Skip to main content
Log in

Upgrading of derived pyrolysis vapors for the production of biofuels from corncobs

  • Research Article
  • Published:
Frontiers of Chemical Science and Engineering Aims and scope Submit manuscript

Abstract

A bubbling fluidized bed pyrolyzer was integrated with an in-situ honeycomb as a catalytic upgrading zone for the conversion of biomass to liquid fuels. In the upgrading zone, zeolite coated ceramic honeycomb (ZCCH) catalysts consisting of ZSM-5 (Si/Al = 25) were stacked and N2 or recycled non-condensable gas was used as a carrier gas. Ground corncob particles were fast pyrolyzed in the bubbling bed using fine sand particles as a heat carrier and the resulting pyrolysis vapors were passed on-line over the catalytic upgrading zone. The influence of carrier gas, temperature, and weight hourly space velocity (WHSV) of catalyst on the oil product properties, distribution and mass balance were studied. Using ZCCH effectively increased the hydrocarbon yield and the heating value of the dry oil, especially in the presence of the recycled noncondensable gas. Even a low usage of zeolite catalyst at WSHVof 180 h‒1 was effective in upgrading the pyrolysis oil and other light olefins. The highest hydrocarbon (⩾C2) and liquid aromatics yields reached to 14.23 and 4.17 wt-%, respectively. The undesirable products including light oxygenates, furans dramatically decreased in the presence of the ZCCH catalyst.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Huber G W, Chheda J N, Barrett C J, Dumesic J A. Production of liquid alkanes by aqueous-phase processing of biomass-derived carbohydrates. Science, 2005, 308(5727): 2075–2078

    Article  Google Scholar 

  2. Cortright R D, Davda R R, Dumesic J A. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water. Nature, 2002, 418(6901): 964–967

    Article  CAS  Google Scholar 

  3. Huber G W, Dumesic J A. An overview of aqueous-phase catalytic processes for production of hydrogen and alkanes in a biorefinery. Catalysis Today, 2006, 111(1-2): 119–132

    Article  CAS  Google Scholar 

  4. Czernik S, Bridgwater A V. Overview of applications of biomass fast pyrolysis oil. Energy & Fuels, 2004, 18(2): 590–598

    Article  CAS  Google Scholar 

  5. Huber G W, Ibarra S, Corma A. Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering. Chemical Reviews, 2006, 106(9): 4044–4098

    Article  CAS  Google Scholar 

  6. Bridgwater A V, Bridge S A. A review of biomass pyrolysis and pyrolysis technologies. In: Bridgwater A V, Grassi G, eds. Biomass Pyrolysis Liquids Upgrading and Utilisation. London: Elsevier Applied Science, 1991, 11–92

    Chapter  Google Scholar 

  7. Zhang H, Carlson T R, Xiao R, Huber G W. Catalytic fast pyrolysis of wood and alcohol mixtures in a fluidized bed reactor. Green Chemistry, 2012, 14(1): 98–110

    Article  CAS  Google Scholar 

  8. Elliott D C, Beckman D, Bridgwater A V, Diebold J P, Gevert S B, Solantausta Y. Developments in direct thermochemical liquefaction of biomass: 1983‒1990. Energy & Fuels, 1991, 5(3): 399–410

    Article  CAS  Google Scholar 

  9. Edward F. Catalytic hydrodeoxygenation. Applied Catalysis A, General, 2000, 199(2): 147–190

    Article  Google Scholar 

  10. Valle B, Gayubo A G, Atutxa A, Alonso A, Bilbao J. Integration of thermal treatment and catalytic transformation for upgrading biomass pyrolysis oil. International Journal of Chemical Reactor Engineering, 2007, 5(1): 1–13

    Article  Google Scholar 

  11. Gayubo A G, Valle B, Aguayo A T, Olazar M, Bilbao J. Olefin production by catalytic transformation of crude bio-oil in a two-step process. Industrial & Engineering Chemistry Research, 2010, 49(1): 123–131

    Article  CAS  Google Scholar 

  12. Srinivas S T, Dalai A K, Bakhshi N N. Thermal and catalytic upgrading of a biomass-derived oil in a dual reaction system. Chemical Engineering Journal, 2000, 78(2): 343–354

    CAS  Google Scholar 

  13. Valle B, Atutxa A, Aguayo A T, Olazar M, Gayubo A G. Effect of nickel incorporation on the acidity and stability of HZSM-5 zeolite in the MTO process. Catalysis Today, 2005, 106(1-4): 118–122

    Article  CAS  Google Scholar 

  14. Corma A. State of the art and future challenges of zeolites as catalysts. Journal of Catalysis, 2003, 216(1): 298–312

    Article  CAS  Google Scholar 

  15. Gayubo A G, Aguayo A T, Atutxa A, Aguado R, Olazar M, Bilbao J, Olazar M, Bilbao J. Transformation of oxygenate components of biomass pyrolysis oil on a HZSM-5 zeolite. II. Aldehydes, ketones, and acids. Industrial & Engineering Chemistry Research, 2004, 43 (11): 2619–2626

    Article  CAS  Google Scholar 

  16. Aho A, Kumar N, Eränen K, Salmi T, Hupa M, Murzin D Y. Catalytic pyrolysis of woody biomass in a fluidized bed reactor: Influence of the zeolite structure. Fuel, 2008, 87(12): 2493–2501

    Article  CAS  Google Scholar 

  17. Alaitz A, Roberto A, Ana G G, Martin O, Javier B. Kinetic description of the catalytic pyrolysis of biomass in a conical spouted bed reactor. Energy & Fuels, 2005, 19(3): 765–774

    Article  Google Scholar 

  18. Lappas A A, Samolada M C, Iatridis D K, Voutetakis S S, Vasalos I A. Biomass pyrolysis in a circulating fluid bed reactor for the production of fuels and chemicals. Fuel, 2002, 81(16): 2087–2095

    Article  CAS  Google Scholar 

  19. Corma A. State of the art and future challenges of zeolites as catalysts. Journal of Catalysis, 2003, 216(1-2): 298–312

    Article  CAS  Google Scholar 

  20. Renaud M, Grandmaison J L, Roy C, Kaliaguine S. Low-Pressure Upgrading of Vacuum-Pyrolysis Oils from Wood. Pyrolysis Oils from Biomass. Washington DC: ACS, 1988, 290–310

    Chapter  Google Scholar 

  21. Sharma R K, Bakhshi N N. Catalytic upgrading of pyrolysis oil. Energy & Fuels, 1993, 7(2): 306–314

    Article  CAS  Google Scholar 

  22. Chantal P D, Kaliaguin S, Grandmaison J L, Mahay A. Production of hydrocarbons from aspen poplar pyrolytic oils over H-ZSM5. Applied Catalysis, 1984, 10(3): 317–332

    Article  CAS  Google Scholar 

  23. Carlson T R, Cheng Y T, Jaea J, Huber G W. Production of green aromatics and olefins by catalytic fast pyrolysis of wood sawdust. Energy & Environmental Science, 2011, 4(1): 145–161

    Article  CAS  Google Scholar 

  24. Williams P T, Horne P A. The influence of catalyst type on the composition of upgraded biomass pyrolysis oils. Journal of Analytical and Applied Pyrolysis, 1995, 31(2): 39–61

    Article  CAS  Google Scholar 

  25. Aho A, Kumar N, Eränen K, Hupa M, Salmi T, Murzin D Y. Zeolite-bentonite hybrid catalysts for the pyrolysis of woody biomass. Studies in Surface Science and Catalysis, 2008, 174(1): 1069–1074

    Article  Google Scholar 

  26. Aho A, Kumar N, Lashkul A V, Eränen K, Murzin D. Catalytic upgrading of woody biomass derived pyrolysis vapours over iron modified zeolites in a dual-fluidized bed reactor. Fuel, 2010, 89(8): 1992–2000

    Article  CAS  Google Scholar 

  27. Adama J, Antonakoub E, Lappasb A, Stöckerc M, Nilsenc M H, Bouzgac A, Hustada J E, Øyed G. In situ catalytic upgrading of biomass derived fast pyrolysis vapours in a fixed bed reactor using mesoporous materials. Microporous and Mesoporous Materials, 2006, 96(1-3): 93–101

    Article  Google Scholar 

  28. Zhang Q, Chang J, Wang T, Xu Y. Review of biomass pyrolysis oil properties and upgrading research. Energy Conversion and Management, 2007, 48(1): 87–92

    Article  CAS  Google Scholar 

  29. Diebold J P, Chum H L, Evans R J, Milne T A, Reed T B, Scahill J W. In: Klass D L. ed. Energy from Biomass and Wastes X. London: IGT Chicago and Elsevier Applied Sciences Publishers, 1987, 801

  30. Diebold J, Scahill J. Biomass to gasoline: Upgrading pyrolysis vapors to aromatic gasoline with zeolites catalysis at atmospheric pressure. In: Soltes E J, Milne T A, eds. Pyrolysis Liquids from Biomass. Washington DC: ACS, 1988, 264–276

    Chapter  Google Scholar 

  31. Diebold J P, Beckman D, Bridgwater A V, Elliott D C, Solantausta Y. IEA technoeconomic analysis of the thermochemical conversion of biomass to gasoline by the NREL process. In: Bridgwater A V, ed. Advances in Thermochemical Biomass Conversion. Berlin: Springer Netherlands, 1994, 1325–1342

    Google Scholar 

  32. Evans R, Milne T. Molecular-beam, mass spectrometric studies of wood vapor and model compounds over an HSZM-5 catalyst. In: Soltes E J, Milne T A, eds. Pyrolysis Liquids from Biomass. Washington DC: ACS, 1988, 311–327

    Chapter  Google Scholar 

  33. French R, Czernik S. Catalytic pyrolysis of biomass for biofuels production. Fuel Processing Technology, 2010, 91(1): 25–32

    Article  CAS  Google Scholar 

  34. Zhang Q, Chang J, Wang T, Xu Y. Review of biomass pyrolysis oil properties and upgrading research. Energy Conversion and Management, 2007, 48(1): 87–92

    Article  CAS  Google Scholar 

  35. Stefanidis S D, Kalogiannis K G, Iliopoulou E F, Lappas A A, Pilavachi P A. In-situ upgrading of biomass pyrolysis vapors: Catalyst screening on a fixed bed reactor. Bioresource Technology, 2011, 102(17): 8261–8267

    Article  CAS  Google Scholar 

  36. Cybulski A, Moulijn J. Monoliths in heterogeneous catalysis. Catalysis Reviews. Science and Engineering, 1994, 36(2): 179–270

    CAS  Google Scholar 

  37. Evans R J, Milne T A. In: Soltes E J, Milne T A, eds. Pyrolysis Oils from Biomass, Producing, Analysing and Upgrading. ACS Symposium Series 376. Washington DC: American Chemical Society, 1988, 328–341

  38. Huber G W, Iborra S, Corma A. Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering. Chemical Reviews, 2006, 106(9): 4044–4098

    Article  CAS  Google Scholar 

  39. Kharas K C, Robota H J, Liu D J. Deactivation in Cu-ZSM-5 leanburn catalysts. Applied Catalysis B: Environmental, 1993, 2(2-3): 225–237

    Article  CAS  Google Scholar 

  40. Vitolo S, Bresci B, Seggiani M, Gallo M G. Catalytic upgrading of pyrolytic oils over HZSM-5 zeolite: Behaviour of the catalyst when used in repeated upgrading-regenerating cycles. Fuel, 2001, 80(1): 17–26

    Article  CAS  Google Scholar 

  41. Foster A J, Jae J, Cheng Y T, Huber GW, Lobo R F. Optimizing the aromatic yield and distribution from catalytic fast pyrolysis of biomass over ZSM-5. Applied Catalysis A, General, 2012, 423-424: 154–161

    Article  CAS  Google Scholar 

  42. Li J, Li X, Zhou G, Wang W, Wang C, Komarneni S, Wang Y. Catalytic fast pyrolysis of biomass with mesoporous ZSM-5 zeolites prepared by desilication with NaOH solutions. Applied Catalysis A, General, 2014, 470(2): 115–122

    CAS  Google Scholar 

Download references

Acknowledgements

This research was supported by the CAS/SAFEA International Partnership Program for Creative Research Teams. The National Science Fund Projects (Y731410602) and the Chinese Government “Thousand Talent” program funding.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Z. Conrad Zhang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mao, L., Li, Y. & Zhang, Z.C. Upgrading of derived pyrolysis vapors for the production of biofuels from corncobs. Front. Chem. Sci. Eng. 12, 50–58 (2018). https://doi.org/10.1007/s11705-017-1685-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11705-017-1685-4

Keywords

Navigation