竹材在LiCl/DMSO溶剂体系中的溶解及再生性能

doi:10.11707/j.1001-7488.20200922

摘要/Abstract

摘要：

目的: 探索竹材在LiCl/DMSO溶剂体系中的溶解行为及再生特点，为全面解析竹材原本木质素结构信息提供一个可行的木质素分离溶剂体系。方法: 竹材及再生后竹材化学成分基于标准方法测定，木质素结构单元变化通过碱性硝基苯氧化分析，采用X射线衍射比较竹材再生前后纤维素结晶区变化。结果: 球磨2 h的竹粉能以质量分数7.5%完全溶解在6% LiCl/DMSO溶剂体系中，溶于8% LiCl/DMSO溶剂体系中的竹粉质量分数达10%；经再生后化学成分分析，木质素基本保留，再生得率约90%；硝基苯氧化分析结果表明，再生前后木质素未缩合单元含量没有变化，其中S单元占50%，碳水化合物有一定损失；通过X射线衍射分析，纤维素结晶度经LiCl/DMSO溶剂体系溶胀处理后从58.7%降至26.5%。结论: 球磨时间、LiCl在DMSO溶液中的质量分数均会影响LiCl/DMSO溶剂体系中的竹粉溶解，再生后，球磨竹粉的化学成分再生能力强，高聚糖在LiCl/DMSO溶剂体系中的再生能力稍低于木质素。竹材中木质素的缩合程度低于稻草，球磨及再生对竹材木质素结构没有影响。竹材原料球磨再生后的纤维结晶区有一定程度破坏，结晶度有所下降。竹材无论是化学成分还是生物结构均与木材类似，在溶解性能上更接近于木材，LiCl/DMSO溶剂体系可尝试作为解译竹材木质素的可行性分离溶剂。

关键词: 木质素, 竹材, LiCl/DMSO, 溶解再生

Abstract:

Objective: The main purpose of this study was to investigate the characteristics of dissolution and regeneration of bamboo in LiCl/DMSO solvent system,and to provide a feasible solvent system for detailed elucidation of structural information of bamboo protolignin. Method: The analysis of general chemical composition was followed by national standard method. The contents of structural unit of lignin were conducted by alkaline nitrobenzene oxidation,the effects of dissolution and regeneration of bamboo on the cellulose crystallinity were investigated by X-ray diffraction. Result: Bamboo samples with 2 h ball milling could be dissolved in 6% LiCl/DMSO solvent system at a mass concentration of 7.5%,even 10% in the 8% LiCl/DMSO solvent system. The lignin yield was about 90%,the phenylpropane unit structure was found to be well preserved by nitrobenzene oxidation reaction after regeneration in water,the S unit was about 50%,while carbohydrate content was a little loss and the crystallinity was decreased from 58.7% to 26.5%. Conclusion: The effects of ball milled time and LiCl concentration in DMSO on dissolution of bamboo in LiCl/DMSO solvent system were showed. Regenerated ability of chemical composition was high. Compared with that of carbohydrate,lignin ability was higher. In addition,condensed degree of lignin unit was lower than that of rice straw,and both effects of ball milling and regeneration treatment on lignin structure were not found from alkaline nitrobenzene oxidation results,and the crystallinity of cellulose was destroyed by regeneration. The bio-structure and the chemical composition of bamboo were similar to those of wood,so its dissolution property was also close to that of wood. The LiCl/DMSO solvent system could be used to elucidation protolignin information of bamboo.

Key words: lignin, bamboo, LiCl/DMSO, dissolution and regeneration

中图分类号:

S781.4

吴文娟,邹春阳,黄丽菁,金永灿. 竹材在LiCl/DMSO溶剂体系中的溶解及再生性能[J]. 林业科学, 2020, 56(9): 201-206.

Wenjuan Wu,Chunyang Zou,Lijing Huang,Yongcan Jin. Dissolution and Regeneration of Bamboo in LiCl/DMSO Solvent System[J]. Scientia Silvae Sinicae, 2020, 56(9): 201-206.

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参考文献 0

	黄曹兴, 何娟, 赖晨欢, 等. 毛竹预处理黑液木质素和酶解木质素的结构与热学性质. 林业科学, 2018. 54 (3): 108- 116.
	Huang C X , He J , Lai C H , et al. structure characterisitics and thermal properties of black liquor lignin and enzymatic hydrolysis lignin from moso bamboo pretreated by kraft pulping. Scientia Silvae Sinicae, 2018. 54 (3): 108- 116.
	Adler E . Lignin chemistry:past, present and future. Wood Science and Technology, 1977. 11, 169- 218. doi: 10.1007/BF00365615
	Borchardt L G , Piper C V . A gas chromatographic method for carbohydrates as alditol-acetates. TAPPI Journal, 1970. 53, 257- 260.
	Cao T Y , Jiang B , Gu F , et al. Characterization of lignin isolated from wheat leaf based on LiCl/DMSO dissolution and regeneration. Bioresources, 2016. 11 (4): 9676- 9685.
	Chang H M , Cowling E , Brown W . Comparative studies on cellulolytic enzyme lignin and milled lignin of sweetgum and spruce. Holzforschung, 1975. 29, 153- 159. doi: 10.1515/hfsg.1975.29.5.153
	Chen C L. 1992. Nitrobenzene and cupric oxide oxidations//Lin S Y, Dence C W. Methods in lignin chemistry. Springer-Verlag, Berlin, 301-321.
	Dence C W , Lin S Y . Introduction in methods in lignin chemistry. Heidelberg: Springer Verlag Press. 1992. 33- 61.
	Fujimoto A , Matsumoto Y , Chang H M , et al. Quantitative evaluation of milling effects on lignin structure during the isolation process of milled wood lignin. Journal of Wood Science, 2005. 51, 89- 91. doi: 10.1007/s10086-004-0682-7
	Gu F , Wu W J , Wang Z G , et al. Effect of complete dissolution in LiCl/DMSO on the isolation and characteristics of lignin from wheat straw internode. Industrial Crops and Products, 2015. 74, 703- 711. doi: 10.1016/j.indcrop.2015.06.002
	Guerra A , Filpponen I , Lucia L , et al. Toward a better understanding of the lignin isolation process from wood. Journal of Agricultural and Food Chemistry, 2006. 54, 5939- 5947. doi: 10.1021/jf060722v
	Heinze T , Dicke R , Koschella A , et al. Effective preparation of cellulose derivatives in a new simple cellulose solvent. Macromolecular Chemistry and Physics, 2000. 201, 627- 631. doi: 10.1002/(SICI)1521-3935(20000301)201:6<627::AID-MACP627>3.0.CO;2-Y
	Holtman K , Chang H , Kadla J . Solution-state nuclear magnetic resonance study of the similarities between milled wood lignin and cellulolytic enzyme lignin. Journal of Agricultural and Food Chemistry, 2004. 52, 720- 726. doi: 10.1021/jf035084k
	Hu Z , Yeh T F , Chang H M , et al. Elucidation of the structure of cellulolytic enzyme lignin. Holzforschung, 2006. 60, 389- 397. doi: 10.1515/HF.2006.061
	Ikeda T , Holtman K , Kadla J , et al. Studies on the effect of ball milling on lignin structure using a modified DFRC method. Journal of Agricultural and Food Chemistry, 2002. 50 (1): 129- 135. doi: 10.1021/jf010870f
	Jiang B , Cao T Y , Gu F , et al. Comparison of the structural characteristics of cellulolytic enzyme lignin preparations isolated from wheat straw stem and leaf. ACS Sustainable Chemistry & Engineering, 2017. 5 (1): 342- 349.
	Kamm B, Kamm M, Gruber P, et al. 2006. Biorefinery systems-an overview//Kamm B, Gruber P, Kamm M. Biorefineries-industrial processes and products. Wiley: Weinheim, Germany, 3-40.
	Kilpeläinen I , Xie H , King A , et al. Dissolution of wood in ionic liquids. Journal of Agricultural and Food Chemistry, 2007. 55, 9142- 9148. doi: 10.1021/jf071692e
	Kubo S , Hashida K , Yamada T , et al. A characteristic reaction of lignin in ionic liquids; glycelol type enol-ether as the primary decomposition product of β-O-4 model compound. Journal of Wood Chemistry and Technology, 2008. 28, 84- 96.
	Lee Z , Meshitsuka G , Cho N , et al. Characteristics of milled wood lignins isolated with different milling times. Mokuzai Gakkaishi, 1981. 27, 671- 677.
	Lu F , Ralph J . Non-degradative dissolution and acetylation of ball-milled plant cell walls:high-resolution solution-state NMR. Plant Journal, 2003. 35, 535- 544. doi: 10.1046/j.1365-313X.2003.01817.x
	Petruš L , Gray D G , BeMiller J N . Homogeneous alkylation of cellulose in lithium chloride/dimethyl sulfoxide solvent with dimsyl sodium activation. A proposal for the mechanism of cellulose dissolution in LiCl/Me₂SO. Carbohydrate Research, 1995. 268 (2): 319- 323.
	Segal 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. Textile Research Journal, 1959. 29 (10): 786- 794. doi: 10.1177/004051755902901003
	Wang Z G , Yokoyama T , Chang H M , et al. Dissolution of beech and spruce milled woods in LiCl/DMSO. Journal of Agricultural and Food Chemistry, 2009. 57, 6167- 6170. doi: 10.1021/jf900441q
	Wu W J , Wang Z G , Jin Y C , et al. Isolation of cellulolytic enzyme lignin from rice straw enhanced by LiCl/DMSO dissolution and regeneration. Bioresources, 2014a. 9 (3): 4382- 4391.
	Wu W J , Wang Z G , Jin Y C , et al. Effects of LiCl/DMSO dissolution and enzymatic hydrolysis on the chemical composition and lignin structure of rice straw. Biomass and Bioenergy, 2014b. 71, 357- 362. doi: 10.1016/j.biombioe.2014.09.021

原料 Raw materials	木质素Lignin(%)			高聚糖Polysaccharide(%)					木质素得率 Lignin yield(%)	高聚糖得率 Sugar yield(%)
原料 Raw materials	酸不溶 Klason	酸溶 Acid soluble	总量 Total	葡聚糖 Glucan	木聚糖 Xylan	阿拉伯聚糖 Araban	其他 Others	总糖 Total	木质素得率 Lignin yield(%)	高聚糖得率 Sugar yield(%)
B	27.6	1.9	29.5	37.4	17.7	1.1	1.7	57.9	—	—
RB	24.9	1.9	26.8	32.3	14.5	0.8	1.7	49.3	90.8	85.2

原料 Raw materials	得率Yield/(mmol·g^-1)				H:V:S
原料 Raw materials	H	V	S	合计Total	H	V	S
B	0.5	0.8	1.2	2.5	19	31	50
RB	0.5	0.8	1.2	2.4	19	31	50

原料Raw materials	I₂₀₀	I₀₀₈	CrI(%)
B	7 315	3 020	58.7
RB	5 587	4 106	26.5

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