A NOVEL APPROACH TO MINERAL CARBONATION: ENHANCING CARBONATION WHILE AVOIDING MINERAL PRETREATMENT PROCESS COST

Abstract

Known fossil fuel reserves, especially coal, can support global energy demands for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Unlike other CO{sub 2} sequestration candidate technologies that propose long-term storage, mineral sequestration provides permanent disposal by forming geologically stable mineral carbonates. Carbonation of the widely occurring mineral olivine (e.g., forsterite, Mg{sub 2}SiO{sub 4}) is a large-scale sequestration process candidate for regional implementation, which converts CO{sub 2} into the environmentally benign mineral magnesite (MgCO{sub 3}). The primary goal is cost-competitive process development. As the process is exothermic, it inherently offers low-cost potential. Enhancing carbonation reactivity is key to economic viability. Recent studies at the U.S. DOE Albany Research Center have established that aqueous-solution carbonation using supercritical CO{sub 2} is a promising process; even without olivine activation, 30-50% carbonation has been achieved in an hour. Mechanical activation (e.g., attrition) has accelerated the carbonation process to an industrial timescale (i.e., near completion in less than an hour), at reduced pressure and temperature. However, the activation cost is too high to be economical and lower cost pretreatment options are needed. Herein, we report our first year progress in exploring a novel approach that offers the potential to substantially enhance carbonation reactivity while bypassing pretreatment activation. We have discovered that robust silica-rich passivating layers form on the olivine surface during carbonation. As carbonation proceeds, these passivating layers thicken, fracture and eventually exfoliate, exposing fresh olivine surfaces during rapidly-stirred/circulating carbonation. We are exploring the mechanisms that govern carbonation reactivity and the impact that (1) modeling/controlling the slurry fluid-flow conditions, (2) varying the aqueous ion species/size and concentration (e.g., Li{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, Cl{sup -}, HCO{sub 3}{sup -}), and (3) incorporating select sonication offer to enhance exfoliation and carbonation. Thus far, we have succeeded in nearly doubling the extent of carbonation observed compared with the optimum procedure previously developed by the Albany Research Center. Aqueous carbonation reactivity was found to be a strong function of the ionic species present and their aqueous activities, as well as the slurry fluid flow conditions incorporated. Synergistic control of these parameters offers the potential for further improvements in carbonation reactivity. A new sonication exfoliation system incorporating a novel sealing system was developed to carry out the sonication studies. Our initial studies that incorporate controlled sonication have not yet lead to a significant improvement in the extent of carbonation observed. Year 2 studies will emphasize those approaches that offer the greatest potential to cost effectively enhance carbonation, as well as combined approaches that may further enhance carbonation. Mechanistic investigations indicate incongruent dissolution results in the observed silica-rich passivating layer formation. Observations of magnesite nanocrystals within the passivating layers that form indicate the layers can exhibit significant permeability to the key reactants present (e.g., Mg{sup 2+}, H{sup +}, H{sub 2}O, CO{sub 2}, and HCO{sub 3} -). Atomistic modeling supports the observation of robust passivating layers that retain significant permeability to the key reaction species involved. Studies in Year 2 will emphasize the impact that controlled aqueous speciation and activity and slurry-flow dynamics have on the mechanisms that control carbonation reactivity and the potential they offer to substantially reduce olivine mineral sequestration process cost.