Title: Catalytic Enhancement of Silicate Mineral Weathering for Direct Carbon Capture and Storage
Description: With the atmospheric concentration of carbon dioxide steadily increasing and little sign of a reduction in fossil fuel demand worldwide, there is a well-established need for an alternative strategy for dealing with carbon emissions from energy production. One possible solution is the accelerated weathering of ultramafic rocks. Accelerated weathering is an environmentally benign route to a thermodynamically and kinetically stable form of carbon. The chemistry is based on naturally occurring reactions and the raw materials are abundant across the earth's surface. However, the reactions are relatively slow, and achieving reaction rates sufficient to match the carbon dioxide production rate at an energy conversion facility is challenging. This work addresses a number of the challenges facing the integration of accelerated weathering with energy conversion, and presents one view of how the integration could be achieved. This work begins by developing a suite of tools necessary for investigating the dissolution and precipitation of minerals.

Chapter 2 starts with a description of the minerals that will be evaluated, and then goes on to develop the techniques that will be used. The first is a differential bed reactor, which is used for measuring the dissolution rates of minerals under tightly controlled conditions. Next a bubble column reactor is developed for the investigating the adsorption of carbon dioxide and the precipitation of mineral carbonates in a single vessel. These techniques, together with a batch reactor for studying direct carbonation reactions, constitute a comprehensive set of tools for the investigation of accelerated mineral weathering. With the necessary techniques developed and proven, Chapter 3 addresses the first challenge faced by accelerated mineral weathering; the dissolution rate of magnesium from a silicate mineral. While the dissolution of this mineral is thermodynamically favorable, the kinetics are prohibitively slow. It is thought that this is because silica from the mineral tends to accumulate on the particle surface creating a passivation layer, which limits the reaction rate of the mineral.

In this work, the effects of a combination of chemical chelating agents, catechol and oxalate, are evaluated for their ability to circumvent this passivation layer. The results indicate that catechol and oxalate modify the passivation layer as it forms, both accelerating the dissolution rate of the mineral and maintaining pore volume, leading to greater dissolution rates. This pore modification process is proposed as the primary mechanism by which catechol affects the passivation layer. The combination of catechol and oxalate under acidic conditions is also shown be effective when the ambient solution approaches the saturation point of silica. Finally, the chelating does not impede the precipitation of carbonate products, a critical hurdle for a carbon storage process. The chelating agent work is extended in Chapter 4, with a sensitivity study that evaluates the response of the dissolution rate to changes in both pH and the concentration of the chelating agents. Oxalate and pH are found to exhibit a strong influence on the mineral dissolution rate, while the effect of catechol is more apparent after significant dissolution has taken place.

These observations are in agreement with the model of passivation layer modification proposed. In addition, some alternatives to the chelating agent catechol are evaluated. It is found that when used in combination with oxalate, these alternatives appeared equivalent to catechol, but alone they had only a minor effect. Catechol was also noted to have a significant effect on the dissolution rate of iron from the silicate mineral, and a mechanism for this effect was proposed. The direct adsorption of carbon dioxide and precipitation of solid carbonates in a single reaction step presents another challenge for accelerated mineral carbonation. In general, the magnesium carbonates formed at ambient pressure and moderate temperatures tend to be hydrated, and at times contain unused hydroxides, leading to inefficiencies in both transport and storage. It is shown in Chapter 5 that by seeding reaction vessels with the anhydrous form of magnesium carbonate, it is possible to grow this desired phase with minimal formation of the metastable hydrated phases.

The formation of this phase is primarily limited by the precipitation rate, but in some situations, carbon dioxide hydration kinetics and magnesium hydroxide precipitation kinetics also play a role. In Chapter 6, these developments in both magnesium silicate dissolution and carbonate precipitation are combined into a proposed technology for the direct capture and storage of carbon dioxide. This application of accelerated mineral weathering is shown to significantly reduce the carbon emissions of an energy conversion technology through life cycle assessment. This novel approach to the mitigation of carbon emissions presents a compelling argument for the continued development of accelerated mineral weathering as a combined carbon capture and storage technology.