纤维素纳米晶体制备工艺优化的研究

doi:10.3969/j.issn.1673-5854.2019.02.008

Abstract

Abstract:

Cellulose nanocrystals(CNC) were prepared from microcrystalline cellulose(MCC) by sulfuric acid hydrolysis. The effects of sulfuric acid mass fraction, reaction temperature and reaction time on the yield and average particle size of cellulose nanocrystals were studied by single factor method combined with orthogonal test. The performance of CNC was characterized by scanning electron microscopy(SEM), atomic force microscopy(AFM), X-ray diffractometer(XRD) and nano-laser particle size analyzer, and the mechanism of acid hydrolysis to prepare CNC was revealed. The results showed that the optimum process parameters of CNC preparation were sulfuric mass fraction 64%, reaction temperature 45 ℃ and reaction time 90 min. Under these conditions, the yield of CNC was 24.6% and the particle size was 204.8 nm. The CNC aqueous suspension was a kind of stable light blue colloidal state, and its microscopic morphology was relatively regular, which was short rod-shaped, with diameter of about 10-20 nm and length between 150-300 nm; XRD results showed that the crystal form of CNC was cellulose type Ⅰ, and the crystallinity was 80.2%.

Key words: cellulose nanocrystals, acid hydrolysis, yield, particle size

CLC Number:

TQ353

Min DUAN,Tao LIN,Xuefeng YIN,Jing LI. Optimization of Preparation Process of Cellulose Nanocrystals[J]. Biomass Chemical Engineering, 2019, 53(2): 47-53.

Figures/Tables 9

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References 16

1	吴开丽, 徐清华, 谭丽萍. 纳米纤维素晶体的制备方法及其在制浆造纸中的应用前景[J]. 造纸科学与技术, 2010, 29 (1): 55- 60.
2	高蓓蓓. 纳米纤维素的概述[J]. 价值工程, 2011, (34): 272- 273. doi: 10.3969/j.issn.1006-4311.2011.34.191
3	DE SOUZA LIMA M M , BORSAIL R . Rodlike cellulose microcrystals:Structure, properties, and applications[J]. Macromolecular Rapid Communications, 2010, 25 (7): 771- 787.
4	AZIZI SAMIR M A , ALLOIN F , DUFRESNE A , et al. Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite filed[J]. Biomacromolecules, 2005, 6 (2): 612- 626. doi: 10.1021/bm0493685
5	胡云, 刘金刚. 纳米纤维素的制备及研究项目[J]. 中华纸业, 2013, 34 (6): 33- 36. doi: 10.3969/j.issn.1007-9211.2013.06.006
6	唐丽荣, 黄彪, 李玉华, 等. 纳米纤维素超微结构的表征与分析[J]. 生物质化学工程, 2010, 44 (2): 1- 4.
7	王海英, 刘志明, 毕晓欣, 等. 桉木浆纳米纤维素制备优化条件初探[J]. 江苏农业科学, 2012, 40 (7): 242- 245. doi: 10.3969/j.issn.1002-1302.2012.07.092
8	黎国康, 丁恩勇, 李小芳, 等. 纳米晶体纤维素Ⅱ的制备与表征研究[J]. 纤维素科学与技术, 2002, (2): 12- 19. doi: 10.3969/j.issn.1004-8405.2002.02.003
9	陆红佳, 文红丽, 刘雄. 超声波辅助酸法制备纳米薯渣纤维素的工艺研究[J]. 中国粮油学报, 2012, 27 (4): 96- 100. doi: 10.3969/j.issn.1003-0174.2012.04.020
10	南福春.纤维素纳米晶基彩色膜的增韧改性研究[D].青岛:青岛科技大学, 2017.
11	SRGAL L , CREELY J J , MARTIN A E , et al. An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer[J]. Textile Research Journal, 1959, 29 (10): 786- 794. doi: 10.1177/004051755902901003
12	吴鹏, 刘志明, 赵煦, 等. 芦苇浆纳米纤维素的制备及其尺寸均一性制备方法初探[J]. 生物质化学工程, 2012, 46 (5): 12- 16.
13	唐丽荣, 黄彪, 戴达松, 等. 纳米纤维素制备优化及其形貌表征[J]. 福建林学院学报, 2010, 30 (1): 88- 91. doi: 10.3969/j.issn.1001-389X.2010.01.018
14	KARGARZADEH H , AHMAD I , ABDULLAH I , et al. Effects of hydrolysis conditions on the morphology, crystallinity, and thermal stability of cellulose nanocrystals extracted from kenaf bast fibers[J]. Cellulose, 2012, 19 (3): 855- 866. doi: 10.1007/s10570-012-9684-6
15	LIU H Y , LIU D G , YAO F , et al. Fabrication and properties of transparent polymethy/methacrylate/cellulose nanocrystals composites[J]. Bioresource Technology, 2010, 101 (14): 5685- 5692. doi: 10.1016/j.biortech.2010.02.045
16	ZHANG J G , ELDERB T J , PU Y Q , et al. Facile synthesis of spherical cellulose nanoparticles[J]. Carbonhydrate Polymers, 2007, 69 (3): 607- 611.

试验号 test number	A 反应温度/℃ reaction temperature	B 反应时间/min reaction time	C 硫酸质量分数/% sulphuric acid mass fraction	空白列 blank	得率/% yield
1	40	60	60	1	18.4
2	40	90	64	2	20.5
3	40	120	70	3	16.2
4	45	90	70	1	20.3
5	45	120	60	2	20.6
6	45	60	64	3	21.3
7	50	120	64	1	20.3
8	50	60	70	2	17.6
9	50	90	60	3	20.7
k₁	18.4	19.1	19.9	19.7
k₂	20.7	20.5	20.7	19.6
k₃	19.5	19.0	18.1	19.4
R	2.3	1.5	2.6	0.3

因素 factor	偏差平方和 sum of squares of deviations	自由度 freedom	F值 F value	显著性¹⁾ saliency
空白列blank	0.109	2	1.000
A	8.402	2	77.083	*
B	4.116	2	37.761	*
C	11.236	2	103.083	*
误差error	0.110	2

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[2]	HAN Binbin, HAN Yuanshuai, WU Yu, JIANG Hua, ZHANG Yang. Preparation and Characterizations of Cellulose Nanocrystals from Hybrid Poplar Residue by Ammonium Persulfate Oxidation [J]. bce, 2017, 51(4): 33-38.
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[5]	WANG Yan-yun, YANG Jing. Influence of Alkaline-Fenton Pretreatment on the Enzymatic Hydrolysis Yield of Yunnan Bamboo [J]. bce, 2015, 49(5): 17-22.
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[7]	FANG Gui-gan, LIU Shan-shan, SHEN Kui-zhong. Optimization of Dilute-sulfuric Acid Pretreatment of Poplar Residues by Using Response Surface Design [J]. bce, 2014, 48(6): 18-24.
[8]	WANG Cun-wen;DUAN Xiao-ling;WANG Wei-guo;LI Zi-hao;LV Ren-liang;QI Yuan-hang. The Effect of Lignin in Straw on Hydrolysis Process by Extremely-low Acid [J]. , 2013, 47(1): 19-26.
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[11]	YANG Jing;JIANG Jian-chun;ZHANG Ning. Oil Productivity Capabilities of Several Microalgae Strains in Different Cultivation Methods [J]. , 2011, 45(2): 15-19.
[12]	CHEN Mu;LIAN Zhi-na;XU Yong;YONG Qiang;YU Shi-yuan;. Determination of Xylo-oligosaccharides by Sulfuric Acid Hydrolysis-High Performance Liquid Chromatography Detection [J]. , 2010, 44(6): 14-17.
[13]	ZHOU Li-dong;ZHOU Jing-hong;QI Yuan-feng. Study on Surfactants Effect on Enzymatic Hydrolysis of Cassava Pole [J]. , 2010, 44(4): 25-28.
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Optimization of Preparation Process of Cellulose Nanocrystals

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