SkyMine Carbon Mineralization Pilot Project

This Topical Report addresses accomplishments achieved during Phase 1 of the SkyMine{reg_sign} Carbon Mineralization Pilot Project. The primary objectives of this project are to design, construct, and operate a system to capture CO{sub 2} from a slipstream of flue gas from a commercial coal-fired cement kiln, convert that CO{sub 2} to products having commercial value (i.e., beneficial use), show the economic viability of the CO{sub 2} capture and conversion process, and thereby advance the technology to a point of readiness for commercial scale demonstration and proliferation. The project will also substantiate market opportunities for the technology by sales of chemicals into existing markets, and identify opportunities to improve technology performance and reduce costs at commercial scale. The primary objectives of Phase 1 of the project were to elaborate proven SkyMine{reg_sign} process chemistry to commercial pilot-scale operation and complete the preliminary design ('Reference Plant Design') for the pilot plant to be built and operated in Phase 2. Additionally, during Phase 1, information necessary to inform a DOE determination regarding NEPA requirements for the project was developed, and a comprehensive carbon lifecycle analysis was completed. These items were included in the formal application for funding under Phase 2. All Phase 1 objectives were successfully met on schedule and within budget

Optimizing complexity in the kinetic modelling of integrated flue gas purification for pressurized oxy-combustion

A 5-step mechanism and a corresponding kinetic model are presented for integrated flue gas purification, where SOx and NOx are removed during pressurized oxy-coal combustion. Three coupled subsystems (''blocks") of gas-liquid transformations are considered: 1) oxidation of NO to NO2 and dissolution of NO2 in water; 2) dissolution of SO2 in the water; and 3) interactions between S- and N- containing substances in the liquid phase. The model has been formulated in terms of only species that can be experimentally measured (model of optimal complexity). Subsystem I is limiting regarding NO removal. Subsystem II is very fast in comparison with the other subsystems and can be treated separately. Analytical expressions for all independent subsystems have been found and compared with computational results for the whole system. The temporal domain of validity of all these subsystems is presented. Finally, the validity of the NO2 quasi-steady-state assumption is verified, and it is reported that variables such as NO, NO2 and HNO3 can be considered decoupled from the whole system since they appear in only Subsystem I, while HSO3- and HNO2 are coupled. The presented kinetic model was verified experimentally by determining the 1:1 ratio of HNO2 and HNO3, in gas-liquid NO-O-2 interaction. Additionally, new experimental facts on kinetic orders and stoichiometry between HNO2 and HSO3- have been used to optimize the model. It is concluded that all NOx- SOx interactions can be essentially grasped by a sequence of only 4 irreversible reactions considering, in addition, the 5th reaction, i.e. the fast 'SO2-water' equilibrium

The Adverse Effect of Benzannelation on the Aromaticity of Oxocinyl Anion: A Combined Experimental and Theoretical Study

A synthesis of 2H-1-benzoxocin from readily available compounds was accomplished. The potentially \u27aromatic\u27 π-excessive systems 2H-1-benzoxocinyl and 6H-dibenz[b,f]oxocinyl anions were generated from their corresponding conjugate acid precursors 7c and 8, respectively. It was found that 2H-1-benzoxocinide 3d lacks the type of π-frame stability associated with the parent 2H-oxocinide 1d and that the dibenzo analog 5b is more unstable than 3d. Both 3d and 5b undergo rapid structural reorganization to form their corresponding stable isomeric anions. We were able to characterize the proton-quenched products of these anions as the ring-opened structures 15 and 18, respectively. 1H-NMR and an ab initio calculation at the 6-31g* level indicated that, unlike the \u27aromatic\u27 parent 2H-oxocinide 1d and the aza analog 3c, 3d incorporates a non-planar oxocinyl ring in which the negative charge is primarily localized on the pentadienyl moiety of the ring, but also partial delocalization of π-electron density onto the benzene ring occurs