Topics in Catalysis

, Volume 59, Issue 1, pp 109–123 | Cite as

Reactions of Mixture of Oxygenates Found in Pyrolysis Vapors: Deoxygenation of Hydroxyacetaldehyde and Guaiacol Catalyzed by HZSM-5

  • Singfoong Cheah
  • Anne K. Starace
  • Erica Gjersing
  • Sarah Bernier
  • Steve Deutch
Original Paper


Pyrolysis is a promising thermochemical process to convert lignocellulosic biomass to renewable biofuel. Much research has been conducted on the catalytic upgrading of either vapors derived from whole biomass scale or on individual model oxygenates. However, not many studies investigated the upgrading and deoxygenation of a mixture of several oxygenates. In this study, we use a combination of techniques to probe the reactions of guaiacol and hydroxyacetaldehyde (HAA) on HZSM-5, their diffusion inside the zeolite catalyst pores, and the extractable products. The techniques we used included several NMR methods, gas chromatography, and thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (TGA-FTIR). In nitrogen at 280 °C with HZSM-5 catalyst, HAA decomposes, cyclizes to form aromatics and phenolic compounds, as well as produces coke. Under the same conditions, guaiacol neither reacts nor forms coke. When the two molecules are present together at 280 °C, their reaction pathways are independent of each other. For HAA at 480 °C, the quantity of aromatics produced is much higher than at 280 °C. At 480 °C guaiacol forms mostly substituted phenolics, BTEX type molecules, and coke. When guaiacol and HAA are mixed together at 480 °C, the amount of coke formed is slightly higher while the aromatics produced in the form of toluene, naphthalene, and their substituted compounds are substantially higher than that can be predicted by simple summation of products in individual cases. After reactions with guaiacol alone or a mixture containing both guaiacol and HAA, the available micropore surface area decreased to zero, indicating plugging of the pores or blocking of pore entrance. However, in both cases the guaiacol and phenolics can be desorbed in an N2 atmosphere at a relatively low temperature range of 100–200 °C. Diffusion measurements indicate that size has a large effect on the pore diffusion coefficients of different oxygen molecules. After coke forms on the catalyst the diffusion coefficients of larger molecules such as guaiacol are affected more significantly than diffusion of small molecules such as water and methanol.


ZSM-5 Guaiacol Hydroxyacetaldehyde Glycolaldehyde Diffusion Deoxygenation 



This work was supported by Laboratory Directed Research and Development Program of the National Renewable Energy Laboratory (NREL) and the Bioenergy Technologies Office (BETO) at the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy. NREL is operated by The Alliance for Sustainable Energy, LLC under Contract no. DE-AC36-08-GO28308.

Supplementary material

11244_2015_510_MOESM1_ESM.docx (4.1 mb)
Supplementary material 1 (docx 4182 kb)


  1. 1.
    French R, Czernik S (2010) Catalytic pyrolysis of biomass for biofuels production. Fuel Process Technol 91:25–32CrossRefGoogle Scholar
  2. 2.
    Diebold J, Scahill J (1988) In: Soltes EJ, Milne TA (eds) Biomass to gasoline—upgrading pyrolysis vapors to aromatic gasoline with zeolite catalysts at atmospheric-pressure, Pyrolysis Oils from Biomass-Producing, Analyzing, and Upgrading, Denver, 1988. The American Chemical Society, Denver, pp 264–276Google Scholar
  3. 3.
    Evans RJ, Milne T (1988) In: Soltes EJ, Milne TA (eds) Molecular-beam, mass-spectrometric studies of wood vapor and model compounds over an HZSM–5 catalyst, pyrolysis oils from biomass-producing, analyzing, and upgrading, Denver, CO, 1988. The American Chemical Society, Denver, CO, pp 311–327Google Scholar
  4. 4.
    Evans RJ, Milne TA (1987) Molecular characterization of the pyrolysis of biomass. 2. Applications. Energy Fuels 1:311–319CrossRefGoogle Scholar
  5. 5.
    Evans RJ, Milne TA (1987) Molecular characterization of the pyrolysis of biomass. 1. Fundamentals. Energy Fuels 1:123–137CrossRefGoogle Scholar
  6. 6.
    Adjaye JD, Bakhshi NN (1995) Catalytic coversion of a biomass-derived oil to fuels and chemicals. 1. Model-compound studies and reaction pathways. Biomass Bioenerg 8:131–149CrossRefGoogle Scholar
  7. 7.
    Adjaye JD, Bakhshi NN (1995) Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. 1. Conversion over various catalysts. Fuel Process Technol 45:161183Google Scholar
  8. 8.
    Gayubo AG, Aguayo AT, Atutxa A, Aguado R, Bilbao J (2004) Transformation of oxygenate components of biomass pyrolysis oil on a HZSM-5 zeolite. I. Alcohols and phenols. Ind Eng Chem Res 43:2610–2618CrossRefGoogle Scholar
  9. 9.
    Gayubo AG, Aguayo AT, Atutxa A, Aguado R, Olazar M, Bilbao J (2004) Transformation of oxygenate components of biomass pyrolysis oil on a HZSM-5 zeolite. H. Aldehydes, ketones, and acids. Ind Eng Chem Res 43:2619–2626CrossRefGoogle Scholar
  10. 10.
    Gayubo AG, Aguayo AT, Atutxa A, Prieto R, Bilbao J (2004) Deactivation of a HZSM-5 zeolite catalyst in the transformation of the aqueous fraction of biomass pyrolysis oil into hydrocarbons. Energy Fuels 18:1640–1647CrossRefGoogle Scholar
  11. 11.
    Corma A, Huber GW, Sauvanauda L, O’Connor P (2008) Biomass to chemicals: Catalytic conversion of glycerol/water mixtures into acrolein, reaction network. J Catal 257:163–171CrossRefGoogle Scholar
  12. 12.
    Vispute TP, Zhang H, Sanna A, Xiao R, Huber GW (2010) Renewable chemical commodity feedstocks from integrated catalytic processing of pyrolysis oils. Science 330:1222–1227CrossRefGoogle Scholar
  13. 13.
    Centeno A, Laurent E, Delmon B (1995) Influence of the support of CoMo sulfide catalysts and of the addition of potassium and platinum on the catalytic performances for the hydrodeoxygenation of carbonyl, carboxyl, and guaiacol-type molecules. J Catal 154:288–298CrossRefGoogle Scholar
  14. 14.
    Nimmanwudipong T, Runnebaum RC, Block DE, Gates BC (2011) Catalytic conversion of guaiacol catalyzed by platinum supported on alumina: reaction network including hydrodeoxygenation reactions. Energy Fuels 25:3417–3427CrossRefGoogle Scholar
  15. 15.
    Gutierrez A, Kaila RK, Honkela ML, Slioor R, Krause AOI (2009) Hydrodeoxygenation of guaiacol on noble metal catalysts. Catal Today 147:239–246CrossRefGoogle Scholar
  16. 16.
    Graca I, Lopes JM, Ribeiro MF, Ribeiro FR, Cerqueira HS, de Almeida MBB (2011) Catalytic cracking in the presence of guaiacol. Appl Catal B-Environ 101:613–621CrossRefGoogle Scholar
  17. 17.
    Milne TA, Agblevor F, Davis M, Deutch S, Johnson D (1997) A review of the chemical composition of fast pyrolysis oils, in developments in thermal biomass conversion. In Bridgwater AV, Boocock DGB (eds). Blackie Academic and Professional, London, UK, pp 409–424Google Scholar
  18. 18.
    Mullen CA, Boateng AA (2008) Chemical composition of bio-oils produced by fast pyrolysis of two energy crops. Energy Fuels 22:2104–2109CrossRefGoogle Scholar
  19. 19.
    GrenierLoustalot MF, Larroque S, Grande D, Grenier P, Bedel D (1996) Phenolic resins.2. Influence of catalyst type on reaction mechanisms and kinetics. Polymer 37:1363–1369CrossRefGoogle Scholar
  20. 20.
    Koch H, Pein J (1985) Condensation reactions between phenol, formaldehyde and 5-hydroxymethylfurfural, formed as intermediate in the acid catalyzed dehydration of starchy products. Polym Bull 13:525–532CrossRefGoogle Scholar
  21. 21.
    Ragnar M, Lindgren CT, Nilvebrant NO (2000) pK(a)-values of guaiacyl and syringyl phenols related to lignin. J Wood Chem Technol 20:277–305CrossRefGoogle Scholar
  22. 22.
    Mullen CA, Strahan GD, Boateng AA (2009) Characterization of various fast-pyrolysis bio-oils by NMR spectroscopy. Energy Fuels 23:2707–2718CrossRefGoogle Scholar
  23. 23.
    Wildschut J, Mahfud FH, Venderbosch RH, Heeres HJ (2009) Hydrotreatment of fast pyrolysis oil using heterogeneous noble-metal catalysts. Ind Eng Chem Res 48:10324–10334CrossRefGoogle Scholar
  24. 24.
    Kerssenbaum, R DOSY and Diffusion by NMR; Bruker BioSpin GmbH: Rheinstetten, Germany 2002Google Scholar
  25. 25.
    Brunauer S, Emmett PH, Teller E (1938) Adsorption of gases in multimolecular layers. J Am Chem Soc 60:309–319CrossRefGoogle Scholar
  26. 26.
    de Boer JH, Linsen BG, van der Plas T, Zondervan GJ (1965) Studies on pore systems in catalysts: VII. Description of the pore dimensions of carbon blacks by the t method. J Catal 4:649–653CrossRefGoogle Scholar
  27. 27.
    Derlacki ZJ, Easteal AJ, Edge AVJ, Woolf LA, Roksandic Z (1985) Diffusion coefficients of methanol and water and the mutual diffusion coefficient in methanol-water solutions at 278 and 298 K. J Phys Chem 89:5318–5322CrossRefGoogle Scholar
  28. 28.
    Caro J, Bulow M, Richter-Mendau J, Karger J, Hunger M, Freude D, Rees LVC (1987) Nuclear magnetic resonance self-diffusion studies of methanol-water mixtures in pentasil-type zeolites. J Chem Soc Faraday Trans 1 Phys Chem Conden Phases 83:1843–1849Google Scholar
  29. 29.
    Krishna R, van Baten JM (2010) Hydrogen bonding effects in adsorption of water-alcohol mixtures in zeolites and the consequences for the characteristics of the Maxwell–Stefan diffusivities. Langmuir 26:10854–10867CrossRefGoogle Scholar
  30. 30.
    Roque-Malherbe R, Wendelbo R, Mifsud A, Corma A (1995) Diffusion of aromatic hydrocarbons in H-ZSM-5, H-Beta, and H-MCM-22 zeolites. J Phys Chem 99:14064–14071CrossRefGoogle Scholar
  31. 31.
    Kua J, Galloway MM, Millage KD, Avila JE, De Haan DO (2013) Glycolaldehyde monomer and oligomer equilibria in aqueous solution: comparing computational chemistry and NMR data. J Phys Chem A 117:2997–3008CrossRefGoogle Scholar
  32. 32.
    Muller G, Narbeshuber T, Mirth G, Lercher JA (1994) Infrared microscopic study of sorption and diffusion of toluene in ZSM-5. J Phys Chem 98:7436–7439CrossRefGoogle Scholar
  33. 33.
    Graca I, Fernandes A, Lopes JM, Ribeiro MF, Laforge S, Magnoux P, Ribeiro FR (2010) Effect of phenol adsorption on HY zeolite for n-heptane cracking: Comparison with methylcyclohexane. Appl Catal A-Gen 385:178–189CrossRefGoogle Scholar
  34. 34.
    Graca I, Fernandes A, Lopes JM, Ribeiro MF, Laforge S, Magnoux P, Ribeiro FR (2011) Bio-oils and FCC feedstocks co-processing: Impact of phenolic molecules on FCC hydrocarbons transformation over MFI. Fuel 90:467–476CrossRefGoogle Scholar
  35. 35.
    Zhong HE, Wang X (2014) Highly selective catalytic hydrodeoxygenation of guaiacol to cyclohexane over Pt/TiO2 and NiMo/Al2O3 catalysts. Front Chem Sci Eng 8:369–377CrossRefGoogle Scholar
  36. 36.
    Sun J, Karim AM, Zhang H, Kovarik L, Li XS, Hensley AJ, McEwen J-S, Wang Y (2013) Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol. J Catal 306:47–57CrossRefGoogle Scholar
  37. 37.
    Olcese RN, Bettahar M, Petitjean D, Malaman B, Giovanella F, Dufour A (2012) Gas-phase hydrodeoxygenation of guaiacol over Fe/SiO2 catalyst. Appl Catal B 115–116:63–73CrossRefGoogle Scholar
  38. 38.
    Lu J, Behtash S, Mamun O, Heyden A (2015) Theoretical investigation of the reaction mechanism of the guaiacol hydrogenation over a Pt(111) catalyst. ACS Catal 5:2423–2435CrossRefGoogle Scholar
  39. 39.
    Lu J, Heyden A (2015) Theoretical investigation of the reaction mechanism of the hydrodeoxygenation of guaiacol over a Ru(0 0 0 1) model surface. J Catal 321:39–50CrossRefGoogle Scholar
  40. 40.
    Lee K, Gu GH, Mullen CA, Boateng AA, Vlachos DG (2015) Guaiacol hydrodeoxygenation mechanism on Pt(111): Insights from density functional theory and linear free energy relations. ChemSusChem 8:315–322CrossRefGoogle Scholar
  41. 41.
    Van Speybroeck V, De Wispelaere K, Van der Mynsbrugge J, Vandichel M, Hemelsoet K, Waroquier M (2014) First principle chemical kinetics in zeolites: the methanol-to-olefin process as a case study. Chem Soc Rev 43:7326–7357CrossRefGoogle Scholar
  42. 42.
    Moore HW, Decker OHW (1986) Conjugated ketenes: new aspects of their synthesis and selected utility for the synthesis of phenols, hydroquinones, and quinones. Chem Rev 86:821–830CrossRefGoogle Scholar
  43. 43.
    Tidwell TT (1990) Ketene chemistry: the second golden age. Acc Chem Res 23:273–279CrossRefGoogle Scholar
  44. 44.
    Hamilton GA, Hanifin JW, Friedman JP (1966) The hydroxylation of aromatic compounds by hydrogen peroxide in the presence of catalytic amounts of ferric ion and catechol. Product studies, mechanism, and relation to some enzymic reaction. J Am Chem Soc 88:5269–5272CrossRefGoogle Scholar
  45. 45.
    Bagchi P, Bergmann F, Bannerjee DK (1949) A new synthesis of 9-hydroxy-sym-octahydrophenanthrene. J Am Chem Soc 71:989–992CrossRefGoogle Scholar
  46. 46.
    Wan H, Chaudhari RV, Subramaniam B (2012) Aqueous phase hydrogenation of acetic acid and its promotional effect on p-cresol hydrodeoxygenation. Energy Fuels 27:487–493CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Singfoong Cheah
    • 1
  • Anne K. Starace
    • 1
  • Erica Gjersing
    • 1
  • Sarah Bernier
    • 1
  • Steve Deutch
    • 1
  1. 1.National Renewable Energy LaboratoryGoldenUSA

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