4.1 Reactive flow and transport modelling for CO2 storage

Long-term estimates of trapping mechanisms introduced in the previous chapters, i.e., structural, solubility and kineral trapping, require the development of a reactive transport model able to accurately describe hydrodynamic and geochemical processes (Audigane, et al., 2007). The potential geochemical feedback on physical properties through highly coupled processes has been recognised as being of great importance for CCS (e.g. Czernichowski-Lauriol et al., 1996). During recent years, chemical and solute transport modelling for CCS has made significant progress, building upon the earlier coupled flow models developed for both geothermal systems and radioactive waste disposal. Reactive modelling has evolved from simple, chemical, batch models assuming only interactions between CO2 dissolved in brine and host rocks, without taking into account any flow aspects, to complex three-dimensional fully coupled chemical and flow models accounting for the geological complexity of the storage reservoir and caprock(s) (Gaus et al., 2008).

Current solute transport model codes consider either two components (e.g. CO2, fluid) or three components (CO2, oil, fluid) as well as density dependent flow, dissolution of CO2, chemical speciation, dissolution of minerals of the host rock and precipitation of new secondary phases, and porosity changes in the host rock as a consequence of these processes. To address these processes the equations of conservation of energy, momentum, mass and solute mass, together with constitutive laws are coupled in either an implicit or an explicit manner (Gaus et al., 2008).

The success of CO2 storage and its worldwide deployment might largely depend on the understanding of the interaction of CO2 with fluids and minerals within the reservoir for thousands of years. Saline reservoirs in sedimentary basins constitute one of the best targets for the CCS projects due to their massive storage capacity. The formation waters in these reservoirs are characterised by salinities ranging from 5,000 to > 350,000 mg/L dissolved solids. They cannot be considered as water resource because they usually contain dissolved species e.g. metals and organic components (Kharaka and Hanor, 2007). The chemistry of these waters is the result of various different hydrogeochemical processes. Hence, the injection of CO2 into such reservoirs constitutes an additional process that influences the chemistry of these waters and increases the chemical reactivity of the system. Although dry CO2 does not react, wet CO2reacts and forms a weak acid (H2CO3) that almost immediately dissociates. This makes the pH of the brine to decrease.

CO2(g) +H2O CO2(aq) +H2O H2CO3° HCO3-+H+ CO32-+2H+

The above series of linked reversible reactions is controlled by in-situ temperature, pressure and salinity. As stated in Gaus et al., 2008, there is evidence that dissolved CO2 may have an important impact during CO2 storage operations and, may influence the success or failure of a carbon storage project. Once injected, CO2 dissolves into the fluids present in the formation and might induce geochemical reactions in the reservoir, the well infrastructure and the reservoir caprock that need to be fully evaluated. From enhanced oil recovery (EOR) operations, there is indirect evidence of geochemical reactions in the near-well environment causing injectivity difficulties (Czernichowski-Lauriol et al., 1996). Generally, injectivity changes are poorly explained and have been tentatively attributed to multiphase flow, CO2/oil interactions and/or CO2/mineral interactions (Cailly et al., 2005). Only occasionally, increased injectivity is observed. Evidence of geochemical interactions caused by the presence of CO2 in geological sequences where CO2 occurs naturally (e.g. natural CO2 storage analogues) is particularly valuable since it illustrates the long-term impact of CO2 on natural rocks that cannot easily be reproduced during experiments or short-term field tests. In some natural analogues, chemical equilibrium is not reached, even over very long (geological) contact times (Haszeldine et al., 2005). This suggests that chemical equilibrium might not be attained during the expected lifetime of a CCS storage site, i.e., thousands to hundreds of thousands of years (Gaus et al., 2008).