Real Time 3D Observations of Portland Cement Carbonation at CO2 Storage Conditions.

Depleted oil reservoirs are considered a viable solution to the global challenge of CO2 storage. A key concern is whether the wells can be suitably sealed with cement to hinder the escape of CO2. Under reservoir conditions, CO2 is in its supercritical state, and the high pressures and temperatures involved make real-time microscopic observations of cement degradation experimentally challenging. Here, we present an in situ 3D dynamic X-ray micro computed tomography (µ-CT) study of well cement carbonation at realistic reservoir stress, pore-pressure, and temperature conditions. The high-resolution time-lapse 3D images allow monitoring the progress of reaction fronts in Portland cement, including density changes, sample deformation, and mineral precipitation and dissolution. By switching between flow and nonflow conditions of CO2-saturated water through cement, we were able to delineate regimes dominated by calcium carbonate precipitation and dissolution. For the first time, we demonstrate experimentally the impact of the flow history on CO2 leakage risk for cement plugging. In-situ µ-CT experiments combined with geochemical modeling provide unique insight into the interactions between CO2 and cement, potentially helping in assessing the risks of CO2 storage in geological reservoirs.

Influence of Chemical, Mechanical, and Transport Processes on Wellbore Leakage from Geologic CO2 Storage Reservoirs.

Wells are considered to be high-risk pathways for fluid leakage from geologic CO2 storage reservoirs, because breaches in this engineered system have the potential to connect the reservoir to groundwater resources and the atmosphere. Given these concerns, a few studies have assessed leakage risk by evaluating regulatory records, often self-reported, documenting leakage in gas fields. Leakage is thought to be governed largely by initial well-construction quality and the method of well abandonment. The geologic carbon storage community has raised further concerns because acidic fluids in the CO2 storage reservoir, alkaline cement meant to isolate the reservoir fluids from the overlying strata, and steel casings in wells are inherently reactive systems. This is of particular concern for storage of CO2 in depleted oil and gas reservoirs with numerous legacy wells engineered to variable standards. Research suggests that leakage risks are not as great as initially perceived because chemical and mechanical alteration of cement has the capacity to seal damaged zones. Our work centers on defining the coupled chemical and mechanical processes governing flow in damaged zones in wells. We have developed process-based models, constrained by experiments, to better understand and forecast leakage risk. Leakage pathways can be sealed by precipitation of carbonate minerals in the fractures and deformation of the reacted cement. High reactivity of cement hydroxides releases excess calcium that can precipitate as carbonate solids in the fracture network under low brine flow rates. If the flow is fast, then the brine remains undersaturated with respect to the solubility of calcium carbonate minerals, and zones depleted in calcium hydroxides, enriched in calcium carbonate precipitates, and made of amorphous silicates leached of original cement minerals are formed. Under confining pressure, the reacted cement is compressed, which reduces permeability and lowers leakage risks. The broader context of this paper is to use our experimentally calibrated chemical, mechanical, and transport model to illustrate when, where, and in what conditions fracture pathways seal in CO2 storage wells, to reduce their risk to groundwater resources. We do this by defining the amount of cement and the time required to effectively seal the leakage pathways associated with peak and postinjection overpressures, within the context of oil and gas industry standards for leak detection, mitigation, and repairs. Our simulations suggest that for many damage scenarios chemical and mechanical processes lower leakage risk by reducing or sealing fracture pathways. Leakage risk would remain high in wells with a large amount of damage, modeled here as wide fracture apertures, where fast flowing fluids are too dilute for carbonate precipitation and subsurface stress does not compress the altered cement. Fracture sealing is more likely as reservoir pressures decrease during the postinjection phase where lower fluxes aid chemical alteration and mechanical deformation of cement. Our results hold promise for the development of mitigation framework to avoid impacting groundwater resources above any geologic CO2 storage reservoir by correlating operational pressures and barrier lengths.

Brownian Dynamics of a Suspension of Particles with Constrained Voronoi Cell Volumes.

Solvent-free polymer-grafted nanoparticle fluids consist of inorganic core particles fluidized by polymers tethered to their surfaces. The attachment of the suspending fluid to the particle surface creates a strong penalty for local variations in the fluid volume surrounding the particles. As a model of such a suspension we perform Brownian dynamics of an equilibrium system consisting of hard spheres which experience a many-particle potential proportional to the variance of the Voronoi volumes surrounding each particle (E = α(Vi-V0)(2)). The coefficient of proportionality α can be varied such that pure hard sphere dynamics is recovered as α → 0, while an incompressible array of hairy particles is obtained as α → ∞. As α is increased the distribution of Voronoi volumes becomes narrower, the mean coordination number of the particle increases and the variance in the number of nearest neighbors decreases. The nearest neighbor peaks in the pair distribution function are suppressed and shifted to larger radial separations as the constraint acts to maintain relatively uniform interstitial regions. The structure factor of the model suspension satisfies S(k=0) → 0 as α → ∞ in accordance with expectation for a single component (particle plus tethered fluid) incompressible system. The tracer diffusivity of the particles is reduced by the volume constraint and goes to zero at ϕ ∼ 0.52, indicating an earlier glass transition than has been observed in hard sphere suspensions. The total pressure of the suspension grows in proportion to (αkBT)(1/2) as the strength of the volume-constraint potential grows. This stress arises primarily from the interparticle potential forces, while the hard-sphere collisional contribution to the stress is suppressed by the volume constraint.

Determination of diffusion profiles in altered wellbore cement using X-ray computed tomography methods.

The development of accurate, predictive models for use in determining wellbore integrity requires detailed information about the chemical and mechanical changes occurring in hardened Portland cements. X-ray computed tomography (XRCT) provides a method that can nondestructively probe these changes in three dimensions. Here, we describe a method for extracting subvoxel mineralogical and chemical information from synchrotron XRCT images by combining advanced image segmentation with geochemical models of cement alteration. The method relies on determining "effective linear activity coefficients" (ELAC) for the white light source to generate calibration curves that relate the image grayscales to material composition. The resulting data set supports the modeling of cement alteration by CO2-rich brine with discrete increases in calcium concentration at reaction boundaries. The results of these XRCT analyses can be used to further improve coupled geochemical and mechanical models of cement alteration in the wellbore environment.

Fracture-scale model of immiscible fluid flow.

We present a method for modeling immiscible fluid flow in narrow fractures. The method combines a parallel-plate flow model with a recoloration approach adapted from multiple-component lattice-Boltzmann methods. The resulting numerical method is straightforward to implement and accurately reproduces the relevant fluid behavior. To demonstrate the method, single-droplet simulations are compared to analytical solutions that isolate the contributions from the in-plane and normal curvature. Simulations reproducing capillary forces inside a widening aperture are also presented. Excellent agreement is found in all cases considered. Finally, the method's ability to model fracture flow is demonstrated by deriving relative permeability curves for flow through a heterogeneous aperture created between two fractal surfaces.

Chemical and mechanical properties of wellbore cement altered by CO2-rich brine using a multianalytical approach.

Defining chemical and mechanical alteration of wellbore cement by CO(2)-rich brines is important for predicting the long-term integrity of wellbores in geologic CO(2) environments. We reacted CO(2)-rich brines along a cement-caprock boundary at 60 °C and pCO(2) = 3 MPa using flow-through experiments. The results show that distinct reaction zones form in response to reactions with the brine over the 8-day experiment. Detailed characterization of the crystalline and amorphous phases, and the solution chemistry show that the zones can be modeled as preferential portlandite dissolution in the depleted layer, concurrent calcium silicate hydrate (CSH) alteration to an amorphous zeolite and Ca-carbonate precipitation in the carbonate layer, and carbonate dissolution in the amorphous layer. Chemical reaction altered the mechanical properties of the core lowering the average Young's moduli in the depleted, carbonate, and amorphous layers to approximately 75, 64, and 34% of the unaltered cement, respectively. The decreased elastic modulus of the altered cement reflects an increase in pore space through mineral dissolution and different moduli of the reaction products.