Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study
International audience 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 met...
Published in: | ACS Sustainable Chemistry & Engineering |
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Main Authors: | , , , , |
Other Authors: | , , , , , , , , , , , , |
Format: | Article in Journal/Newspaper |
Language: | English |
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HAL CCSD
2022
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Online Access: | https://hal.science/hal-03772161 https://hal.science/hal-03772161/document https://hal.science/hal-03772161/file/manuscript_F.pdf https://doi.org/10.1021/acssuschemeng.2c03530 |
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HAL-CEA (Commissariat à l'énergie atomique et aux énergies alternatives) |
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language |
English |
topic |
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry [CHIM.GENI]Chemical Sciences/Chemical engineering [SPI.MAT]Engineering Sciences [physics]/Materials [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering |
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[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry [CHIM.GENI]Chemical Sciences/Chemical engineering [SPI.MAT]Engineering Sciences [physics]/Materials [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering Omran, Ahmed Nesterenko, Nikolay Paecklar, Arnold, A Barrier, Nicolas Valtchev, Valentin Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study |
topic_facet |
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry [CHIM.GENI]Chemical Sciences/Chemical engineering [SPI.MAT]Engineering Sciences [physics]/Materials [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering |
description |
International audience 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 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 and aromatic amino acids (L-valine and L-tryptophane) 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 hydrates 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 conditions 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 proper manipulation of 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 KHPs for synthetic natural gas (SGH) on a continuous process and industrial scale. |
author2 |
École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN) Normandie Université (NU) Laboratoire catalyse et spectrochimie (LCS) Université de Caen Normandie (UNICAEN) Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN) Normandie Université (NU)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) TotalEnergies OneTech Belgium Laboratoire de cristallographie et sciences des matériaux (CRISMAT) Normandie Université (NU)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA) Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN) Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie) Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN) Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS) |
format |
Article in Journal/Newspaper |
author |
Omran, Ahmed Nesterenko, Nikolay Paecklar, Arnold, A Barrier, Nicolas Valtchev, Valentin |
author_facet |
Omran, Ahmed Nesterenko, Nikolay Paecklar, Arnold, A Barrier, Nicolas Valtchev, Valentin |
author_sort |
Omran, Ahmed |
title |
Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study |
title_short |
Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study |
title_full |
Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study |
title_fullStr |
Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study |
title_full_unstemmed |
Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study |
title_sort |
toward economical seawater-based methane hydrate formation at ambient temperature: a combined experimental and computational study |
publisher |
HAL CCSD |
publishDate |
2022 |
url |
https://hal.science/hal-03772161 https://hal.science/hal-03772161/document https://hal.science/hal-03772161/file/manuscript_F.pdf https://doi.org/10.1021/acssuschemeng.2c03530 |
genre |
Methane hydrate |
genre_facet |
Methane hydrate |
op_source |
EISSN: 2168-0485 ACS Sustainable Chemistry & Engineering https://hal.science/hal-03772161 ACS Sustainable Chemistry & Engineering, 2022, 10 (35), pp.11617-11626. ⟨10.1021/acssuschemeng.2c03530⟩ |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1021/acssuschemeng.2c03530 hal-03772161 https://hal.science/hal-03772161 https://hal.science/hal-03772161/document https://hal.science/hal-03772161/file/manuscript_F.pdf doi:10.1021/acssuschemeng.2c03530 |
op_rights |
info:eu-repo/semantics/OpenAccess |
op_doi |
https://doi.org/10.1021/acssuschemeng.2c03530 |
container_title |
ACS Sustainable Chemistry & Engineering |
container_volume |
10 |
container_issue |
35 |
container_start_page |
11617 |
op_container_end_page |
11626 |
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1810456784940302336 |
spelling |
ftceafr:oai:HAL:hal-03772161v1 2024-09-15T18:18:42+00:00 Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study Omran, Ahmed Nesterenko, Nikolay Paecklar, Arnold, A Barrier, Nicolas Valtchev, Valentin École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN) Normandie Université (NU) Laboratoire catalyse et spectrochimie (LCS) Université de Caen Normandie (UNICAEN) Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN) Normandie Université (NU)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) TotalEnergies OneTech Belgium Laboratoire de cristallographie et sciences des matériaux (CRISMAT) Normandie Université (NU)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA) Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN) Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie) Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN) Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS) 2022 https://hal.science/hal-03772161 https://hal.science/hal-03772161/document https://hal.science/hal-03772161/file/manuscript_F.pdf https://doi.org/10.1021/acssuschemeng.2c03530 en eng HAL CCSD American Chemical Society info:eu-repo/semantics/altIdentifier/doi/10.1021/acssuschemeng.2c03530 hal-03772161 https://hal.science/hal-03772161 https://hal.science/hal-03772161/document https://hal.science/hal-03772161/file/manuscript_F.pdf doi:10.1021/acssuschemeng.2c03530 info:eu-repo/semantics/OpenAccess EISSN: 2168-0485 ACS Sustainable Chemistry & Engineering https://hal.science/hal-03772161 ACS Sustainable Chemistry & Engineering, 2022, 10 (35), pp.11617-11626. ⟨10.1021/acssuschemeng.2c03530⟩ [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry [CHIM.GENI]Chemical Sciences/Chemical engineering [SPI.MAT]Engineering Sciences [physics]/Materials [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering info:eu-repo/semantics/article Journal articles 2022 ftceafr https://doi.org/10.1021/acssuschemeng.2c03530 2024-07-22T13:10:06Z International audience 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 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 and aromatic amino acids (L-valine and L-tryptophane) 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 hydrates 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 conditions 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 proper manipulation of 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 KHPs for synthetic natural gas (SGH) on a continuous process and industrial scale. Article in Journal/Newspaper Methane hydrate HAL-CEA (Commissariat à l'énergie atomique et aux énergies alternatives) ACS Sustainable Chemistry & Engineering 10 35 11617 11626 |