Fluid-Rock Interactions in Carbonates: Applications to CO2 Storage

Abstract

It is well established that more than half of the world’s hydrocarbon reserves are contained in carbonate reservoirs. In a global context, which is characterized by an increasing demand in energy, population growth and overall economic development, it is very important to unlock potential carbonate resources while mitigating the effects of climate change. Moreover, significant volumes of carbon dioxide – the major greenhouse gas contributor to global warming – can be stored in carbonate subsurface formations such as carbonate depleted reservoirs and deep saline aquifers. Therefore, better understanding of carbonate porous media has a wide range of major industrial and environmental applications. However, because of complex pore structures, including the presence of micro-porosity, heterogeneities at different scales, combined with high chemical reactivity, it remains very challenging to describe flow and transport in carbonates. In this thesis, we focus on carbonate porous media and aim to better describe flow, transport and reaction in them. The main application of this work is related to carbon storage in deep saline carbonate aquifers. More particularly, we address fluid-rock interactions e.g. wettability alterations and reactive transport, that occur in carbonate formations.

First, we investigate the impact of wettability alteration on multi-phase flow properties. We use pore-network modelling to analyze the impact of wettability alteration by modelling water-flood relative permeability for six different carbonate samples with different connectivity. Pore-scale multi-phase flow physics is described in detail and the efficiency of water-flooding in mixed-wet carbonates is related to the wettability and pore connectivity. We study six carbonate samples. Four quarry samples – Indiana, Portland, Guiting and Mount Gambier – and two subsurface samples obtained from a deep saline Middle Eastern aquifer. The pore space is imaged in three dimensions using X-ray micro-tomography at a resolution of a few microns. The images are segmented into pore and void and a topologically representative network of pores and throats is extracted from these images. We then simulate quasi-static displacement in the networks. We represent mixed-wet behaviour by varying the oil-wet fraction of the pore space. The relative permeability is strongly dependent on both the wettability and the average coordination number of the network. We show that traditional measures of wettability based on the point where the relative permeability curves cross are not reliable. Good agreement is found between our calculations and measurements of relative permeability on carbonates in the literature. The work helps establish a library of benchmark samples for multi-phase flow and transport computations. The implications of the results for field-scale displacement mechanisms are discussed, and the efficiency of waterflooding as an oil recovery process in carbonate reservoirs is assessed depending on the wettability and pore space connectivity. Secondly, we investigate at the laboratory column scale (50 cm), fluid-rock interactions that occur through the injection of an acidic solution into carbonate porous media. Laboratory columns are packed with crushed and sieved porous Guiting carbonate grains. Therefore a homogenous porous medium at the Darcy scale is created and the effect of micro-heterogeneities on transport and reactive transport properties is highlighted. We first conduct a series of passive tracer experiments. Salinity is used as a non-reactive tracer as brine is injected at a constant flow rate into columns pre-saturated with equilibrated deionised water. Solute breakthrough curves are experimentally obtained by measuring the conductivity of collected effluent samples. Subsequently, by solving the advection-dispersion equations using PHREEQC geochemical software, we compare the experimental measurements with numerical predictions of breakthrough curves. A good match is obtained for a dual porosity model and a dispersion coefficient is estimated. We then investigate reactive transport by injecting at constant flow rate acidic brine (hydrochloric acid diluted in saline brine with an overall pH of 3) into columns pre-saturated with equilibrated brine. We measure the effluent concentrations using ICP-AES (inductively coupled plasma atomic emission spectroscopy) Moreover; scanning electron microscopy (SEM) is used to determine single grain-scale changes. We assess the impact of flow rate on the resident time distribution of solutes and reaction profiles along the columns. We discuss challenges encountered regarding the reproducibility of the results and we highlight the implications of such phenomenological studies on carbon storage in carbonates. Finally, we experimentally examine fluid-rock interactions that are induced by the injection of supercritical CO2 (sc-CO2) in carbonate formations at the pore scale. I designed and built a novel experimental apparatus that allows the injection of brine enriched with sc-CO2 at typical CO2 storage conditions. In our experiments the temperature is 500C and the injecting pressure is 9MPa. A novel methodology that combines pore-scale imaging, core flooding and pore-scale modelling is applied in the context of CO2-carbonate-brine interactions. We experimentally use a high pressure and temperature mixing vessel to generate brines enriched with sc-CO2.The mixture is then injected using high precision piston pumps at a constant flow rate (Q=0.1 ml/min) into carbonate micro samples (5 mm diameter and 20 mm length) saturated with pre-equilibrated high salinity brine. We measure the permeability changes in real time during the injection of reactive fluids, In addition, dry high-resolution micro-computed tomography scans are obtained prior to and after the experiments and the pore structure, connectivity and computed flow fields are compared using image analysis and pore-scale modelling techniques. We perform direct simulations of transport properties and velocity fields on the three-dimensional scans and we extract representative pore-throat networks to compute average coordination number and assess changes in pore and throat size distributions. Moreover, we assess the impact of reaction rate on reactive transport. We alter the reaction rate and hence the Damkӧhler number by under saturating the sc-CO2/brine mixture with crushed and sieved carbonate grains. Two regimes of dissolution are experimentally observed: dominant wormholing and a more uniform dissolution regime. High resolution 3D scans of the dissolution patterns confirm these observations. Permeability increases over several order of magnitude with wormholing whereas for the uniform dissolution, the increase in permeability is less pronounced. Overall, fewer pore and throats are present after dissolution while the average coordination number does not change significantly. Flow becomes concentrated in the wormhole regions after reactions although a very wide range of velocities is still observed. We then compare the observed results for single phase flow (wormholing induced by the injection of single phase brine saturated with sc-CO2) to two-phase flow reactive flow experiments (co injection of sc-CO2 and brine). Results show that wormholing is also seen in the two-phase experiments. Directions for future research in the area of fluid-rock interactions are then discussed.