Carbon dioxide hydrate crystallization thickening & morphology in a micro-confined environment for carbon capture & sequestration processes

Abstract

Carbon dioxide capture and sequestration (CCS) are critical processes that are necessary to mitigate the impacts of climate change. In pipelines used for CCS and for ocean sequestration, the formation of CO2 hydrates can occur and be detrimental to the safety and integrity of the CCS equipment and process. Understanding the crystallization thickening behavior of CO2 hydrates is vital for understanding hydrate formation in CO2 pipelines and in other CCS applications, such as sequestration and CO2 capture or storage. In this study, a microfluidic chip reactor was used to crystalize and thicken CO2 hydrates at the channel walls. The morphology of the CO2 hydrates was visually analyzed and quantified using in situ Raman spectroscopy. Two hydrate layers were consistently observed. An annealed, dense layer of hydrate shared an interface with liquid water, while a porous hydrate layer shared an interface with CO2 gas. Capillary-like pore spaces could be observed in the porous layer, which confirms one proposed mechanism for hydrate film thickening. Subcooling (0.5–1.5 K), pressure (2.51, 3.10 MPa), and flow rate of CO2 (0.167, 1.67 mm3/s) were studied for their impact on the overall CO2 hydrate film thickness over time. Over the ranges of these chosen parameters, only CO2 flow rate was found to have a significant impact on the thickening of CO2 hydrates, and a higher flow rate led to thicker crystalline hydrate films. A first principles mass transfer model for hydrate film thickness was developed and applied to the measurement data collected for overall hydrate film thickness.