Calculation of hydrogen adsorption isotherms and Henry coefficients with mixed CO2 and CH4 gases on hydroxylated quartz surface: Implications to hydrogen geo-storage

Abstract

Hydrogen is a clean fuel that is becoming increasingly popular in addressing future energy challenges, however, its viable storage requires an understanding of its interaction with underground rock minerals. For this purpose, this study focuses on developing adsorption isotherms and Henry coefficients for hydrogen in hydroxylated quartz surfaces, which are predominant in sandstone and shale rocks. In this study, a molecular-scale hydroxylated quartz structure with a pore space is generated and the Monte Carlo (MC) simulation is utilized to assess the adsorption isotherms and Henry coefficients. Initially, the CO2 adsorption with the hydroxylated quartz is matched with the published data to determine the accuracy of MC simulation and the mineral-fluid interaction. After that, the concentration of H2 within the pore is progressively increased and the competitive adsorption is calculated under various subsurface temperature and pressure conditions. Additionally, CH4 is introduced to understand the competitive adsorption dynamics between H2 and CH4. The findings indicate that increasing pressure results in increasing molecules of hydrogen that monotonically increase H2 adsorption. On the contrary, increasing temperature reduces the affinity of hydrogen with the quartz surface causing a decrease in adsorption capacity and Henry coefficients. Furthermore, a weak single hydrogen adsorption layer is developed at all pressure and temperature conditions, while most of the hydrogen remains as a free gas in the pore. In addition, the hydroxyl group controls most of the adsorption of hydrogen in the hydroxylated quartz. Furthermore, the addition of water film (approximately 1 wt%) reduces the hydrogen adsorption by around 3 %. The H2 adsorption values further experience a notable decrease with the introduction of CO2 and CH4, primarily due to the establishment of a strong adsorption layer caused by the high electrostatic attraction between these gases and the quartz mineral. The study offers crucial microscopic details regarding H2 adsorption alongside CO2 and CH4 gases within hydroxylated quartz pores. These insights support efficient hydrogen geo-storage and larger-scale simulation research.