Structure I methane hydrate confined in C8-grafted SBA-15: A highly efficient storage system enabling ultrafast methane loading and unloading

Emile Jules Beckwée; Maarten Houlleberghs; Radu George Ciocarlan; C. Vinod Chandran; Sambhu Radhakrishnan; Lucas Hanssens; Pegie Cool; Johan Martens; Eric Breynaert; Gino V. Baron; Joeri F.M. Denayer

doi:10.1016/j.apenergy.2023.122120

Structure I methane hydrate confined in C₈-grafted SBA-15: A highly efficient storage system enabling ultrafast methane loading and unloading

Emile Jules Beckwée, Maarten Houlleberghs, Radu George Ciocarlan, C. Vinod Chandran, Sambhu Radhakrishnan, Lucas Hanssens, Pegie Cool, Johan Martens, Eric Breynaert, Gino V. Baron, Joeri F.M. Denayer

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Abstract

Confinement of water and methane in mesopores of hydrophobized SBA-15 is demonstrated to promote methane hydrate formation. In comparison to as-synthesized SBA-15, hydrophobization by C₈ grafting accelerates the kinetics of methane storage in and delivery from the hydrate. C₈ grafting density was determined at 0.5 groups nm⁻² based on TGA and quantitative NMR spectroscopy. Multinuclear ¹H-¹H DQSQ and ¹H-¹H RFDR NMR provided spectroscopic evidence for the occurrence of C₈ chains inside the mesopores of SBA-15, by showcasing close spatial proximity between the grafted C₈ chains and pore-intruded water species. X-ray diffraction demonstrates formation of Structure I hydrate on SBA-15 C₈. At 7.0 MPa and 248 K, the water-to-hydrate conversion on hydrophobized SBA-15 C₈ reaches 96% as compared to only 71% on a pristine SBA-15 sample with comparable pore size, pore volume and surface area. The clathrate loading amounted to 14.8 g/g. 2D correlation NMR spectroscopy (¹H-¹³C CP-HETCOR, ¹H-¹H RFDR) reveals hydrate formation occurs within pores of SBA-15 C₈ as well as in interparticle volumes. Following the initial crystallization of SBA-15 C₈-supported methane hydrate taking several hours, a pressure swing process at 248 K allows to desorb and re-adsorb methane from the structure within minutes and without thawing the frozen water structure. Fast loading and unloading of methane was achieved in 19 subsequent cycles without losses in kinetics. The ability to harvest the gas and regenerate the structure without the need to re-freeze the water represents a 50% energy gain with respect to melting and subsequently recrystallizing the hydrate at 298 K and 248 K, respectively. After methane desorption, a small amount of residual methane hydrate in combination with an amorphous yet locally ordered ice phase is observed using ¹³C and ²H NMR spectroscopy. This effect offers an explanation for the enhanced hydrate formation kinetics in adsorption-desorption cycles. These findings open new perspectives for clathrate hydrate-based methane storage.

Original language	English
Article number	122120
Pages (from-to)	1-33
Number of pages	33
Journal	Applied Energy
Volume	353
DOIs	https://doi.org/10.1016/j.apenergy.2023.122120
Publication status	Published - 1 Jan 2024

Bibliographical note

Funding Information:
M.H. acknowledges FWO for an FWO-SB fellowship. All authors acknowledge VLAIO for Moonshot funding (ARCLATH, n° HBC.2019.0110, ARCLATH2, n° HBC.2021.0254). J.A.M. acknowledges the Flemish Government for long-term structural funding (Methusalem) and Department EWI for Infrastructure Investment via the Hermes Fund (AH.2016.134). NMRCoRe thanks the Flemish government for financial support as International Research Infrastructure (I001321N: Nuclear Magnetic Resonance Spectroscopy Platform for Molecular Water Research) and acknowledges infrastructure funding from the Department EWI via the Hermes Fund (AH.2016.134). J.A.M. acknowledges the European Research Council (ERC) for an Advanced Research Grant under the European Union's Horizon 2020 Research and Innovation Program under grant agreement No. 834134 (WATUSO).

Funding Information:
M.H. acknowledges FWO for an FWO-SB fellowship. All authors acknowledge VLAIO for Moonshot funding ( ARCLATH , n° HBC.2019.0110 , ARCLATH2 , n° HBC.2021.0254 ). J.A.M. acknowledges the Flemish Government for long-term structural funding (Methusalem) and Department EWI for Infrastructure Investment via the Hermes Fund ( AH.2016.134 ). NMRCoRe thanks the Flemish government for financial support as International Research Infrastructure (I001321N: Nuclear Magnetic Resonance Spectroscopy Platform for Molecular Water Research ) and acknowledges infrastructure funding from the Department EWI via the Hermes Fund ( AH.2016.134 ). J.A.M. acknowledges the European Research Council (ERC) for an Advanced Research Grant under the European Union's Horizon 2020 Research and Innovation Program under grant agreement No. 834134 ( WATUSO ).

Publisher Copyright:
© 2023 Elsevier Ltd

Keywords

Clathrate hydrate
Ice
Kinetics
Methane hydrate
NMR
SBA-15

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10.1016/j.apenergy.2023.122120

Manuscript SBA-15 C8 - 230926Accepted author manuscript, 1.25 MBLicence: CC BY-NC-ND

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Beckwée, E. J., Houlleberghs, M., Ciocarlan, R. G., Chandran, C. V., Radhakrishnan, S., Hanssens, L., Cool, P., Martens, J., Breynaert, E., Baron, G. V., & Denayer, J. F. M. (2024). Structure I methane hydrate confined in C₈-grafted SBA-15: A highly efficient storage system enabling ultrafast methane loading and unloading. Applied Energy, 353, 1-33. Article 122120. https://doi.org/10.1016/j.apenergy.2023.122120

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title = "Structure I methane hydrate confined in C8-grafted SBA-15: A highly efficient storage system enabling ultrafast methane loading and unloading",

abstract = "Confinement of water and methane in mesopores of hydrophobized SBA-15 is demonstrated to promote methane hydrate formation. In comparison to as-synthesized SBA-15, hydrophobization by C8 grafting accelerates the kinetics of methane storage in and delivery from the hydrate. C8 grafting density was determined at 0.5 groups nm−2 based on TGA and quantitative NMR spectroscopy. Multinuclear 1H-1H DQSQ and 1H-1H RFDR NMR provided spectroscopic evidence for the occurrence of C8 chains inside the mesopores of SBA-15, by showcasing close spatial proximity between the grafted C8 chains and pore-intruded water species. X-ray diffraction demonstrates formation of Structure I hydrate on SBA-15 C8. At 7.0 MPa and 248 K, the water-to-hydrate conversion on hydrophobized SBA-15 C8 reaches 96% as compared to only 71% on a pristine SBA-15 sample with comparable pore size, pore volume and surface area. The clathrate loading amounted to 14.8 g/g. 2D correlation NMR spectroscopy (1H-13C CP-HETCOR, 1H-1H RFDR) reveals hydrate formation occurs within pores of SBA-15 C8 as well as in interparticle volumes. Following the initial crystallization of SBA-15 C8-supported methane hydrate taking several hours, a pressure swing process at 248 K allows to desorb and re-adsorb methane from the structure within minutes and without thawing the frozen water structure. Fast loading and unloading of methane was achieved in 19 subsequent cycles without losses in kinetics. The ability to harvest the gas and regenerate the structure without the need to re-freeze the water represents a 50% energy gain with respect to melting and subsequently recrystallizing the hydrate at 298 K and 248 K, respectively. After methane desorption, a small amount of residual methane hydrate in combination with an amorphous yet locally ordered ice phase is observed using 13C and 2H NMR spectroscopy. This effect offers an explanation for the enhanced hydrate formation kinetics in adsorption-desorption cycles. These findings open new perspectives for clathrate hydrate-based methane storage.",

keywords = "Clathrate hydrate, Ice, Kinetics, Methane hydrate, NMR, SBA-15",

author = "Beckw{\'e}e, {Emile Jules} and Maarten Houlleberghs and Ciocarlan, {Radu George} and Chandran, {C. Vinod} and Sambhu Radhakrishnan and Lucas Hanssens and Pegie Cool and Johan Martens and Eric Breynaert and Baron, {Gino V.} and Denayer, {Joeri F.M.}",

note = "Funding Information: M.H. acknowledges FWO for an FWO-SB fellowship. All authors acknowledge VLAIO for Moonshot funding (ARCLATH, n° HBC.2019.0110, ARCLATH2, n° HBC.2021.0254). J.A.M. acknowledges the Flemish Government for long-term structural funding (Methusalem) and Department EWI for Infrastructure Investment via the Hermes Fund (AH.2016.134). NMRCoRe thanks the Flemish government for financial support as International Research Infrastructure (I001321N: Nuclear Magnetic Resonance Spectroscopy Platform for Molecular Water Research) and acknowledges infrastructure funding from the Department EWI via the Hermes Fund (AH.2016.134). J.A.M. acknowledges the European Research Council (ERC) for an Advanced Research Grant under the European Union's Horizon 2020 Research and Innovation Program under grant agreement No. 834134 (WATUSO). Funding Information: M.H. acknowledges FWO for an FWO-SB fellowship. All authors acknowledge VLAIO for Moonshot funding ( ARCLATH , n° HBC.2019.0110 , ARCLATH2 , n° HBC.2021.0254 ). J.A.M. acknowledges the Flemish Government for long-term structural funding (Methusalem) and Department EWI for Infrastructure Investment via the Hermes Fund ( AH.2016.134 ). NMRCoRe thanks the Flemish government for financial support as International Research Infrastructure (I001321N: Nuclear Magnetic Resonance Spectroscopy Platform for Molecular Water Research ) and acknowledges infrastructure funding from the Department EWI via the Hermes Fund ( AH.2016.134 ). J.A.M. acknowledges the European Research Council (ERC) for an Advanced Research Grant under the European Union's Horizon 2020 Research and Innovation Program under grant agreement No. 834134 ( WATUSO ). Publisher Copyright: {\textcopyright} 2023 Elsevier Ltd",

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doi = "10.1016/j.apenergy.2023.122120",

language = "English",

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Beckwée, EJ, Houlleberghs, M, Ciocarlan, RG, Chandran, CV, Radhakrishnan, S, Hanssens, L, Cool, P, Martens, J, Breynaert, E, Baron, GV & Denayer, JFM 2024, 'Structure I methane hydrate confined in C₈-grafted SBA-15: A highly efficient storage system enabling ultrafast methane loading and unloading', Applied Energy, vol. 353, 122120, pp. 1-33. https://doi.org/10.1016/j.apenergy.2023.122120

TY - JOUR

T1 - Structure I methane hydrate confined in C8-grafted SBA-15

T2 - A highly efficient storage system enabling ultrafast methane loading and unloading

AU - Beckwée, Emile Jules

AU - Houlleberghs, Maarten

AU - Ciocarlan, Radu George

AU - Chandran, C. Vinod

AU - Radhakrishnan, Sambhu

AU - Hanssens, Lucas

AU - Cool, Pegie

AU - Martens, Johan

AU - Breynaert, Eric

AU - Baron, Gino V.

AU - Denayer, Joeri F.M.

N1 - Funding Information: M.H. acknowledges FWO for an FWO-SB fellowship. All authors acknowledge VLAIO for Moonshot funding (ARCLATH, n° HBC.2019.0110, ARCLATH2, n° HBC.2021.0254). J.A.M. acknowledges the Flemish Government for long-term structural funding (Methusalem) and Department EWI for Infrastructure Investment via the Hermes Fund (AH.2016.134). NMRCoRe thanks the Flemish government for financial support as International Research Infrastructure (I001321N: Nuclear Magnetic Resonance Spectroscopy Platform for Molecular Water Research) and acknowledges infrastructure funding from the Department EWI via the Hermes Fund (AH.2016.134). J.A.M. acknowledges the European Research Council (ERC) for an Advanced Research Grant under the European Union's Horizon 2020 Research and Innovation Program under grant agreement No. 834134 (WATUSO). Funding Information: M.H. acknowledges FWO for an FWO-SB fellowship. All authors acknowledge VLAIO for Moonshot funding ( ARCLATH , n° HBC.2019.0110 , ARCLATH2 , n° HBC.2021.0254 ). J.A.M. acknowledges the Flemish Government for long-term structural funding (Methusalem) and Department EWI for Infrastructure Investment via the Hermes Fund ( AH.2016.134 ). NMRCoRe thanks the Flemish government for financial support as International Research Infrastructure (I001321N: Nuclear Magnetic Resonance Spectroscopy Platform for Molecular Water Research ) and acknowledges infrastructure funding from the Department EWI via the Hermes Fund ( AH.2016.134 ). J.A.M. acknowledges the European Research Council (ERC) for an Advanced Research Grant under the European Union's Horizon 2020 Research and Innovation Program under grant agreement No. 834134 ( WATUSO ). Publisher Copyright: © 2023 Elsevier Ltd

PY - 2024/1/1

Y1 - 2024/1/1

N2 - Confinement of water and methane in mesopores of hydrophobized SBA-15 is demonstrated to promote methane hydrate formation. In comparison to as-synthesized SBA-15, hydrophobization by C8 grafting accelerates the kinetics of methane storage in and delivery from the hydrate. C8 grafting density was determined at 0.5 groups nm−2 based on TGA and quantitative NMR spectroscopy. Multinuclear 1H-1H DQSQ and 1H-1H RFDR NMR provided spectroscopic evidence for the occurrence of C8 chains inside the mesopores of SBA-15, by showcasing close spatial proximity between the grafted C8 chains and pore-intruded water species. X-ray diffraction demonstrates formation of Structure I hydrate on SBA-15 C8. At 7.0 MPa and 248 K, the water-to-hydrate conversion on hydrophobized SBA-15 C8 reaches 96% as compared to only 71% on a pristine SBA-15 sample with comparable pore size, pore volume and surface area. The clathrate loading amounted to 14.8 g/g. 2D correlation NMR spectroscopy (1H-13C CP-HETCOR, 1H-1H RFDR) reveals hydrate formation occurs within pores of SBA-15 C8 as well as in interparticle volumes. Following the initial crystallization of SBA-15 C8-supported methane hydrate taking several hours, a pressure swing process at 248 K allows to desorb and re-adsorb methane from the structure within minutes and without thawing the frozen water structure. Fast loading and unloading of methane was achieved in 19 subsequent cycles without losses in kinetics. The ability to harvest the gas and regenerate the structure without the need to re-freeze the water represents a 50% energy gain with respect to melting and subsequently recrystallizing the hydrate at 298 K and 248 K, respectively. After methane desorption, a small amount of residual methane hydrate in combination with an amorphous yet locally ordered ice phase is observed using 13C and 2H NMR spectroscopy. This effect offers an explanation for the enhanced hydrate formation kinetics in adsorption-desorption cycles. These findings open new perspectives for clathrate hydrate-based methane storage.

AB - Confinement of water and methane in mesopores of hydrophobized SBA-15 is demonstrated to promote methane hydrate formation. In comparison to as-synthesized SBA-15, hydrophobization by C8 grafting accelerates the kinetics of methane storage in and delivery from the hydrate. C8 grafting density was determined at 0.5 groups nm−2 based on TGA and quantitative NMR spectroscopy. Multinuclear 1H-1H DQSQ and 1H-1H RFDR NMR provided spectroscopic evidence for the occurrence of C8 chains inside the mesopores of SBA-15, by showcasing close spatial proximity between the grafted C8 chains and pore-intruded water species. X-ray diffraction demonstrates formation of Structure I hydrate on SBA-15 C8. At 7.0 MPa and 248 K, the water-to-hydrate conversion on hydrophobized SBA-15 C8 reaches 96% as compared to only 71% on a pristine SBA-15 sample with comparable pore size, pore volume and surface area. The clathrate loading amounted to 14.8 g/g. 2D correlation NMR spectroscopy (1H-13C CP-HETCOR, 1H-1H RFDR) reveals hydrate formation occurs within pores of SBA-15 C8 as well as in interparticle volumes. Following the initial crystallization of SBA-15 C8-supported methane hydrate taking several hours, a pressure swing process at 248 K allows to desorb and re-adsorb methane from the structure within minutes and without thawing the frozen water structure. Fast loading and unloading of methane was achieved in 19 subsequent cycles without losses in kinetics. The ability to harvest the gas and regenerate the structure without the need to re-freeze the water represents a 50% energy gain with respect to melting and subsequently recrystallizing the hydrate at 298 K and 248 K, respectively. After methane desorption, a small amount of residual methane hydrate in combination with an amorphous yet locally ordered ice phase is observed using 13C and 2H NMR spectroscopy. This effect offers an explanation for the enhanced hydrate formation kinetics in adsorption-desorption cycles. These findings open new perspectives for clathrate hydrate-based methane storage.

KW - Clathrate hydrate

KW - Ice

KW - Kinetics

KW - Methane hydrate

KW - NMR

KW - SBA-15

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DO - 10.1016/j.apenergy.2023.122120

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M1 - 122120

ER -

Structure I methane hydrate confined in C₈-grafted SBA-15: A highly efficient storage system enabling ultrafast methane loading and unloading

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Structure I methane hydrate confined in C8-grafted SBA-15: A highly efficient storage system enabling ultrafast methane loading and unloading

Abstract

Bibliographical note

Keywords

Access to Document

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SRP70: SRP-Onderzoekszwaartepunt: Sustainable chemical technology using multifunctional structured materials

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Structure I methane hydrate confined in C₈-grafted SBA-15: A highly efficient storage system enabling ultrafast methane loading and unloading