Comparison of adsorption models in reservoir simulation of enhanced coalbed methane recovery and CO2 sequestration in coal

Coalbed methane is an important resource of energy. Meanwhile CO₂ sequestration in coal is a potential management option for greenhouse gas emissions. An attractive aspect to this process is that CO₂ is adsorbed to the coal, reducing the risk of CO₂ migration to the surface. Another aspect to this is that the injected CO₂ could displace adsorbed methane leading to enhanced coalbed methane recovery. Therefore, in order to understand gas migration within the reservoir, mixed-gas adsorption models are required. Moreover, coal reservoir permeability will be significantly affected by adsorption-induced coal swelling during CO₂ injection. Coal swelling is directly related to reservoir pressure and gas content which is calculated by adsorption models in reservoir simulation. Various models have been studied to describe the pure- and mixed-gas adsorption on coal. Nevertheless, only the Langmuir and Extended Langmuir models are usually applied in coal reservoir simulations. This paper presents simulation work using several approaches to representing gas adsorption, implemented into the coal seam gas reservoir simulator SIMED II. The adsorption models are the Extended Langmuir model (ELM), the Ideal Adsorbed Solution (IAS) model and the Two-Dimensional Equation of State (2D EOS). The simulations based on one Australian and one American coal sample demonstrated that (1) the Ideal Adsorbed Solution model, in conjunction with Langmuir model as single-component isotherm, shows similar simulation results as the ELM for both coals, with the IAS model representing the experimental adsorption data more accurately than the ELM for one coal and identically with the ELM for the other coal; (2) simulation results using the 2D EOS, however, are significantly different to the ELM or IAS model for both coal samples. The magnitude of the difference is also dependent on coal swelling and the well operating conditions, such as injection pressure.     

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.     

Certification framework based on effective trapping for geologic carbon sequestration

We have developed a certification framework (CF) for certifying the safety and effectiveness of geologic carbon sequestration (GCS) sites. Safety and effectiveness are achieved if CO₂ and displaced brine have no significant impact on humans, other living things, resources, or the environment. In the CF, we relate effective trapping to CO₂ leakage risk which takes into account both the impact and probability of leakage. We achieve simplicity in the CF by using (1) wells and faults as the potential leakage pathways, (2) compartments to represent environmental resources that may be impacted by leakage, (3) CO₂ fluxes and concentrations in the compartments as proxies for impact to vulnerable entities, (4) broad ranges of storage formation properties to generate a catalog of simulated plume movements, and (5) probabilities of intersection of the CO₂ plume with the conduits and compartments. We demonstrate the approach on a hypothetical GCS site in a Texas Gulf Coast saline formation. Through its generality and flexibility, the CF can contribute to the assessment of risk of CO₂ and brine leakage as part of the certification process for licensing and permitting of GCS sites around the world regardless of the specific regulations in place in any given country.     

Site selection in CO2 ocean sequestration: Dependence of CO2 injection rate on eddy activity distribution

Site selection in CO₂ ocean sequestration is examined based on the idea that a site where injected CO₂ is efficiently diluted is favourable in reducing/avoiding biological impacts. Simulations of CO₂ injection into several sites by an eddy-resolving oceanic general circulation model (OGCM) show that the maximum CO₂ concentration differs by a factor of 10 among sites. The distribution of eddy activity is the most important causative factor producing the geographical differences in CO₂ dilution. Based on the relationship between the maximum CO₂ concentration and eddy activity, we estimated the distribution of the maximum CO₂ injection rate by a proposed method, which does not cause chronic impacts on biota. Around Japan, extensive ocean volume has the potential to dilute 20 million tonnes per year without chronic impacts, and some areas can be injected with 80 million tonnes per year.     

Assessment of basin-scale hydrologic impacts of CO2 sequestration,Illinois basin

Idealized, basin-scale sharp-interface models of CO₂ injection were constructed for the Illinois basin. Porosity and permeability were decreased with depth within the Mount Simon Formation. Eau Claire confining unit porosity and permeability were kept fixed. We used 726 injection wells located near 42 power plants to deliver 80 million metric tons of CO₂/year. After 100 years of continuous injection, deviatoric fluid pressures varied between 5.6 and 18 MPa across central and southern part of the Illinois basin. Maximum deviatoric pressure reached about 50% of lithostatic levels to the south. The pressure disturbance (>0.03 MPa) propagated 10–25 km away from the injection wells resulting in significant well–well pressure interference. These findings are consistent with single-phase analytical solutions of injection. The radial footprint of the CO₂ plume at each well was only 0.5–2 km after 100 years of injection. Net lateral brine displacement was insignificant due to increasing radial distance from injection well and leakage across the Eau Claire confining unit. On geologic time scales CO₂ would migrate northward at a rate of about 6 m/1000 years. Because of paleo-seismic events in this region (M5.5–M7.5), care should be taken to avoid high pore pressures in the southern Illinois basin.     

The role of optimality in characterizing CO2 seepage from geologic carbon sequestration sites

Storage of large amounts of carbon dioxide (CO₂) in deep geologic formations for greenhouse-gas mitigation is gaining momentum and moving from its conceptual and testing stages towards widespread application. In this work we explore various optimization strategies for characterizing surface leakage (seepage) using near-surface measurement approaches such as accumulation chambers and eddy covariance towers. Seepage characterization objectives and limitations need to be defined carefully from the outset especially in light of large natural background variations that can mask seepage. The cost and sensitivity of seepage detection are related to four critical length scales pertaining to the size of the: (1) region that needs to be monitored; (2) footprint of the measurement approach, and (3) main seepage zone; (4) region in which concentrations or fluxes are influenced by seepage. Seepage characterization objectives may include one or all of the tasks of detecting, locating, and quantifying seepage. Each of these tasks has its own optimal strategy. Detecting and locating seepage in a region in which there is no expected or preferred location for seepage nor existing evidence for seepage requires monitoring on a fixed grid, e.g., using eddy covariance towers. The fixed-grid approaches needed to detect seepage are expected to require large numbers of eddy covariance towers for large-scale geologic CO₂ storage. Once seepage has been detected and roughly located, seepage zones and features can be optimally pinpointed through a dynamic search strategy, e.g., employing accumulation chambers and/or soil-gas monitoring. Quantification of seepage rates can be done through measurements on a localized fixed grid once the seepage is pinpointed. Background measurements are essential for seepage detection in natural ecosystems. Artificial neural networks are considered as regression models useful for distinguishing natural system behavior from anomalous behavior suggestive of CO₂ seepage without need for detailed understanding of natural system processes. Because of the local extrema in CO₂ fluxes and concentrations in natural systems, simple steepest-descent algorithms are not effective and evolutionary computation algorithms are proposed as a paradigm for dynamic monitoring networks to pinpoint CO₂ seepage areas.     

The consequences of failure should be considered in siting geologic carbon sequestration projects

Geologic carbon sequestration is the injection of anthropogenic CO₂ into deep geologic formations where the CO₂ is intended to remain indefinitely. If successfully implemented, geologic carbon sequestration will have little or no impact on terrestrial ecosystems aside from the mitigation of climate change. However, failure of a geologic carbon sequestration site, such as large-scale leakage of CO₂ into a potable groundwater aquifer, could cause impacts that would require costly remediation measures. Governments are attempting to develop regulations for permitting geologic carbon sequestration sites to ensure their safety and effectiveness. At present, these regulations focus largely on decreasing the probability of failure. In this paper we propose that regulations for the siting of early geologic carbon sequestration projects should emphasize limiting the consequences of failure because consequences are easier to quantify than failure probability.     

Carbonation of brine impacted fractionated coal fly ash: implications for CO2 sequestration

Coal combustion by-products such as fly ash (FA), brine and CO(2) from coal fired power plants have the potential to impact negatively on the environment. FA and brine can contaminate the soil, surface and ground water through leaching of toxic elements present in their matrices while CO(2) has been identified as a green house gas that contributes significantly towards the global warming effect. Reaction of CO(2) with FA/brine slurry can potentially provide a viable route for CO(2) sequestration via formation of mineral carbonates. Fractionated FA has varying amounts of CaO which not only increases the brine pH but can also be converted into an environmentally benign calcite. Carbonation efficiency of fractionated and brine impacted FA was investigated in this study. Controlled carbonation reactions were carried out in a reactor set-up to evaluate the effect of fractionation on the carbonation efficiency of FA. Chemical and mineralogical characteristics of fresh and carbonated ash were evaluated using XRF, SEM, and XRD. Brine effluents were characterized using ICP-MS and IC. A factorial experimental approach was employed in testing the variables. The 20-150 μm size fraction was observed to have the highest CO(2) sequestration potential of 71.84 kg of CO(2) per ton of FA while the >150 μm particles had the lowest potential of 36.47 kg of CO(2) per ton of FA. Carbonation using brine resulted in higher degree of calcite formation compared to the ultra-pure water carbonated residues.     

3D geomechanical modelling for CO2 geologic storage in the Dogger carbonates of the Paris Basin

CO₂ injection into a depleted hydrocarbon field or aquifer may give rise to a variety of coupled physical and chemical processes. During CO₂ injection, the increase in pore pressure can induce reservoir expansion. As a result the in situ stress field may change in and around the reservoir. The geomechanical behaviour induced by oil production followed by CO₂ injections into an oil field reservoir in the Paris Basin has been numerically modelled. This paper deals with an evaluation of the induced deformations and in situ stress changes, and their potential effects on faults, using a 3D geomechanical model. The geomechanical analysis of the reservoir–caprock system was carried out as a feasibility study using pressure information in a “one way” coupling, where pressures issued from reservoir simulations were integrated as input for a geomechanical model. The results show that under specific assumptions the mechanical effects of CO₂ injection do not affect the mechanical stability of the reservoir–caprock system. The ground vertical movement at the surface ranges from ?2 mm during oil production to +2.5 mm during CO₂ injection. Furthermore, the changes in in situ stresses predicted under specific assumptions by geomechanical modelling are not significant enough to jeopardize the mechanical stability of the reservoir and caprock. The stress changes issued from the 3D geomechanical modelling are also combined with a Mohr–Coulomb analysis to determine the fault slip tendency. By integrating the stress changes issued from the geomechanical modelling into the fault stability analysis, the critical pore pressure for fault reactivation is higher than calculated for the fault stability analysis considering constant horizontal stresses.     

Coal energy conversion with carbon sequestration via combustion in supercritical saline aquifer water

The standard idea for deep saline aquifer sequestration is to separate carbon dioxide from a process stream, compress it, and inject it underground. However, since carbon dioxide is less dense than water, even at the high pressures found in aquifers, it is buoyant and will move towards the surface unless trapped by an impermeable seal. Also, significant energy expenditure is required to separate and compress carbon dioxide, even though neat carbon dioxide is not a desired product. These issues may be addressed by combining the idea of fast dissolution at the surface with supercritical water oxidation (SCWO). By burning coal at high pressure in supercritical water drawn from an aquifer, and then sequestering the entire pre-equilibrated effluent, all carbon from the fuel is captured, as well as all non-mineral coal combustion products including sulfur and metals.A possible block diagram of an SCWO-based electric power plant is proposed, including processes to handle salts from the aquifer brine and minerals from coal. The plant is thermodynamically modeled, using an indirectly fired combined cycle to convert energy from hot combustion products to work. This model estimates the overall thermal efficiency that can be achieved, and reveals unanticipated interactions within the plant that have significant effects on efficiency. The assumptions and results of the model highlight design challenges for an actual system.     

Training carbon management engineers: Removing a major hurdle for geologic CO2 storage by increasing educational capacity

Implementing geologic storage of CO₂ at a material scale (ca. 1 Gt C/year) will require an industry comparable in size to the current oil and gas industry and a workforce trained in subsurface engineering. Since the same technologies that apply to hydrocarbon production apply to the subsurface storage of CO₂, petroleum engineering (PE) graduates will be valuable candidates to work in the carbon storage industry. We expect however that the demand for PEs from the oil and gas industry will increase, and that already strained educational capacity will not be sufficient to supply both industries. Thus we advocate building new targeted educational infrastructure. We present a model curriculum based on an existing accredited multidisciplinary degree program. This program combines the fundamentals of petroleum engineering with the subsurface architecture emphasis of geology and the environmental perspective of hydrogeology. We indicate key elements of this program that could be integrated with other, more traditional undergraduate engineering majors that also deal with the subsurface.     

Design considerations for financing a national trust to advance the deployment of geologic CO2 storage and motivate best practices

This paper explores how the widely held public policy view of the evolution of the risk profile associated with geologic carbon dioxide (CO₂) storage profoundly influences the public policy dialogue about how to best address the long-term risk profile for geologic storage. Evidence emerging from research and pilot scale field demonstrations of CO₂ storage demonstrates that, with proper site characterization and sound operating practices, retention of stored CO₂ will increase with time thus invalidating the premise of an ever growing risk. The authors focus on key issues of fit, interplay, and scalability associated with the ability of a trust fund funded by a hypothetical $1 per tonCO₂ tipping fee for each ton of CO₂ stored in the United States under WRE450 and WRE550 climate policies to manage such risks in an economically efficient and environmentally effective manner. The authors conclude there is no intrinsic value – in terms of risk management or risk reduction – in creating a trust fund predicated solely on collecting a universally applied tipping fee that does not take into account site-specific risk profiles. If left to grow unchecked, a trust fund that is predicated on a constant stream of payments unrelated to each contributing site's risk profile could result in the accumulation of hundreds of billions to more than a trillion dollars contributing to significant opportunity cost of capital. Further, rather than mitigating the financial consequences of long-term CCS risks, this analysis suggests a blanket $1 per tonCO₂ tipping fee, if combined with a concomitant limitation of liability may increase the probability and frequency of long-term risk by eliminating financial incentives for sound operating behavior and site selection criteria—contribute to moral hazard. At a minimum, effective use of a trust fund requires: (1) strong oversight regarding site selection and fund management, and (2) a clear process by which the fund is periodically valued and funds collected are mapped to the risk profile of the pool of covered CCS sites. Without appropriate checks and balances, there is no a priori reason to believe that the amount of funds held in trust will map to the actual amount of funds needed to address long-term care expenses and delimited compensatory damages. For this reason, the authors conclude that financing a trust fund or other risk management instrument should be based on a site delimited estimate of potential future expected financial consequences rather than on the random adoption of a fixed funding stream, e.g., a blanket $1 per ton, because it “sounds” reasonable.     

Evaluating geological sequestration of CO2 in bituminous coals: The southern Sydney Basin,Australia as a natural analogue

Carbon dioxide contents of coals in the Sydney Basin vary both aerially and stratigraphically. In places, the coal seam gas is almost pure CO₂ that was introduced from deep magmatic sources via faults and replaced pre-existing CH₄. In some respects this process is analogous to sequestration of anthropogenic CO₂. Laboratory studies indicate that CO₂:CH₄ storage capacity ratios for Sydney Basin coals are up to ∼2 and gas diffusivity is greater for CO₂ by a factor of up to 1.5.Present-day distribution of CO₂ in the coals is controlled by geological structure, depth and a combination of hydrostatic and capillary pressures. Under present-day P–T conditions, most of the CO₂ occurs in solution at depths greater than about 650 m; at shallower depths, larger volumes of CO₂ occur in gaseous form and as adsorbed molecules in the coal due to rapidly decreasing CO₂ solubility. The CO₂ has apparently migrated up to structural highs and is concentrated in anticlines and in up-dip sections of monoclines and sealing faults. CO₂ sequestered in coal measure sequences similar to those of the Sydney Basin may behave in a similar way and, in the long term, equilibrate according to the prevailing P–T conditions.In situ CO₂ contents of Sydney Basin coals range up to 20 m³/t. Comparisons of adsorption isotherm data measured on ground coal particles with in situ gas contents of Sydney Basin coals indicate that the volumes of CO₂ stored do not exceed ∼60% of the total CO₂ storage capacity. Therefore, the maximum CO₂ saturation that may be achieved during sequestration in analogous coals is likely to be considerably lower than the theoretical values indicated by adsorption isotherms.     

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.     

The potential for increased atmospheric CO2 emissions and accelerated consumption of deep geologic CO2 storage resources resulting from the large-scale deployment of a CCS-enabled unconventional fossil fuels industry in the U.S.

Desires to enhance the energy security of the United States have spurred renewed interest in the development of abundant domestic heavy hydrocarbon resources including oil shale and coal to produce unconventional liquid fuels to supplement conventional oil supplies. However, the production processes for these unconventional fossil fuels create large quantities of carbon dioxide (CO₂) and this remains one of the key arguments against such development. Carbon dioxide capture and storage (CCS) technologies could reduce these emissions and preliminary analysis of regional CO₂ storage capacity in locations where such facilities might be sited within the U.S. indicates that there appears to be sufficient storage capacity, primarily in deep saline formations, to accommodate the CO₂ from these industries. Nevertheless, even assuming wide-scale availability of cost-effective CO₂ capture and geologic storage resources, the emergence of a domestic U.S. oil shale or coal-to-liquids (CTL) industry would be responsible for significant increases in CO₂ emissions to the atmosphere. The authors present modeling results of two future hypothetical climate policy scenarios that indicate that the oil shale production facilities required to produce 3 MMB/d from the Eocene Green River Formation of the western U.S. using an in situ retorting process would result in net emissions to the atmosphere of between 3000 and 7000 MtCO₂, in addition to storing potentially 900–5000 MtCO₂ in regional deep geologic formations via CCS in the period up to 2050. A similarly sized, but geographically more dispersed domestic CTL industry could result in 4000–5000 MtCO₂ emitted to the atmosphere in addition to potentially 21,000–22,000 MtCO₂ stored in regional deep geologic formations over the same period. While this analysis shows that there is likely adequate CO₂ storage capacity in the regions where these technologies are likely to deploy, the reliance by these industries on large-scale CCS could result in an accelerated rate of utilization of the nation's CO₂ storage resource, leaving less high-quality storage capacity for other carbon-producing industries including electric power generation.     

Integration of CO2 capture unit using single- and blended-amines into supercritical coal-fired power plants: Implications for emission and energy management

This work provides the essential information and approaches for integration of carbon dioxide (CO₂) capture units into power plants, particularly the supercritical type, so that energy utilization and CO₂ emissions can be well managed in the subject power plants. An in-house model, developed at the University of Regina, Canada, was successfully used for simulating a 500 MW supercritical coal-fired power plant with a post-combustion CO₂ capture unit. The simulations enabled sensitivity and parametric study of the net efficiency of the power plant, the coal consumption rate, and the amounts of CO₂ captured and avoided. The parameters of interest include CO₂ capture efficiency, type of coal, flue gas delivery scheme, type of amine used in the capture unit, and steam pressure supplied to the capture unit for solvent regeneration. The results show that the advancement of MEA-based CO₂ capture units through uses of blended monoethanolamine–methyldiethanolamine (MEA–MDEA) and split flow configuration can potentially make the integration of power plant and CO₂ capture unit less energy intensive. Despite the increase in energy penalty, it may be worth capturing CO₂ at a higher efficiency to achieve greater CO₂ emissions avoided. The flue gas delivery scheme and the steam pressure drawn from the power plant to the CO₂ capture unit should be considered for process integration.     

Purification of oxyfuel-derived CO2

Oxyfuel combustion in a pulverised fuel coal-fired power station produces a raw CO₂ product containing contaminants such as water vapour plus oxygen, nitrogen and argon derived from the excess oxygen for combustion, impurities in the oxygen used, and any air leakage into the system. There are also acid gases present, such as SO₃, SO₂, HCl and NO_x produced as byproducts of combustion. At GHGT8 (White and Allam, 2006) we presented reactions that gave a path-way for SO₂ to be removed as H₂SO₄ and NO and NO₂ to be removed as HNO₃. In this paper we present initial results from the OxyCoal-UK project in which these reactions are being studied experimentally to provide the important reaction kinetic information that is so far missing from the literature. This experimental work is being carried out at Imperial College London with synthetic flue gas and then using actual flue gas via a sidestream at Doosan Babcock's 160 kW coal-fired oxyfuel rig. The results produced support the theory that SO_x and NO_x components can be removed during compression of raw oxyfuel-derived CO₂ and therefore, for emissions control and CO₂ product purity, traditional FGD and deNO_x systems should not be required in an oxyfuel-fired coal power plant.     

Development and Experimental Study of CO2 Expander in CO2 Supercritical Refrigeration Cycles

Abstract

As one of the natural working fluids for the refrigeration system, CO₂ has been attracting increasing attention over the last ten years. But CO₂ has to work at the supercritical region for the so-called “condensation” process regarding the conventional refrigerants and evaporate at the two-phase region, and therefore results in larger throttling loss for the practical refrigeration application. Consequently, new technologies must be developed to improve the performance efficiency of the CO₂ transcritical cycle, and make it to be equal or closer to that of the refrigeration system with the conventional refrigerants. In this study, an expander is employed in the CO₂ transcritical cycle to replace the throttling valve, and as a result the throttling loss can be decreased significantly. The paper presents the development of a rolling piston expander and the activity items in the expander design, including the seal technology, the contact friction control, the suction design, etc. The performance experiments for the expander are conducted in the present testing system for the CO₂ transcritical cycle. The results show that the recovery power of the expander is related to the revolution speed of the expander. The efficiency of the expander prototype is observed to be about 32%.     

Permanent shallow subsoil CO2 flux chambers for monitoring of onshore CO2 geological storage sites

Public concern over the possibility of migration of stored CO₂ to the surface with resulting damage to vegetation or hazard to humans and animals is a matter which will need to be addressed to be able to satisfy likely regulatory requirements for onshore CO₂ storage in a number of jurisdictions. While soil CO₂ concentration is readily measured continuously and in situ with current technology, the measurement of CO₂ flux at depths below the soil A horizon may be a more sensitive and meaningful technique for early detection of a near surface CO₂ plume. We describe a system for the continuous measurement of soil CO₂ flux at a depth of approximately 1.3 m and present results from three instruments deployed at the Otway Basin Pilot Project in Victoria, Australia and one development system deployed at Sutton, near the Australian Capital Canberra.