Methane and Carbon Dioxide Separation Characteristics of Quaternary Ammonium Salt Hydrates for Biogas Upgrading under Static Conditions of Gas–Solid Contact

Abstract

This report describes the methane and carbon dioxide separation characteristics of stoichiometric quaternary ammonium salt (QAS) hydrates for gas–solid contact with simulated biogas (CH4, 0.613 mol fraction; CO2, 0.387 mol fraction). Tests for elucidating the separation characteristics were conducted using tetra-n-butylammonium fluoride (TBAF), tetra-n-butylammonium chloride (TBAC), and tetra-n-butylammonium bromide (TBAB) hydrates as solid phases. To ascertain system temperature and pressure effects on their gas separation performance, the tests were conducted at 253–293 K under the initial fed pressures of 3.0 and 0.9 MPa. The gas–solid contact between the simulated biogas with 0.387 mol fraction of CO2 and the QAS hydrates reduced CO2 in the gas phase to 0.26–0.37 mol fraction and enriched CO2 in the hydrate phases to 0.54–0.89 mol fraction. All QAS hydrates showed selective incorporation of carbon dioxide into the hydrate phase. Under all comparable conditions, TBAC hydrate exhibited the highest separation factor (15.2 ± 3.0 under initial pressure of 3.0 MPa at 253 K and 13.9 ± 2.5 under initial pressure of 0.9 MPa at 253 K), indicating that TBAC hydrate had the highest CO2 separation performance for biogas upgrading among the QAS hydrates we examined. At the same initial pressure, high gas separation performance was shown for low-temperature ranges. The separation factors of the QAS hydrates were maintained or improved by lowering the initial pressure at the same contact temperature, suggesting that the separation performance of the QAS hydrates, even at lower pressures, was nearly equal to or better than that achieved at higher pressures. The results contrasted against those reported for tetrahydrofuran hydrate, for which the separation factor decreases with lower initial pressure. The use of the QAS hydrates is expected to lower a system’s operating pressure without compromising separation performance.