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.     

Power generation with CO2 capture: Technology for CO2 purification

The goal of this paper is to find methodologies for removing a selection of impurities (H₂O, O₂, Ar, N₂, SO_x and NO_x) from CO₂ present in the flue gas of two oxy-combustion power plants fired with either natural gas (467 MW) or pulverized fuel (596 MW). The resulting purified stream, containing mainly CO₂, is assumed to be stored in an aquifer or utilized for enhanced oil recovery (EOR) purposes. Focus has been given to power cycle efficiency i.e.: work and heat requirements for the purification process, CO₂ purity and recovery factor (kg of CO₂ that is sent to storage per kg of CO₂ in the flue gas). Two different methodologies (here called Case I and Case II) for flue gas purification have been developed, both based on phase separation using simple flash units (Case I) or a distillation column (Case II). In both cases purified flue gas is liquefied and its pressure brought to 110 atm prior to storage.Case I: A simple flue gas separation takes place by means of two flash units integrated in the CO₂ compression process. Heat in the process is removed by evaporating the purified liquid CO₂ streams coming out from both flashes. Case I shows a good performance when dealing with flue gases with low concentration of impurities. CO₂ fraction after purification is over 96% with a CO₂ recovery factor of 96.2% for the NG-fired flue gas and 88.1% for the PF-fired flue gas. Impurities removal together with flue gas compression and liquefaction reduces power plant output of 4.8% for the NG-fired flue gas and 11.6% for the PF-fired flue gas. The total amount of work requirement per kg stored CO₂ is 453 kJ for the NG-fired flue gas and 586 kJ for the PF-fired flue gas.Case II: Impurities are removed from the flue gas in a distillation column. Two refrigeration loops (ethane and propane) have been used in order to partially liquefy the flue gas and for heat removal from a partial condenser. Case II can remove higher amounts of impurities than Case I. CO₂ purity prior to storage is over 99%; CO₂ recovery factor is somewhat lower than in Case I: 95.4% for the NG-fired flue gas and 86.9% for the PF-fired flue gas, reduction in the power plant output is similar to Case I.Due to the lower CO₂ recovery factor the total amount of work per kg stored CO₂ is somewhat higher for Case II: 457 kJ for the NG-fired flue gas and 603 kJ for the PF-fired flue gas.     

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.     

Integration of counter-current relative permeability in the simulation of CO2 injection into saline aquifers

Carbon dioxide (CO₂) injection into saline aquifers is one of the promising options to sequester large amounts of CO₂ in geological formations. During as well as after injection of CO₂ into an aquifer, CO₂ migrates towards the top of the formation due to density differences between the formation brine and the injected CO₂. The time scales of CO₂ migration towards the top of an aquifer and the fraction of CO₂ that is trapped as residual gas depends strongly on the driving forces that are acting on the injected CO₂.When CO₂ migrates to the top of an aquifer, brine may be displaced downwards in a counter-current flow setting particularly during the injection period. A majority of the published work on counter-current flow settings have reported significant reductions in the associated relative permeability functions as compared to co-current measurements. However, this phenomenon has not yet been considered in the simulation of CO₂ storage into saline aquifers.In this paper we study the impact of changes in mobility for the two-phase brine/CO₂ system as a result of transitions between co- and counter-current flow settings. We have included this effect in a simulator and studied the impact of the related mobility reduction on the saturation distribution and residual saturation of CO₂ in aquifers over relevant time scales. We demonstrate that the reduction in relative permeability in the vertical direction changes the plume migration pattern and has an impact on the amount of gas that is trapped as a function of time. This is to our best knowledge the first attempt to integrate counter-current relative permeability into the simulation of injection and subsequent migration of CO₂ in aquifers. The results and analysis presented in this paper are directly relevant to all ongoing activities related to the design of large-scale CO₂ storage in saline aquifers.     

Dynamis CO2 quality recommendations

In the carbon capture and storage (CCS) chain, transport and storage set different requirements for the composition of the gas stream mainly containing carbon dioxide (CO₂). Currently, there is a lack of standards to define the required quality for CO₂ pipelines. This study investigates and recommends likely maximum allowable concentrations of impurities in the CO₂ for safe transportation in pipelines. The focus is on CO₂ streams from pre-combustion processes. Among the issues addressed are safety and toxicity limits, compression work, hydrate formation, corrosion and free water formation, including the cross-effect of H₂S and H₂O and of H₂O and CH₄.     

Simultaneous CO2 injection and water production to optimise aquifer storage capacity

The estimates for geological CO₂ storage capacity worldwide vary, but it is generally believed that the capacity in saline aquifers will be sufficient for the amounts of CO₂ that will need to be stored. The effort required to select and qualify a geological storage site for safe storage will, however, be significant and storage capacity may be a limited resource regionally. Both from a economic and resource management perspective it is therefore important that potential storage sites are exploited to their full potential.In static capacity estimates, where the maximum stored amount of CO₂ is given as a fraction of the formation pore volume, typically arrive at efficiency factors in the range of a few per cents. Recent work has shown that when the dynamic behaviour of the injected CO₂ is taken into account, the efficiency factor will be reduced because of the increase in pore pressure in the region around the injection well(s). The increase in pore pressure will propagate much further than the CO₂. The EU directive on geological CO₂ storage specifically addresses the restriction that will apply when different storage sites are interacting due to pressure communication. Consequently, the pore pressure increase at the boundary of the storage license area will be an important limiting factor for the amount of CO₂ that can be injected.One obvious method to control the pore pressure is to produce water from the aquifer at some distance from the CO₂ injection wells. This paper discusses results from simulations of CO₂ injection in two aquifers on the Norwegian Continental Shelf; the Johansen aquifer and the southern part of the Utsira aquifer. These aquifers are candidates for injection of CO₂ shipped out via pipeline from the Norwegian West Coast. The injected amounts of CO₂ over a period of 50 years are 0.518 Gtonne for the Johansen aquifer and 1.04 Gtonne for the Utsira aquifer.Several design options for the injection operations are investigated: Injection of CO₂ without water production; injection into several wells to distribute the injected fluids and reduce the local pressure increase around each injection well; and injection with simultaneous production of water from one or more wells. The boundaries of the aquifer formations are assumed closed in all simulations. The possible consequences of other types of boundary conditions (semi-closed or open) are briefly discussed.     

Evaluating the impact of fractures on the performance of the In Salah CO2 storage site

The In Salah Gas Joint Venture CO₂ storage project has been in operation in Algeria since 2004 and is currently the world's largest onshore CO₂ storage project. CO₂ is injected into the saline aquifer of a gas reservoir several kilometres away from the gas producers. Current focus in the project is on implementing a comprehensive monitoring strategy and modelling the injection behaviour in order to ensure and verify safe long-term storage. A key part of this effort is the understanding of the processes involved in CO₂ migration within relatively low-permeability sandstones and shales influenced by fractures and faults. We summarise our current understanding of the fault and fracture pattern at this site and show preliminary forecasts of the system performance using discrete fracture models and fluid flow simulations. Despite evidence of fractures at the reservoir/aquifer level, the thick mudstone caprock sequence is expected to provide an effective flow and mechanical seal for the storage system; however, quantification of the effects of fracture flow is essential to the site verification.     

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.     

Assessment of the different parameters affecting the CO2 purity from coal fired oxyfuel process

The oxyfuel process is one of the most promising options to capture CO₂ from coal fired power plants. The combustion takes place in an atmosphere of almost pure oxygen, delivered from an air separation unit (ASU), and recirculated flue gas. This provides a flue gas containing 80–90 vol% CO₂ on a dry basis. Impurities are caused by the purity of the oxygen from the ASU, the combustion process and air ingress. Via liquefaction a CO₂ stream with purity in the range from 85 to 99.5 vol% can be separated and stored geologically. Impurities like O₂, NO_X, SO_X, and CO may negatively influence the transport infrastructure or the geological storage site by causing geochemical reactions. Therefore the maximum acceptable concentrations of the impurities in the separated CO₂ stream must be defined regarding the requirements from transportation and storage. The main objective of the research project COORAL therefore is to define the required CO₂ purity for capture and storage.     

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

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

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.     

Capture of carbon dioxide from flue or fuel gas mixtures by clathrate crystallization in a silica gel column

A column of silica gel was employed to contact water with flue gas (CO₂/N₂) mixture to assess if CO₂ can be separated by hydrate crystallization. Three different silica gels were used. One with a pore size of 30 nm (particle size 40–75 μm) and two with a pore size of 100 nm and particle sizes of 40–75 and 75–200 μm respectively. The observed trends indicate that larger pores and particle size increase the gas consumption, CO₂ recovery, separation factor and water conversion to hydrate. Thus, the gel (gel #3) with the larger particle size and larger pore size was chosen to carry out experiments with concentrated CO₂ mixtures and for experiments in the presence of tetrahydrofuran (THF), which itself is a hydrate forming substance. Addition of THF reduces the operating pressure in the crystallizer but it also reduces the gas uptake. Gel #3 was also used in experiments with a fuel gas (CO₂/H₂) mixture in order to recover CO₂ and H₂. It was found that the gel column performs as well as a stirred reactor in separating the gas components from both flue gas and fuel gas mixtures. However, the crystallization rate and hydrate yield are considerably enhanced in the former. Finally the need for stirring is eliminated with the gel column which is enormously beneficial economically.     

Application of crosswell seismic tomography using difference analysis with data normalization to monitor CO2 flooding in an aquifer

A pilot-scale experiment for carbon dioxide (CO₂) sequestration was undertaken at the Nagaoka test field in Japan. Time-lapse crosswell seismic tomography was conducted to detect and monitor the movement of CO₂ injected into an aquifer. We applied difference analysis with data normalization (DADN) to the time-lapse data to eliminate false images that were apparent in a conventionally processed difference section. Conventional difference analysis calculates travel-time delays after inversion, whereas the DADN method calculates them from raw travel-time records before inversion. Thus, fewer errors are generated with the DADN method compared to a conventional inversion analysis. We applied the DADN method to time-lapse tomography data recorded before and after the injection of CO₂ and computed the velocity variation in a subsurface section, which clearly showed the distribution of CO₂ flooding within a high permeability zone in the aquifer and showed no CO₂ leakage into the caprock. Our results also show the maximum velocity decrease as a result of CO₂ injection was about 9%, which is close to the results obtained in laboratory experiments. Finally, numerical simulations were inverted to test the effectiveness of the conventional and DADN methods in dealing with noise. These tests showed that the DADN method effectively reduces unique coherent noise for particular receiver and source combinations. We concluded that the DADN method provides useful data for monitoring the flow of CO₂ sequestered in underground aquifers.     

Gas conditioning—The interface between CO2 capture and transport

Gas conditioning is commonly referred to as the required processing for a produced natural gas to achieve transport and sales specifications. In this paper, gas conditioning as the processing required in the interface between CO₂ capture and transport is studied for nine different natural gas fired power plant concepts and three different CO₂ transport processes. Conditioning processes for both pipeline and ship transport are described and an enhanced process for volatile removal is developed. The energy requirement for the conditioning processes is normally between 90 and 120 kWh/tonne CO₂; however, this depends on the pressure and composition of the captured CO₂-rich stream. The loss of CO₂ in the water purge is small for most capture processes. The waste streams from the gas conditioning processes can contain large amounts of CO₂ and should therefore be further processed or reintroduced at an appropriate point upstream in the capture or gas conditioning process if possible. The integration benefit may vary depending on the composition of the CO₂-rich stream. It could be particularly interesting for processes with “innovative reactors” (membranes, sorbents, chemical looping) to integrate CO₂ capture and gas conditioning.     

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.     

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.     

Optimization of a membrane process for CO2 capture in the steelmaking industry

Three different types of membranes were experimentally evaluated for CO₂ recovery from blast furnace effluents: semi-commercial adsorption selective carbon membranes, in-house tailored carbon molecular sieving membranes, and fixed site carrier (FSC) membranes with amine groups in the polymer backbone for active transport of CO₂. In the single gas experiments the FSC membranes showed superior selectivity for CO₂ over the other relevant gases (CO, N₂ and H₂) and high CO₂ permeance (productivity). In addition, it is easy to process and handle, relatively inexpensive to produce and the water in the feed gas is an advantage rather than a problem, since the membrane must be humidified during operation. Based on these experiments a simulation study of a full scale process was performed. The technology showed notable low energy cost, even when converted to the thermal equivalent. Total costs for the CO₂ recovery unit (CO₂ prepared for pipeline transport) were estimated to be in the range 15.0–17.5 €/tonnes CO₂.     

Measurements of non-wetting phase trapping applied to carbon dioxide storage

We measure the trapped non-wetting phase saturation as a function of the initial saturation in sand packs. The application of the work is for CO₂ storage in aquifers where capillary trapping is a rapid and effective mechanism to render injected CO₂ immobile. The CO₂ is injected into the formation followed by chase brine injection, or natural groundwater flow, which displaces and traps CO₂ on the pore scale as a residual immobile phase. Current models to predict the amount of trapping are based on experiments in consolidated media, while CO₂ may be stored in relatively shallow, poorly consolidated systems. We use analogue fluids at ambient conditions. The trapped saturation initially rises linearly with initial saturation to a value of approximately 0.13 for oil/water systems and 0.14 for gas/water systems. There then follows a region where the residual saturation is constant with further increases in initial saturation. This behaviour is not predicted by the traditional literature trapping models, but is physically consistent with unconsolidated media where most of the larger pores can easily be invaded at relatively low saturation and there is, overall, relatively little trapping. A good match to our experimental data was achieved with the trapping model proposed by Aissaoui.