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A one-pot microwave-assisted NaCl–H2O/GVL solvent system for cellulose conversion to 5-hydroxymethylfurfural and saccharides with in situ separation of the products

  • Zhicheng Jiang
  • Javier RemónEmail author
  • Tianzong Li
  • Vitaliy L. Budarin
  • Jiajun Fan
  • Changwei HuEmail author
  • James H. Clark
Original Research


This work addresses a microwave-assisted, NaCl–H2O/γ-valerolactone (GVL) solvent system for the co-production of 5-hydroxymethylfurfural (HMF) and saccharides from cellulose, examining the effects of the solvent system (H2O/GVL), NaCl concentration and reaction time. Oligosaccharides and glucose were completely recovered in the aqueous phase and their yields varied between 4–67 and 0–16 wt%, respectively, while HMF was largely recovered in the organic phase, in a yield between 0 and 13 wt%. Increasing the proportion of H2O in the system promoted cellulose depolymerisation and increased the production of oligosaccharides and glucose. This latter underwent a further decomposition to yield HMF and carboxylic acids when long times were used. An increase in NaCl not only kinetically promoted cellulose decomposition, but also modified the solubility of cellulose decomposition products in the aqueous phase, thus playing a very important role on the products distribution within both phases. With a solvent system consisting of 67/33 vol% H2O/GVL, with 30 wt% NaCl at 220 °C for 18 min, it is possible to selectively convert 76% of the cellulose into a sugar-rich aqueous solution and a rich HMF organic phase. The former was made up of glucose (25%) and oligosaccharides (64%), while the later mainly comprised HMF (75%). This might help the development of new biomass pre-processing technologies, allowing the co-production of precursors for the chemical and biological industries.

Graphical abstract


Cellulose Depolymerisation Microwaves NaCl Water γ-Valerolactone 



This work is financially supported by National Natural Science Foundation of China (No. 21536007), the 111 project (B17030), EPSRC for research Grant No. EP/K014773/1 and the Industrial Biotechnology Catalyst (Innovate UK, BBSRC, EPSRC) to support the translation, development and commercialisation of innovative industrial Biotechnology processes (EP/N013522/1). In addition, Zhicheng Jiang acknowledges support from China Scholarship Council (CSC No. 201501310005).


  1. Abdullah R, Ueda K, Saka S (2014) Hydrothermal decomposition of various crystalline celluloses as treated by semi-flow hot-compressed water. J Wood Sci 60:278–286CrossRefGoogle Scholar
  2. Alonso DM, Gallo JMR, Mellmer MA, Wettstein SG, Dumesic JA (2013a) Direct conversion of cellulose to levulinic acid and gamma-valerolactone using solid acid catalysts. Catal Sci Technol 3:927–931CrossRefGoogle Scholar
  3. Alonso DM, Wettstein SG, Mellmer MA, Gurbuz EI, Dumesic JA (2013b) Integrated conversion of hemicellulose and cellulose from lignocellulosic biomass. Energy Environ Sci 6:76–80CrossRefGoogle Scholar
  4. Atanda L, Konarova M, Ma Q, Mukundan S, Shrotri A, Beltramini J (2016) High yield conversion of cellulosic biomass into 5-hydroxymethylfurfural and a study of the reaction kinetics of cellulose to HMF conversion in a biphasic system. Catal Sci Technol 6:6257–6266CrossRefGoogle Scholar
  5. Atia H, Armbruster U, Martin A (2011) Influence of alkaline metal on performance of supported silicotungstic acid catalysts in glycerol dehydration towards acrolein. Appl Catal A 393:331–339CrossRefGoogle Scholar
  6. Bicker M, Hirth J, Vogel H (2003) Dehydration of fructose to 5-hydroxymethylfurfural in sub- and supercritical acetone. Green Chem 5:280–284CrossRefGoogle Scholar
  7. Bodachivskyi I, Kuzhiumparambil U, Williams DBG (2018) Acid-catalyzed conversion of carbohydrates into value-added small molecules in aqueous media and ionic liquids. Chemsuschem 11:642–660CrossRefGoogle Scholar
  8. Cao X, Teong SP, Wu D, Yi G, Su H, Zhang Y (2015) An enzyme mimic ammonium polymer as a single catalyst for glucose dehydration to 5-hydroxymethylfurfural. Green Chem 17:2348–2352CrossRefGoogle Scholar
  9. Chheda JN, Dumesic JA (2007) An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass-derived carbohydrates. Catal Today 123:59–70CrossRefGoogle Scholar
  10. De S, Dutta S, Saha B (2011) Microwave assisted conversion of carbohydrates and biopolymers to 5-hydroxymethylfurfural with aluminium chloride catalyst in water. Green Chem 13:2859–2868CrossRefGoogle Scholar
  11. Fan J, De bruyn M, Budarin VL, Gronnow MJ, Shuttleworth PS, Breeden S, Macquarrie DJ, Clark JH (2013) Direct microwave-assisted hydrothermal depolymerization of cellulose. J Am Chem Soc 135:11728–11731CrossRefGoogle Scholar
  12. Haber J, Pamin K, Matachowski L, Napruszewska B, Połtowicz J (2002) Potassium and silver salts of tungstophosphoric acid as catalysts in dehydration of ethanol and hydration of ethylene. J Catal 207:296–306CrossRefGoogle Scholar
  13. Hu L, Luo Y, Cai B, Li J, Tong D, Hu C (2014) The degradation of the lignin in Phyllostachys heterocycla cv. pubescens in an ethanol solvothermal system. Green Chem 16:3107–3116CrossRefGoogle Scholar
  14. Huang Y, Fu Y (2013) Hydrolysis of cellulose to glucose by solid acid catalysts. Green Chem 15:1095–1111CrossRefGoogle Scholar
  15. Huang R, Qi W, Su R, He Z (2010) Integrating enzymatic and acid catalysis to convert glucose into 5-hydroxymethylfurfural. Chem Commun (Camb) 46:1115–1117CrossRefGoogle Scholar
  16. Huber GW, Dumesic JA (2006) An overview of aqueous-phase catalytic processes for production of hydrogen and alkanes in a biorefinery. Catal Today 111:119–132CrossRefGoogle Scholar
  17. Jiang Z, Hu C (2016) Selective extraction and conversion of lignin in actual biomass to monophenols: a review. J Energy Chem 25:947–956CrossRefGoogle Scholar
  18. Jiang Z, Yi J, Li J, He T, Hu C (2015) Promoting effect of sodium chloride on the solubilization and depolymerization of cellulose from raw biomass materials in water. Chemsuschem 8:1901–1907CrossRefGoogle Scholar
  19. Jiang Z, Budarin VL, Fan J, Remón J, Li T, Hu C, Clark JH (2018a) Sodium chloride-sssisted depolymerization of xylo-oligomers to xylose. ACS Sustain Chem Eng 6:4098–4104CrossRefGoogle Scholar
  20. Jiang Z, Fan J, Budarin VL, Macquarrie DJ, Gao Y, Li T, Hu C, Clark JH (2018b) Mechanistic understanding of salt-assisted autocatalytic hydrolysis of cellulose. Sustain Energy Fuels 2:936–940CrossRefGoogle Scholar
  21. Jiang Z, Zhao P, Hu C (2018c) Controlling the cleavage of the inter- and intra-molecular linkages in lignocellulosic biomass for further biorefining: a review. Bioresour Technol 256:466–477CrossRefGoogle Scholar
  22. Jiang Z, Zhao P, Li J, Liu X, Hu C (2018d) Effect of tetrahydrofuran on the solubilization and depolymerization of cellulose in a biphasic system. Chemsuschem 11:397–405CrossRefGoogle Scholar
  23. Kirilin AV, Tokarev AV, Kustov LM, Salmi T, Mikkola JP, Murzin DY (2012) Aqueous phase reforming of xylitol and sorbitol: comparison and influence of substrate structure. Appl Catal A 435–436:172–180CrossRefGoogle Scholar
  24. Li W, Xu Z, Zhang T, Li G, Jameel H, Chang H, Ma L (2016a) Catalytic conversion of biomass-derived carbohydrates into 5-hydroxymethylfurfural using a strong solid acid catalyst in aqueous γ-valerolactone. BioResources 11:5839–5853Google Scholar
  25. Li X, Fang Z, Luo J, Su T (2016b) Coproduction of furfural and easily hydrolyzable residue from sugar cane bagasse in the MTHF/aqueous biphasic system: influence of acid species, NaCl addition, and MTHF. ACS Sustain Chem Eng 4:5804–5813CrossRefGoogle Scholar
  26. Li OL, Ikurac R, Ishizaki T (2017a) Hydrolysis of cellulose to glucose over carbon catalysts sulfonated via a plasma process in dilute acids. Green Chem 19:4774–4777CrossRefGoogle Scholar
  27. Li T, Remón J, Shuttleworth PS, Jiang Z, Fan J, Clark JH, Budarin VL (2017b) Controllable production of liquid and solid biofuels by doping-free, microwave-assisted, pressurised pyrolysis of hemicellulose. Energy Convers Manag 144:104–113CrossRefGoogle Scholar
  28. Li T, Remón J, Jiang Z, Budarin VL, Clark JH (2018) Towards the development of a novel “bamboo-refinery” concept: selective bamboo fractionation by means of a microwave-assisted, acid-catalysed, organosolv process. Energy Convers Manag 155:147–160CrossRefGoogle Scholar
  29. Luterbacher JS, Rand JM, Alonso DM, Han J, Youngquist JT, Maravelias CT, Pfleger BF, Dumesic JA (2014) Nonenzymatic sugar production from biomass using biomass derived γ-valerolactone. Science 343:277–280CrossRefGoogle Scholar
  30. 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 96:673–686CrossRefGoogle Scholar
  31. Rackemann DW, Bartley JP, Doherty WOS (2014) Methanesulfonic acid-catalyzed conversion of glucose and xylose mixtures to levulinic acid and furfural. Ind Crops Prod 52:46–57CrossRefGoogle Scholar
  32. Remón J, García L, Arauzo J (2016a) Cheese whey management by catalytic steam reforming and aqueous phase reforming. Fuel Process Technol 154:66–81CrossRefGoogle Scholar
  33. Remón J, Laseca M, García L, Arauzo J (2016b) Hydrogen production from cheese whey by catalytic steam reforming: preliminary study using lactose as a model compound. Energy Convers Manag 114:122–141CrossRefGoogle Scholar
  34. Remón J, Ruiz J, Oliva M, García L, Arauzo J (2016c) Cheese whey valorisation: production of valuable gaseous and liquid chemicals from lactose by aqueous phase reforming. Energy Convers Manag 124:453–469CrossRefGoogle Scholar
  35. Román-Leshkov Y, Dumesic JA (2009) Solvent effects on fructose dehydration to 5-hydroxymethylfurfural in biphasic systems saturated with inorganic salts. Top Catal 52:297–303CrossRefGoogle Scholar
  36. Roman-Leshkov Y, Barrett CJ, Liu ZY, Dumesic JA (2007) Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates. Nature 447:982–985CrossRefGoogle Scholar
  37. Sadula S, Athaley A, Zheng W, Ierapetritou M, Saha B (2017) Process intensification for cellulosic biorefineries. Chemsuschem 10:2566–2572CrossRefGoogle Scholar
  38. Shen Y, Sun J, Yi Y, Li M, Wang B, Xu F, Sun R (2014) InCl3-catalyzed conversion of carbohydrates into 5-hydroxymethylfurfural in biphasic system. Bioresour Technol 172:457–460CrossRefGoogle Scholar
  39. Shi N, Liu Q, Zhang Q, Wang T, Ma L (2013) High yield production of 5-hydroxymethylfurfural from cellulose by high concentration of sulfates in biphasic system. Green Chem 15:1967–1974CrossRefGoogle Scholar
  40. Tang J, Zhu L, Fu X, Dai J, Guo X, Hu C (2017) Insights into the kinetics and reaction network of aluminum chloride-catalyzed conversion of glucose in NaCl–H2O/THF biphasic system. ACS Catal 7:256–266CrossRefGoogle Scholar
  41. Taylor MJ, Durndell LJ, Isaacs MA, Parlett CMA, Wilson K, Lee AF, Kyriakou G (2016) Highly selective hydrogenation of furfural over supported Pt nanoparticles under mild conditions. Appl Catal B 180:580–585CrossRefGoogle Scholar
  42. Tong X, Ma Y, Li Y (2010) Biomass into chemicals: conversion of sugars to furan derivatives by catalytic processes. Appl Catal A 385:1–13CrossRefGoogle Scholar
  43. Tuteja J, Nishimura S, Ebitani K (2012) One-pot synthesis of furans from various saccharides using a combination of solid acid and base catalysts. Bull Chem Soc Jpn 85:275–281CrossRefGoogle Scholar
  44. Wei W, Wu S (2016) Conversion of eucalyptus cellulose into 5-hydroxymethylfurfural using lewis acid catalyst in biphasic solvent system. Waste Biomass Valoriz 8:1303–1311CrossRefGoogle Scholar
  45. Wettstein SG, Alonso DM, Chong Y, Dumesic JA (2012) Production of levulinic acid and gamma-valerolactone (GVL) from cellulose using GVL as a solvent in biphasic systems. Energy Environ Sci 5:8199–8203CrossRefGoogle Scholar
  46. Xiouras C, Radacsi N, Sturm G, Stefanidis GD (2016) Furfural synthesis from d-xylose in the presence of sodium chloride: microwave versus conventional heating. Chemsuschem 9:2159–2166CrossRefGoogle Scholar
  47. Xu S, Yan X, Bu Q, Xia H (2016) Highly efficient conversion of carbohydrates into 5-hydroxymethylfurfural using the bi-functional CrPO4 catalyst. RSC Adv 6:8048–8052CrossRefGoogle Scholar
  48. Yan K, Wu G, Lafleur T, Jarvis C (2014) Production, properties and catalytic hydrogenation of furfural to fuel additives and value-added chemicals. Renew Sustain Energy Rev 38:663–676CrossRefGoogle Scholar
  49. Yang Y, Hu C, Abu-Omar MM (2012) Conversion of carbohydrates and lignocellulosic biomass into 5-hydroxymethylfurfural using AlCl3·6H2O catalyst in a biphasic solvent system. Green Chem 14:509–513CrossRefGoogle Scholar
  50. Yang H, Wang L, Jia L, Qiu C, Pang Q, Pan X (2014) Selective decomposition of cellulose into glucose and levulinic acid over Fe-resin catalyst in NaCl solution under hydrothermal conditions. Ind Eng Chem Res 53:6562–6568CrossRefGoogle Scholar
  51. Yang P, Xia Q, Liu X, Wang Y (2016) High-yield production of 2,5-dimethylfuran from 5-hydroxymethylfurfural over carbon supported Ni-Co bimetallic catalyst. J Energy Chem 25:1015–1020CrossRefGoogle Scholar
  52. Zhang J, Yan N (2017) Production of glucosamine from chitin by co-solvent promoted hydrolysis and deacetylation. ChemCatChem 9:2790–2796CrossRefGoogle Scholar
  53. Zhao H, Holladay JE, Brown H, Zhang Z (2007) Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural. Science 316:1597–1600CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  • Zhicheng Jiang
    • 1
    • 2
    • 3
  • Javier Remón
    • 2
    Email author
  • Tianzong Li
    • 2
  • Vitaliy L. Budarin
    • 2
  • Jiajun Fan
    • 2
  • Changwei Hu
    • 1
    Email author
  • James H. Clark
    • 2
  1. 1.Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of ChemistrySichuan UniversityChengduPeople’s Republic of China
  2. 2.Green Chemistry Centre of Excellence, Department of ChemistryUniversity of YorkYorkUK
  3. 3.National Engineering Laboratory for Clean Technology of Leather ManufactureSichuan UniversityChengduPeople’s Republic of China

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