Hydrothermal and supercritical ethanol processing of woody biomass with a high-silica zeolite catalyst

  • Koray Alper
  • Kubilay Tekin
  • Selhan KaragözEmail author
Original Article


The effects of high-silica ZSM-5 on the yields, as well as compositions, of bio-oil and solid residue obtained from oak wood sawdust were investigated. The catalyst, in concentrations from 5 to 40 wt% of the raw lignocellulose material, was tested in hydrothermal (HT) and supercritical ethanol (SCE) media. The highest bio-oil yields were 11.0 and 32.4 wt% for HT and SCE processing, respectively, and were obtained by using 20 wt% ZSM-5. After the noncatalytic and catalytic HT processing and noncatalytic SCE processing of lignocellulose, the major products were phenols, whereas esters were the major products in the bio-oils obtained from the catalytic SCE processing of oak wood sawdust. The use of ZSM-5 increased the relative contents of the ester compounds in the bio-oils from the SCE processing, while the catalyst did not significantly change the composition of the bio-oils produced from the HT processing of oak wood sawdust. The highest heating values of the bio-oils were 27.11 and 25.65 MJ kg−1 for HT and SCE processing, respectively, and were obtained from the noncatalytic runs. The amount of recovered carbon in the bio-oils from the catalytic runs was higher than that from the noncatalytic runs for both HT and SCE processing. The carbon content of the solid residues for both HT and SCE processing decreased with the use of a catalyst. An increase in the catalyst concentration led to a decrease in the carbon content of the solid residues in SCE and HT processing.


Hydrothermal liquefaction Supercritical ethanol Wood sawdust Zeolite 


Funding information

This study is financially supported by Karabük University (KBÜ-BAP-14/2-DR-010).

Supplementary material

13399_2019_376_MOESM1_ESM.docx (838 kb)
Supplementary Information 1 A brief scheme of the product recovery and separation procedure. SEM images and EDS spectrum of the oak wood. SEM images and EDS spectra of the oak wood. SEM images and EDS spectra of solid residues obtained from the HT processing of oak wood without and with catalysts. SEM images and EDS spectra of solid residues obtained from the SCE processing of oak wood without and with catalysts. A list of identified compounds in the bio-oils obtained from the HT processing of oak wood without and with the use of catalyst. A list of identified compounds in the bio-oils obtained from the SCE processing of oak wood without and with the use of catalyst. (DOCX 837 kb)


  1. 1.
    Sipponen MH, Özdenkci K, Muddassar HR, Melin K, Golam S, Oinas P (2016) Hydrothermal liquefaction of softwood: selective chemical production under oxidative conditions. ACS Sustain Chem Eng 4:3978–3984. CrossRefGoogle Scholar
  2. 2.
    Kruse A, Dahmen N (2018) Hydrothermal biomass conversion: quo vadis? J Supercrit Fluids 134:114–123. CrossRefGoogle Scholar
  3. 3.
    Steinbach D, Kruse A, Sauer J (2017) Pretreatment technologies of lignocellulosic biomass in water in view of furfural and 5-hydroxymethylfurfural production—a review. Biomass Convers Biorefin 7(2):247–274. CrossRefGoogle Scholar
  4. 4.
    Sintamarean IM, Pedersen TH, Zhao X, Kruse A, Rosendahl LA (2017) Application of algae as cosubstrate to enhance the processability of willow wood for continuous hydrothermal liquefaction. Ind Eng Chem Res 56(15):4562–4571. CrossRefGoogle Scholar
  5. 5.
    Yu J, Biller P, Mamahkel A, Klemmer M, Becker J, Glasius M, Iversen BB (2017) Catalytic hydrotreatment of bio-crude produced from the hydrothermal liquefaction of aspen wood: a catalyst screening and parameter optimization study. Sustain Energy Fuels 1(4):832–841. CrossRefGoogle Scholar
  6. 6.
    Brand S, Kim J (2015) Liquefaction of major lignocellulosic biomass constituents in supercritical ethanol. Energy 80:64–74. CrossRefGoogle Scholar
  7. 7.
    Tekin K, Karagöz S, Bektaş S (2014) A review of hydrothermal biomass processing. Renew Sust Energ Rev 40:673–687. CrossRefGoogle Scholar
  8. 8.
    Akalın MK, Tekin K, Karagöz S (2017) Supercritical fluid extraction of biofuels from biomass. Environ Chem Lett 15:29–41. CrossRefGoogle Scholar
  9. 9.
    Jensen MM, Madsen RB, Becker J, Iversen BB, Glasius M (2017) Products of hydrothermal treatment of lignin and the importance of ortho-directed repolymerization reactions. J Anal Appl Pyrolysis 126:371–379. CrossRefGoogle Scholar
  10. 10.
    Leng LJ, Yuan XZ, Huang HJ, Wang H, Wu ZB, Fu LH, Peng X, Chen XH, Zeng GM (2015) Characterization and application of bio-chars from liquefaction of microalgae, lignocellulosic biomass and sewage sludge. Fuel Process Technol 129:8–14. CrossRefGoogle Scholar
  11. 11.
    Riaz A, Kim CS, Kim Y, Kim J (2016) High-yield and high-calorific bio-oil production from concentrated sulfuric acid hydrolysis lignin in supercritical ethanol. Fuel 172:238–247. CrossRefGoogle Scholar
  12. 12.
    Hardi F, Mäkelä M, Yoshikawa K (2017) Non-catalytic hydrothermal liquefaction of pine sawdust using experimental design: material balances and products analysis. Appl Energy 204:1026–1034. CrossRefGoogle Scholar
  13. 13.
    Li M, Liu D, Wu PP, Cong XS, Song LH, Chen QT, Liu J, Wu H, Yan ZF (2016) Efficient hydroliquefaction of sawdust over a novel silica-supported monoclinic molybdenum dioxide catalyst. Energy Fuels 30:6495–6499. CrossRefGoogle Scholar
  14. 14.
    Park J, Riaz A, Insyani R, Kim J (2018) Understanding the relationship between the structure and depolymerization behavior of lignin. Fuel 217:202–210. CrossRefGoogle Scholar
  15. 15.
    Akalin MK, Das P, Alper K, Tekin K, Ragauskas AJ, Karagöz S (2017) Deconstruction of lignocellulosic biomass with hydrated cerium (III) chloride in water and ethanol. Appl Catal A Gen 546:67–78. CrossRefGoogle Scholar
  16. 16.
    Ma R, Hao W, Ma X, Tian Y, Li Y (2014) Catalytic ethanolysis of Kraft lignin into high-value small-molecular chemicals over a nanostructured α-molybdenum carbide catalyst. Angew Chem Int Ed 53:7310–7315. CrossRefGoogle Scholar
  17. 17.
    Govindasamy G, Sharma R, Subramanian S (2018) Studies on the effect of heterogeneous catalysts on the hydrothermal liquefaction of sugarcane bagasse to low-oxygen-containing bio-oil. Biofuels 7269:1–11. CrossRefGoogle Scholar
  18. 18.
    Huang X, Korányi TI, Boot MD, Hensen EJM (2014) Catalytic depolymerization of lignin in supercritical ethanol. ChemSusChem 7:2276–2288. CrossRefGoogle Scholar
  19. 19.
    Jacobs PA, Dusselier M, Sels BF (2014) Will zeolite-based catalysis be as relevant in future biorefineries as in crude oil refineries? Angew Chem Int Ed 53:8621–8626. CrossRefGoogle Scholar
  20. 20.
    Fan D, Xie X, Li Y, Li L, Sun J (2018) Aromatic compounds from lignin liquefaction over ZSM-5 catalysts in supercritical ethanol. Chem Eng Technol 41:509–516. CrossRefGoogle Scholar
  21. 21.
    Qin Y, Wang H, Ruan H, Feng M, Yang B (2018) High catalytic efficiency of lignin depolymerization over low Pd-zeolite Y loading at mild temperature. Front Energy Res 6:2. CrossRefGoogle Scholar
  22. 22.
    Kim BS, Kim YM, Lee HW, Jae J, Kim DH, Jung SC, Watanabe C, Park YK (2016) Catalytic copyrolysis of cellulose and thermoplastics over HZSM-5 and HY. ACS Sustain Chem Eng 4:1354–1363. CrossRefGoogle Scholar
  23. 23.
    Wang K, Kim KH, Brown RC (2014) Catalytic pyrolysis of individual components of lignocellulosic biomass. Green Chem 16:727–735. CrossRefGoogle Scholar
  24. 24.
    Kuznetsov BN, Sharypov VI, Chesnokov NV, Beregovtsova NG, Baryshnikov SV, Lavrenov AV, Vosmerikov AV, Agabekov VE (2015) Lignin conversion in supercritical ethanol in the presence of solid acid catalysts. Kinet Catal 56:434–441. CrossRefGoogle Scholar
  25. 25.
    Kuznetsov BN, Sharypov VI, Beregovtsova NG, Baryshnikov SV, Pestunov AV, Vosmerikov АV, Djakovitch L (2018) Thermal conversion of mechanically activated mixtures of aspen wood-zeolite catalysts in a supercritical ethanol. J Anal Appl Pyrolysis 132:237–244. CrossRefGoogle Scholar
  26. 26.
    Teramoto Y, Tanaka N, Lee SH, Endo T (2008) Pretreatment of eucalyptus wood chips for enzymatic saccharification using combined sulfuric acid-free ethanol cooking and ball milling. Biotechnol Bioeng 99(1):75–85. CrossRefGoogle Scholar
  27. 27.
    Anastasakis K, Ross AB (2015) Hydrothermal liquefaction of four brown macro-algae commonly found on the UK coasts: an energetic analysis of the process and comparison with bio-chemical conversion methods. Fuel 139:546–553. CrossRefGoogle Scholar
  28. 28.
    Tekin K, Akalin MK, Karagöz S (2016) Experimental design for extraction of bio-oils from flax seeds under supercritical ethanol conditions. Clean Techn Environ Policy 18:461–471. CrossRefGoogle Scholar
  29. 29.
    Limarta SO, Ha JM, Park YK, Lee H, Suh DJ, Jae J (2018) Efficient depolymerization of lignin in supercritical ethanol by a combination of metal and base catalysts. J Ind Eng Chem 57:45–54. CrossRefGoogle Scholar
  30. 30.
    Li R, Li B, Yang T, Xie Y, Kai X (2014) Production of bio-oil from rice stalk supercritical ethanol liquefaction combined with the torrefaction process. Energy Fuels 28:1948–1955. CrossRefGoogle Scholar
  31. 31.
    Benning A, Novotny R (1968) Process for the production of carboxylic acid esters in the presence of a fluidized catalyst bed. U.S. Patent and Trademark Office U.S. Patent No. 3,364,251. Washington, DC. Accessed 1 Nov 2018
  32. 32.
    Lai FY, Chang YC, Huang HJ, Wu GQ, Xiong JB, Pan ZQ, Zhou CF (2018) Liquefaction of sewage sludge in ethanol-water mixed solvents for bio-oil and biochar products. Energy 148:629–641. CrossRefGoogle Scholar
  33. 33.
    Peng X, Ma X, Lin Y (2016) Investigation on characteristics of liquefied products from solvolysis liquefaction of Chlorella pyrenoidosa in ethanol–water systems. Energy Fuel 30(8):6475–6485. CrossRefGoogle Scholar
  34. 34.
    Anastasakis K, Ross AB (2011) Hydrothermal liquefaction of the brown macro-alga Laminaria saccharina: effect of reaction conditions on product distribution and composition. Bioresour Technol 102(7):4876–4883. CrossRefGoogle Scholar
  35. 35.
    Speight JG (2001) Handbook of petroleum analysis. Wiley, New YorkGoogle Scholar
  36. 36.
    Brown TM, Duan P, Savage PE (2010) Hydrothermal liquefaction and gasification of Nannochloropsis sp. Energy Fuels 24:3639–3646. CrossRefGoogle Scholar
  37. 37.
    Kim JY, Oh S, Hwang H, Cho TS, Choi IG, Choi JW (2013) Effects of various reaction parameters on solvolytical depolymerization of lignin in sub- and supercritical ethanol. Chemosphere 93:1755–1764. CrossRefGoogle Scholar
  38. 38.
    Tekin K, Pileidis FD, Akalin MK, Karagöz S (2016) Cellulose-derived carbon spheres produced under supercritical ethanol conditions. Clean Techn Environ Policy 18:331–338. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of ChemistryKarabük UniversityKarabükTurkey
  2. 2.Science and Technology, Application and Research CenterBülent Ecevit UniversityZonguldakTurkey
  3. 3.Department of Environmental EngineeringKarabük UniversityKarabükTurkey

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