WU Qinglin,MEI Changtong,HAN Jingquan,et al.Preparation technology and industrialization status of nanocellulose[J].Journal of Forestry Engineering,2018,3(01):1-9.





Preparation technology and industrialization status of nanocellulose
1.美国路易斯安那州立大学可再生自然资源学院,巴吞鲁日 70803;
2.南京林业大学材料科学与工程学院,南京 210037;
3.南京林业大学生物与环境学院,南京 210037
WU Qinglin12 MEI Changtong2 HAN Jingquan2 YUE Yiying3 XU Xinwu2
1.School of Renewable Natural Resources, Louisiana State University, Baton Rouge 70803, USA;
2.College of Material Science and Engineering, Nanjing Forestry University, Nanjing 210037, China;
3.College of Biology and Environment, Nanjing Forestry University, Nanjing 210037, China
纤维素 纳米晶体 纳米纤维 制备技术 产业化
cellulose nanocrystals nanofibers preparation technology industrialization
During the past decade, nanocellulose has attracted a considerable attention because of its unique properties and growing interests in the bioconversion of renewable lignocellulosic biomass. Substantial academic and industrial interests have been directed toward potential applications of nanocellulose for various fields including high performance composites, electronics, catalysis, biomedical materials and energy. Nanocellulose will have to compete with petrochemical products from the industry with nearly a century of development experience. Partnerships among forest products, construction, petrochemical and manufacturing industries are the key to introduce green nanocellulose to a large consumer market with competitive cost and performance for its two main product lines: cellulose nanofiber(CNF)and cellulose nanocrystal(CNC). Currently, the CNF extraction is mainly completed by mechanical fibrillation to separate and reduce the size of the CNFs after pretreating cellulose fibers by using chemicals and enzyme. The CNC extraction is carried out by using mineral acids, organic acids, oxidation, enzyme, ionic liquids, deep eutectic solvents(DES), and supercritical water with purified cellulose. Future market expansion for both CNFs and CNCs will hinge on the development of new solvent systems for pretreating lignocellulosic fibers for more efficient nanocellulose production(e.g., DES and solid organic acids); large volume applications for the related products to help lower overall product costs(e.g., drilling fluids, cement composites and modified plastics), international standards for cellulose nanomaterials to help multiple industrial sectors for developing and using the materials, and more eco-toxicological understanding and regulations for using the nanomaterial in various applications.


[1] HABIBI Y, LUCIA L A, ROJAS O J. Cellulose nanocrystals: chemistry, self-assembly, and applications[J]. Chemical Reviews, 2010, 110(6): 3479-3500.
[2] MOON R J, MARTINI A, NAIRN J, et al. Cellulose nanomaterials review: structure, properties and nanocomposites[J]. Chemical Society Reviews, 2011, 40: 3941-3994.
[3] ZHU H L, LUO W, CIESIELSKI P N, et al. Wood-derived materials for green electronics, biological devices, and energy applications[J]. Chemical Reviews, 2016, 116(16): 9305-9374.
[4] SIQUEIRA G, BRAS J, DUFRESNE A. Cellulose whiskers versus microfibrils: influence of the nature of the nanoparticle and its surface functionalization on the thermal and mechanical properties of nanocomposites[J]. Biomacromolecules, 2009, 10(2): 425-432.
[5] GRISHKEWICH N, MOHAMMED N, TANG J T, et al. Recent advances in the application of cellulose nanocrystals[J]. Current Opinion in Colloid & Interface Science, 2017, 29: 32-45.
[6] ZHOU C J, SHI Q F, GUO W H, et al. Electrospun bio-nanocomposite scaffolds for bone tissue engineering by cellulose nanocrystals reinforcing maleic anhydride grafted PLA[J]. ACS Applied Materials & Interfaces, 2013, 5(9): 3847-3854.
[7] LI M C, WU Q L, SONG K L, et al. Cellulose nanoparticles as modifiers for rheology and fluid loss in bentonite water-based fluids[J]. ACS Applied Materials & Interfaces, 2015, 7(8): 5006-5016.
[8] CHOI K H, CHO S J, CHUN S J, et al. Heterolayered, one-dimensional nanobuilding block mat batteries[J]. Nano Letters, 2014, 14(10): 5677-5686.
[9] CHO S J, CHOI K H, YOO J T, et al. Hetero-nanonet rechargeable paper batteries: toward ultrahigh energy density and origami foldability[J]. Advanced Functional Materials, 2015, 25(38): 6029-6040.
[10] HABIBI Y. Key advances in the chemical modification of nanocelluloses[J]. Chemical Society Reviews, 2014, 43(5): 1519-1542.
[11] TRACHE D, HUSSIN M H, HAAFIZ M K, et al. Recent progress in cellulose nanocrystals: sources and production[J]. Nanoscale, 2017, 9(5): 1763-1786.
[12] MOON R J, SCHUENEMAN G T, SIMONSEN J. Overview of cellulose nanomaterials, their capabilities and applications[J]. JOM, 2016, 68(9): 2383-2394.
[13] GAO X Y, CHEN X, ZHANG J G, et al. Transformation of chitin and waste shrimp shells into acetic acid and pyrrole[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(7): 3912-3920.
[14] NO H K, MEYERS S P, LEE K S. Isolation and characterization of chitin from crawfish shell waste[J]. Journal of Agricultural and Food Chemistry, 1989, 37(3): 575-579.
[15] IFUKU S, MOROOKA S, NAKAGAITO A N, et al. Preparation and characterization of optically transparent chitin nanofiber/(meth)acrylic resin composites[J]. Green Chemistry, 2011, 13(7): 1708-1711.
[16] GOODRICH J D, WINTER W T. Alpha-chitin nanocrystals prepared from shrimp shells and their specific surface area measurement[J]. Biomacromolecules, 2007, 8(1): 252-257.
[17] LI M C, WU Q L, SONG K L, et al. Chitin nanofibers as reinforcing and antimicrobial agents in carboxymethyl cellulose films: influence of partial deacetylation[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(8): 4385-4395.
[18] KROON-BATENBURG L M, KROON J. The crystal and molecular structures of cellulose I and II[J]. Glycoconjugate Journal, 1997, 14(5): 677-690.
[19] CIACCO G T, MORGADO D L, FROLLINI E, et al. Some aspects of acetylation of untreated and mercerized sisal cellulose[J]. Journal of The Brazilian Chemical Society, 2010, 21(1): 71-77.
[20] DINAND E, VIGNON M, CHANZY H, et al. Mercerization of primary wall cellulose and its implication for the conversion of cellulose I→cellulose II[J]. Cellulose, 2002, 9(1): 7-18.
[21] EL-WAKIL N A, HASSAN M L. Structural changes of regenerated cellulose dissolved in FeTNa, NaOH/thiourea, and NMMO systems[J]. Journal of Applied Polymer Science, 2008, 109(5): 2862-2871.
[22] YUE Y Y, ZHOU C J, FRENCH A D, et al. Comparative properties of cellulose nano-crystals from native and mercerized cotton fibers[J]. Cellulose, 2012, 19(4): 1173-1187.
[23] JOHAR N, AHMAD I, DUFRESNE A. Extraction, preparation and characterization of cellulose fibres and nanocrystals from rice husk[J]. Industrial Crops and Products, 2012, 37(1): 93-99.
[24] SUN X F, SUN R C, FOWLER P, et al. Isolation and characterisation of cellulose obtained by a two-stage treatment with organosolv and cyanamide activated hydrogen peroxide from wheat straw[J]. Carbohydrate Polymers, 2004, 55(4): 379-391.
[25] SIDDIQUI N, MILLS R H, GARDNER D J, et al. Production and characterization of cellulose nanofibers from wood pulp[J]. Journal of Adhesion Science and Technology, 2011, 25(6/7): 709-721.
[26] SAITO T, KIMURA S, NISHIYAMA Y, et al. Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose[J]. Biomacromolecules, 2007, 8(8): 2485-2491.
[27] LIIMATAINEN H, VISANKO M, SIRVIÖ J A, et al. Enhancement of the nanofibrillation of wood cellulose through sequential periodate-chlorite oxidation[J]. Biomacromolecules, 2012,13(5): 1592-1597.
[28] YANG H, CHEN D Z, VAN DE VEN T G M. Preparation and characterization of sterically stabilized nanocrystalline cellulose obtained by periodate oxidation of cellulose fibers[J]. Cellulose, 2015, 22(3): 1743-1752.
[29] KOS T, ANLOVAR A, KUNAVER M, et al. Fast preparation of nanocrystalline cellulose by microwave-assisted hydrolysis[J]. Cellulose, 2014, 21(4): 2579-2585.
[30] KHALIL H P S A, DAVOUDPOUR Y, ISLAM M N, et al. Production and modification of nanofibrillated cellulose using various mechanical processes: a review[J]. Carbohydrate Polymers, 2014, 99: 649-665.
[31] DEEPA B, ABRAHAM E, CHERIAN B M, et al. Structure, morphology and thermal characteristics of banana nano fibers obtained by steam explosion[J]. Bioresource Technology, 2011,102(2): 1988-1997.
[32] DONALDSON L A, WONG K K Y, MACKIE K L. Ultrastructure of steam-exploded wood[J]. Wood Science and Technology 1988, 22(2): 103-114.
[33] SILVA G G D, COUTURIER M, BERRIN J G, et al. Effects of grinding processes on enzymatic degradation of wheat straw[J]. Bioresource Technology, 2012, 103(1): 192-200.
[34] PÖHLER T, LAPPALAINEN T, TAMMELIN T, et al. Influence of fibrillation method on the character of nanofibrillated cellulose(NFC)[C]∥TAPPI International Conference on Nanotechnology for Renewable Materials, June 5-7, 2012, Montreal, Canada.
[35] LINDSTRÖM T. Production methods of nanocellulose(CNF)-principles[C]∥COST FP1205 4th Training School on Innovative Application of Regenerated Wood Cellulose Fibers, April 25-27, 2016. Stockholm, Sweden.
[36] WÅGBERG L, WINTER L, ÖDBERG L, et al. On the charge stoichiometry upon adsorption of a cationic polyelectrolyte on cellulosic materials[J]. Colloids and Surfaces, 1987, 27(4): 163-173.
[37] NADERI A, LINDSTRÖM T, SUNDSTRÖM J. Repeated homogenization, a route for decreasing the energy consumption in the manufacturing process of carboxymethylated nanofibrillated cellulose?[J]. Cellulose, 2015, 22(2): 1147-1157.
[38] NADERI A, LINDSTRÖM T, SUNDSTRÖM J, et al. Microfluidized carboxymethyl cellulose modified pulp: a nanofibrillated cellulose system with some attractive properties[J]. Cellulose, 2015, 22(2): 1159-1173.
[39] MILLER J. Nanocellulose state of industry December 2015[Z]. http:∥www.tappinano.org/media/1114/cellulose-nanomaterials-production-state-of-the-industry-dec-2015.pdf.
[40] PENG Y C, GARDNER D J, HAN Y S. Drying cellulose nanofibrils: in search of a suitable method[J]. Cellulose, 2012, 19(1): 91-102.
[41] VORONOVA M I, ZAKHAROV A G, KUZNETSOV O Y, et al. The effect of drying technique of nanocellulose dispersions on properties of dried materials[J]. Materials Letters, 2012, 68: 164-167.
[42] BECK S, BOUCHARD J, BERRY R. Dispersibility in water of dried nanocrystalline cellulose[J]. Biomacromolecules, 2012, 13(5): 1486-1494.
[43] HAN J Q, ZHOU C J, WU Y Q, et al. Self-assembling behavior of cellulose nanoparticles during freeze-drying: effect of suspension concentration, particle size, crystal structure, and surface charge[J]. Biomacromolecules, 2013, 14(5): 1529-1540.
[44] QUIÉVY N, JACQUET N, SCLAVONS M, et al. Influence of homogenization and drying on the thermal stability of microfibrillated cellulose[J]. Polymer Degradation and Stability, 2010, 95(3): 306-314.
[45] METI. Survey on the actual status of manufacturing infrastructure technology 2013, future prospects and issues of the paper industry[R]. Japan: METI(Minister of Economy, Trade and Industry), 2014.
[46] NAIR S S, YAN N. Effect of high residual lignin on the thermal stability of nanofibrils and its enhanced mechanical performance in aqueous environments[J]. Cellulose, 2015, 22(5): 3137-3150.
[47] YANAMALA N, KISIN E R, MENAS A L, et al. In vitro toxicity evaluation of lignin-(Un)coated cellulose based nanomaterials on human A549 and THP-1 cells[J]. Biomacromolecules, 2016, 17(11): 3464-3473.
[48] YU H Y, QIN Z Y, LIANG B L, et al. Facile extraction of thermally stable cellulose nanocrystals with a high yield of 93% through hydrochloric acid hydrolysis under hydrothermal conditions[J]. Journal of Materials Chemistry A, 2013, 1(12): 3938-3944.
[49] KONTTURI E, MERILUOTO A, PENTTILÄ P A, et al. Degradation and crystallization of cellulose in hydrogen chloride vapor for high-yield isolation of cellulose nanocrystals[J]. Angewandte Chemie, 2016, 55(46): 14455-14458.
[50] ANDERSON S R, ESPOSITO D, GILLETTE W, et al. Enzymatic preparation of nanocrystalline and microcrystalline cellulose[J]. TAPPI Journal, 2014, 13(5): 35-42.
[51] CHEN L H, ZHU J Y, BAEZ C, et al. Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids[J]. Green Chemistry, 2016, 18(13): 3835-3843.
[52] BONDESON D, MATHEW A, OKSMAN K. Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis[J]. Cellulose, 2006, 13(2): 171-180.
[53] ESPINOSA S C, KUHNT T, FOSTER E J, et al. Isolation of thermally stable cellulose nanocrystals by phosphoric acid hydrolysis[J]. Biomacromolecules, 2013, 14(4): 1223-1230.
[54] ROMAN M, WINTER W T. Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose[J]. Biomacromolecules, 2004, 5(5): 1671-1677.
[55] HUANG Y B, FU Y. Hydrolysis of cellulose to glucose by solid acid catalysts[J]. Green Chemistry, 2013, 15(5): 1095-1111.
[56] SHIMIZU K I, SATSUMA A. Toward a rational control of solid acid catalysis for green synthesis and biomass conversion[J]. Energy and Environmental Science, 2011, 4(9): 3140-3153.
[57] GUO F, FANG Z, XU C C, et al. Solid acid mediated hydrolysis of biomass for producing biofuels[J]. Progress in Energy and Combustion Science, 2012, 38(5): 672-690.
[58] WANG Q Q, ZHU J Y, REINER R S, et al. Approaching zero cellulose loss in cellulose nanocrystal(CNC)production: recovery and characterization of cellulosic solid residues(CSR)and CNC[J]. Cellulose, 2012, 19(6): 2033-2047.
[59] LEUNG A C W, HRAPOVIC S, LAM E, et al. Characteristics and properties of carboxylated cellulose nanocrystals prepared from a novel one-step procedure[J]. Small, 2010, 7(3): 302-305.
[60] MONTANARI S, ROUMANI M, HEUX L, et al. Topochemistry of carboxylated cellulose nanocrystals resulting from TEMPO-mediated oxidation[J]. Macromolecules, 2005, 38(5): 1665-1671.
[61] FUKUZUMI H, SAITO T, OKITA Y, et al. Thermal stabilization of TEMPO-oxidized cellulose[J]. Polymer Degradation and Stability, 2010, 95(9): 1502-1508.
[62] BONDESON D, MATHEW A, OKSMAN K. Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis[J]. Cellulose, 2006, 13(2): 171.
[63] DONG X M, KIMURA T, REVOL J F, et al. Effects of ionic strength on the isotropic-chiral nematic phase transition of suspensions of cellulose crystallites[J]. Langmuir, 1996, 12(8): 2076-2082.
[64] SADEGHIFAR H, FILPPONEN I, CLARKE S P, et al. Production of cellulose nanocrystals using hydrobromic acid and click reactions on their surface[J]. Journal of Materials Science, 2011, 46(22): 7344-7355.
[65] TANG L R, HUANG B, LU Q L, et al. Ultrasonication-assisted manufacture of cellulose nanocrystals esterified with acetic acid[J]. Bioresource Technology, 2013, 127: 100-105.
[66] LIU Y F, WANG H S, YU G, et al. A novel approach for the preparation of nanocrystalline cellulose by using phosphotungstic acid[J]. Carbohydrate Polymers, 2014, 110: 415-422.
[67] HABIBI Y, CHANZY H, VIGNON M R. TEMPO-mediated surface oxidation of cellulose whiskers[J]. Cellulose, 2006, 13(6): 679-687.
[68] AZZAM F, GALLIOT M, PUTAUX J L, et al. Surface peeling of cellulose nanocrystals resulting from periodate oxidation and reductive amination with water-soluble polymers[J]. Cellulose, 2015, 22(6): 3701-3714.
[69] MAO J, OSORIO-MADRAZO A, LABORIE M P. Preparation of cellulose I nanowhiskers with a mildly acidic aqueous ionic liquid: reaction efficiency and whiskers attributes[J]. Cellulose, 2013, 20(4): 1829-1840.
[70] TAN X Y, ABD HAMID S B, LAI C W. Preparation of high crystallinity cellulose nanocrystals(CNCs)by ionic liquid solvolysis[J]. Biomass and Bioenergy, 2015, 81: 584-591.
[71] SIRVIÖ J A, VISANKO M, LIIMATAINEN H. Acidic deep eutectic solvents as hydrolytic media for cellulose nanocrystal production[J]. Biomacromolecules, 2016, 17(9): 3025-3032.
[72] LAITINEN O, OJALA J, SIRVIÖ J A, et al. Sustainable stabilization of oil in water emulsions by cellulose nanocrystals synthesized from deep eutectic solvents[J]. Cellulose, 2017, 24(4): 1679-1689.
[73] SIRVIÖ J A, VISANKO M, LIIMATAINEN H. Deep eutectic solvent system based on choline chloride-urea as a pre-treatment for nanofibrillation of wood cellulose[J]. Green Chemistry, 2015, 17(6): 3401-3406.
[74] NOVO L P, BRAS J, GARCÍA A, et al. A study of the production of cellulose nanocrystals through subcritical water hydrolysis[J]. Industrial Crops and Products, 2016, 93: 88-95.
[75] NOVO L P, BRAS J, GARCÍA A, et al. Subcritical water: a method for green production of cellulose nanocrystals[J]. ACS Sustainable Chemistry & Engineering, 2015, 3(11): 2839-2846.


 WU Yan.Research on melamine formaldehyde resin modified by cellulose micro/nano fibrils[J].Journal of Forestry Engineering,2013,27(01):71.
[4]忻萍萍,史浩婷,牛逊,等.纤维素在四己基醋酸铵/ 助溶剂 混合体系中的溶解及再生[J].林业工程学报,2016,1(05):58.
 XIN Pingping,SHI Haoting,NIU Xun,et al.Dissolution and regeneration of cellulose in tetrahexylammonium acetate/co-solvent system[J].Journal of Forestry Engineering,2016,1(01):58.
 MA Mingguo,FU Lianhua,LI Yayu,et al.Research progress of cellulose-based biomedical functional composites[J].Journal of Forestry Engineering,2017,2(01):1.


收稿日期:2017-10-15 修回日期:2017-11-06
更新日期/Last Update: 2018-01-10