Energy & Fuels, Vol.35, No.2, 1080-1089, 2021
Mixed CO2+CH4 Hydrate Formation Kinetics: Experimental Study and Modeling
Multifaceted benefits of natural gas as the cleanest fossil fuel resulted in significant shift from other forms of fossil fuels to natural gas in different sectors over the past years. Applying natural gas as the medium-term future energy source is an effective climate strategy. Recently, gas hydrate gained significant attention as a solution for purification and storage of natural gas. Additionally, naturally occurring methane hydrate deposits as the most abundant unconventional natural gas source can secure the global energy demand for decades. Macroscopic kinetic study and modeling of mixed CO2+CH4 hydrate formation is necessary for commercialization of SNG technology as an applicable method for hydrate-based transportation of natural gas, hydrate-based biogas upgrading, and CH4-CO2 hydrate replacement process for exploitation of naturally occurring methane hydrate reservoirs. Here, the results for CO2+CH4 mixed hydrate formation experiments are reported over a wide range of operational conditions to investigate the kinetics of hydrate formation. The mass transfer limited hydrate formation kinetic approach was applied to model the kinetics of mixed CO2+CH4 hydrate formation. Investigation of the effect of operational conditions revealed that the rate of mixed CO2+CH4 hydrate formation is increased at higher pressures and higher mole fractions of CO2 in the gas phase. At a constant degree of supersaturation, the mixed hydrate formation rate initially decreases by temperature, goes from a minimum around 277 K, and then increases by temperature. Kinetic parameters extracted from the kinetic modeling correlated as functions of pressure, temperature, and gas phase composition.