Hydrothermal Liquefaction of Biomass

  • Saqib Sohail ToorEmail author
  • Lasse Aistrup Rosendahl
  • Jessica Hoffmann
  • Thomas Helmer Pedersen
  • Rudi Pankratz Nielsen
  • Erik Gydesen Søgaard
Part of the Green Chemistry and Sustainable Technology book series (GCST)


Biomass is one of the most abundant sources of renewable energy, and will be an important part of a more sustainable future energy system. In addition to direct combustion, there is growing attention on conversion of biomass into liquid energy carriers. These conversion methods are divided into biochemical/biotechnical methods and thermochemical methods, such as direct combustion, pyrolysis, gasification, liquefaction, etc. This chapter focuses on hydrothermal liquefaction, where high pressures and intermediate temperatures together with the presence of water are used to convert biomass into liquid biofuels, with the aim of describing the current status and development challenges of the technology. During the hydrothermal liquefaction process, the biomass macromolecules are first hydrolyzed and/or degraded into smaller molecules. Many of the produced molecules are unstable and reactive and can recombine into larger ones. During this process, a substantial part of the oxygen in the biomass is removed by dehydration or decarboxylation. The chemical properties of the product are mostly dependent of the biomass substrate composition. Biomass consists of various components such as carbohydrates, lignin, protein, and fat, and each of them produce distinct groups of compounds when processed individually. When processed together in different ratios, they will most likely cross-influence each other and thus the composition of the product. Processing conditions including temperature, pressure, residence time, catalyst, and type of solvent are important for the bio-oil yield and product quality.


Supercritical Water Subcritical Water Subcritical Condition Coniferyl Alcohol Hydrothermal Liquefaction 
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.


  1. 1.
    Behrendt F, Neubauer Y, Oevermann M, Wilmes B, Zobel N (2008) Direct liquefaction of biomass-review. Chem Eng Technol 31:667–677CrossRefGoogle Scholar
  2. 2.
    Bobleter O (1994) Hydrothermal degradation of polymers derived from plants. Polym Sci 19:797–841Google Scholar
  3. 3.
    Yu Y, Lou X, Wu H (2008) Some recent advances in hydrolysis of biomass in hot-compressed water and its comparisons with other hydrolysis methods. Energy Fuels 22:46–60CrossRefGoogle Scholar
  4. 4.
    Delmer DP, Amor Y (1995) Cellulose biosynthesis. Plant Cell 7:987–1000Google Scholar
  5. 5.
    Rogalinski T, Liu K, Albrecht T, Brunner G (2008) Hydrolysis kinetics of biopolymers in subcritical water. J Supercrit Fluids 46:335–341CrossRefGoogle Scholar
  6. 6.
    Sasaki M, Fang Z, Fukushima Y, Adschiri T, Arai K (2000) Dissolution and hydrolysis of cellulose in subcritical and supercritical water. Ind Eng Chem Res 39:2883–2890CrossRefGoogle Scholar
  7. 7.
    Sasaki M, Adschiri T, Arai K (2004) Kinetics of cellulose conversion at 25 MPa in sub- and supercritical water. AIChE J 50:192–202CrossRefGoogle Scholar
  8. 8.
    Kamio E, Sato H, Takahashi S, Noda H, Fukuhara C, Okamura T (2008) Liquefaction kinetics of cellulose treated by hot compressed water under variable temperature conditions. J Mater Sci 43:2179–2188CrossRefGoogle Scholar
  9. 9.
    Mok WSL, Antal MJ (1992) Uncatalyzed solvolysis of whole biomass hemicellulose by hot compressed liquid water. Ind Eng Chem Res 31:1157–1161CrossRefGoogle Scholar
  10. 10.
    Sasaki M, Hayakawa T, Arai K, Adichiri T (2003) Measurement of the rate of retro-aldol condensation of D- xylose in subcritical and supercritical water. In: Presented at the proceeding of the 7th international symposium on hydrothermal reactions, pp 169–176Google Scholar
  11. 11.
    Peterson AA, Vogel F, Lachance RP, Fröling M, Antal MJ, Tester JW (2008) Thermochemical biofuel production in hydrothermal media: a review of sub- and supercritical water technologies. Energy Environ Sci 1:32–65CrossRefGoogle Scholar
  12. 12.
    Nagamori M, Funazukuri T (2004) Glucose production by hydrolysis of starch under hydrothermal conditions. J Chem Technol Biotechnol 79:229–233CrossRefGoogle Scholar
  13. 13.
    Miyazawa T, Funazukuri T (2005) Polysaccharide hydrolysis accelerated by adding carbon dioxide under hydrothermal conditions. Biotechnol Prog 21:1782–1786CrossRefGoogle Scholar
  14. 14.
    Miyazawa T, Ohtsu S, Nakagawa Y, Funazukuri T (2006) Solvothermal treatment of starch for the production of glucose and maltooligosaccharides. J Mater Sci 41:1489–1494CrossRefGoogle Scholar
  15. 15.
    Liu A, Park YK, Huang Z, Wang B, Ankumah RO, Biswas PK (2006) Product identification and distribution from hydrothermal conversion of walnut shells. Energy Fuel 20:446–454CrossRefGoogle Scholar
  16. 16.
    Khuwijitjaru P, Adachi S, Matsuno R (2002) Solubility of saturated fatty acids in water at elevated temperatures. Biosci Biotechnol Biochem 66:1723–1726CrossRefGoogle Scholar
  17. 17.
    Holliday RL, King JW, List GR (1997) Hydrolysis of vegetable oils in sub- and supercritical water. Ind Eng Chem Res 36:932–935CrossRefGoogle Scholar
  18. 18.
    King JW, Holliday RL, List GR (1999) Hydrolysis of soybean oil in a subcritical water flow reactor. Green Chem 1:261–264CrossRefGoogle Scholar
  19. 19.
    Brunner G (2009) Near critical and supercritical water. Part I. Hydrolytic and hydrothermal processes. J Supercrit Fluids 47:373–381CrossRefGoogle Scholar
  20. 20.
    Xian Z, Chao Z, Liang Z, Hongbin C (2008) Amino acid production from fish proteins hydrolysis in subcritical Water. Chin J Chem Eng 16:456–460CrossRefGoogle Scholar
  21. 21.
    Rogalinski T, Herrmann S, Brunner G (2005) Production of amino acids from bovine serum albumin by continuous sub-critical water hydrolysis. J Supercrit Fluids 36:49–58CrossRefGoogle Scholar
  22. 22.
    Saha BC (2004) Lignocellulose biodegradation and applications in biotechnology. American Chemical Society, Washington, pp 2–34Google Scholar
  23. 23.
    Lee S, Shah YT, (eds) (2013) Biofuels and bioenergy processes and technologies. CRC Press, Boca RatonGoogle Scholar
  24. 24.
    Mosier N, Wyman C, Dale B, Elander R, Lee YY, Holtzapple M et al (2005) Features of promising technologies for pretreatment of lignocellulosic biomass. Bioresour Technol 4:673–686CrossRefGoogle Scholar
  25. 25.
    Deguchi S, Tsujii K, Horikoshi K (2006) Cooking cellulose in hot and compressed water. Chem Commun 31:3293–3295. doi: 10.1039/B605812D CrossRefGoogle Scholar
  26. 26.
    Mochidzuki K, Sakoda A, Suzuki M (2000) Measurement of the hydrothermal reaction rate of cellulose using novel liquid-phase thermogravimetry. Thermochim Acta 348(1–2):69–76Google Scholar
  27. 27.
    Olanrewaju KB (2012) Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Dissertation, University of IowaGoogle Scholar
  28. 28.
    Kruse A, Dinjus E (2007) Hot compressed water as reaction medium and reactant: 2. Degradation reactions. J Supercrit Fluids 41(3):361–379CrossRefGoogle Scholar
  29. 29.
    Bobleter O, Pape G (1968) Der hydrothermale abbau von glucose. Monatshefte Fur Chemie 99(4):1560–1567CrossRefGoogle Scholar
  30. 30.
    Watanabe M, Aizawa Y, Iida T, Levy C, Aida TM, Inomata H (2005) Glucose reactions within the heating period and the effect of heating rate on the reactions in hot compressed water. Carbohydr Res 340(12):1931–1939CrossRefGoogle Scholar
  31. 31.
    Matsumura Y, Yanachi S, Yoshida T (2013) Glucose decomposition kinetics in water at 25 MPa in the temperature range of 448–673 K. Ind Eng Chem Res 45(6):1875–1879CrossRefGoogle Scholar
  32. 32.
    Sasaki M, Furukawa M, Minami K, Adschiri T, Arai K (2002) Kinetics and mechanism of cellobiose hydrolysis and retro-aldol condensation in subcritical and supercritical water. Ind Eng Chem Res 41(26):6642–6649CrossRefGoogle Scholar
  33. 33.
    Kabyemela BM, Adschiri T, Malaluan RM, Arai K (1997) Kinetics of glucose epimerization and decomposition in subcritical and supercritical water. Ind Eng Chem Res 36(5):1552–1558CrossRefGoogle Scholar
  34. 34.
    Yin S, Mehrotra AK, Tan Z (2011) Alkaline hydrothermal conversion of cellulose to bio-oil: influence of alkalinity on reaction pathway change. Bioresour Technol 102(11):6605–6610CrossRefGoogle Scholar
  35. 35.
    Yin S, Tan Z (2012) Hydrothermal liquefaction of cellulose to bio-oil under acidic, neutral and alkaline conditions. Appl Energy 92:234–239CrossRefGoogle Scholar
  36. 36.
    Chuntanapum A, Matsumura Y (2009) Formation of tarry material from 5-HMF in subcritical and supercritical water. Ind Eng Chem Res 48(22):9837–9846CrossRefGoogle Scholar
  37. 37.
    Lü X, Saka S (2012) New insights on monosaccharides’ isomerization, dehydration and fragmentation in hot-compressed water. J Supercrit Fluids 61:146–156CrossRefGoogle Scholar
  38. 38.
    Abatzoglou N, Chornet E, Belkacemi K, Overend RP (1992) Phenomenological kinetics of complex systems: the development of a generalized severity parameter and its application to lignocellulosics fractionation. Chem Eng Sci 47(5):1109–1122CrossRefGoogle Scholar
  39. 39.
    Pińkowska H, Wolak P, Złocińska A (2011) Hydrothermal decomposition of xylan as a model substance for plant biomass waste—hydrothermolysis in subcritical water. Biomass Bioenergy 35(9):3902–3912CrossRefGoogle Scholar
  40. 40.
    Aida TM, Shiraishi N, Kubo M, Watanabe M, Smith RL Jr (2010) Reaction kinetics of d-xylose in sub- and supercritical water. J Supercrit Fluids 55(1):208–216CrossRefGoogle Scholar
  41. 41.
    Jing Q, Lü X (2007) Kinetics of non-catalyzed decomposition of D-xylose in high temperature liquid water. Chin J Chem Eng 15(5):666–669CrossRefGoogle Scholar
  42. 42.
    Oefner PJ, Lanziner AH, Bonn G, Bobleter O (1992) Quantitative studies on furfural and organic acid formation during hydrothermal, acidic and alkaline degradation of D-xylose. Monatsh Chem 123(6–7):547–556CrossRefGoogle Scholar
  43. 43.
    Antal MJ Jr, Leesomboon T, Mok WS, Richards GN (1991) Mechanism of formation of 2-furaldehyde from d-xylose. Carbohydr Res 217:71–85CrossRefGoogle Scholar
  44. 44.
    Gao Y, Chen HP, Wang J, Shi T, Yang HP, Wang XH (2011) Characterization of products from hydrothermal liquefaction and carbonation of biomass model compounds and real biomass. J Fuel Chem Technol 39(12):893–900 Google Scholar
  45. 45.
    Hashaikeh R, Fang Z, Butler IS, Hawari J, Kozinski JA (2007) Hydrothermal dissolution of willow in hot compressed water as a model for biomass conversion. Fuel 86(10–11):1614–1622CrossRefGoogle Scholar
  46. 46.
    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(11):1363–1366CrossRefGoogle Scholar
  47. 47.
    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
  48. 48.
    Nielsen RP (2010) The physical chemistry of the CatLiq process. PhD Thesis, Aalborg University, Esbjerg, DenmarkGoogle Scholar
  49. 49.
    Nielsen RP, Olofsson G, Søgaard EG (2012) CatLiq—high pressure and temperature catalytic conversion of biomass: the CatLiq technology in relation to other thermochemical conversion technologies. Biomass Bioenergy 43:2–5Google Scholar
  50. 50.
    Toor SS (2010) Modelling and optimization of Catliq Liquid biofuel process. PhD Thesis, Aalborg University, Aalborg, DenmarkGoogle Scholar
  51. 51.
    Toor SS, Rosendahl L, Rudolf A (2011) Hydrothermal liquefaction of biomass: a review of subcritical water technologies. Energy 36:2328–2342CrossRefGoogle Scholar
  52. 52.
    Schmieder H, Abeln J, Boukis N, Dinjus E, Kruse A, Kluth M, Petrich G, Sadri E, Schacht M (2000) Hydrothermal gasification of biomass and organic wastes. J Supercrit Fluids 17:145–153CrossRefGoogle Scholar
  53. 53.
    Balat M, Kırtay E, Balat H (2009) Main routes for the thermo-conversion of biomass into fuels and chemicals. Part 2: gasification systems. Energy Convers Manag 50:3158–3168CrossRefGoogle Scholar
  54. 54.
    Kruse A, Dinjus E (2007) Hot compressed water as reaction medium and reactant Properties and synthesis reactions. J Supercrit Fluids 39:362–380CrossRefGoogle Scholar
  55. 55.
    Kruse A, Dinjus E (2005) Influence of salts during hydrothermal biomass gasification: the role of the catalysed water-gas shift reaction. Z Phys Chem 219:341–366CrossRefGoogle Scholar
  56. 56.
    Kruse A, Henningsen T, Sınag A, Pfeiffer J (2003) Biomass gasification in supercritical water: influence of the dry matter content and the formation of phenols. Ind Eng Chem Res 42:3711–3717CrossRefGoogle Scholar
  57. 57.
    Gasafi E, Reinecke M-Y, Kruse A, Schebek L (2008) Economic analysis of sewage sludge gasification in supercritical water for hydrogen production. Biomass Bioenergy 32:1085–1096CrossRefGoogle Scholar
  58. 58.
    Sinag A, Kruse A, Schwarzkopf V (2003) Formation and degradation pathways of intermediate products formed during the hydropyrolysis of glucose as a model substance for wet biomass in a tubular reactor. Eng Life Sci 3:469–473CrossRefGoogle Scholar
  59. 59.
    Boukis N, Galla U, D’Jesus P, Müller H, Dinjus E (2005) gasification of wet biomass in supercritical water: results of pilot plant experiments. In: Proceedings of the 14 European biomass conference. Paris, pp 964–967Google Scholar
  60. 60.
    Iversen SB, Larsen T, Lüthje V, Felsvang K, Nielsen RP, Galla U, Boukis N (2005) CatLiq—a disruptive technology for biomass conversion. In: Proceedings of the 14th European Biomass Conference. Paris, pp 1450–1452Google Scholar
  61. 61.
    Hammerschmidt A, Boukis N, Hauer E, Galla U, Dinjus E, Hitzmann B, Larsen T, Nygaard SD (2011) Catalytic conversion of waste biomass by hydrothermal treatment. Fuel 90:555–562CrossRefGoogle Scholar
  62. 62.
    Karagöz 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
  63. 63.
    Demirbas A (2004) Current technologies for the thermo-conversion of biomass into fuels and chemicals. Energy Sources Part A: Recovery Utilization Environ Eff 26:715–730CrossRefGoogle Scholar
  64. 64.
    Balat M (2008) Mechanisms of thermochemical biomass conversion processes. Part 1: reactions of pyrolysis. Energy Sources Part A: Recovery Utilization Environ Eff 30:620–635CrossRefGoogle Scholar
  65. 65.
    Balat M (2008) Mechanisms of thermochemical biomass conversion processes. Part 2: reactions of gasification. Energy Sources Part A: Recovery Utilization Environ Eff 30:636–648CrossRefGoogle Scholar
  66. 66.
    Balat M (2008) Mechanisms of thermochemical biomass conversion processes. Part 3: reactions of liquefaction. Energy Sources Part A: Recovery Utilization Environ Eff 30:649–659CrossRefGoogle Scholar
  67. 67.
    Demirbas A (2004) Conversion of agricultural residues to fuel products via supercritical fluid extraction. Energy Sources Part A: Recovery Utilization Environ Eff 26:1095–1103CrossRefGoogle Scholar
  68. 68.
    Demirbas A (2005) Thermochemical conversion of biomass to liquid products in the aqueous medium. Energy Sources Part A: Recovery Utilization Environ Eff 27:1235–1243CrossRefGoogle Scholar
  69. 69.
    Demirbas A (2008) Production of biodiesel from algae oils. Energy Sources Part A: Recovery Utilization Environ Eff 31:163–168CrossRefGoogle Scholar
  70. 70.
    Kruse A, Gawlik A (2003) Biomass conversion in water at 330–410 & #xB0;C and 30–50 MPa. Identification of key compounds for indicating different chemical reaction pathways. Ind Eng Chem Res 42:267–279CrossRefGoogle Scholar
  71. 71.
    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 hydropyrolysis of glucose in supercritical water in a batch reactor. Ind Eng Chem Res 43:502–508CrossRefGoogle Scholar
  72. 72.
    Sinag A, Kruse A, Schwarzkopf V (2003) Key compounds of the hydropyrolysis of glucose in supercritical water in the presence of K2CO3. Ind Eng Chem Res 42:3516–3521CrossRefGoogle Scholar
  73. 73.
    Kruse A, Meier D, Rimbrecht P, Schacht M (2000) Gasification of pyrocatechol in supercritical water in the presence of potassium hydroxide. Ind Eng Chem Res 39:4842–4848CrossRefGoogle Scholar
  74. 74.
    Akiya N, Savage PE (2002) Roles of water for chemical reactions in high-temperature water. Chem Rev 102:2725–2750CrossRefGoogle Scholar
  75. 75.
    Savage PE (1999) Organic chemical reactions in supercritical water. Chem Rev 99:63CrossRefGoogle Scholar
  76. 76.
    Savage PE, Gopalan S, Mizan TI, Martino CJ, Brock EE (1995) Reactions at supercritical conditions: applications and fundamentals. AIChE J 41:1723–1778CrossRefGoogle Scholar
  77. 77.
    Bühler W, Dinjus E, Ederer HJ, Kruse A, Mas C (2002) Ionic reactions and pyrolysis of glycerol as competing reaction pathways in near- and supercritical water. J Supercrit Fluids 22:37–53CrossRefGoogle Scholar
  78. 78.
    Yoshida T, Oshima Y, Matsumura Y (2004) Gasification of biomass model compounds and real biomass in supercritical water. Biomass Bioenergy 26:71–78CrossRefGoogle Scholar
  79. 79.
    Matsumura Y, Minowa T, Potic B et al (2005) Biomass gasification in near- and super-critical water: status and prospects. Biomass Bioenergy 29:269–292CrossRefGoogle Scholar
  80. 80.
    Peterson AA, Vontobel P, Vogel F, Tester JW (2008) In situ visualization of the performance of a supercritical-water salt separator using neutron radiography. J Supercrit Fluids 43:490–499CrossRefGoogle Scholar
  81. 81.
    Czernik S, French R, Feik C, Chornet E (2002) Hydrogen by catalytic steam reforming of liquid byproducts from biomass thermoconversion processes. Ind Eng Chem Res 41:4209–4215CrossRefGoogle Scholar
  82. 82.
    Trimm DL (1997) Coke formation and minimisation during steam reforming reactions. Catal Today 37:233–238CrossRefGoogle Scholar
  83. 83.
    Kruse A, Dinjus E (2007) Hot compressed water as reaction medium and reactant 2. Degradation reactions. J Supercrit Fluids 41:361–379CrossRefGoogle Scholar
  84. 84.
    Padban N, Wang W, Ye Z, Bjerle I, Odenbrand I (2000) Tar formation in pressurized fluidized bed air gasification of woody biomass. Energy Fuels 14:603–611Google Scholar
  85. 85.
    Inoue S, Sawayama S, Dote Y, Ogi T (1997) Behaviour of nitrogen during liquefaction of dewatered sewage sludge. Biomass Bioenergy 12:473–475CrossRefGoogle Scholar
  86. 86.
    Watanabe M, Inomata H, Osada M, Sato T, Adschiri T, Arai K (2003) Catalytic effects of NaOH and ZrO2 for partial oxidative gasification of n-hexadecane and lignin in supercritical water. Fuel 82:545–552CrossRefGoogle Scholar
  87. 87.
    Watanabe M, Takahashi M, Inomata H (2008) Hydrogen production reaction with a metal oxide catalyst in high pressure high temperature water. J Phys Conf Ser 121:082008CrossRefGoogle Scholar
  88. 88.
    Watanabe M, Inomata H, Smith RL, Arai K (2001) Catalytic decarboxylation of acetic acid with zirconia catalyst in supercritical water. Appl Catal A 219:149–156CrossRefGoogle Scholar
  89. 89.
    Watanabe M, Inomata H, Arai K (2002) Catalytic hydrogen generation from biomass (glucose and cellulose) with ZrO2 in supercritical water. Biomass Bioenergy 22:405–410CrossRefGoogle Scholar
  90. 90.
    Lee G, Nunoura T, Matsumura Y, Yamamoto K (2002) Comparison of the effects of the addition of NaOH on the decomposition of 2-chlorophenol and phenol in supercritical water and under supercritical water oxidation conditions. J Supercrit Fluids 24:239–250CrossRefGoogle Scholar
  91. 91.
    Antal MJ Jr, Xu X (1999) Hydrogen production from high moisture content biomass in supercritical water. In: U.S. DOE hydrogen program reviewGoogle Scholar
  92. 92.
    Ahmad MM (2010) Upgrading of bio-oil into high-value hydrocarbons via hydrodeoxygenation. Am J Appl Sci 7:746–755CrossRefGoogle Scholar
  93. 93.
    Mercader, FM, Hoogendorn, K (2010) Production of advanced bio-fuels: Co-refning upgraded pyrolysis oil, BerlinGoogle Scholar
  94. 94.
    Furimsky E (2000) Review: catalytic hydrodeoxygenation. Appl Catal A 199:147–190CrossRefGoogle Scholar
  95. 95.
    Furimsky E (2012) Hydroprocessing challenges in biofuels production, catalysis today. Available via online. Accessed 12 Feb 2013
  96. 96.
    Kersten SRA, van Swaaij WPM, Lefferts L, Seshan K (2007) Options for catalysis in the thermochemical conversion of biomass into fuels. In: Centi G, van Santen RA (eds) Catalysis for renewables: From feedstock to energy production. Chichester, Wiley-VCHGoogle Scholar
  97. 97.
    Wildschut J (2009) Pyrolysis oil upgrading to transportation fuels by catalytic hydrotreatment. PhD Thesis, Rijkuniversitet GroningenGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Saqib Sohail Toor
    • 1
    Email author
  • Lasse Aistrup Rosendahl
    • 1
  • Jessica Hoffmann
    • 1
  • Thomas Helmer Pedersen
    • 1
  • Rudi Pankratz Nielsen
    • 2
  • Erik Gydesen Søgaard
    • 2
  1. 1.Department of Energy TechnologyAalborg UniversityAalborg ØDenmark
  2. 2.Department of Biotechnology, Chemistry and Environmental Engineering, Section of Chemical EngineeringAalborg UniversityAalborg ØDenmark

Personalised recommendations