Topics in Catalysis

, Volume 59, Issue 1, pp 65–72 | Cite as

Characterization of Deactivated Bio-oil Hydrotreating Catalysts

  • Huamin WangEmail author
  • Yong Wang
Original Paper


Deactivation of bio-oil hydrotreating catalysts remains a significant challenge because of the poor quality of pyrolysis bio-oil input for hydrotreating and understanding their deactivation mode is critical to developing improved catalysts and processes. In this research, we developed an understanding of the deactivation of two-step bio-oil hydrotreating catalysts (sulfided Ru/C and sulfided CoMo/C) through detailed characterization of the catalysts using various analytical techniques. Severe fouling of both catalysts by carbonaceous species was the major form of deactivation, which is consistent with the significant loss of surface area and pore volume of both deactivated catalysts and the significant increase of the bulk density. Further analysis of the carbonaceous species by thermogravimetric analysis and X-ray photoelectron spectroscopy indicated that the carbonaceous species was formed by condensation reaction of active species such as sugars and sugar derivatives (aldehydes and ketones) in bio-oil feedstock during bio-oil hydrotreating under the conditions and catalysts used. Microscopy results did not show metal sintering of the Ru/C catalyst. However, X-ray diffraction indicated a probable transformation of the highly-active CoMoS phase in the sulfided CoMo/C catalyst to Co8S9 and MoS2 phase with low activity. Loss of the active site by transport of inorganic elements from the bio-oil and the reactor construction material onto the catalyst surface also might be a cause of deactivation as indicated by elemental analysis of spent catalysts.


Bio-oil hydrotreating Catalyst Deactivation XPS 



The authors gratefully acknowledge the United States Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office for the support of this work. XRD and XPS measurements were performed at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for DOE. The authors also thank Shari X. Li (PNNL) for surface area/pore volume measurement, Karl Albrecht (PNNL) for TGA-MS measurements, Mark Engelhard (PNNL) for XPS measurements, and Chongmin Wang (PNNL) for TEM measurements.


  1. 1.
    Huber GW, Iborra S, Corma A (2006) Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. Chem Rev 106:4044–4098CrossRefGoogle Scholar
  2. 2.
    Gallezot P (2012) Conversion of biomass to selected chemical products. Chem Soc Rev 41:1538–1558CrossRefGoogle Scholar
  3. 3.
    Elliott DC (2007) Historical developments in hydroprocessing bio-oils. Energy Fuels 21:1792–1815CrossRefGoogle Scholar
  4. 4.
    Bridgwater AV (2012) Review of fast pyrolysis of biomass and product upgrading. Biomass Bioenergy 38:68–94CrossRefGoogle Scholar
  5. 5.
    Wang H, Male J, Wang Y (2013) Recent Advances in Hydrotreating of Pyrolysis Bio-Oil and Its Oxygen-Containing Model Compounds. ACS Catal 3:1047–1070CrossRefGoogle Scholar
  6. 6.
    Zacher AH, Olarte MV, Santosa DM, Elliott DC, Jones SB (2014) A review and perspective of recent bio-oil hydrotreating research. Green Chem 16:491–515CrossRefGoogle Scholar
  7. 7.
    Venderbosch RH, Ardiyanti AR, Wildschut J, Oasmaa A, Heeresb HJ (2010) Stabilization of biomass-derived pyrolysis oils. J Chem Technol Biotechnol 85:674–686CrossRefGoogle Scholar
  8. 8.
    Wildschut J, Iqbal M, Mahfud FH, Melian-Cabrera I, Venderbosch RH, Heeres HJ (2010) Insights in the hydrotreatment of fast pyrolysis oil using a ruthenium on carbon catalyst. Energy Environ Sci 3:962–970CrossRefGoogle Scholar
  9. 9.
    Wildschut J, Melian-Cabrera I, Heeres HJ (2010) Catalyst studies on the hydrotreatment of fast pyrolysis oil. Appl Catal B 99:298–306CrossRefGoogle Scholar
  10. 10.
    Elliott DC, Hart TR, Neuenschwander GG, Rotness LJ, Olarte MV, Zacher AH, Solantausta Y (2012) Catalytic hydroprocessing of fast pyrolysis bio-oil from pine sawdust. Energy Fuels 26:3891–3896CrossRefGoogle Scholar
  11. 11.
    Elliott DC, Wang H, French R, Deutch S, Iisa K (2014) Hydrocarbon liquid production from biomass via hot-vapor-filtered fast pyrolysis and catalytic hydroprocessing of the bio-oil. Energy Fuels 28:5909–5917CrossRefGoogle Scholar
  12. 12.
    Schwaiger N, Elliott DC, Ritzberger J, Wang H, Pucher P, Siebenhofe MM (2015) Hydrocarbon liquid production via the bioCRACK process and catalytic hydroprocessing of the product oil. Green Chem 17:2487–2494CrossRefGoogle Scholar
  13. 13.
    Samolada MC, Baldauf W, Vasalos IA (1998) Production of a bio-gasoline by upgrading biomass flash pyrolysis liquids via hydrogen processing and catalytic cracking. Fuel 77:1667–1675CrossRefGoogle Scholar
  14. 14.
    Wang I, Lin H, Zheng Y (2014) Hydrotreatment of lignocellulosic biomass derived oil using a sulfided NiMo/[gamma]-Al2O3 catalyst. Catal Sci Tech 4:109–119CrossRefGoogle Scholar
  15. 15.
    Li Y, Zhou W, Wang H, Xie L, Liang Y, Wei F, Idrobo JC, Pennycook SJ, Dai H (2012) An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. Nat Nano 7:394–400CrossRefGoogle Scholar
  16. 16.
    Furimsky E, Massoth FE (1999) Deactivation of hydroprocessing catalysts. Catal Today 52:381–495CrossRefGoogle Scholar
  17. 17.
    Guichard B, Roy-Auberger M, Devers E, Rebours B, Quoineaud AA, Digne M (2009) Characterization of aged hydrotreating catalysts. Part I: coke depositions, study on the chemical nature and environment. Appl Catal A 367:1–8CrossRefGoogle Scholar
  18. 18.
    Hu X, Wang Y, Mourant D, Gunawan R, Lievens C, Chaiwat W, Gholizadeh M, Wu L, Li X, Li CZ (2013) Polymerization on heating up of bio-oil: a model compound study. AIChE J 59:888–900CrossRefGoogle Scholar
  19. 19.
    Inamura K, Prins R (1994) The role of Co in unsupported Co-Mo sulfides in the hydrodesulfurization of thiophene. J Catal 147:515–524CrossRefGoogle Scholar
  20. 20.
    Moses PG, Hinnemann B, Topsøe H, Nørskov JK (2009) The effect of Co-promotion on MoS2 catalysts for hydrodesulfurization of thiophene: a density functional study. J Catal 268:201–208CrossRefGoogle Scholar
  21. 21.
    Topsøe H (2007) The role of Co–Mo–S type structures in hydrotreating catalysts. Appl Catal A 322:3–8CrossRefGoogle Scholar
  22. 22.
    Oasmaa A, Elliott DC, Korhonen J (2010) Acidity of biomass fast pyrolysis bio-oils. Energy Fuels 24:6548–6554CrossRefGoogle Scholar
  23. 23.
    Jendoubi N, Broust F, Commandre JM, Mauviel G, Sardin M, Lede J (2011) Inorganics distribution in bio oils and char produced by biomass fast pyrolysis: the key role of aerosols. J Anal Appl Pyrolysis 92:59–67CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York (outside the USA) 2015

Authors and Affiliations

  1. 1.Pacific Northwest National LaboratoryRichlandUSA
  2. 2.Voiland School of Chemical Engineering and BioengineeringWashington State UniversityPullmanUSA

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