CO2 capture for refineries,a practical approach

This paper evaluates the opportunities and associated costs for post-combustion capture at a world-scale complex refinery. It is concluded that it is technically feasible to apply post-combustion capture at such a refinery. The costs for capture and sequestration from a gasifier are calculated to be lowest at about 30 Euro per ton; this process currently already produces a concentrated CO₂ stream. Next, the CO₂ source most suited for capture appears to be a combined stack, but there are a number of other sources that may be targeted at comparable costs. In total these sources may form about 40% of the overall refinery emissions. Our evaluations show the costs of capture from such sources based on available amine technology will be in the range of 90–120 Euro per ton, which is about 3–4 times higher than the current carbon trading values. The capture of CO₂ from a large amount of smaller CO₂ sources will bring along even much higher costs. A high-level study of the CO₂ emissions profile of a number of Shell refineries shows that, typically, up to 50% of the emitted CO₂ may be captured at similar costs. About 10–20% of concentrated CO₂ associated with hydrogen manufacturing may be captured at lower costs. The remainder of emitted dilute CO₂ will bring along significantly higher costs. Based on this study, it is concluded for the justification of the implementation of post-combustion capture at refineries, either a significant increase in carbon trading values, mandatory regulations, or a major technological break-through is required.     

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.     

Chromatographic partitioning of impurities (H2S) contained in a CO2 stream injected into a deep saline aquifer: Part 2. Effects of flow conditions

Laboratory experiments reported in a companion paper were carried out to examine the chromatographic partitioning of impurities contained in a stream of CO₂ injected into a deep saline aquifer. The solubility of the impurity gas in the CO₂ stream compared to that of CO₂, the in situ conditions of pressure, temperature and water salinity, and the concentration of the impurity gas affect the partitioning of the two gases. For CO₂ streams containing H₂S, numerical simulations reported here have successfully replicated the laboratory results including the breakthrough of CO₂ ahead of H₂S. Sensitivity analysis performed with the numerical model has shown that flow conditions, controlled by such parameters as medium permeability, pressure gradient, dispersion, gas mobility and flow direction, affect the breakthrough time and separation of the two gases, leading to delayed or earlier breakthrough, and increasing or decreasing the time lag between the breakthrough of the two gases. Vertical bottom-up flow leads to earlier breakthrough, while top-down flow leads to delayed breakthrough. These results are important in establishing monitoring strategies at CO₂ storage sites and in evaluating the risks associated with the possible leakage of injected CO₂ that contains impurities.     

Natural analogue of the rise and dissolution of liquid CO2 in the ocean

The behavior of natural carbon dioxide (CO₂) droplets (8–10 mm in diameter) were observed in a seafloor hydrothermal system at the Okinawa Trough. The natural CO₂ droplet contain 95–98% of CO₂, 2–3% of H₂S, and other gas species. The ascending CO₂ droplets were tracked by a remotely operated vehicle (ROV), and depth, temperature, salinity, pH and partial pressure of CO₂ (pCO₂) in seawater near the CO₂ droplets were measured during droplet ascent by a conductivity-temperature-depth sensor (CTD) and in situ pH/pCO₂ sensor. The visual images of the rising CO₂ droplets were recorded with a high definition television camera on the ROV. A mapping survey (400 m × 400 m; 4 horizontal layers) revealed a dominant distribution of low pH area over the natural CO₂ venting site. The size and rise rate of CO₂ droplets decreased during their ascent in the water column from depths of 1424 to 679 m (a tracking interval of 745 m). The CO₂ droplets dissolved gradually to become small flakes of CO₂ hydrate while rising, and these ascending flakes were found to disappear at 679 m depth. Although a pH as low as 5 was detected just above the liquid CO₂ venting site on the seafloor, no detectable pH depression in the water column ambient to the rising CO₂ droplets was observed. The results of the pH mapping survey showed only localized pH depression over the CO₂ venting site.     

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.     

Worst case scenario study to assess the environmental impact of amine emissions from a CO2 capture plant

Use of amines is one of the leading technologies for post-combustion carbon dioxide capture from gas and coal-fired power plants. This study assesses the potential environmental impact of emissions to air that result from use of monoethanol amine (MEA) as an absorption solvent for the capture of carbon dioxide (CO₂). Depending on operation conditions and installed reduction technology, emissions of MEA to the air due to solvent volatility losses are expected to be in the range of 0.01–0.8 kg/tonne CO₂ captured. Literature data for human and environmental toxicity, together with atmospheric dispersion model calculations, were used to derive maximum tolerable emissions of amines from CO₂ capture. To reflect operating conditions with typical and with elevated emissions, we defined a scenario MEA-LOW, with emissions of 40 t/year MEA and 5 t/year diethyl amine (DEYA), and a scenario MEA-HIGH, with emissions of 80 t/year MEA and 15 t/year DEYA. Maximum MEA deposition fluxes would exceed toxicity limits for aquatic organisms by about a factor of 3–7 depending on the scenario. Due to the formation of nitrosamines and nitramines, the estimated emissions of DEYA are close to or exceed safety limits for drinking water and aquatic ecosystems. The “worst case” scenario approach to determine maximum tolerable emissions of MEA and other amines is in particular useful when both expected environmental loads and the toxic effects are associated with high uncertainties.     

Carbonation of wellbore cement by CO2 diffusion from caprock

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

Corrective measures based on pressure control strategies for CO2 geological storage in deep aquifers

A prerequisite to the wide deployment at an industrial scale of CO₂ geological storage is demonstrating that potential risks can be efficiently managed. Corrective measures in case of significant irregularities, such as CO₂ leakage, are hence required as advocated by the recent European directive on Carbon Capture and Storage operations. In this regard, the objective of the present paper is to investigate four different corrective measures aiming at controlling the overpressure induced by the injection operations in the reservoir: stopping the CO₂ injection and relying on the natural pressure recovery in the reservoir; extracting the stored CO₂ at the injection well; extracting brine at a distant well while stopping the CO₂ injection, and extracting at a distant well without stopping the CO₂ injection. The efficiency of the measures is assessed using multi-phase fluid flow numerical simulations. The application case is the deep carbonate aquifer of the Dogger geological unit in the Paris Basin. A comparative study between the four corrective measures is then carried using a cost-benefit approach. Results show that an efficient overpressure reduction can be achieved by simply shutting-in the well. The overpressure reduction can be significantly accelerated by means of fluid extraction but the adverse consequences are the associated higher costs of the intervention operations.     

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.     

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.     

Quantitative evaluation of the chilled-ammonia process for CO2 capture using thermodynamic analysis and process simulation

There is strong world-wide interest in developing new and improved processes for post-combustion capture of CO₂, often using chemical absorption. Developers of new processes make positive claims for their proposals in terms of low energy consumption, but these are usually difficult to validate. This paper demonstrates that rigorous application of thermodynamic analysis and process simulation provides a powerful way to quantitatively estimate the energy requirements of CO₂-capture processes by applying the methodology to the analysis and evaluation of the chilled-ammonia process.     

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

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

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.     

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.     

Experimental study on CO2 monitoring and quantification of stored CO2 in saline formations using resistivity measurements

This paper reports CO₂ saturation estimations based on resistivity data obtained from laboratory measurements and induction logging results at the Nagaoka pilot CO₂ injection site. The laboratory experiments put in evidence that the presence of clay content tends to reduce the increase of resistivity caused by the displacement of brine by less conductive CO₂. As a result, CO₂ saturations estimated from resistivity measurements without any correction for the clay effect are considerably lower than the actual saturations. The resistivity index (RI) provides better estimates of CO₂ saturations than the Archie's equation because it requires the determination or assumption of only one rock parameter: the saturation exponent. CO₂ saturations estimated from the induction logging data acquired at Nagaoka are considerably lower than the neutron porosity changes due to displacement between brine and CO₂ in the reservoir. Even in the case of considering the De Witte's equation and the Poupon's to account for the clay effect, it was still difficult to get a good agreement with the neutron logging results. New relations based on the resistivity index with correction factors for the clay effect are developed and implemented in this study. One of these relations has proved to be effective to estimate CO₂ saturations in saline formations with high clay content.     

The impact of heterogeneity on the distribution of CO2: Numerical simulation of CO2 storage at Ketzin

Numerical modelling of multiphase flow is an essential tool to ensure the viability of long-term and safe CO₂ storage in geological formations. Uncertainties arising from the heterogeneity of the formation and lack of knowledge of formation properties need to be assessed in order to create a model that can reproduce the data available from monitoring. In this study, we investigated the impact of unknown spatial variability in the petrophysical properties within a sandy channel facies of a fluviatile storage formation using stochastic methods in a Monte Carlo approach. The stochastic method has been applied to the Ketzin test site (CO₂SINK), and demonstrates that the deterministic homogeneous model satisfactorily predicts the first CO₂ arrival time at the Ketzin site. The equivalent permeability was adjusted to the injection pressure and is in good agreement with the hydraulic test. It has been shown that with increasing small-scale heterogeneity, the sharpness of the CO₂ front decreases and a greater volume of the reservoir is affected, which is also seen in an increased amount of dissolved CO₂. Increased anisotropy creates fingering effects, which result in higher probabilities for earlier arrival times. Generally, injectivity decreases with increasing heterogeneity.     

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%.     

A response surface methodology to address uncertainties in cap rock failure assessment for CO2 geological storage in deep aquifers

Cap rock failure assessment, either tensile fracturing or shear slip reactivation of pre-existing fault, is a key issue for preventing CO₂ leakage from deep aquifer reservoirs up to the surface. For an appropriate use in risk management, the uncertainties associated with such studies should be investigated. Nevertheless, uncertainty analysis requires multiple simulations and a direct use of conventional numerical approaches might be too computer time consuming. An alternative is to use conventional analytical models, but their assumptions appear to be too conservative. An intermediate approach is then proposed based on the response surface methodology, consisting in estimating the effective stress state after CO₂ injection as a linear combination of the most influential site properties based on a limited number of numerical simulations. The decision maker is provided with three levels of information: (1) the identification of the most important site properties; (2) an analytical model for a quick assessment of the maximal sustainable overpressure and (3) a simplified model to be used in a computationally intensive uncertainty analysis framework. This generic methodology is illustrated with the Paris Basin case using a large-scale hydromechanical model to assess cap rock failure in the injector zone.