Reforming Biomass Derived Pyrolysis Bio-Oil Aqueous Phase to Fuels

Calvin Mukarakate, Robert J. Evans, Steve Deutch, Tabitha Evans, Anne K. Starace, Jeroen Ten Dam, Michael J. Watson, Kim Magrini

Research output: Contribution to journalArticlepeer-review

37 Scopus Citations


Fast pyrolysis and catalytic fast pyrolysis (CFP) of biomass produce a liquid product stream comprised of various classes of organic compounds having different molecule size and polarity. This liquid, either spontaneously in the case of catalytic fast pyrolysis or by water addition for the noncatalytic process separates into a nonpolar organic-rich fraction and a highly polar water-rich fraction. The organic fraction can be used as a blendstock or feedstock for further processing in a refinery while, in the CFP process design, the aqueous phase is currently sent to wastewater treatment, which results in a loss of residual biogenic carbon present in this stream. This work focuses on the catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce hydrocarbons using a vertical microreactor coupled to a molecular beam mass spectrometer (MBMS). The MBMS provides real-time analysis of products while also tracking catalyst deactivation. The catalyst used in this work was HZSM-5, which upgraded the oxygenated organics in the aqueous fraction from noncatalytic fast pyrolysis of oak wood to fuels comprising small olefins and aromatic hydrocarbons. During processing of the aqueous bio-oil fraction, the HZSM-5 catalyst exhibited higher activity and coke resistance than those observed in similar experiments using biomass or whole bio-oils. Reduced coking is likely due to ejection of coke precursors from the catalyst pores that was enhanced by excess process water available for steam stripping. The water reacted with coke precursors to form phenol, methylated phenols, naphthol, and methylated naphthols. Conversion data shows that up to 40 wt % of the carbon in the feed stream is recovered as hydrocarbons.

Original languageAmerican English
Pages (from-to)1600-1607
Number of pages8
JournalEnergy and Fuels
Issue number2
StatePublished - 16 Feb 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

NREL Publication Number

  • NREL/JA-5100-67160


  • bio-oil aqueous fraction
  • fuels and chemicals
  • hydrocarbons
  • HZSM-5
  • upgrading


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