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Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss

Nature Energy volume 2, pages 923–931 (2017)Cite this article

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Abstract

Conventional production of hydrogen requires large industrial plants to minimize energy losses and capital costs associated with steam reforming, water–gas shift, product separation and compression. Here we present a protonic membrane reformer (PMR) that produces high-purity hydrogen from steam methane reforming in a single-stage process with near-zero energy loss. We use a BaZrO3-based proton-conducting electrolyte deposited as a dense film on a porous Ni composite electrode with dual function as a reforming catalyst. At 800 °C, we achieve full methane conversion by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermo-chemical processes. Modelling of a small-scale (10 kg H2 day−1) hydrogen plant reveals an overall energy efficiency of >87%. The results suggest that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture.

Membranes that simultaneously enable chemical reaction and product separation hold promise for process intensification1,2,3. Currently, the most energy-efficient production pathway for hydrogen from methane combines steam reforming (CH4 + H2O = 3H2 + CO, ΔH1,073K = 226 kJ mol−1) and water–gas shift (WGS; CO + H2O = H2 + CO2, ΔH1,073K = −34 kJ mol−1) in a multistep process4, where heat management is crucial. The produced hydrogen is conventionally separated downstream using, for example, pressure swing absorption5. Alternatively, hydrogen separation can be included in the steam reforming process using hydrogen-selective membranes6,7 with the benefit of simultaneously separating hydrogen while shifting the thermodynamic equilibrium, resulting in process intensification. Most membranes used in practice are metallic, predominantly based on Pd or Pd–Ag alloys8. The separation is driven by the hydrogen partial pressure difference across the membrane, from which it follows that the pressure of the produced hydrogen is low, and further compression requires multistage compressors, increasing both the capital as well as the energy costs.

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Fig. 1: Schematic of the protonic membrane reformer.
Fig. 2: Protonic membrane reformer for production of compressed hydrogen.
Fig. 3: Breakdown of voltage losses and microthermal integration at 800 °C.
Fig. 4: Thermo-fluid dynamic simulations.
Fig. 5: Techno-economic evaluation of centralized hydrogen production plant.
Fig. 6: Techno-economic evaluation of distributed hydrogen production.

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Acknowledgements

This work was supported by the Research Council of Norway (grant 256264) and the Spanish Government (SEV-2016-0683 grant). NORTEM is acknowledged for access to transmission electron microscopes.

Author contributions

H.M.-F., D.C., R.Z. and C.K. performed the experiments. H.M.-F., J.M.S., R.H., D.C., P.K.V., T.N. and C.K. designed the experiments. D.B. fabricated the tubular membrane electrode assembly. H.M.-F., C.K., R.H., T.N. and J.M.S. analysed electrochemical data. H.M.-F., J.M.S., S.H.M., R.Z. and C.K. analysed the catalytic data. I.Y.-T. and D.C.-M. designed and performed modelling studies. D.C. collected scanning and transmission electron microscope data. P.K.V. and C.K. initiated the project. H.M.-F., D.C., I.Y.-T., D.C.-M., D.B., S.H.M., P.K.V., T.N., R.H., J.M.S. and C.K. wrote the manuscript, while all authors discussed the results and commented on the manuscript.

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Authors and Affiliations

  1. CoorsTek Membrane Sciences AS, 0349, Oslo, Norway

    Harald Malerød-Fjeld, Daniel Clark, Irene Yuste-Tirados, Dustin Beeaff, Selene H. Morejudo, Per K. Vestre & Christian Kjølseth

  2. Department of Chemistry, Centre for Materials Science and Nanotechnology, University of Oslo, Oslo, Norway

    Daniel Clark, Truls Norby & Reidar Haugsrud

  3. Instituto de Tecnología Química (ITQ), Universitat Politècnica de València (UPV) - Consejo Superior de Investigaciones Científicas (CSIC), Valencia, Spain

    Raquel Zanón, David Catalán-Martinez & José M. Serra

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  1. Harald Malerød-Fjeld
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Correspondence to José M. Serra or Christian Kjølseth.

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Competing interests

H.M.-F., D.C., I.Y.-T, D.B., S.H.M., P.K.V. and C.K. are employed by CoorsTek Membrane Sciences (CTMS). T.N. is member of the CTMS board. D.C. postdoctoral research at University of Oslo is partially funded by CTMS. The other authors declare no competing financial interests.

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Supplementary Methods, Supplementary Figures 1–15, Supplementary Tables 1–2 and Supplementary References

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Malerød-Fjeld, H., Clark, D., Yuste-Tirados, I. et al. Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss. Nat Energy 2, 923–931 (2017). https://doi.org/10.1038/s41560-017-0029-4

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