An-Najah Staff

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. 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+, Na+, K+, Rb+, Cl-, 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. High concentration sodium, potassium, and sodium/potassium bicarbonate aqueous solutions have been found to be the most effective solutions for enhancing aqueous olivine carbonation to date. Slurry-flow modeling using Fluent indicates that the slurry-flow dynamics are a strong function of particle size and mass, suggesting that controlling these parameters may offer substantial potential to enhance carbonation. During the first project year we developed a new sonication exfoliation apparatus with a novel sealing system to carry out the sonication studies. We also initiated investigations to explore the potential that sonication may offer to enhance carbonation reactivity. During the second project year, we extended our investigations of the effects of sonication on the extent of carbonation as a function of the following parameters: particle size distribution, the mass of solid reactant, volume fraction of aqueous solution present, sonication power, time, temperature, and CO{sub 2} pressure. To date, none of the conditions investigated have significantly enhanced carbonation. Mechanistic investigations of the stirred ({approx}1,500 rpm) aqueous olivine carbonation process indicate the carbonation process involves both incongruent magnesium dissolution and silica precipitation, which results in robust silica-rich passivating layer formation. Secondary ion mass spectrometry observation of H within the passivating layer that forms during static carbonation suggests 2H{sup +}/Mg{sup 2+} ion exchange is associated with incongruent dissolution. Apparently, H{sub 2}O forms at or near the olivine/passivating-layer interface during the process and diffuses out through the passivating layers during the carbonation reaction. This is also consistent with the observation that magnesite nanocrystals form within the passivating layers, further indicating the layers offer significant permeability to the key solution reaction species present during carbonation (e.g., Mg2+, H+, H{sub 2}O, CO{sub 2}, and HCO{sub 3}{sup -}). Cracking of the passivating layer surface during carbonation is routinely observed and can be related to the tensile stress associated with the dramatic volume decrease as olivine forms silica at the reaction surface. In our YEAR 2 studies we also demonstrated that the addition of quartz particles as an abrasive slurry component significantly enhanced carbonation, further substantiating the importance of particle-particle abrasion in enhancing passivating layer exfoliation and carbonation.

Gas-phase magnesium hydroxide carbonation processes were investigated at high CO₂ pressures to better understand the reaction mechanisms involved. Carbon and hydrogen elemental analysis, secondary ion mass spectrometry, ion beam analysis, X-ray diffraction, and thermogravimetric analysis were used to follow dehydroxylation/rehydroxylation/carbonation reaction processes. Dehydroxylation is found to generally precede carbonation as a distinct but interrelated process. Above the minimum CO₂ pressure for brucite carbonation, both carbonation and dehydroxylation reactivity decrease with increasing CO₂ pressure. Low-temperature dehydroxylation before carbonation can form porous intermediate materials with enhanced carbonation reactivity at reduced (e.g., ambient) temperature and pressure. Control of dehydroxylation/rehydroxylation reactions before and/or during carbonation can substantially enhance carbonation reactivity.