Simplified Models of the Bicarbonate Buffer for Scaled Simulations of CO2 Electrolyzers

Moore, Thomas; Lin, Tiras Y.; Roy, Thomas; Baker, Sarah E.; Duoss, Eric B.; Hahn, Christopher; Beck, Victor A.

doi:10.1021/acs.iecr.3c02504

Title: Simplified Models of the Bicarbonate Buffer for Scaled Simulations of CO₂ Electrolyzers

Journal Article · 01 October 2023 · Industrial and Engineering Chemistry Research

DOI: https://doi.org/10.1021/acs.iecr.3c02504 · OSTI ID:2204470

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^[1]; Roy, Thomas ^[1]; Baker, Sarah E. ^[1]; Duoss, Eric B. ^[1];

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Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Bosch USA, Sunnyvale, CA (United States)

Bicarbonate electrolytes are used in a range of chemical processes; however, resolved simulation of these electrolytes is difficult, as disparate reaction time scales lead to numerical stiffness and the formation of fine boundary layers. Based on several physically motivated approximations, we reduce the full set of chemical reactions within a bicarbonate electrolyte to a simpler subset, eliminating the numerical stiffness. We supported this simplification via a two-variable singular perturbation expansion and demonstrated that under neutral conditions (6 < pH < 10) typically found within a fluid-fed CO₂ electrolyzer, the simplifications lead to negligible error. Here, we also discuss two alternative simplifications, one valid at high pH and another valid at arbitrary pH. These simplifications reduce the condition number of the matrices resulting from spatiotemporal discretization by up to 10 orders of magnitude and enable three-dimensional (3D) simulation of CO₂ electrolyzers containing carbonate solutions.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2204470

Report Number(s):: LLNL--JRNL-823726; {1036540,"Journal ID: ISSN 0888-5885"}

Journal Information:: Industrial and Engineering Chemistry Research, Journal Name: Industrial and Engineering Chemistry Research Journal Issue: 40 Vol. 62; ISSN 0888-5885

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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