Evaluation of four ionic liquids for pretreatment of lignocellulosic biomass

BMC Biotechnology

John Gräsvik¹  Sandra Winestrand¹  Monica Normark¹  Leif J Jönsson¹  Jyri-Pekka Mikkola² 

[1] Department of Chemistry, Umeå University, Umeå SE-901 87, Sweden

[2] Industrial Chemistry & Reaction Engineering, Åbo Akademi University, Åbo-Turku FI-20500, Finland

关键词: Enzymatic saccharification;    Lignocellulose;    Pretreatment;    Ionic liquid;   

Others  :  834867
DOI  :  10.1186/1472-6750-14-34

 received in 2014-01-10, accepted in 2014-04-23,  发布年份 2014

【 摘 要 】

Background

Lignocellulosic biomass is highly recalcitrant and various pretreatment techniques are needed to facilitate its effective enzymatic hydrolysis to produce sugars for further conversion to bio-based chemicals. Ionic liquids (ILs) are of interest in pretreatment because of their potential to dissolve lignocellulosic materials including crystalline cellulose.

Results

Four imidazolium-based ionic liquids (ILs) ([C=C₂C₁im][MeCO₂], [C₄C₁im][MeCO₂], [C₄C₁im][Cl], and [C₄C₁im][HSO₄]) well known for their capability to dissolve lignocellulosic species were synthesized and then used for pretreatment of substrates prior to enzymatic hydrolysis. In order to achieve a broad evaluation, seven cellulosic, hemicellulosic and lignocellulosic substrates, crystalline as well as amorphous, were selected. The lignocellulosic substrates included hybrid aspen and Norway spruce. The monosaccharides in the enzymatic hydrolysate were determined using high-performance anion-exchange chromatography. The best results, as judged by the saccharification efficiency, were achieved with [C₄C₁im][Cl] for cellulosic substrates and with the acetate-based ILs for hybrid aspen and Norway spruce. After pretreatment with acetate-based ILs, the conversion to glucose of glucan in recalcitrant softwood lignocellulose reached similar levels as obtained with pure crystalline and amorphous cellulosic substrates. IL pretreatment of lignocellulose resulted in sugar yields comparable with that obtained with acidic pretreatment. Heterogeneous dissolution with [C₄C₁im][HSO₄] gave promising results with aspen, the less recalcitrant of the two types of lignocellulose included in the investigation.

Conclusions

The ability of ILs to dissolve lignocellulosic biomass under gentle conditions and with little or no by-product formation contributes to making them highly interesting alternatives for pretreatment in processes where high product yields are of critical importance.

【 授权许可】

   
2014 Gräsvik et al.; licensee BioMed Central Ltd.

【 图 表 】

Figure 1.

Figure 2.

Figure 3.

【 参考文献 】

• [1]Perlack RD, Wright LL, Turhollow AF, Graham RL, Stokes BJ, Erbach DC: Biomass as a feedstock for a bioenergy and bioproducts industry: the technical feasibility of a billion-ton annual supply. Springfield, VA: U.S. Department of Commerce, National Technical Information Service; 2005.
• [2]Lichtenthaler FW, Peters S: Carbohydrates as green raw materials for the chemical industry. C R Chim 2004, 7:65-90.
• [3]Mosier N, Wyman C, Dale B, Elander R, Lee YY, Holtzapple M, Ladisch M: Features of promising technologies for pretreatment of lignocellulosic biomass. Bioresour Technol 2005, 96:673-686.
• [4]Chandra RP, Bura R, Mabee WE, Berlin A, Pan X, Saddler JN: Substrate pretreatment: the key to effective enzymatic hydrolysis of lignocellulosics? Adv Biochem Eng Biotechnol 2007, 108:67-93.
• [5]Zhang YHP, Lynd LR: Toward an aggregated understanding of enzymatic hydrolysis of cellulose: noncomplexed cellulase systems. Biotech Bioeng 2004, 88:797-824.
• [6]Biermann O, Hadicke E, Koltzenburg S, Muller-Plathe F: Hydrophilicity and lipophilicity of cellulose crystal surfaces. Angew Chem Int Edit 2001, 40:3822-3825.
• [7]Yamane C, Aoyagi T, Ago M, Sato K, Okajima K, Takahashi T: Two different surface properties of regenerated cellulose due to structural anisotropy. Polym J 2006, 38:819-826.
• [8]Lindman B, Karlström G, Stigsson L: On the mechanism of dissolution of cellulose. J Mol Liq 2010, 156:76-81.
• [9]Liebert TF, Heinze TJ, Edgar KJ: Cellulose solvents: for analysis, shaping and chemical modification. Washington: American Chemical Society; 2009.
• [10]Hermanutz F, Gaehr F, Uerdingen E, Meister F, Kosan B: New developments in dissolving and processing of cellulose in ionic liquids. Macromol Symp 2008, 262:23-27.
• [11]Heinze T, Dicke R, Koschella A, Kull AH, Klohr EA, Koch W: Effective preparation of cellulose derivatives in a new simple cellulose solvent. Macromol Chem Phys 2000, 201:627-631.
• [12]Yan LF, Chen J, Bangal PR: Dissolving cellulose in a NaOH/thiourea aqueous solution: a topochemical investigation. Macromol Biosci 2007, 7:1139-1148.
• [13]Yan LF, Gao ZJ: Dissolving of cellulose in PEG/NaOH aqueous solution. Cellulose 2008, 15:789-796.
• [14]Liu SL, Zhang LN: Effects of polymer concentration and coagulation temperature on the properties of regenerated cellulose films prepared from LiOH/urea solution. Cellulose 2009, 16:189-198.
• [15]Swatloski RP, Spear SK, Holbrey JD, Rogers RD: Dissolution of cellose with ionic liquids. J Am Chem Soc 2002, 124:4974-4975.
• [16]Tan SSY, MacFarlane DR: Ionic liquids in biomass processing. Ionic Liquids 2009, 290:311-339.
• [17]Pinkert A, Marsh KN, Pang SS, Staiger MP: Ionic liquids and their interaction with cellulose. Chem Rev 2009, 109:6712-6728.
• [18]Brandt A, Ray MJ, To TQ, Leak DJ, Murphy RJ, Welton T: Ionic liquid pretreatment of lignocellulosic biomass with ionic liquid-water mixtures. Green Chem 2011, 13:2489-2499.
• [19]Sun N, Rodriguez H, Rahman M, Rogers RD: Where are ionic liquid strategies most suited in the pursuit of chemicals and energy from lignocellulosic biomass? Chem Commun 2011, 47:1405-1421.
• [20]Zhao H, Baker GA, Song ZY, Olubajo O, Crittle T, Peters D: Designing enzyme-compatible ionic liquids that can dissolve carbohydrates. Green Chem 2008, 10:696-705.
• [21]Turner MB, Spear SK, Huddleston JG, Holbrey JD, Rogers RD: Ionic liquid salt-induced inactivation and unfolding of cellulase from Trichoderma reesei. Green Chem 2003, 5:443-447.
• [22]Engel P, Mladenov R, Wulfhorst H, Jager G, Spiess AC: Point by point analysis: how ionic liquid affects the enzymatic hydrolysis of native and modified cellulose. Green Chem 2010, 12:1959-1966.
• [23]Brandt A, Hallett JP, Leak DJ, Murphy RJ, Welton T: The effect of the ionic liquid anion in the pretreatment of pine wood chips. Green Chem 2010, 12:672-679.
• [24]Doherty TV, Mora-Pale M, Foley SE, Linhardt RJ, Dordick JS: Ionic liquid solvent properties as predictors of lignocellulose pretreatment efficacy. Green Chem 2010, 12:1967-1975.
• [25]Gräsvik J, Eliasson B, Mikkola JP: Halogen-free ionic liquids and their utilization as cellulose solvents. J Mol Struct 2012, 1028:156-163.
• [26]Sun N, Rahman M, Qin Y, Maxim ML, Rodriguez H, Rogers RD: Complete dissolution and partial delignification of wood in the ionic liquid 1-ethyl-3-methylimidazolium acetate. Green Chem 2009, 11:646-655.
• [27]Fort DA, Remsing RC, Swatloski RP, Moyna P, Moyna G, Rogers RD: Can ionic liquids dissolve wood? processing and analysis of lignocellulosic materials with 1-n-butyl-3-methylimidazolium chloride. Green Chem 2007, 9:63-69.
• [28]Padmanabhan S, Kim M, Blanch HW, Prausnitz JM: Solubility and rate of dissolution for Miscanthus in hydrophilic ionic liquids. Fluid Phase Equilibr 2011, 309:89-96.
• [29]Fukaya Y, Hayashi K, Wada M, Ohno H: Cellulose dissolution with polar ionic liquids under mild conditions: required factors for anions. Green Chem 2008, 10:44-46.
• [30]Brandt A, Gräsvik J, Hallett JP, Welton T: Deconstruction of lignocellulosic biomass with ionic liquids. Green Chem 2013, 15:550-583.
• [31]Young RA, Rowell RM: Cellulose: structure, modification and hydrolysis. New York: John Wiley and Sons; 1986.
• [32]Fengel D, Wegner G: Wood: chemistry, ultrastructure, reactions. New York: Walter de Gruyter; 1989.
• [33]Krässig HA: Cellulose: structure, accessibility and reactivity: polymer monographs vol. 11. Amsterdam: Gordon and Breach Science Publishers; 1996.
• [34]Van de Vyver S, Thomas J, Geboers J, Keyzer S, Smet M, Dehaen W, Jacobs PA, Sels BF: Catalytic production of levulinic acid from cellulose and other biomass-derived carbohydrates with sulfonated hyperbranched poly(arylene oxindole)s. Energy Environ Sci 2011, 4:3601-3610.
• [35]Zhang Y-HP, Lynd LR: Determination of the number-average degree of polymerization of cellodextrins and cellulose with application to enzymatic hydrolysis. Biomacromolecules 2005, 6:1510-1515.
• [36]Zhang YHP, Cui JB, Lynd LR, Kuang LR: A transition from cellulose swelling to cellulose dissolution by o-phosphoric acid: evidence from enzymatic hydrolysis and supramolecular structure. Biomacromolecules 2006, 7:644-648.
• [37]Wang H, Gurau G, Rogers RD: Ionic liquid processing of cellulose. Chem Soc Rev 2012, 41:1519-1537.
• [38]Kilpeläinen I, Xie H, King A, Granstrom M, Heikkinen S, Argyropoulos DS: Dissolution of wood in ionic liquids. J Agr Food Chem 2007, 55:9142-9148.
• [39]Zavrel M, Bross D, Funke M, Buchs J, Spiess AC: High-throughput screening for ionic liquids dissolving (ligno-)cellulose. Bioresour Technol 2009, 100:2580-2587.
• [40]Brandt A: Ionic liquid pretreatment of lignocellulosic biomass. London: Imperial College London; 2012.
• [41]Troshenkova S, Sashina E, Novoselov N, Arndt K, Jankowsky S: Structure of ionic liquids on the basis of imidazole and their mixtures with water. Russ J Gen Chem 2010, 80:106-111.
• [42]Saddler JN: Bioconversion of forest and agricultural plant residues. Wallingford: CAB International; 1993.
• [43]Arora R, Manisseri C, Li CL, Ong MD, Scheller HV, Vogel K, Simmons BA, Singh S: Monitoring and analyzing process streams towards understanding ionic liquid pretreatment of switchgrass (Panicum virgatum L.). Bioenergy Res 2010, 3:134-145.
• [44]Gottlieb HE, Kotlyar V, Nudelman A: NMR chemical shifts of common laboratory solvents as trace impurities. J Org Chem 1997, 62:7512-7515.
• [45]Lestander TA, Geladi P, Larsson SH, Thyrel M: Near infrared image analysis for online identification and separation of wood chips with elevated levels of extractives. J Near Infrared Spec 2012, 20:591-599.
• [46]Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, Crocker D: Determination of structural carbohydrates and lignin in biomass. Technical Report NREL/TP-510-42618. Golden, CO: National Renewable Energy Laboratory; 2011.