Large-scale impact of CO2 storage in deep saline aquifers: A sensitivity study on pressure response in stratified systems

Large volumes of CO₂ captured from carbon emitters (such as coal-fired power plants) may be stored in deep saline aquifers as a means of mitigating climate change. Storing these additional fluids may cause pressure changes and displacement of native brines, affecting subsurface volumes that can be significantly larger than the CO₂ plume itself. This study aimed at determining the three-dimensional region of influence during/after injection of CO₂ and evaluating the possible implications for shallow groundwater resources, with particular focus on the effects of interlayer communication through low-permeability seals. To address these issues quantitatively, we conducted numerical simulations that provide a basic understanding of the large-scale flow and pressure conditions in response to industrial-scale CO₂ injection into a laterally open saline aquifer. The model domain included an idealized multilayered groundwater system, with a sequence of aquifers and aquitards (sealing units) extending from the deep saline storage formation to the uppermost freshwater aquifer. Both the local CO₂-brine flow around the single injection site and the single-phase water flow (with salinity changes) in the region away from the CO₂ plume were simulated. Our simulation results indicate considerable pressure buildup in the storage formation more than 100 km away from the injection zone, whereas the lateral distance migration of brine is rather small. In the vertical direction, the pressure perturbation from CO₂ storage may reach shallow groundwater resources only if the deep storage formation communicates with the shallow aquifers through sealing units of relatively high permeabilities (higher than 10^?18 m²). Vertical brine migration through a sequence of layers into shallow groundwater bodies is extremely unlikely. Overall, large-scale pressure changes appear to be of more concern to groundwater resources than changes in water quality caused by the migration of displaced saline water.     

Experimental assessment of brine and/or CO2 leakage through well cements at reservoir conditions

Two sets of experiments on typical Class G well cement were carried out in the laboratory to understand better the potential processes involved in well leakage in the presence of CO₂. In the first set, good-quality cement samples of permeability in the order of 0.1 μD (10^?19 m²) were subjected to 90 days of flow through with CO₂-saturated brine at conditions of pressure, temperature and water salinity characteristic of a typical geological sequestration zone. Cement permeability dropped rapidly at the beginning of the experiment and remained almost constant thereafter, most likely mainly as a result of CO₂ exsolution from the saturated brine due to the pressure drop along the flow path which led to multi-phase flow, relative-permeability effects and the observed reduction in permeability. These processes are identical to those which would occur in the field as well if the cement sheath in the wellbore annulus is of good quality. The second set of experiments, carried out also at in situ conditions and using ethane rather than CO₂ to eliminate any possible geochemical effects, assessed the effect of annular spaces between wellbore casing and cement, and of radial cracks in cement on the effective permeability of the casing-cement assemblage. The results show that, if both the cement and the bond are of good quality, the effective permeability of the assemblage is extremely low (in the order of 1 nD, or 10^?21 m²). The presence of an annular gap and/or cracks in the order of 0.01–0.3 mm in aperture leads to a significant increase in effective permeability, which reaches values in the range of 0.1–1 mD (10^?15 m²). The results of both sets of experiments suggest that good cement and good bonding with casing and the surrounding rock will likely constitute a good and reliable barrier to the upward flow of CO₂ and/or CO₂-saturated brine. The presence of mechanical defects such as gaps in bonding between the casing or the formation, or cracks in the cement annulus itself, leads to flow paths with significant effective permeability. This indicates that the external and internal interfaces of cements in wells would most probably constitute the main flow pathways for fluids leakage in wellbores, including both gaseous/supercritical phase CO₂ and CO₂-saturated brine.     

A 13C NMR investigation of CO2 absorption and desorption in aqueous 2,2′-iminodiethanol and N-methyl-2,2′-iminodiethanol

The carbon dioxide capture and release from aqueous 2,2′-iminodiethanol (DEA) and N-methyl-2,2′-iminodiethanol (MDEA) have been investigated by means of ¹³C NMR spectroscopy. We have designed two experimental procedures using a gas mixture containing 12% (v/v) CO₂ in N₂ or air and 0.667 M aqueous solutions of DEA and MDEA. To understand the CO₂–amine reaction equilibria, separate experiments of CO₂ absorption (at 293, 313 and 333 K) and desorption (at boiling temperature, room pressure) were carried out. The ¹³C NMR analysis has allowed us to establish: (1) the percentage of CO₂ stored in solution as HCO₃^?, CO₃^2? and DEA carbamate; (2) the formation of DEA carbamate as a function of absorption temperature and time; (3) the slower decomposition of DEA carbamate than that of bicarbonate. In the experiments planned to test the reuse of the regenerated amines, the absorbent solution was continuously circulated in a closed cycle while it was absorbing CO₂ in the absorber (set at 293 K) and simultaneously regenerating amine in the desorber (set at 388 K). After the equilibrium has been reached (13 h), the CO₂ absorption efficiency is comprised between 84.0% (DEA) and 82.6% (MDEA) and the average amine regeneration efficiency ranges between 69.6% (DEA) and 78.2% (MDEA). Additionally, MDEA is more stable towards thermal degradation than DEA.     

Monitoring of the microbial community composition in saline aquifers during CO2 storage by fluorescence in situ hybridisation

This study reveals the first analyses of the composition and activity of the microbial community of a saline CO₂ storage aquifer. Microbial monitoring during CO₂ injection has been reported. By using fluorescence in situ hybridisation (FISH), we have shown that the microbial community was strongly influenced by the CO₂ injection. Before CO₂ arrival, up to 6 × 10⁶ cells ml⁻¹ were detected by DAPI staining at a depth of 647 m below the surface. The microbial community was dominated by the domain Bacteria that represented approximately 60% to 90% of the total cell number, with Proteobacteria and Firmicutes as the most abundant phyla comprising up to 47% and 45% of the entire population, respectively. Both the total cell counts as well as the counts of the specific physiological groups revealed quantitative and qualitative changes after CO₂ arrival. Our study revealed temporal outcompetition of sulphate-reducing bacteria by methanogenic archaea. In addition, an enhanced activity of the microbial population after five months CO₂ storage indicated that the bacterial community was able to adapt to the extreme conditions of the deep biosphere and to the extreme changes of these atypical conditions.     

Techno-economic evaluation of biogas upgrading process using CO2 facilitated transport membrane

The biogas upgrading by membrane separation process using a highly efficient CO₂-selective polyvinylamine/polyvinylalcohol (PVAm/PVA) blend membrane was investigated by experimental study and simulation with respect to process design, operation optimization and economic evaluation. This blend membrane takes advantages of the unique CO₂ facilitated transport from PVAm and the robust mechanical properties from PVA, exhibits both high CO₂/CH₄ separation efficiency and very good stability. CO₂ transports through the water swollen membrane matrix in the form of bicarbonate. CO₂/CH₄ selectivity up to 40 and CO₂ permeance up to 0.55 m³(STP)/m² h bar at 2 bar were documented in lab with synthesized biogas (35% CO₂ and 65% CH₄). Membrane performances at varying feed pressures were recorded and used as the simulation basis in this work. The process simulation of an on-farm scale biogas upgrading plant (1000 Nm³/h) was conducted. Processes with four different membrane module configurations with or without recycle were evaluated technically and economically, and the 2-stage in cascade with recycle configuration was proven optimal among the four processes. The sensitivity of the process to various operation parameters was analyzed and the operation conditions were optimized.     

Chromatographic partitioning of impurities contained in a CO2 stream injected into a deep saline aquifer: Part 1. Effects of gas composition and in situ conditions

A series of laboratory experiments were carried out to examine the chromatographic partitioning of impurities contained in a stream of CO₂ injected into a deep saline aquifer. The experiments were carried out under static (no flow) and dynamic conditions, mainly with H₂S as the impurity in the CO₂ stream, for 2%, 5% and 30% concentrations, and for in situ conditions of high pressure, temperature and water salinity, and also for pure water at a lower pressure and temperature. In addition, experiments were conducted using CH₄, N₂ and SO₂ at 5% concentration as the ‘Impurity’ in the CO₂ stream. The experiments show that gases in an impure stream of CO₂ being injected into a deep saline aquifer will chromatographically partition at the leading edge of the gas advancing through the water-saturated porous medium as a result of differential solubility in aquifer water. The solubility of the impurity gas in the CO₂ stream compared to that of CO₂ is the most dominant factor in regard to the breakthrough time and initial gas concentrations in the effluent. The in situ conditions of pressure, temperature and water salinity also affect the chromatographic partitioning of CO₂ and impurities contained in the injection stream through their general effect on the solubility of all gases. The concentration of the impurity gas in the feed gas stream has a secondary effect on the breakthrough and time lag decreasing with increasing concentration of the impurity gas. These experimental findings are significant for understanding the fate of the injected CO₂ and associated impurities contained in an injection stream, in devising monitoring procedures and protocols, and in developing emergency response plans in case of leakage of CO₂ and associated impurities.     

Effect of synthesis parameters on single gas permeation through T-type zeolite membranes

In this research, nanoporous zeolite T membranes were synthesized at three levels of synthesis temperature: 100, 120 and 140 °C and synthesis time: 15, 30 and 50 h and characterized by gas permeation. Effects of synthesis parameters on CO₂ and CH₄ permeances and CO₂/CH₄ ideal separation factors were studied. All experiments were conducted at 1 bar feed pressure and 30 °C module temperature. Normally, it is anticipated that increasing synthesis temperature and synthesis time increase gas permeances and consequently decrease ideal separation factor. This prediction was not observed in the case of synthesis temperature increase from 100 to 120 °C as well as synthesis time increase from 15 to 30 h, due to the dual effect of increasing synthesis temperature and synthesis time on gas permeances and ideal separation factor. More zeolites are deposited and larger crystals are formed at higher synthesis temperatures and times. Forming the larger crystals accelerates the rate of zeolite layer integration, which is responsible for gas separation, in one hand and reduces the density of deposited zeolite layer on the support, due to the formation of more voids, on the other hand. In terms of maximizing the CO₂/CH₄ ideal separation factor, medium synthesis temperature and synthesis time (120 °C and 30 h) can be selected, however, maximum gas permeances are obtained at low levels of synthesis temperature and time (100 °C and 15 h). According to the ranges of gas permeances (10⁻¹¹ to 10⁻⁶ mol/m² s Pa) and CO₂/CH₄ ideal separation factors (1.4–70.3), it is concluded that the zeolite T membranes synthesized at optimum conditions can be employed for membrane separation of CO₂/CH₄ mixtures.     

Development of novel absorbents for CO2 capture from blast furnace gas

In order to establish energy-saving technology for CO₂ capture from blast furnace gas, novel absorbents were developed in the laboratory and evaluated at a 1 t_CO2/d test plant. At first, CO₂ absorption and desorption behaviors of single-component amine solvents for simulated blast furnace gas (CO₂/N₂ = 20%/80%) were investigated through a screening test using a small scrubbing bottle. These amine solvents were additionally analyzed using nuclear magnetic resonance (¹³C NMR) spectroscopy and reaction calorimetry. The results of the laboratory experiments showed that there was a trade-off between absorption rate and enthalpy of absorption but some absorbents had unique features. For example, 2-isopropylaminoethanol (IPAE) had high absorption rate and small enthalpy of absorption. Then, new IPAE-based amine solvents (RITE solvents: RITE-A and RITE-B) were formulated and evaluated at the 1 t_CO2/d test plant. CO₂ regeneration energies of the RITE solvents were 3.3 and 3.1 GJ/t_CO2, respectively. With certain process conditions and plant specifications optimized, RITE-B was estimated to have the potential to achieve 2.5 GJ/t_CO2.     

Highly siliceous MCM-48 from rice husk ash for CO2 adsorption

Mesoporous MCM-48 silica was synthesized using a cationic-neutral surfactant mixture as the structure-directing template and rice husk ash (RHA) as the silica source. The MCM-48 samples were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N₂ physisorption and SEM. X-ray diffraction pattern of the resulting MCM-48 revealed typical pattern of cubic Ia3d mesophase. BET results showed the MCM-48 to have a surface area of 1024 m²/g and FT-IR revealed a silanol functional group at about 3460 cm⁻¹. Breakthrough experiments in the presence of MCM-48 were also carried out to test the material's CO₂ adsorption capacity. The breakthrough time for CO₂ was found to decrease as the temperature increased from 298 K to 348 K. The steep slopes observed shows the CO₂ adsorption occurred very quickly, with only a minimal mass transfer effect and very fast kinetics. In addition, amine grafted MCM-48, APTS-MCM-48 (RHA), was prepared with the 3-aminopropyltriethoxysilane (APTS) to investigate the effect of amine functional group in CO₂ separation. An order of magnitude higher CO₂ adsorption capacity was obtained in the presence of APTS-MCM-48 (RHA) compared to that with MCM-48 (RHA). These results suggest that MCM-48 synthesized from rice husk ash could be usefully applied for CO₂ removal.     

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 new apparatus to enhance the rate of gas hydrate formation: Application to capture of carbon dioxide

A new apparatus employing a modular, mechanically agitated gas-inducing crystallizer is used to demonstrate the capture of CO₂ via hydrate crystallization. The crystallizer enhances the contact of hydrate forming gases with water and thus the rate of hydrate crystallization increases. Flue gas (CO₂/N₂) and fuel gas (CO₂/H₂) mixtures were used to represent post- and precombustion capture. A comparison between the rates of hydrate formation in different crystallizers is presented by defining a metric called the normalized rate of hydrate formation. The gas uptake and the separation efficiency for the fuel and flue gas mixtures were found to be greater compared to the results obtained in a smaller scale stirred tank reactor (Kumar et al., 2009c, Linga et al., 2008). The gas uptake and CO₂ recovery for flue gas mixture in the presence of THF obtained in this work was higher than that reported in the literature with tetra-n-butyl ammonium bromide and tetra-n-butyl ammonium fluoride (Fan et al., 2009, Li et al., 2009). Although hydrate crystallization is able to capture CO₂, the power required for mechanical agitation was found to be very significant. If the hydrate process is to be used industrially then hydrate crystallization must be carried out without mechanical agitation.     

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.     

Experimental investigation of wellbore integrity and CO2–brine flow along the casing–cement microannulus

Wellbore integrity is one of the key performance criteria in the geological storage of CO₂. It is significant in any proposed storage site but may be critical to the suitability of depleted oil and gas reservoirs that may have 10’s to 1000’s of abandoned wells. Much previous work has focused on Portland cement which is the primary material used to seal wellbore systems. This work has emphasized the potential dissolution of Portland cement. However, an increasing number of field studies (e.g., Carey et al., 2007), experimental studies (e.g., Kutchko et al., 2006) and theoretical considerations indicate that the most significant leakage mechanism is likely to be flow of CO₂ along the casing–cement microannulus, cement–cement fractures, or the cement–caprock interface.In this study, we investigate the casing–cement microannulus through core-flood experiments. The experiments were conducted on a synthetic wellbore system consisting of a 5-cm diameter sample of cement that was cured with an embedded rectangular length of steel casing that had grooves to accommodate fluid flow. The experiments were conducted at 40 $°$ C and 14 MPa pore pressure for 394 h. During the experiment, 6.2 l of a 50:50 mixture of supercritical CO₂ and 30,000 ppm NaCl-rich brine flowed through 10-cm of limestone before flowing through the 6-cm length cement–casing wellbore system. Approximately 59,000 pore volumes of fluid moved through the casing–cement grooves. Scanning electron microscopy revealed that the CO₂–brine mixture impacted both the casing and the cement. The Portland cement was carbonated to depths of 50–250 $\mu$m by a diffusion-dominated process. There was very little evidence for mass loss or erosion of the Portland cement. By contrast, the steel casing reacted to form abundant precipitates of mixed calcium and iron carbonate that lined the channels and in one case almost completely filled a channel. The depth of steel corroded was estimated at 25– $30\mu$m and was similar in value to results obtained with a simplified corrosion model.The experimental results were applied to field observations of carbonated wellbore cement by Carey et al. (2007) and Crow et al. (2009) to show that carbonation of the field samples was not accompanied by significant CO₂–brine flow at the casing–cement interface. The sensitivity of standard-grade steel casing to corrosion suggests that relatively straight-forward wireline logging of external casing corrosion could be used as a useful indicator of flow behind casing. These experiments also reinforce other studies that indicate rates of Portland cement deterioration are slow, even in the high-flux CO₂–brine experiments reported here.     

Molecular analysis of carbon dioxide adsorption processes on steel slag oxides

This review presents a summary of the main interactions that occur during the carbon dioxide (CO₂) adsorption at the surface of steel slags with basic (CaO, MgO), amphoteric (Al₂O₃, Cr₂O₃, TiO₂, MnO, iron oxides) and acidic (SiO₂) oxides. The high content of metal oxides in steel slags gives them a great potential to adsorb CO₂, reaching a saturation value of about 0.25 kg of CO₂/kg of slag. CO₂ is physisorbed and chemisorbed on the most of metal oxide types. Generally, the CO₂ physisorption on the basic and amphoteric metal oxides involves an electrostatic interaction between the CO₂ and the cation from the oxides while the CO₂ chemisorption rather implicates the basic sites that acts as the electron donor, and which are associated with O^2? ions localized at surface defects. These interactions result in the formation of carbonates (monodentates or unidentates and bidentates). The affinity of oxides for the CO₂ and the carbonate formation principally depend of the strength and number of basic sites at their surface and varies as following: basic oxides > amphoteric oxides > acidic oxides. The basic metal oxides generally represent the best electron donors and thus the best CO₂ adsorbents due to the high basicity and their great number of reaction sites. Hence, it appears that the surface structure of basic and amphoteric metal oxides which may favour their interaction with the CO₂, as well as their basicity is the determinant factor contributing to the formation of carbonate species. The molecular analysis of CO₂ adsorption on steel slag metal oxides will provide useful data to identify rate-controlling mechanisms and should be considered for the development of new effective methods for the capture of atmospheric CO₂ emissions released from industries.     

Laboratory calibration of the seismo-acoustic response of CO2 saturated sandstones

Ultrasonic experiments were undertaken on CO₂ flooded sandstone core samples, both synthetic sandstones and core plugs from the CRC1 CO₂ injection well in the Otway Basin, Victoria, South Eastern. Australia. The aim of these laboratory tests was to investigate the effects of CO₂ as a pore fluid on the seismo-acoustic response of the sandstone and ultimately to provide an indication of the sensitivity of time-lapse seismic imaging of the eventual CO₂/CH₄ plume in the Otway, Waarre C formation.The synthetic sandstones were manufactured using both a proprietary calcium in situ precipitation (CIPS) process and a silica cementing technique. Samples were tested in a computer controlled triaxial pressure cell where pore pressures can be controlled independently of the confining pressures. The pressure cell is equipped with ultrasonic transducers housed in the loading platens. Consequently, effective pressures equivalent to those expected in the reservoir can be applied while ultrasonic testing is undertaken. Both compressional, P and shear waves, S were recorded via a digital oscilloscope at a range of effective pressure steps. Pore pressures were varied from 4 MPa to 17 MPa to represent both the gaseous and liquid phase regions of the CO₂ phase diagram. Similar experiments were conducted on core plugs from the Waarre C reservoir horizon obtained from the CRC1 injection well, but with an intervening brine-saturated step and in some cases with a CO₂/CH₄ mix of 80%/20% molar fraction which is representative of the field situation. However, the pore pressure in these experiments was held at 4 MPa. Finally, acoustic impedances and reflection coefficients were calculated for the reservoir using Gassmann theory and the implications for imaging the CO₂ plume is discussed.     

Analytical solution for estimating storage efficiency of geologic sequestration of CO2

During injection of carbon dioxide (CO₂) into deep saline aquifers, the available pore volume of the aquifer may be used inefficiently, thereby decreasing the effective capacity of the repository for CO₂ storage. Storage efficiency is the fraction of the available pore space that is utilized for CO₂ storage, or, in other words, it is the ratio between the volume of stored CO₂ and the maximum available pore volume. In this note, we derive and present simple analytical expressions for estimating CO₂ storage efficiency under the scenario of a constant-rate injection of CO₂ into a confined, homogeneous, isotropic, saline aquifer. The expressions for storage efficiency are derived from models developed previously by other researchers describing the shape of the CO₂-brine interface. The storage efficiency of CO₂ is found to depend on three dimensionless groups, namely: (1) the residual saturation of brine after displacement by CO₂; (2) the ratio of CO₂ mobility to brine mobility; (3) a dimensionless group (which we call a “gravity factor”) that quantifies the importance of CO₂ buoyancy relative to CO₂ injection rate. In the particular case of negligible residual brine saturation and negligible buoyancy effects, the storage efficiency is approximately equal to the ratio of the CO₂ viscosity to the brine viscosity. Storage efficiency decreases as the gravity factor increases, because the buoyancy of the CO₂ causes it to occupy a thin layer at the top of the confined formation, while leaving the lower part of the aquifer under-utilized. Estimates of storage efficiency from our simple analytical expressions are in reasonable agreement with values calculated from simulations performed with more complicated multi-phase-flow simulation software. Therefore, we suggest that the analytical expressions presented herein could be used as a simple and rapid tool to screen the technical or economic feasibility of a proposed CO₂ injection scenario.     

Model prediction on the rise of pCO2 in uniform flows by leakage of CO2 purposefully stored under the seabed

A numerical study was conducted to predict pCO₂ change in the ocean on a continental shelf by the leakage of CO₂, which is originally stored in the aquifer under the seabed, in the case that a large fault connects the CO₂ reservoir and the seabed by an earthquake or other diastrophism. The leakage rate was set to be 6.025 × 10⁻⁴ kg/m²/sec from 2 m × 100 m fault band, which corresponds to 3800 t-CO₂/year, referring to the monitored seepage rate from an existing EOR field. The target space in this study was limited to the ocean above the seabed, the depth of which was 200 or 500 m. The computational domain was idealistically rectangular with the seabed fault-band perpendicular to the uniform flow. The CO₂ takes a form of bubbles or droplets, depending on the depth of water, and their behaviour and dissolution were numerically simulated during their rise in seawater flow. The advection–diffusion of dissolved CO₂ was also simulated. As a result, it was suggested that the leaked CO₂ droplets/bubbles all dissolve in the seawater before spouting up to the atmosphere, and that the increase in pCO₂ in the seawater was smaller than 500 μ atm.     

Testing of hydrotalcite-based sorbents for CO2 and H2S capture for use in sorption enhanced water gas shift

The feasibility of the sorption enhanced water gas shift (SEWGS) process under sour conditions is shown. The sour-SEWGS process constitutes a second generation pre-combustion carbon capture technology for the application in an IGCC. As a first critical step, the suitability of a K₂CO₃ promoted hydrotalcite-based CO₂ sorbent is demonstrated by means of adsorption and regeneration experiments in the presence of 2000 ppm H₂S. In multiple cycle experiments at 400 °C and 5 bar, the sorbent displays reversible co-adsorption of CO₂ and H₂S. The CO₂ sorption capacity is not significantly affected compared to sulphur-free conditions. A mechanistic model assuming two different sites for H₂S interaction explains qualitatively the interactions of CO₂ and H₂S with the sorbent. On the type A sites, CO₂ and H₂S display competitive sorption where CO₂ is favoured. The type B sites only allow H₂S uptake and may involve the formation of metal sulphides. This material behaviour means that the sour-SEWGS process likely eliminates CO₂ and H₂S simultaneously from the syngas and that an almost CO₂ and H₂S-free H₂ stream and a CO₂ + H₂S stream can be produced.     

Modelling of CO2 arrival time at Ketzin – Part I

The injection of CO₂ at the Ketzin storage site and the chemical detection of its arrival in the observation well allowed testing of different numerical simulation codes. ECLIPSE 100 (E100, black-oil simulator), ECLIPSE 300 (E300, compositional CO₂STORE) and MUFTE-UG were used for predictive modelling applying a constant injection rate of 1 kg s^?1 CO₂ and for a history match applying the actual variable injection rate which ranged from 0 to 0.7 kg s^?1 and averaged 0.23 kg s^?1. The geological model applied, is based on all available geophysical and geological information and has been the same for all programs.The results of the constant injection regime show a good agreement among the programs with a discrepancy of 21–33% for the CO₂ arrival times. However, it is determined from the comparison of the cumulative mass of CO₂ at the time of CO₂ arrival that the injection regime is an important factor for the accurate prediction of CO₂ migration within a saline aquifer. Comparing the actual variable injection regime with the simulations applying a constant injection rate the results are relatively inaccurate.Regarding the actual variable injection regime, which was evaluated using all three simulators, the computational results show a good agreement with the data actually measured at the first observation well. Here, the calculated arrival times exceeded the actual ones by 8.1% (E100), 9.2% (E300) and 17.7% (MUFTE-UG).It can be concluded that irrespective of the deviations of the simulations, due to combinations of different codes and slight differences in input parameters, all three programs are well equipped to give a reliable estimate of the arrival of CO₂. Deviations in the results mainly occur due to different input data and grid size choices done by the different modelling teams working independently of each other. Deviations of the simulations results compared to the actual CO₂ arrival time result from uncertainties in the implementation of the geological model, which was set up based on well log data and analogue studies.     

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.