Analytical solution for estimating storage efficiency of geologic sequestration of CO2

During injection of carbon dioxide (CO₂) into deep saline aquifers, the available pore volume of the aquifer may be used inefficiently, thereby decreasing the effective capacity of the repository for CO₂ storage. Storage efficiency is the fraction of the available pore space that is utilized for CO₂ storage, or, in other words, it is the ratio between the volume of stored CO₂ and the maximum available pore volume. In this note, we derive and present simple analytical expressions for estimating CO₂ storage efficiency under the scenario of a constant-rate injection of CO₂ into a confined, homogeneous, isotropic, saline aquifer. The expressions for storage efficiency are derived from models developed previously by other researchers describing the shape of the CO₂-brine interface. The storage efficiency of CO₂ is found to depend on three dimensionless groups, namely: (1) the residual saturation of brine after displacement by CO₂; (2) the ratio of CO₂ mobility to brine mobility; (3) a dimensionless group (which we call a “gravity factor”) that quantifies the importance of CO₂ buoyancy relative to CO₂ injection rate. In the particular case of negligible residual brine saturation and negligible buoyancy effects, the storage efficiency is approximately equal to the ratio of the CO₂ viscosity to the brine viscosity. Storage efficiency decreases as the gravity factor increases, because the buoyancy of the CO₂ causes it to occupy a thin layer at the top of the confined formation, while leaving the lower part of the aquifer under-utilized. Estimates of storage efficiency from our simple analytical expressions are in reasonable agreement with values calculated from simulations performed with more complicated multi-phase-flow simulation software. Therefore, we suggest that the analytical expressions presented herein could be used as a simple and rapid tool to screen the technical or economic feasibility of a proposed CO₂ injection scenario.     

A solution against well cement degradation under CO2 geological storage environment

Capturing and storing carbon dioxide (CO₂) underground for thousands of years is one way to reduce atmospheric greenhouse gases, often associated with global warming. Leakage through wells is one of the major issues when storing CO₂ in depleted oil or gas reservoirs. CO₂-injection candidates may be new wells, or old wells that are active, closed or abandoned. In all cases, it is critical to ensure that the long-term integrity of the storage wells is not compromised. The loss of well integrity may often be explained by the geochemical alteration of hydrated cement that is used to isolate the annulus across the producing/injection intervals in CO₂-related wells. However, even before any chemical degradation, changes in downhole conditions due to supercritical CO₂ injections can also be responsible for cement debonding from the casing and/or from the formation, leading to rapid CO₂ leakage. A new cement with better CO₂ resistance is compared with conventional cement using experimental procedure and methodology simulating the interaction of set cement with injected, supercritical CO₂ under downhole conditions. Geochemical experimental data and a mechanical modeling approach are presented. The use of adding expanding property to this new cement to avoid microannulus development during the CO₂ injection is discussed.     

Electricity systems with near-zero emissions of CO2 based on wind energy and coal gasification with CCS and hydrogen storage

Emissions from electricity generation will have to be reduced to near-zero to meet targets for reducing overall greenhouse gas emissions. Variable renewable energy sources such as wind will help to achieve this goal but they will have to be used in conjunction with other flexible power plants with low-CO₂ emissions. A process which would be well suited to this role would be coal gasification hydrogen production with CCS, underground buffer storage of hydrogen and independent gas turbine power generation. The gasification hydrogen production and CO₂ capture and storage equipment could operate at full load and only the power plants would need to operate flexibly and at low load, which would result in substantial practical and economic advantages. This paper analyses the performances and costs of such plants in scenarios with various amounts of wind generation, based on data for power demand and wind energy variability in the UK. In a scenario with 35% wind generation, overall emissions of CO₂ could be reduced by 98–99%. The cost of abating CO₂ emissions from the non-wind residual generation using the technique proposed in this paper would be less than 40% of the cost of using coal-fired power plants with integrated CCS.     

CO2 storage capacity estimation: Issues and development of standards

Associated with the endeavours of geoscientists to pursue the promise that geological storage of CO₂ has of potentially making deep cuts into greenhouse gas emissions, Governments around the world are dependent on reliable estimates of CO₂ storage capacity and insightful indications of the viability of geological storage in their respective jurisdictions. Similarly, industry needs reliable estimates for business decisions regarding site selection and development. If such estimates are unreliable, and decisions are made based on poor advice, then valuable resources and time could be wasted. Policies that have been put in place to address CO₂ emissions could be jeopardised. Estimates need to clearly state the limitations that existed (data, time, knowledge) at the time of making the assessment and indicate the purpose and future use to which the estimates should be applied. A set of guidelines for estimation of storage capacity will greatly assist future deliberations by government and industry on the appropriateness of geological storage of CO₂ in different geological settings and political jurisdictions. This work has been initiated under the auspices of the Carbon Sequestration Leadership Forum (www.cslforum.org), and it is intended that it will be an ongoing taskforce to further examine issues associated with storage capacity estimation.     

Basin-scale hydrogeologic impacts of CO2 storage: Capacity and regulatory implications

Industrial-scale injection of CO₂ into saline formations in sedimentary basins will cause large-scale fluid pressurization and migration of native brines, which may affect valuable groundwater resources overlying the deep sequestration aquifers. In this paper, we discuss how such basin-scale hydrogeologic impacts (1) may reduce current storage capacity estimates, and (2) can affect regulation of CO₂ storage projects. Our assessment arises from a hypothetical future carbon sequestration scenario in the Illinois Basin, which involves twenty individual CO₂ storage projects (sites) in a core injection area most suitable for long-term storage. Each project is assumed to inject five million tonnes of CO₂ per year for 50 years. A regional-scale three-dimensional simulation model was developed for the Illinois Basin that captures both the local-scale CO₂–brine flow processes and the large-scale groundwater flow patterns in response to CO₂ storage. The far-field pressure buildup predicted for this selected sequestration scenario support recent studies in that environmental concerns related to near- and far-field pressure buildup may be a limiting factor on CO₂ storage capacity. In other words, estimates of storage capacity, if solely based on the effective pore volume available for safe trapping of CO₂, may have to be revised based on assessments of pressure perturbations and their potential impacts on caprock integrity and groundwater resources. Our results suggest that (1) the area that needs to be characterized in a permitting process may comprise a very large region within the basin if reservoir pressurization is considered, and (2) permits cannot be granted on a single-site basis alone because the near- and far-field hydrogeologic response may be affected by interference between individual storage sites. We also discuss some of the challenges in making reliable predictions of large-scale hydrogeologic impacts related to CO₂ sequestration projects.     

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.     

Kinetics of CO2 absorption in aqueous ammonia solution

The kinetics of CO₂ absorption in unloaded aqueous ammonia solution were measured using a string of discs contactor with the aqueous ammonia concentrations ranging 0.9–5.4 kmol/m³ and temperatures ranging 298.3–321.9 K. The reaction rates strongly increase with the concentration and less strongly with temperature. Both the termolecular and zwitterion models were applied in this study as amine solutions. The parameters for both of the models were interpreted. The kinetic rate constants for CO₂ absorption in aqueous ammonia were compared with those for other amines and were found to be around 1/10 that for monoethanolamine. The fitting results for the termolecular mechanism seem more robust than those for the zwitterion mechanism from a statistical perspective.     

Preliminary assessment of CO2 geological storage opportunities in Greece

This paper provides a preliminary assessment of the suitability of Tertiary sedimentary basins in Northern, Western and Eastern Greece in order to identify geological structures close to major CO₂ emission sources with the potential for long-term storage of CO₂. The term “emissions” refers to point source emissions as defined by the International Energy Agency, including power generation, the cement sector and other industrial processes. The Prinos oil field and saline aquifer, along with the saline formations of the Thessaloniki Basin and the Mesohellenic Trough have been identified as prospective CO₂ geological storage sites. In addition, a carbonate deep saline aquifer occurring at appropriate depths beneath the Neogene-Quaternary sediments of Ptolemais-Kozani graben (NW Greece) is considered. The proximity of this geological formation to Greece's largest lignite-fired power plants suggests that it would be worthwhile undertaking further site-specific studies to quantify its storage capacity and assess its structural integrity.     

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.     

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.     

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.     

CO2 recycling by reaction with renewably-generated hydrogen

A laboratory-scale reactor system was built and operated to demonstrate the feasibility of catalytically reacting carbon dioxide (CO₂) with renewably-generated hydrogen (H₂) to produce methane (CH₄) according to the Sabatier reaction: CO₂ + 4H₂ → CH₄ + 2H₂O. A cylindrical reaction vessel packed with a commercial methanation catalyst (Haldor Topsøe PK-7R) was used. Renewable H₂ produced by electrolysis of water (from solar- and wind-generated electricity) was fed into the reactor along with a custom blend of 2% CO₂ in N₂, meant to represent a synthetic exhaust mixture. Reaction conditions of temperature, flow rates, and gas mixing ratios were varied to determine optimum performance. The extent of reaction was monitored by real-time measurement of CO₂ and CH₄. Maximum conversion of CO₂ occurred at 300–350 °C. Approximately 60% conversion of CO₂ was realized at a space velocity of about 10,000 h^?1 with a molar ratio of H₂/CO₂ of 4/1. Somewhat higher total CO₂ conversion was possible by increasing the H₂/CO₂ ratio, but the most efficient use of available H₂ occurs at a lower H₂/CO₂ ratio.     

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.     

Rate modeling of CO2 stripping from potassium carbonate promoted by piperazine

This work presents results from a rate-based model of strippers at normal pressure (160 kPa) and vacuum (30 kPa) in Aspen Custom Modeler^® (ACM) for the desorption of CO₂ from 5 m K⁺/2.5 m piperazine (PZ). The model solves the material, equilibrium, summation and enthalpy (MESH) equations, the heat and mass transfer rate equations, and computes the reboiler duty and equivalent work for the stripping process. Simulations were performed with IMTP #40 random packing and a temperature approach on the hot side of the cross-exchanger of 5 °C and 10 °C. A “short and fat” stripper requires 7–15% less total equivalent work than a “tall and skinny” one because of the reduced pressure drop. The vacuum and normal pressure strippers require 230 s and 115 s of liquid retention time to get an equivalent work 4% greater than the minimum work. Stripping at 30 kPa was controlled by mass transfer with reaction in the boundary layer and diffusion of reactants and products (88% resistance at the rich end and 71% resistance at the lean end). Stripping at 160 kPa was controlled by mass transfer with equilibrium reactions (84% resistance at the rich end and 74% resistance at the lean end) at 80% flood. The typical predicted energy requirement for stripping and compression to 10 MPa to achieve 90% CO₂ removal was 37 kJ/gmol CO₂. This is about 25% of the net output of a 500 MW power plant with 90% CO₂ removal.     

Economic evaluation of the geological storage of CO2 considering the scale of economy

CO₂ capture and storage (CCS) technology is expected to play an important role in the efforts directed toward long-term CO₂ emission reduction. This paper analyzes the cost of the geological storage of CO₂ in Japan in order to consider future research, development and deployment (RD&D); these would be based on the information of the obtained cost structure. According to the analysis results, the costs, particularly those of the transportation by pipeline and of CO₂ injection, strongly depend on the scale of the facilities. Therefore, the distance of the transportation of CO₂ should be minimized in the case of small-scale storage, particularly in Japan. In addition, the potential injection rate per well is another key factor for the injection cost. Based on the analyzed cost, the injection cost of the geological storage of CO₂ in Japan for individual storage sites is estimated, and the cost–potential curve is obtained. A mixed-integer programming model has been developed to take into account these characteristics of the CCS technology and its adverse effects arising from the scale of economy with regard to the transportation and injection cost for the geological storage of CO₂. The model is designed to evaluate CCS and other CO₂ mitigation technologies in the energy systems of Japan. With all these adverse effects due to the scale of economy, the geological storage of CO₂ will be one of the important options for CO₂ emission reduction in Japan.     

CO2 capture by adsorption: Materials and process development

Vacuum swing adsorptive (VSA) capture of CO₂ from flue gas and related process streams is a promising technology for greenhouse gas mitigation. Although early reports suggested that VSA was problematic and expensive, through the application of more logical process configurations that are appropriately coupled to the composition of the feed and product gas streams, we can now refute this early assertion. Improved cycle designs coupled with tighter temperature control are also helping to optimise performance for CO₂ separation. Simultaneously, new adsorbent materials are being developed. These separate CO₂ by selective (acid-base) reaction with surface bound amine groups (chemisorption), rather than on the basis of non-bonding interactions (physisorption). This report describes some of these recent developments from our own laboratories and points to synergies that are anticipated as a result of combining these improvements in adsorbent properties and VSA process cycles.     

Geomechanical analysis of the Naylor Field,Otway Basin,Australia: Implications for CO2 injection and storage

A geomechanical assessment of the Naylor Field, Otway Basin, Australia has been undertaken to investigate the possible geomechanical effects of CO₂ injection and storage. The study aims to evaluate the geomechanical behaviour of the caprock/reservoir system and to estimate the risk of fault reactivation. The stress regime in the onshore Victorian Otway Basin is inferred to be strike–slip if the maximum horizontal stress is calculated using frictional limits and DITF (drilling induced tensile fracture) occurrence, or normal if maximum horizontal stress is based on analysis of dipole sonic log data. The NW–SE maximum horizontal stress orientation (142°N) determined from a resistivity image log is broadly consistent with previous estimates and confirms a NW–SE maximum horizontal stress orientation for the Otway Basin.An analytical geomechanical solution is used to describe stress changes in the subsurface of the Naylor Field. The computed reservoir stress path for the Naylor Field is then incorporated into fault reactivation analysis to estimate the minimum pore pressure increase required to cause fault reactivation (ΔP_p).The highest reactivation propensity (for critically-oriented faults) ranges from an estimated pore pressure increase (ΔP_p) of 1 MPa to 15.7 MPa (estimated pore pressure of 18.5–33.2 MPa) depending on assumptions made about maximum horizontal stress magnitude, fault strength, reservoir stress path and Biot's coefficient. The critical pore pressure changes for known faults at Naylor Field range from an estimated pore pressure increase (ΔP_p) of 2 MPa to 17 MPa (estimated pore pressure of 19.5–34.5 MPa).     

CO2 capture from combined cycles integrated with Molten Carbonate Fuel Cells

In this paper Molten Carbonate Fuel Cells (MCFCs) are considered for their potential application in carbon dioxide separation when integrated into natural gas fired combined cycles. The MCFC performs on the anode side an electrochemical oxidation of natural gas by means of CO₃^2? ions which, as far as carbon capture is concerned, results in a twofold advantage: the cell removes CO₂ fed at the cathode to promote carbonate ion transport across the electrolyte and any dilution of the oxidized products is avoided.The MCFC can be “retrofitted” into a combined cycle, giving the opportunity to remove most of the CO₂ contained in the gas turbine exhaust gases before they enter the heat recovery steam generator (HRSG), and allowing to exploit the heat recovery steam cycle in an efficient “hybrid” fuel cell + steam turbine configuration. The carbon dioxide can be easily recovered from the cell anode exhaust after combustion with pure oxygen (supplied by an air separation unit) of the residual fuel, cooling of the combustion products in the HRSG and water separation. The resulting power cycle has the potential to keep the overall cycle electrical efficiency approximately unchanged with respect to the original combined cycle, while separating 80% of the CO₂ otherwise vented and limiting the size of the fuel cell, which contributes to about 17% of the total power output so that most of the power capacity relies on conventional low cost turbo-machinery. The calculated specific energy for CO₂ avoided is about 4 times lower than average values for conventional post-combustion capture technology. A sensitivity analysis shows that positive results hold also changing significantly a number of MCFC and plant design parameters.     

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.