Promoting Methane Hydrate Formation for Natural Gas Storage over Chabazite Zeolites

Clathrate hydrates are emerging as a novel storage medium for safe and compact methane storage. However, their industrial-scale applicability is hindered by relatively lower gas uptake and sluggish formation kinetics. In this study, we have employed zeolites with acidic (H-Y, FAU-type) and basic (Na-X, FAU-type) surface properties as kinetic hydrate promoters (KHPs). The impact of physical parameters as pressure and the gas-to-liquid ratio has also been studied. In a combined experimental and computational study, we assessed the performance of the two types of zeolites in different concentrations and pressures for binary CH 4 -THF clathrate hydrate synthesis in 1 a non-stirred configuration. The kinetic study results showed that the acidic zeolite (H-Y) exhibited superior performance over the basic one (Na-X), reaching its optimum at 0.5 wt% zeolite, which agreed well with the DFT calculations. The methane conversion reached 94.25% at this concentration and a relatively mild pressure (6 MP). The induction time and t 90 (time to reach 90% of final gas uptake) were reduced by 35% and 31%, respectively. Our results open the door for a better understanding of the role of acidic zeolites as possible environmental benign KHPs that can help the utilization of water as a medium for green energy storage and transportation.

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“…(Si/Al ratio = 0.6) 26 . Thus, the absence of soduim cation and the higher Si/Al ratio of H-Y resulted in enhanced hydrophobicity.…”

Section: Influence Of Zeolite Kinetic Promotersmentioning

confidence: 99%

“…Other zeolites such as RHO 43 , SSZ-13 26 were also studied in the confinement approach as described above, but the methane hydrate kinetic data were not reported.…”

Section: Introductionmentioning

confidence: 99%

Revealing Zeolites Active Sites Role as Kinetic Hydrate Promoters: Combined Computational and Experimental Study

Omran

Nesterenko

Valtchev

2022

ACS Sustainable Chem. Eng.

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“…(Si/Al ratio = 0.6) 34 . Thus, the absence of sodium cation and the higher Si/Al ratio of USY-40 resulted in enhanced hydrophobicity.…”

Section: Effect Of Zeolite Promoters On Mixed Ch 4 -Thf Hydrate Forma...mentioning

confidence: 99%

“…In addition to amino acids, porous material that can act as nucleation sites that accelerate the nucleation process was employed as KHPs [33][34][35][36][37][38][39][40][41] . Among porous materials, zeolites are green materials with low cost, large surface area, tunable acidity and hydrophobicity, and above all high stability in aqueous medium 42,43 .…”

Section: Introductionmentioning

confidence: 99%

Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study

Omran

Nesterenko

Paecklar

et al. 2022

ACS Sustainable Chem. Eng.

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Clathrate hydrates are emerging as a novel storage medium for safe and compact methane storage. However, their industrial-scale applicability is hindered by sluggish formation kinetics and intense energy cooling requirements. The present study is the first report on binary methane-tetrahydrofuran (THF) formation using the combination 1 of seawater and an unstirred reactor at ambient temperature (298.2 K) that would improve the process economics. Acidic zeolites with different Si/Al ratios (USY-40 and USY-10) as well as aliphatic (L-valine) and aromatic (L-tryptophane) amino acids are employed as environmentally benign kinetic hydrate promoters. The experimental study is combined with DFT calculations to shed light on the role of kinetic promoters in hydrate formation. The set of experimental data revealed that hydrophobic zeolites with a higher Si/Al ratio performed better than the more hydrophilic ones. Moreover, the aliphatic amino acid L-valine showed better kinetic promotion performance for hydrate formation in natural and artificial seawater than the aromatic amino acid L-tryptophan.The optimization of the experimental condition allowed a controlled hydrate growth boosting the gas uptake to 40 mmol gas/mol water, which is the highest reported under mild conditions using seawater. In addition, the induction time is reduced to less than 10 minutes, and a methane recovery of 97% is reached without any foaming signs. Thus, this study demonstrates the possibility of controlling the stochastic nature of nucleation and hydrate growth by properly manipulating the reaction system. Our results provide a better understanding of hydrate nucleation enhancement under realistic conditions and open the door for a possible application of these environmentally benign kinetic hydrate promoters (KHPs) for synthetic natural gas (SGH) on a continuous process and industrial scale.

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“…In another aspect of industrial applications, hydrate formation needs to be hindered in the subsea oil-gas pipelines while promoted to efficiently store and transport gases under milder conditions. To achieve these targets, several thermodynamic inhibitors, antiagglomerates, and promoters have been proposed. − One of these types is NPs. − Solid NPs have been utilized to stabilize emulsions, the so-called Pickering emulsions, and thus to disperse gas hydrates in slurry flow to prevent gas hydrate agglomeration . At the same time, it is known that heterogeneous nucleation is generally more likely to occur than homogeneous nucleation, which means that NPs in solution might induce more rapid nucleation of gas hydrates.…”

Section: Introductionmentioning

confidence: 99%

Molecular Insights into the Impacts of Calcite Nanoparticles on Methane Hydrate Formation

Zhang

Kusalik

et al. 2022

ACS Sustainable Chem. Eng.

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Despite the potential broad utility of nanoparticles in hydrate-related fields, there remains a paucity of studies on the impacts of nanoparticles on gas hydrate formation. In this study, massive microsecond molecular dynamics simulations were performed to investigate the roles of calcite nanoparticles on the formation processes of methane hydrate. Our results indicate that calcite nanoparticles prefer to be in the water phase close to the water/gas interface. They inhibit methane hydrate nucleation because a layer of bound water with a thickness of 0.75 nm forms around each nanoparticle which results in an extremely low methane concentration region. Thus, methane hydrate nucleates away from the nanoparticle, and no clear connection between the nucleated hydrate and the nanoparticle is observed. The nanoparticles associate easily, and a water layer with a thickness of 1.15 nm forms between the associated nanoparticles. Moreover, methane hydrate growth is not influenced by calcite nanoparticles until the growth front approaches the bound water around the nanoparticle. These molecular insights of the impacts of calcite nanoparticles on methane hydrate formation are beneficial for the application of nanoparticles in hydrate mining and hydrate-related technologies.

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Promoting Methane Hydrate Formation for Natural Gas Storage over Chabazite Zeolites

Cited by 23 publications

References 27 publications

Revealing Zeolites Active Sites Role as Kinetic Hydrate Promoters: Combined Computational and Experimental Study

Revealing Zeolites Active Sites Role as Kinetic Hydrate Promoters: Combined Computational and Experimental Study

Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study

Molecular Insights into the Impacts of Calcite Nanoparticles on Methane Hydrate Formation

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