Hydrothermal Liquefaction of Biomass in Hot-Compressed Water, Alcohols, and Alcohol-Water Co-solvents for Biocrude Production

  • Chunbao Charles XuEmail author
  • Yuanyuan Shao
  • Zhongshun Yuan
  • Shuna Cheng
  • Shanghuang Feng
  • Laleh Nazari
  • Matthew Tymchyshyn
Part of the Green Chemistry and Sustainable Technology book series (GCST)


Hydrothermal liquefaction (HTL) is a technology for directly converting biomass into clean liquid fuels (biocrude) in the presence of water or water-containing solvent/co-solvent and more commonly a suitable catalyst at a temperature of 200–400 °C and under moderate to high pressure (5–25 MPa). Two key operating parameters, solvent type/composition and catalysts play significant roles in the performance of a HTL process including biomass conversion, biocrude oil yield and oil quality, etc., which are closely related to the economic feasibility of the process for industrial/commercial applications. A HTL process with properly designed solvent and catalysts would lead to a high yield of biocrude oil (up to 65 %) with a high quality (lower oxygen content). This chapter provides an overview on the effects of solvents (focusing on water, alcohols, and alcohol-water co-solvents) and catalysts on the HTL processes, and their industrial applications.


Rice Straw Supercritical Water Fast Pyrolysis Biomass Conversion Supercritical Methanol 
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.



The authors are grateful for the financial support from the Natural Science and Engineering Research Council of Canada (NSERC) through the Discovery Grant. We also acknowledge the funding from the NSERC/FPInnovations Industrial Research Chair Program and Ontario Research Fund—Research Excellence Program in Forest Biorefinery, partnered with FPInnovations, Arclin and Bioindustrial Innovation Center. “In addition, the financial support from Lignoworks, BioFuelNet, MITACS and CENNATEK is gratefully acknowledged.”


  1. 1.
    Kucuk M, Demirbas A (1997) Biomass conversion processes. Energy Convers Manage 38:151–165CrossRefGoogle Scholar
  2. 2.
    McKendry P (2002) Energy production from biomass (Part 1): overview of biomass. Bioresour Technol 83:37–46CrossRefGoogle Scholar
  3. 3.
    Harms H (1998) Wood, a versatile chemical material. In: European conference on renewable raw materials, Gmunden, 1998Google Scholar
  4. 4.
    (S&T)2 Consultants Inc (2000) Liquid fuels from biomass: North America impact of non-technical barriers on implementation, prepared for IEA Bioenergy Task 27.
  5. 5.
    Wood S, Layzell DB (2003) A Canadian biomass inventory: feedstocks for a bio-based economy. BIOCAP Canada Foundation.
  6. 6.
    Yang B, Wyman CE (2008) Pretreatment: the key to unlocking low-cost cellulosic ethanol. Biofuels Bioprod Biorefin 2:26–40CrossRefGoogle Scholar
  7. 7.
    Bridgwater AV, Bridge SA (1991) Review of biomass pyrolysis processes. In biomass pyrolysis liquids upgrading and utilisation. Elsevier, New York, pp 11–92CrossRefGoogle Scholar
  8. 8.
    Demirbas A (2005) Pyrolysis of ground beech wood in irregular heating rate conditions. J Anal Appl Pyrolysis 73:39–43CrossRefGoogle Scholar
  9. 9.
    Bridgwater AV, Cottam ML (1992) Opportunities for biomass pyrolysis liquids production and upgrading. Energy Fuels 6(2):113–120CrossRefGoogle Scholar
  10. 10.
    Guo Y, Wang Y, Wei F (2001) Research progress in biomass flash pyrolysis technology for liquids production. Chem Ind Eng Progr 8:13–17Google Scholar
  11. 11.
    Appell HR, Fu YC, Friedman S, Yavorsky PM, Wender I (1971) Converting organic wastes to oil. US Bureau of Mines, Report of Investigation, No. 7560Google Scholar
  12. 12.
    Elliott DC (1980) Bench-scale research in biomass liquefaction by the CO-steam process. Can J Chem Eng 58:730–734Google Scholar
  13. 13.
    Schirmer RE, Pahl TR, Elliott DC (1984) Analysis of a thermochemically-derived wood oil. Fuel 63:368–372CrossRefGoogle Scholar
  14. 14.
    Yamazaki J, Minami E, Saka S (2006) Liquefaction of beech wood in various supercritical alcohols. J Wood Sci 52:527–532CrossRefGoogle Scholar
  15. 15.
    Xu C, Etcheverry T (2008) Hydro-liquefaction of woody biomass in sub- and super-critical ethanol with iron-based catalysts. Fuel 87:335–345CrossRefGoogle Scholar
  16. 16.
    Cheng S, Dcruz I, Wang M, Leitch M, Xu C (2010) Highly efficient liquefaction of woody biomass in hot-compressed alcohol-water co-solvents. Energy Fuels 24:4659–4667CrossRefGoogle Scholar
  17. 17.
    Behrendt F, Neubauer Y, Oevermann M, Wilmes B, Zobel N (2008) Direct liquefaction of biomass. Chem Eng Technol 31:667–677CrossRefGoogle Scholar
  18. 18.
    Toor SS, Rosendahl L, Rudolf A (2011) Hydrothermal liquefaction of biomass: a review of subcritical water technologies. Energy 36:2328–2342CrossRefGoogle Scholar
  19. 19.
    Zhang Y (2010) Hydrothermal liquefaction to convert biomass into crude oil. In: Ezeji TC, Jürgen S, Blaschek HP (eds) Biofuels from agricultural wastes and byproducts. Blackwell, LondonGoogle Scholar
  20. 20.
    Chornet E, Overend RP (1985) Biomass liquefaction: an overview. In: Overend RP, Milne TA, Mudge LK (eds) Fundamentals of thermochemical biomass conversion. Elsevier, LondonGoogle Scholar
  21. 21.
    Peterson AA, Vogel F, Lachance RP, Froling M, Antal MJ et al (2008) Thermochemical biofuel production in hydrothermal media: A review of sub- and supercritical water technologies. Energy Environ Sci 1:32–65CrossRefGoogle Scholar
  22. 22.
    Akhtar J, Amin NAS (2011) A review on process conditions for optimum bio-oil yield in hydrothermal liquefaction of biomass. Renew Sustain Energy Rev 15:1615–1624CrossRefGoogle Scholar
  23. 23.
    Mazaheri H, Lee KT, Bhatia S, Mohamed AR (2010) Sub/supercritical liquefaction of oil palm fruit press fiber for the production of bio-oil: effect of solvents. Bioresour Technol 101:7641–7647CrossRefGoogle Scholar
  24. 24.
    Liu Z, Zhang F (2008) Effects of various solvents on the liquefaction of biomass to produce fuels and chemical feedstocks. Energy Convers Manag 49:3498–3504CrossRefGoogle Scholar
  25. 25.
    Fan S, Zakaria S, Chia C, Jamaluddin F, Nabihah S et al (2011) Comparative studies of products obtained from solvolysis liquefaction of oil palm empty fruit bunch fibres using different solvents. Bioresour Technol 102:3521–3526CrossRefGoogle Scholar
  26. 26.
    Pan H (2011) Synthesis of polymers from organic solvent liquefied biomass: a review. Renew Sustain Energy Rev 15:3454–3463CrossRefGoogle Scholar
  27. 27.
    Zou X, Qin T, Wang Y, Huang L (2011) Mechanisms and product specialties of the alcoholysis processes of poplar components. Energy Fuels 25:3786–3792CrossRefGoogle Scholar
  28. 28.
    Li H, Yuan X, Zeng G, Tong J, Yan Y et al (2009) Liquefaction of rice straw in sub- and supercritical 1,4-dioxane-water mixture. Fuel Process Technol 90:657–663CrossRefGoogle Scholar
  29. 29.
    Wang Y, Wu L, Wang C, Yu J, Yang Z (2011) Investigating the influence of extractives on the oil yield and alkane production obtained from three kinds of biomass via deoxy-liquefaction. Bioresour Technol 102:7190–7195CrossRefGoogle Scholar
  30. 30.
    Wang M (2011) Reductive degradation of lignin in supercritical solvent and application in phenolic resin synthesis. Acta Polym Sin 12:1433–1438Google Scholar
  31. 31.
    Yuan X, Li H, Zeng G, Tong J, Xie W (2007) Sub- and supercritical liquefaction of rice straw in the presence of ethanol-water and 2-prop anol-water mixture. Energy 32:2081–2088CrossRefGoogle Scholar
  32. 32.
    Savage PE (1999) Organic chemical reactions in supercritical water. Chem Rev 99:603–621CrossRefGoogle Scholar
  33. 33.
    Savage PE (1996) Reaction model of cellulose decomposition in near-critical water and fermentation of products. Bioresour Technol 58:197–202CrossRefGoogle Scholar
  34. 34.
    Zhang L, Champagne P, Xu C (2011) Bio-crude production from secondary pulp/paper-mill sludge and waste newspaper via co-liquefaction in hot-compressed water. Energy 36:2142–2150CrossRefGoogle Scholar
  35. 35.
    Tymchyshyn M, Xu C (2010) Liquefaction of bio-mass in hot-compressed water for the production of phenolic compounds. Bioresour Technol 101:2483–2490CrossRefGoogle Scholar
  36. 36.
    Xu C, Lad N (2008) Production of heavy oils with high caloric values by direct liquefaction of woody biomass in sub/near-critical water. Energy Fuels 22:635–642CrossRefzbMATHGoogle Scholar
  37. 37.
    Xu C, Lancaster J (2008) Conversion of secondary pulp/paper sludge powder to liquid oil products for energy recovery by direct liquefaction in hot-compressed water. Water Res 42:1571–1582CrossRefGoogle Scholar
  38. 38.
    Ramsurn H, Gupta RB (2012) Production of bio-crude from biomass by acidic subcritical water followed by alkaline supercritical water two-step liquefaction. Energy Fuels 26:2365–2375CrossRefGoogle Scholar
  39. 39.
    Goudnaan F, van de Beld B, Boerefijn FR, Bos GM, Naber JE et al (2008) Thermal efficiency of the HTU® process for biomass liquefaction. In: Bridgwater AV (ed) Progress in thermochemical biomass conversion. Blackwell Science Ltd, OxfordGoogle Scholar
  40. 40.
    He B, Zhang Y, Yin Y, Funk TL, Riskowski GL (2001) Preliminary characterization of raw oil products from the thermochemical conversion of swine manure. Trans Asae 44:1865–1871Google Scholar
  41. 41.
    Theegala CS, Midgett JS (2012) Hydrothermal liquefaction of separated dairy manure for production of bio-oils with simultaneous waste treatment. Bioresour Technol 107:456–463CrossRefGoogle Scholar
  42. 42.
    Alba LG, Torri C, Samori C, van der Spek J, Fabbri D et al (2012) Hydrothermal treatment (HIT) of microalgae: evaluation of the process as conversion method in an algae bio-refinery concept. Energy Fuels 26:642–657CrossRefGoogle Scholar
  43. 43.
    Akalin MK, Tekin K, Karagoz S (2012) Hydrothermal liquefaction of cornelian cherry stones for bio-oil production. Bioresour Technol 110:682–687CrossRefGoogle Scholar
  44. 44.
    Liu H, Xie X, Li M, Sun R (2012) Hydrothermal liquefaction of cypress: effects of reaction conditions on 5-lump distribution and composition. J Anal Appl Pyrol 94:177–183CrossRefGoogle Scholar
  45. 45.
    Amen-Chen C, Pakdel H, Roy C (2001) Production of monomeric phenols by thermochemical conversion of biomass: a review. Bioresour Technol 79:277–299CrossRefGoogle Scholar
  46. 46.
    Demirbas A (2000) Effect of lignin content on aqueous liquefaction products of biomass. Energy Convers Manag 41:1601–1607CrossRefGoogle Scholar
  47. 47.
    Demirbas A (2010) Sub- and super-critical water depolymerization of biomass. Energy Sources Part A 32:1100–1110CrossRefGoogle Scholar
  48. 48.
    Durot N, Gaudard F, Kurek B (2003) The unmasking of lignin structures in wheat straw by alkali. Phytochemistry 63:617–623CrossRefGoogle Scholar
  49. 49.
    Demirbas A (2000) Mechanisms of liquefaction and pyrolysis reactions of biomass. Energy Convers Manag 41:633–646CrossRefGoogle Scholar
  50. 50.
    Bobleter O (1994) Hydrothermal degradation of polymers derived from plants. Prog Polym Sci 19:797–841CrossRefGoogle Scholar
  51. 51.
    Matsumura Y, Sasaki M, Okuda K, Takami S, Ohara S et al (2006) Supercritical water treatment of biomass for energy and material recovery. Combust Sci Technol 178:509–536CrossRefGoogle Scholar
  52. 52.
    Xu C, Donald J (2012) Upgrading peat to gas and liquid fuels in supercritical water with catalysts. Fuel 102:16–25CrossRefGoogle Scholar
  53. 53.
    Shiraishi N, Kishi H (1986) Wood-phenol adhesives prepared from carboxymet hylated wood. J Appl Polym Sci 32:3189–3209CrossRefGoogle Scholar
  54. 54.
    Alma M, Basturk M (2006) Liquefaction of grapevine cane (Vitis vinisera L.) waste and its application to phenol-formaldehyde type adhesive. Ind Crops Prod 24:171–176Google Scholar
  55. 55.
    Hassan ME, Mun SH (2002) Liquefaction of pine bark using phenol and lower alcohols with methane sulfonic acid catalyst. J Ind Chem 8:359–364Google Scholar
  56. 56.
    Yamada T, Ono H (1999) Rapid liquefaction of lignocellulosic waste by using ethylene carbonate. Bioresour Technol 70:61–67CrossRefGoogle Scholar
  57. 57.
    Minami E, Kawamoto H, Saka S (2003) Reaction behaviors of lignin in supercritical methanol as studied with lignin model compounds. Jpn Wood Res Soc 49:158–165CrossRefGoogle Scholar
  58. 58.
    Minami E, Saka S (2003) Comparison of decomposition behaviors of hard wood and soft wood in supercritical methanol. Jpn Wood Res Soc 49:73–78CrossRefGoogle Scholar
  59. 59.
    Minami E, Saka S (2005) Decomposition behavior of woody biomass in water-added supercritical methanol. Jpn Wood Res Soc 51:395–400CrossRefGoogle Scholar
  60. 60.
    Ishikawa Y, Saka S (2001) Chemical conversion of cellulose as treated in supercritical methanol. Cellulose 8:189–195CrossRefGoogle Scholar
  61. 61.
    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
  62. 62.
    Miller JE, Evans L, Littlewolf A, Trudell DE (1999) Batch micro-reactor studies of lignin and lignin model compound depolymerization by bases in alcohol solvents. Fuel 78:1363–1366CrossRefGoogle Scholar
  63. 63.
    Cemek M, Kucuk MM (2001) Liquid products from verbascum stalk by supercritical fluid extraction. Energy Convers Manag 42:125–130CrossRefGoogle Scholar
  64. 64.
    Georget DMR, Cairns P, Smith AC, Waldron KW (1999) Crystallinity of lyophilised carrot cell wall components. Int J Biol Macromol 26:325–331CrossRefGoogle Scholar
  65. 65.
    Maldas D, Shiraishi N (1997) Liquefaction of biomass in the presence of phenol and H2O using alkalies and salts as the catalyst. Biomass Bioenergy 12:273–279CrossRefGoogle Scholar
  66. 66.
    Saisu M, Sato T, Watanabe M, Adschiri T, Arai K (2003) Conversion of lignin with supercritical water-phenol mixtures. Energy Fuels 17:922–928CrossRefGoogle Scholar
  67. 67.
    Wang M, Leitch M, Xu C (2009) Synthesis of phenolic resol resins using cornstalk-derived bio-oil produced by direct liquefaction in hot-compressed phenol-water. J Ind Eng Chem 15:870–875CrossRefGoogle Scholar
  68. 68.
    Wang M, Xu C, Leitch M (2009) Liquefaction of cornstalk in hot-compressed phenol-water medium to phenolic feedstock for the synthesis of phenol-formaldehyde resin. Bioresour Technol 100:2305–2307CrossRefGoogle Scholar
  69. 69.
    Okuda K, Umetsu M, Takami S, Adschiri T (2004) Disassembly of lignin and chemical recovery-rapid depolymerizatin of lignin without char formation in water-phenol mixtures. Fuel Process Technol 85:803–813CrossRefGoogle Scholar
  70. 70.
    Pasquini D, Pimenta MTB, Ferreira LH, Curvelo AAS (2005) Extraction of lignin from sugar cane bagasse and Pinus taeda wood chips using ethanol-water mixtures and carbon dioxide at high pressures. J Supercrit Fluids 36:31–39CrossRefGoogle Scholar
  71. 71.
    Kleinert M, Barth T (2008) Towards a lignocellulosic bio-refinery: direct one-step conversion of lignin to hydrogen-enriched bio-fuel. Energy Fuels 22:1371–1379CrossRefGoogle Scholar
  72. 72.
    Yuan Z, Cheng S, Leitch M, Xu C (2010) Hydrolytic degradation of alkaline lignin in hot-compressed water and ethanol. Bioresour Technol 101:9308–9313CrossRefGoogle Scholar
  73. 73.
    Cheng S, Wilks C, Yuan Z, Leitch M, Xu C (2012) Hydrothermal degradation of alkali lignin to bio-phenolic compounds in sub/supercritical ethanol and water–ethanol co-solvent. Polym Degrad Stab 97:839–848CrossRefGoogle Scholar
  74. 74.
    Karagoz S, Bhaskar T, Muto A, Sakata Y (2004) Effect of Rb and Cs carbonates for production of phenols from liquefaction of wood biomass. Fuel 83:2293–2299CrossRefGoogle Scholar
  75. 75.
    Qian Y, Zuo C, Tan H, He J (2007) Structural analysis of bio-oils from sub- and supercritical water liquefaction of woody biomass. Energy 32:196–202CrossRefGoogle Scholar
  76. 76.
    Appell HR (1967) Fuels from waste. Academic Press, New YorkGoogle Scholar
  77. 77.
    Appell HR, Wender I, Miller RD (1969) Conversion of urban refues to oil. US Bureau of MinesGoogle Scholar
  78. 78.
    Karagoz S, Bhaskar T, Muto A, Sakata Y, Oshiki T et al (2005) Low-temperature catalytic hydrothermal treatment of wood biomass: analysis of liquid products. Chem Eng J 108:127–137CrossRefGoogle Scholar
  79. 79.
    Karagoz S, Bhaskar T, Muto A, Sakata Y (2006) Hydrothermal upgrading of biomass: Effect of K2CO3 concentration and biomass/water ratio on products distribution. Bioresour Technol 97:90–98CrossRefGoogle Scholar
  80. 80.
    Song C, Hu H, Zhu S, Wang G, Chen G (2004) Non-isothermal catalytic liquefaction of corn stalk in subcritical and supercritical water. Energy Fuels 18:90–96CrossRefGoogle Scholar
  81. 81.
    Zhong C, Wei X (2004) A comparative experimental study on the liquefaction of wood. Energy 29:1731–1741CrossRefGoogle Scholar
  82. 82.
    Zhang Q, Zhao G, Chen J (2006) Effects of inorganic acid catalysts on liquefaction of wood in phenol. Front For China 2:214–218CrossRefGoogle Scholar
  83. 83.
    Mazaheri H, Lee KT, Bhatia S, Mohamed AR (2010) Subcritical water liquefaction of oil palm fruit press fiber in the presence of sodium hydroxide: an optimisation study using response surface methodology. Bioresour Technol 101:9335–9341CrossRefGoogle Scholar
  84. 84.
    Li H, Hurley S, Xu C (2011) Liquefactions of peat in supercritical water with a novel iron catalyst. Fuel 90:412–420CrossRefGoogle Scholar
  85. 85.
    Minowa T, Zhen F, Ogi T (1998) Cellulose decomposition in hot-compressed water with alkali or nickel catalyst. J Supercrit Fluids 13:253–259CrossRefGoogle Scholar
  86. 86.
    Sinag A, Kruse A, Rathert J (2004) Influence of the heating rate and the type of catalyst on the formation of key intermediates and on the generation of gases during hydroprolysis of glucose in supercritical water in a batch reactor. Ind Eng Chem Res 43:502–508CrossRefGoogle Scholar
  87. 87.
    Watanabe M, Aizawa Y, Lida T, Aida TM, Levy C et al (2005) Glucose reactions with acid and base catalysts in hot compressed water at 473 K. Carbohydr Res 340:1925–1930CrossRefGoogle Scholar
  88. 88.
    Watanabe M, Bayer F, Kruse A (2006) Oil formation from glucose with formic acid and cobalt catalyst in hot-compressed water. Carbohydr Res 341:2891–2900CrossRefGoogle Scholar
  89. 89.
    Alma MH, Yoshioka M, Yao Y, Shiraishi N (1998) Preparation of sulfuric acid-catalyzed phenolated wood resin. Wood Sci Technol 32:297–308CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Chunbao Charles Xu
    • 1
    Email author
  • Yuanyuan Shao
    • 1
  • Zhongshun Yuan
    • 1
  • Shuna Cheng
    • 1
  • Shanghuang Feng
    • 1
  • Laleh Nazari
    • 1
  • Matthew Tymchyshyn
    • 1
  1. 1.Institute for Chemical and Fuels from Alternative Resources (ICFAR)The University of Western OntarioLondonCanada

Personalised recommendations