Topics in Catalysis

, Volume 59, Issue 1, pp 94–108 | Cite as

Catalytic Pyrolysis of Pine Over HZSM-5 with Different Binders

  • Kristiina IisaEmail author
  • Richard J. French
  • Kellene A. Orton
  • Sridhar Budhi
  • Calvin Mukarakate
  • Alexander R. Stanton
  • Matthew M. Yung
  • Mark R. Nimlos
Original Paper


Three HZSM-5 catalysts with different binders (alumina, silica, and clay) were evaluated for upgrading of pine pyrolysis vapors. All catalysts were based on the same HZSM-5 with silica to alumina molar ratio of 30. Experiments in micro-scale analytical Py-GCMS/FID showed that fresh catalysts with silica and clay produced predominantly aromatic hydrocarbons at similar carbon yields. The catalyst with alumina gave lower vapor yields and produced both hydrocarbons and partially deoxygenated products, in particular furans. The catalyst with alumina also gave higher coke yields and exhibited faster deactivation than the catalysts with clay and silica binders. The low hydrocarbon yields and coke formation were attributed to the acidic sites provided by alumina and blocking of the zeolite sites. The catalysts with silica and clay as binders were further tested in a 2-inch fluidized bed system for ex situ catalytic pyrolysis of pine. Similar oils were produced over both catalysts with carbon yields of approximately 23 % and oxygen contents of 20–21 %.


Catalytic pyrolysis Biomass HZSM-5 Binder Alumina Silica Clay 



This work was supported by the U.S. Department of Energy under Contract No. DE-AC36-08GO28308 with the National Renewable Energy Laboratory. Funding provided by U.S. DOE Office of Energy Efficiency and Renewable Energy Bioenergy Technologies Office is gratefully acknowledged. We wish to thank Scott Palmer, Michele Myers, Matt Plumb, Bill Michener, and Haoxi Ben for their technical assistance and discussions. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes.

Supplementary material

11244_2015_509_MOESM1_ESM.docx (23 kb)
Supplementary material 1 (DOCX 23 kb)


  1. 1.
    Bridgwater AV, Peacocke GVC (2000) Fast pyrolysis process for biomass. Renew Sustain Energy Rev 4:1–73CrossRefGoogle Scholar
  2. 2.
    Czernik S, Bridgwater AV (2004) Overview of applications of biomass fast pyrolysis oil. Energy Fuels 18:590–598CrossRefGoogle Scholar
  3. 3.
    Bridgwater AV (2012) Review of fast pyrolysis of biomass and product upgrading. Biomass Bioenergy 38:68–94CrossRefGoogle Scholar
  4. 4.
    Mohan D, Pittman CU Jr, Steele PH (2006) Pyrolysis of wood/biomass for bio-oil: a critical review. Energy Fuels 20:848–889CrossRefGoogle Scholar
  5. 5.
    Bridgwater AV, Czernik S, Piskorz J (2001) An overview of fast pyrolysis. In: Bridgwater AV (ed) Progress in thermochemical biomass conversion. Blackwell Science Ltd, Oxford, pp 977–997CrossRefGoogle Scholar
  6. 6.
    Oasmaa A, Solantausta Y, Arpiainen V, Kuoppala E, Sipilä K (2010) Fast pyrolysis bio-oils from wood and agricultural residues. Energy Fuels 24:1380–1388CrossRefGoogle Scholar
  7. 7.
    Chen NY, Degnan TF Jr, Koenig LR (1986) Liquid fuel from carbohydrates. ChemTech 16:506–511Google Scholar
  8. 8.
    Diebold J, Scahill J (1988) Biomass to gasoline. Upgrading pyrolysis vapors to aromatic gasoline with zeolite catalysis at atmospheric pressure. In: Soltes EJ, Milne TA (eds) Pyrolysis oils from biomass, vol 376., ACS symposium series, pp 311–327CrossRefGoogle Scholar
  9. 9.
    Horne PA, Williams PT (1996) Premium grade hydrocarbons from the catalytic treatment of pyrolysis vapors derived from biomass. In: Chartier P (ed) Biomass for energy and the environment: proceedings of the 9th European bioenergy conference. Pergamon, Oxford, pp 1601–1606Google Scholar
  10. 10.
    Corma A, Huber G, Sauvanaud L, O’Connor P (2007) Processing biomass-derived oxygenates in the oil refinery: catalytic cracking (FCC) reaction pathways and role of catalyst. J Catal 247:307–327CrossRefGoogle Scholar
  11. 11.
    Adjaye JD, Bakhshi NN (1995) Production of hydrocarbons by catalytic upgrading of a fast pyrolysis oil. Part I: conversion over various catalysts. Fuel Process Technol 45:161–183CrossRefGoogle Scholar
  12. 12.
    French R, Czernik S (2010) Catalytic pyrolysis of biomass for biofuels production. Fuel Process Technol 91:25–32CrossRefGoogle Scholar
  13. 13.
    Carlson TR, Tompsett GA, Conner WC, Huber GW (2009) Aromatic production from catalytic pyrolysis of biomass-derived feedstocks. Top Catal 52:241–252CrossRefGoogle Scholar
  14. 14.
    Sharma RK, Bakhshi NN (1993) Catalytic upgrading of fast pyrolysis oil over HZSM-5. Can J Chem Eng 71:381–391Google Scholar
  15. 15.
    Aho A, Kumar N, Eränen K, Salmi T, Hupa M, Murzin DY (2008) Catalytic pyrolysis of woody biomass in a fluidized bed reactor: influence of the zeolite structure. Fuel 87:2493–2501CrossRefGoogle Scholar
  16. 16.
    Mihalcik DJ, Mullen CA, Boateng AA (2011) Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components. J Anal Appl Pyrolysis 92:224–232CrossRefGoogle Scholar
  17. 17.
    Pattiya A, Titiloye JO, Bridgwater AV (2008) Fast pyrolysis of cassava rhizome in the presence of catalysts. J Anal Appl Pyrolysis 81:72–79CrossRefGoogle Scholar
  18. 18.
    Lappas AA, Samolada MC, Iatridis DK, Voutetakis SS, Vasalos IA (2002) Biomass pyrolysis in a circulating fluid bed reactor for the production of fuels and chemicals. Fuel 81:2087–2095CrossRefGoogle Scholar
  19. 19.
    Iliopoulou EF, Stefanidis S, Kalogiannis K, Psarras AC, Delimitis A, Triantafyllidis KS, Lappas AA (2014) Pilot-scale validation of Co-ZSM-5 catalyst performance in the catalytic upgrading of biomass pyrolysis vapours. Green Chem 16:662–674CrossRefGoogle Scholar
  20. 20.
    Dutta A, Sahir A, Tan E, Humbird D, Snowden-Swan LJ, Meyer P, Ross J, Sexton D, Yap R, Lukas J (2015) process design and economics for the conversion of lignocellulosic biomass to hydrocarbon fuels thermochemical research pathways with in situ and ex situ upgrading of fast pyrolysis vapors, process design and economics for the conversion of lignocellulosic biomass to hydrocarbon fuels thermochemical research pathways with in situ and ex situ upgrading of fast pyrolysis vapors, Technical Report NREL/TP-5100-62455, PNNL-23823, 275 ppGoogle Scholar
  21. 21.
    Hargreaves JSJ, Munnoch AL (2013) A survey of the influence of binders in zeolite catalysis. Catal Sci Technol 3:1165–1171CrossRefGoogle Scholar
  22. 22.
    Choudhary VR, Devadas E, Kinage AK, Guisnet M (1997) Influence of binder on the acidity and performance of H-Gallosilicate (MFI) zeolite in propane aromatization. Appl Catal A 162:223–233CrossRefGoogle Scholar
  23. 23.
    Zhang Y-Z, Yong X-J, Zhang K, Wang J, Jiang Y-J, Li Y, Qi J (2014) Effect of shape-forming method on performance of ZSM-5 zeolite catalyst for MTP. Tianranqi Huagong 39(32–35):51Google Scholar
  24. 24.
    Liu G, Guo J, Meng F, Zhang X, Wan L (2014) Effects of colloidal silica binder on catalytic activity and adhesion of HZSM-5 coatings for structured reactors. Chin J Chem Eng 22:875–881CrossRefGoogle Scholar
  25. 25.
    Du X, Kong X, Chen L (2014) Influence of binder on catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone. Catal Commun 45:109–113CrossRefGoogle Scholar
  26. 26.
    Devadas P, Kinage AK, Choudhary VR (1993) Effect of silica binder on acidity, catalytic activity and deactivation due to coking in propane aromatization over H-gallosilicate (MFI). Stud Surf Sci Catal 76:293–338CrossRefGoogle Scholar
  27. 27.
    Demiral I, Sensoz S (2008) The effects of different catalysts on the pyrolysis of industrial wastes (olive and hazelnut bagasse). Bioresour Technol 99:8002–8007CrossRefGoogle Scholar
  28. 28.
    Ates F, Isikdag M (2009) Influence of temperature and alumina catalyst on pyrolysis of corncob. Fuel 88:1991–1997CrossRefGoogle Scholar
  29. 29.
    Yorgun S, Simsek YE (2008) Catalytic pyrolysis of Miscanthus × giganteus over activated alumina. Bioresour Technol 99:8095–8100CrossRefGoogle Scholar
  30. 30.
    Samolada MC, Papafotica A, Vasalos IA (2000) catalyst evaluation for catalytic biomass pyrolysis. Energy Fuels 14:1161–1167CrossRefGoogle Scholar
  31. 31.
    Stefanidis SD, Kalogiannis KG, Iliopoulou E, Lappas AA, Pilavachi PA (2011) In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor. Bioresour Technol 102:8261–8267CrossRefGoogle Scholar
  32. 32.
    Zhang H, Xiao R, Jin B, Shen D, Chen R, Xiao G (2013) Catalytic fast pyrolysis of straw biomass in an internally interconnected fluidized bed to produce aromatics and olefins: effect of different catalysts. Bioresour Technol 137:82–87CrossRefGoogle Scholar
  33. 33.
    Zhang H, Xiao R, Jin B, Xiao G, Chen R (2013) Biomass catalytic pyrolysis to produce olefins and aromatics with a physically mixed catalyst. Bioresour Technol 140:256–262CrossRefGoogle Scholar
  34. 34.
    Elordi G, Olazar M, Artetxe M, Castano P, Bilbao J (2012) Effect of the acidity of the HZSM-5 zeolite catalyst on the cracking of high density polyethylene in a conical spouted bed reactor. Appl Catal A 415–416:89–95CrossRefGoogle Scholar
  35. 35.
    Mukarakate C, Zhang X, Stanton AR, Robichaud DJ, Ciesielski PN, Malhotra K, Donohoe BS, Gjersing E, Evans RJ, Heroux DS, Richards R, Iisa K, Nimlos MR (2014) Real-time monitoring of the deactivation of HZSM-5 during upgrading of pine pyrolysis vapors. Green Chem 16:1444–1461CrossRefGoogle Scholar
  36. 36.
    Nicolaides G (1984) The chemical characterization of pyrolytic oils. University of Waterloo, Department of Chemical Engineering, Waterloo, Ontario, pp. 17–26, 30–42Google Scholar
  37. 37.
    Dahl IM, Kolboe S (1993) On the reaction mechanism for propene formation in the MTO reaction over SAPO-34. Catal Lett 20:329–336CrossRefGoogle Scholar
  38. 38.
    Dahl IM, Kolboe S (1994) On the reaction mechanism for hydrocarbon formation from methanol over SAPO-34: I. isotopic labeling studies of the co-reaction of ethene and methanol. J Catal 149:458–464CrossRefGoogle Scholar
  39. 39.
    Dahl IM, Kolboe S (1996) On the reaction mechanism for hydrocarbon formation from methanol over SAPO-34 2. isotopic labeling studies of the co-reaction of propene and methanol. J Catal 161:304–309CrossRefGoogle Scholar
  40. 40.
    Hemelsoet K, Van der Mynsbrugge J, De Wispelaere K, Waroquier M, Van Speybroeck V (2013) Unraveling the reaction mechanisms governing methanol-to-olefins catalysis by theory and experiment. ChemPhysChem 14:1526–1545CrossRefGoogle Scholar
  41. 41.
    Bjørgen M, Svelle S, Joensen F, Nerlov J, Kolboe S, Bonino F, Palumbo L, Bordiga S, Olsbye U (2007) Conversion of methanol to hydrocarbons over zeolite H-ZSM-5: on the origin of the olefinic species. J Catal 249:20–195CrossRefGoogle Scholar
  42. 42.
    Carlson TR, Jae J, Huber GW (2009) Mechanistic insights from isotopic studies of glucose conversion to aromatics over ZSM-5. ChemCatChem 1:107–110CrossRefGoogle Scholar
  43. 43.
    Carlson TR, Vispute TP, Huber GW (2008) Green gasoline by catalytic fast pyrolysis of solid biomass derived compounds. ChemSusChem 1:39–400Google Scholar
  44. 44.
    Jackson MA, Compton DL, Boateng AA (2009) Screening heterogeneous catalysts for the pyrolysis of lignin. J Anal Appl Pyrolysis 85:226–230CrossRefGoogle Scholar
  45. 45.
    Mullen CA, Boateng AA (2010) Catalytic pyrolysis-CC/MS of lignin from several sources. Fuel Process Technol 91:1446–1458CrossRefGoogle Scholar
  46. 46.
    Mukarakate C, McBrayer JD, Evans TJ, Budhi S, Robichaud DJ, Iisa K, ten Dam J, Watson MJ, Baldwin RM, Nimlos MR (2015) Catalytic fast pyrolysis of biomass: the reactions of water and aromatic intermediates produces phenols. Green Chem 17:4217–4227CrossRefGoogle Scholar
  47. 47.
    Wan S, Wang Y (2014) A review on ex situ catalytic fast pyrolysis of biomass. Front Chem Sci Eng 8:280–294CrossRefGoogle Scholar
  48. 48.
    Gamliel DP, Du S, Bollas GM, Valla JA (2015) Investigation of in situ and ex situ catalytic pyrolysis of miscanthus giganteus using a PyGC–MS microsystem and comparison with a bench-scale spouted-bed reactor. Bioresour Technol 191:187–196CrossRefGoogle Scholar
  49. 49.
    Lourvanij K, Rorrer GL (1997) Reaction rates for the partial dehydration of glucose to organic acids in solid-acid, molecular-sieving catalyst powders. J Chem Tech Biotechnol 69:35–44CrossRefGoogle Scholar
  50. 50.
    Carlson TR, Jae J, Lin Y-C, Tompsett GA, Huber GW (2010) Catalytic fast pyrolysis of glucose with HZSM-5: the combined homogeneous and heterogeneous reactions. J Catal 270:110–124CrossRefGoogle Scholar
  51. 51.
    Mettler MS, Mushrif SH, Paulsen AD, Javadekar AD, Vlachos DG, Dauenhauer PJ (2012) Revealing pyrolysis chemistry for biofuels production: conversion of cellulose to furans and small oxygenates. Energy Environ Sci 5:5414–5424CrossRefGoogle Scholar
  52. 52.
    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
  53. 53.
    Howe D, Santosa D, Kutnyakova I, Lukins C, Westover T, Emerson R, Carpenter D, Deutch S, Starace A (2015) Field-to-fuel performance testing of lignocellulosic feedstocks: an integrated study of the fast pyrolysis/hydrotreating pathway. Energy Fuels 29:3188–3197CrossRefGoogle Scholar
  54. 54.
    Czernik S (2012) Catalytic pyrolysis of biomass. In: Lee J (ed) Advanced biofuels and bioproducts. Springer, New York, pp 119–128Google Scholar
  55. 55.
    Wang K, Kima KH, Brown RC (2014) Catalytic pyrolysis of individual components of lignocellulosic biomass. Green Chem 16:727–735CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Kristiina Iisa
    • 1
    Email author
  • Richard J. French
    • 1
  • Kellene A. Orton
    • 1
  • Sridhar Budhi
    • 1
  • Calvin Mukarakate
    • 1
  • Alexander R. Stanton
    • 1
  • Matthew M. Yung
    • 1
  • Mark R. Nimlos
    • 1
  1. 1.National Renewable Energy LaboratoryGoldenUSA

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