Overcoming chemical equilibrium limitations using a thermodynamically reversible chemical reactor

Ian S.  Metcalfe; Brian Ray; Catherine  Dejoie; Wenting Hu; Christopher  de Leeuwe; Cristina  Dueso; Francisco Rafael Garcia Garcia; Cheuk-Man Mak; Evangelos I.  Papaioannou; Claire R.  Thompson; John S. O. Evans

doi:https://doi.org/10.1038/s41557-019-0273-2

Overcoming chemical equilibrium limitations using a thermodynamically reversible chemical reactor

Ian S. Metcalfe, Brian Ray, Catherine Dejoie, Wenting Hu, Christopher de Leeuwe, Cristina Dueso, Francisco Rafael Garcia Garcia, Cheuk-Man Mak, Evangelos I. Papaioannou, Claire R. Thompson, John S. O. Evans

School of Engineering

Research output: Contribution to specialist publication › Article

Abstract / Description of output

All real processes, be they chemical, mechanical or electrical, are thermodynamically irreversible and therefore suffer from thermodynamic losses. Here, we report the design and operation of a chemical reactor capable of approaching thermodynamically reversible operation. The reactor was employed for hydrogen production via the water–gas shift reaction, an important
route to ‘green’ hydrogen. The reactor avoids mixing reactant gases by transferring oxygen from the (oxidizing) water stream to the (reducing) carbon monoxide stream via a solid-state oxygen reservoir consisting of a perovskite phase (La0.6Sr0.4FeO3-δ). This reservoir is able to remain close to equilibrium with the reacting gas streams because of its variable degree of non-stoichiometry and thus develops a ‘chemical memory’ that we employ to approach reversibility. We demonstrate this memory using
operando, spatially resolved, real-time, high-resolution X-ray powder diffraction on a working reactor. The design leads to a reactor unconstrained by overall chemical equilibrium limitations, which can produce essentially pure hydrogen and carbon dioxide as separate product streams.

Original language	English
Pages	638–643
Volume	11
Specialist publication	Nature Chemistry
DOIs	https://doi.org/10.1038/s41557-019-0273-2 https://doi.org/10.1038/s41557-019-0273-2
Publication status	Published - 27 May 2019

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Metcalfe, I. S., Ray, B., Dejoie, C., Hu, W., de Leeuwe, C., Dueso, C., Garcia Garcia, F. R., Mak, C.-M., Papaioannou, E. I., Thompson, C. R., & Evans, J. S. O. (2019). Overcoming chemical equilibrium limitations using a thermodynamically reversible chemical reactor. Nature Chemistry, 11, 638–643. https://doi.org/10.1038/s41557-019-0273-2, https://doi.org/10.1038/s41557-019-0273-2

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title = "Overcoming chemical equilibrium limitations using a thermodynamically reversible chemical reactor",

abstract = "All real processes, be they chemical, mechanical or electrical, are thermodynamically irreversible and therefore suffer from thermodynamic losses. Here, we report the design and operation of a chemical reactor capable of approaching thermodynamically reversible operation. The reactor was employed for hydrogen production via the water–gas shift reaction, an importantroute to {\textquoteleft}green{\textquoteright} hydrogen. The reactor avoids mixing reactant gases by transferring oxygen from the (oxidizing) water stream to the (reducing) carbon monoxide stream via a solid-state oxygen reservoir consisting of a perovskite phase (La0.6Sr0.4FeO3-δ). This reservoir is able to remain close to equilibrium with the reacting gas streams because of its variable degree of non-stoichiometry and thus develops a {\textquoteleft}chemical memory{\textquoteright} that we employ to approach reversibility. We demonstrate this memory usingoperando, spatially resolved, real-time, high-resolution X-ray powder diffraction on a working reactor. The design leads to a reactor unconstrained by overall chemical equilibrium limitations, which can produce essentially pure hydrogen and carbon dioxide as separate product streams.",

author = "Metcalfe, {Ian S.} and Brian Ray and Catherine Dejoie and Wenting Hu and {de Leeuwe}, Christopher and Cristina Dueso and {Garcia Garcia}, {Francisco Rafael} and Cheuk-Man Mak and Papaioannou, {Evangelos I.} and Thompson, {Claire R.} and Evans, {John S. O.}",

year = "2019",

month = may,

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doi = "https://doi.org/10.1038/s41557-019-0273-2",

language = "English",

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Metcalfe, IS, Ray, B, Dejoie, C, Hu, W, de Leeuwe, C, Dueso, C, Garcia Garcia, FR, Mak, C-M, Papaioannou, EI, Thompson, CR & Evans, JSO 2019, 'Overcoming chemical equilibrium limitations using a thermodynamically reversible chemical reactor' Nature Chemistry, vol. 11, pp. 638–643. https://doi.org/10.1038/s41557-019-0273-2, https://doi.org/10.1038/s41557-019-0273-2

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T1 - Overcoming chemical equilibrium limitations using a thermodynamically reversible chemical reactor

AU - Metcalfe, Ian S.

AU - Ray, Brian

AU - Dejoie, Catherine

AU - Hu, Wenting

AU - de Leeuwe, Christopher

AU - Dueso, Cristina

AU - Garcia Garcia, Francisco Rafael

AU - Mak, Cheuk-Man

AU - Papaioannou, Evangelos I.

AU - Thompson, Claire R.

AU - Evans, John S. O.

PY - 2019/5/27

Y1 - 2019/5/27

N2 - All real processes, be they chemical, mechanical or electrical, are thermodynamically irreversible and therefore suffer from thermodynamic losses. Here, we report the design and operation of a chemical reactor capable of approaching thermodynamically reversible operation. The reactor was employed for hydrogen production via the water–gas shift reaction, an importantroute to ‘green’ hydrogen. The reactor avoids mixing reactant gases by transferring oxygen from the (oxidizing) water stream to the (reducing) carbon monoxide stream via a solid-state oxygen reservoir consisting of a perovskite phase (La0.6Sr0.4FeO3-δ). This reservoir is able to remain close to equilibrium with the reacting gas streams because of its variable degree of non-stoichiometry and thus develops a ‘chemical memory’ that we employ to approach reversibility. We demonstrate this memory usingoperando, spatially resolved, real-time, high-resolution X-ray powder diffraction on a working reactor. The design leads to a reactor unconstrained by overall chemical equilibrium limitations, which can produce essentially pure hydrogen and carbon dioxide as separate product streams.

AB - All real processes, be they chemical, mechanical or electrical, are thermodynamically irreversible and therefore suffer from thermodynamic losses. Here, we report the design and operation of a chemical reactor capable of approaching thermodynamically reversible operation. The reactor was employed for hydrogen production via the water–gas shift reaction, an importantroute to ‘green’ hydrogen. The reactor avoids mixing reactant gases by transferring oxygen from the (oxidizing) water stream to the (reducing) carbon monoxide stream via a solid-state oxygen reservoir consisting of a perovskite phase (La0.6Sr0.4FeO3-δ). This reservoir is able to remain close to equilibrium with the reacting gas streams because of its variable degree of non-stoichiometry and thus develops a ‘chemical memory’ that we employ to approach reversibility. We demonstrate this memory usingoperando, spatially resolved, real-time, high-resolution X-ray powder diffraction on a working reactor. The design leads to a reactor unconstrained by overall chemical equilibrium limitations, which can produce essentially pure hydrogen and carbon dioxide as separate product streams.

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VL - 11

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EP - 643

JO - Nature Chemistry

JF - Nature Chemistry

ER -

Overcoming chemical equilibrium limitations using a thermodynamically reversible chemical reactor

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