autoclave system induces reduced strength parameters, modified elastic deformation behaviour and changes of the effective porosity in comparison to untreated sandstone samples. Experimental results show that the volume of pore fluid fluxing into the pore space of the sandstones clearly depends on the saturation level of the sample.     

Laboratory Investigations of the Hydro-Mechanical–Chemical Coupling Behaviour of Sandstone in CO2 Storage in Aquifers

This paper is devoted to experimental investigations of the hydro-mechanical–chemical coupling behaviour of sandstone in the context of CO₂ storage in aquifers. We focused on the evolution of creep strain, the transport properties and the elastic modulus of sandstone under the effect of CO₂–brine or CO₂ alone. A summary of previous laboratory results is first presented, including mechanical, poromechanical and hydro-mechanical–chemical coupling properties. Tests were then performed to investigate the evolution of the creep strain and permeability during the injection of CO₂–brine or CO₂ alone. After the injection of CO₂–brine or CO₂ alone, an instantaneous volumetric dilatancy was observed due to the decrease in the effective confining stress. However, CO₂ alone had a significant influence on the creep strain and permeability compared to the small influence of CO₂–brine. This phenomenon can be attributed to the acceleration of the CO₂–brine–rock reaction by the generation of carbonic acid induced by the dissolution of CO₂ into the brine. The original indentation tests on samples after the CO₂–brine–rock reaction were also performed and indicated that the elastic modulus decreased with an increasing reaction time. The present laboratory results can advance our knowledge of the hydro-mechanical–chemical coupling behaviour of sandstone in CO₂ storage in aquifers.     

Alteration processes of cement induced by CO2-saturated water and its effect on physical properties: Experimental and geochemical modeling study

The objective of this study is to understand cement alteration processes with the evolution of porosity and hardness under geologic CO₂ storage conditions. For this study, the cylindrical cement cores (class G) were reacted with CO₂–saturated water in a vessel (40 °C and 8 MPa) for 10 and 100 days. After the experiment, the CO₂ concentration and Vickers hardness were measured in the hydrated cement core to estimate the carbonation depth and to identify the change in hardness, respectively. Diffusive-reactive transport modeling was also performed to trace the alteration processes and subsequent porosity changes. The results show that cement alteration mainly results from carbonation. With alteration processes, four different reaction zones are developed: degradation zone, carbonation zone, portlandite depletion zone, and unreacted zone. In the degradation zone, the re-dissolution of calcite formed in the carbonation zone leads to the increase of porosity. In contrast, the carbonation zone is characterized by calcite formation resulting mainly from the dissolution of portlandite. The carbonation zone acts as a barrier to CO₂ intrusion by consuming dissolved CO₂. Especially in this zone, although the porosity decreases, the Vickers hardness increases. Our results show that cement alteration processes can affect the physical and hydrological properties of the hydrated cement under CO₂-saturated conditions. Further long-term observation is required to confirm our results under in-situ fluid chemistry of a CO₂ storage reservoir. Nonetheless, this study would be helpful to understand alteration processes of wellbore cements under CO₂ storage conditions.     

昭通示范区黄金坝气田五峰—龙马溪组页岩气储层地质特征

昭通国家级页岩气示范区黄金坝气田是继礁石坝和长宁—威远之后中国又一个在页岩气勘探、开发领域实现重大突破的地区,为了系统地展示黄金坝气田页岩气资源富集的储层条件,为未来的勘探工作提供参考,以五峰—龙马溪组页岩气储层为研究对象,从区域地质条件、储层岩石学、物性和地球化学4个方面对该页岩气储层进行了综合研究。结果表明稳定的区域构造和良好的顶底板条件是黄金坝地区页岩气资源富集的关键,良好的保存条件使储层维持了较高的压力(压力系数1);较高的孔隙度(平均4%)和TOC含量(目的层2%)提供了良好的储集空间,使储层具有较高的含气量(1.35~3.48 cm3/g,平均2.50 cm3/g);天然气地球化学数据表明,区内天然气主要成分为CH4(97%),其次还含有少量的C2H6、C3H8和CO2;天然气同位素数据表明烃类C同位素组成发生了倒转,表明储层具有良好的封闭性。但储层孔隙系统较为复杂,且非均质性极强,从而导致渗透率较低,在储层改造施工过程中应予以充分考虑。总体上,黄金坝气田具有较好的开发前景,生产测试表明,区内直井压裂产量为0.5×104~3.5×104m3/d/井,水平井压裂产量可达12×104~40×104m3/d/井。     

The Effects of Diagenesis on the Reservoir Characters in Ridge sandstone of Jurassic Jumara dome,Kachchh, Western India

Ridge sandstone of Jurassic Jumara dome of Kachchh was studied in an attempt to quantify the effects of diagenetic process such as compaction, cementation and dissolution on reservoir properties. The average framework composition of Ridge sandstone is Q₈₀F₁₇L₃, medium-to coarse grained and subarkose to arkose. Syndepositional silty to clayey matrix (3% average) is also observed that occurs as pore filling. The diagenetic processes include compaction, cementation and precipitation of authigenic cements, dissolution of unstable grains and grain replacement and development of secondary porosity. The major cause of intense reduction in primary porosity of Ridge sandstone is early cementation which include silica, carbonate, iron, kaolinite, illite, smectite, mixed layer illite-smectite and chlorite, which prevents mechanical compaction. The plots of COPL versus CEPL and IGV versus total cement suggest the loss of primary porosity in Ridge sandstone is due to cementation. Cements mainly iron and carbonate occurs in intergranular pores of detrital grains and destroys porosity. The clay mineral occurs as pore filling and pore lining and deteriorates the porosity and permeability of the Ridge sandstone. The reservoir quality of the studied sandstone is reduced by clay minerals (kaolinite, illite, smectite, mixed layer illitesmectite, chlorite), carbonate, iron and silica cementation but on the other hand, it is increased by alteration and dissolution of the unstable grain, in addition to partial dissolution of carbonate cements. The potential of the studied sandstone to serve as a reservoir is strongly related to sandstone diagenesis.     

Potential environmental issues of CO2 storage in deep saline aquifers: Geochemical results from the Frio-I Brine Pilot test,Texas, USA

Sedimentary basins in general, and deep saline aquifers in particular, are being investigated as possible repositories for large volumes of anthropogenic CO₂ that must be sequestered to mitigate global warming and related climate changes. To investigate the potential for the long-term storage of CO₂ in such aquifers, 1600 t of CO₂ were injected at 1500 m depth into a 24-m-thick “C” sandstone unit of the Frio Formation, a regional aquifer in the US Gulf Coast. Fluid samples obtained before CO₂ injection from the injection well and an observation well 30 m updip showed a Na–Ca–Cl type brine with ∼93,000 mg/L TDS at saturation with CH₄ at reservoir conditions; gas analyses showed that CH₄ comprised ∼95% of dissolved gas, but CO₂ was low at 0.3%. Following CO₂ breakthrough, 51 h after injection, samples showed sharp drops in pH (6.5–5.7), pronounced increases in alkalinity (100–3000 mg/L as HCO₃) and in Fe (30–1100 mg/L), a slug of very high DOC values, and significant shifts in the isotopic compositions of H₂O, DIC, and CH₄. These data, coupled with geochemical modeling, indicate corrosion of pipe and well casing as well as rapid dissolution of minerals, especially calcite and iron oxyhydroxides, both caused by lowered pH (initially ∼3.0 at subsurface conditions) of the brine in contact with supercritical CO₂.     

Wellbore cement fracture evolution at the cement–basalt caprock interface during geologic carbon sequestration

Composite Portland cement–basalt caprock cores with fractures, as well as neat Portland cement columns, were prepared to understand the geochemical and geomechanical effects on the integrity of wellbores with defects during geologic carbon sequestration. The samples were reacted with CO₂–saturated groundwater at 50 °C and 10 MPa for 3 months under static conditions, while one cement–basalt core was subjected to mechanical stress at 2.7 MPa before the CO₂ reaction. Micro-XRD and SEM–EDS data collected along the cement–basalt interface after 3-month reaction with CO₂–saturated groundwater indicate that carbonation of cement matrix was extensive with the precipitation of calcite, aragonite, and vaterite, whereas the alteration of basalt caprock was minor. X-ray microtomography (XMT) provided three-dimensional (3-D) visualization of the opening and interconnection of cement fractures due to mechanical stress. Computational fluid dynamics (CFD) modeling further revealed that this stress led to the increase in fluid flow and hence permeability. After the CO₂-reaction, XMT images displayed that calcium carbonate precipitation occurred extensively within the fractures in the cement matrix, but only partially along the fracture located at the cement–basalt interface. The 3-D visualization and CFD modeling also showed that the precipitation of calcium carbonate within the cement fractures after the CO₂-reaction resulted in the disconnection of cement fractures and permeability decrease. The permeability calculated based on CFD modeling was in agreement with the experimentally determined permeability. This study demonstrates that XMT imaging coupled with CFD modeling represent a powerful tool to visualize and quantify fracture evolution and permeability change in geologic materials and to predict their behavior during geologic carbon sequestration or hydraulic fracturing for shale gas production and enhanced geothermal systems.     

OpenGeoSys-ChemApp: a coupled simulator for reactive transport in multiphase systems and application to CO2 storage formation in Northern Germany

Sequestration of CO₂ into a deep geological reservoir causes a complex interaction of different processes such as multiphase flow, phase transition, multicomponent transport, and geochemical reactions between dissolved CO₂ and the mineral matrix of the porous medium. A prognosis of the reservoir behaviour and the feedback from large-scale geochemical alterations require efficient process-based numerical models. For this purpose, the multiphase flow and multicomponent transport code OpenGeoSys-Eclipse have been coupled to the geochemical model ChemApp. The newly developed coupled simulator was successfully verified for correctness and accuracy of the implemented reaction module by benchmarking tests. The code was then applied to assess the impact of geochemical reactions during CO₂ sequestration at a hypothetical but typical Bunter sandstone formation in the Northern German Basin. Injection and spreading of 1.48 × 10⁷ t of CO₂ in an anticline structure of the reservoir were simulated over a period of 20 years of injection plus 80 years of post-injection time. Equilibrium geochemical calculations performed by ChemApp show only a low reactivity to the geochemical system. The increased acidity of the aqueous solution results in dissolution of small amounts of calcite, anhydrite, and quartz. Geochemical alterations of the mineral phase composition result in slight increases in porosity and permeability, which locally may reach up to +0.02 and 0.1 %, respectively.     

Reactive transport simulation study of geochemical CO2 trapping on the Tokyo Bay model – With focus on the behavior of dawsonite

A long-term (up to 10 ka) geochemical change in saline aquifer CO₂ storage was studied using the TOUGHREACT simulator, on a 2-dimensional, 2-layered model representing the underground geologic and hydrogeologic conditions of the Tokyo Bay area that is one of the areas of the largest CO₂ emissions in the world. In the storage system characterized by low permeability of reservoir and cap rock, the dominant storage mechanism is found to be solubility trapping that includes the dissolution and dissociation of injected CO₂ in the aqueous phase followed by geochemical reactions to dissolve minerals in the rocks. The CO₂–water–rock interaction in the storage system (mainly in the reservoir) changes the properties of water in a mushroom-like CO₂ plume, which eventually leads to convective mixing driven by gravitational instability. The geochemically evolved aqueous phase precipitates carbonates in the plume front due to a local rise in pH with mixing of unaffected reservoir water. The carbonate precipitation occurs extensively within the plume after the end of its enlargement, fixing injected CO₂ in a long, geologic period.Dawsonite, a Na–Al carbonate, is initially formed throughout the plume from consumption of plagioclase in the reservoir rock, but is found to be a transient phase finally disappearing from most of the CO₂-affected part of the system. The mineral is unstable relative to more common types of carbonates in the geochemical evolution of the CO₂ storage system initially having formation water of relatively low salinity. The exception is the reservoir-cap rock boundary where CO₂ saturation remains very high throughout the simulation period.