Intermediate storage of carbon dioxide in geological formations: A technical perspective

Enhanced oil recovery (EOR) through CO₂ flooding has been practiced on a commercial basis for the last 35 years and continues today at several sites, currently injecting in total over 30 million tons of CO₂ annually. This practice is currently exclusively for economic gain, but can potentially contribute to the reduction of emissions of greenhouse gases provided it is implemented on a large scale. Optimal operations in distributing CO₂ to CO₂-EOR or enhanced gas recovery (EGR) projects (referred to here collectively as CO₂-EHR) on a large scale and long time span imply that intermediate storage of CO₂ in geological formations may be a key component. Intermediate storage is defined as the storage of CO₂ in geological media for a limited time span such that the CO₂ can be sufficiently reproduced for later use in CO₂-EHR. This paper investigates the technical aspects, key individual parameters and possibilities of intermediate storage of CO₂ in geological formations aiming at large scale implementation of carbon dioxide capture and storage (CCS) for deep emission reduction. The main parameters are thus the depth of injection and density, CO₂ flow and transport processes, storage mechanisms, reservoir heterogeneity, the presence of impurities, the type of the reservoirs and the duration of intermediate storage. Structural traps with no flow of formation water combined with proper injection planning such as gas-phase injection favour intermediate storage in deep saline aquifers. In depleted oil and gas fields, high permeability, homogeneous reservoirs with structural traps (e.g. anticlinal structures) are good candidates for intermediate CO₂ storage. Intuitively, depleted natural gas reservoirs can be potential candidates for intermediate storage of carbon dioxide due to similarity in storage characteristics.     

Time-lapse carbon dioxide monitoring with pulsed neutron logging

Elevated levels of CO₂ in the atmosphere have been linked to the rise in land and sea temperature [Climate Change, 2001. In: Houghton, J.T., Ding, Y., Griggs, D.J., Noguer, M., van der Linden, P.J., Xiaosu, D. (Eds.), The Scientific Basis Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change (IPCC). Cambridge University Press, UK, p. 944]. To demonstrate geological carbon sequestration as a mitigation technique, a carbon dioxide injection experiment was conducted in East Texas. The target – Frio formation – is a highly porous, permeable and unconsolidated sandstone. The specific interval is the Frio C sand, which originally was saturated with saline formation water. At the injection location, the Frio C sand dips 18° to the south. To monitor the injected CO₂ spreading in the formation, an old well from 1956 drilled into the deeper Yegua formation was selected as the observation well. The injection well was drilled at a distance of 100 ft downdip from the monitoring well. Several borehole measurement methods were available to monitor the CO₂ injection, but the most suitable technology was thought to be the pulsed neutron logging. This logging is used widely in cased hole, and the measured macroscopic thermal absorption cross-section (Σ) is sensitive to CO₂ saturation in high porosity saline water environments. Several log examples are given demonstrating successful the monitoring of the CO₂ plume moving through the two boreholes and the resulting saturation changes.     

CO2 transportation for carbon capture and storage: Sublimation of carbon dioxide from a dry ice bank

Climate change is being caused by greenhouse gases such as carbon dioxide (CO₂). Carbon capture and storage (CCS) is of interest to the scientific community as one way of achieving significant global reductions of atmospheric CO₂ emissions in the medium term. CO₂ would be captured from large stationary sources such as power plants and transported via pipelines under high pressure conditions to underground storage. If a downward leakage from a surface transportation system module occurs, the CO₂ would undergo a large temperature reduction and form a bank of “dry ice” on the ground surface; the sublimation of the gas from this bank represents an area source term for subsequent atmospheric dispersion, with an emission rate dependent on the energy balance at the bank surface. Gaseous CO₂ is denser than air and tends to remain close to the surface; it is an asphyxiant, a cerebral vasodilator and at high concentrations causes rapid circulatory insufficiency leading to coma and death. Hence a subliming bank of dry ice represents safety hazard. A model is presented for evaluating the energy balance and sublimation rate at the surface of a solid frozen CO₂ bank under different environmental conditions. The results suggest that subliming gas behaves as a proper dense gas (i.e. it remains close to the ground surface) only for low ambient wind speeds.     

Value of information analysis for adequate monitoring of carbon dioxide storage in geological reservoirs under uncertainty

As monitoring is essential for the proper management of geological storage of carbon dioxide (CO₂), the ability to value information from monitoring is indispensable to adequately design a monitoring program. It is necessary to judge whether the expected improvement in management is worth the cost of monitoring. The value of information (VOI) is closely related to the possible increase in expected utility gained by gathering the information, the concept of which can be applied to such judgement. Although VOI analysis has been extensively studied in the context of decision analysis, its application to the management of carbon dioxide capture and storage (CCS) operations is rare. This paper introduces and discusses the methodology of VOI analyses in the context of monitoring CO₂ storage. A motivating problem with discrete probabilities is used to illustrate the concept of VOI. It is demonstrated that information is not always of value; for information to be worthwhile, monitoring under uncertainty must satisfy certain conditions. This concept is then extended to continuous probability distributions. The effects of prior uncertainty and information reliability on the VOI are examined. It is shown that an excessive improvement in information accuracy yields little value and that the optimal level of reliability can be inferred. VOI analyses provide quantitative insights into the value of information-gathering activities and therefore can be an objective means to adequately design and impartially justify a monitoring program.     

Performance assessments for the geological storage of carbon dioxide: Learning from the radioactive waste disposal experience

The geological storage of carbon dioxide is currently being considered as a possible technology for reducing emissions to atmosphere. Although there are several operational sites where carbon dioxide is stored in this way, methods for assessing the long-term performance and safety of geological storage are at an early stage of development. In this paper the similarities and differences between this field and the geological disposal of radioactive wastes are considered. Priorities are suggested for the development of performance assessment methods for carbon dioxide storage based on areas where experience from radioactive waste disposal can be usefully applied. These include, inter alia, dealing with the various types of uncertainty, using systematic methodologies to ensure an auditable and transparent assessment process, developing whole system models and gaining confidence to model the long-term system evolution by considering information from natural systems. An important area of data shortage remains the potential impacts on humans and ecosystems.     

Experimental measurement and modeling of the rate of absorption of carbon dioxide by aqueous ammonia

In this work, the rate of absorption of carbon dioxide by aqueous ammonia solvent has been studied by applying a newly built wetted wall column. The absorption rate in aqueous ammonia was measured at temperatures from 279 to 304 K for 1 to 10 wt% aqueous ammonia with loadings varying from 0 to 0.8 mol CO₂/mol NH₃. The absorption rate in 30 wt% aqueous mono-ethanolamine (MEA) was measured at 294 and 314 K with loadings varying from 0 to 0.4 as comparison.It was found that at 304 K, the rate of absorption of carbon dioxide by 10 wt% NH₃ solvent was comparable to the rates for 30 wt% MEA at 294 and 314 K (a typical absorption temperature for this process). The absorption rate using ammonia was however significantly lower at temperatures of 294 K and lower as applied in the Chilled Ammonia Process. However, at these low temperatures, the rate of absorption in ammonia has only a small temperature dependency.The rate of absorption decreases strongly with decreasing ammonia concentrations and increasing CO₂ loadings.The rate of absorption of carbon dioxide by aqueous ammonia solvent was modeled using the measurements of the unloaded solutions and the zwitter-ion mechanism. The model could successfully predict the experimental measurements of the absorption rate of CO₂ in loaded ammonia solutions.     

Comparison and application of different component municipal solid wastes based carbon on adsorption of carbon dioxide

The prepared different components municipal solid wastes based carbons were used to investigate the adsorption of CO₂. The optimum conditions for CO₂ adsorption were investigated firstly. And then, the CO₂ adsorption performance of different components based carbon adsorbents were compared with each other under the optimum parameters. The results illustrated that the triple components (pinewood, acrylic textile, and tire) based carbon exhibited the best adsorption performance, which is 1.522 mmol/g and its physical prosperity was also conducted to interpret the adsorption mechanism. Besides, to further approach to the actual gas, the influence of additional O₂ and SO₂ on CO₂ adsorption properties of ternary-component-based carbon was investigated. The results illustrate that O₂ concentration exerts little effect on adsorption capacity. SO₂ plays the dominated role in the competitive adsorption effect.     

Water/acid gas interfacial tensions and their impact on acid gas geological storage

Acid gas geological disposal is a promising process to reduce CO₂ atmospheric emissions and an environment-friendly and economic alternative to the transformation of H₂S into sulphur by the Claus process. Acid gas confinement in geological formations is to a large extent controlled by the capillary properties of the water/acid–gas/caprock system, because a significant fraction of the injected gas rises buoyantly and accumulates beneath the caprock. These properties include the water/acid gas interfacial tension (IFT), to which the so-called capillary entry pressure of the gas in the water-saturated caprock is proportional. In this paper we present the first ever systematic water/acid gas IFT measurements carried out by the pendant drop technique under geological storage conditions. We performed IFT measurements for water/H₂S systems over a large range of pressure (up to P = 15 MPa) and temperature (up to T = 120 °C). Water/H₂S IFT decreases with increasing P and levels off at around 9–10 mN/m at high T (≥70 °C) and P (>12 MPa). The latter values are around 30–40% of water/CO₂ IFTs, and around 20% of water/CH₄ IFTs at similar T and P conditions. The IFT between water and a CO₂ + H₂S mixture at T = 77 °C and P > 7.5 MPa is observed to be approximately equal to the molar average IFT of the water/CO₂ and water/H₂S binary mixtures. Thus, when the H₂S content in the stored acid gas increases the capillary entry pressure decreases, together with the maximum height of acid gas column and potential storage capacity of a given geological formation. Hence, considerable attention should be exercised when refilling with a H₂S-rich acid gas a depleted gas reservoir, or a depleted oil reservoir with a gas cap: in the case of hydrocarbon reservoirs that were initially (i.e., at the time of their discovery) close to capillary leakage, acid gas leakage through the caprock will inevitably occur if the refilling pressure approaches the initial reservoir pressure.     

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.     

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.     

A statistical analysis of the carbon dioxide capture process

Post combustion carbon dioxide (CO₂) capture is one of the most commonly adopted technologies for reducing industrial CO₂ emissions, which is now an important goal given the widespread concern over global warming. Research on amine-based CO₂ capture has mainly focused on improving effectiveness and efficiency of the CO₂ capture process. Our research work focuses on studying the relationships among the significant parameters influencing CO₂ production because an enhanced understanding of the intricate relationships among the parameters involved in the process is critical for improving efficiency of the CO₂ capture process. This paper presents a statistical study that explores the relationships among parameters involved in the amine-based post combustion CO₂ capture process at the International Centre for CO₂ Capture (ITC) located in Regina, Saskatchewan of Canada. A multiple regression technique has been applied for analysis of data collected at the CO₂ capture pilot plant at ITC. The parameters have been carefully selected to avoid issues of multicollinearity, and four mathematical models among the key parameters identified have been developed. The models have been tested, and accuracy of the models is found to be satisfactory. The models developed in this study describe part of the CO₂ capture process and can help to predict performance of the CO₂ capture process at ITC under different conditions. Some results from a preliminary validation process will also be presented.     

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.     

CO2SINK—From site characterisation and risk assessment to monitoring and verification: One year of operational experience with the field laboratory for CO2 storage at Ketzin, Germany

The CO₂SINK pilot project at Ketzin is aimed at a better understanding of geological CO₂ storage operation in a saline aquifer. The reservoir consists of fluvial deposits with average permeability ranging between 50 and 100 mDarcy. The main focus of CO₂SINK is developing and testing of monitoring and verification technologies. All wells, one for injection and two for observation, are equipped with smart casings (sensors behind casing, facing the rocks) containing a Distributed Temperature Sensing (DTS) and electrodes for Electrical Resistivity Tomography (ERT). The in-hole Gas Membrane Sensors (GMS) observed the arrival of tracers and CO₂ with high temporal resolution. Geophysical monitoring includes Moving Source Profiling (MSP), Vertical Seismic Profiling (VSP), crosshole, star and 4-D seismic experiments. Numerical models are benchmarked via the monitoring results indicating a sufficient match between observation and prediction, at least for the arrival of CO₂ at the first observation well. Downhole samples of brine showed changes in the fluid composition and biocenosis. First monitoring results indicate anisotropic flow of CO₂ coinciding with the “on-time” arrival of CO₂ at observation well one (Ktzi 200) and the later arrival at observation well two (Ktzi 202). A risk assessment was performed prior to the start of injection. After one year of operations about 18,000 t of CO₂ were injected safely.     

Methodology for CO2 chain analysis

The paper presents a methodology for CO₂ chain analysis with particular focus on the impact of technology development on the total system economy. The methodology includes the whole CO₂ chain; CO₂ source, CO₂ capture, transport and storage in aquifers or in oil reservoirs for enhanced oil recovery. It aims at supporting the identification of feasible solutions and assisting the selection of the most cost-effective options for carbon capture and storage. To demonstrate the applicability of the methodology a case study has been carried out to illustrate the possible impact of technology improvements and market development. The case study confirms that the CO₂-quota price to a large extent influence the project economy and dominates over potential technology improvements. To be economic feasible, the studied chains injecting the CO₂ in oil reservoirs for increased oil production require a CO₂-quota price in the range of 20–27 €/tonne CO₂, depending on the technology breakthrough. For the chains based on CO₂ storage in saline aquifers, the corresponding CO₂-quota price varies up to about 40 €/tonne CO₂.     

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.     

A method for quick assessment of CO2 storage capacity in closed and semi-closed saline formations

Saline aquifers of high permeability bounded by overlying/underlying seals may be surrounded laterally by low-permeability zones, possibly caused by natural heterogeneity and/or faulting. Carbon dioxide (CO₂) injection into and storage in such “closed” systems with impervious seals, or “semi-closed” systems with non-ideal (low permeability) seals, is different from that in “open” systems, from which the displaced brine can easily escape laterally. In closed or semi-closed systems, the pressure buildup caused by continuous industrial-scale CO₂ injection may have a limiting effect on CO₂ storage capacity, because geomechanical damage caused by overpressure needs to be avoided. In this research, a simple analytical method was developed for the quick assessment of the CO₂ storage capacity in such closed and semi-closed systems. This quick-assessment method is based on the fact that native brine (of an equivalent volume) displaced by the cumulative injected CO₂ occupies additional pore volume within the storage formation and the seals, provided by pore and brine compressibility in response to pressure buildup. With non-ideal seals, brine may also leak through the seals into overlying/underlying formations. The quick-assessment method calculates these brine displacement contributions in response to an estimated average pressure buildup in the storage reservoir. The CO₂ storage capacity and the transient domain-averaged pressure buildup estimated through the quick-assessment method were compared with the “true” values obtained using detailed numerical simulations of CO₂ and brine transport in a two-dimensional radial system. The good agreement indicates that the proposed method can produce reasonable approximations for storage–formation–seal systems of various geometric and hydrogeological properties.     

Study on the failure mechanism of potassium-based sorbent for CO2 capture and the improving measure

With thermogravimetric apparatus (TGA), X-ray diffraction (XRD) and barium sulfate gravimetric methods, the carbonation reactivities of K₂CO₃ and K₂CO₃/Al₂O₃ in the simulated flue gases with SO₂ are investigated and the reaction equations are inferred. Results show that there are KHCO₃ and K₂SO₃ generated. The generation K₂SO₃ reduces the utilization ratio of the sorbent. H₂O may accelerates the sulfation reaction of AR K₂CO₃ as K₄H₂(CO₃)₃·1.5H₂O is generated in the reaction among K₂CO₃, SO₂ and H₂O. K₂SO₃ is directly generated from sulfation reaction of K₂CO₃/Al₂O₃, because there are K₂CO₃·1.5H₂O and K₂SO₃ generated in the reaction among K₂CO₃/Al₂O₃, SO₂ and H₂O. K₂CO₃·1.5H₂O does not react with SO₂, and K₂CO₃·1.5H₂O/Al₂O₃ reacts with SO₂ slowly. Compare with the reaction process without H₂O pretreatment, the reaction rates of KAl30 increased after H₂O pretreatment and the failure ratio is about a half of that without H₂O pretreatment. So, K₂CO₃/Al₂O₃ shows good carbonation and anti-sulfation characteristic after H₂O pretreatment.     

The influence of different surface-modification treatments on biomass-based carbons and their effects on adsorption of carbon dioxide

Surface modification of biomass-based carbon with nitrogen-containing functional groups is performed by the different modification method, including the thermal and chemical methods. We also investigate the effect of the different reaction parameters on their pore structure using the Brunauer–Emmett–Teller surface area and adsorption performance based on methylene blue value. Fourier transforms infrared spectroscopy methods are performed to confirm the presence of N-containing groups. Based on above results, the comparison effect of different modification methods on physico-chemical propriety and adsorption properties of biomass-based carbon materials are carried out. In conclusion, all modification methods could enhance CO₂ adsorption capability. However, the carbon materials treated with ammonia using thermal method show the best performance.     

Embodied energy and CO2 in UK dimension stone

A process based life cycle assessment of dimension stone production in the UK has been carried out according to PAS 2050. From a survey of eight production operations, on a cradle-to-site basis for UK destinations the carbon footprint of sandstone is 77 kgCO₂e/tonne, that of granite is 107 kgCO₂e/tonne and that of slate is 251 kgCO₂e/tonne. These values are considerably higher for stone imported from abroad due to the impact of transport. Reducing the reliance on imported stone will contribute to emissions reduction targets as well as furthering the goals of sustainable development.