Coupled Kinetic and Mechanistic Study of Carbonation of Silicate Materials with Tailored Transport Behaviors for CO2 Utilization

Since the industrial revolution, the atmospheric CO2 concentration has steadily increased due to the combustion of fossil fuels, reaching 410 ppm. According to the 2018 IPCC report, it was recognized that the anthropogenic greenhouse gas emissions caused by human activities are major drivers for global warming of 1.0 oC above the pre-industrial level. Due to the unprecedented scale of human driven CO2 emission and its environmental impact, the mitigation of climate change requires a wide range of multifaceted solutions. Thus, enormous global efforts have been placed on the development of Carbon Capture, Utilization, and Storage (CCUS) to mitigate CO2 emissions in the immediate future. Most recent reports by the U.S. National Academies and the Mission Innovation presented that ex-situ carbon mineralization is a CO2 utilization technology with a great carbon storage potential and a large market size. Also, fixing CO2 into a solid matrix of carbonate minerals is one of the most permanent methods for carbon storage. Although the ex-situ carbon mineralization presents many advantages and great potential as CCUS technology, its commercialization has been limited due to the mammoth scale of the process, slow reaction kinetic between CO2 and silicate minerals, and high energy and operating cost. In order to minimize energy and chemical (acid and base) consumption of this technology, recent researches have been focused on a two-step carbon mineralization via Pco2 swing using highly reactive heat-treated serpentine mineral. However, the elemental (Mg and Si) extractions from the complex silicate structures of heat-treated serpentine are still poorly understood and a more fundamental understanding of the Pco2 swing process is required to develop a commercial-scale plant. Thus, the objectives of this study are directed toward addressing these technical challenges. The effect of operating conditions, such as temperature, slurry density, and CO2 partial pressure, on the dissolution of heat-treated serpentine and subsequent Mg-carbonate precipitation behaviors, were studied to provide a fundamental understanding of the Pco2 swing carbon mineralization process of highly reactive silicate materials. The dissolution experiments with a wide range of temperature and slurry densities provided valuable insights into the formation of the Si-rich passivation layer and its role in the mass transfer limitation during mineral dissolution. The heat-treated serpentine dissolution behaviors with chemical additives (ligand) were also investigated to overcome the effect of the Si-rich passivation layer on Mg extraction kinetics. What is more, a unique internal grinding system was proposed and integrated with the Pco2 swing process to physically remove the Si-rich passivation layer. The diffusion-limited slow elemental (Mg and Si) extraction from the heat-treated serpentine silicate structures was significantly enhanced in the internal grinding system. A stress intensity, which is proportional to the energy transferred from grinding media to the heat-treated serpentine particles during a stress event, was used to describe the effect of the reaction parameters on the extent of the physical activation and the enhancements in mineral dissolution. For the fundamental understanding of the complex dissolution behaviors of heat-treated serpentine, the changes in the silicate structures (Q0 – Q4) of heat-treated Mg-bearing mineral (serpentine) exposed to a CO2-water system (carbonic acid) was investigated using 29Si MAS NMR and XRPD. The identified silicate structures were employed to provide insight into how Mg and Si are liberated from the different silicate structures during the dissolution process. Thermodynamic and kinetic modeling was performed to understand the Mg-carbonate precipitation behaviors in the Pco2 swing process. The effects of carbonic anhydrase, seed particles, and ligand (citrate) on precipitation behaviors were studied to improve the precipitation kinetics. This approach will bring a great paradigm shift in the energy and environmental field since the less energy-intensive and low-cost ex-situ carbon mineralization process via Pco2 swing will be able to allow long-term and sustainable carbon utilization