| This dissertation is a unique integration of experimental and theoretical methods. The central issue that is being addressed is to find a long term and economically viable solution to the disposal of carbon dioxide gas from coal power plants. Mineral carbonation reactions have emerged as a permanent solution to the well-known "Greenhouse Gas" issue. Our group here at ASU along with groups at Los Alamos National Laboratory (LANL), National Energy Technology Laboratory (NETL), Pennsylvania State in Utah (SAIC), and the Albany Research Center (ARC) comprise the working group managed by the US Department of Energy (DOE). We have been collaborating to develop a fundamental understanding of the carbonation reactions of candidate minerals which will ultimately be used to develop a pilot plant process.; Two of the candidate minerals used in mineral sequestration processes are forsterite (olivine) and lizardite (serpentine). Both candidates require pre-treatment prior to reaction with carbon dioxide. Forsterite requires attrition (grinding), while lizardite requires a pre-heat treatment (dehydroxylation) step which removes chemically bound water. In Chapter 3 of this thesis, the thermodynamic properties of seven primary oxides involved in reactions with forsterite and lizardite are compared. A novel method was developed using a theoretical molecular quantum physics approach which reproduced experimental results with great accuracy. This method can now be used for other systems where experimental thermodynamic data is unavailable. In Chapters 4 and 5, the dehydroxylation mechanism for lizardite is studied using theoretical models in conjunction with experimental results. A possible mechanism for the dehydroxylation pathway is suggested. This long-awaited result may provide new insight regarding carbonation reactions in lizardite. Chapters 6 and 7 explore the carbonation reactions in forsterite. With the help of high resolution electron microscopy images and extremely large, 10,000 atom models, we have gained new understanding of the reaction layer on the surface of the forsterite crystal. Several computer codes were tested for calculations of electron energy loss near edge spectra, as comparison with experimental electron energy loss spectra, and a reliable strategy for calculation has been suggested. The electron energy loss results have enhanced our knowledge of the forsterite reaction layer. |
