低共熔溶剂在木质素分离方面的研究进展

doi:10.3969/j.issn.0253-2417.2020.03.002

摘要/Abstract

摘要：

木质素是自然界中含量丰富的可再生芳香族聚合物，其结构复杂并与碳水化合物之间存在致密连接，这使得木质素难以高效分离。低共熔溶剂（DES）是一种新型绿色离子液体，凭借着独特的物化性质已被成功应用于木质素的溶解和分离。本文从低共熔溶剂溶解木质素及其相关机理出发，综述了低共熔溶剂分离提取木质素的研究进展，重点阐述了木质素在分离提取过程中受DES的组成、配比、酸碱度、官能团，体系的水含量，原料，反应时间、温度，外加催化剂、共熔剂及其他辅助方式的影响，并介绍了DES提取分离所得木质素产物低共熔溶剂木质素（DESL）的结构特征，最后对DES在木质素分离提取方面的研究工作进行了总结与展望。

关键词: 低共熔溶剂, 木质素, 溶解, 分离

Abstract:

Lignin is the most abundant renewable aromatic polymer in nature, which complex structure and compact connection with cellulose and hemicellulose through covalent bond and hydrogen bond make it difficult to be separated efficiently. Deep eutectic solvents (DES) is a novel kind of green ionic liquid, which has been successfully applied to lignin isolation due to its unique physical and chemical properties. The research progress of dissolution and extraction of lignin by deep eutectic solvents (DES) is reviewed in detail. From the point of view of the mechanism of dissolving lignin by DES, the effects of different factors(composition, proportion, pH value, functional groups of DES, water content of system, raw material, reaction time, temperature, catalyst, co-solvent, and so on) on lignin removal were emphatically expounded. Based on the research progress of DES in lignin extraction, the research progress and futuer application of lignin extraction were summarized and prospected.

Key words: deep eutectic solvents, lignin, dissolution, extraction

中图分类号:

TQ35

钟磊,王超,吕高金,吉兴香,杨桂花,陈嘉川. 低共熔溶剂在木质素分离方面的研究进展[J]. 林产化学与工业, 2020, 40(3): 12-22.

Lei ZHONG,Chao WANG,Gaojin LYU,Xingxiang JI,Guihua YANG,Jiachuan CHEN. A Review of Deep Eutectic Solvents for Lignin Isolation[J]. Chemistry and Industry of Forest Products, 2020, 40(3): 12-22.

图/表 4

图1

图2

图3

表1

低共熔溶剂分离木质素的研究"

原料 material	DES(物质的量比) DES (molar ratio)	固液比 solid-liquid ratio	反应条件¹⁾ reaction conditions	木质素溶出率/% lignin dissolution rate	文献 literature
麦秸秆 wheat straw	ChCl-乳酸lactic acid(LA)(1:2)	—	14~16 h，60 ℃	少量minimal	[27]
	四甲基氯化铵(TMACL)-LA(1:3)	1:20	14 h，60或85 ℃	9.5	[43]
	ChCl-丙二酸malonic acid(1:1)	5%	24 h，60 ℃	3.8	[44]
	ChCl-LA(1:10)	5%	24 h，60 ℃	29.1	[44]
	ChCl-二水草酸oxalic acid·2H₂O(1:1)	5%	24 h，60 ℃	57.9	[44]
	ChCl-LA-丙三醇glycerol(Gly)(1:1:1)	2%	30 min，120 ℃(MW 1500 W)	45	[48]
	ChCl-LA(1:10)	2%	30 min，120 ℃(MW 1500 W)	30	[48]
	ChCl-单乙醇胺monoethanolamine(1:6)	1:20	12 h，90 ℃	81.0	[49]
	ChCl-二乙醇胺diethanolamine(1:8)	1:20	12 h，90 ℃	73.5	[49]
	ChCl-N-甲基二乙醇胺MDEA(1:10)	1:20	12 h，90 ℃	44.6	[49]
	ChCl-间苯二酚resorcinol(1:1)	—	超声波ultrasound 50 min	~100	[28]
玉米芯 corn cob	ChCl-咪唑imidazole(3:7)	1:16	15 h，150 ℃	88	[45]
	苄基三甲基氯化铵TMBAC-LA(1:2)	5%	2 h，140 ℃	63.4	[50]
	苄基三乙基氯化铵TEBA-LA(1:2)	5%	2 h，140 ℃	56.5	[50]
	ChCl-草酸oxalic acid(OA)(1:1)	5%	24 h，90 ℃	98.5	[41]
	ChCl-苹果酸malic acid(MA)(1:1)	5%	24 h，90 ℃	22.4	[41]
	ChCl-甲酸formic acid(FA)(1:2)	10%	2 h，115 ℃	81.49	[51]
稻草straw	ChCl-羟基乙酸glycolic acid(1:1)	5%	6 h，80 ℃	33.1
	ChCl-LA(1:1)	5%	6 h，80 ℃	51.3	[36]
	ChCl-氯丙酸chloropropionic acid(1:1)	5%	6 h，80 ℃	51.9
	ChCl-LA(1:5)	5%	12 h，60 ℃	60±5	[52]
	ChCl-LA(1:5)+5% H₂O	5%	12 h，60 ℃	82	[52]
稻壳 rice husk	ChCl-OA-正丁醇n-butanol(1:1:1)	15%	1 h，120 ℃	49
	ChCl-OA-正丙醇n-propanol(1:1:1)	15%	1 h，120 ℃	41	[53]
	ChCl-OA-乙酸乙酯ethyl acetate(1:1:1)	15%	1 h，120 ℃	15
玉米秸秆 corn stalks	ChCl-LA(1:2)	10%	45 s，152 ℃(MW 800 W)	80	[54]
松木pine	二氯胆碱chlormequat chloride-LA(1:5)	1:20	14 h，60或85 ℃	7.8	[43]
杨木 poplar	ChCl-LA(1:10)	5%	12 h，120 ℃	90.4	[55]
	甘氨酸glycine- LA(1:9)	5%	12 h，120 ℃	51.9	[55]
	ChCl-LA	10%	6 h，145 ℃	78	[37]
	ChCl-OA·2H₂O(1:1)	5%	3 min，80 ℃(MW 800 W)	80	[35]
	ChCl-OA·2H₂O(1:1)	5%	9 h，110 ℃	90	[35]
花旗松 douglas fir	ChCl-LA	10%	9 h，145 ℃	58	[37]
竹柳willow	ChCl-LA(1:10)	1:30	12 h，120 ℃	91.8	[40]
尾叶桉 E. urophylla	TEBA-LA(1:9)	1:30	10 h，90 ℃	92.3	[29]
山毛榉beech	ChCl-KOH(1:4)	2.5%	2~24 h，60~100 ℃	极少minimal	[42]
赤桉 E.camaldulensis	ChCl- LA(1:10)	10%	6 h，110 ℃	44.8	[46]
柳枝稷 switchgrass	ChCl-乙二醇ethylene glycol(EG)(1:2)	10%	30 min，130 ℃	24	[47]
	ChCl-EG(1:2)+1% H₂SO₄	10%	30 min，130 ℃	87	[47]
	ChCl-对香豆酸p-coumaric acid(1:1)	5%	3 h，160 ℃	60.8	[56]
	ChCl-香草醛vanillin(1:2)	5%	3 h，160 ℃	52.5
	ChCl-儿茶酚catechol(1:1)	5%	3 h，160 ℃	49.0
	ChCl-对羟基苄醇p-hydroxybenzyl(1:1)	5%	3 h，160 ℃	0.4
油棕榈空果束 oil palm empty fruit bunch	ChCl-LA(1:1)	10%	8 h，120 ℃	33	[57]
	ChCl-LA(1:15)	10%	8 h，120 ℃	61
	LA	10%	8 h，120 ℃	39
	ChCl-乙酸acetic acid(1:5)	10%	8 h，120 ℃	40
	ChCl-苹果酸MA(1:2)	10%	8 h，120 ℃	28.9
	ChCl-FA(1:2)	10%	8 h，120 ℃	62
	ChCl-FA(1:5)	10%%	8 h，120 ℃	25
	ChCl-丁二酸succinic acid(2:1)	10%	8 h，120 ℃	10.7
	ChCl-丙酸propionic acid(1:2)	10%	8 h，120 ℃	20.4
	ChCl-丁酸butyric acid(1:2)	10%	8 h，120 ℃	14.3
	ChCl-柠檬酸citric acid(1:2)	10%	8 h，120 ℃	20.6
	ChCl-LA(1:5)	10%	8 h，120 ℃	88	[58]
	葡萄糖glucose(Glu)- LA(1:5)	10%	8 h，120 ℃	55
	ChCl-Glu(1:1)	10%	8 h，120 ℃	22
	ChCl-丙三醇gly(1:2)	10%	8 h，120 ℃	17
	ChCl-尿素urea(U)(1:2)	10%	8 h，120 ℃	34
	K₂CO₃-丙三醇gly(1:6)	10%	8 h，120 ℃	51
合欢皮草药渣 herb residues of Cortex albiziae	ChCl-PCA(1:1)	1:10	5 h，160 ℃	30	[59]
合欢皮草药渣 herb residues of Cortex albiziae	ChCl-PCA(1:1)+50% H₂O	1:10	5 h，160 ℃	39.89	[59]
油棕叶 oil palm fronds	ChCl-U(1:2)	1:10	4 h，120 ℃	11	[60]
油棕叶 oil palm fronds	ChCl-U(1:2)+30% H₂O	1:10	4 h，120 ℃	16	[60]
大芒 Miscanthus × giganteus	ChCl-丙三醇gly(1:2)	5%	3 h，120 ℃	1.6	[61]
大芒 Miscanthus × giganteus	ChCl-丙三醇gly(1:2)+杂多酸heteropoly acids	5%	3 h，120 ℃	56.5~89.5	[61]

表1

参考文献 81

1	JIN X L , CHEN X L , SHI C H , et al. Determination of hemicellulose, cellulose and lignin content using visible and near infrared spectroscopy in Miscanthus sinensis[J]. Bioresource Technology, 2017, 241, 603- 609. doi: 10.1016/j.biortech.2017.05.047
2	RAGAUSKAS A J , BECKHAM G T , BIDDY M J , et al. Lignin valorization:Improving lignin processing in the biorefinery[J]. Science, 2014, 344 (6185): 709- 719.
3	李利芬, 胡英成. 离子液体在木质素研究中的应用[J]. 林产化学与工业, 2015, 35 (2): 163- 170.
	LI L F , HU Y C . Application of ionic liquids in lignin processing[J]. Chemistry and Industry of Forest Products, 2015, 35 (2): 163- 170.
4	FACHE M , BOUTEVIN B , CAILLOL S . Vanillin production from lignin and its use as a renewable chemical[J]. ACS Sustainable Chemistry & Engineering, 2016, 4 (1): 6379- 6401.
5	曹金珍, 张璧光, 赵广杰. 木质生物质在能源方面的开发与利用[J]. 华北电力大学学报(自然科学版), 2003, 30 (5): 102- 104. doi: 10.3969/j.issn.1007-2691.2003.05.026
	CAO J Z , ZHANG B G , ZHAO G J . Development and application of wooden biomass[J]. Journal of North China Electric Power University (Natural Science Edition), 2003, 30 (5): 102- 104. doi: 10.3969/j.issn.1007-2691.2003.05.026
6	ZHAO C X , JIANG E C , CHEN A H . Volatile production from pyrolysis of cellulose, hemicellulose and lignin[J]. Journal of the Energy Institute, 2017, 90 (6): 902- 913. doi: 10.1016/j.joei.2016.08.004
7	CHUNDAWAT S P S , BECKHAM G T , HIMMEL M E , et al. Deconstruction of lignocellulosic biomass to fuels and chemicals[J]. Annual Review of Chemical and Biomolecular Engineering, 2011, 2 (2): 121- 145. doi: 10.1146/annurev-chembioeng-061010-114205
8	谢宜彤, 郭鑫, 吕艳娜, 等. 低共熔溶剂在木质纤维原料溶解及其组分分离中的研究进展[J]. 林产化学与工业, 2019, 39 (5): 11- 18.
	XIE Y T , GUO X , LYU Y N , et al. Research progress on the dissolution of lignocellulose and separation of its components by deep eutectic solvents[J]. Chemistry and Industry of Forest Products, 2019, 39 (5): 11- 18.
9	司马国宝, 王帅, 崔莹, 等. 低共熔溶剂对木质纤维素分离及木质素提取的研究进展[J]. 现代化工, 2019, 39 (9): 26- 30.
	SIMA G B , WANG S , CUI Y , et al. Research progress in lignocellulose separation and lignin extraction by deep eutectic solvents[J]. Modern Chemical Industry, 2019, 39 (9): 26- 30.
10	鲁超, 苏二正, 魏东芝, 等. 深共熔溶剂的生物催化应用[J]. 分子催化, 2015, 29 (4): 390- 401.
	LU C , SU E Z , WEI D Z , et al. The applications of deep eutectic solvents in biocatalysis[J]. Journal of Molecular Catalysis(China), 2015, 29 (4): 390- 401.
11	TROTER D Z , TODOROVIC' Z B , DOKIC' STOJANOVIC' D R , et al. Application of ionic liquids and deep eutectic solvents in biodiesel production:A review[J]. Renewable & Sustainable Energy Reviews, 2016, 61, 473- 500. doi: 10.1016/j.rser.2016.04.011
12	WANG J F , WANG P , WANG Q , et al. Low temperature electrochemical deposition of aluminum in organic bases/thiourea-based deep eutectic solvents[J]. ACS Sustainable Chemistry & Engineering, 2018, 6 (11): 15480- 15486.
13	ADHIKARI L , LARM N E , BHAWAWET N , et al. Rapid microwave-assisted synthesis of silver nanoparticles in a halide-free deep eutectic solvent[J]. ACS Sustainable Chemistry & Engineering, 2018, 6 (5): 5725- 5731.
14	LERON R B , LI M H . Solubility of carbon dioxide in a choline chloride-ethylene glycol based deep eutectic solvent[J]. Thermochimica Acta, 2013, 551 (1): 14- 19. doi: 10.1016/j.tca.2012.09.041
15	SILVA J M , REIS R L , PAIVA A , et al. Design of functional therapeutic deep eutectic solvents based on choline chloride and ascorbic acid[J]. ACS Sustainable Chemistry & Engineering, 2018, 6 (8): 10355- 10363.
16	LARRIBA M , AYUSO M , NAVARRO P , et al. Choline chloride-based deep eutectic solvents in the dearomatization of gasolines[J]. ACS Sustainable Chemistry & Engineering, 2018, 6 (1): 1039- 1047.
17	LIU Y Z , GUO B T , XIA Q Q , et al. Efficient cleavage of strong hydrogen bonds in cotton by deep eutectic solvents and facile fabrication of cellulose nanocrystals in high yields[J]. ACS Sustainable Chemistry & Engineering, 2017, 5 (9): 7623- 7631.
18	XIA Q Q , LIU Y Z , MENG J , et al. Multiple hydrogen bond coordination in three-constituent deep eutectic solvents enhances lignin fractionation from biomass[J]. Green Chemistry, 2018, 20 (12): 2711- 2721. doi: 10.1039/C8GC00900G
19	LACERDA V D , LOPEZ-SOTELO J B , CORREA-GUIMARAES A , et al. A kinetic study on microwave-assisted conversion of cellulose and lignocellulosic waste into hydroxymethylfurfural/furfural[J]. Bioresource Technology, 2015, 180, 88- 96. doi: 10.1016/j.biortech.2014.12.089
20	KUMAR A K , PARIKH B S , SHAH E , et al. Cellulosic ethanol production from green solvent-pretreated rice straw[J]. Biocatalysis and Agricultural Biotechnology, 2016, 7, 14- 23. doi: 10.1016/j.bcab.2016.04.008
21	张金猛, 郭大亮, 郭云朴, 等. 低共熔溶剂分离木质素研究进展[J]. 中国造纸, 2019, 38 (9): 1- 6.
	ZHANG J M , GUO D L , GUO Y P , et al. Research progress in lignin separation with deep eutectic solvent[J]. China Pulp & Paper, 2019, 38 (9): 1- 6.
22	WANG H J , FRITS P D , JIN Y C . A win-win technique of stabilizing sand dune and purifying paper mill black-liquor[J]. Journal of Environmental Sciences, 2009, 21 (4): 488- 493. doi: 10.1016/S1001-0742(08)62296-2
23	HAGE R E , BROSSE N , CHRUSCIEL L , et al. Characterization of milled wood lignin and ethanol organosolv lignin from Miscanthus[J]. Polymer Degradation & Stability, 2009, 94 (10): 1632- 1638.
24	PANDEY M P , KIM C S . Lignin depolymerization and conversion:A review of thermochemical methods[J]. Chemical Engineering & Technology, 2011, 34 (1): 29- 41. doi: 10.1002/ceat.201000270
25	MOOD S H , GOLFESHAN A H , TABATABAEI M , et al. Lignocellulosic biomass to bioethanol, a comprehensive review with a focus on pretreatment[J]. Renewable & Sustainable Energy Reviews, 2013, 27 (6): 77- 93.
26	ABBOTT A P , BELL T J , HANDA S , et al. Cationic functionalisation of cellulose using a choline based ionic liquid analogue[J]. Green Chemistry, 2006, 8 (9): 784- 786. doi: 10.1039/b605258d
27	FRANCISCO M , VAN D B A , KROON M C . New natural and renewable low transition temperature mixtures (LTTMs):Screening as solvents for lignocellulosic biomass processing[J]. Green Chemistry, 2012, 14 (8): 2153- 2157. doi: 10.1039/c2gc35660k
28	MALAEKE H , HOUSAINDOKHT M R , MONHEMI H , et al. Deep eutectic solvent as an efficient molecular liquid for lignin solubilization and wood delignification[J]. Journal of Molecular Liquids, 2018, 263, 193- 199. doi: 10.1016/j.molliq.2018.05.001
29	刘钧, 王菊, 岳莺莺, 等. 深度共熔溶剂对尾叶桉木质素的溶解选择性[J]. 精细化工, 2016, 33 (11): 1287- 1294.
	LIU J , WANG J , YUE Y Y , et al. Solubility selectivity for lignin of eucalyptus in deep eutectic solvents[J]. Fine Chemicals, 2016, 33 (11): 1287- 1294.
30	KROON M C, FRANCISCO CASAL M, VAN D B A.Pretreatment of lignocellulosic biomass and recovery of substituents using natural deep eutectic solvents/compound mixtures with low transition temperatures: WO2013153203[P].2013-10-17.
31	LYNAM J G , KUMAR N , WONG M J . Deep eutectic solvents' ability to solubilize lignin, cellulose, and hemicellulose; thermal stability; and density[J]. Bioresource Technology, 2017, 238, 684- 689. doi: 10.1016/j.biortech.2017.04.079
32	HOU X D , FENG G J , YE M , et al. Significantly enhanced enzymatic hydrolysis of rice straw via a high-performance two-stage deep eutectic solvents synergistic pretreatment[J]. Bioresource Technology, 2017, 238, 139- 146. doi: 10.1016/j.biortech.2017.04.027
33	LI W J , ZHANG Z F , HAN B X , et al. Switching the basicity of ionic liquids by CO₂[J]. Green Chemistry, 2008, 10 (11): 1142- 1145. doi: 10.1039/b811624e
34	LIU Q L , ZHAO X H , YU D K , et al. Novel deep eutectic solvents with different functional groups towards highly efficient dissolution of lignin[J]. Green Chemistry, 2019, 21 (19): 5291- 5297. doi: 10.1039/C9GC02306B
35	LIU Y Z , CHEN W S , XIA Q Q , et al. Efficient cleavage of lignin-carbohydrate complexes and ultrafast extraction of lignin oligomers from wood biomass by microwave-assisted treatment with deep eutectic solvent[J]. ChemSusChem, 2017, 10 (8): 1692- 1700. doi: 10.1002/cssc.201601795
36	HOU X D , LI A L , LIN K P , et al. Insight into the structure-function relationships of deep eutectic solvents during rice straw pretreatment[J]. Bioresource Technology, 2018, 249, 261- 267. doi: 10.1016/j.biortech.2017.10.019
37	ALVAREZ-VASCO C , MA R , QUINTERO M , et al. Unique low-molecular-weight lignin with high purity extracted from wood by deep eutectic solvents (DES):A source of lignin for valorization[J]. Green Chemistry, 2016, 18 (19): 5133- 5141. doi: 10.1039/C6GC01007E
38	HILTUNEN J , KUUTTI L , ROVIO S , et al. Using a low melting solvent mixture to extract value from wood biomass[J]. Scientific Reports, 2016, 6 (1): 32420. doi: 10.1038/srep32420
39	HONG S , LIAN H L , SUN X , et al. Zinc-based deep eutectic solvent-mediated hydroxylation and demethoxylation of lignin for the production of wood adhesive[J]. RSC Advances, 2016, 6 (92): 89599- 89608.
40	LI T F , LYU G J , LIU Y , et al. Deep eutectic solvents (DESs) for the isolation of willow lignin (Salix matsudana cv. Zhuliu)[J]. International Journal of Molecular Sciences, 2017, 18 (11): 1- 11.
41	ZHANG C W , XIA S Q , MA P S . Facile pretreatment of lignocellulosic biomass using deep eutectic solvents[J]. Bioresource Technology, 2016, 219, 1- 5. doi: 10.1016/j.biortech.2016.07.026
42	MAMILLA J L K , NOVAK U , GRILC M , et al. Natural deep eutectic solvents (DES) for fractionation of waste lignocellulosic biomass and its cascade conversion to value-added bio-based chemicals[J]. Biomass and Bioenergy, 2019, 120, 417- 425. doi: 10.1016/j.biombioe.2018.12.002
43	DIOS S L G D.Phase equilibria for extraction processes with designer solvents[D].Santiago: Santiago de Compostela University, 2013.
44	JABLONSKY M , SKULCOVA A , KAMENSKA L , et al. Deep eutectic solvents:Fractionation of wheat straw[J]. Bioresources, 2015, 10 (4): 8039- 8047. doi: 10.15376/biores.10.4.8039-8047
45	PROCENTESE A , JOHNSON E , ORR V , et al. Deep eutectic solvent pretreatment and subsequent saccharification of corncob[J]. Bioresource Technology, 2015, 192, 31- 36. doi: 10.1016/j.biortech.2015.05.053
46	SHEN X J , WEN J L , MEI Q Q , et al. Facile fractionation of lignocelluloses by biomass-derived deep eutectic solvent (DES) pretreatment for cellulose enzymatic hydrolysis and lignin valorization[J]. Green Chemistry, 2019, 21 (2): 275- 283. doi: 10.1039/C8GC03064B
47	CHEN Z , BAI X , LUSI A , et al. High-solid lignocellulose processing enabled by natural deep eutectic solvent for lignin extraction and industrially relevant production of renewable chemicals[J]. ACS Sustainable Chemistry & Engineering, 2018, 6 (9): 12205- 12216.
48	GAUDINO E C , TABASSO S , GRILLO G , et al. Wheat straw lignin extraction with bio-based solvents using enabling technologies[J]. Comptes Rendus Chimie, 2018, 21 (6): 563- 571. doi: 10.1016/j.crci.2018.01.010
49	ZHAO Z , CHEN X C , ALI M F , et al. Pretreatment of wheat straw using basic ethanola mine-based deep eutectic solvents for improving enzymatic hydrolysis[J]. Bioresource Technology, 2018, 263, 325- 333. doi: 10.1016/j.biortech.2018.05.016
50	GUO Z W , ZHANG Q L , YOU T T , et al. Short-time deep eutectic solvent pretreatment for enhanced enzymatic saccharification and lignin valorization[J]. Green Chemistry, 2019, 21 (11): 3099- 3108. doi: 10.1039/C9GC00704K
51	王冬梅, 刘云. 低共熔溶剂(DES)分级分离木质纤维素组分新技术[J]. 北京化工大学学报(自然科学版), 2018, 45 (6): 40- 47.
	WANG D M , LIU Y . Fractionation of lignocellulose with deep eutectic solvent (DES)[J]. Journal of Beijing University of Chemical Technology (Natural Science), 2018, 45 (6): 40- 47.
52	KUMAR A K , PARIKH B S , PRAVAKAR M . Natural deep eutectic solvent mediated pretreatment of rice straw:Bioanalytical characterization of lignin extract and enzymatic hydrolysis of pretreated biomass residue[J]. Environmental Science and Pollution Research, 2016, 23 (10): 9265- 9275. doi: 10.1007/s11356-015-4780-4
53	KANDANELLI R , THULLURI C , MANGALA R , et al. A novel ternary combination of deep eutectic solvent-alcohol (DES-OL) system for synergistic and efficient delignification of biomass[J]. Bioresource Technology, 2018, 265, 573- 576. doi: 10.1016/j.biortech.2018.06.002
54	CHEN Z , WAN C X . Ultrafast fractionation of lignocellulosic biomass by microwave-assisted deep eutectic solvent pretreatment[J]. Bioresource Technology, 2018, 250, 532- 537. doi: 10.1016/j.biortech.2017.11.066
55	李利芬.基于氯化胆碱低共熔溶剂的木质素提取改性和降解研究[D].哈尔滨:东北林业大学, 2015.
	LI L F.Extraction, modification and degradation of lignin with choline chloride-based deep eutectic solvents[D].Harbin: Northeast Forestry University, 2015.
56	KIM K H , DUTTA T , SUN J , et al. Biomass pretreatment using deep eutectic solvents from lignin derived phenols[J]. Green Chemistry, 2018, 20 (4): 809- 815. doi: 10.1039/C7GC03029K
57	TAN Y T , NGOH G C , CHUA A S M . Effect of functional groups in acid constituent of deep eutectic solvent for extraction of reactive lignin[J]. Bioresource Technology, 2019, 281, 359- 366. doi: 10.1016/j.biortech.2019.02.010
58	TAN Y T , NGOH G C , CHUA A S M . Evaluation of fractionation and delignification efficiencies of deep eutectic solvents on oil palm empty fruit bunch[J]. Industrial Crops and Products, 2018, 123, 271- 277. doi: 10.1016/j.indcrop.2018.06.091
59	CHEN L , YU Q , WANG Q , et al. A novel deep eutectic solvent from lignin-derived acids for improving the enzymatic digestibility of herbal residues from cellulose[J]. Cellulose, 2019, 26 (3): 1- 13.
60	NEW E K , WU T Y , LEE C B T L , et al. Potential use of pure and diluted choline chloride-based deep eutectic solvent in delignification of oil palm fronds[J]. Process Safety and Environmental Protection, 2019, 123, 190- 198. doi: 10.1016/j.psep.2018.11.015
61	GUO Z W , ZHANG Q L , YOU T T , et al. Heteropoly acids enhanced neutral deep eutectic solvent pretreatment for enzymatic hydrolysis and ethanol fermentation of Miscanthus×giganteus under mild conditions[J]. Bioresource Technology, 2019, 293, 1- 6. doi: 10.1016/j.biortech.2019.122036
62	ADLER E . Lignin chemistry:Past, present and future[J]. Wood Science & Technology, 1977, 11 (3): 169- 218.
63	DAI Y , VAN SPRONSEN J , WITKAMP G J , et al. Natural deep eutectic solvents as new potential media for green technology[J]. Analytica Chimica Acta, 2013, 766, 61- 68. doi: 10.1016/j.aca.2012.12.019
64	D'AGOSTINO C , HARRIS R C , ABBOTT A P , et al. Molecular motion and ion diffusion in choline chloride based deep eutectic solvents studied by ¹H pulsed field gradient NMR spectroscopy[J]. Physical Chemistry Chemical Physics, 2011, 13 (48): 21383- 21391. doi: 10.1039/c1cp22554e
65	TELES A R R , CAPELA E V , CARMO R S , et al. Solvatochromic parameters of deep eutectic solvents formed by ammonium-based salts and carboxylic acids[J]. Fluid Phase Equilibria, 2017, 448, 15- 21. doi: 10.1016/j.fluid.2017.04.020
66	DAI Y , VERPOORTE R , CHOI Y H . Natural deep eutectic solvents providing enhanced stability of natural colorants from safflower (Carthamus tinctorius)[J]. Food Chemistry, 2014, 159 (6): 116- 121.
67	LIU N A , HUO K F , MCDOWELL M T , et al. Rice husks as a sustainable source of nanostructured silicon for high performance Li-ion battery anodes[J]. Scientific Reports, 2013, 3, 1919. doi: 10.1038/srep01919
68	BRANDT A , GRASVIK J , HALLETT J P , et al. Deconstruction of lignocellulosic biomass with ionic liquids[J]. Green Chemistry, 2013, 15 (3): 550- 583. doi: 10.1039/c2gc36364j
69	BUBALO M C , ĆURKO N , TOMAŠEVIĆ M , et al. Green extraction of grape skin phenolics by using deep eutectic solvents[J]. Food Chemistry, 2016, 200, 159- 166. doi: 10.1016/j.foodchem.2016.01.040
70	WEN C S , WONG D S H , MENG H L . Effect of water on solubility of carbon dioxide in (aminomethanamide+2-hydroxy-N, N, N-trimethylethanaminium chloride)[J]. Journal of Chemical & Engineering Data, 2009, 54 (6): 1951- 1955.
71	GARCÍA G , APARICIO S , ULLAH R , et al. Deep eutectic solvents:Physicochemical properties and gas separation applications[J]. Energy Fuels, 2015, 29, 2616- 2644. doi: 10.1021/ef5028873
72	YIIN C L , QUITAIN A T , YUSUP S , et al. Sustainable green pretreatment approach to biomass-to-energy conversion using natural hydro-low-transition-temperature mixtures[J]. Bioresource Technology, 2018, 261, 361- 369. doi: 10.1016/j.biortech.2018.04.039
73	WENG L D , TONER M . Janus-faced role of water in defining nanostructure of choline chloride/glycerol deep eutectic solvent[J]. Physical Chemistry Chemical Physics, 2018, 20 (35): 22455- 22462. doi: 10.1039/C8CP03882A
74	HAMMOND O S , BOWRON D T , EDLER K J . Effect of water upon deep eutectic solvent nanostructure:An unusual transition from ionic mixture to aqueous solution[J]. Angewandte Chemie, 2017, 56 (33): 9782- 9785. doi: 10.1002/anie.201702486
75	CHEN Z , REZNICEK W D , WAN C . Deep eutectic solvent pretreatment enabling full utilization of switchgrass[J]. Bioresource Technology, 2018, 263, 40- 48. doi: 10.1016/j.biortech.2018.04.058
76	SHARMA M , MUKESH C , MONDAL D , et al. Dissolution of α-chitin in deep eutectic solvents[J]. RSC Advances, 2013, 3 (39): 18149- 18155. doi: 10.1039/c3ra43404d
77	YUNUS R , SALLEH S F , ABDULLAH N , et al. Effect of ultrasonic pre-treatment on low temperature acid hydrolysis of oil palm empty fruit bunch[J]. Bioresource Technology, 2010, 101 (24): 9792- 9796. doi: 10.1016/j.biortech.2010.07.074
78	PINJARI D V , PANDIT A B . Cavitation milling of natural cellulose to nanofibrils[J]. Ultrasonics Sonochemistry, 2010, 17 (5): 845- 852. doi: 10.1016/j.ultsonch.2010.03.005
79	LYU G J , LI T F , JI X X , et al. Characterization of lignin extracted from willow by deep eutectic solvent treatments[J]. Polymers, 2018, 10 (8): 1- 11. doi: 10.3390/polym10080869
80	DAS A , RAHIMI A , ULBRICH A , et al. Lignin conversion to low-molecular-weight aromatics via an aerobic oxidation-hydrolysis sequence:Comparison of different lignin sources[J]. ACS Sustainable Chemistry & Engineering, 2018, 6 (3): 3367- 3374. doi: 10.1021/acssuschemeng.7b03541
81	LOU R , MA R , LIN K T , et al. Facile extraction of wheat straw by deep eutectic solvent (DES) to produce lignin nanoparticles[J]. ACS Sustainable Chemistry & Engineering, 2019, 7 (12): 10248- 10256.

[1]	侯兴隆, 郭奇, 建晓朋, 吴迪超, 许伟, 刘军利. 响应面法优化设计木质素基活性炭的制备[J]. 林产化学与工业, 2020, 40(3): 115-122.
[2]	储秋露,陈雪艳,宋凯,王静,张晓东,施爱平. 两步法预处理对杨木酶水解及木质素吸附性能的影响[J]. 林产化学与工业, 2019, 39(6): 68-74.
[3]	卢传巍,郭晓亮,蔡青云,王春鹏,储富祥,王基夫. 甲基丙烯酸化木质素磺酸钙/聚丙烯酰胺复合水凝胶的制备与性能研究[J]. 林产化学与工业, 2019, 39(6): 75-80.
[4]	李宁,陈智糠,张一甫. 酚化木质素改性酚醛树脂胶黏剂的制备及性能表征[J]. 林产化学与工业, 2019, 39(6): 95-101.
[5]	谢宜彤, 郭鑫, 吕艳娜, 王海松. 低共熔溶剂在木质纤维原料溶解及其组分分离中的研究进展[J]. 林产化学与工业, 2019, 39(5): 11-18.
[6]	陈雪艳, 储秋露, 王静, 张晓东, 施爱平. 两步法预处理脱除木质素对杨木酶水解的影响[J]. 林产化学与工业, 2019, 39(5): 73-79.
[7]	王兴佳, 乔炜, 肖达明, 李淑君. 铝氧单钠固体超强碱催化降解木质素的研究[J]. 林产化学与工业, 2019, 39(5): 80-86.
[8]	张清桐,运晓静,颜德鹏,李明富,王双飞,闵斗勇. 太阳光催化木质素制备银纳米颗粒[J]. 林产化学与工业, 2019, 39(4): 35-41.
[9]	孙永昌,张冰清,刘力鸣,刘肖南,史正军. 木质素基炭材料的制备及其对Cr(Ⅵ)的吸附机制研究[J]. 林产化学与工业, 2019, 39(4): 120-128.
[10]	陈超,王傲,孙康,卢辛成,许伟,蒋剑春. 生物质原料的Ni催化石墨化研究[J]. 林产化学与工业, 2019, 39(3): 94-100.
[11]	赵存异,应文俊,史正军,杨海艳,郑志锋,杨静. 羟丙基化碱木质素的制备及其对纤维素酶水解的影响[J]. 林产化学与工业, 2019, 39(2): 109-114.
[12]	王培燕,黄元波,刘守庆,郑志锋,宁德鲁. 三聚氰胺包合法分离不饱和脂肪酸[J]. 林产化学与工业, 2019, 39(2): 115-121.
[13]	许利娜,杨小华,丁海阳,李梅,夏建陵. 氧化改性木质素磺酸钠-石墨烯复合量子点的制备及性能[J]. 林产化学与工业, 2019, 39(1): 29-34.
[14]	张昌伟,马余璐,陶冉,叶建中,王成章. 银杏叶聚戊烯醇的分离纯化及其亲水衍生物的合成[J]. 林产化学与工业, 2019, 39(1): 41-45.
[15]	李继辉,孙康,宋曜光,王傲,蒋剑春. 木质素基炭纳米片的制备及其电化学性能[J]. 林产化学与工业, 2019, 39(1): 67-74.