Skip to main content

Relationship Between Sulfidation and HDS Catalytic Activity of Activated Carbon Supported Mo, Fe–Mo, Co–Mo and Ni–Mo Carbides

Abstract

Temperature-programmed sulfiding (TPS) and temperature-programmed reduction of the sulfided catalysts (TPR-S) have been employed to evaluate Mo, Fe–Mo, Co–Mo and Ni–Mo carbide catalysts supported on activated carbon (AC). The carbides were prepared by carbothermal hydrogen reduction from co-impregnated precursors, and submitted to presulfiding prior to HDS. Samples of passivated catalysts prepared from the sulfates of Fe and Co contained variable amounts of sulfur, as shown by XPS and elemental analysis, while all samples showed increased sulfur contents after HDS. The TPS traces (up to 400 °C) of the Mo and Co–Mo samples exhibited two H2S consumption peaks, the first one starting at 100 °C and the second within the 400 °C isothermal region, located immediately after a H2S production peak centered at 400 °C for Mo and at 340 °C for Co–Mo. The Fe–Mo and Ni–Mo carbides exhibited a broad H2S consumption signal between 100 and 400 °C. The low temperature signals can be attributed to reduction of Mo(VI) oxide into Mo(V) or Mo(IV) sulfides, while the broad, higher temperature band is assigned to further reduction to the fully sulfided surface species. The TPR-S spectra showed three H2S evolution peaks, where the area of the first peak (assigned to reduction of sulfur species adsorbed on coordinatively unsaturated edge/corner sites) follows the order Co–Mo ≫ Ni–Mo ≈ Mo > Fe–Mo, which fully agrees with the order of HDS activities at steady state. Elemental analysis of the pre-sulfided AC support suggest that a large part of the sulfur consumed in sulfiding the catalysts is retained as elemental sulfur within the microporous structure of the support, although HRTEM observations confirm that MoS2-like structures are present in these samples. These results reinforce the importance of sulfided surface phases in HDS on carbides of transition metal catalysts.

Graphical Abstract

Transmission electron microscopy shows that activated carbon supported (M-)Mo carbide catalysts (M = Fe, Co, Ni) present MoS2-like fringes on top of bimetallic carbide crystals. Temperature-programmed techniques and elemental analysis prove that a large amount of sulfur is retained in the catalyst, likely within the slit-shaped microporous structure of the support. A good correlation was established between thiophene HDS activity at steady state and the size of a TPR peak of sulfided catalyst samples.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

References

  1. 1.

    Levy RB, Boudart M (1973) Science 181:547–549

    Article  CAS  Google Scholar 

  2. 2.

    Mordenti D, Brodzki D, Djéga-Mariadassou G (1998) J Solid State Chem 141:114–120

    Article  CAS  Google Scholar 

  3. 3.

    Sayag C, Benkhaled M, Suppan S, Trawczynski J, Djega-Mariadassou G (2004) Appl Catal A 275:15–24

    Article  CAS  Google Scholar 

  4. 4.

    McCrea KR, Logan JW, Tarbuck TL, Heiser JL, Bussell ME (1997) J Catal 171:255–267

    Article  CAS  Google Scholar 

  5. 5.

    Liu P, Rodriguez JA, Muckerman JT (2005) J Mol Catal A 239:116–124

    Article  CAS  Google Scholar 

  6. 6.

    Sundaramurthy V, Dalai AK, Adjaye J (2007) Catal Today 125:239–247

    Article  CAS  Google Scholar 

  7. 7.

    Aegerter PA, Quigley WWC, Simpson GJ, Ziegler DD, Logan JW, McCrea KR, Glazier S, Bussell ME (1996) J Catal 164:109–121

    Article  CAS  Google Scholar 

  8. 8.

    Díaz B, Sawhill SJ, Bale DH, Main R, Phillips DC, Korlann S, Self R, Bussell ME (2003) Catal Today 86:191–209

    Article  Google Scholar 

  9. 9.

    Ramanathan S, Oyama ST (1995) J Phys Chem 99:16365–16372

    Article  CAS  Google Scholar 

  10. 10.

    Dhandapani B, St. Clair T, Oyama ST (1998) Appl Catal A 168:219–228

    Article  CAS  Google Scholar 

  11. 11.

    Szymanska-Kolasa A, Lewandowski M, Sayag C, Djéga-Mariadassou G (2006) Catal Today 119:7–12

    Article  Google Scholar 

  12. 12.

    Puello-Polo E, Brito JL (2008) J Mol Cat A 281:85–92

    Article  CAS  Google Scholar 

  13. 13.

    Bouchy C, Pham-Huu C, Heinrich B, Chaumont C, Ledoux MJ (2000) J Catal 190:92–103

    Article  CAS  Google Scholar 

  14. 14.

    Puello-Polo E (2009) Ph. D. Thesis, IVIC, Caracas

  15. 15.

    Puello-Polo E, Brito JL (2010) Catal Today 149:316–320

    Article  CAS  Google Scholar 

  16. 16.

    Puello-Polo E, Brito JL (2008) In: Proceedings of the “XXI Simposio Iberoamericano de Catálisis” (SICAT 2008). Benalmádena-Costa, Málaga, Spain

  17. 17.

    Laine J, Labady M, Severino F, Yunes S (1997) J Catal 166:384–387

    Article  CAS  Google Scholar 

  18. 18.

    Liu P, Rodriguez JA, Asakura T, Gomes J, Nakamura K (2005) J Phys Chem B 109:4575–4583

    Article  CAS  Google Scholar 

  19. 19.

    Scheffer B, de Jonge JCM, Arnoldy P, Moulijn JA (1984) Bull Soc Chim Belg 93:751–762

    CAS  Google Scholar 

  20. 20.

    Arnoldy P, van den Heijkant JAM, de Bok GD, Moulijn JA (1985) J Catal 92:35–55

    Article  CAS  Google Scholar 

  21. 21.

    Mangnus PJ, Poels EK, Moulijn JA (1993) Ind Eng Chem Res 32:1818–1821

    Article  CAS  Google Scholar 

  22. 22.

    Scheffer B, Dekker NJJ, Mangnus PJ, Moulijn JA (1990) J Catal 121:31–46

    Article  CAS  Google Scholar 

  23. 23.

    Mangnus PJ, Riezebos A, van Langeveld AD, Moulijn JA (1995) J Catal 151:178–191

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Financial support through FONACIT Grant G-2000001537 is gratefully acknowledged. Technical assistance of Petra Hernández and Eleinne Severino (IVIC) with the CHNS elemental analysis, and of Iván Puente Lee (UNAM) with the microscopy experiments is also acknowledged. E.P–P thanks UNICAT-UNAM, C.E.A-IVIC, and his family for financing his visit to Mexico, and dedicates this work to Ofelia Polo, Marina Bono (Q.E.P.D), Gory and the family Puello Polo in Cartagena de Indias-Colombia.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Joaquín L. Brito.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Puello-Polo, E., Gutiérrez-Alejandre, A., González, G. et al. Relationship Between Sulfidation and HDS Catalytic Activity of Activated Carbon Supported Mo, Fe–Mo, Co–Mo and Ni–Mo Carbides. Catal Lett 135, 212–218 (2010). https://doi.org/10.1007/s10562-010-0303-6

Download citation

Keywords

  • Activated carbon support
  • Carbides
  • Sulfided surface
  • Thiophene hydrodesulfurization
  • TPR-S
  • TPS