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Magnesium–Aluminum Mixed Oxides as Basic Catalysts for the Synthesis of Methanethiol

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Abstract

Aluminum–magnesium oxides are excellent catalysts for the thiolation of methanol with H2S. The substitution of the alcohol OH with SH groups requires balanced Lewis acid and base sites. This is achieved by varying the aluminum and magnesium concentrations in the mixed oxide. The highest rate and selectivity was obtained for equal concentrations.

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References

  1. 1.

    Pashigreva AV, Kondratieva E, Bermejo-Deval R, Gutiérrez OY, Lercher JA (2017) Methanol thiolation over Al2O3 and WS2 catalysts modified with cesium. J Catal 345:308–318

  2. 2.

    Gutiérrez OY, Kaufmann C, Hrabar A, Zhu Y, Lercher JA (2011) Synthesis of methyl mercaptan from carbonyl sulfide over sulfide K2MoO4/SiO2. J Catal 280:264–273

  3. 3.

    Gutiérrez OY, Kaufmann C, Lercher JA (2011) Synthesis of methanethiol from carbonyl sulfide and carbon disulfide on (Co)K-promoted sulfide Mo/SiO2 catalysts. ACS Catal 1:1595–1603

  4. 4.

    Kaufmann C, Gutiérrez OY, Zhu Y, Lercher JA (2010) Effect of H2 in the synthesis of COS using liquid sulfur and CO or CO2 as reactants. Res Chem Intermed 36:211–225

  5. 5.

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

  6. 6.

    Liu P, Cao J, Xu Z, Yang C, Wang X, Liu F (2020) Thiolation of methanol with H2S using core-shell structured ZSM-5@t-ZrO2 catalyst. Chem Eng Sci 211:115273

  7. 7.

    Lamonier C, Lamonier J-F, Aellach B, Ezzamarty A, Leglise J (2011) Specific tuning of acid/base sites in apatite materials to enhance their methanol thiolation catalytic performances. Catal Today 164:124–130

  8. 8.

    Weber-Stockbauer M, Gutiérrez OY, Bermejo-Deval R, Lercher JA (2019) The role of weak Lewis acid sites for methanol thiolation. Catal Sci Technol 9:509–516

  9. 9.

    Bermejo-Deval R, Walter RMH, Gutierrez OY, Lercher JA (2017) On the role of the alkali cations on methanol thiolation. Catal Sci Technol 7:4437–4443

  10. 10.

    Sauer J, Boeck W, Von Hippel L, Burkhardt W, Rautenberg S, Arntz D, Hofen W (1998) Catalyst, process for its preparation, and use for synthesis of methyl mercaptan, United States Patent 5,852,219

  11. 11.

    Weber-Stockbauer M, Gutiérrez OY, Bermejo-Deval R, Lercher JA (2019) Cesium induced changes in the acid–base properties of metal oxides and the consequences for methanol thiolation. ACS Catal 9:9245–9252

  12. 12.

    Lercher JA (1982) Acid–base properties of Al2O3/MgO oxides I: I.r. study of adsorption of acetone. Z Phys Chem 129:209

  13. 13.

    Lercher JA (1982) Acid–base properties of Al2O3/MgO oxides II: Infrared study of adsorption of pyridine. Z Phys Chem 20 :409–413

  14. 14.

    Lercher JA, Colombier C, Noller H (1982) Acid–base properties of Al2O3/MgO oxides III: I.r. Study of adsorption of pyrrole. Z Phys Chem 131:111

  15. 15.

    Lercher JA, Colombier C, Noller H (1984) Acid–base properties of alumina–magnesia mixed oxides. Part 4.—Infrared study of adsorption of carbon dioxide. J Chem Soc Faraday Trans 80:949–959

  16. 16.

    Shen J, Kobe JM, Chen Y, Dumesic JA (1994) synthesis and surface acid/base properties of magnesium-aluminum mixed oxides obtained from hydrotalcites. Langmuir 10:3902–3908

  17. 17.

    Abelló S, Medina F, Tichit D, Pérez-Ramírez J, Groen JC, Sueiras JE, Salagre P, Cesteros Y (2005) Aldol condensations over reconstructed Mg–Al hydrotalcites: structure–activity relationships related to the rehydration method. Chem A Eur J 11:728–739

  18. 18.

    Saoud KM, Saeed S, Al-Soubaihi RM, Bertino MF (2014) Microwave assisted preparation of magnesium hydroxide nano-sheets. Am J Nanomater 2:21–25

  19. 19.

    Parker LM, Milestone NB, Newman RH (1995) The use of hydrotalcite as an anion absorbent. Ind Eng Chem Res 34:1196–1202

  20. 20.

    Busca G, Lorenzelli V (1982) Infrared spectroscopic identification of species arising from reactive adsorption of carbon oxides on metal oxide surfaces. Mater Chem 7:89–126

  21. 21.

    Montanari T, Castoldi L, Lietti L, Busca G (2011) Basic catalysis and catalysis assisted by basicity: FT-IR and TPD characterization of potassium-doped alumina. Appl Catal A Gen 400:61–69

  22. 22.

    Morterra C, Magnacca G (1996) A case study: surface chemistry and surface structure of catalytic aluminas, as studied by vibrational spectroscopy of adsorbed species. Catal Today 27:497–532

  23. 23.

    Ziolek M, Kujawa J, Saur O, Lavalley JC (1993) Metal oxides as catalysts for the reaction between methanol and hydrogen sulfide. J Phys Chem 97:9761–9766

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Correspondence to Ricardo Bermejo-Deval or Johannes A. Lercher.

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Weber-Stockbauer, M., Baumgärtl, M., Gutiérrez, O.Y. et al. Magnesium–Aluminum Mixed Oxides as Basic Catalysts for the Synthesis of Methanethiol. Catal Lett (2020). https://doi.org/10.1007/s10562-020-03128-9

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Keywords

  • Thiolation
  • Aluminium–magnesium oxides
  • Alcohol
  • Hydrogen sulfide
  • Lewis acid catalysis