Browsing by Subject "Supercritical"
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Item Examining supercritical CO₂ dissolution kinetics during carbon sequestration through column experiments(2011-08) Kent, Molly Elizabeth; Bennett, Philip C. (Philip Charles), 1959-; Romanak, Katherine; Cardenas, Meinhard B.Carbon sequestration is a method of capturing and storing excess anthropogenic CO₂ in the subsurface. When CO₂ is injected, the temperature and pressure at depth turn it into a supercritical (SC) fluid, where density is that of a liquid, but viscosity and compressibility resemble a gas. Ultimately the SC CO₂ is trapped at depth either by low permeability sealing layers, by reactions with minerals, or by dissolving into fluids. The injected CO₂ is buoyant and initially exists as a non-aqueous hydrophobic layer floating on top of the subsurface brine, up against the upper sealing formation, but over time it will dissolve into the brine and potentially react with minerals. The details of that initial dissolution reaction, however, are only poorly understood, and I address three basic questions for this research: What is the fundamental kinetics of SC CO₂ dissolution into water? How fast does dissolved CO₂ diffuse away from the source point? And what geochemical conditions influence the dissolution rate? To answer these questions I employed a high pressure flow-through approach using a column packed with coarse quartz sand. The system was both pressure and temperature controlled to have either liquid or SC CO₂ present, and was typically run at 100 Bar, 0.5 to 2.5 mls/min, and 28-60°C. After establishing the hydraulic parameters for the column using two conservative tracers (Br, As), injections (5 and 20 [mu]l) were made either as aqueous solutions equilibrated to high pressure CO₂, or as pure liquid or SC CO₂ into 0.1 mmol NaOH. For all experiments the pH of the system was monitored, and [CO₂] over time was calculated from those data. For injections of brine with dissolved CO₂, transport was conservative and was nearly identical to the conservative tracers. The CO₂ quickly mixes in the column and does not react with the quartz. The liquid and SC CO₂ injections, however, do not act conservatively, and have a very long tailing breakthrough curve that extends to tens of pore volumes. I hypothesize that the SC CO₂ is becoming trapped as a droplet or many droplets in the pore spaces, and the long breakthrough tail is related either to the rate of dissolution into the aqueous phase, the diffusion of dissolved CO₂ away from the phase boundary, or the reaction with the NaOH, limited to the narrow contact zones in the pore throats. Because of the speed at which acid-base reactions occur (nanosecond kinetics), I infer that the rate limiting step is either surface dissolution or diffusion. From plots of ln[CO₂] v. time I obtained values for k, the specific rate of the dissolution reaction R=-k[CO₂]. No trend for k was seen with respect to changes in temperature, but k did show a trend with respect to changing flow rate. k increased from an average value of 3.05x10⁻³ at 0.5 ml/min to an average value of 3.38x10⁻³ at 1.6 ml/min, and then held constant at the higher flow rates, up to 2.5 ml/min. I interpret these data to show that at low flow rates, the reaction is diffusion limited; the fluid nearest the contact zone becomes saturated with dissolved CO₂. At higher flow rates, the fluid is moving fast enough that saturation cannot occur, and the kinetics of the dissolution reaction dominate. Simple geometric models indicate that the CO₂/water interface is shaped like a spherical cap, indicating that the snapped-off CO₂ is forming a meniscus in the pore throat, limiting the surface area across which dissolution can occur.Item Nanoparticle-stabilized supercritical CO₂ foam for mobility control in CO₂ enhanced oil recovery(2014-08) Aroonsri, Archawin; Bryant, Steven L.Foam has been used as a mobility control technique in CO₂ flooding to improve volumetric sweep efficiency. Stabilizing CO₂ foam with nanoparticle instead of surfactant has some notable advantages. Nanoparticle-stabilized foam is very stable because a large adsorption energy is required to bring nanoparticles to the bubble interfaces. As a solid, nanoparticle can potentially withstand the high temperature in the reservoir, providing a robust foam stability for an extended period of time. The ability of nanoparticles to generate foam only above a threshold shear rate is promising as foam can be engineered to form only in the high permeability zone. These nanoparticles are hundreds of times smaller than pore throats and thus can travel in the reservoir without plugging the pore throats. Surface-modified silica nanoparticle was found to stabilize CO₂ -in-water foam at temperature up to 80 ˚C and salinity as high as 7.2 wt%. The foam was generated through the co-injection of aqueous nanoparticle dispersion and CO₂ into consolidated rock cores, primarily sandstones, with and without an induced fracture in the core. A critical shear rate for foam generation was found to exist in both matrix and fracture, however, this critical rate varied with the experiment conditions. The effects of experimental parameters on the critical shear rate and foam apparent viscosity were also investigated. Additionally, the flow distribution calculation in fractured sandstone cores revealed a diversion of flow from fracture toward matrix once foam was generated, suggesting conformance control potential in fractured reservoirs. In order to study foam rheology, high-permeability beadpack was installed upstream of the core to serve as a foam generator. This allows the foam mobility to be measured solely while being transported through the core, without the complicating effect of transient foam generation in the core. The injection of the pre-generated foam into the core at residual oil condition was found to reduce the residual oil saturation to the same level as CO₂ flood, however, with the advantage of mobility control. The 'coalescence-regeneration' mechanism of foam transport in porous media possibly allowed the foam's CO₂ to contact and mobilize the residual oil. The injection of the foam slug followed by a slug of only CO₂ was also tested, showing similar viscosification as the continuous foam injection, however, required less nanoparticles.Item Nanoparticle-stabilized supercritical CO₂ foams for potential mobility control applications(2011-05) Espinosa, David Ryan; Bryant, Steven L.; Huh, ChunThe petroleum industry has been utilizing surfactant stabilized foams for mobility control and enhanced oil recovery applications. However, if surface-treated nanoparticles were utilized instead of surfactants, the foams could have a number of important advantages. The solid-stabilized foams are known to have a much better stability than the surfactant-stabilized foams, because the energy required to bring nanoparticles to, and detach from the foam bubble surface is much larger than that of surfactants, and thus the resulting foam will be more stable. Since nanoparticles are the stabilizing component of the foam and are solid, they have potential to stabilize foam at high temperature conditions for extended periods of time. Since they are inherently small, nanoparticles, as well as the foam that they stabilize, can be transported through rocks without causing plugging in pore throats. Stable supercritical carbon dioxide-in-water foams were created using 5 nm silica-core nanoparticles whose surface had short polyethylene-glycol chains covalently bonded to it. The foams were made by injecting CO2 and an dispersion of with surface-treated nanoparticles simultaneously through a glass-bead pack. The fluids flowing through this permeable media created shear rates of about 1350 sec-1. Nanoparticle concentration, nanoparticle coating, water salinity, volume ratios between CO2 and water, temperature and shear rates were systematically varied in order to define the range of conditions for foam generation. Using de-ionized water to dilute the nanoparticle concentration, we were able to generate stable foams were at nanoparticle concentrations as low as 0.05 weight percent. Among the different surface coatings that we tested PEG coatings were the only type that was able to stabilize foam. As the salinity of the aqueous phase increased, the nanoparticle concentration required to maintain foam also increased; for example, 0.5 weight percent nanoparticles were required for 4 weight percent NaCl brine. Foam stability was weakly correlated with volume ratios as foams were made across ratios from two to fourteen, and the normalized viscosity ratio increased with the increase of the phase ratio. Foams were created at temperatures up to 95 degrees Celsius. Foam generation was also determined to require a critical shear rate, which increased with temperature. When foam was stabilized by the nanoparticles, the foam exhibited an increase of between two and twenty times in the resistance of flow compared to the two fluids flowing without nanoparticles.Item Numerical Investigation of Thermal Hydraulic Behavior of Supercritical Carbon Dioxide in Compact Heat Exchangers(2012-02-14) Fatima, RomaThe present work seeks to investigate the thermal hydraulic (heat transfer and fluid dynamics) behavior of supercritical (Sc) fluids at both the fundamental and applied levels. The thermal hydraulics of these fluids is not very well known although they have been used in various applications. There are drastic changes in the thermal and hydraulic properties of fluids at supercritical conditions. There has been a lot of focus to effectively utilize these properties changes in many applications such as heat exchangers. This work focuses on studying the forced convective heat transfer of Sc-CO2 in a series of mini semi-circular horizontal tubes and a zig-zag shaped horizontal channel. The problems were investigated numerically by second-order finite volume method using a commercial software FLUENT. Three dimensional Computational Fluid Dynamics (CFD) models were developed to simulate the flow and heat transfer for three different geometries ? a single semi-circular channel, a series of nine parallel semi-circular channels and a zig-zag channel. Grid and accuracy refinement studies were carried out to assess numerical errors. All the computational meshes developed for this study incorporated the first node cell within the viscous sub-layer i.e. y <1. Since the flow is turbulent, an appropriate choice of turbulence model is highly desirable. Henceforth, various turbulence models were used to study their impact on the heat transfer solution for these problems. The present numerical work focuses on improving the CFD model and methodologies in order to capture the experimental data of the heat transfer spike at the super critical conditions. Local and average heat transfer coefficients near the critical point were determined from measured wall temperatures and calculated local bulk temperatures. The numerical results are compared with the experiments. The numerical predictions do not convincingly agree with the experiments. This could be because of the incapability of turbulent models to capture the flow physics accurately due to the rapid changes in the fluid properties near critical conditions.