Analytical Solution Incorporating History-Dependent Processes for Quick Assessment of Capillary Trapping During CO<Subscript>2</Subscript> Geological Storage

Carbon storage in saline formations is considered as a promising option to ensure the necessary decrease of CO₂ anthropogenic emissions. Its industrial development in those formations is above all conditioned by its safety demonstration. Assessing the evolution of trapped and mobile CO₂ across time is essential in the perspective of reducing leakage risks. In this work, we focus on residual trapping phenomenon occurring during the wetting of the injected CO₂ plume. History dependent effects are of first importance when dealing with capillary trapping. We then apply the classical fractional flow theory (Buckley–Leverett type model) and include trapping and hysteresis models; we derive an analytical solution for the temporal evolution of saturation profile and of CO₂ trapped quantity when injecting water after the gas injection (“artificial imbibition”). The comparison to numerical simulations for different configurations shows satisfactory match and justifies, in the case of industrial CO₂ storage, the assumptions of incompressible flow with no consideration of capillary pressure. The obtained analytical solution allows the quick assessment of both the quantity and the location of mobile gas left during imbibition.     

Effects of CO<Subscript>2</Subscript> Compressibility on CO<Subscript>2</Subscript> Storage in Deep Saline Aquifers

The injection of supercritical CO₂ in deep saline aquifers leads to the formation of a CO₂ plume that tends to float above the formation brine. As pressure builds up, CO₂ properties, i.e. density and viscosity, can vary significantly. Current analytical solutions do not account for CO₂ compressibility. In this article, we investigate numerically and analytically the effect of this variability on the position of the interface between the CO₂-rich phase and the formation brine. We introduce a correction to account for CO₂ compressibility (density variations) and viscosity variations in current analytical solutions. We find that the error in the interface position caused by neglecting CO₂ compressibility is relatively small when viscous forces dominate. However, it can become significant when gravity forces dominate, which is likely to occur at late times of injection.     

Sensitivity Study of Simulation Parameters Controlling CO<Subscript>2</Subscript> Trapping Mechanisms in Saline Formations

The primary purpose of this study is to understand quantitative characteristics of mobile, residual, and dissolved CO₂ trapping mechanisms within ranges of systematic variations in different geologic and hydrologic parameters. For this purpose, we conducted an extensive suite of numerical simulations to evaluate the sensitivities included in these parameters. We generated two-dimensional numerical models representing subsurface porous media with various permutations of vertical and horizontal permeability (k _v and k _h), porosity (f{\phi}), maximum residual CO₂ saturation (S_gr^max{S_{\rm gr}^{\max}}), and brine density (ρ _br). Simulation results indicate that residual CO₂ trapping increases proportionally to k_v, k_h, S_gr^max{k_{\rm v}, k_{\rm h}, S_{\rm gr}^{\max}} and ρ _br but is inversely proportional to f.{\phi.} In addition, the amount of dissolution-trapped CO₂ increases with k _v and k _h, but does not vary with f{\phi } , and decreases with S_gr^max{S_{\rm gr}^{\max}} and ρ _br. Additionally, the distance of buoyancy-driven CO₂ migration increases proportionally to k _v and ρ _br only and is inversely proportional to k_h, f{k_{\rm h}, \phi } , and S_gr^max{S_{\rm gr}^{\max}} . These complex behaviors occur because the chosen sensitivity parameters perturb the distances of vertical and horizontal CO₂ plume migration, pore volume size, and fraction of trapped CO₂ in both pores and formation fluids. Finally, in an effort to characterize complex relationships among residual CO₂ trapping and buoyancy-driven CO₂ migration, we quantified three characteristic zones. Zone I, expressing the variations of S_gr^max{S_{\rm gr}^{\max}} and k _h, represents the optimized conditions for geologic CO₂ sequestration. Zone II, showing the variation of f{\phi} , would be preferred for secure CO₂ sequestration since CO₂ has less potential to escape from the target formation. In zone III, both residual CO₂ trapping and buoyancy-driven migration distance increase with k _v and ρ _br.     

An Experimental Study of CO<Subscript>2</Subscript> Exsolution and Relative Permeability Measurements During CO<Subscript>2</Subscript> Saturated Water Depressurization

Dissolution of CO₂ into brine is an important and favorable trapping mechanism for geologic storage of CO₂. There are scenarios, however, where dissolved CO₂ may migrate out of the storage reservoir. Under these conditions, CO₂ will exsolve from solution during depressurization of the brine, leading to the formation of separate phase CO₂. For example, a CO₂ sequestration system with a brine-permeable caprock may be favored to allow for pressure relief in the sequestration reservoir. In this case, CO₂-rich brine may be transported upwards along a pressure gradient caused by CO₂ injection. Here we conduct an experimental study of CO₂ exsolution to observe the behavior of exsolved gas under a wide range of depressurization. Exsolution experiments in highly permeable Berea sandstones and low permeability Mount Simon sandstones are presented. Using X-ray CT scanning, the evolution of gas phase CO₂ and its spatial distribution is observed. In addition, we measure relative permeability for exsolved CO₂ and water in sandstone rocks based on mass balances and continuous observation of the pressure drop across the core from 12.41 to 2.76 MPa. The results show that the minimum CO₂ saturation at which the exsolved CO₂ phase mobilization occurs is from 11.7 to 15.5%. Exsolved CO₂ is distributed uniformly in homogeneous rock samples with no statistical correlation between porosity and CO₂ saturation observed. No gravitational redistribution of exsolved CO₂ was observed after depressurization, even in the high permeability core. Significant differences exist between the exsolved CO₂ and water relative permeabilities, compared to relative permeabilities derived from steady-state drainage relative permeability measurements in the same cores. Specifically, very low CO₂ and water relative permeabilities are measured in the exsolution experiments, even when the CO₂ saturation is as high as 40%. The large relative permeability reduction in both the water and CO₂ phases is hypothesized to result from the presence of disconnected gas bubbles in this two-phase flow system. This feature is also thought to be favorable for storage security after CO₂ injection.     

Enhanced CO<Subscript>2</Subscript> Storage and Sequestration in Deep Saline Aquifers by Nanoparticles: Commingled Disposal of Depleted Uranium and CO<Subscript>2</Subscript>

Geological storage of anthropogenic CO₂ emissions in deep saline aquifers has recently received tremendous attention in the scientific literature. Injected buoyant CO₂ accumulates at the top part of the aquifer under a sealing cap rock. Potential buoyant movement of CO₂ has caused some concern that the high-pressure CO₂ could breach the seal rock. However, CO₂ will diffuse into the brine underneath and generate a slightly denser fluid that may induce instability and convective mixing. Onset times of instability and convective mixing performance depend on the physical properties of the rock and fluids, such as permeability and density contrast. We present the novel idea of adding nanoparticles (NPs) to injected CO₂ to increase density contrast between the CO₂-rich brine and the underlying resident brine and, consequently, decrease onset time of instability and increase convective mixing. The analyses show that 0.001 volume fraction of NPs added to the CO₂ stream shortens onset time of mixing by approximately 80% and increases convective mixing by 50%. If it thus originally takes 5 years for the overlying CO₂ to start convective mixing, by adding NPs, onset time of mixing reduces to 1 year, and after initiation of convective mixing, mixing improves by 50%. A reduction of the CO₂ leakage risk ensues. In addition to other metallic NPs, use of processed depleted uranium oxide (DU) as the NPs is also proposed. DU-NPs are potentially stable and might be safely commingled with CO₂ to store in saline aquifers.     

Injection and Storage of CO<Subscript>2</Subscript> in Deep Saline Aquifers: Analytical Solution for CO<Subscript>2</Subscript> Plume Evolution During Injection

Injection of fluids into deep saline aquifers is practiced in several industrial activities, and is being considered as part of a possible mitigation strategy to reduce anthropogenic emissions of carbon dioxide into the atmosphere. Injection of CO₂ into deep saline aquifers involves CO₂ as a supercritical fluid that is less dense and less viscous than the resident formation water. These fluid properties lead to gravity override and possible viscous fingering. With relatively mild assumptions regarding fluid properties and displacement patterns, an analytical solution may be derived to describe the space–time evolution of the CO₂ plume. The solution uses arguments of energy minimization, and reduces to a simple radial form of the Buckley–Leverett solution for conditions of viscous domination. In order to test the applicability of the analytical solution to the CO₂ injection problem, we consider a wide range of subsurface conditions, characteristic of sedimentary basins around the world, that are expected to apply to possible CO₂ injection scenarios. For comparison, we run numerical simulations with an industry standard simulator, and show that the new analytical solution matches a full numerical solution for the entire range of CO₂ injection scenarios considered. The analytical solution provides a tool to estimate practical quantities associated with CO₂ injection, including maximum spatial extent of a plume and the shape of the overriding less-dense CO₂ front.     

The Footprint of the CO<Subscript>2</Subscript> Plume during Carbon Dioxide Storage in Saline Aquifers: Storage Efficiency for Capillary Trapping at the Basin Scale

We study a sharp-interface mathematical model of CO₂ migration in deep saline aquifers, which accounts for gravity override, capillary trapping, natural groundwater flow, and the shape of the plume during the injection period. The model leads to a nonlinear advection–diffusion equation, where the diffusive term is due to buoyancy forces, not physical diffusion. For the case of interest in geological CO₂ storage, in which the mobility ratio is very unfavorable, the mathematical model can be simplified to a hyperbolic equation. We present a complete analytical solution to the hyperbolic model. The main outcome is a closed-form expression that predicts the ultimate footprint on the CO₂ plume, and the time scale required for complete trapping. The capillary trapping coefficient and the mobility ratio between CO₂ and brine emerge as the key parameters in the assessment of CO₂ storage in saline aquifers. Despite the many approximations, the model captures the essence of the flow dynamics and therefore reflects proper dependencies on the mobility ratio and the capillary trapping coefficient, which are basin-specific. The expressions derived here have applicability to capacity estimates by capillary trapping at the basin scale.     

STREAMLINE-BASED MATHEMATICAL MODEL FOR CO2 MISCIBLE FLOODING

According to the research theory of improved black oil simulator, a practical mathematical model for C02 miscible flooding was presented. In the model, the miscible process simulation was realized by adjusting oil/gas relative permeability and effective viscosity under the condition of miscible flow. In order to predict the production performance fast, streamline method is employed to solve this model as an alternative to traditional finite difference methods. Based on streamline distribution of steady-state flow through porous media with complex boundary confirmed with the boundary element method (BEM), an explicit total variation diminishing (TVD) method is used to solve the one-dimensional flow problem. At the same time, influences of development scheme, solvent slug size, and injection periods on CO2 drive recovery are discussed. The model has the advantages of less information need, fast calculation, and adaptation to calculate CO2 drive performance of all kinds of patterns in a random shaped porous media with assembly boundary. It can be an effective tool for early stage screening andmiscible oil field.reservoir dynamic management of the CO2 miscible oil field.     

Nonequilibrium molecular radiation behind the front of a strong shock wave in the CO<Subscript>2</Subscript>-N<Subscript>2</Subscript>-O<Subscript>2</Subscript> mixture

Models of population of some radiating electron-vibrational states of CO, CN, and C₂ molecules are developed. The characteristics of radiation in a chemically nonequilibrium flow behind the front of a strong shock wave in a mixture of gases constituting the Martian atmosphere are calculated. The numerical data are compared with experimental results.Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 46, No. 2, pp. 13–22, March–April, 2005     

Investigation of hydrodynamic instability of CO<Subscript>2</Subscript> injection into an aquifer

The two-dimensional problem of supercritical carbon dioxide injection into an aquifer is solved. Shocks and rarefaction waves propagating in a sequence from an injection well into the formation are described within the framework of a complete nonisothermal model of flows in a porous medium. In the approximation of isothermal immiscible water and carbon dioxide flow the hydrodynamic stability of the leading displacement front is investigated for various reservoir pressures and temperatures. The parameters of unstable fronts are determined using a sufficient instability condition formulated in analytic form. The approximate analytic results are supported by the direct numerical simulation of CO₂ injection using the complete model in which thermal effects and phase transitions are taken into account.     

Production of nanomaterials by vaporizing ceramic targets irradiated by a moderate-power continuous-wave CO<Subscript>2</Subscript> laser

The efficiency of utilization of CO ₂ laser energy for vaporization of Al ₂ O ₃ ceramics is evaluated using a mathematical model for the interaction of laser radiation with materials. It is shown that the calculated efficiency of radiation-energy utilization is not higher than 15% at a radiation power density of 10⁵ W/cm ² on the target. On the experimental facility designed for the synthesis of nanopowders, a vaporization rate of 1 g/h was achieved for Al ₂ O ₃, which corresponds to a 3% efficiency of radiation-energy utilization. The dependence of the characteristic particle size of a zirconium oxide nanopowder on helium pressure in the range of 0.01–1.00 atm was studied. Results of experiments on vaporization of multicomponent materials (LaNiO ₃ and the Tsarev meteorite) are given. __________ Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 48, No. 2, pp. 172–184, March–April, 2007.     

Initiation of Combustion in a Supersonic Hydrogen-Air Mixture Flow by CO<Subscript>2</Subscript>-Laser Radiation

Features of the ignition kinetics of an H₂/air mixture in the supersonic flow behind an inclined shock front are analyzed when asymmetric vibrations of a small amount (<1%) of O₃ molecules specially introduced into the initial mixture are excited by 9.7 μm wavelength radiation. It is shown that this radiation leads to intensification of the chain reactions and makes it possible to organize combustion at small distances from the front (of the order of 1 m) of even relatively weak shocks at small values of the laser radiation energies absorbed by the gas. This method of initiating combustion in a supersonic flow is 10–100 times more efficient than the thermal method.__________Translated from Izvestiya Rossiiskoi Academii Nauk, Mekhanika Zhidkosti i Gaza, No. 2, 2005, pp. 157–167.Original Russian Text Copyright © 2005 by Lukhovitskii, Starik, and Titova.     

Pressure Buildup During CO<Subscript>2</Subscript> Injection into a Closed Brine Aquifer

CO₂ injected into porous formations is accommodated by reduction in the volume of the formation fluid and enlargement of the pore space, through compression of the formation fluids and rock material, respectively. A critical issue is how the resulting pressure buildup will affect the mechanical integrity of the host formation and caprock. Building on an existing approximate solution for formations of infinite radial extent, this article presents an explicit approximate solution for estimating pressure buildup due to injection of CO₂ into closed brine aquifers of finite radial extent. The analysis is also applicable for injection into a formation containing multiple wells, in which each well acts as if it were in a quasi-circular closed region. The approximate solution is validated by comparison with vertically averaged results obtained using TOUGH2 with ECO2N (where many of the simplifying assumptions are relaxed), and is shown to be very accurate over wide ranges of the relevant parameter space. The resulting equations for the pressure distribution are explicit, and can be easily implemented within spreadsheet software for estimating CO₂ injection capacity.     

Impact of CO<Subscript>2</Subscript> Injection on Flow Behavior of Coalbed Methane Reservoirs

On the basis of observations at four enhanced coalbed methane (ECBM)/CO₂ sequestration pilots, a laboratory-scale study was conducted to understand the flow behavior of coal in a methane/CO₂ environment. Sorption-induced volumetric strain was first measured by flooding fresh coal samples with adsorptive gases (methane and CO₂). In order to replicate the CO₂–ECBM process, CO₂ was then injected into a methane-saturated core to measure the incremental “swelling.” As a separate effort, the permeability of a coal core, held under triaxial stress, was measured using methane. This was followed by CO₂ flooding to replace the methane. In order to best replicate the conditions in situ, the core was held under uniaxial strain, that is, no horizontal strain was permitted during CO₂ flooding. Instead, the horizontal stress was adjusted to ensure zero strain. The results showed that the relative strain ratio for CO₂/methane was between 2 and 3.5. The measured volumetric strains were also fitted using a Langmuir-type model, thus enabling calculation of the strain at any gas pressure and using the analytical permeability models. For permeability work, effort was made to increase the horizontal stress to achieve the desired zero horizontal strain condition expected under in situ condition, but this became impossible because the “excess” stress required to maintain this condition was very large, resulting in sample failure. Finally, when CO₂ was introduced and horizontal strain was permitted, permeability reduction was an order of magnitude greater, suggesting that the “excess” stress would have reduced it significantly further. The positive finding of the work was that the “excess” stresses associated with injection of CO₂ are large. The excess stresses generated might be sufficient to cause microfracturing and increased permeability, and improved injectivity. Also, there might be a weakening effect resulting from repeated CO₂ injection, as has been found to be the case with thermal cycling of rocks.     

Pore Scale Modeling of Reactive Transport Involved in Geologic CO<Subscript>2</Subscript> Sequestration

We apply a multi-component reactive transport lattice Boltzmann model developed in previous studies for modeling the injection of a CO₂-saturated brine into various porous media structures at temperatures T = 25 and 80°C. In the various cases considered the porous medium consists initially of calcite with varying grain size and shape. A chemical system consisting of Na⁺, Ca²⁺, Mg²⁺, H⁺, CO₂^°(aq){{\rm CO}_2^{\circ}{\rm (aq)}}, and Cl⁻ is considered. Flow and transport by advection and diffusion of aqueous species, combined with homogeneous reactions occurring in the bulk fluid, as well as the dissolution of calcite and precipitation of dolomite are simulated at the pore scale. The effects of the structure of the porous media on reactive transport are investigated. The results are compared with a continuum-scale model and the discrepancies between the pore- and continuum-scale models are discussed. This study sheds some light on the fundamental physics occurring at the pore scale for reactive transport involved in geologic CO₂ sequestration.     

Quantification of Density-Driven Natural Convection for Dissolution Mechanism in CO<Subscript>2</Subscript> Sequestration

Dissolution of CO₂ into brine causes the density of the mixture to increase. The density gradient induces natural convection in the liquid phase, which is a favorable process of practical interest for CO₂ storage. Correct estimation of the dissolution rate is important because the time scale for dissolution corresponds to the time scale over which free phase CO₂ has a chance to leak out. However, for this estimation, the challenging simulation on the basis of convection–diffusion equation must be done. In this study, pseudo-diffusion coefficient is introduced which accounts for the rate of mass transferring by both convection and diffusion mechanisms. Experimental tests in fluid continuum and porous media were performed to measure the real rate of dissolution of CO₂ into water during the time. The pseudo diffusion coefficient of CO₂ into water was evaluated by the theory of pressure decay and this coefficient is used as a key parameter to quantify the natural convection and its effect on mass transfer of CO₂. For each experiment, fraction of ultimate dissolution is calculated from measured pressure data and the results are compared with predicted values from analytical solution. Measured CO₂ mass transfer rate from experiments are in reasonable agreement with values calculated from diffusion equation performed on the basis of pseudo-diffusion coefficient. It is suggested that solving diffusion equation with pseudo diffusion coefficient herein could be used as a simple and rapid tool to calculate the rate of mass transfer of CO₂ in CCS projects.     

Matched Boundary Extrapolation Solutions for CO<Subscript>2</Subscript> Well-Injection into a Saline Aquifer

The injection of supercritical CO₂ through wells into deep brine reservoirs is a topic of interest for geologic carbon sequestration. The injected CO₂ is predominantly immiscible with the brine and its low density relative to brine leads to strong buoyancy effects. The displacement of brine by CO₂ in general is a multidimensional, complex nonlinear problem that requires numerical methods to solve. The approximations of vertical equilibrium and complete gravity segregation (sharp interface) have been introduced to reduce the complexity and dimensionality of the problem. Furthermore, for the radial displacement process considered here, the problem can be formulated in terms of a similarity variable that reduces spatial and temporal dependencies to a single variable. However, the resulting ordinary differential equation is still nonlinear and exact solutions are not available. The existing analytical solutions are approximations limited to certain parameter ranges that become inaccurate over a large portion of the parameter space. Here, I use a matched boundary extrapolation method to provide much greater accuracy for analytical/semi-analytical approximations over the full parameter range.     

CO<Subscript>2</Subscript> injection into saline carbonate aquifer formations I: laboratory investigation

Although there are a number of mathematical modeling studies for carbon dioxide (CO₂) injection into aquifer formations, experimental studies are limited and most studies focus on injection into sandstone reservoirs as opposed to carbonate ones. This study presents the results of computerized tomography (CT) monitored laboratory experiments to analyze permeability and porosity changes as well as to characterize relevant chemical reactions associated with injection and storage of CO₂ in carbonate formations. CT monitored experiments are designed to model fast near well bore flow and slow reservoir flows. Highly heterogeneous cores drilled from a carbonate aquifer formation located in South East Turkey were used during the experiments. Porosity changes along the core plugs and the corresponding permeability changes are reported for different CO₂ injection rates and different salt concentrations of formation water. It was observed that either a permeability increase or a permeability reduction can be obtained. The trend of change in rock properties is very case dependent because it is related to distribution of pores, brine composition and thermodynamic conditions. As the salt concentration decreases, porosity and the permeability decreases are less pronounced. Calcite deposition is mainly influenced by orientation, with horizontal flow resulting in larger calcite deposition compared to vertical flow.     

Effect of Vertical Heterogeneity on Long-Term Migration of CO<Subscript>2</Subscript> in Saline Formations

For deep injection of CO₂ in thick saline formations, the movements of both the free gas phase and dissolved CO₂ are sensitive to variations in vertical permeability. A simple model for vertical heterogeneity was studied, consisting of a random distribution of horizontal impermeable barriers with a given overall volume fraction and distribution of lengths. Analytical results were obtained for the distribution of values for the permeability, and compared to numerical simulations of deep CO₂ injection and convection in heterogeneous formations, using multiple realizations for the permeability distribution. It is shown that for a formation of thickness H, the breakthrough times in two dimensions for deep injection scale as H ² for moderate injection rates. In comparison to heterogeneous shale distributions, a homogeneous medium with equivalent effective vertical permeability has a longer breakthrough time for deep injection, and a longer onset time for convection.