BioEnergy Research

, Volume 10, Issue 4, pp 1018–1024 | Cite as

Concentrated HCl Catalyzed 5-(Chloromethyl)furfural Production from Corn Stover of Varying Particle Sizes

  • Ximing Zhang
  • Necla Mine Eren
  • Thomas Kreke
  • Nathan S. Mosier
  • Abigail S. Engelberth
  • Gozdem KilazEmail author


5-(Chloromethyl) Furfural (CMF) is a potential chemical building block for replacing petroleum-derived chemicals derived from lignocellulosic feedstocks. In this study, hand harvested corn stover and mechanically forage chopped corn stover was processed in a 1 L hydrolysis reactor to produce CMF in a biphasic, two solvent system. Both 1,2 dichloroethane (DCE) and dichloromethane (DCM) were tested as organic solvents. The results showed that DCE performed better than DCM due to temperature and pressure limitations of the reactor system. Using DCE as the extracting solvent, the effects of solids loading, particle size, and moisture content of the corn stover on the hydrolysis efficiency were determined. One liter acid hydrolysis reactor provides consistent and reproducible yields of 63% CMF from hand harvested corn stover as feedstock at solid loading of 10% wt/v, 100C for 1 h. For the forage chopped corn stover, increasing particle size brings an increase in the feedstock sugar content. Foraged chopped corn stover (FCCS) particle sizes larger than 19 mm (0.75 in.) results in significant reduction in CMF yield from 43 to 35%.


Alternative aviation fuels Acid hydrolysis Furfural Corn stover Biomass Sustainable energy 



This research is funded by Indiana corn marketing council (ICMC). The authors would like to thank James Streater for providing the forage chopped material. Assistance of Patrick Canepa and Caleb Leuck with reactor runs, guidance of Xingya Liu with HPLC runs, feedbacks of Ron Brander as the project consultant are deeply appreciated. Also it is important to acknowledge Aleksei Bredihhin and Lauri Vares from University of Tartu as well as Ian Klein from Purdue University for their endless support and expertise regarding CMF synthesis and purification for our HPLC standards.


  1. 1.
    Solecki M, Scodel A, Epstein B (2011) Adv Biofuel Mark Rep:2013Google Scholar
  2. 2.
    Aeschelmann F, Carus M (2015) Biobased building blocks and polymers in the world: capacities, production, and applications—status quo and trends towards 2020. Ind Biotechnol 11(3):154–159CrossRefGoogle Scholar
  3. 3.
    de Jong E, Higson A, Walsh P, Wellisch M (2012) Bio-based chemicals value added products from biorefineries. IEA Bioenergy, Task42 BiorefineryGoogle Scholar
  4. 4.
    Perras FA, Luo H, Zhang X, Mosier NS, Pruski M, Abu-Omar MM (2017) Atomic level structure characterization of biomass pre and post lignin treatment by dynamic nuclear polarization-enhanced solid state NMR. J Phys Chem A 121(3):623–630CrossRefPubMedGoogle Scholar
  5. 5.
    Hewetson BB, Zhang X, Mosier NS (2016) Enhanced acid-catalyzed biomass conversion to Hydroxymethylfurfural following cellulose solvent-and organic solvent-based lignocellulosic fractionation pretreatment. Energy Fuel 30(11):9975–9977CrossRefGoogle Scholar
  6. 6.
    Xu J, Zhang X, Sharma-Shivappa RR, Eubanks MW (2012) Gamagrass varieties as potential feedstock for fermentable sugar production. Bioresour Technol 116:540–544CrossRefPubMedGoogle Scholar
  7. 7.
    Zhang X, Hewetson BB, Mosier NS (2015) Kinetics of maleic acid and aluminum chloride catalyzed dehydration and degradation of glucose. Energy Fuel 29(4):2387–2393CrossRefGoogle Scholar
  8. 8.
    Zhang X, Murria P, Jiang Y, Xiao W, Kenttämaa HI, Abu-Omar MM, Mosier NS (2016) Maleic acid and aluminum chloride catalyzed conversion of glucose to 5-(hydroxymethyl) furfural and levulinic acid in aqueous media. Green Chem 18:5219–5229CrossRefGoogle Scholar
  9. 9.
    Mascal M (2015) 5-(Chloromethyl) furfural is the new HMF: functionally equivalent but more practical in terms of its production from biomass. ChemSusChem 8(20):3391–3395CrossRefPubMedGoogle Scholar
  10. 10.
    Mascal M, Nikitin EB (2008) Direct, high-yield conversion of cellulose into biofuel. Angew Chem Int Ed 120(41):8042–8044CrossRefGoogle Scholar
  11. 11.
    Lane DR, Mascal M, Stroeve P (2016) Experimental studies towards optimization of the production of 5-(chloromethyl) furfural (CMF) from glucose in a two-phase reactor. Renew Energy 85:994–1001CrossRefGoogle Scholar
  12. 12.
    Xu J, Zhang X, Cheng JJ (2012) Pretreatment of corn stover for sugar production with switchgrass-derived black liquor. Bioresour Technol 111:255–260CrossRefPubMedGoogle Scholar
  13. 13.
    Zhang X, Xu J, Cheng JJ (2011) Pretreatment of corn stover for sugar production with combined alkaline reagents. Energy Fuel 25(10):4796–4802CrossRefGoogle Scholar
  14. 14.
    Xiao W, Zhang X, Wang X, Niu W, Han L (2015) Rapid liquefaction of corn stover with microwave heating. Bioresources 10(3):4038–4047CrossRefGoogle Scholar
  15. 15.
    Vadas PA, Digman MF (2013) Production costs of potential corn stover harvest and storage systems. Biomass Bioenergy 54:133–139CrossRefGoogle Scholar
  16. 16.
    Mascal M, Nikitin EB (2009) Dramatic advancements in the saccharide to 5-(Chloromethyl) furfural conversion reaction. ChemSusChem 2(9):859–861CrossRefPubMedGoogle Scholar
  17. 17.
    Bredihhin A, Mäeorg U, Vares L (2013) Evaluation of carbohydrates and lignocellulosic biomass from different wood species as raw material for the synthesis of 5-bromomethyfurfural. Carbohydr Res 375:63–67CrossRefPubMedGoogle Scholar
  18. 18.
    Sluiter J, Sluiter A (2011) Summative mass closure. NREL, NREL/TP-510-48087 1-10Google Scholar
  19. 19.
    Alamouti AA, Alikhani M, Ghorbani GR, Zebeli Q (2009) Effects of inclusion of neutral detergent soluble fibre sources in diets varying in forage particle size on feed intake, digestive processes, and performance of mid-lactation Holstein cows. Anim Feed Sci Technol 154(1):9–23CrossRefGoogle Scholar
  20. 20.
    Sako T, Hakuta T, Yoshitome H (1985) Vapor pressures of binary (water-hydrogen chloride,-magnesium chloride, and-calcium chloride) and ternary (water-magnesium chloride-calcium chloride) aqueous solutions. J Chem Eng Data 30(2):224–228CrossRefGoogle Scholar
  21. 21.
    Zeng M, Ximenes E, Ladisch MR, Mosier NS, Vermerris W, Huang CP, Sherman DM (2012) Tissue-specific biomass recalcitrance in corn stover pretreated with liquid hot-water: enzymatic hydrolysis (part 1). Biotechnol Bioeng 109(2):390–397CrossRefPubMedGoogle Scholar
  22. 22.
    Zeng M, Ximenes E, Ladisch MR, Mosier NS, Vermerris W, Huang CP, Sherman DM (2012) Tissue-specific biomass recalcitrance in corn stover pretreated with liquid hot-water: SEM imaging (part 2). Biotechnol Bioeng 109(2):398–404CrossRefPubMedGoogle Scholar
  23. 23.
    Kim Y, Kreke T, Mosier NS, Ladisch MR (2014) Severity factor coefficients for subcritical liquid hot water pretreatment of hardwood chips. Biotechnol Bioeng 111(2):254–263CrossRefPubMedGoogle Scholar
  24. 24.
    Womac AR, Igathinathane C, Sokhansanj S, Pordesimo LO (2005) Biomass moisture relations of an agricultural field residue: corn stover. Trans ASAE 48(6):2073–2083CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2017

Authors and Affiliations

  1. 1.Laboratory of Renewable Resources EngineeringPurdue UniversityWest LafayetteUSA
  2. 2.Department of Agricultural and Biological EngineeringPurdue UniversityWest LafayetteUSA
  3. 3.School of Engineering TechnologyPurdue UniversityWest LafayetteUSA

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