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Catalytic reforming of methane with H2S via dynamically stabilized sulfur on transition metal oxides and sulfides

Nature Catalysis volume 6, pages 204–214 (2023)Cite this article

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Abstract

Reforming of methane with H2S is a promising path to directly utilize sour natural gas reserves, although some aspects of the mechanism and structure–function relations remain elusive. Here we show that metal oxides of group 4–6 elements, which are inert for steam and dry methane reforming reactions, are active and stable (pre)catalysts for the H2S reforming of methane. The key active sites are sulfur species (S*) that are dynamically bound to metal cations during catalysis. Similar H/D isotope exchange patterns and universal rate inhibition by H2 on representative catalysts indicate that H2S decomposition and recombination of surface hydrogen atoms are quasi-equilibrated, whereas CH4 dissociation steps are reversible, yet not quasi-equilibrated. An in-depth analysis of the kinetic data and isotopic substitution effects identifies S*-mediated C–H bond cleavage as the most plausible rate-limiting step common for all catalysts, with subtle yet essential differences between 3d and 4d/5d catalysts in the thermodynamic stability of S*.

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Fig. 1: Activity and stability of group 3–6 catalysts in CH4-H2S reforming.
Fig. 2: Structural and compositional analysis of post-reaction catalysts in post-reaction group 3–6 catalysts.
Fig. 3: Comparison between H2S reforming and dry reforming of CH4.
Fig. 4: Effects of co-fed H2 on the forward CH4 conversion rate in CH4–H2S reforming.
Fig. 5: Normalized isotopomer distributions during the reactions of CH4–H2S–D2 mixtures.
Fig. 6: Parity plots of the predicted and measured forward CH4 conversion rates.
Fig. 7: A pictorial catalytic cycle for CH4–H2S reforming mediated by sulfur adatoms.

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All data supporting this work are available in the main text and Supplementary Information. Source data are provided with this paper.

References

  1. York, A. P. E., Xiao, T. C., Green, M. L. H. & Claridge, J. B. Methane oxyforming for synthesis gas production. Catal. Rev. 49, 511–560 (2007).

    Article  CAS  Google Scholar 

  2. Choudhary, T. V. & Choudhary, V. R. Energy-efficient syngas production through catalytic oxy-methane reforming reactions. Angew. Chem. Int. Ed. 47, 1828–1847 (2008).

    Article  CAS  Google Scholar 

  3. Taifan, W. & Baltrusaitis, J. Minireview: direct catalytic conversion of sour natural gas (CH4 + H2S + CO2) components to high-value chemicals and fuels. Catal. Sci. Technol. 7, 2919–2929 (2017).

  4. Gutiérrez, O. Y., Kaufmann, C. & Lercher, J. A. Synthesis of methanethiol from carbonyl sulfide and carbon disulfide on (Co)K-promoted sulfide Mo/SiO2 catalysts. ACS Catal. 1, 1595–1603 (2011).

    Article  Google Scholar 

  5. Gutiérrez, O. Y., Zhong, L., Zhu, Y. & Lercher, J. A. Synthesis of methanethiol from CS2 on Ni-, Co-, and K-doped MoS2/SiO2 catalysts. ChemCatChem 5, 3249–3259 (2013).

    Article  Google Scholar 

  6. Olah, G. A. et al. Onium ylide chemistry. 1. Bifunctional acid-base-catalyzed conversion of heterosubstituted methanes into ethylene and derived hydrocarbons. The onium ylide mechanism of the C → C2 conversion. J. Am. Chem. Soc. 106, 2143–2149 (1984).

    Article  CAS  Google Scholar 

  7. Huguet, E. et al. A highly efficient process for transforming methyl mercaptan into hydrocarbons and H2S on solid acid catalysts. Appl. Catal. B 134–135, 344–348 (2013).

    Article  Google Scholar 

  8. Hulea, V. et al. Conversion of methyl mercaptan and methanol to hydrocarbons over solid acid catalysts—a comparative study. Appl. Catal. B 144, 547–553 (2014).

    Article  CAS  Google Scholar 

  9. Cammarano, C. et al. Selective transformation of methyl and ethyl mercaptans mixture to hydrocarbons and H2S on solid acid catalysts. Appl. Catal. B 156–157, 128–133 (2014).

    Article  Google Scholar 

  10. Erekson, E. J. Gasoline from Natural Gas by Sulfur Processing Final Technical Report, June 1993–July 1996 (OSTI, 1996); https://doi.org/10.2172/303990

  11. Miao, F. Q. & Erekson, E. J. Method for direct production of carbon disulfide and hydrogen from hydrocarbons and hydrogen sulfide feedstock. US patent 9018957 (1998).

  12. Espinosa, G., Dominguez, J. M., Diaz, L. & Angeles, C. Catalytic behavior of CoMo/ZSM5 catalysts for CS2 conversion. Catal. Today 148, 153–159 (2009).

    Article  CAS  Google Scholar 

  13. Martínez-Salazar, A. L. et al. Technoeconomic analysis of hydrogen production via hydrogen sulfide methane reformation. Int. J. Hydrogen Energy 44, 12296–12302 (2019).

  14. Huang, C. & T-Raissi, A. Liquid hydrogen production via hydrogen sulfide methane reformation. J. Power Sources 175, 464–472 (2008).

    Article  CAS  Google Scholar 

  15. Waterman, H. I. & Van Vlodrop, C. The preparation of carbon disulfide from methane and hydrogen sulfide. J. Soc. Chem. Ind. Lond. 58, 109–110 (1939).

  16. Karan, K. & Behie, L. A. CS2 formation in the Claus reaction furnace: a kinetic study of methane−sulfur and methane−hydrogen sulfide reactions. Ind. Eng. Chem. Res. 43, 3304–3313 (2004).

    Article  CAS  Google Scholar 

  17. El-Melih, A. M., Al Shoaibi, A. & Gupta, A. K. Hydrogen sulfide reformation in the presence of methane. Appl. Energy 178, 609–615 (2016).

    Article  CAS  Google Scholar 

  18. El-Melih, A. M., Iovine, L., Al Shoaibi, A. & Gupta, A. K. Production of hydrogen from hydrogen sulfide in presence of methane. Int. J. Hydrogen Energy 42, 4764–4773 (2017).

  19. Li, Y. et al. Kinetic study of decomposition of H2S and CH4 for H2 production using detailed mechanism. Energy Procedia 142, 1065–1070 (2017).

    Article  CAS  Google Scholar 

  20. Megalofonos, S. K. & Papayannakos, N. G. Hydrogen production from natural gas and hydrogen sulphide. Int. J. Hydrogen Energy 16, 319–327 (1991).

  21. Megalofonos, S. K. & Papayannakos, N. G. Kinetics of catalytic reaction of methane and hydrogen sulphide over MoS2. Appl. Catal. A 165, 249–258 (1997).

    Article  CAS  Google Scholar 

  22. Megalofonos, S. K. & Papayannakos, N. G. Kinetics of the catalytic reaction of methane and hydrogen sulphide over a Pt–Al2O3 catalyst. Appl. Catal. A 138, 39–55 (1996).

    Article  CAS  Google Scholar 

  23. Galindo-Hernández, F., Domínguez, J. M. & Portales, B. Structural and textural properties of Fe2O3/γ-Al2O3 catalysts and their importance in the catalytic reforming of CH4 with H2S for hydrogen production. J. Power Sources 287, 13–24 (2015).

    Article  Google Scholar 

  24. Martínez-Salazar, A. L. et al. Hydrogen production by methane reforming with H2S using Mo,Cr/ZrO2–SBA15 and Mo,Cr/ZrO2–La2O3 catalysts. Int. J. Hydrogen Energy 40, 17272–17283 (2015).

  25. Martínez-Salazar, A. L. et al. Hydrogen production by methane and hydrogen sulphide reaction: kinetics and modeling study over Mo/La2O3–ZrO2 catalyst. Int. J. Hydrogen Energy 40, 17354–17360 (2015).

  26. Wang, H. et al. Sulfidation of MoO3/γ-Al2O3 towards a highly efficient catalyst for CH4 reforming with H2S. Catal. Sci. Technol. 11, 1125–1140 (2021).

    Article  Google Scholar 

  27. Fremy, G., Barre, P. & Raymond, J.-M. Method for preparing methyl mercaptan. US patent 2017/0158631 (2017).

  28. Kaloidas, V. & Papayannakos, N. Kinetics of thermal, non-catalytic decomposition of hydrogen sulphide. Chem. Eng. Sci. 44, 2493–2500 (1989).

    Article  CAS  Google Scholar 

  29. Liu, S. et al. ‘Soft’ oxidative coupling of methane to ethylene: mechanistic insights from combined experiment and theory. Proc. Natl Acad. Sci. USA 118, e2012666118 (2021).

  30. Peter, M. & Marks, T. J. Platinum metal-free catalysts for selective soft oxidative methane → ethylene coupling. Scope and mechanistic observations. J. Am. Chem. Soc. 137, 15234–15240 (2015).

  31. Zhu, Q. et al. Sulfur as a selective ‘soft’ oxidant for catalytic methane conversion probed by experiment and theory. Nat. Chem. 5, 104–109 (2013).

    Article  CAS  PubMed  Google Scholar 

  32. Ashcroft, A. T., Cheetham, A. K., Green, M. L. H. & Vernon, P. D. F. Partial oxidation of methane to synthesis gas using carbon dioxide. Nature 352, 225–226 (1991).

    Article  CAS  Google Scholar 

  33. Akri, M. et al. Atomically dispersed nickel as coke-resistant active sites for methane dry reforming. Nat. Commun. 10, 5181 (2019).

    Article  PubMed  PubMed Central  Google Scholar 

  34. Yamaguchi, A. & Iglesia, E. Catalytic activation and reforming of methane on supported palladium clusters. J. Catal. 274, 52–63 (2010).

    Article  CAS  Google Scholar 

  35. Wei, J. & Iglesia, E. Structural and mechanistic requirements for methane activation and chemical conversion on supported iridium clusters. Angew. Chem. Int. Ed. 43, 3685–3688 (2004).

    Article  CAS  Google Scholar 

  36. Wei, J. & Iglesia, E. Isotopic and kinetic assessment of the mechanism of methane reforming and decomposition reactions on supported iridium catalysts. Phys. Chem. Chem. Phys. 6, 3754–3759 (2004).

    Article  CAS  Google Scholar 

  37. Wei, J. & Iglesia, E. Isotopic and kinetic assessment of the mechanism of reactions of CH4 with CO2 or H2O to form synthesis gas and carbon on nickel catalysts. J. Catal. 224, 370–383 (2004).

    Article  CAS  Google Scholar 

  38. Wei, J. & Iglesia, E. Mechanism and site requirements for activation and chemical conversion of methane on supported Pt clusters and turnover rate comparisons among noble metals. J. Phys. Chem. B 108, 4094–4103 (2004).

    Article  CAS  Google Scholar 

  39. Wei, J. & Iglesia, E. Structural requirements and reaction pathways in methane activation and chemical conversion catalyzed by rhodium. J. Catal. 225, 116–127 (2004).

    Article  CAS  Google Scholar 

  40. Wei, J. & Iglesia, E. Reaction pathways and site requirements for the activation and chemical conversion of methane on Ru-based catalysts. J. Phys. Chem. B 108, 7253–7262 (2004).

    Article  CAS  Google Scholar 

  41. Toulhoat, H. & Raybaud, P. Kinetic interpretation of catalytic activity patterns based on theoretical chemical descriptors. J. Catal. 216, 63–72 (2003).

    Article  CAS  Google Scholar 

  42. Shang, H., Wang, T. & Zhang, W. Sulfur vacancy formation at different MoS2 edges during hydrodesulfurization process: a DFT study. Chem. Eng. Sci. 195, 208–217 (2019).

    Article  CAS  Google Scholar 

  43. Dibeler, V. H. & Mohler, F. L. Mass spectra of the deuteromethanes. J. Res. Natl Bur. Stand. 45, 441–444 (1950).

    Article  CAS  Google Scholar 

  44. Dibeler, V. H. & Rosenstock, H. M. Mass spectra and metastable transitions of H2S, HDS, and D2S. J. Chem. Phys. 39, 3106–3111 (1963).

    Article  CAS  Google Scholar 

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Acknowledgements

This work was financially supported by Evonik Industries. J.A.L. acknowledges support by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Impact of catalytically active centers and their environment on rates and thermodynamic states along reaction paths, FWP 47319). We thank L. Wahl and X. Hecht for the construction of the reaction device, S. Ren and F. Chew for catalyst screening, R. Weindl, A. Wellmann (Technical University of Munich) and J. Hu (Xiamen University) for transmission electron microscopy and Raman characterizations.

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Authors and Affiliations

  1. Department of Chemistry and Catalysis Research Center, Technische Universität München, Garching, Germany

    Yong Wang, Xiaofeng Chen & Johannes A. Lercher

  2. School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, People’s Republic of China

    Hui Shi

  3. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, WA, USA

    Johannes A. Lercher

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Contributions

Y.W. and X.C. performed the experiments; Y.W. and H.S. conceived the work, designed the experiments and analysed the data; H.S. and J.A.L. supervised the project. All the authors discussed the results and were involved in the writing of the manuscript.

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Correspondence to Hui Shi or Johannes A. Lercher.

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Nature Catalysis thanks Ping Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Wang, Y., Chen, X., Shi, H. et al. Catalytic reforming of methane with H2S via dynamically stabilized sulfur on transition metal oxides and sulfides. Nat Catal 6, 204–214 (2023). https://doi.org/10.1038/s41929-023-00922-7

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