Abstract
This work studied the feasibility of potassium carbonate-glycerol deep eutectic solvent (K2CO3-Gly DES) as a potential green solvent applied in lignocellulose pulping. Cellulose fibers were extracted from rice straw via novel alkaline DES pulping technique using 1:7 molar ratio of K2CO3-Gly DES. Optimum pulping parameters were determined using the one-factor-at-a-time (OFAT) method. The cellulose fibers were characterized for chemical composition of cellulose, hemicellulose, lignin and extractives. Changes in physical structure, chemical structure, morphological structure, functional groups and crystallinity index (CrI) were investigated using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results revealed that the optimum pulping temperature at 140 °C, reaction time of 100 min and 1:10 rice straw to DES mass ratio produced the highest cellulose content of 73.8% for unbleached DES treated pulp. Chemical composition analysis and FTIR verified that this alkaline DES pulping method was able to achieve partial removal of hemicellulose and lignin from lignocellulosic matrix. Moreover, XRD result demonstrated that the CrI of cellulose fiber increased from 52.8 to 60.0% after pretreatment. The cellulose fibers had diameters ranging from 3.58 to 5.68 µm. This study proved that the specifically-designed K2CO3-Gly DES could successfully isolate cellulose from lignocellulosic biomass through alkaline DES pulping.
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Abbott AP, Capper G, Davies DL, Munro HL, Rasheed RK, Tambyrajah V (2001) Preparation of novel, moisture-stable, Lewis-acidic ionic liquids containing quaternary ammonium salts with functional side chains. Chem Commun. https://doi.org/10.1039/b106357j
Abbott AP, Capper G, Davies DL, Rasheed RK, Tambyrajah V (2003) Novel solvent properties of choline chloride/urea mixtures. Chem Commun. https://doi.org/10.1039/b210714g
Abbott AP, Frisch G, Hartley J, Ryder KS (2011) Processing of metals and metal oxides using ionic liquids. Green Chem 13:471–481. https://doi.org/10.1039/c0gc00716a
Ayeni AO, Hymore FK, Mudliar SN, Deshmukh SC, Satpute DB, Omoleye JA, Pandey RA (2013) Hydrogen peroxide and lime based oxidative pretreatment of wood waste to enhance enzymatic hydrolysis for a biorefinery: process parameters optimization using response surface methodology. Fuel 106:187–194. https://doi.org/10.1016/j.fuel.2012.12.078
Azadi P, Inderwildi OR, Farnood R, King DA (2013) Liquid fuels, hydrogen and chemicals from lignin: a critical review. Renew Sust Energy Rev 21:506–523. https://doi.org/10.1016/j.rser.2012.12.022
Azizi N, Manocheri Z (2012) Eutectic salts promote green synthesis of bis(indolyl) methanes. Res Chem Intermed 38:1495–1500. https://doi.org/10.1007/s11164-011-0479-4
Brandt A, Gräsvik J, Hallett JP, Welton T (2013) Deconstruction of lignocellulosic biomass with ionic liquids. Green Chem 15:550–583. https://doi.org/10.1039/c2gc36364j
Cao Y, Mu T (2014) Comprehensive investigation on the thermal stability of 66 ionic liquids by thermogravimetric analysis. Ind Eng Chem Res 53:8651–8664. https://doi.org/10.1021/ie5009597
Chancelier L, Diallo AO, Santini CC, Marlair G, Gutel T, Mailley S, Len C (2014) Targeting adequate thermal stability and fire safety in selecting ionic liquid-based electrolytes for energy storage. Phys Chem Chem Phys 16:1967–1976. https://doi.org/10.1039/C3CP54225D
Chen X, Yu J, Zhang Z, Lu C (2011) Study on structure and thermal stability properties of cellulose fibers from rice straw. Carbohyd Polym 85:245–250. https://doi.org/10.1016/j.carbpol.2011.02.022
Choi YH, van Spronsen J, Dai Y, Verberne M, Hollmann F, Arends IWCE, Witkamp G-J, Verpoorte R (2011) Are natural deep eutectic solvents the missing link in understanding cellular metabolism and physiology? Plant Physiol 156:1701–1705. https://doi.org/10.1104/pp.111.178426
Czitrom V (1999) One-factor-at-a-time versus designed experiments. Am Stat 53:126–131. https://doi.org/10.1080/00031305.1999.10474445
Dai Y, van Spronsen J, Witkamp G-J, Verpoorte R, Choi YH (2013) Natural deep eutectic solvents as new potential media for green technology. Anal Chim Acta 766:61–68. https://doi.org/10.1016/j.aca.2012.12.019
Ebrahimi M, Villaflores OB, Ordono EE, Caparanga AR (2017) Effects of acidified aqueous glycerol and glycerol carbonate pretreatment of rice husk on the enzymatic digestibility, structural characteristics, and bioethanol production. Bioresour Technol 228:264–271. https://doi.org/10.1016/j.biortech.2016.12.106
Fan G, Wang M, Liao C, Fang T, Li J, Zhou R (2013) Isolation of cellulose from rice straw and its conversion into cellulose acetate catalyzed by phosphotungstic acid. Carbohyd Polym 94:71–76. https://doi.org/10.1016/j.carbpol.2013.01.073
Francis RC, Shin S-J, Omori S, Amidon TE, Blain TJ (2006) Soda pulping of hardwoods catalyzed by anthraquinone and methyl substituted anthraquinones. J Wood Chem Technol 26:141–152. https://doi.org/10.1080/02773810600701737
García G, Aparicio S, Ullah R, Atilhan M (2015) Deep eutectic solvents: physicochemical properties and gas separation applications. Energy Fuel 29:2616–2644. https://doi.org/10.1021/ef5028873
García A, Gandini A, Labidi J, Belgacem N, Bras J (2016) Industrial and crop wastes: a new source for nanocellulose biorefinery. Ind Crop Prod 93:26–38. https://doi.org/10.1016/j.indcrop.2016.06.004
Gong J, Li J, Xu J, Xiang Z, Mo L (2017) Research on cellulose nanocrystals produced from cellulose sources with various polymorphs. RSC Adv 7:33486–33493. https://doi.org/10.1039/C7RA06222B
Gorke JT, Srienc F, Kazlauskas RJ (2008) Hydrolase-catalyzed biotransformations in deep eutectic solvents. Chem Commun. https://doi.org/10.1039/b716317g
Gunny AAN, Arbain D, Nashef EM, Jamal P (2015) Applicability evaluation of deep eutectic solvents–cellulase system for lignocellulose hydrolysis. Bioresour Technol 181:297–302. https://doi.org/10.1016/j.biortech.2015.01.057
He Y, Pang Y, Liu Y, Li X, Wang K (2008) Physicochemical characterization of rice straw pretreated with sodium hydroxide in the solid state for enhancing biogas production. Energy Fuel 22:2775–2781. https://doi.org/10.1021/ef8000967
Hinterstoisser B, Salmén L (1999) Two-dimensional step-scan FTIR: a tool to unravel the OH-valency-range of the spectrum of cellulose I. Cellulose 6:251–263. https://doi.org/10.1023/A:1009225815913
Ibrahim MM, El-Zawawy WK, Abdel-Fattah YR, Soliman NA, Agblevor FA (2011) Comparison of alkaline pulping with steam explosion for glucose production from rice straw. Carbohyd Polym 83:720–726. https://doi.org/10.1016/j.carbpol.2010.08.046
Ibrahim MM, El-Zawawy WK, Jüttke Y, Koschella A, Heinze T (2013) Cellulose and microcrystalline cellulose from rice straw and banana plant waste: preparation and characterization. Cellulose 20:2403–2416. https://doi.org/10.1007/s10570-013-9992-5
Isa KM, Abdullah TAT, Ali UFM (2018) Hydrogen donor solvents in liquefaction of biomass: a review. Renew Sust Energy Rev 81:1259–1268. https://doi.org/10.1016/j.rser.2017.04.006
Jiménez L, Pérez I, López F, Ariza J, Rodríguez A (2002) Ethanol-acetone pulping of wheat straw. Influence of the cooking and the beating of the pulps on the properties of the resulting paper sheets. Bioresour Technol 83:139–143. https://doi.org/10.1016/S0960-8524(01)00196-1
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 23:9265–9275. https://doi.org/10.1007/s11356-015-4780-4
Li G, Fu S, Zhou A, Zhan H (2014) Improved cellulose yield in the production of dissolving pulp from bamboo using acetic acid in prehydrolysis. BioResources 10:877–886. https://doi.org/10.15376/biores.10.1.877-886
Lin L, Yan R, Liu Y, Jiang W (2010) In-depth investigation of enzymatic hydrolysis of biomass wastes based on three major components: cellulose, hemicellulose and lignin. Bioresour Technol 101:8217–8223. https://doi.org/10.1016/j.biortech.2010.05.084
Liu Y, Zhang L, Li Y, Xu Y (2015) The influence of chloride-based 1-butyl-3-methylimidazolium ionic liquid on the pulping process of wheat straw cooking. J Mol Liq 208:196–201. https://doi.org/10.1016/j.molliq.2015.04.037
Lobo HR, Singh BS, Shankarling GS (2012) Deep eutectic solvents and glycerol: a simple, environmentally benign and efficient catalyst/reaction media for synthesis of N-aryl phthalimide derivatives. Green Chem Lett Rev 5:487–533. https://doi.org/10.1080/17518253.2012.669500
Lu P, Hsieh Y-L (2012) Preparation and characterization of cellulose nanocrystals from rice straw. Carbohyd Polym 87:564–573. https://doi.org/10.1016/j.carbpol.2011.08.022
Lynam JG, Coronella CJ (2014) Glycerol as an ionic liquid co-solvent for pretreatment of rice hulls to enhance glucose and xylose yield. Bioresour Technol 166:471–478. https://doi.org/10.1016/j.biortech.2014.05.086
Marques AP, Evtuguin DV, Magina S, Amado FML, Prates A (2009) Structure of lignosulphonates from acidic magnesium-based sulphite pulping of Eucalyptus globulus. J Wood Chem Technol 29:337–357. https://doi.org/10.1080/02773810903207762
Mjalli FS, Naser J, Jibril B, Al-Hatmi SS, Gano ZS (2014) Ionic liquids analogues based on potassium carbonate. Thermochim Acta 575:135–143. https://doi.org/10.1016/j.tca.2013.10.028
Nazir MS, Wahjoedi BA, Yussof AW, Abdullah MA (2013) Eco-friendly extraction and characterization of cellulose from oil palm empty fruit bunches. BioResources 8:2161–2172. https://doi.org/10.15376/biores.8.2.2161-2172
Oun AA, Rhim J-W (2016) Isolation of cellulose nanocrystals from grain straws and their use for the preparation of carboxymethyl cellulose-based nanocomposite films. Carbohyd Polym 150:187–200. https://doi.org/10.1016/j.carbpol.2016.05.020
Park S-B, Lee H, Lee K-H (1998) Solubilities of carbon dioxide in aqueous potassium carbonate solutions mixed with physical solvents. Int J Thermophys 19:1421–1428. https://doi.org/10.1023/A:1021935619427
Pavlostathis SG, Gossett JM (1985) Modeling alkali consumption and digestibility improvement from alkaline treatment of wheat straw. Biotechnol Bioeng 27:345–354. https://doi.org/10.1002/bit.260270320
Pilate G, Guiney E, Holt K, Petit-Conil M, Lapierre C, Leplé J-C, Pollet B, Mila I, Webster EA, Marstorp HG, Hopkins DW, Jouanin L, Boerjan W, Schuch W, Cornu D, Halpin C (2002) Field and pulping performances of transgenic trees with altered lignification. Nat Biotechnol 20:607–612. https://doi.org/10.1038/nbt0602-607
Rahnama N, Mamat S, Shah UKM, Ling FH, Rahman NAA, Arif AB (2013) Effect of alkali pretreatment of rice straw on cellulase and xylanase production by local trichoderma harzianum SNRS3 under solid state fermentation. BioResources 8:2881–2896. https://doi.org/10.15376/biores.8.2.2881-2896
Rodríguez A, Sánchez R, Requejo A, Ferrer A (2010) Feasibility of rice straw as a raw material for the production of soda cellulose pulp. J Clean Prod 18:1084–1091. https://doi.org/10.1016/j.jclepro.2010.03.011
Ruß C, König B (2012) Low melting mixtures in organic synthesis-an alternative to ionic liquids? Green Chem 14:2969–2982. https://doi.org/10.1039/c2gc36005e
Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794. https://doi.org/10.1177/004051755902901003
Škulcová A, Majová V, Šima J, Jablonsky M (2017) Mechanical properties of pulp delignified by deep eutectic solvents. BioResources 12:7479–7486
Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, Crocker D (2008) Determination of structural carbohydrates and lignin in biomass. Lab Anal Proced 1617:1–6
Song W, Deng Y, Zhu H (2016) Research on wheat straw pulping with ionic liquid 1-ethyl-3-methylimidazole bromide. Kem Ind 65:579–585. https://doi.org/10.15255/KUI.2016.032
Sun F, Chen H (2008) Organosolv pretreatment by crude glycerol from oleochemicals industry for enzymatic hydrolysis of wheat straw. Bioresour Technol 99:5474–5479. https://doi.org/10.1016/j.biortech.2007.11.001
Sun N, Rahman M, Qin Y, Maxim ML, Rodríguez H, Rogers RD (2009) Complete dissolution and partial delignification of wood in the ionic liquid 1-ethyl-3-methylimidazolium acetate. Green Chem 11:646–655. https://doi.org/10.1039/b822702k
Sun N, Rodríguez H, Rahman M, Rogers RD (2011) Where are ionic liquid strategies most suited in the pursuit of chemicals and energy from lignocellulosic biomass? Chem Commun 47:1405–1421. https://doi.org/10.1039/C0CC03990J
Swatloski RP, Spear SK, Holbrey JD, Rogers RD (2002) Dissolution of cellose with ionic liquids. J Am Chem Soc 124:4974–4975. https://doi.org/10.1021/ja025790m
Toledano A, Serrano L, Labidi J (2012) Organosolv lignin depolymerization with different base catalysts. J Chem Technol Biotechnol 87:1593–1599. https://doi.org/10.1002/jctb.3799
Updegraff DM (1969) Semimicro determination of cellulose inbiological materials. Anal Biochem 32:420–424. https://doi.org/10.1016/S0003-2697(69)80009-6
Vigier KDO, Chatel G, Jérôme F (2015) Contribution of deep eutectic solvents for biomass processing: opportunities, challenges, and limitations. ChemCatChem 7:1250–1260. https://doi.org/10.1002/cctc.201500134
Wolfson A, Dlugy C, Shotland Y, Tavor D (2009) Glycerol as solvent and hydrogen donor in transfer hydrogenation-dehydrogenation reactions. Tetrahedron Lett 50:5951–5953. https://doi.org/10.1016/j.tetlet.2009.08.035
Xie H, King A, Kilpelainen I, Granstrom M, Argyropoulos DS (2007) Thorough chemical modification of wood-based lignocellulosic materials in ionic liquids. Biomacromolecules 8:3740–3748. https://doi.org/10.1021/bm700679s
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 203:364–369. https://doi.org/10.1016/j.biortech.2015.11.002
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The authors would like to thank the School of Bioprocess Engineering, Universiti Malaysia Perlis (UniMAP) for their support in this research.
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Lim, WL., Gunny, A.A.N., Kasim, F.H. et al. Alkaline deep eutectic solvent: a novel green solvent for lignocellulose pulping. Cellulose 26, 4085–4098 (2019). https://doi.org/10.1007/s10570-019-02346-8
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DOI: https://doi.org/10.1007/s10570-019-02346-8