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Optimizing hierarchical membrane/catalyst systems for oxidative coupling of methane using additive manufacturing

Nature Materials volume 22, pages 1523–1530 (2023)Cite this article

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Abstract

The advantage of a membrane/catalyst system in the oxidative coupling of methane compared with conventional reactive systems is that by introducing oxygen into the catalytic sites through a membrane, the parasitic gas-phase reactions of O2(g)—responsible for lowering product selectivity—can be avoided. The design and fabrication of membrane/catalyst systems has, however, been hampered by low volumetric chemical conversion rates, high capital cost and difficulties in co-designing membrane and catalyst properties to optimize the performance. Here we solve these issues by developing a dual-layer additive manufacturing process, based on phase inversion, to design, fabricate and optimize a hollow-fibre membrane/catalyst system for the oxidative coupling of methane. We demonstrate the approach through a case study using BaCe0.8Gd0.2O3–δ as the basis of both catalyst and separation layers. We show that by using the manufacturing approach, we can co-design the membrane thickness and catalyst surface area so that the flux of oxygen transport through the membrane and methane activation rates in the catalyst layer match each other. We demonstrate that this ‘rate matching’ is critical for maximizing the performance, with the membrane/catalyst system substantially overperforming conventional reactor designs under identical conditions.

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Fig. 1: Hierarchical membrane/catalyst synthesis approach using additive manufacturing.
Fig. 2: Characterization of BCG AMCHFMs.
Fig. 3: OCM performance of symmetric and AMCHFM BCG membrane/catalyst systems.
Fig. 4: Kinetic studies of rate-determining steps during OCM in membrane/catalyst systems.
Fig. 5: Optimized OCM performance of BCG AMCHFM system.

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Data availability

All the relevant data generated during this study are available either in the main text or Supplementary Information. Data are also available from the corresponding author upon request. Source data are provided with this paper.

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Acknowledgements

We thank R. J. Meyer, S. F. Liu and J. R. Johnson at ExxonMobil for helpful discussions. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences (DE-SC0021008). We acknowledge financial support from the University of Michigan College of Engineering and technical support from the Michigan Center for Materials Characterization. R.A. acknowledges support from the National Science Foundation Graduate Research Fellowship under grant DGE 1256260.

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Authors and Affiliations

  1. Department of Chemical Engineering, University of Michigan, Ann Arbor, MI, USA

    James Wortman, Valentina Omoze Igenegbai, Rawan Almallahi, Ali Hussain Motagamwala & Suljo Linic

  2. Catalysis Science and Technology Institute, University of Michigan, Ann Arbor, MI, USA

    James Wortman, Valentina Omoze Igenegbai, Rawan Almallahi, Ali Hussain Motagamwala & Suljo Linic

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Contributions

All authors designed the plan of the project and experiments. J.W. and A.H.M. designed the additive manufacturing equipment setup. J.W. fabricated the membranes and performed the measurements. J.W., R.A., V.O.I. and A.H.M. performed the membrane/catalyst characterization and characterization data analysis. All authors analysed the data. J.W. and S.L. wrote the paper. All authors edited the paper. S.L. supervised the project.

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Correspondence to Suljo Linic.

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Wortman, J., Igenegbai, V.O., Almallahi, R. et al. Optimizing hierarchical membrane/catalyst systems for oxidative coupling of methane using additive manufacturing. Nat. Mater. 22, 1523–1530 (2023). https://doi.org/10.1038/s41563-023-01687-x

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