, Volume 26, Issue 18, pp 9517–9528 | Cite as

Enhanced cellulase accessibility using acid-based deep eutectic solvent in pretreatment of empty fruit bunches

  • Yit Wen Sai
  • Kiat Moon LeeEmail author
Original Research


Deep eutectic solvents (DESs) are new and rapid emerging green solvents that have been gaining much attention lately. In this work, DES was prepared by mixing choline chloride with lactic acid with the molar ratio of 1:10 to pretreat empty fruit bunches. The effects of pretreatment temperature, pretreatment time and solid-to-solvent ratio were investigated. A maximum reducing sugars yield of 51.1% was obtained at the operating conditions of 100 °C for 1 h with solid-to-solvent ratio of 1:10 (w/v). The reducing sugars yield obtained for DES pretreatment was higher than dilute acid, alkaline and organosolv pretreatment suggesting DES pretreatment is a promising alternative to conventional pretreatment techniques. Furthermore, there was no reducing sugar loss during DES pretreatment. The outstanding DES pretreatment performance was further confirmed by both Fourier-transform infrared spectroscopy and scanning electron microscopy indicated that DES pretreatment was effective in altering biomass structure by disrupting the hydrogen bonding interactions within the chains of cellulose molecules and lignin extraction.

Graphic abstract


Deep eutectic solvent Choline chloride Lactic acid Pretreatment Empty fruit bunches Lignocellulosic biomass 



This work was supported by the UCSI University Pioneer Scientist Incentive Fund (Grant Number: Proj-In-FETBE-043).


  1. Barr CJ, Hanson BL, Click K, Perrotta G, Schall CA (2014) Influence of ionic-liquid incubation temperature on changes in cellulose structure, biomass composition, and enzymatic digestibility. Cellulose 21:973–982Google Scholar
  2. Bensah EC, Mensah M (2013) Chemical pretreatment methods for the production of cellulosic ethanol: technologies and innovation. Int J Chem Eng 2013:1–21Google Scholar
  3. Brodeur G, Yau E, Badal K, Collier J, Ramachandran KB, Ramakrishnan S (2011) Chemical and physicochemical pretreatment of lignocellulosic biomass: a review. Enzyme Res 2011:1–17Google Scholar
  4. Chen W-H, Tu Y-J, Sheen HK (2010) Impact of dilute acid pretreatment on the structure of bagasse for bioethanol production. Int J Energy Res 34:265–274Google Scholar
  5. Chen Y, Stevens MA, Zhu Y, Holmes J, Xu H (2013) Understanding of alkaline pretreatment parameters for corn stover enzymatic saccharification. Biotechnol Biofuels 6:8PubMedPubMedCentralGoogle Scholar
  6. Chen W, Xue Z, Wang J, Jiang J, Zhao X, Mu T (2018) Investigation on the thermal stability of deep eutectic solvents. Acta Phys Chim Sin 34:904–911Google Scholar
  7. Chen Y, Yu D, Chen W, Fu L, Mu T (2019) Water absorption by deep eutectic solvents. Phys Chem Chem Phys 21:2601–2610PubMedGoogle Scholar
  8. Chiaramonti D, Prussi M, Ferrero S, Oriani L, Ottonello P, Torre P, Cherchi F (2012) Review of pretreatment processes for lignocellulosic ethanol production, and development of an innovative method. Biomass Bioenergy 46:25–35Google Scholar
  9. Coleman D, Gathergood N (2010) Biodegradation studies of ionic liquids. Chem Soc Rev 39:600–637PubMedGoogle Scholar
  10. Dománska U, Bogel-Lukasik R (2005) Physicochemical properties and solubility of alkyl-(2-hydroxyethyl)-dimethylammonium bromide. J Phys Chem B 109:12124–12132PubMedGoogle Scholar
  11. Dominguez de Maria P, Maugeri Z (2011) Ionic liquids in biotransformation: from proof-of-concept to emerging deep-eutectic-solvents. Curr Opin Chem Biol 15:220–225PubMedGoogle Scholar
  12. Du J, Cao Y, Liu G, Zhao J, Li X, Qu Y (2017) Identifying and overcoming the effect of mass transfer limitation on decreased yield in enzymatic hydrolysis of lignocellulose at high solid concentrations. Bioresour Technol 229:88–95PubMedGoogle Scholar
  13. Earle MJ, Seddon KR (2009) Ionic liquids: green solvents for the future. Pure Appl Chem 72:1391–1398Google Scholar
  14. García G, Aparicio S, Ullah R, Atilhan M (2015) Deep eutectic solvents: physicochemical properties and gas separation applications. Energy Fuels 29:2616–2644Google Scholar
  15. Gorke JT, Srienc F, Kazlauskas RJ (2008) Hydrolase-catalyzed biotransformations in deep eutectic solvents. Chem Commun 10:1235–1237Google Scholar
  16. Harmsen PFH, Huijgen WJJ, López LMB, Bakker RRC (2010) Literature review of physical and chemical pretreatment processes for lignocellulosic biomass. Wageningen UR—Food & Biobased Research, WageningenGoogle Scholar
  17. Hodge DB, Karim MN, Schell DJ, McMillan JD (2009) Model-based fed-batch for high solids enzymatic cellulose hydrolysis. Appl Biochem Biotechnol 152:88–107PubMedGoogle Scholar
  18. Huijgen WJJ, Smit AT, de Wild PJ, den Uil H (2012) Fractionation of wheat straw by prehydrolysis, organosolv delignification and enzymatic hydrolysis for production of sugars and lignin. Bioresour Technol 114:389–398PubMedGoogle Scholar
  19. Isroi Ishola MM, Millati R, Syamsiah S, Cahyanto MN, Niklasson C, Taherzadeh MJ (2012) Structural changes of oil palm empty fruit bunch (OPEFB) after fungal and phosphoric acid pretreatment. Molecules 17:14995–15002PubMedPubMedCentralGoogle Scholar
  20. Kabo GJ, Blokhin AV, Paulechka YU, Kabo AG, Shymanovich MP, Magee JW (2004) Thermodynamic properties of 1-butyl-3-methylimidazolium hexafluorophosphate in the condensed state. J Chem Eng Data 49:453–461Google Scholar
  21. Kumar AK, Parikh BS, Pravakar M (2016) Natural deep eutectic solvent mediated pretreatment of rice straw: bioanalytical characterization of lignin extract and enzymatic hydrolysis of pretreated biomass residue. Environ Sci Pollut Res 23:9265–9275Google Scholar
  22. Laureano-Perez L, Teymouri F, Alizadeh H, Dale BE (2005) Understanding factors that limit enzymatic hydrolysis of biomass. Appl Biochem Biotechnol 124:1081–1099Google Scholar
  23. Lee KM, Ngoh GC, Chua ASM (2013) Process optimization and performance evaluation on sequential ionic liquid dissolution-solid acid saccharification of sago waste. Bioresour Technol 130:1–7PubMedGoogle Scholar
  24. Lee KM, Ngoh GC, Chua ASM, Yoon LW, Ang TN, Lee M-G (2014) Comparison study of different ionic liquid pretreatments in maximizing total reducing sugars recovery. BioResources 9:1552–1564Google Scholar
  25. Li T, Lyu G, Liu Y, Lou R, Lucia LA, Yang G, Chen J, Saeed HAM (2017) Deep eutectic solvents (DESs) for the isolation of willow lignin (Salix matsudana cv. Zhuliu). Int J Mol Sci 18:2266PubMedCentralGoogle Scholar
  26. Lima MA, Lavorente GB, da Silva HKP, Bragatto J, Rezende CA, Bernardinelli OD, Eduardo RD, Gomez LD, McQueen-Mason SJ, Labate CA, Polikarpov I (2013) Effects of pretreatment on morphology, chemical composition and enzymatic digestibility of eucalyptus bark: a potentially valuable source of fermentable sugars for biofuel production—part 1. Biotechnol Biofuels 6:75–92PubMedPubMedCentralGoogle Scholar
  27. Loow Y-L, Wu TY, Md. Jahim J, Mohammad AW, Teoh WH (2016) Typical conversion of lignocellulosic biomass into reducing sugars using dilute acid hydrolysis and alkaline pretreatment. Cellulose 23:1491–1520Google Scholar
  28. Loow Y-L, New EK, Yang GH, Ang LY, Foo LYW, Wu TY (2017) Potential use of deep eutectic solvents to facilitate lignocellulosic biomass utilization and conversion. Cellulose 24:3591–3618Google Scholar
  29. Lynd LR (1996) Overview and evaluation of fuel ethanol from cellulosic biomass: technology, economics, the environment, and policy. Annu Rev Energy Environ 21:403–465Google Scholar
  30. Mielenz JR (2001) Ethanol production from biomass: technology and commercialization status. Curr Opin Microbiol 4:324–329PubMedGoogle Scholar
  31. Miller GL (1959) Use of dinitrosalicylic acid reagent for determination of reducing sugar. Anal Chem 31:426–428Google Scholar
  32. Mood SH, Golfeshan AH, Tabatabaei M, Jouzani GS, Najafi GH, Gholami M, Ardjmand M (2013) Lignocellulosic biomass to bioethanol, a comprehensive review with a focus on pretreatment. Renew Sustain Energy Rev 27:77–93Google Scholar
  33. Mosier N, Wyman C, Dale B, Elander R, Lee YY, Holtzapple M, Ladisch M (2005) Features of promising technologies for pretreatment of lignocellulosic biomass. Bioresour Technol 96:673–686PubMedPubMedCentralGoogle Scholar
  34. Nelson ML, O’Connor RT (1964) Relation of certain infrared bands to cellulose crystallinity and crystal lattice type. Part II. A new infrared ratio for estimation of crystallinity in celluloses I and II. J Appl Polym Sci 8(1964):1325–1341Google Scholar
  35. Pan X, Xie D, Gilkes N, Gregg DJ, Saddler JN (2005) Strategies to enhance the enzymatic hydrolysis of pretreated softwood with high residual lignin content. Appl Biochem Biotechnol 124:1069Google Scholar
  36. Pan X, Gilkes N, Saddler JN (2006) Effect of acetyl groups on enzymatic hydrolysis of cellulosic substrates. Holzforschung 60:398–401Google Scholar
  37. Park YC, Kim TH, Kim JS (2017) Effect of organosolv pretreatment on mechanically pretreated biomass by use of concentrated ethanol as the solvent. Biotechnol Bioprocess Eng 22:431–439Google Scholar
  38. Paulechka YU, Kabo GJ, Blokhin AV, Vydrov OA, Magee JW, Frenkel M (2003) Thermodynamic properties of 1-butyl-3-methylimidazolium hexafluorophosphate in the ideal gas state. J Chem Eng Data 48:457–462Google Scholar
  39. Procentese A, Raganati F, Olivieri G, Russo ME, Rehmann L, Marzocchella A (2018) Deep eutectic solvents pretreatment of agro-industrial food waste. Biotechnol Biofuels 11:37PubMedPubMedCentralGoogle Scholar
  40. Quijano G, Couvert A, Amrane A (2010) Ionic liquids: applications and future trends in bioreactor technology. Bioresour Technol 101:8923–8930PubMedGoogle Scholar
  41. Rodriguez NR, van den Bruinhorst A, Kollau LJBM, Kroon MC, Binnemans K (2019) Degradation of deep-eutectic solvents based on choline chloride and carboxylic acids. ACS Sustain Chem Eng 7:11521–11528Google Scholar
  42. Skulcova A, Majova V, Haz A, Kreps F, Russ A, Jablonsky M (2017) Long-term isothermal stability of deep eutectic solvents based on choline chloride with malonic or lactic or tartaric acid. Int J Sci Eng Res 8(7):2249–2252Google Scholar
  43. Smith EL, Abbott AP, Ryder KS (2014) Deep eutectic solvents (DESs) and their applications. Chem Rev 114:11060–11082PubMedGoogle Scholar
  44. Sudiyani Y, Styarini D, Triwahyuni E, Sudiyarmanto Sembiring KC, Aristiawan Y, Abimanyu H, Han MH (2013) Utilization of biomass waste empty fruit bunch fiber of palm oil for bioethanol production using pilot-scale unit. Energy Procedia 32:31–38Google Scholar
  45. Sun Y, Cheng J (2002) Hydrolysis of lignocellulosic materials for ethanol production: a review. Bioresour Technol 83:1–11PubMedPubMedCentralGoogle Scholar
  46. Sun XF, Xu F, Sun RC, Fowler P, Baird MS (2005) Characteristics of degraded cellulose obtained from steam-exploded wheat straw. Carbohydr Res 340:97–106PubMedGoogle Scholar
  47. Tang X, Zuo M, Li Z, Liu H, Xiong C, Zheng X, Sun Y, Hu L, Liu S, Lei T, Lin L (2017) Green processing of lignocellulosic biomass and its derivatives in deep eutectic solvents. Chemsuschem 10:2696–2706PubMedGoogle Scholar
  48. Thi S, Lee KM (2019) Comparison of deep eutectic solvents (DES) on pretreatment of oil palm empty fruit bunch (OPEFB): cellulose digestibility, structural and morphology changes. Bioresour Technol 282:525–529PubMedGoogle Scholar
  49. Wang Z, Li R, Xu J, Marita JM, Hatfield RD, Qu R, Cheng JJ (2012) Sodium hydroxide pretreatment of genetically modified switchgrass for improved enzymatic release of sugars. Bioresour Technol 110:364–370PubMedGoogle Scholar
  50. Weil J, Westgate P, Kohlmann K, Ladisch MR (1994) Cellulose pretreatments of lignocellulosic substrates. Enzyme Microb Tehnol 16:1002–1004Google Scholar
  51. Xu G-C, Ding J-C, Han R-Z, Dong J-J, Ni Y (2016) Enhancing cellulose accessibility of corn stover by deep eutectic solvent pretreatment for butanol fermentation. Bioresour Technol 203:364–369PubMedGoogle Scholar
  52. Yoshida M, Liu Y, Uchida S, Kawarada K, Ukagami Y, Ichinose H, Kaneko S, Fukuda K (2008) Effects of cellulose crystallinity, hemicellulose, and lignin on the enzymatic hydrolysis of Miscanthus sinesis to monosaccharides. Biosci Biotechnol Biochem 72:805–810PubMedGoogle Scholar
  53. Zhang Q, De Oliveira Vigier K, Royer S, Jérôme F (2012) Deep eutectic solvents: synthesis, properties and applications. Chem Soc Rev 41:7108–7146PubMedGoogle Scholar
  54. Zhang C-W, Xia S-Q, Ma P-S (2016) Facile pretreatment of lignocellulosic biomass using deep eutectic solvents. Bioresour Technol 219:1–5PubMedGoogle Scholar
  55. Zheng Y, Pan Z, Zhang R (2009) Overview of biomass pretreatment for cellulosic ethanol production. Int J Agric Biol Eng 2:51–68Google Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Department of Chemical and Petroleum Engineering, Faculty of Engineering, Technology and Built EnvironmentUCSI University (Block E)Cheras, Kuala LumpurMalaysia

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