纳米纤维素因其独特的结构及优越的性能引起了学术和企业界的广泛关注与重视，日渐成为新材料和纤维素科学领域的研究热点。以木质纤维资源为原料，可分离出两种主要类型的纳米纤维素：纤维素纳米晶体（CNC）和纤维素纳米纤丝（CNF）。本文详细综述了CNC和CNF的制备方法，着重介绍了近几年新兴的制备方法，包括可回收的有机酸水解法综合制备CNC和CNF，美国高附加值制浆（AVAP）法制备木质素包覆的CNC和CNF，低共熔溶剂预处理结合机械剪切高效制备CNC和CNF，以及微极性环境下可调控机械剥离制备亲疏水性CNF等。同时，讨论了各种制备方法的优缺点，并介绍了国内外纳米纤维素的产业化研究进展。最后，我们提出纳米纤维素的制备方法未来将朝着绿色、高效和可持续的方向发展。
Nanocellulose is drawing extensive concern and attention from the academic and industrial circles due to its unique structure and exceptional properties, and it is the research hotspot in the field of new material and cellulose science. Nanocellulose isolated from lignocellulosic biomass can be divided into two main categories: cellulose nanocrystal (CNC) and cellulose nanofibril (CNF). The preparation methods of CNC and CNF are detailedly summarized in this review, with the focus on some new methods developed in recent years, such as the integrated preparation of CNC and CNF via recoverable organic acid hydrolysis, tuneable preparation of lignin-coated CNC and CNF via AVAP method, high efficiency preparation of CNC and CNF via deep eutectic solvents pretreatment combined with mechanical shearing, as well as the controllable isolation of hydrophilic or hydrophobic CNF by mechanical disintegration in polar microenvironment. Meanwhile, the advantages and shortcomings of the preparation methods are discussed, and the industrialization status of nanocellulose production is introduced as well. Finally, it’s believed that the development of green, effective and sustainable preparation methods will be the main trend for manufacturing nanocellulose.
Contents
1 Introduction
2 Preparation of CNC
2.1 Oxidative degradation
2.2 Ionic liquid treatment
2.3 Solid acid hydrolysis
2.4 Organic acid hydrolysis
2.5 Subcritical water hydrolysis
2.6 AVAP method
3 Preparation of CNF
3.1 Mechanical methods
3.2 Pretreatment methods
4 Industrialization status of nanocellulose
5 Conclusion
[1] Sticklen M B. Nat. Rev. Genet., 2008, 9(6):433.
[2] Klemm D, Heublein B, Fink H P, Bohn A. Angew. Chem. Int. Ed., 2005, 44(22):3358.
[3] 张金明(Zhang J J), 张军(Zhang J). 高分子学报(Acta Polymerica Sinica), 2012, (12):1376.
[4] Seppala J V. Express Polym. Lett., 2012, 6(4):257.
[5] Song J K, Tang A M, Liu T T, Wang J F. Nanoscale, 2013, 5(6):2482.
[6] Lavoine N, Bergstrom L. J. Mater. Chem., 2017, 5(31):16105.
[7] Laitinen O, Suopajarvi T, Osterberg M, Liimatainen H. ACS Appl. Mater. Interfaces, 2017, 9(29):25029.
[8] Ye C H, Malak S T, Hu K S, Wu W B, Tsukruk V V. ACS Nano, 2015, 9(11):10887.
[9] Mertaniemi H, Escobedo-Lucea C, Sanz-Garcia A, Gandia C, Makitie A, Partanen J, Ikkala O, Yliperttula M. Biomaterials, 2016, 82:208.
[10] Herrera M A, Mathew A P, Oksman K. Cellulose, 2017, 24(9):3969.
[11] Azeredo H M C, Rosa M F, Mattoso L H C. Ind. Crops Prod., 2017, 97:664.
[12] Moreau C, Villares A, Capron I, Cathala B. Ind. Crops Prod., 2016, 93:96.
[13] Oksman K, Aitomäki Y, Mathew A P, Siqueira G, Zhou Q, Butylina S, Tanpichai S, Zhou X J, Hooshmand S. Compos. Part A:Appl. S., 2016, 83:18.
[14] Klemm D, Kramer F, Moritz S, Lindstrom T, Ankerfors M, Gray D, Dorris A. Angew. Chem. Int. Ed., 2011, 50(24):5438.
[15] Hoeng F, Denneulin A, Bras J. Nanoscale, 2016, 27(8):13131.
[16] Zhu H L, Luo W, Ciesielski P N, Fang Z Q, Zhu J Y, Henriksson G, Himmel M E, Hu L B. Chem. Rev., 2016, 116(16):9305.
[17] Brinchi L, Cotana F, Fortunati E, Kenny J M. Carbohydr. Polym., 2013, 94(1):154.
[18] Nechyporchuk O, Belgacem M N, Bras J. Ind. Crops Prod., 2016, 93:2.
[19] 汪丽粉(Wang L F), 李政(Li Z), 贾士儒(Jia S R), 张健飞(Zhang J F). 微生物学通报(Microbiology China), 2014, 41(8):1675.
[20] 叶代勇(Ye D Y). 化学进展(Progress in Chemistry), 2007, 19(10):1568.
[21] 郭娟丽(Guo J L), 周玉生(Zhou Y S), 刘珊(Liu S), 刘建辉(Liu J H), 周明吉(Zhou M J). 科技导报(Science & Technology Review), 2014, 28:26.
[22] Trache D, Hussin M H, Haafiz M K, Thakur V K. Nanoscale, 2017, 9(5):1763.
[23] Siqueira G, Bras J, Dufresne A. Polymers, 2010, 2(4):728.
[24] Nickerson R, Habrle J. Ind. Eng. Chem., 1947, 39:1507.
[25] Yu H Y, Qin Z Y, Liang B L, Liu N, Zhou Z, Chen L. J. Mater. Chem., 2013, 1(12):3938.
[26] Kontturi E, Meriluoto A, Penttila P A, Baccile N, Malho J M, Potthast A, Rosenau T, Ruokolainen J, Serimaa R, Laine J, Sixta H. Angew. Chem. Int. Ed., 2016, 55(46):14455.
[27] Camarero Espinosa S, Kuhnt T, Foster E J, Weder C. Biomacromolecules, 2013, 14(4):1223.
[28] Li Y, Li G Z, Zou Y L, Zhou Q J, Lian X X. Cellulose, 2013, 21(1):301.
[29] Cheng M, Qin Z Y, Chen Y Y, Liu J M, Ren Z C. Cellulose, 2017, 24(8):3243.
[30] Filson P B, Dawson-Andoh B E, Schwegler-Berry D. Green Chem., 2009, 11(11):1808.
[31] 李伟(Li W), 王锐(Wang R), 刘守新(Liu S X). 化学进展(Progress in Chemistry), 2010, 22(10):2060.
[32] Lagerwall J P F, Schütz C, Salajkova M, Noh J, Hyun-Park J, Scalia G, Bergström L. NPG Asia Mater., 2014, 6(1):e80.
[33] 代林林(Dai L L), 李伟(Li W), 曹军(Cao J), 李坚(Li J), 刘守新(Liu S X). 化学进展(Progress in Chemistry), 2015, 27(7):861.
[34] Cheng S L, Zhang Y P, Cha R T, Yang J L, Jiang X Y. Nanoscale, 2015, 8(2):973.
[35] Wang Q, Zhao X, Zhu J Y. Ind. Eng. Chem. Res., 2014, 53(27):11007.
[36] Leung A C, Hrapovic S, Lam E, Liu Y, Male K B, Mahmoud K A, Luong J H. Small, 2011, 7(3):302.
[37] Miao J J, Yu Y Q, Jiang Z M, Zhang L P. Cellulose, 2016, 23(2):1209.
[38] Liu Y F, Wang H S, Yu G, Yu Q X, Li B, Mu X D. Carbohydr. Polym., 2014, 110:415.
[39] Du H S, Liu C, Mu X D, Gong W B, Lv D, Hong Y M, Si C L, Li B. Cellulose, 2016, 23(4):2389.
[40] Novo L P, Bras J, Garcia A, Belgacem N, Curvelo A A S. ACS Sustainable Chem. Eng., 2015, 3(11):2839.
[41] Nelson K, Retsina T, Iakovlev M, van-Heiningen A, Deng Y, Shatkin J A, Mulyadi A. "American Process:Production of Low Cost Nanocellulose for Renewable, Advanced Materials Applications," in:Materials Research for Manufacturing:An Industrial Perspective of Turning Materials into New Products. Madsen L D and Svedberg E B (Eds.), Springer Ser. Mater. Sci., 2016, 224:267.
[42] 刘颖(Liu Y), 任学宏(Ren X H). 材料导报(Materials Review), 2015, 29(11):133.
[43] Yang H, Alam M N, van de Ven T G M. Cellulose, 2013, 20(4):1865.
[44] Hu Y, Tang L R, Lu Q L, Wang S Q, Chen X R, Huang B. Cellulose, 2014, 21(3):1611.
[45] Cheng M, Qin Z Y, Liu Y N, Qin Y F, Li T, Chen L, Zhu M F. J. Mater. Chem. A, 2014, 2(1):251.
[46] Earle M J, Seddon K R. ChemInform, 2002, 819:10.
[47] Man Z, Muhammad N, Sarwono A, Bustam M A, Vignesh Kumar M, Rafiq S. J. Polym. Environ., 2011, 19(3):726.
[48] Mao J, Osorio-Madrazo A, Laborie M P. Cellulose, 2013, 20(4):1829.
[49] Mao J, Heck B, Reiter G, Laborie M P. Carbohydr. Polym., 2015, 117:443.
[50] Lazko J, Sénéchal T, Landercy N, Dangreau L, Raquez J M, Dubois P. Cellulose, 2014, 21(6):4195.
[51] Abushammala H, Krossing I, Laborie M P. Carbohydr. Polym., 2015, 134:609.
[52] Tang L R, Huang B, Ou W, Chen X R, Chen Y D. Bioresour. Technol., 2011, 102(23):10973.
[53] Lu Q L, Cai Z H, Lin F C, Tang L R, Wang S Q, Huang B. ACS Sustainable Chem. Eng., 2016, 4(4):2165.
[54] Torlopov M A, Udoratina E V, Martakov I S, Sitnikov P A. Cellulose, 2017, 24(5):2153.
[55] Li B, Xu W Y, Kronlund D, Maattanen A, Liu J, Smatt J H, Peltonen J, Willfor S, Mu X D, Xu C L. Carbohydr. Polym., 2015, 133:605.
[56] Liu C, Li B, Du H S, Lv D, Zhang Y D, Yu G, Mu X D, Peng H. Carbohydr. Polym., 2016, 151:716.
[57] Du H S, Liu C, Wang D, Zhang Y D, Yu G, Si C L, Li B, Mu X D, Peng H. J. Bioresour. Bioprod., 2017, 2(1):10.
[58] Chen L H, Zhu J Y, Baez C, Kitin P, Elder T. Green Chem., 2016, 18(13):3835.
[59] Jia C, Chen L H, Shao Z Q, Agarwal U P, Hu L B, Zhu J Y. Cellulose, 2017, 24(6):2483.
[60] Bian H Y, Chen L H, Dai H Q, Zhu J Y. Carbohydr. Polym., 2017, 167:167.
[61] Xu W Y, Grénman H, Liu J, Kronlund D, Li B, Backman P, Peltonen J, Willför S, Sundberg A, Xu C L. ChemNanoMat, 2017, 3(2):109.
[62] Novo L P, Bras J, García A, Belgacem N, Curvelo A A D S. Ind. Crops Prod., 2016, 93:88.
[63] Nelson K, Retsina T. Tappi J., 2014, 13(5):19.
[64] Turbak A F, Snyder F W, Sandberg K R. Appl. Polym. Symp., 1983, 815.
[65] Herrick F W, Casebier R L, Hamilton J K, Sandberg K R. Appl. Polym. Symp., 1983:797.
[66] Zimmermann T, Pohler E, Geiger T. Adv. Eng. Mater., 2004, 6(9):754.
[67] Qing Y, Sabo R, Zhu J Y, Agarwal U, Cai Z Y, Wu Y Q. Carbohydr. Polym., 2013, 97(1):226.
[68] Carrillo C A, Laine J, Rojas O J. ACS Appl. Mater. Interfaces, 2014, 6(24):22622.
[69] Taniguchi T, Okamura K. Polym. Int., 1998, 47(3):291.
[70] Hu C S, Zhao Y, Li K C, Zhu J Y, Gleisner R. Holzforschung, 2015, 69(8):993.
[71] Chen W S, Yu H P, Liu Y X. Carbohydr. Polym., 2011, 86(2):453.
[72] Chen W S, Yu H P, Liu Y X, Hai Y F, Zhang M X, Chen P. Cellulose, 2011, 18(2):433.
[73] Alemdar A, Sain M. Bioresour. Technol., 2008, 99(6):1664.
[74] Chakraborty A, Sain M, Kortschot M. Holzforschung, 2005, 59(1):102.
[75] Tian X F, Lu P, Song X P, Nie S X, Liu Y, Liu M Y, Wang Z W. Cellulose, 2017, 24(9):3929.
[76] Tarrés Q, Oliver-Ortega H, Llop M, Pèlach M À, Delgado-Aguilar M, Mutjé P. Cellulose, 2016, 23(5):3077.
[77] Rol F, Karakashov B, Nechyporchuk O, Terrien M, Meyer V, Dufresne A, Belgacem M N, Bras J. ACS Sustainable Chem. Eng., 2017, 5(8):6524.
[78] Ho T T T, Abe K, Zimmermann T, Yano H. Cellulose, 2014, 22(1):421.
[79] Uetani K, Yano H. Biomacromolecules, 2011, 12(2):348.
[80] Chaker A, Alila S, Mutjé P, Vilar M R, Boufi S. Cellulose, 2013, 20(6):2863.
[81] Manhas N, Balasubramanian K, Prajith P, Rule P, Nimje S. RSC Adv., 2015, 5(31):23999.
[82] Mohd Amin K N, Annamalai P K, Morrow I C, Martin D. RSC Adv., 2015, 5(70):57133.
[83] Zhang L Y, Tsuzuki T, Wang X G. Cellulose, 2015, 22(3):1729.
[84] Kondo T, Kose R, Naito H, Kasai W. Carbohydr. Polym., 2014, 112:284.
[85] Hsieh M C, Koga H, Suganuma K, Nogi M. Sci. Rep., 2017, 7:41590.
[86] Eriksen O, Syverud K, Gregersen O. Nord. Pulp Pap. Res. J., 2008, 23(3):299.
[87] Wang Q Q, Zhu J Y, Gleisner R, Kuster T A, Baxa U, McNeil S E. Cellulose, 2012, 19(5):1631.
[88] Du H S, Liu C, Zhang Y D, Yu G, Si C L, Li B. Ind. Crops Prod., 2016, 94:736.
[89] Henriksson M, Henriksson G, Berglund L A, Lindström T. Eur. Polym. J., 2007, 43(8):3434.
[90] Paakko M, Ankerfors M, Kosonen H, Nykanen A, Ahola S, Osterberg M, Ruokolainen J, Laine J, Larsson P T, Ikkala O, Lindstrom T. Biomacromolecules, 2007, 8(6):1934.
[91] Wang W, Mozuch M D, Sabo R C, Kersten P, Zhu J Y, Jin Y. Cellulose, 2016, 23(3):1859.
[92] Saito T, Nishiyama Y, Putaux J L, Vignon M, Isogai A. Biomacromolecules, 2006, 7(6):1687.
[93] Fukuzumi H, Saito T, Wata T, Kumamoto Y, Isogai A. Biomacromolecules, 2009, 10(1):162.
[94] Isogai A, Saito T, Fukuzumi H. Nanoscale, 2011, 3(1):71.
[95] Eyholzer C, Bordeanu N, Lopez-Suevos F, Rentsch D, Zimmermann T, Oksman K. Cellulose, 2009, 17(1):19.
[96] Siró I, Plackett D, Hedenqvist M, Ankerfors M, Lindström T. J. Appl. Polym. Sci., 2011, 119(5):2652.
[97] Naderi A, Lindström T, Sundström J. Cellulose, 2014, 21(3):1561.
[98] Ho T T T, Zimmermann T, Hauert R, Caseri W. Cellulose, 2011, 18(6):1391.
[99] Chaker A, Boufi S. Carbohydr. Polym., 2015, 131:224.
[100] Saini S, Yücel Falco Ç, Belgacem M N, Bras J. Carbohydr. Polym., 2016, 135:239.
[101] Lee S Y, Chun S J, Kang I A, Park J Y. J. Ind. Eng. Chem., 2009, 15(1):50.
[102] Bharimalla A K, Deshmukh S P, Patil P G, Vigneshwaran N. World J. Nano Sci. Eng., 2015, 5(4):204.
[103] 周素坤(Zhou S K), 毛健贞(Mao J Z), 许凤(Xu F). 化学进展(Progress in Chemistry), 2014, 26(10):1752.
[104] Taipale T, Österberg M, Nykänen A, Ruokolainen J, Laine J. Cellulose, 2010, 17(5):1005.
[105] Wang R B, Chen L H, Zhu J Y, Yang R D. ChemNanoMat, 2017, 3(5):328.
[106] Bian H Y, Chen L H, Gleisner R, Dai H Q, Zhu J Y. Green Chem., 2017, 19(14):3370.
[107] Chen L H, Dou J Z, Ma Q L, Li N, Wu R C, Bian H Y, Yelle D J, Vuorinen T, Fu S Y, Pan X J, Zhu J Y. Sci. Adv., 2017, 3(9):e1701735.
[108] Liimatainen H, Visanko M, Sirviö J A, Hormi O E O, Niinimaki J. Biomacromolecules, 2012, 13(5):1592.
[109] Liimatainen H, Visanko M, Sirviö J, Hormi O, Niinimäki J. Cellulose, 2013, 20(2):741.
[110] Liimatainen H, Sirviö J, Pajari H, Hormi O, Niinimäki J. J. Wood Chem. Technol., 2013, 33(4):258.
[111] Abbott A P, Capper G, Davies D L, Rasheed R K, Tambyrajah V. Chem. Commun., 2003, (1):70.
[112] Loow Y L, New E K, Yang G H, Ang L Y, Foo L Y W, Wu T Y. Cellulose, 2017, 24(9):3591.
[113] Alvarez-Vasco C, Ma R, Quintero M, Guo M, Geleynse S, Ramasamy K K, Wolcott M, Zhang X. Green Chem., 2016, 18(19):5133.
[114] Procentese A, Johnson E, Orr V, Garruto Campanile A, Wood J A, Marzocchella A, Rehmann L. Bioresour. Technol., 2015, 192:31.
[115] Qin Y Z, Li Y M, Zong M H, Wu H, Li N. Green Chem., 2015, 17(7):3718.
[116] Tang X, Zuo M, Li Z, Liu H, Xiong C X, Zeng X H, Sun Y, Hu L, Liu S J, Lei T Z, Lin L. ChemSusChem, 2017, 10(13):2696.
[117] Sirviö J A, Visanko M, Liimatainen H. Green Chem., 2015, 17(6):3401.
[118] Selkala T, Sirviö J A, Lorite G S, Liimatainen H. ChemSusChem, 2016, 21(9):3074.
[119] Sirviö J A, Visanko M, Liimatainen H. Biomacromolecules, 2016, 17(9):3025.
[120] Laitinen O, Ojala J, Sirviö J A, Liimatainen H. Cellulose, 2017, 24(4):1679.
[121] Liu Y Z, Guo B T, Xia Q Q, Meng J, Chen W S, Liu S X, Wang Q W, Liu Y X, Li J, Yu H P. ACS Sustainable Chem. Eng., 2017, 5(9):7623.
[122] Huang P, Wu M, Kuga S, Wang D Q, Wu D Y, Huang Y. ChemSusChem, 2012, 5(12):2319.
[123] Huang P, Wu M, Kuga S, Huang Y. Cellulose, 2013, 20(4):2175.
[124] Huang P, Zhao Y, Kuga S, Wu M, Huang Y. Nanoscale, 2016, 8(6):3753.
[125] Zhao M M, Kuga S, Jiang S D, Wu M, Huang Y. Cellulose, 2016, 23(5):2809.
[126] Zhao M M, Kuga S, Wu M, Huang Y. Green Chem., 2016, 18(10):3006.
[127] 王超(Wang C), 赵猛猛(Zhao M M), 黄培(Huang P), 饶显孟(Rao X M), 吴敏(Wu M), 黄勇(Huang Y). 高分子学报(Acta Polymerica Sinica), 2017, (9):1415.
[128] Shen J, He Z B, Xiao H N. J. Bioresour. Bioprod., 2017, 2(3):93.
[129] An X Y, Cheng D, Shen J, Jia Q M, He Z B, Zheng L Q, Khan A, Sun B, Ni Y H, Xiong B T. J. Bioresour. Bioprod., 2017, 2(2):45.
[130] Miller J. Cellulose nanomaterials production-state of the industry,December, 2015.[2017-07].http://www.tappinano.org/media/1114/cellulose-nanomaterials-production-state-of-the-industry-dec-2015.pdf.
[131] CelluForce Inc.[2017-07].http://www.celluforce.com/en/technology/
[132] Nelson K, Retsina T, Pylkkanen V, Iakovlev M, van Heiningen A. AIChE Annual Meeting, 2013.
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