Abstract
In this paper, a cellulase pretreatment was studied prior to the acid hydrolysis to decrease the total acid usage during the cellulose nano-crystals (CNC) preparation from a bleached softwood kraft pulp. Cellulase pretreatment facilitates the subsequent acid hydrolysis to produce CNC with similar quality to that of the control, but at a lower sulfuric acid concentration. The underline mechanism is that cellulase pretreatment led to the formation of more carbonyl groups which can be oxidized into carboxyl groups in the subsequent acid hydrolysis, furthermore, more hydroxyl groups are exposed, thus esterification into sulfonic groups can be enhanced. The results showed that with a cellulase dosage of 4.8 u/g (based on dry pulp) in the pretreatment stage, the sulfuric acid concentration can be decreased from 64 to 40 wt% without compromising the quality of resulting CNC particles. Other results from charge properties, Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) analyses also supported the conclusions.
Similar content being viewed by others
References
Abitbol T, Kloser E, Gray DG (2013) Estimation of the surface sulfur content of cellulose nanocrystals prepared by sulfuric acid hydrolysis. Cellulose 20(2):785–794
Antczak T (2012) Nanotechnology-methods of manufacturing cellulose nanofibres. Fibres Text East Eur 20(2):91
Araki J, Wada M, Kuga S, Okano T (1998) Flow properties of microcrystalline cellulose suspension prepared by acid treatment of native cellulose. Colloids Surf, A 142(1):75–82
Bansal P, Hall M, Realff MJ, Lee JH, Bommarius AS (2009) Modeling cellulase kinetics on lignocellulosic substrates. Biotechnol Adv 27(6):833–848
Barichievich EM, Calza RE (1990) Supernatant protein and cellulase activities of the anaerobic ruminal fungus Neocallimastix frontalis EB188. Appl Environ Microbiol 56(1):43–48
Battista OA (1950) Hydrolysis and crystallization of cellulose. Ind Eng Chem 42(3):502–507
Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromolecules 6(2):1048–1054
Beltramino F, Roncero MB, Vidal T, Torres AL, Valls C (2015) Increasing yield of nanocrystalline cellulose preparation process by a cellulase pretreatment. Bioresour Technol 192:574–581
Chen Q, Marshall MN, Geib SM, Tien M, Richard TL (2012) Effects of laccase on lignin depolymerization and enzymatic hydrolysis of ensiled corn stover. Bioresour Technol 117:186–192
Chen L, Wang Q, Hirth K, Baez C, Agarwal UP, Zhu JY (2015) Tailoring the yield and characteristics of wood cellulose nanocrystals (CNC) using concentrated acid hydrolysis. Cellulose 22(3):1753–1762
de Campos A, Correa AC, Cannella D, de M Teixeira E, Marconcini JM, Dufresne A, Sanadi AR (2013) Obtaining nanofibers from curauá and sugarcane bagasse fibers using enzymatic hydrolysis followed by sonication. Cellulose 20(3):1491–1500
Dong XM, Gray DG (1997) Effect of counterions on ordered phase formation in suspensions of charged rodlike cellulose crystallites. Langmuir 13(8):2404–2409
Dong XM, Kimura T, Revol JF, Gray DG (1996) Effects of ionic strength on the isotropic-chiral nematic phase transition of suspensions of cellulose crystallites. Langmuir 12(8):2076–2082
Dong H, Strawhecker KE, Snyder JF, Orlicki JA, Reiner RS, Rudie AW (2012) Cellulose nanocrystals as a reinforcing material for electrospun poly (methyl methacrylate) fibers: formation, properties and nanomechanical characterization. Carbohydr Polym 87(4):2488–2495
Elazzouzi-Hafraoui S, Nishiyama Y, Putaux JL et al (2008) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9(1):57–65
Filson PB, Dawson-Andoh BE, Schwegler-Berry D (2009) Enzymatic-mediated production of cellulose nanocrystals from recycled pulp. Green Chem 11(11):1808–1814
Gutiérrez A, Rencoret J, Cadena EM, Rico A, Barth D, José C, Martínez ÁT (2012) Demonstration of laccase-based removal of lignin from wood and non-wood plant feedstocks. Bioresour Technol 119:114–122
Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110(6):3479–3500
Hamad WY, Hu TQ (2010) Structure–process–yield interrelations in nanocrystalline cellulose extraction. Can J Chem Eng 88(3):392–402
Hayashi N, Kondo T, Ishihara M (2005) Enzymatically produced nano-ordered short elements containing cellulose I β crystalline domains. Carbohydr Polym 61(2):191–197
Henriksson M, Henriksson G, Berglund LA, Lindström T (2007) An environmentally friendly method for enzyme-assisted preparation of microfibrillated cellulose (MFC) nanofibers. Eur Polym J 43(8):3434–3441
Hubbe MA, Rojas OJ, Lucia LA, Sain M (2008) Cellulosic nanocomposites: a review. BioResources 3(3):929–980
Jiang Z, Liu Y, Sun X, Tian F, Sun F, Liang C, Li C (2003) Activated carbons chemically modified by concentrated H2SO4 for the adsorption of the pollutants from wastewater and the dibenzothiophene from fuel oils. Langmuir 19(3):731–736
Kurašin M, Väljamäe P (2011) Processivity of cellobiohydrolases is limited by the substrate. J Biol Chem 286(1):169–177
Lavoine N, Desloges I, Dufresne A, Bras J (2012) Microfibrillated cellulose–Its barrier properties and applications in cellulosic materials: a review. Carbohydr Polym 90(2):735–764
Liu X, Fatehi P, Ni Y (2011) Adsorption of lignocelluloses dissolved in prehydrolysis liquor of kraft-based dissolving pulp process on oxidized activated carbons. Ind Eng Chem Res 50(20):11706–11711
Lloyd JA, Horne CW (1993) The determination of fibre charge and acidic groups of radiata pine pulps. Nordic Pulp Pap Res J (Sweden)
Lu P, Hsieh YL (2012) Preparation and characterization of cellulose nanocrystals from rice straw. Carbohydr Polym 87(1):564–573
Menon V, Prakash G, Prabhune A, Rao M (2010) Biocatalytic approach for the utilization of hemicellulose for ethanol production from agricultural residue using thermostable xylanase and thermotolerant yeast. Bioresour Technol 101(14):5366–5373
Miao Q, Chen L, Huang L, Tian C, Zheng L, Ni Y (2014) A process for enhancing the accessibility and reactivity of hardwood kraft-based dissolving pulp for viscose rayon production by cellulase treatment. Bioresour Technol 154:109–113
Mukherjee SM, Woods HJ (1953) X-ray and electron microscope studies of the degradation of cellulose by sulphuric acid. Biochim Biophys Acta 10:499–511
Nickerson RF, Habrle JA (1947) Cellulose intercrystalline structure. Ind Eng Chem 39:1507–1512
Qiu W, Chen H (2012) Enhanced the enzymatic hydrolysis efficiency of wheat straw after combined steam explosion and laccase pretreatment. Bioresour Technol 118:8–12
Rahkamo L, Vehviläinen L, Viikari L, Nousiainen P, Buchert J (1997) In: Eriksson K-EL, Cavaco-Paulo A (ed) Enzyme applications in fiber processing. American Chemical Society, Washington, pp 318–326
Rånby BG (1951) The colloidal properties of cellulose micelles. Discuss Faraday Soc 11:158–164
Revol JF, Bradford H, Giasson J, Marchessault RH, Gray DG (1992) Helicoidal self-ordering of cellulose microfibrils in aqueous suspension. Int J Biol Macromol 14(3):170–172
Röhrling J, Potthast A, Rosenau T, Lange T, Borgards A, Sixta H, Kosma P (2002) A novel method for the determination of carbonyl groups in cellulosics by fluorescence labeling. 2. Validation and applications. Biomacromolecules 3(5):969–975
Shen F, Kumar L, Hu J, Saddler JN (2011) Evaluation of hemicellulose removal by xylanase and delignification on SHF and SSF for bioethanol production with steam-pretreated substrates. Bioresour Technol 102(19):8945–8951
Shimizu M, Fukuzumi H, Saito T, Isogai A (2013) Preparation and characterization of TEMPO-oxidized cellulose nanofibrils with ammonium carboxylate groups. Int J Biol Macromol 59:99–104
Siqueira G, Bras J, Dufresne A (2010a) Cellulosic bionanocomposites: a review of preparation, properties and applications. Polymers 2(4):728–765
Siqueira G, Tapin-Lingua S, Bras J, da Silva Perez D, Dufresne A (2010b) Morphological investigation of nanoparticles obtained from combined mechanical shearing, and enzymatic and acid hydrolysis of sisal fibers. Cellulose 17(6):1147–1158
Ståhlberg J, Johansson G, Pettersson G (1993) Trichoderma reesei has no true exo-cellulase all intact and truncated cellulases produce new reducing end groups on cellulose. Biochim Biophys Acta (BBA)-Gen Subj 1157(1):107-113
Sun B, Hou Q, Liu Z, He Z, Ni Y (2014) Stability and efficiency improvement of ASA in internal sizing of cellulosic paper by using cationically modified cellulose nanocrystals. Cellulose 21(4):2879–2887
Sun X, Wu Q, Ren S, Lei T (2015) Comparison of highly transparent all-cellulose nanopaper prepared using sulfuric acid and TEMPO-mediated oxidation methods. Cellulose 22(2):1123–1133
Virtanen T, Penttilä PA, Maloney TC, Grönqvist S, Kamppuri T, Vehviläinen M, Maunu SL (2015) Impact of mechanical and enzymatic pretreatments on softwood pulp fiber wall structure studied with NMR spectroscopy and X-ray scattering. Cellulose 22(3):1565–1576
Vlasenko EY, Ryan AI, Shoemaker CF, Shoemaker SP (1998) The use of capillary viscometry, reducing end-group analysis, and size exclusion chromatography combined with multi-angle laser light scattering to characterize endo-1,4-β-d-glucanases on carboxymethylcellulose: a comparative evaluation of the three methods. Enzyme Microb Technol 23(6):350–359
Vršanská M, Biely P (1992) The cellobiohydrolase I from Trichoderma reesei QM 9414: action on cello-oligosaccharides. Carbohydr Res 227:19–27
Wang QQ, Zhu JY, Reiner RS, Verrill SP, Baxa U, McNeil SE (2012) Approaching zero cellulose loss in cellulose nanocrystal (CNC) production: recovery and characterization of cellulosic solid residues (CSR) and CNC. Cellulose 19(6):2033–2047
Wang Q, Jahan MS, Liu S, Miao Q, Ni Y (2014a) Lignin removal enhancement from prehydrolysis liquor of kraft-based dissolving pulp production by laccase-induced polymerization. Bioresour Technol 164:380–385
Wang Q, Zhao X, Zhu J (2014b) Kinetics of strong acid hydrolysis of a bleached kraft pulp for producing cellulose nanocrystals (CNCs). Ind Eng Chem Res 53(27):11007–11014
Wang Q, Liu S, Yang G, Chen J (2015) Modeling laccase-induced lignin removal in prehydrolysis liquor from kraft-based dissolving pulp production. Bioresour Technol 175:638–641
Zaman M, Xiao H, Chibante F, Ni Y (2012) Synthesis and characterization of cationically modified nanocrystalline cellulose. Carbohydr Polym 89(1):163–170
Zhang Y, Lu XB, Gao C, Lv WJ, Yao JM (2012) Preparation and characterization of nano crystalline cellulose from bamboo fibers by controlled cellulase hydrolysis. J Fiber Bioeng Inform 5(3):263–271
Acknowledgments
The authors wish to acknowledge the financial support from the Tianjin Municipal Science and Technology Commission (Grant No. 12ZCZDGX01100).
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
An, X., Wen, Y., Cheng, D. et al. Preparation of cellulose nano-crystals through a sequential process of cellulase pretreatment and acid hydrolysis. Cellulose 23, 2409–2420 (2016). https://doi.org/10.1007/s10570-016-0964-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-016-0964-4