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


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.

This is a preview of subscription content, log in to check access.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12


  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. https://doi.org/10.1021/acssuschemeng.6b00846

    Article  Google Scholar 

  2. 2.

    Kruse A, Dahmen N (2018) Hydrothermal biomass conversion: quo vadis? J Supercrit Fluids 134:114–123. https://doi.org/10.1016/j.supflu.2017.12.035

    Article  Google 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. https://doi.org/10.1007/s13399-017-0243-0

    Article  Google 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. https://doi.org/10.1021/acs.iecr.7b00327

    Article  Google 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. https://doi.org/10.1039/C7SE00090A

    Article  Google Scholar 

  6. 6.

    Brand S, Kim J (2015) Liquefaction of major lignocellulosic biomass constituents in supercritical ethanol. Energy 80:64–74. https://doi.org/10.1016/j.energy.2014.11.043

    Article  Google Scholar 

  7. 7.

    Tekin K, Karagöz S, Bektaş S (2014) A review of hydrothermal biomass processing. Renew Sust Energ Rev 40:673–687. https://doi.org/10.1016/j.rser.2014.07.216

    Article  Google Scholar 

  8. 8.

    Akalın MK, Tekin K, Karagöz S (2017) Supercritical fluid extraction of biofuels from biomass. Environ Chem Lett 15:29–41. https://doi.org/10.1007/s10311-016-0593-z

    Article  Google 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. https://doi.org/10.1016/j.jaap.2017.05.009

    Article  Google 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. https://doi.org/10.1016/j.fuproc.2014.08.016

    Article  Google 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. https://doi.org/10.1016/j.fuel.2015.12.051

    Article  Google 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. https://doi.org/10.1016/j.apenergy.2017.04.033

    Article  Google 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. https://doi.org/10.1021/acs.energyfuels.6b01166

    Article  Google 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. https://doi.org/10.1016/j.fuel.2017.12.079

    Article  Google 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. https://doi.org/10.1016/j.apcata.2017.08.010

    Article  Google 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. https://doi.org/10.1002/anie.201402752

    Article  Google 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. https://doi.org/10.1080/17597269.2018.1433967

    Article  Google Scholar 

  18. 18.

    Huang X, Korányi TI, Boot MD, Hensen EJM (2014) Catalytic depolymerization of lignin in supercritical ethanol. ChemSusChem 7:2276–2288. https://doi.org/10.1002/cssc.201402094

    Article  Google 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. https://doi.org/10.1002/anie.201400922

    Article  Google 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. https://doi.org/10.1002/ceat.201700396

    Article  Google 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. https://doi.org/10.3389/fenrg.2018.00002

    Article  Google 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. https://doi.org/10.1021/acssuschemeng.5b01381

    Article  Google Scholar 

  23. 23.

    Wang K, Kim KH, Brown RC (2014) Catalytic pyrolysis of individual components of lignocellulosic biomass. Green Chem 16:727–735. https://doi.org/10.1039/C3GC41288A

    Article  Google 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. https://doi.org/10.1134/S0023158415040114

    Article  Google 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. https://doi.org/10.1016/j.jaap.2018.01.022

    Article  Google 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. https://doi.org/10.1002/bit.21522

    Article  Google 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. https://doi.org/10.1016/j.fuel.2014.09.006

    Article  Google 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. https://doi.org/10.1007/s10098-015-1021-y

    Article  Google 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. https://doi.org/10.1016/j.jiec.2017.08.006

    Article  Google 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. https://doi.org/10.1021/ef402075e

    Article  Google 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. https://patents.google.com/patent/US3364251A/en. 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. https://doi.org/10.1016/j.energy.2018.01.186

    Article  Google 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. https://doi.org/10.1021/acs.energyfuels.6b01103

    Article  Google 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. https://doi.org/10.1016/j.biortech.2011.01.031

    Article  Google Scholar 

  35. 35.

    Speight JG (2001) Handbook of petroleum analysis. Wiley, New York

    Google Scholar 

  36. 36.

    Brown TM, Duan P, Savage PE (2010) Hydrothermal liquefaction and gasification of Nannochloropsis sp. Energy Fuels 24:3639–3646. https://doi.org/10.1021/ef100203u

    Article  Google 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. https://doi.org/10.1016/j.chemosphere.2013.06.003

    Article  Google 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. https://doi.org/10.1007/s10098-015-1014-x

    Article  Google Scholar 

Download references


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

Author information



Corresponding author

Correspondence to Selhan Karagöz.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

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)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Alper, K., Tekin, K. & Karagöz, S. Hydrothermal and supercritical ethanol processing of woody biomass with a high-silica zeolite catalyst. Biomass Conv. Bioref. 9, 669–680 (2019). https://doi.org/10.1007/s13399-019-00376-7

Download citation


  • Hydrothermal liquefaction
  • Supercritical ethanol
  • Wood sawdust
  • Zeolite