Impact of temperature on fluid-rock interactions during CO2 injection in depleted limestone aquifers: Laboratory and modelling studies

When CO₂ is injected into an aquifer, the injected CO₂ is generally colder than the reservoir rock; this results in thermal gradients along the flow path. The temperature variation has an impact on CO₂ solubility and the kinetics of any mineral reactions. Core flood experiments and associated reactive transport simulations were conducted to analyse thermal effects during CO₂ injection in a dolomitic limestone aquifer and to quantify how CO₂ solubility and mineral reactivity are affected. The experiments were conducted by injecting acidified brine into an Edwards Limestone core sample. A back pressure of 400 psi and injection rates of 30 mL/hr and 300 mL/hr were used. A range of temperatures from 21 °C to 70 °C were examined. Changes in the outlet fluid composition and changes in porosity and permeability were analysed. A compositional simulation model was used to further analyse the experiments. The simulations were history-matched to the experimental data by changing the reactive surface area and the kinetic rate parameter. The calibrated model was then used to test the sensitivity to CO₂ injection rate and temperature. The impact of temperature on CO₂-induced mineral reactions was observed from changes in mineral volume, porosity and permeability. The reaction rate constants estimated from the outlet solution concentrations are much lower than existing data for individual minerals. The estimated specific surface areas for carbonate minerals are in reasonable agreement with published values. The numerical investigations showed that at the lower temperatures, despite the reaction rates being slower, the solubility of the minerals was higher, and so as a result of these competing effects, moderately elevated calcium and magnesium concentrations were observed in the effluent. At higher temperatures, the solubilities of the minerals were lower, but now the reactions rates were higher, so similar effluent concentrations could be achieved. However, at higher flow rates, characterized by a lower Damköhler number, the residence times were shorter, and so lower effluent concentrations were observed. Additionally, the solubilities of calcite and dolomite varied to different extents with temperature, and so the calcium to magnesium molar ratio in the effluent brine increased with increasing temperature.