Advertisement

Liquefaction of Softwoods and Hardwoods in Supercritical Methanol: A Novel Approach to Bio-Oil Production

  • J. Andres Soria
  • Armando G. McDonald
Chapter

Abstract

The production of consistent renewable-based hydrocarbons from woody biomass involves the efficient conversion into stable product streams. Supercritical methanol treatment is a new approach to efficiently convert woody biomass into bio-oil at modest processing temperatures (> 238 °C) and pressures (> 8.1 MPa). The conversion of common Alaskan tree species namely, Alaskan birch and Sitka spruce, was evaluated using the supercritical methanol liquefaction process to yield bio-oil and biochar fractions. Results show that liquefaction of softwoods and hardwoods can be achieved in excess of 90 wt%. The biochar was characterized by Fourier transform infrared spectroscopy and showed that this was lignin derived. The volatile components from the resultant bio-oil were chemically characterized (composition) by gas chromatography-mass spectrometry. The resulting bio-oil was comprised of partially methylated lignin-derived monomers and sugar derivatives which results in a stable and consistent product platform that can be followed by catalytic upgrading into a drop-in-fuel. The broader implications of this novel approach to obtain sustainable bioenergy and biofuel infrastructure are discussed.

Keywords

Thermochemical Conversion Generation Biofuel Supercritical Methanol Liquid Biofuel Biochar Sample 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgments

This project was supported by USDA-CSREES Wood Utilization Research program grant #2008-34158-19486. The FTIR spectrometer was supported by a USDA-CSREES-NRI equipment grant #2005-35103–15243.

References

  1. 1.
    EIA (U.S. Energy Information Administration) (2010) Annual Energy Review 2009. DOE/EIA-0384 (2009). Department of Energy, Energy Information Administration, Washington, DCGoogle Scholar
  2. 2.
    Tyner WE (2008) The U.S. ethanol and biofuels boom: its origins, current status, and future prospects. Bioscience 58(7):646–653CrossRefGoogle Scholar
  3. 3.
    Searchinger T, Heimlich R, Houghton RA, Dong F, Elobeid A, Fabiosa J, Tokgoz S, Hayes D, Yu T-H (2008) Use of U.S. croplands for biofuels increases greenhouse gases through emissions from land-use change. Science 319(5867):1238–1240Google Scholar
  4. 4.
    Sheehan J (2009) Biofuels and the conundrum of sustainability. Curr Opin Biotechnol 20:318–324CrossRefGoogle Scholar
  5. 5.
    NAS-NAE-NRC (National Academy of Sciences, National Academy of Engineering, National Research Council) (2009) Liquid transportation fuels from coal and biomass: technological status, costs, and environmental impacts. The National Academies Press, Washington, DCGoogle Scholar
  6. 6.
    Bridgwater AV, Peacocke GVC (1994) Engineering development in fast pyrolysis for bio-oils. In: Proceedings of biomass pyrolysis oil properties and combustion meeting, Estes Park, Co., Sept 26–28, pp 110–127Google Scholar
  7. 7.
    Bridgwater AV, Czernik S, Piskorz J (2001) An overview of fast pyrolysis. In: Bridgwater AV (ed) Progress in thermochemical biomass conversion. IEA Bioenergy. Blackwell Sciences, Oxford, pp 977–997Google Scholar
  8. 8.
    Czernik S, Bridgwater AV (2004) Overview of applications of biomass fast pyrolysis oil. Energy Fuel 18(2):977–997CrossRefGoogle Scholar
  9. 9.
    Mohan D, Pittman CU, Steele PH (2006) Pyrolysis of wood/biomass: a critical review. Energy Fuel 20(3):848–889CrossRefGoogle Scholar
  10. 10.
    Perego C (2007) Development of a Fischer-Tropsch catalyst: from laboratory to commercial scale demonstration. Rend Fis Acc Lincea 18(9):305–317CrossRefGoogle Scholar
  11. 11.
    Elliott DC (2007) Historical developments in hydroprocessing bio-oils. Energy Fuels 21:1792–1815CrossRefGoogle Scholar
  12. 12.
    Diebold J, Scahill J (1988) Biomass to gasoline. In: Soltes EJ, Milne TA (eds) Pyrolysis oils from biomass, ACS Symposium Series 376Google Scholar
  13. 13.
    Evans RJ, Milne T (1988) Molecular-beam, mass-spectrometric studies of wood vapor and model compounds over an HZSM-5 catalyst. In: Soltes EJ, Milne TA (eds) Pyrolysis oils from biomass, ACS Symposium Series 376Google Scholar
  14. 14.
    Horne P, Nugranad AN, Williams PT (1997) The influence of steam on the zeolite catalytic upgrading of biomass pyrolysis oils. In: Bridgewater AV, Boocock DGB (eds) Developments in thermochemical biomass conversion, vol 1. Blackie Academic and Professional, London, p 1648Google Scholar
  15. 15.
    Sharma RK, Bakhshi NN (1993) Catalytic upgrading of fast pyrolysis oil over HZSM-5. Can J Chem Eng 71:383–391CrossRefGoogle Scholar
  16. 16.
    Hayes DJ (2009) An examination of biorefining processes, catalysts and challenges. Catal Today 145(1–2):138–151MathSciNetCrossRefGoogle Scholar
  17. 17.
    Diebold JP (2000) A review of the chemical and physical mechanisms of the storage stability of fast pyrolysis bio-oils. National Renewable Energy Laboratory Report NREL/SR-570-27613. U.S. Department of Energy, Office of Scientific and Technical InformationGoogle Scholar
  18. 18.
    Soria AJ, McDonald AG, Shook SJ (2008) Wood solubilization and depolymerization using supercritical methanol. Part 1: process optimization and analysis of methanol insoluble components (bio-char). Holzforschung 62:402–408Google Scholar
  19. 19.
    Moldoveanu SC (1998) Analytical pyrolysis of natural organic polymers. Tech Instrum Anal Chem 20:3–31CrossRefGoogle Scholar
  20. 20.
    Ishikawa Y, Saka S (2001) Chemical conversion of cellulose as treated in supercritical methanol. Cellulose 8:189–195CrossRefGoogle Scholar
  21. 21.
    Minami E, Saka S (2003) Comparison of the decomposition behaviors of hardwood and softwood in supercritical methanol. J Wood Sci 49:73–78CrossRefGoogle Scholar
  22. 22.
    Clifford A (1998) Analytical supercritical fluid extraction techniques. Kluwer Academic Publishers, PontypriddGoogle Scholar
  23. 23.
    Johnson DK, Chum HL, Anzick R, Baldwin RM (1988) Lignin liquefaction in supercritical water. In: Bridgewater AV, Kuester JL (eds) Research in thermochemical biomass conversion. Elsevier Applied Science, Phoenix, Arizona, pp 485–496CrossRefGoogle Scholar
  24. 24.
    Soria AJ, McDonald AG, He BB (2008) Wood solubilization and depolymerization by supercritical methanol. Part 2: analysis of methanol soluble compounds. Holzforschung 62:409–416Google Scholar
  25. 25.
    Ehara K, Takada D, Saka S (2005) GC-MS and IR spectroscopic analyses of the lignin-derived products from softwood and hardwood treated in supercritical water. J Wood Sci 51:256–261CrossRefGoogle Scholar
  26. 26.
    Lee SH, Ohkita T (2003) Rapid wood liquefaction by supercritical phenol. Wood Sci Technol 37(1):29–38CrossRefGoogle Scholar
  27. 27.
    Schacht C, Zetzl C, Brunner G (2008) From plant materials to ethanol by means of supercritical fluid technology. J Supercrit Fluids 46:299–321CrossRefGoogle Scholar
  28. 28.
    Saka S, Ueno T (1999) Chemical conversion of various celluloses to glucose and its derivatives in superscritical water. Cellulose 6:177–191CrossRefGoogle Scholar
  29. 29.
    Faix O (1991) Condensation indices of lignins determined by FTIR spectroscopy. Holz als Roh- und Werkstoff 49:356CrossRefGoogle Scholar
  30. 30.
    Herring AM, McKinnon JT, Gneshin KW, Pavelka R, Petrick DE, McCloskey BD, Filley J (2004) Detection of reactive intermediates from and characterization of biomass char by laser pyrolysis molecular beam mass spectroscopy. Fuel 83:1483–1494CrossRefGoogle Scholar
  31. 31.
    Faix O (1992) Fourier transform infrared spectroscopy. In: Lin SY, Dence CW (eds) Methods in lignin chemistry. Springer, Berlin, pp 83–132CrossRefGoogle Scholar
  32. 32.
    Sharma RK, Wooten JB, Baliga VL, Lin X, Chan WG, Hajaligol MR (2004) Characterization of chars from pyrolysis of lignin. Fuel 83:1469–1482CrossRefGoogle Scholar
  33. 33.
    Shabaka AA, Nada AMA (1990) Infrared spectroscopic study of thermally treated lignin. J Mater Sci 25:2925–2928CrossRefGoogle Scholar
  34. 34.
    Colom X, Carrillo F, Nogues F, Garriga P (2003) Structural analysis of photodegraded wood by means of FTIR spectroscopy. Polym Degrad Stab 80:543–549CrossRefGoogle Scholar
  35. 35.
    Fox SC, McDonald AG (2010) Chemical and thermal characterizaion of three industrial lignins and their corresponding lignin esters. BioResources 5(2):990–1009Google Scholar
  36. 36.
    Miller JE, Evans L, Littlewolf A, Trudell DE (1999) Batch microreactor studies of lignin and lignin model compound depolymerization by bases in alcohol solvents. Fuel 78:1363–1366CrossRefGoogle Scholar
  37. 37.
    Tsujino J, Kawamoto H, Saka S (2003) Reactivity of lignin in supercritical methanol studied with various lignin model compounds. Wood Sci Technol 37:299–307CrossRefGoogle Scholar
  38. 38.
    Erickson M, Larsson S, Miksche GE (1973) Gaschromatographische analyse von ligninoxydations-produkten. VIII: Zur struktur des lignins der fichte. Acta Chem Scand 27(3):903–914CrossRefGoogle Scholar
  39. 39.
    Oliet M, Rodrıguez F, Santos A, Gilarranz MA, Garcıa-Ochoa F, Tijero J (2000) Organosolv delignification of Eucalyptus globulus: kinetic study of autocatalyzed ethanol pulping. Ind Eng Chem Res 39:34–39CrossRefGoogle Scholar
  40. 40.
    Kirci H, Akgul M (2002) Production of dissolving grade pulp from poplar wood by ethanol-water process. Turk J Agric For 26:239–245Google Scholar
  41. 41.
    Sannigrahi P, Ragauskas AJ, Miller SJ (2010) Lignin structural modifications resulting from ethanol organosolv treatment of loblolly pine. Energy Fuels 24:683–689CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  1. 1.Agricultural and Forestry Experiment StationUniversity of Alaska FairbanksPalmerUSA
  2. 2.School of EngineeringUniversity of Alaska AnchoragePalmerUSA
  3. 3.Renewable Materials Program, College of Natural ResourcesUniversity of IdahoMoscowUSA

Personalised recommendations