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

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

doi:10.1038/s41563-023-01687-x

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

Journal Article · 11 October 2023 · Nature Materials

DOI: https://doi.org/10.1038/s41563-023-01687-x · OSTI ID:2338175

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University of Michigan, Ann Arbor, MI (United States); University of Michigan - Ann Arbor, MI (United States). Department of Chemical Engineering
University of Michigan, Ann Arbor, MI (United States)

The advantage of a membrane/catalyst system in oxidative coupling of methane (OCM) compared to conventional reactive systems is that by introducing oxygen to the OCM catalytic sites through a membrane, 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 codesigning membrane and catalyst properties to optimize the performance. We solve these issues by developing a dual-layer additive manufacturing process, based on phase inversion, to design, fabricate and optimize a hollow fiber membrane/catalyst system for OCM. We demonstrate the approach though a case study using BaCe_0.8Gd_0.2O_3-δ (BCG) as the basis of both the catalyst and separation layers. We show that by using the manufacturing approach we can codesign 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. Here, we demonstrate that this “rate matching” is critical for maximizing the performance, with the membrane/catalyst system significantly overperforming conventional reactor designs under identical conditions.

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Research Organization:: University of Michigan, Ann Arbor, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Science Foundation Graduate Research Fellowship

Grant/Contract Number:: SC0021008

OSTI ID:: 2338175

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 12 Vol. 22; ISSN 1476-1122

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Real time chemical imaging of a working catalytic membrane reactor during oxidative coupling of methane Vamvakeros, A.; Jacques, S. D. M.; Middelkoop, V. Chemical Communications, Vol. 51, Issue 64 https://doi.org/10.1039/C5CC03208C	journal	January 2015
Methane Activation by Heterogeneous Catalysis Horn, Raimund; Schlögl, Robert Catalysis Letters, Vol. 145, Issue 1 https://doi.org/10.1007/s10562-014-1417-z	journal	November 2014
X-ray tomography-assisted study of a phase inversion process in ceramic hollow fiber systems – Towards practical structural design Li, Tao; Lu, Xuekun; Wang, Bo Journal of Membrane Science, Vol. 528 https://doi.org/10.1016/j.memsci.2017.01.004	journal	April 2017
Oxidative coupling of methane in Ba0.5Sr0.5Co0.8Fe0.2O3−δ tubular membrane reactors Wang, Haihui; Cong, You; Yang, Weishen Catalysis Today, Vol. 104, Issue 2-4 https://doi.org/10.1016/j.cattod.2005.03.079	journal	June 2005
Evaluation of direct methane conversion to higher hydrocarbons and oxygenates Kuo, J. C. W.; Kresge, C. T.; Palermo, R. E. Catalysis Today, Vol. 4, Issue 3-4 https://doi.org/10.1016/0920-5861(89)85042-4	journal	February 1989
Real-time tomographic diffraction imaging of catalytic membrane reactors for the oxidative coupling of methane Vamvakeros, Antonis; Matras, Dorota; Jacques, Simon D. M. Catalysis Today, Vol. 364 https://doi.org/10.1016/j.cattod.2020.05.045	journal	March 2021
In search of membrane-catalyst materials for oxidative coupling of methane: Performance and phase stability studies of gadolinium-doped barium cerate and the impact of Zr doping Igenegbai, Valentina Omoze; Meyer, Randall J.; Linic, Suljo Applied Catalysis B: Environmental, Vol. 230 https://doi.org/10.1016/j.apcatb.2018.02.040	journal	August 2018
Strategies for the Direct Catalytic Valorization of Methane Using Heterogeneous Catalysis: Challenges and Opportunities Olivos-Suarez, Alma I.; Szécsényi, Àgnes; Hensen, Emiel J. M. ACS Catalysis, Vol. 6, Issue 5 https://doi.org/10.1021/acscatal.6b00428	journal	April 2016
Permeation model and experimental investigation of mixed conducting membranes Zhu, Xuefeng; Liu, Huanying; Cong, You AIChE Journal, Vol. 58, Issue 6 https://doi.org/10.1002/aic.12710	journal	July 2011
Catalyst-modified perovskite hollow fiber membrane for oxidative coupling of methane Song, Jian; Li, Claudia; Zhang, Shao Chinese Journal of Chemical Engineering, Vol. 41 https://doi.org/10.1016/j.cjche.2021.11.012	journal	January 2022
Influence of oxygen supply rates on performances of catalytic membrane reactorsApplication to the oxidative coupling of methane Haag, Stéphane; van Veen, Andre C.; Mirodatos, Claude Catalysis Today, Vol. 127, Issue 1-4 https://doi.org/10.1016/j.cattod.2007.05.011	journal	September 2007
Solid oxide fuel cells Ormerod, R. Mark Chemical Society Reviews, Vol. 32, Issue 1, p. 17-28 https://doi.org/10.1039/b105764m	journal	November 2002
Synthesis of ethylene via oxidative coupling of methane I. Determination of active catalysts Keller, G. Journal of Catalysis, Vol. 73, Issue 1 https://doi.org/10.1016/0021-9517(82)90075-6	journal	January 1982
Feasibility and mechanism of lithium oxide as sintering aid for Ce0.8Sm0.2Oδ electrolyte Li, Shuai; Xian, Cunni; Yang, Kai Journal of Power Sources, Vol. 205 https://doi.org/10.1016/j.jpowsour.2012.01.010	journal	May 2012
Unconventional Chemistry for Unconventional Natural Gas McFarland, E. Science, Vol. 338, Issue 6105 https://doi.org/10.1126/science.1226840	journal	October 2012
A Viewpoint on Direct Methane Conversion to Ethane and Ethylene Using Oxidative Coupling on Solid Catalysts Farrell, Brittany Lancaster; Igenegbai, Valentina Omoze; Linic, Suljo ACS Catalysis, Vol. 6, Issue 7 https://doi.org/10.1021/acscatal.6b01087	journal	June 2016
Advanced reactor concepts for oxidative coupling of methane Cruellas, A.; Melchiori, T.; Gallucci, F. Catalysis Reviews, Vol. 59, Issue 3 https://doi.org/10.1080/01614940.2017.1348085	journal	July 2017
Preparation of LSCF Ceramic Hollow-Fiber Membranes for Oxygen Production by a Phase-Inversion/Sintering Technique Tan, Xiaoyao; Liu, Yutie; Li, K. Industrial & Engineering Chemistry Research, Vol. 44, Issue 1 https://doi.org/10.1021/ie040179c	journal	January 2005
Oxygen permeation flux through La1-ySryFeO3 limited by carbon monoxide oxidation rate van Hassel, B. A.; ten Elshof, J. E.; Bouwmeester, H. J. M. Applied Catalysis A: General, Vol. 119, Issue 2 https://doi.org/10.1016/0926-860X(94)85197-2	journal	November 1994
Towards single step production of multi-layer inorganic hollow fibers de Jong, J.; Benes, N. E.; Koops, G. H. Journal of Membrane Science, Vol. 239, Issue 2 https://doi.org/10.1016/j.memsci.2004.02.039	journal	August 2004
Inorganic Membranes for Process Intensification: Challenges and Perspective Lin, Y. S. Industrial & Engineering Chemistry Research, Vol. 58, Issue 15 https://doi.org/10.1021/acs.iecr.8b04539	journal	November 2018
Catalytic aromatization of methane Spivey, James J.; Hutchings, Graham Chem. Soc. Rev., Vol. 43, Issue 3 https://doi.org/10.1039/C3CS60259A	journal	January 2014
Oxidative Coupling of Methane over Oxide-Supported Sodium-Manganese Catalysts Wang, D. J.; Rosynek, M. P.; Lunsford, J. H. Journal of Catalysis, Vol. 155, Issue 2 https://doi.org/10.1006/jcat.1995.1221	journal	September 1995
Chemical Kinetic Data Base for Combustion Chemistry. Part I. Methane and Related Compounds Tsang, W.; Hampson, R. F. Journal of Physical and Chemical Reference Data, Vol. 15, Issue 3 https://doi.org/10.1063/1.555759	journal	July 1986
Flower-like Sr-La₂O₃ Microspheres with Hierarchically Porous Structures for Oxidative Coupling of Methane Zhao, Mingquan; Ke, Sichao; Wu, Huiqing Industrial & Engineering Chemistry Research, Vol. 58, Issue 51 https://doi.org/10.1021/acs.iecr.9b03676	journal	November 2019
Correlation of Methane Activation and Oxide Catalyst Reducibility and Its Implications for Oxidative Coupling Kumar, Gaurav; Lau, Sai Lap Jacky; Krcha, Matthew D. ACS Catalysis, Vol. 6, Issue 3 https://doi.org/10.1021/acscatal.5b02657	journal	February 2016
A Critical Assessment of Li/MgO-Based Catalysts for the Oxidative Coupling of Methane Arndt, Sebastian; Laugel, Guillaume; Levchenko, Sergey Catalysis Reviews, Vol. 53, Issue 4 https://doi.org/10.1080/01614940.2011.613330	journal	October 2011
Gas-Phase Reaction Network of Li/MgO-Catalyzed Oxidative Coupling of Methane and Oxidative Dehydrogenation of Ethane Luo, Liangfeng; You, Rui; Liu, Yiming ACS Catalysis, Vol. 9, Issue 3 https://doi.org/10.1021/acscatal.8b04728	journal	February 2019
Statistical Analysis of Past Catalytic Data on Oxidative Methane Coupling for New Insights into the Composition of High-Performance Catalysts Zavyalova, Ulyana; Holena, Martin; Schlögl, Robert ChemCatChem, Vol. 3, Issue 12 https://doi.org/10.1002/cctc.201100186	journal	September 2011
Oxidative Coupling of Methane over Hybrid Membrane/Catalyst Active Centers: Chemical Requirements for Prolonged Lifetime Igenegbai, Valentina Omoze; Almallahi, Rawan; Meyer, Randall J. ACS Energy Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsenergylett.9b01075	journal	June 2019
C 2 Selectivity Enhancement in Chemical Looping Oxidative Coupling of Methane over a Mg–Mn Composite Oxygen Carrier by Li-Doping-Induced Oxygen Vacancies Cheng, Zhuo; Baser, Deven S.; Nadgouda, Sourabh G. ACS Energy Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsenergylett.8b00851	journal	June 2018
A novel dual-layer ceramic hollow fibre membrane reactor for methane conversion Wu, Zhentao; Wang, Bo; Li, K. Journal of Membrane Science, Vol. 352, Issue 1-2 https://doi.org/10.1016/j.memsci.2010.01.062	journal	April 2010
Oxidative Coupling of Methane in a Perovskite Hollow-Fiber Membrane Reactor Tan, Xiaoyao; Li, K. Industrial & Engineering Chemistry Research, Vol. 45, Issue 1 https://doi.org/10.1021/ie0506320	journal	November 2005
Scaling Relations for Autothermal Operation of Catalytic Reactors Balakotaiah, Vemuri; Sun, Zhe; Gu, Tian Industrial & Engineering Chemistry Research, Vol. 60, Issue 18 https://doi.org/10.1021/acs.iecr.0c05594	journal	January 2021
Oxidative dimerization of methane over a lithium-promoted magnesium oxide catalyst Ito, Tomoyasu; Wang, Jixiang; Lin, Chiu Hsun Journal of the American Chemical Society, Vol. 107, Issue 18 https://doi.org/10.1021/ja00304a008	journal	September 1985
Oxygen permeation modelling of perovskites Vanhassel, B.; Kawada, T.; Sakai, N. Solid State Ionics, Vol. 66, Issue 3-4 https://doi.org/10.1016/0167-2738(93)90419-4	journal	November 1993
Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen Guo, X.; Fang, G.; Li, G. Science, Vol. 344, Issue 6184 https://doi.org/10.1126/science.1253150	journal	May 2014
Mn–Na2WO4/SiO2 as catalyst for the oxidative coupling of methane. What is really known? Arndt, S.; Otremba, T.; Simon, U. Applied Catalysis A: General, Vol. 425-426 https://doi.org/10.1016/j.apcata.2012.02.046	journal	May 2012
Oxidative coupling of methane—A complex surface/gas phase mechanism with strong impact on the reaction engineering Beck, Benjamin; Fleischer, Vinzenz; Arndt, Sebastian Catalysis Today, Vol. 228 https://doi.org/10.1016/j.cattod.2013.11.059	journal	June 2014
Proton conductive properties of gadolinium-doped barium cerates at high temperatures Taniguchi, Noboru; Hatoh, Kazuhito; Niikura, Junji Solid State Ionics, Vol. 53-56 https://doi.org/10.1016/0167-2738(92)90283-U	journal	July 1992
The Effect of Oxygen-Anion Conductivity of Metal–Oxide Doped Lanthanum Oxide Catalysts on Hydrocarbon Selectivity in the Oxidative Coupling of Methane Borchert, Holger; Baerns, Manfred Journal of Catalysis, Vol. 168, Issue 2 https://doi.org/10.1006/jcat.1997.1662	journal	June 1997
Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects Schwach, Pierre; Pan, Xiulian; Bao, Xinhe Chemical Reviews, Vol. 117, Issue 13 https://doi.org/10.1021/acs.chemrev.6b00715	journal	March 2017
Oxidative Coupling of Methane in a BCFZ Perovskite Hollow Fiber Membrane Reactor Czuprat, Oliver; Schiestel, Thomas; Voss, Hartwig Industrial & Engineering Chemistry Research, Vol. 49, Issue 21 https://doi.org/10.1021/ie100282g	journal	April 2010
An oxygen permeable membrane microreactor with an in-situ deposited Bi1.5Y0.3Sm0.2O3− catalyst for oxidative coupling of methane Othman, Nur Hidayati; Wu, Zhentao; Li, K. Journal of Membrane Science, Vol. 488 https://doi.org/10.1016/j.memsci.2015.04.027	journal	August 2015
Oxidative coupling of methane in a mixed-conducting perovskite membrane reactor ten Elshof, J. E.; Bouwmeester, H. J. M.; Verweij, H. Applied Catalysis A: General, Vol. 130, Issue 2 https://doi.org/10.1016/0926-860X(95)00098-4	journal	September 1995
Recent advances and future prospect in catalysts for oxidative coupling of methane to ethylene: A review Gambo, Y.; Jalil, A. A.; Triwahyono, S. Journal of Industrial and Engineering Chemistry, Vol. 59 https://doi.org/10.1016/j.jiec.2017.10.027	journal	March 2018
Hollow fibre perovskite membranes for oxygen separation Schiestel, T.; Kilgus, M.; Peter, S. Journal of Membrane Science, Vol. 258, Issue 1-2 https://doi.org/10.1016/j.memsci.2005.03.035	journal	August 2005
Real-time multi-length scale chemical tomography of fixed bed reactors during the oxidative coupling of methane reaction Vamvakeros, Antonis; Matras, Dorota; Jacques, Simon D. M. Journal of Catalysis, Vol. 386 https://doi.org/10.1016/j.jcat.2020.03.027	journal	June 2020
Melt-spun polymer fibers with liquid core exhibit enhanced mechanical damping Hufenus, Rudolf; Gottardo, Laura; Leal, A. Andrés Materials & Design, Vol. 110 https://doi.org/10.1016/j.matdes.2016.08.042	journal	November 2016
Perovskite-type oxide membranes for the oxidative coupling of methane Xu, Sherman J.; Thomson, William J. AIChE Journal, Vol. 43, Issue S11 https://doi.org/10.1002/aic.690431319	journal	January 1997
The Effect of Strontium Content on the Activity and Selectivity of Sr-Doped La2O3 Catalysts in Oxidative Coupling of Methane Schucker, Robert C.; J. Derrickson, Katarzyna; K. Ali, Azim Applied Catalysis A: General, Vol. 607 https://doi.org/10.1016/j.apcata.2020.117827	journal	October 2020
Comprehensive Kinetics of Oxidative Coupling of Methane over the La₂O₃/CaO Catalyst Stansch, Z.; Mleczko, L.; Baerns, M. Industrial & Engineering Chemistry Research, Vol. 36, Issue 7 https://doi.org/10.1021/ie960562k	journal	July 1997
Oxygen-permeable dense membrane reactor for the oxidative coupling of methane Lu, Y. Journal of Membrane Science, Vol. 170, Issue 1 https://doi.org/10.1016/S0376-7388(99)00354-3	journal	May 2000
Highly Durable C₂ Hydrocarbon Production via the Oxidative Coupling of Methane Using a BaFe_0.9Zr_0.1O_3−δ Mixed Ionic and Electronic Conducting Membrane and La₂O₃ Catalyst Dimitrakopoulos, Georgios; Koo, Bonjae; Yildiz, Bilge ACS Catalysis, Vol. 11, Issue 6 https://doi.org/10.1021/acscatal.0c04888	journal	March 2021
Investigation of the role of the Na2WO4/Mn/SiO2 catalyst composition in the oxidative coupling of methane by chemical looping experiments Fleischer, Vinzenz; Simon, Ulla; Parishan, Samira Journal of Catalysis, Vol. 360 https://doi.org/10.1016/j.jcat.2018.01.022	journal	April 2018
Oxidative Coupling of Methane in Membrane Reactors; A Techno-Economic Assessment Cruellas, Aitor; Heezius, Jelle; Spallina, Vincenzo Processes, Vol. 8, Issue 3 https://doi.org/10.3390/pr8030274	journal	February 2020

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

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