Molecular dynamics study on growth of carbon dioxide and methane hydrate from a seed crystal

doi:10.1016/j.cjche.2019.02.006

Abstract

Abstract: In the current work, molecular dynamics simulation is employed to understand the intrinsic growth of carbon dioxide and methane hydrate starting from a seed crystal of methane and carbon dioxide respectively. This comparison was carried out because it has relevance to the recovery of methane gas from natural gas hydrate reservoirs by simultaneously sequestering a greenhouse gas like CO₂. The seed crystal of carbon dioxide and methane hydrate was allowed to grow from a super-saturated mixture of carbon dioxide or methane molecules in water respectively. Two different concentrations (1:6 and 1:8.5) of CO₂/CH₄ molecules per water molecule were chosen based on gas-water composition in hydrate phase. The molecular level growth as a function of time was investigated by all atomistic molecular dynamics simulation under suitable temperature and pressure range which was well above the hydrate stability zone to ensure significantly faster growth kinetics. The concentration of CO₂ molecules in water played a significant role in growth kinetics, and it was observed that maximizing the CO₂ concentration in the aqueous phase may not result in faster growth of CO₂ hydrate. On the contrary, methane hydrate growth was independent of methane molecule concentration in the aqueous phase. We have validated our results by performing experimental work on carbon dioxide hydrate where it was seen that under conditions appropriate for liquid CO₂, the growth for carbon dioxide hydrate was very slow in the beginning.

Key words: CH₄ recovery, Natural gas hydrate, CO₂ sequestration, Kinetics, F₄ order parameter, Cage dynamics, Thermodynamics

摘要： In the current work, molecular dynamics simulation is employed to understand the intrinsic growth of carbon dioxide and methane hydrate starting from a seed crystal of methane and carbon dioxide respectively. This comparison was carried out because it has relevance to the recovery of methane gas from natural gas hydrate reservoirs by simultaneously sequestering a greenhouse gas like CO₂. The seed crystal of carbon dioxide and methane hydrate was allowed to grow from a super-saturated mixture of carbon dioxide or methane molecules in water respectively. Two different concentrations (1:6 and 1:8.5) of CO₂/CH₄ molecules per water molecule were chosen based on gas-water composition in hydrate phase. The molecular level growth as a function of time was investigated by all atomistic molecular dynamics simulation under suitable temperature and pressure range which was well above the hydrate stability zone to ensure significantly faster growth kinetics. The concentration of CO₂ molecules in water played a significant role in growth kinetics, and it was observed that maximizing the CO₂ concentration in the aqueous phase may not result in faster growth of CO₂ hydrate. On the contrary, methane hydrate growth was independent of methane molecule concentration in the aqueous phase. We have validated our results by performing experimental work on carbon dioxide hydrate where it was seen that under conditions appropriate for liquid CO₂, the growth for carbon dioxide hydrate was very slow in the beginning.

关键词: CH₄ recovery, Natural gas hydrate, CO₂ sequestration, Kinetics, F₄ order parameter, Cage dynamics, Thermodynamics

Prajakta Nakate, Bappa Ghosh, Subhadip Das, Sudip Roy, Rajnish Kumar. Molecular dynamics study on growth of carbon dioxide and methane hydrate from a seed crystal[J]. Chinese Journal of Chemical Engineering, 2019, 27(9): 2074-2080.

Prajakta Nakate, Bappa Ghosh, Subhadip Das, Sudip Roy, Rajnish Kumar. Molecular dynamics study on growth of carbon dioxide and methane hydrate from a seed crystal[J]. 中国化学工程学报, 2019, 27(9): 2074-2080.

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