Numerical simulations on the influence of matrix diffusion to carbon sequestration in double porosity fissured aquifers

The double porosity model for fissured rocks, such as limestones and dolomites, has some features that may be relevant for carbon sequestration. Numerical simulations were conducted to study the influence of matrix diffusion on the trapping mechanisms relevant for the long-term fate of CO₂ injected in fissured rocks. The simulations show that, due to molecular diffusion of CO₂ into the rock matrix, dissolution trapping and hydrodynamic trapping are more effective in double porosity aquifers than in an equivalent porous media. Mineral trapping, although assessed indirectly, is also probably more relevant in double porosity aquifers due to the larger contact surface and longer contact time between dissolved CO₂ and rock minerals. However, stratigraphic/structural trapping is less efficient in double porosity media, because at short times CO₂ is stored only in the fissures, requiring large aquifer volumes and increasing the risk associated to the occurrence of imperfections in the cap-rock through which leakage can occur. This increased risk is also a reality when considering storage in aquifers with a regional flow gradient, since the CO₂ free-phase will move faster due to the higher flow velocities in fissured media and discharge zones may be reached sooner.     

Long-term variations of CO2 trapped in different mechanisms in deep saline formations: A case study of the Songliao Basin,China

The geological storage of CO₂ in deep saline formations is increasing seen as a viable strategy to reduce the release of greenhouse gases to the atmosphere. There are numerous sedimentary basins in China, in which a number of suitable CO₂ geologic reservoirs are potentially available. To identify the multi-phase processes, geochemical changes and mineral alteration, and CO₂ trapping mechanisms after CO₂ injection, reactive geochemical transport simulations using a simple 2D model were performed. Mineralogical composition and water chemistry from a deep saline formation of Songliao Basin were used. Results indicate that different storage forms of CO₂ vary with time. In the CO₂ injection period, a large amount of CO₂ remains as a free supercritical phase (gas trapping), and the amount dissolved in the formation water (solubility trapping) gradually increases. Later, gas trapping decrease, solubility trapping increases significantly due to the migration and diffusion of CO₂ plume and the convective mixing between CO₂-saturated water and unsaturated water, and the amount trapped by carbonate minerals increases gradually with time. The residual CO₂ gas keeps dissolving into groundwater and precipitating carbonate minerals. For the Songliao Basin sandstone, variations in the reaction rate and abundance of chlorite, and plagioclase composition affect significantly the estimates of mineral alteration and CO₂ storage in different trapping mechanisms. The effect of vertical permeability and residual gas saturation on the overall storage is smaller compared to the geochemical factors. However, they can affect the spatial distribution of the injected CO₂ in the formations. The CO₂ mineral trapping capacity could be in the order of 10 kg/m³ medium for the Songliao Basin sandstone, and may be higher depending on the composition of primary aluminosilicate minerals especially the content of Ca, Mg, and Fe.     

A natural analogue for CO2 mineral sequestration in Miocene basalt in the Kuanhsi-Chutung area, Northwestern Taiwan

In general, CO₂ sequestration by carbonation is estimated by laboratory experimentation and geochemical simulation. In this study, however, estimation is based on a natural analogue study of the Miocene basalt in the Kuanhsi-Chutung area, Northwestern Taiwan. This region has great potential in terms of geological and geochemical environments for CO₂ sequestration. Outcropping Miocene basalt in the study area shows extensive serpentinization and carbonation. The carbon stable isotopes of carbonates lie on the depleted side of the Lohmann meteoric calcite line, which demonstrates that the carbonates most probably precipitate directly from meteoric fluid, and water–rock interaction is less involved in the carbonation process. Oxygen stable isotope examinations also show much depleted ratios, representative of product formation under low temperatures (∼50–90 °C). This translates to a depth of 1–2 km, which is a practical depth for a CO₂ sequestration reservoir. According to petrographic observation and electron microprobe analysis, the diopside grains in the basalt are resistant to serpentinization and carbonation; therefore, the fluid causing alteration is likely enriched with calcium and there must be additional sources of calcium for carbon mineralization. These derived geochemical properties of the fluid support the late Miocene sandstone and enclosed basalts as having high potential for being a CO₂ sequestration reservoir. Moreover, the existing geochemical environments allow for mineralogical assemblages of ultramafic xenoliths, indicating that forsterite, orthopyroxene and feldspar minerals are readily replaced by carbonates. Based on the mineral transformation in xenoliths, the capacity of CO₂ mineral sequestration of the Miocene basalt is semi-quantitatively estimated at 94.15 kg CO₂ chemically trapped per 1 m³ basalt. With this value, total CO₂ sequestration capacity can be evaluated by a geophysical survey of the amount of viable Miocene basalt at the potential sites. Such a survey is required in the near future.     

Petrophysical analysis to investigate the effects of carbon dioxide storage in a subsurface saline aquifer at Ketzin, Germany (CO2SINK)

To test the injection behaviour of CO₂ into brine-saturated rock and to evaluate the dependence of geophysical properties on CO₂ injection, flow and exposure experiments with brine and CO₂ were performed on sandstone samples of the Stuttgart Formation representing potential reservoir rocks for CO₂ storage. The sandstone samples studied are generally fine-grained with porosities between 17 and 32% and permeabilities between 1 and 100 mD.Additional batch experiments were performed to predict the long-term behaviour of geological CO₂ storage. Reservoir rock samples were exposed over a period of several months to CO₂-saturated reservoir fluid in high-pressure vessels under in situ temperature and pressure conditions. Petrophysical parameters, porosity and the pore radius distribution were investigated before and after the experiments by NMR (Nuclear Magnetic Resonance) relaxation and mercury injection. Most of the NMR measurements of the tested samples showed a slight increase of porosity and a higher proportion of large pores.     

Carbonation of wellbore cement by CO2 diffusion from caprock

To evaluate the risk of corrosion of cement by geosequestered CO₂, samples are being retrieved from wells placed in natural CO₂ deposits [e.g., Crow et al., 2009]. If the cement passing through the cap rock is carbonated, it may indicate that annular gaps or cracks have allowed carbonic acid to come into contact with the cement. However, it must be recognized that the pore water in the cap rock has become saturated with CO₂ over geological time. After the well is placed, the CO₂ will diffuse toward the cement and react with it. A simple analysis of the diffusion kinetics demonstrates that carbonation depths of millimeters to centimeters can be expected from this reaction within the lifetime of a well, in the absence of any cracks or gaps. Therefore, the occurrence of carbonation in cement sealing natural CO₂ deposits must be interpreted with caution.     

Role and impact of CO2–rock interactions during CO2 storage in sedimentary rocks

Before implementing CO₂ storage on a large scale its viability regarding injectivity, containment and long-term safety for both humans and environment is crucial. Assessing CO₂–rock interactions is an important part of that as these potentially affect physical properties through highly coupled processes. Increased understanding of the physical impact of injected CO₂ during recent years including buoyancy driven two-phase flow and convective mixing elucidated potential CO₂ pathways and indicated where and when CO₂–rock interactions are potentially occurring. Several areas of interactions can be defined: (1) interactions during the injection phase and in the near well environment, (2) long-term reservoir and cap rock interactions, (3) CO₂–rock interactions along leakage pathways (well, cap rock and fault), (4) CO₂–rock interactions causing potable aquifer contamination as a consequence of leakage, (5) water–rock interactions caused by aquifer contamination through the CO₂ induced displacement of brines and finally engineered CO₂–rock interactions (6). The driving processes of CO₂–rock interactions are discussed as well as their potential impact in terms of changing physical parameters. This includes dissolution of CO₂ in brines, acid induced reactions, reactions due to brine concentration, clay desiccation, pure CO₂–rock interactions and reactions induced by other gases than CO₂. Based on each interaction environment the main aspects that are possibly affecting the safety and/or feasibility of the CO₂ storage scheme are reviewed and identified. Then the methodologies for assessing CO₂–rock interactions are discussed. High priority research topics include the impact of other gaseous compounds in the CO₂ stream on rock and cement materials, the reactivity of dry CO₂ in the absence of water, how CO₂ induced precipitation reactions affect the pore space evolution and thus the physical properties and the need for the development of coupled flow, geochemical and geomechanical models.     

Carbonate mineralization of volcanic province basalts

Flood basalts are receiving increasing attention as possible host formations for geologic sequestration of anthropogenic CO₂, with studies underway in the United States, India, Iceland, and Canada. Basalts from the United States, India, and South Africa were reacted with aqueous dissolved CO₂ and aqueous dissolved CO₂–H₂S mixtures under supercritical CO₂ (scCO₂) conditions to study the geochemical reactions resulting from injection of CO₂ in such formations. Despite the basalt samples having similar bulk chemical composition, mineralogy and dissolution kinetics, long-term static experiments show significant differences in rates of mineralization as well as compositions and morphologies of precipitates that form when the basalts are reacted with CO₂ and CO₂–H₂S mixtures in water. For example, basalt from the Newark Basin in the United States was by far the most reactive of any basalt tested to date. Reacted grains from the Newark Basin basalt appeared severely weathered and contained extensive carbonate precipitates with significant Fe content. In comparison, the post-reacted samples associated with the Columbia River basalts from the United States contained calcite grains with classic “dogtooth spar” morphology and trace cation substitution (Mg and Mn). Carbonation of the other basalts produced precipitates with compositions that varied chemically throughout the entire testing period. The Karoo basalt from South Africa appeared the least reactive, with very limited mineralization occurring during the testing with CO₂-saturated water. Compositional differences in the precipitates suggest changes in fluid chemistry unique to the dissolution behavior of each basalt sample reacted with CO₂-saturated water. No convincing correlations were identified between basalt reactivity and differences in bulk composition, mineralogy, glassy mesostasis quantity or composition. Moreover, the relative reactivity of different basalt samples was unexpectedly different in the experiments conducted with aqueous dissolved CO₂–H₂S mixtures versus those with CO₂ only. For example, the Karoo basalt was highly reactive in the presence of aqueous dissolved CO₂–H₂S, as evident by nodules of carbonate coating the basalt grains after 181 days of testing. However, the most reactive basalt in CO₂–H₂O, Newark Basin, formed only iron sulfide coatings in tests with a CO₂–H₂S mixture, which inhibited carbonate mineralization.     

Scenario simulations of CO2 injection feasibility, plume migration and storage in a saline aquifer, Scania, Sweden

Deep saline aquifers have large capacity for geological CO₂ storage, but are generally not as well characterized as petroleum reservoirs. We here aim at quantifying effects of uncertain hydraulic parameters and uncertain stratigraphy on CO₂ injectivity and migration, and provide a first feasibility study of pilot-scale CO₂ injection into a multilayered saline aquifer system in southwest Scania, Sweden. Four main scenarios are developed, corresponding to different possible interpretations of available site data. Simulation results show that, on the one hand, stratigraphic uncertainty (presence/absence of a thin mudstone/claystone layer above the target storage formation) leads to large differences in predicted CO₂ storage in the target formation at the end of the test (ranging between 11% and 98% of injected CO₂ remaining), whereas other parameter uncertainty (in formation and cap rock permeabilities) has small impact. On the other hand, the latter has large impact on predicted injectivity, on which stratigraphic uncertainty has small impact. Salt precipitation at the border of the target storage formation affects CO₂ injectivity for all considered scenarios and injection rates. At low injection rates, salt is deposited also within the formation, considerably reducing its availability for CO₂ storage.     

An experimental and numerical investigation into the impact of dissolution/precipitation mechanisms on CO2 injectivity in the wellbore and far field regions

Carbon dioxide capture and storage (CCS) technology is gaining credibility as the best short to medium term solution for significantly reducing net carbon emissions into the atmosphere. From a capacity point of view, deep saline aquifers offer the greatest potential for CO₂ storage. In this respect, well injectivity is considered a key technical and economical issue. Rock/fluid interactions – dissolution/precipitation of minerals, in particular carbonates – are currently considered as one of the principal reasons for wellbore injectivity changes in aquifers.This research investigated the mechanisms involved in injectivity losses through experimental and theoretical methods. The impact on injectivity of permeability changes occurring at various distances from the wellbore was studied using an idealised CO₂ injection well flow model. A new experimental set-up was used to investigate the effect on dissolution/precipitation mechanisms of the pressure and temperature changes that the fluid is subjected to as it advances from the wellbore.Numerical modelling of the injection wellbore has shown that changes in the petrophysical properties of the reservoir several metres away from the wellbore can still have a significant impact on injectivity. As indicated by the experimental research carried out, pressure and temperature gradients that exist inside the reservoirs may lead to re-precipitation in the far field, however no significant permeability and porosity changes were detected to suggest major losses of injectivity due to these effects.     

Experimental investigation of the CO2 sealing efficiency of caprocks

Using a combination of experimental (petrophysical and mineralogical) methods, the effects of high-pressure CO₂ exposure on fluid transport properties and mineralogical composition of two pelitic caprocks, a limestone and a clay-rich marl lithotype have been studied. Single and multiphase permeability tests, gas breakthrough and diffusion experiments were conducted under in situ p/T conditions on cylindrical plugs (28.5 mm diameter, 10–20 mm thickness).The capillary CO₂ sealing efficiency of the initially water-saturated sample plugs was found to decrease in repetitive gas breakthrough experiments on the same sample from 0.74 to 0.41 MPa for the limestone and from 0.64 to 0.43 MPa for the marl. Helium breakthrough experiments before and after the CO₂ tests showed a decrease in capillary threshold (snap-off) pressure from 1.81 to 0.62 MPa for the limestone.Repetitive CO₂ diffusion experiments on the marlstone revealed an increase in the effective diffusion coefficient from 7.8 × 10^?11 to 1.2 × 10^?10 m².Single-phase (water) permeability coefficients derived from steady-state permeability tests ranged between 7 and 56 nano-Darcy and showed a consistent increase after each CO₂ test cycle. Effective gas permeabilities were generally one order of magnitude lower than water permeabilities and exhibit the same trend. XRD measurements performed before and after exposure to CO₂ did not reveal any distinct change in the mineral composition for both samples. Similarly, no significant changes were observed in specific surface areas (determined by BET) and pore-size distributions (determined by mercury injection porosimetry). High-pressure CO₂ sorption experiments on powdered samples revealed significant CO₂ sorption capacities of 0.27 and 0.14 mmol/g for the marlstone and the limestone, respectively.The changes in transport parameters in the absence of detectable mineral alterations may be explained by carbonate dissolution and further precipitation along a pH profile across the sample plug which would not be subject to quantitative mineral alteration.     

Preliminary assessment of CO2 geological storage opportunities in Greece

This paper provides a preliminary assessment of the suitability of Tertiary sedimentary basins in Northern, Western and Eastern Greece in order to identify geological structures close to major CO₂ emission sources with the potential for long-term storage of CO₂. The term “emissions” refers to point source emissions as defined by the International Energy Agency, including power generation, the cement sector and other industrial processes. The Prinos oil field and saline aquifer, along with the saline formations of the Thessaloniki Basin and the Mesohellenic Trough have been identified as prospective CO₂ geological storage sites. In addition, a carbonate deep saline aquifer occurring at appropriate depths beneath the Neogene-Quaternary sediments of Ptolemais-Kozani graben (NW Greece) is considered. The proximity of this geological formation to Greece's largest lignite-fired power plants suggests that it would be worthwhile undertaking further site-specific studies to quantify its storage capacity and assess its structural integrity.     

Characterization of MSWI fly ash through mineralogy and water extraction

This paper investigates the mineralogical characteristics of fresh, aged and hot water extracted MSWI fly ash for providing the baseline information of minerals stability which controls the released heavy metals into the environment. Quantitative determination of bulk phase abundance in the fresh fly ash by the XRD Rietveld refinement method provided composition levels for amorphous and crystalline phases such as potassium tetrachlorozincate (K₂ZnCl₄), gehlenite, halite, quartz, anhydrite, and feldspar. The minerals association in the fly ash is clearly unstable and subject to mineralogical reactions. The phases of K₂ZnCl₄, halite and anhydrite in the fresh fly ash were involved in hydration and dissolution/precipitation processes to form new minerals such as the Zn-bearing mineral gordaite, syngenite, gypsum and hydrocalumite. The solubility-controlling phases and extractability of heavy metals were examined in a Soxhlet hot water-extractor. Here the soluble salts were simply removed from fly ash while Ca-, Al-, Si- and SO₄²⁻-bearing hydrate minerals were precipitated from the extraction solution. Furthermore, a low release of heavy metals Zn, Pb and Cd in hot water was noticed, indicating a strong retention of the trace metals in the mineral phases remaining in the insoluble fly ash residues.     

Life cycle modelling of fossil fuel power generation with post-combustion CO2 capture

Due to its compatibility with the current energy infrastructures and the potential to reduce CO₂ emissions significantly, CO₂ capture and geological storage is recognised as one of the main options in the portfolio of greenhouse gas mitigation technologies being developed worldwide. The CO₂ capture technologies offer a number of alternatives, which involve different energy consumption rates and subsequent environmental impacts. While the main objective of this technology is to minimise the atmospheric greenhouse gas emissions, it is also important to ensure that CO₂ capture and storage does not aggravate other environmental concerns. This requires a holistic and system-wide environmental assessment rather than focusing on the greenhouse gases only. Life Cycle Assessment meets this criteria as it not only tracks energy and non-energy-related greenhouse gas releases but also tracks various other environmental releases, such as solid wastes, toxic substances and common air pollutants, as well as the consumption of other resources, such as water, minerals and land use. This paper presents the principles of the CO₂ capture and storage LCA model developed at Imperial College and uses the pulverised coal post-combustion capture example to demonstrate the methodology in detail. At first, the LCA models developed for the coal combustion system and the chemical absorption CO₂ capture system are presented together with examples of relevant model applications. Next, the two models are applied to a plant with post-combustion CO₂ capture, in order to compare the life cycle environmental performance of systems with and without CO₂ capture. The LCA results for the alternative post-combustion CO₂ capture methods (including MEA, K⁺/PZ, and KS-1) have shown that, compared to plants without capture, the alternative CO₂ capture methods can achieve approximately 80% reduction in global warming potential without a significant increase in other life cycle impact categories. The results have also shown that, of all the solvent options modelled, KS-1 performed the best in most impact categories.     

Predicting δCDIC dynamics in CCS: A scheme based on a review of inorganic carbon chemistry under elevated pressures and temperatures

Stable carbon isotopes are important tools to assess potential storage sites for CO₂, as they allow the quantification of ionic trapping via isotope mass balances. In deep geological formations high p/T conditions need to be considered, because CO₂ dissolution, equilibrium constants and isotope fractionation of dissolved inorganic carbon (DIC) depend on temperature, pressure and solute composition. After reviewing different approaches to account for these dependencies, an expanded scheme is presented for speciation and carbon isotope fractionation of DIC and dissolution of CaCO₃ for pCO₂ up to 100 bar, pH down to 3 and temperatures of up to 200 °C. The scheme evaluates the influence of respective parameters on isotope ratios during CO₂ sequestration. The pCO₂ and pH are the dominant controlling factors in the DIC/δ¹³C/pH system. The fugacity of CO₂ has major impact on DIC concentrations at temperatures below 100 °C at high pCO₂. Temperature dependency of activities and equilibrium dominates at temperatures above 100 °C. Isotope ratios of DIC are expected to be about 1–2‰ more depleted in ¹³C compared to the free CO₂ at pCO₂ values above 10 bar. This depletion is controlled by carbon isotope fractionation between CO₂ and H₂CO₃* which is the dominant species of DIC at the resulting pH below 5.     

Exergy analysis as a tool for the integration of very complex energy systems: The case of carbonation/calcination CO2 systems in existing coal power plants

A common characteristic of carbon capture and storage systems is the important energy consumption associated with the CO₂ capture process. This important drawback can be solved with the analysis, synthesis and optimization of this type of energy systems. The second law of thermodynamics has proved to be an essential tool in power and chemical plant optimization. The exergy analysis method has demonstrated good results in the synthesis of complex systems and efficiency improvements in energy applications.In this paper, a synthesis of pinch analysis and second law analysis is used to show the optimum window design of the integration of a calcium looping cycle into an existing coal power plant for CO₂ capture. Results demonstrate that exergy analysis is an essential aid to reduce energy penalties in CO₂ capture energy systems. In particular, for the case of carbonation/calcination CO₂ systems integrated in existing coal power plants, almost 40% of the additional exergy consumption is available in the form of heat. Accordingly, the efficiency of the capture cycle depends strongly on the possibility of using this heat to produce extra steam (live, reheat and medium pressure) to generate extra power at steam turbine. The synthesis of pinch and second law analysis could reduce the additional coal consumption due to CO₂ capture 2.5 times, from 217 to 85 MW.     

CO2 capture from coal-fired power plants based on sodium carbonate slurry; a systems feasibility and sensitivity study

In this work the feasibility of a CO₂ capture system based on sodium carbonate–bicarbonate slurry and its integration with a power plant is studied. The results are compared to monoethanolamine (MEA)-based capture systems. Condensing power plant and combined heat and power plant with CO₂ capture is modelled to study the feasibility of combined heat and power plant for CO₂ capture.Environmental friendly sodium carbonate would be an interesting chemical for CO₂ capture. Sodium carbonate absorbs CO₂ forming sodium bicarbonate. The low solubility of sodium bicarbonate is a weak point for the sodium carbonate based liquid systems since it limits the total concentration of carbonate. In this study the formation of solid bicarbonate is allowed, thus forming slurry, which can increase the capacity of the solvent. With this the energy requirement of stripping of the solvent could potentially be around 3.22 MJ/kg of captured CO₂ which is significantly lower than with MEA based systems which typically have energy consumption around 3.8 MJ/kg of captured CO₂.Combined heat and power plants seem to be attractive for CO₂ capture because of the high total energy efficiency of the plants. In a condensing power plant the CO₂ capture decreases directly the electricity production whereas in a combined heat and power plant the loss can be divided between district heat and electricity according to demand.     

Limitations for brine acidification due to SO2 co-injection in geologic carbon sequestration

Co-injection of sulfur dioxide during geologic carbon sequestration can cause enhanced brine acidification. The magnitude and timescale of this acidification will depend, in part, on the reactions that control acid production and on the extent and rate of SO₂ dissolution from the injected CO₂ phase. Here, brine pH changes were predicted for three possible SO₂ reactions: hydrolysis, oxidation, or disproportionation. Also, three different model scenarios were considered, including models that account for diffusion-limited release of SO₂ from the CO₂ phase. In order to predict the most extreme acidification potential, mineral buffering reactions were not modeled. Predictions were compared to the case of CO₂ alone which would cause a brine pH of 4.6 under typical pressure, temperature, and alkalinity conditions in an injection formation. In the unrealistic model scenario of SO₂ phase equilibrium between the CO₂ and brine phases, co-injection of 1% SO₂ is predicted to lead to a pH close to 1 with SO₂ oxidation or disproportionation, and close to 2 with SO₂ hydrolysis. For a scenario in which SO₂ dissolution is diffusion-limited and SO₂ is uniformly distributed in a slowly advecting brine phase, SO₂ oxidation would lead to pH values near 2.5 but not until almost 400 years after injection. In this scenario, SO₂ hydrolysis would lead to pH values only slightly less than those due to CO₂ alone. When SO₂ transport is limited by diffusion in both phases, enhanced brine acidification occurs in a zone extending only 5 m proximal to the CO₂ plume, and the effect is even less if the only possible reaction is SO₂ hydrolysis. In conclusion, the extent to which co-injected SO₂ can impact brine acidity is limited by diffusion-limited dissolution from the CO₂ phase, and may also be limited by the availability of oxidants to produce sulfuric acid.     

Comparison of several packings for CO2 chemical absorption in a packed column

CO₂ capture and storage has gained widespread attention as an option for reducing greenhouse gas emissions. Chemical absorption and stripping of CO₂ with hot potassium carbonate (K₂CO₃) solutions has been used in the past, however potassium carbonate solutions have a low CO₂ absorption efficiency. Various techniques can be used to improve the absorption efficiency of this system with one option being the addition of promoters to the solvent and another option being an improvement in the mass transfer efficiency of the equipment. This study has focused on improving the efficiency of the packed column by replacing traditional packings with newer types of packing which have been shown to have enhanced mass transfer performance. Three different packings (Super Mini Rings (SMRs), Pall Rings and Mellapak) have been studied under atmospheric conditions in a laboratory scale column for CO₂ absorption using a 30 wt% K₂CO₃ solution. It was found that SMR packing resulted in a mass transfer coefficient approximately 20% and 30% higher than that of Mellapak and Pall Rings, respectively. Therefore, the height of packed column with SMR packing would be substantially lower than with Pall Rings or Mellapak. Meanwhile, the pressure drop using SMR was comparable to other packings while the gas flooding velocity was higher when the liquid load was above 25 kg m⁻² s⁻¹. Correlations for predicting flooding gas velocities and pressure drop were fitted to the experimental data, allowing the relevant parameters to be estimated for use in later design.