Abstract
Carbon-enriched lignocelluloses are regarded as the perfect alternative for nonrenewable fossil fuel, and have a great potential to alleviate the increasing energy crisis and climate change. However, the tightly covalent structure and strong intra and inter-molecular hydrogen bonding in lignocellulose make it high recalcitrance to transformation due to the poor solubility in water or common organic solvents. Dissolution and transformation of lignocellulose and its constituents in ionic liquids have therefore attracted much attention recently due to the tunable physical-chemical properties. Here, ionic liquids with excellent dissolving capability for biomass and its ingredients were examined. The technologies for lignocellulose biorefining in the presence of ionic liquid solvents or catalysts were also summarized. Some pertinent suggestions for the future catalytic conversion and unitization of this sustained carbon-rich resource are proposed.
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Grassian VH, Meyer G, Abruna H, Coates GW, Achenie LE, Allison T, Brunschwig B, Ferry J, Garcia-Garibay M, Gardea-Torresdey J, Grey CP, Hutchison J, Li CJ, Liotta C, Ragauskas A, Minteer S, Mueller K, Roberts J, Sadik O, Schmehl R, Schneider W, Selloni A, Stair P, Stewart J, Thorn D, Tyson J, Voelker B, White JM, Wood-Black F. Chemistry for a sustainable future. Environ Sci Technol, 2007, 41: 4840–4846
Zakrzewska ME, Bogel-Lukasik E, Bogel-Lukasik R. Ionic liquid-mediated formation of 5-hydroxymethylfurfural-A promising biomass-derived building block. Chem Rev, 2011, 111: 397–417
Luo J, Li J, Shen D, He L, Tong D, Hu C. Catalytic pyrolysis of Pubescens to phenols over Ni/C catalyst. Sci China Chem, 2010, 53: 1487–1491
Wu J, Zhang J, Zhang H, He JS, Ren Q, Guo M. Homogeneous acetylation of cellulose in a new ionic liquid. Biomacromolecules, 2004, 5: 266–268
Zhang SJ, Lv XM. Ionic liquids: From Basic Research To Industrial Applications. Science Press, 2006
Li XH, Zhao DB, Fei ZF, Wang LF. Applications of functionalized ionic liquids. Sci China Ser B-Chem, 2006, 49: 385–401
Chen XW, Li XH, Hu AX, Wang FR. Advances in chiral ionic liquids derived from natural amino acids. Tetrahedron: Asymmetry, 2008, 19: 1–14
Pei Y, Li Z, Liu L, Wang J, Wang H. Selective separation of protein and saccharides by ionic liquids aqueous two-phase systems. Sci China Chem, 2010, 53: 1554–1560
Zhang S, Zhang X, Zhao Y, Zhao G, Yao X, Yao H. A novel ionic liquids-based scrubbing process for efficient CO2 capture. Sci China Chem, 2010, 53: 1549–1553
Li J, Guo X, Wang L, Ma X, Zhang Q, Shi F, Deng Y. Co(acac)3/bmimCl as a base-free catalyst system for clean syntheses of N,N′-disubstituted ureas from amines and CO2. Sci China Chem, 2010, 53: 1534–1540
Swatloski RP, Spear SK, Holbrey JD, Rogers RD. Dissolution of cellose with ionic liquids. J Am Chem Soc, 2002, 124: 4974–4975
Moulthrop JS, Swatloski RP, Moyna G, Rogers RD. High-resolution C-13 NMR studies of cellulose and cellulose oligomers in ionic liquid solutions. Chem Commun, 2005: 1557–1559
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
Kilpelainen I, Xie H, King A, Granstrom M, Heikkinen S, Argyropoulos DS. Dissolution of wood in ionic liquids. J Agric Food Chem, 2007, 55: 9142–9148
Schlufter K, Schmauder HP, Dorn S, Heinze T. Efficient homogeneous chemical modification of bacterial cellulose in the ionic liquid 1-N-butyl-3-methylimidazolium chloride. Macromol Rapid Commun, 2006, 27: 1670–1676
Pu YQ, Jiang N, Ragauskas AJ. Ionic liquid as a green solvent for lignin. J Wood Chem Technol, 2007, 27: 23–33
Duan YP, Shi TJ, Guo LY, Li Z. Comparative studies on synthesis of three kinds of ionic liquids and their dissolution of cotton cellulose. Acta Chim Sin, 2009, 67: 1116–1122
Fukaya Y, Sugimoto A, Ohno H. Superior solubility of polysaccharides in low viscosity, polar, and halogen-free 1,3-dialkylimidazolium formates. Biomacromolecules, 2006, 7: 3295–3297
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
Zhang H, Wu J, Zhang J, He JS. 1-Allyl-3-methylimidazolium chloride room temperature ionic liquid: A new and powerful nonderivatizing solvent for cellulose. Macromolecules, 2005, 38: 8272–8277
Wu Y, Sasaki T, Irie S, Sakurai K. A novel biomass-ionic liquid platform for the utilization of native chitin. Polymer, 2008, 49: 2321–2327
Ren Q, Wu J, Zhang J, He JS, Guo ML. Synthesis of 1-allyl,3-methyle mazolium-based roomtemperature ionic liquid and preluviinary study of its dissolving cellulose. Acta Polymer Sin, 2003, 3: 448–451
Graenacher C, Inventor. Cellulose Solution1934.
Erdmenger T, Haensch C, Hoogenboom R, Schubert US. Homogeneous tritylation of cellulose in 1-butyl-3-methyl imidazolium chloride. Macromol Biosci, 2007, 7: 440–445
Wang ML, Zang HJ, Cai BX, Cheng BW. Dissolubility of the cellulose in [AmMorCl/[Amim]Cl. Chem J Chin Univ, 2009, 30: 1469–1472
Luo HM, Li YQ, Zhou CR. Study on the dissolubility of the cellulose in the functionalized ionic liquid. Poly Mater Sci Engineer, 2005, 21: 233–235
Kosan B, Schwikal K, Meister F. Solution states of cellulose in selected direct dissolution agents. Cellulose, 2010, 17: 495–506
Kosan B, Michels C, Meister F. Dissolution and forming of cellulose with ionic liquids. Cellulose, 2008, 15: 59–66
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
Barthel S, Heinze T. Acylation and carbanilation of cellulose in ionic liquids. Green Chem, 2006, 8: 301–306
El Seoud OA, Koschella A, Fidale LC, Don S, Heinze T. Applications of ionic liquids in carbohydrate chemistry: A window of opportunities. Biomacromolecules, 2007, 8: 2629–2647
Heinze T, Schwikal K, Barthel S. Ionic liquids as reaction medium in cellulose functionalization. Macromol Biosci, 2005, 5: 520–525
Mazza M, Catana DA, Vaca-Garcia C, Cecutti C. Influence of water on the dissolution of cellulose in selected ionic liquids. Cellulose, 2009, 16: 207–215
Mitsuru Abe, Yukinobu Fukaya, Ohno H. Fast and facile dissolution of cellulose with tetrabutylphosphonium hydroxide containing 40 wt% water. Chem Commun, 2012, 48: 1808–1810
Rinaldi R. Instantaneous dissolution of cellulose in organic electrolyte solutions. Chem Commun, 2011, 47: 511–513
Zakzeski J, Bruijnincx PCA, Jongerius AL, Weckhuysen BM. The catalytic valorization of lignin for the production of renewable chemicals. Chem Rev, 2010, 110: 3552–3599
Klein AP, Beach ES, Emerson JW, Zimmerman JB. Accelerated solvent extraction of lignin from Aleurites moluccana (Candlenut) nutshells. J Agric Food Chem, 2010, 58: 10045–10048
Aaltonen O, Jauhiainen O. The preparation of lignocellulosic aerogels from ionic liquid solutions. Carbohyd Polym, 2009, 75: 125–129
Tan SSY, MacFarlane DR, Upfal J, Edye LA, Doherty WOS, Patti AF, Pringle JM, Scott JL. Extraction of lignin from lignocellulose at atmospheric pressure using alkylbenzenesulfonate ionic liquid. Green Chem, 2009, 11: 339–345
Pinkert A, Goeke DF, Marsh KN, Pang S. Extracting wood lignin without dissolving or degrading cellulose: investigations on the use of food additive-derived ionic liquids. Green Chem, 2011, 13: 3124–3136
Sun N, Rahman M, Qin Y, Maxim M L, 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
Li W, Sun N, Stoner B, Jiang X, Lu X, Rogers RD. Rapid dissolution of lignocellulosic biomass in ionic liquids using temperatures above the glass transition of lignin. Green Chem, 2011, 13: 2038–2047
Kilpelainen I, Xie H, King A, Granstrom M, Heikkinen S, Argyropoulos DS. Dissolution of wood in ionic liquids. J Agric Food Chem, 2007, 55: 9142–9148
King AWT, Zoia L, Filpponen I, et al. In Situ Determination of lignin phenolics and wood solubility in imidazolium chlorides using (31)P NMR. J Agric Food Chem, 2009, 57: 8236–8243
Muhammad N, Man Z, Bustam MA, Mutalib MIA, Wilfred CD, Rafiq S. Dissolution and delignification of bamboo biomass using amino acid-based ionic liquid. Appl Biochem Biotechnol, 2011, 165: 998–1009
Abe M, Fukaya Y, Ohno H. Extraction of polysaccharides from bran with phosphonate or phosphinate-derived ionic liquids under short mixing time and low temperature. Green Chem, 2010, 12, 1274–1280
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
Remsing RC, Swatloski RP, Rogers RD, Moyna G. Mechanism of cellulose dissolution in the ionic liquid 1-n-butyl-3-methylimidazolium chloride: A C-13 and Cl-35/37 NMR relaxation study on model systems. Chem Commun, 2006, 12: 1271–1273
Youngs TGA, Holbrey JD, Deetlefs M, Nieuwenhuyzen M, Gomes MFC, Hardacre C. A molecular dynamics study of glucose solvation in the ionic liquid 1,3-dimethylimidazolium chloride. Chemphyschem, 2006, 7: 2279–2281
Lindman B, Karlström G, Stigsson L. On the mechanism of dissolution of cellulose. J Mol Liq, 2010, 156: 76–81
van Spronsen J, Cardoso MAT, Witkamp G-J, de Jong W, Kroon MC. Separation and recovery of the constituents from lignocellulosic biomass by using ionic liquids and acetic acid as co-solvents for mild hydrolysis. Chem Eng Process, 2011, 50: 196–199
Li C, Zhao ZK. Efficient acid-catalyzed hydrolysis of cellulose in ionic liquid. Adv Synth Catal, 2007, 349: 1847–1850
Li CZ, Wang Q, Zhao ZK. Acid in ionic liquid: An efficient system for hydrolysis of lignocellulose. Green Chem, 2008, 10: 177–182
Zhang ZH, Li CZ, Wang Q, Zhao ZBK. Efficient hydrolysis of chitosan in ionic liquids. Carbohydr Polym, 2009, 78: 685–689
Rinaldi R, Palkovits R, Schuth F. Depolymerization of cellulose using solid catalysts in ionic liquids. Angew Chem Int Ed, 2008, 47: 8047–8050
Rinaldi R, Schuth F. Acid hydrolysis of cellulose as the entry point into biorefinery schemes. ChemsusChem, 2009, 2: 1096–1107
Rinaldi R, Meine N, vom Stein J, Palkovits R, Schuth F. Which controls the depolymerization of cellulose in ionic liquids: the solid acid catalyst or cellulose? ChemsusChem, 2010, 3: 266–276
Jiang F, Ma D, Bao XH. Acid ionic liquid catalyzed hydrolysis of cellulose. Chinese J Catal, 2009, 30: 279–283
Jiang F, Zhu QJ, Ma D, Liu XM, Han XW. Direct conversion and NMR observation of cellulose to glucose and 5-hydroxymethylfurfural (HMF) catalyzed by the acidic ionic liquids. J Mol Catal A Chem, 2011, 334: 8–12
Lee SH, Doherty TV, Linhardt RJ, Dordick JS. Ionic liquid-mediated selective extraction of lignin from wood leading to enhanced enzymatic cellulose hydrolysis. Biotechnol Bioengineer, 2009, 102: 1368–1376
Ogeda TL, Petri DFS. Biomass enzymatic hydrolysis. Quimica Nova, 2010, 33: 1549–1558
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
Li Q, He YC, Xian M, et al. Improving enzymatic hydrolysis of wheat straw using ionic liquid 1-ethyl-3-methyl imidazolium diethyl phosphate pretreatment. Bioresour Technol, 2009, 100: 3570–3575
Bharadwaj R, Wong A, Knierim B, et al. High-throughput enzymatic hydrolysis of lignocellulosic biomass via in-situ regeneration. Bioresour Technol, 2011, 102: 1329–1337
Zhao H, Holladay JE, Brown H, Zhang ZC. Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural. Science, 2007, 316: 1597–1600
Pidko EA, Degirmenci V, van Santen RA, Hensen EJM. Glucose activation by transient Cr2+ dimers. Angew Chem Int Ed, 2010, 49: 2530–2534
Yong G, Zhang Y, Ying JY. Efficient catalytic system for the selective production of 5-hydroxymethylfurfural from glucose and fructose. Angew Chem Int Ed, 2008, 47: 9345–9348
Binder JB, Raines RT. Simple Chemical transformation of lignocellulosic biomass into furans for fuels and chemicals. J Am Chem Soc, 2009, 131: 1979–1985
Zhang Z, Zhao ZK. Microwave-assisted conversion of lignocellulosic biomass into furans in ionic liquid. Bioresour Technol, 2010, 101: 1111–1114
Kim B, Jeong J, Lee D, et al. Direct transformation of cellulose into 5-hydroxymethyl-2-furfural using a combination of metal chlorides in imidazolium ionic liquid. Green Chem, 2011, 13: 1503–1506
Long JX, Guo B, Teng JJ, Yu YH, Wang LF, Li XH. SO3H-functionalized ionic liquid: Efficient catalyst for bagasse liquefaction. Bioresour Technol, 2011, 102: 10114–10123
Long JX, Guo B, Li XH, et al. One step catalytic conversion of cellulose to sustainable chemicals utilizing cooperative ionic liquid pairs. Green Chem, 2011, 13: 2334–2338
Long JX, Guo B, Li XH, Wang FR, Wang LF. Catalytic decomposition of cellulose in cooperative ionic liquids. Acta Phys Chim Sin, 2011, 27: 995–999
Long JX, Li XH, Guo B, Wang FR, Yu YH, Wang LF. Simultaneous delignification and selective catalytic transformation of agricultural lignocellulose in cooperative ionic liquid pairs, Green Chem, 2012, DOI: 10.1039/C2GC35105F
Villandier N, Corma A. One pot catalytic conversion of cellulose into biodegradable surfactants. Chem Commun, 2010, 46: 4408–4410
Kohler S, Heinze T. Efficient synthesis of cellulose furoates in 1-N-butyl-3-methylimidazolium chloride. Cellulose, 2007, 14: 489–495
Kohler S, Liebert T, Heinze T, et al. Interactions of ionic liquids with polysaccharides 9. Hydroxyalkylation of cellulose without additional inorganic bases. Cellulose, 2010, 17: 437–448
Brennan TCR, Datta S, Blanch HW, Simmons BA, Holmes BM. Recovery of sugars from ionic liquid biomass liquor by solvent extraction. Bioenerg Res, 2010, 3: 123–133
Shill K, Padmanabhan S, Xin Q, Prausnitz JM, Clark DS, Blanch HW. Ionic liquid pretreatment of cellulosic biomass: Enzymatic hydrolysis and ionic liquid recycle. Biotechnol Bioeng, 2011, 108: 511–520
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Long, J., Li, X., Wang, L. et al. Ionic liquids: Efficient solvent and medium for the transformation of renewable lignocellulose. Sci. China Chem. 55, 1500–1508 (2012). https://doi.org/10.1007/s11426-012-4633-7
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DOI: https://doi.org/10.1007/s11426-012-4633-7