ATOMIC-LEVEL IMAGING OF CO2 DISPOSAL AS A CARBONATE MINERAL: OPTIMIZING REACTION PROCESS DESIGN

Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar-hydroxide based minerals (e.g., brucite and serpentine) offer a class of widely available, low-cost materials, with intriguing mineral carbonation potential. Carbonation of such materials inherently involves dehydroxylation, which can disrupt the material down to the atomic level. As such, controlled dehydroxylation before and/or during carbonation may provide an important parameter for enhancing carbonation reaction processes. Mg(OH){sub 2} was chosen as the model material for investigating lamellar hydroxide mineral dehydroxylation/carbonation mechanisms due to (i) its structural and chemical simplicity, (ii) interest in Mg(OH){sub 2} gas-solid carbonation as a potentially cost-effective CO{sub 2} mineral sequestration process component, and (iii) its structural and chemical similarity to other lamellar-hydroxide-based minerals (e.g., serpentine-based minerals) whose carbonation reaction processes are being explored due to their low-cost CO{sub 2} sequestration potential. Fundamental understanding of the mechanisms that govern dehydroxylation/carbonation processes is essential for cost optimization of any lamellar-hydroxide-based mineral carbonation sequestration process

ATOMIC-LEVEL IMAGING OF CO2 DISPOSAL AS A CARBONATE MINERAL: OPTIMIZING REACTION PROCESS DESIGN

Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg(OH){sub 2} carbonation is a leading process candidate, which generates the stable naturally occurring mineral magnesite (MgCO{sub 3}) and water. Key to process cost and viability are the carbonation reaction rate and its degree of completion. This process, which involves simultaneous dehydroxylation and carbonation is very promising, but far from optimized. In order to optimize the dehydroxylation/carbonation process, an atomic-level understanding of the mechanisms involved is needed. Since Mg(OH){sub 2} dehydroxylation is intimately associated with the carbonation process, its mechanisms are also of direct interest in understanding and optimizing the process. In the first project year, our investigations have focused on developing an atomic-level understanding of the dehydroxylation/carbonation reaction mechanisms that govern the overall carbonation reaction process in well crystallized material. In years two and three, we will also explore the roles of crystalline defects and impurities. Environmental-cell, dynamic high-resolution transmission electron microscopy has been used to directly observe the dehydroxylation process at the atomic-level for the first time. These observations were combined with advanced computational modeling studies to better elucidate the atomic-level process. These studies were combined with direct carbonation studies to better elucidate dehydroxylation/carbonation reaction mechanisms. Dehydroxylation follows a lamellar nucleation and growth process involving oxide layer formation. These layers form lamellar oxyhydroxide regions, which can grow both parallel and perpendicular to the Mg(OH){sub 2} lamella. The number of oxide layers within the regions increases as they grow during dehydroxylation. Selected area diffraction suggests a novel two-dimensional variant of Vegard's law can describe the oxyhydroxide regions, with intralamellar Mg-Mg packing distances observed between those known for Mg(OH){sub 2} and MgO. Intralamellar and interlamellar elastic stress induced during dehydroxylation can contribute to crystallite cracking and MgO surface reconstruction, which may serve to enhance carbonation reactivity. The observed dehydroxylation process indicates a range of candidate materials for carbonation may be present during the carbonation process (i) the hydroxide, (ii) a range of intermediate oxyhydroxides, and (iii) the oxide, potentially in more-reactive, very small particle size form. Partial carbonation of single-crystal Mg(OH){sub 2} fragments over a wide range of reaction conditions (varying CO{sub 2} pressure and temperature) shows a linear or near-linear correlation between carbonation and dehydroxylation, with the extent of dehydroxylation substantially greater than the extent of carbonation. This suggests carbonation primarily occurs via intermediate oxyhydroxide or oxide formation. The range and type of intermediate oxyhydroxides/oxides that can form in advance of carbonation should provide a degree of control over both their formation and the overall reactivity observed for the carbonation process

Understanding Olivine CO2 Mineral Sequestration Mechanisms at the Atomic Level: Optimizing Reaction Process Design

Carbonation of Mg-rich minerals offers an intriguing candidate carbon sequestration process technology, which can provide large-scale CO{sub 2} disposal. Such disposal bypasses many long-term storage problems by (i) providing containment in the form of mineral carbonates that have proven stable over geological time, (ii) generating only environmentally benign materials, and (iii) essentially eliminating the need for continuous site monitoring. The primary challenge for viable process development is reducing process cost. This is the primary focus of the CO{sub 2} Mineral Sequestration Working Group managed by Fossil Energy at DOE, which includes members from the Albany Research Center, Los Alamos National Laboratory, the National Energy Technology Laboratory, Penn State University, Science Applications International Corporation, and the University of Utah, as well as from our research group at Arizona State University. Carbonation of the widely occurring mineral olivine (e.g., forsterite, Mg{sub 2}SiO{sub 4}) is a leading process candidate, which converts CO{sub 2} into the mineral magnesite (MgCO{sub 3}). As olivine carbonation is exothermic, it offers intriguing low-cost potential. Recent studies at the Albany Research Center have found aqueous-solution carbonation is a promising approach. Cost effectively enhancing carbonation reactivity is central to reducing process cost. Many of the mechanisms that impact reactivity occur at the solid/solution interface. Understanding these mechanisms is central to the ability to engineer new and modified processes to enhance carbonation reactivity and lower cost. Herein, we report the results of our UCR I project, which focused on exploring the reaction mechanisms that govern aqueous-solution olivine carbonation using model olivine feedstock materials. Carbonation was found to be a complex process associated with passivating silica layer formation, which includes the trapping of magnesite nanocrystals within the passivating silica layers, cracking and exfoliation of the layers, silica surface migration, olivine etch pit formation, transfer of the Mg and Fe in the olivine into the product carbonate, and the nucleation and growth of magnesite crystals on/in the silica/olivine reaction matrix. These phenomena occur in concert with the large solid volume changes that accompany the carbonation process, which can substantially impact carbonation reactivity. Passivating silica layer formation appears to play a major role in inhibiting carbonation reactivity. New approaches that can mitigate the effectiveness of passivating layer formation may offer intriguing potential to enhance carbonation reactivity and lower process cost

Analcime crystallization and compositional profiles - Comparing approaches to detect post-depositional alterations in archaeological pottery

The approaches of comparative studies and profile measurements, often used in order to detect post-depositional alterations of ceramics, have been applied simultaneously to two sets of Roman pottery, both of which include altered individuals. As analytical techniques, Neutron Activation Analysis and X-Ray Diffraction have been used. Both approaches lead to substantially different results. This shows that they detect different levels of alteration and should complement each other rather than being used exclusively. For the special process of a glassy phase decomposition followed by a crystallization of the Na-zeolite analcime, the results suggest that it changes high-fired calcareous pottery rapidly, and so fundamentally that the results of various archaeometric techniques can be severely disturbed