Geological storage of CO2 in saline aquifers—A review of the experience from existing storage operations

The experience from CO₂ injection at pilot projects (Frio, Ketzin, Nagaoka, US Regional Partnerships) and existing commercial operations (Sleipner, Snøhvit, In Salah, acid-gas injection) demonstrates that CO₂ geological storage in saline aquifers is technologically feasible. Monitoring and verification technologies have been tested and demonstrated to detect and track the CO₂ plume in different subsurface geological environments. By the end of 2008, approximately 20 Mt of CO₂ had been successfully injected into saline aquifers by existing operations. Currently, the highest injection rate and total storage volume for a single storage operation are approximately 1 Mt CO₂/year and 25 Mt, respectively. If carbon capture and storage (CCS) is to be an effective option for decreasing greenhouse gas emissions, commercial-scale storage operations will require orders of magnitude larger storage capacity than accessed by the existing sites. As a result, new demonstration projects will need to develop and test injection strategies that consider multiple injection wells and the optimisation of the usage of storage space. To accelerate large-scale CCS deployment, demonstration projects should be selected that can be readily employed for commercial use; i.e. projects that fully integrate the capture, transport and storage processes at an industrial emissions source.     

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.     

Geoelectrical methods for monitoring geological CO2 storage: First results from cross-hole and surface–downhole measurements from the CO2SINK test site at Ketzin (Germany)

The feasibility of monitoring CO₂ migration in a saline aquifer at a depth of about 650 m with cross-hole and surface–downhole electrical resistivity tomography (ERT) is investigated at the CO₂SINK test site close to Ketzin (Germany). The permanent vertical electrical resistivity array (VERA) consists of 45 electrodes (15 in the injection well Ktzi201 and 15 in each of the two observation wells Ktzi200 and Ktzi202), successfully placed on the electrically insulated casings, in the depth range of about 590–740 m with a spacing of about 10 m. The three Ketzin wells are arranged as perpendicular triangle with distances of 50 and 100 m.First synthetic modelling studies indicate an increase of the electrical resistivity of about 200% caused by CO₂ injection, corresponding to a bulk CO₂ saturation of 50%, which is in good agreement with laboratory studies. Finite difference inversion of field data delivers three-dimensional resistivity distributions between the wells which are consistent with the reservoir modelling studies.To increase the limited observation area provided by the cross-hole measurements, additional surface–downhole measurements were deployed. A main CO₂ migration in SE–NW direction is deduced from surface to downhole resistivity experiments.The first cross-hole time-lapse results show that the resolution and the coverage of the electrode array in the Ketzin setting are sufficient to resolve the expected resistivity changes on the characteristic length scale of the electrode array. Significant resistivity changes could be measured, however, detailed information on the CO₂ plume could not be resolved yet by VERA under the existing geological circumstances.     

Seismic detection of CO2 leakage along monitoring wellbores

A pilot carbon dioxide (CO₂) sequestration experiment was carried out in the Michigan Basin in which ～10,000 tonnes of supercritical CO₂ was injected into the Bass Island Dolomite (BILD) at 1050 m depth. A passive seismic monitoring (PSM) network was operated before, during and after the ～17-day injection period. The seismic monitoring network consisted of two arrays of eight, three-component sensors, deployed in two monitoring wells at only a few hundred meters from the injection point. 225 microseismic events were detected by the arrays. Of these, only one event was clearly an injection-induced microearthquake. It occurred during injection, approximately 100 m above the BILD formation. No events, down to the magnitude ?3 detection limit, occurred within the BILD formation during the injection. The observed seismic waveforms associated with the other 224 events were quite unusual in that they appear to contain dominantly compressional (P) but no (or extremely weak) shear (S) waves, indicating that they are not associated with shear slip on faults. The microseismic events were unusual in two other ways. First, almost all of the events occurred prior to the start of injection into the BILD formation. Second, hypocenters of the 94 locatable events cluster around the wells where the sensor arrays were deployed, not the injection well. While the temporal evolution of these events shows no correlation with the BILD injection, they do correlate with CO₂ injection for enhanced oil recovery (EOR) into the 1670 m deep Coral Reef formation that had been going on for ～2.5 years prior to the pilot injection experiment into the BILD formation. We conclude that the unusual microseismic events reflect degassing processes associated with leakage up and around the monitoring wells from the EOR-related CO₂ injection into the Coral Reef formation, ～700 m below the depth of the monitoring arrays. This conclusion is also supported by the observation that as soon as injection into the Coral Reef formation resumed at the conclusion of the BILD demonstration experiment, seismic events (essentially identical to the events associated with the Coral Reef injection prior to the BILD experiment) again started to occur close to a monitoring arrays. Taken together, these observations point to vertical migration around the casings of the monitoring wellbores. Detection of these unusual microseismic events was somewhat fortuitous in that the arrays were deployed at the depth where the CO₂ undergoes a strong volume increase during transition from a supercritical state to a gas. Given the large number of pre-existing wellbores that exist in depleted oil and gas reservoirs that might be considered for CO₂ sequestration projects, passive seismic monitoring systems could be deployed at appropriate depths to systematically detect and monitor leakage along them.     

Prospects for cost-effective post-combustion CO2 capture from industrial CHPs

Industrial Combined Heat and Power plants (CHPs) are often operated at partial load conditions. If CO₂ is captured from a CHP, additional energy requirements can be fully or partly met by increasing the load. Load increase improves plant efficiency and, consequently, part of the additional energy consumption would be offset. If this advantage is large enough, industrial CHPs may become an attractive option for CO₂ capture and storage CCS. We therefore investigated the techno-economic performance of post-combustion CO₂ capture from small-to-medium-scale (50–200 MWe maximum electrical capacity) industrial Natural Gas Combined Cycle- (NGCC-) CHPs in comparison with large-scale (400 MWe) NGCCs in the short term (2010) and the mid-term future (2020–2025). The analyzed system encompasses NGCC, CO₂ capture, compression, and branch CO₂ pipeline.The technical results showed that CO₂ capture energy requirement for industrial NGCC-CHPs is significantly lower than that for 400 MWe NGCCs: up to 16% in the short term and up to 12% in the mid-term future. The economic results showed that at low heat-to-power ratio operations, CO₂ capture from industrial NGCC-CHPs at 100 MWe in the short term (41–44 €/tCO₂ avoided) and 200 MWe in the mid-term future (33–36 €/tCO₂ avoided) may compete with 400 MWe NGCCs (46–50 €/tCO₂ avoided short term, 30–35 €/tCO₂ avoided mid-term).     

Energy and carbon dioxide intensity of Thailand's steel industry and greenhouse gas emission projection toward the year 2050

The purpose of this article is to study the energy and carbon dioxide intensities of Thailand's steel industry and to propose greenhouse gas emission trends from the year 2011 to 2050 under plausible scenarios. The amount of CO₂ emission from iron and steel production was calculated using the 2006 Intergovernmental Panel on Climate Change (IPCC) guidelines in the boundary of production process (gate to gate). The results showed that energy intensity of semi-finished steel product was 2.84 GJ/t semi-finished steel and CO₂ intensity was 0.37 tCO_2eq/t semi-finished steel. Energy intensity of steel finishing process was 1.86 GJ/t finished steel and CO₂ intensity was 0.16 tCO_2eq/t finished steel. Using three plausible scenarios from Thailand's steel industry, S1: without integrated steel plant (baseline scenario), S2: with a traditional integrated BF–BOF route and S3: with an alternative integrated DR-EAF route; the Greenhouse Gas emissions from the year 2011 to 2050 were projected. In 2050, the CO₂ emission from S1 (baseline scenario) was 4.84 million tonnes, S2 was 21.96 million tonnes increasing 4.54 times from baseline scenario. The CO₂ emission from S3 was 7.12 million tonnes increasing 1.47 times from baseline scenario.     

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.     

Analytical solution for Joule–Thomson cooling during CO2 geo-sequestration in depleted oil and gas reservoirs

Mathematical tools are needed to screen out sites where Joule–Thomson cooling is a prohibitive factor for CO₂ geo-sequestration and to design approaches to mitigate the effect. In this paper, a simple analytical solution is developed by invoking steady-state flow and constant thermophysical properties. The analytical solution allows fast evaluation of spatiotemporal temperature fields, resulting from constant-rate CO₂ injection. The applicability of the analytical solution is demonstrated by comparison with non-isothermal simulation results from the reservoir simulator TOUGH2. Analysis confirms that for an injection rate of 3 kg s^?1 (0.1 MT yr^?1) into moderately warm (>40 °C) and permeable formations (>10^?14 m² (10 mD)), JTC is unlikely to be a problem for initial reservoir pressures as low as 2 MPa (290 psi).     

Carbon dioxide storage capacity in uneconomic coal beds in Alberta,Canada: Methodology,potential and site identification

Methodology is presented for a first-order regional-scale estimation of CO₂ storage capacity in coals under sub-critical conditions, which is subsequently applied to Cretaceous-Tertiary coal beds in Alberta, Canada. Regions suitable for CO₂ storage have been defined on the basis of groundwater depth and CO₂ phase at in situ conditions. The theoretical CO₂ storage capacity was estimated on the basis of CO₂ adsorption isotherms measured on coal samples, and it varies between ∼20 kt CO₂/km² and 1260 kt CO₂/km², for a total of approximately 20 Gt CO₂. This represents the theoretical storage capacity limit that would be attained if there would be no other gases present in the coals or they would be 100% replaced by CO₂, and if all the coals will be accessed by CO₂. A recovery factor of less than 100% and a completion factor less than 50% reduce the theoretical storage capacity to an effective storage capacity of only 6.4 Gt CO₂. Not all the effective CO₂ storage capacity will be utilized because it is uneconomic to build the necessary infrastructure for areas with low storage capacity per unit surface. Assuming that the economic threshold to develop the necessary infrastructure is 200 kt CO₂/km², then the CO₂ storage capacity in coal beds in Alberta is greatly reduced further to a practical capacity of only ∼800 Mt CO₂.     

Heat of absorption of CO2 in aqueous ammonia and ammonium carbonate/carbamate solutions

A reaction calorimeter was used to determine the enthalpies of absorption of CO₂ in aqueous ammonia and in aqueous solutions of ammonium carbonate at temperatures of 35–80 °C. The heat of absorption of CO₂ with 2.5 wt% aqueous ammonia solution was found to be about 70 kJ/mol CO₂, which is lower than that with MEA (around 85 kJ/mol) at 35 and 40 °C. The value decreases with increased loading, but not to as low a value as expected by the carbonate–bicarbonate reaction (26.88 kJ/mol). The enthalpy of absorption of CO₂ in aqueous ammonia at 60 and 80 °C decreases with loadings at first, then increases between 0.2 mol CO₂/mol NH₃ and 0.6 mol CO₂/mol NH₃, and then decreases again. The behavior of the heat of absorption of CO₂ in 10 wt% ammonium carbonate solution was found to be the same as that of aqueous ammonia at loadings above 0.6 mol CO₂/mol NH₃. The heat of absorption increases with increasing temperature. The heats of absorption are directly related to the extent of the various reactions with CO₂ and can be assessed from the species variation in the liquid phase.     

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.     

Pathways towards large-scale implementation of CO2 capture and storage: A case study for the Netherlands

We sketch four possible pathways how carbon dioxide capture and storage (CCS) (r)evolution may occur in the Netherlands, after which the implications in terms of CO₂ stored and avoided, costs and infrastructural requirements are quantified. CCS may play a significant role in decarbonising the Dutch energy and industrial sector, which currently emits nearly 100 Mt CO₂/year. We found that 15 Mt CO₂ could be avoided annually by 2020, provided some of the larger gas fields that become available the coming decade could be used for CO₂ storage. Halfway this century, the mitigation potential of CCS in the power sector, industry and transport fuel production is estimated at maximally 80–110 Mt CO₂/year, of which 60–80 Mt CO₂/year may be avoided at costs between 15 and 40 €/t CO₂, including transport and storage. Avoiding 30–60 Mt CO₂/year by means of CCS is considered realistic given the storage potential represented by Dutch gas fields, although it requires planning to assure that domestic storage capacity could be used for CO₂ storage. In an aggressive climate policy, avoiding another 50 Mt CO₂/year may be possible provided that nearly all capture opportunities that occur are taken. Storing such large amounts of CO₂ would only be possible if the Groningen gas field or large reservoirs in the British or Norwegian part of the North Sea will become available.     

Novel lithium-based sorbents from fly ashes for CO2 capture at high temperatures

In this work several Li₄SiO₄-based sorbents from fly ashes for CO₂ capture at high temperatures have been developed. Three fly ash samples were collected and subjected to calcination at 950 °C in the presence of Li₂CO₃. Both pure Li₄SiO₄ and fly ash-based sorbents were characterised and tested for CO₂ sorption at different temperatures between 400 and 650 °C and adding different amounts of K₂CO₃ (0–40 mol%). To examine the sorbents performance, multiple CO₂ sorption/desorption cycles were carried out. The temperature and the presence of K₂CO₃ strongly affect the CO₂ sorption capacity for the sorbents prepared from fly ashes. When the sorption temperature increases by up to 600 °C both the CO₂ sorption capacity and the sorption rate increase significantly. Moreover when the amount of K₂CO₃ increases, the CO₂ sorption capacity also increases. At optimal experimental conditions (600 °C and 40 mol% K₂CO₃), the maximum CO₂ sorption capacity for the sorbent derived from fly ash was 107 mg CO₂/g sorbent. The Li₄SiO₄-based sorbents can maintain its original capacity during 10 cycle processes and reach the plateau of maximum capture capacity in less than 15 min, while pure Li₄SiO₄ presents a continual upward tendency for the 15 min of the capture step and attains no equilibrium capacity.     

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

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

Constraints on the in situ density of CO2 within the Utsira formation from time-lapse seafloor gravity measurements

At Sleipner, CO₂ is being separated from natural gas and injected into an underground saline aquifer for environmental purposes. Uncertainty in the aquifer temperature leads to uncertainty in the in situ density of CO₂. In this study, gravity measurements were made over the injection site in 2002 and 2005 on top of 30 concrete benchmarks on the seafloor in order to constrain the in situ CO₂ density. The gravity measurements have a repeatability of 4.3 μGal for 2003 and 3.5 μGal for 2005. The resulting time-lapse uncertainty is 5.3 μGal. Unexpected benchmark motions due to local sediment scouring contribute to the uncertainty. Forward gravity models are calculated based on both 3D seismic data and reservoir simulation models. The time-lapse gravity observations best fit a high temperature forward model based on the time-lapse 3D seismics, suggesting that the average in situ CO₂ density is about to 530 kg/m³. Uncertainty in determining the average density is estimated to be ±65 kg/m³ (95% confidence), however, this does not include uncertainties in the modeling. Additional seismic surveys and future gravity measurements will put better constraints on the CO₂ density and continue to map out the CO₂ flow.     

CO2 capture from hot stove gas in steel making process

The capture of CO₂ from a hot stove gas in steel making process containing 30 vol% CO₂ by chemical absorption in a rotating packed bed (RPB) was studied. The RPB had an inner diameter of 7.6 cm, an outer diameter of 16 cm, and a height of 2 cm. The aqueous solutions containing 30 wt% of single and mixed monoethanolamine (MEA), 2-(2-aminoethylamino)ethanol (AEEA), and piperazine (PZ) were used. The CO₂ capture efficiency was found to increase with increasing temperature in a range of 303–333 K. It was also found to be more dependent on gas and liquid flow rates but less dependent on rotating speed when the speed was higher than 700 rpm. The obtained results indicated that the mixed alkanolamine solutions containing PZ were more effective than the single alkanolamine solutions. This was attributed to the highest reaction rate of PZ with CO₂. A higher portion of PZ in the mixture was more favorable to CO₂ capture. The highest gas flow rates allowed to achieve a desired CO₂ capture efficiency and the correspondent height of transfer unit (HTU) were determined at different aqueous solution flow rates. Because all the 30 wt% single and mixed alkanolamine solutions could result in a HTU less than 5.0 cm at a liquid flow rate of 100 mL/min, chemical absorption in a RPB instead of a packed bed adsorber is therefore suggested to capture CO₂ from the flue gases in steel making processes.     

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.     

Kinetics of sulfur dioxide- and oxygen-induced degradation of aqueous monoethanolamine solution during CO2 absorption from power plant flue gas streams

Studies of the kinetics of sulfur dioxide (SO₂)- and oxygen (O₂)-induced degradation of aqueous monoethanolamine (MEA) during the absorption of carbon dioxide (CO₂) from flue gases derived from coal- or natural gas-fired power plants were conducted as a function of temperature and the liquid phase concentrations of MEA, O₂, SO₂ and CO₂. The kinetic data were based on the initial rate which shows the propensity for amine degradation and obtained under a range of conditions typical of the CO₂ absorption process (3–7 kmol/m³ MEA, 6% O₂, 0–196 ppm SO₂, 0–0.55 CO₂ loading, and 328–393 K temperature). The results showed that an increase in temperature and the concentrations of MEA, O₂ and SO₂ resulted in a higher MEA degradation rate. An increase in CO₂ concentration gave the opposite effect. A semi-empirical model based on the initial rate, ?r_MEA = {6.74 × 10⁹ e^?(29,403/RT)[MEA]^0.02([O]^2.91 + [SO₂]^3.52)}/{1 + 1.18[CO₂]^0.18} was developed to fit the experimental data. With the higher order of reaction, SO₂ has a higher propensity to cause MEA to degrade than O₂. Unlike previous models, this model shows an improvement in that any of the parameters (i.e. O₂, SO₂, and CO₂) can be removed without affecting the usability of the model.     

Integration and evaluation of a power plant with a CaO-based CO2 capture system

This paper explores the integration and evaluation of a power plant with a CaO-based CO₂ capture system. There is a great amount of recoverable heat in the CaO-based CO₂ capture process. Five cases for the possible integration of a 600 MW power plant with CaO-based CO₂ capture process are considered in this paper. When the system is configured so that recovered heat is used to replace part of the boiler heat load (Case 2), modelling not only shows that this is the system recovering the most heat of 1008.8 MW but also results in the system with the lowest net power output of 446 MW and the second lowest of efficiency of 34.1%. It is indicated that system performance depends both on the amount of heat recovery and the type of heat utilization. When the system is configured so that a 400 MW power plant is built using the recovered heat (Case 4), modelling shows that this is the system with the most net power output of 846 MW, the highest efficiency of 36.8%, the lowest cost of electricity of 54.3 €/MWh and the lowest cost of CO₂ avoided of 28.9 €/tCO₂. This new built steam cycle will not affect the operation of the reference plant which vents its CO₂ to the atmosphere, highly reducing the connection between the CO₂ capture process and the reference plant which vents its CO₂ to the atmosphere. The average cost of electricity and the cost of CO₂ avoided of the five cases are about 58.9 €/kWh and 35.9 €/tCO₂, respectively.     

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.