Factor effects and interactions in steam reforming of biomass bio-oil

  • Joshua O. IghaloEmail author
  • Adewale George Adeniyi
Original Paper


One of the current methods of converting pyrolysis oil and its aqueous phase into more useful biofuels with higher heating value is by the steam reforming technique. In this study, a thermodynamic model for the steam reforming of the aqueous phase of biomass bio-oil was developed. The optimal values of the process parameters for the steam reforming of the aqueous phase of biomass bio-oil are reforming temperature of 773 °C, reforming pressure of 1 atm and steam-to-oil ratio of 20 kg/kg. The synthesis gas obtained at optimal conditions has a hydrogen gas content of 76%, carbon dioxide content of 22%, carbon monoxide content of 2% and only trace quantities of methane. For a theoretical feed of 100 kg/h bio-oil, a water flow rate of 2000 kg/h will be required. Simulation showed that overall gas yield under such feed rate at optimal conditions will generate 131.3 kg/h synthesis gas (with 76% H2 content) and 1968.7 kg/h of condensate water. The interaction of the factors with regard to all chemical species was also extensively investigated.


Interactions Bio-oil Steam reforming Hydrogen Biomass Thermodynamics 



Gibbs free energy (kJ/mol)


Temperature (°C or K)


Pressure (bar and atm)

\( n_{i} \)

Number of moles of species i (mol)


Total number of chemical species in the reaction mixture


Gas constant (J/mol K)

\( \mu_{i} \)

Chemical potential of species i (kJ/mol)

\( y_{i} \)

Mole fraction of species i

\( \Delta G_{i}^{0} \)

Standard Gibbs free energy of the formation of species i (kJ/mol)


Total number of moles of all species in the gas mixture (mol)

\( a_{li} \)

Number of gram atoms of element l in 1 mol of species i

\( b_{l} \)

Total number of gram atoms of element l in the reaction mixture


Total number of atomic elements

\( {\text{STOR}} \)

Steam-to-oil mass ratio (kg/kg)


Compliance with ethical standards

Conflict of interest

No potential conflict of interest was reported by the authors.


  1. Adeniyi AG, Ighalo JO (2018) Study of process factor effects and interactions in synthesis gas production via a simulated model for glycerol steam reforming. Chem Prod Process Model. CrossRefGoogle Scholar
  2. Adeniyi AG, Ighalo JO (2019a) Hydrogen production by the steam reforming of waste lubricating oil. Indian Chem Eng. CrossRefGoogle Scholar
  3. Adeniyi AG, Ighalo JO (2019b) A review of steam reforming of glycerol. Chem Pap. CrossRefGoogle Scholar
  4. Adeniyi AG, Ighalo JO, Abdulsalam A (2019a) Modelling of integrated processes for the recovery of the energetic content of sugarcane bagasse. Biofuels Bioprod Biorefin. CrossRefGoogle Scholar
  5. Adeniyi AG, Ighalo JO, Otoikhian KS (2019b) Steam reforming of acetic acid: response surface modelling and study of factor interactions. Chem Prod Process Model. CrossRefGoogle Scholar
  6. Adeniyi AG, Otoikhian KS, Ighalo JO (2019c) Steam reforming of biomass pyrolysis oil: a review. Int J Chem React Eng. CrossRefGoogle Scholar
  7. Adhikari S, Fernando S, Gwaltney SR, To SF, Bricka RM, Steele PH, Haryanto A (2007a) A thermodynamic analysis of hydrogen production by steam reforming of glycerol. Int J Hydrogen Energy 32(14):2875–2880. CrossRefGoogle Scholar
  8. Adhikari S, Fernando S, Haryanto A (2007b) A comparative thermodynamic and experimental analysis on hydrogen production by steam reforming of glycerin. Energy Fuels 21(4):2306–2310. CrossRefGoogle Scholar
  9. Arregi A, Lopez G, Amutio M, Barbarias I, Bilbao J, Olazar M (2016) Hydrogen production from biomass by continuous fast pyrolysis and in-line steam reforming. RSC Adv 6(31):25975–25985. CrossRefGoogle Scholar
  10. Arregi A, Amutio M, Lopez G, Bilbao J, Olazar M (2018) Evaluation of thermochemical routes for hydrogen production from biomass: a review. Energy Convers Manag 165:696–719. CrossRefGoogle Scholar
  11. Basagiannis AC, Verykios XE (2007) Steam reforming of the aqueous fraction of bio-oil over structured Ru/MgO/Al2O3 catalysts. Catal Today 127(1–4):256–264. CrossRefGoogle Scholar
  12. Bimbela F, Chen D, Ruiz J, García L, Arauzo J (2012) Ni/Al coprecipitated catalysts modified with magnesium and copper for the catalytic steam reforming of model compounds from biomass pyrolysis liquids. Appl Catal B 119:1–12. CrossRefGoogle Scholar
  13. Bleeker M, Gorter S, Kersten S, van der Ham L, van den Berg H, Veringa H (2010) Hydrogen production from pyrolysis oil using the steam-iron process: a process design study. Clean Technol Environ Policy 12(2):125–135. CrossRefGoogle Scholar
  14. Bulushev DA, Ross JR (2011) Catalysis for conversion of biomass to fuels via pyrolysis and gasification: a review. Catal Today 171(1):1–13. CrossRefGoogle Scholar
  15. Calles JA, Carrero A, Vizcaíno AJ, García-Moreno L, Megía PJ (2019) Steam reforming of model bio-oil aqueous fraction using Ni–(Cu Co, Cr)/SBA-15 catalysts. Int J Mol Sci 20(3):512. CrossRefPubMedCentralGoogle Scholar
  16. Chattanathan SA, Adhikari S, Abdoulmoumine N (2012) A review on current status of hydrogen production from bio-oil. Renew Sustain Energy Rev 16(5):2366–2372. CrossRefGoogle Scholar
  17. Chen T, Wu C, Liu R (2011) Steam reforming of bio-oil from rice husks fast pyrolysis for hydrogen production. Biores Technol 102(19):9236–9240. CrossRefGoogle Scholar
  18. Czernik S, Bridgwater A (2004) Overview of applications of biomass fast pyrolysis oil. Energy Fuels 18(2):590–598. CrossRefGoogle Scholar
  19. Davidian T, Guilhaume N, Iojoiu E, Provendier H, Mirodatos C (2007) Hydrogen production from crude pyrolysis oil by a sequential catalytic process. Appl Catal B 73(1–2):116–127. CrossRefGoogle Scholar
  20. Gayubo AG, Valle B, Aramburu B, Montero C, Bilbao J (2018) Kinetic model considering catalyst deactivation for the steam reforming of bio-oil over Ni/La2O3–αAl2O3. Chem Eng J 332:192–204. CrossRefGoogle Scholar
  21. Gollakota ARK, Reddy M, Subramanyam MD, Kishore N (2016) A review on the upgradation techniques of pyrolysis oil. Renew Sustain Energy Rev 58:1543–1568. CrossRefGoogle Scholar
  22. Goyal N, Pant K, Gupta R (2013) Hydrogen production by steam reforming of model bio-oil using structured Ni/Al2O3 catalysts. Int J Hydrog Energy 38(2):921–933. CrossRefGoogle Scholar
  23. Heracleous E (2011) Well-to-Wheels analysis of hydrogen production from bio-oil reforming for use in internal combustion engines. Int J Hydrogen Energy 36(18):11501–11511. CrossRefGoogle Scholar
  24. Hou T, Yuan L, Ye T, Gong L, Tu J, Yamamoto M, Torimoto Y, Li Q (2009) Hydrogen production by low-temperature reforming of organic compounds in bio-oil over a CNT-promoting Ni catalyst. Int J Hydrogen Energy 34(22):9095–9107. CrossRefGoogle Scholar
  25. Iordanidis A, Kechagiopoulos P, Voutetakis S, Lemonidou A, Vasalos I (2006) Autothermal sorption-enhanced steam reforming of bio-oil/biogas mixture and energy generation by fuel cells: concept analysis and process simulation. Int J Hydrogen Energy 31(8):1058–1065. CrossRefGoogle Scholar
  26. Kinoshita C, Turn S (2003) Production of hydrogen from bio-oil using CaO as a CO2 sorbent. Int J Hydrog Energy 28(10):1065–1071. CrossRefGoogle Scholar
  27. Montero C, Oar-Arteta L, Remiro A, Arandia A, Bilbao J, Gayubo AG (2015) Thermodynamic comparison between bio-oil and ethanol steam reforming. Int J Hydrogen Energy 40(46):15963–15971. CrossRefGoogle Scholar
  28. Neumann J, Binder S, Apfelbacher A, Gasson JR, García PR, Hornung A (2015) Production and characterization of a new quality pyrolysis oil, char and syngas from digestate–introducing the thermo-catalytic reforming process. J Anal Appl Pyrol 113:137–142. CrossRefGoogle Scholar
  29. Peters JF, Iribarren D, Dufour J (2015) Simulation and life cycle assessment of biofuel production via fast pyrolysis and hydroupgrading. Fuel 139:441–456. CrossRefGoogle Scholar
  30. Remiro A, Valle B, Aguayo A, Bilbao J, Gayubo AG (2013a) Operating conditions for attenuating Ni/La2O3–αAl2O3 catalyst deactivation in the steam reforming of bio-oil aqueous fraction. Fuel Process Technol 115:222–232. CrossRefGoogle Scholar
  31. Remiro A, Valle B, Aguayo A, Bilbao J, Gayubo AG (2013b) Steam reforming of raw bio-oil in a fluidized bed reactor with prior separation of pyrolytic lignin. Energy Fuels 27(12):7549–7559. CrossRefGoogle Scholar
  32. Remón J, Broust F, Valette J, Chhiti Y, Alava I, Fernandez-Akarregi A, Arauzo J, Garcia L (2014) Production of a hydrogen-rich gas from fast pyrolysis bio-oils: comparison between homogeneous and catalytic steam reforming routes. Int J Hydrog Energy 39(1):171–182. CrossRefGoogle Scholar
  33. Remón J, Broust F, Volle G, García L, Arauzo J (2015) Hydrogen production from pine and poplar bio-oils by catalytic steam reforming: Influence of the bio-oil composition on the process. Int J Hydrog Energy 40(16):5593–5608. CrossRefGoogle Scholar
  34. Rioche C, Kulkarni S, Meunier FC, Breen JP, Burch R (2005) Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts. Appl Catal B 61(1–2):130–139. CrossRefGoogle Scholar
  35. Santamaria L, Lopez G, Arregi A, Amutio M, Artetxe M, Bilbao J, Olazar M (2018) Influence of the support on Ni catalysts performance in the in-line steam reforming of biomass fast pyrolysis derived volatiles. Appl Catal B 229:105–113. CrossRefGoogle Scholar
  36. Sarkar S, Kumar A (2010) Large-scale biohydrogen production from bio-oil. Biores Technol 101(19):7350–7361. CrossRefGoogle Scholar
  37. Shen L, Gao Y, Xiao J (2008) Simulation of hydrogen production from biomass gasification in interconnected fluidized beds. Biomass Bioenerg 32(2):120–127. CrossRefGoogle Scholar
  38. Spragg J, Mahmud T, Dupont V (2018) Hydrogen production from bio-oil: a thermodynamic analysis of sorption-enhanced chemical looping steam reforming. Int J Hydrog Energy 43(49):22032–22045. CrossRefGoogle Scholar
  39. Trane R, Dahl S, Skjøth-Rasmussen M, Jensen A (2012) Catalytic steam reforming of bio-oil. Int J Hydrog Energy 37(8):6447–6472. CrossRefGoogle Scholar
  40. Vagia EC, Lemonidou AA (2007) Thermodynamic analysis of hydrogen production via steam reforming of selected components of aqueous bio-oil fraction. Int J Hydrog Energy 32(2):212–223. CrossRefGoogle Scholar
  41. Vagia EC, Lemonidou AA (2008) Thermodynamic analysis of hydrogen production via autothermal steam reforming of selected components of aqueous bio-oil fraction. Int J Hydrog Energy 33(10):2489–2500. CrossRefGoogle Scholar
  42. Valle B, Gayubo AG, Atutxa A, Alonso A, Bilbao J (2007) Integration of thermal treatment and catalytic transformation for upgrading biomass pyrolysis oil. Int J Chem React Eng. CrossRefGoogle Scholar
  43. Valle B, Remiro A, Aguayo AT, Bilbao J, Gayubo AG (2013) Catalysts of Ni/α-Al2O3 and Ni/La2O3–αAl2O3 for hydrogen production by steam reforming of bio-oil aqueous fraction with pyrolytic lignin retention. Int J Hydrog Energy 38(3):1307–1318. CrossRefGoogle Scholar
  44. Valle B, Aramburu B, Benito PL, Bilbao J, Gayubo AG (2018a) Biomass to hydrogen-rich gas via steam reforming of raw bio-oil over Ni/La2O3-αAl2O3 catalyst: effect of space-time and steam-to-carbon ratio. Fuel 216:445–455. CrossRefGoogle Scholar
  45. Valle B, Aramburu B, Olazar M, Bilbao J, Gayubo AG (2018b) Steam reforming of raw bio-oil over Ni/La2O3–αAl2O3: influence of temperature on product yields and catalyst deactivation. Fuel 216:463–474. CrossRefGoogle Scholar
  46. Van Rossum G, Kersten SR, van Swaaij WP (2007) Catalytic and noncatalytic gasification of pyrolysis oil. Ind Eng Chem Res 46(12):3959–3967. CrossRefGoogle Scholar
  47. Wang D, Czernik S, Montane D, Mann M, Chornet E (1997) Biomass to hydrogen via fast pyrolysis and catalytic steam reforming of the pyrolysis oil or its fractions. Ind Eng Chem Res 36(5):1507–1518. CrossRefGoogle Scholar
  48. Wildschut J, Mahfud FH, Venderbosch RH, Heeres HJ (2009) Hydrotreatment of fast pyrolysis oil using heterogeneous noble-metal catalysts. Ind Eng Chem Res 48(23):10324–10334. CrossRefGoogle Scholar
  49. Wongkhorsub C, Chindaprasert N (2013) A comparison of the use of pyrolysis oils in diesel engine. Energy Power Eng 5(04):350. CrossRefGoogle Scholar
  50. Wright MM, Daugaard DE, Satrio JA, Brown RC (2010) Techno-economic analysis of biomass fast pyrolysis to transportation fuels. Fuel 89:S2–S10. CrossRefGoogle Scholar
  51. Wu C, Liu R (2010) Carbon deposition behavior in steam reforming of bio-oil model compound for hydrogen production. Int J Hydrogen Energy 35(14):7386–7398. CrossRefGoogle Scholar
  52. Wu C, Huang Q, Sui M, Yan Y, Wang F (2008) Hydrogen production via catalytic steam reforming of fast pyrolysis bio-oil in a two-stage fixed bed reactor system. Fuel Process Technol 89(12):1306–1316. CrossRefGoogle Scholar
  53. Xie H, Yu Q, Wang K, Shi X, Li X (2014) Thermodynamic analysis of hydrogen production from model compounds of bio-oil through steam reforming. Environ Progress Sustain Energy 33(3):1008–1016. CrossRefGoogle Scholar
  54. Xie H, Yu Q, Wei M, Duan W, Yao X, Qin Q, Zuo Z (2015) Hydrogen production from steam reforming of simulated bio-oil over Ce–Ni/Co catalyst with in continuous CO2 capture. Int J Hydrog Energy 40(3):1420–1428. CrossRefGoogle Scholar
  55. Xie H, Yu Q, Zuo Z, Han Z, Yao X, Qin Q (2016) Hydrogen production via sorption-enhanced catalytic steam reforming of bio-oil. Int J Hydrog Energy 41(4):2345–2353. CrossRefGoogle Scholar
  56. Xu Q, Lan P, Zhang B, Ren Z, Yan Y (2010) Hydrogen production via catalytic steam reforming of fast pyrolysis bio-oil in a fluidized-bed reactor. Energy Fuels 24(12):6456–6462. CrossRefGoogle Scholar
  57. Yan C-F, Cheng F-F, Hu R-R (2010) Hydrogen production from catalytic steam reforming of bio-oil aqueous fraction over Ni/CeO2–ZrO2 catalysts. Int J Hydrog Energy 35(21):11693–11699. CrossRefGoogle Scholar
  58. Zhang Q, Chang J, Wang T, Xu Y (2007) Review of biomass pyrolysis oil properties and upgrading research. Energy Convers Manage 48(1):87–92. CrossRefGoogle Scholar
  59. Zhang L, Liu R, Yin R, Mei Y (2013a) Upgrading of bio-oil from biomass fast pyrolysis in China: a review. Renew Sustain Energy Rev 24:66–72. CrossRefGoogle Scholar
  60. Zhang Y, Brown TR, Hu G, Brown RC (2013b) Comparative techno-economic analysis of biohydrogen production via bio-oil gasification and bio-oil reforming. Biomass Bioenerg 51:99–108. CrossRefGoogle Scholar
  61. Zhao B, Zhang X, Sun L, Meng G, Chen L, Xiaolu Y (2010) Hydrogen production from biomass combining pyrolysis and the secondary decomposition. Int J Hydrog Energy 35(7):2606–2611. CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2019

Authors and Affiliations

  1. 1.Chemical Engineering Department, Faculty of Engineering and TechnologyUniversity of IlorinIlorinNigeria

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