有机溶剂自催化和协同预处理促进木质纤维原料酶解研究进展

doi:10.3969/j.issn.1673-5854.2020.06.012

摘要/Abstract

摘要：

木质纤维原料资源储量丰富且可再生，适当的预处理可打破纤维原料细胞壁的天然抗降解屏障，促使其在后续加工中有效转化为低聚糖或可发酵糖，用于高效制备生物乙醇。有机溶剂预处理是有效的预处理方法之一，在提高酶解效率的同时可有效分离木质素，实现纤维原料各组分的高效利用。根据是否添加催化剂，有机溶剂预处理可分为自催化预处理和催化剂-有机溶剂协同预处理2种方式。木质素是限制木质纤维原料酶解的重要因素之一，本文简单介绍了有机溶剂种类、催化剂类型对木质素脱除的影响，并概括性探讨了有机溶剂和催化剂协同的反应机理。

关键词: 木质纤维, 有机溶剂, 预处理, 催化剂, 酶解

Abstract:

The lignocellulosic materials are renewable and abundant in resource, and the natural anti-degradation barrier of the cell wall of lignocellulosic materials could be broken through appropriate pretreatment, which promote its effective conversion to oligosaccharides or fermentable sugars in subsequent processing, and then efficiently preparing bioethanol. Organic solvent pretreatment is considered to be one of the effective pretreatment methods. It can not only improve the enzymatic hydrolysis efficiency but also effectively separate the lignin, which provides the efficient utilization of the components in the lignocellulose. Organic solvent pretreatment can be divided into autocatalytic pretreatment and catalyst-organic solvent synergistic pretreatment, according to adding catalyst or not. Lignin is one of the important factors that limiting the enzymatic hydrolysis of lignocellulosic materials. This paper reviewed the effects of type of organic solvents and catalysts on the removal of lignin. The reaction mechanism of catalyst-organic solvent co-pretreatment also was reviewed.

Key words: lignocellulose, organic solvent, pretreatment, catalyst, enzymatic hydrolysis

中图分类号:

TQ352

阚玉娜, 陈冰炜, 翟胜丞, 潘明珠, 梅长彤. 有机溶剂自催化和协同预处理促进木质纤维原料酶解研究进展[J]. 生物质化学工程, 2020, 54(6): 74-82.

Yuna KAN, Bingwei CHEN, Shengcheng ZHAI, Mingzhu PAN, Changtong MEI. Progress in Organic Solvent Autocatalytic and Synergistic Pretreatment to Promote the Enzymatic Hydrolysis of Lignocellulosic Materials[J]. Biomass Chemical Engineering, 2020, 54(6): 74-82.

图/表 2

表1

图1

参考文献 62

1	FATMA S , HAMEED A , NOMAN , et al. Lignocellulosic biomass:A sustainable bioenergy source for future[J]. Protein and Peptide Letters, 2018, 25 (2): 148- 163. doi: 10.2174/0929866525666180122144504
2	CHEN H Y , LIU J B , CHANG X , et al. A review on the pretreatment of lignocellulose for high-value chemicals[J]. Fuel Processing Technology, 2017, 160, 196- 206. doi: 10.1016/j.fuproc.2016.12.007
3	HUIJGEN W J J , SMIT A T , REITH J H , et al. Catalytic organosolv fractionation of willow wood and wheat straw as pretreatment for enzymatic cellulose hydrolysis[J]. Journal of Chemical Technology and Biotechnology, 2011, 86 (11): 1428- 1438. doi: 10.1002/jctb.2654
4	ZHOU Z Y , LEI F H , LI P F , et al. Lignocellulosic biomass to biofuels and biochemicals:A comprehensive review with a focus on ethanol organosolv pretreatment technology[J]. Biotechnology and Bioengineering, 2018, 115 (11): 2683- 2702. doi: 10.1002/bit.26788
5	GAO D H , HAARMEYER C , BALAN V , et al. Lignin triggers irreversible cellulase loss during pretreated lignocellulosic biomass saccharification[J]. Biotechnology for Biofuels, 2014, 7 (1): 175- 188.
6	LU X Q , ZHENG X J , LI X Z , et al. Adsorption and mechanism of cellulase enzymes onto lignin isolated from corn stover pretreated with liquid hot water[J]. Biotechnology for Biofuels, 2016, 9 (1): 118- 130.
7	TANG C L , CHEN Y J , LIU J , et al. Sustainable biobutanol production using alkali-catalyzed organosolv pretreated cornstalks[J]. Industrial Crops and Products, 2017, 95, 383- 392. doi: 10.1016/j.indcrop.2016.10.048
8	SUN F F , WANG L , HONG J P , et al. The impact of glycerol organosolv pretreatment on the chemistry and enzymatic hydrolyze ability of wheat straw[J]. Bioresource Technology, 2015, 187, 354- 361. doi: 10.1016/j.biortech.2015.03.051
9	HUIJGEN W J J , REITH J H , UIL H D . Pretreatment and fractionation of wheat straw by an acetone-based organosolv process[J]. Industrial and Engineering Chemistry Research, 2010, 49 (20): 10132- 10140. doi: 10.1021/ie101247w
10	WILDSCHUT J , SMIT A T , REITH J H , et al. Ethanol-based organosolv fractionation of wheat straw for the production of lignin and enzymatically digestible cellulose[J]. Bioresource Technology, 2013, 135, 58- 66. doi: 10.1016/j.biortech.2012.10.050
11	LIU J , LI R Q , SHUAI L , et al. Comparison of liquid hot water(LHW) and high boiling alcohol/water(HBAW) pretreatments for improving enzymatic saccharification of cellulose in bamboo[J]. Industrial Crops & Products, 2017, 107 (1): 139- 148.
12	洪嘉鹏.甘蔗渣的常压甘油有机溶剂短时预处理及其纤维素乙醇浓醪发酵[D].无锡:江南大学, 2017.
13	岳军, 姚兰, 赵建, 等. 木糖渣的有机溶剂预处理及酶解性能[J]. 化工学报, 2011, 62 (11): 3256- 3262.
14	KOO B W , PARK N , JEONG H S , et al. Characterization of by-products from organosolv pretreatments of yellow poplar wood(Liriodendron tulipifera) in the presence of acid and alkali catalysts[J]. Journal of Industrial and Engineering Chemistry, 2011, 17 (1): 18- 24. doi: 10.1016/j.jiec.2010.10.003
15	PARK N , KIM H Y , KOO B W . Organosolv pretreatment with various catalysts for enhancing enzymatic hydrolysis of pitch pine(Pinus rigida)[J]. Bioresource Technology, 2010, 101 (18): 7046- 7053. doi: 10.1016/j.biortech.2010.04.020
16	CHENG F C , ZHAO X , HU Y C . Lignocellulosic biomass delignification using aqueous alcohol solutions with the catalysis of acidic ionic liquids:A comparison study of solvents[J]. Bioresource Technology, 2018, 249, 969- 976. doi: 10.1016/j.biortech.2017.10.089
17	陈冰炜, 阚玉娜, 袁诚, 等. 乙醇预处理对芦竹细胞壁的影响及荧光可视化分析[J]. 林业工程学报, 2019, 4 (4): 59- 65.
18	YUAN W , GONG Z W , WANG G H , et al. Alkaline organosolv pretreatment of corn stover for enhancing the enzymatic digestibility[J]. Bioresource Technology, 2018, 265, 464- 470. doi: 10.1016/j.biortech.2018.06.038
19	RAITA M , DENCHOKEPRAGUY N , CHAMPRED V , et al. Effects of alkaline catalysts on acetone-based organosolv pretreatment of rice straw[J]. 3 Biotrch, 2017, 7 (5): 340- 350.
20	ZHANG K , PEI Z J , WANG D H . Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals:A review[J]. Bioresource Technology, 2016, 199, 21- 33. doi: 10.1016/j.biortech.2015.08.102
21	HU F , RAGAUSKAS A . Pretreatment and lignocellulosic chemistry[J]. Bioenergy Research, 2012, 5 (4): 1043- 1066. doi: 10.1007/s12155-012-9208-0
22	HAGE R E , BROSSE N , SANNIGRAHI P , et al. Effects of process severity on the chemical structure of Miscanthus ethanol organosolv lignin[J]. Polymer Degradation and Stability, 2010, 95 (6): 997- 1003. doi: 10.1016/j.polymdegradstab.2010.03.012
23	ZHAO X B , LI S M , WU R C . Organosolv fractionating pre-treatment of lignocellulosic biomass for efficient enzymatic saccharification:Chemistry, kinetics, and substrate structures[J]. Biofuels, Bioproducts and Biorefining, 2017, 11 (3): 567- 590. doi: 10.1002/bbb.1768
24	WANG Q , CHEN K F , LI J , et al. The solubility of lignin from bagasse in a 1, 4-butanediol/water system[J]. Bioresources, 2011, 6 (3): 3034- 3043.
25	QUESADA-MEDINA J , LÓPEZ-CREMADES F J , OLIVARES-CARRILLO P . Organosolv extraction of lignin from hydrolyzed almond shells and application of the delta-value theory[J]. Bioresource Technology, 2010, 101 (21): 8252- 8260. doi: 10.1016/j.biortech.2010.06.011
26	WU X X , HUANG C , ZHAI S C , et al. Improving enzymatic hydrolysis effciency of wheat straw through sequential autohydrolysis and alkaline post-extraction[J]. Bioresource Technology, 2018, 251, 374- 380. doi: 10.1016/j.biortech.2017.12.066
27	RABEMANOLONTSOA H , SAKA S . Various pretreatments of lignocellulosics[J]. Bioresource Technology, 2016, 199, 83- 91. doi: 10.1016/j.biortech.2015.08.029
28	许成功, 崔金龙, 陈志伟, 等. 热水预处理提取半纤维素及其还原糖的研究进展[J]. 生物质化学工程, 2019, 53 (3): 59- 66.
29	KUMAR P , BARRETT D M , DELWICHE M J , et al. Methods for pretreatment of lignocellulosic biomass for efficient hydrolysis and biofuel production[J]. Industrial and Engineering Chemistry Research, 2009, 48 (8): 3713- 3729. doi: 10.1021/ie801542g
30	TAN X S , ZHANG Q , WANG W , et al. Comparison study of organosolv pretreatment on hybrid Pennisetum for enzymatic saccharification and lignin isolation[J]. Fuel, 2019, 249, 334- 340. doi: 10.1016/j.fuel.2019.03.117
31	CHEN H M , ZHAO J , HU T H , et al. A comparison of several organosolv pretreatments for improving the enzymatic hydrolysis of wheat straw:Substrate digestibility, fermentability and structural features[J]. Applied Energy, 2015, 150, 224- 232. doi: 10.1016/j.apenergy.2015.04.030
32	陈红梅, 赵雪冰, 刘德华. 乙醇预处理麦秆的酶解性能研究[J]. 生物加工过程, 2014, 12 (1): 1- 7.
33	夏青, 田彦, 姚兰, 等. 乙醇预处理前后玉米秸秆半纤维素的提取及性质研究[J]. 中国造纸学报, 2015, 30 (2): 12- 17.
34	TAHERZADEH M J , KARIMI K . Pretreatment of lignocellulosic wastes to improve ethanol and biogas production:A review[J]. Molecular Sciences, 2008, 9 (9): 1621- 1651. doi: 10.3390/ijms9091621
35	PARK Y C , KIM T H , KIM J S . Effect of organosolv pretreatment on mechanically pretreated biomass by use of concentrated ethanol as the solvent[J]. Biotechnology and Bioprocess Engineering, 2017, 22 (4): 431- 439.
36	HALLAC B B , PU Y Q , RAGAUSKAS A J . Chemical transformations of Buddleja davidii lignin during ethanol organosolv pretreatment[J]. Energy and Fuels, 2010, 24 (2): 2723- 2732.
37	WEN J L , XUE B L , SUN S L , et al. Quantitative structural characterization and thermal properties of birch lignins after auto-catalyzed organosolv pretreatment and enzymatic hydrolysis[J]. Journal of Chemical Technology and Biotechnology, 2013, 88 (9): 1663- 1671. doi: 10.1002/jctb.4017
38	RIO L F D , CHANDRA R P , SADDLER J N . The effect of varying organosolv pretreatment chemicals on the physicochemical properties and cellulolytic hydrolysis of mountain pine beetle-killed lodgepole pine[J]. Applied Biochemistry and Biotechnology, 2010, 161 (1): 1- 21.
39	TERAMURA H , SASAKI K , OSHIMA T , et al. Effective usage of sorghum bagasse optimization of organosolv pretreatment using 25% 1-butanol and subsequent nanofiltration membrane separation[J]. Bioresource Technology, 2018, 252, 157- 164. doi: 10.1016/j.biortech.2017.12.100
40	TERAMURA H , SASAKI K , OSHIMA T , et al. Organosolv pretreatment of sorghum bagasse using a low concentration of hydrophobic solvents such as 1-butanol or 1-pentanol[J]. Biotechnology for Biofuels, 2016, 9 (1): 27- 38.
41	ZHAO X B , CHENG K K , LIU D H . Organosolv pretreatment of lignocellulosic biomass for enzymatic hydrolysis[J]. Applied Microbiology and Biotechnology, 2009, 82 (5): 815- 827. doi: 10.1007/s00253-009-1883-1
42	KISHIMOTO T , UEKI A , SANO Y . Delignification mechanism during high-boiling solvent pulping:Part 3.Structural changes in lignin analyzed by ¹³C-NMR spectroscopy[J]. Holzforschung, 2003, 57 (6): 602- 610. doi: 10.1515/HF.2003.091
43	王亮, 刘建权, 张喆, 等. 常压甘油自催化预处理麦草浓醪发酵纤维素乙醇[J]. 生物工程学报, 2015, 31 (10): 1468- 1483.
44	HⅡ K L , YEAP S P , MASHITAH M D . Pretreatment of pressed pericarp fibers(PPF) using alcohols as solvent to increase the accessibility of cellulose for cellulase production[J]. Pournal of the Korean Society for Applied Biological Chemistry, 2012, 55 (4): 507- 514. doi: 10.1007/s13765-012-2015-7
45	SHI J H , LIU J , LI M , et al. Acid-free ethanol-water pretreatment with low ethanol concentration for robust enzymatic saccharification of cellulose in bamboo[J]. Bioenergy Research, 2018, 11 (3): 665- 676.
46	YÁÑEZ-S M , MATSUHIRO B , NUÑEZ C , et al. Physicochemical characterization of ethanol organosolv lignin(EOL) from Eucalyptus globulus:Effect of extraction conditions on the molecular structure[J]. Polymer Degradation and Stability, 2014, 110, 184- 194. doi: 10.1016/j.polymdegradstab.2014.08.026
47	NI Y , HU Q . Alcell^® lignin solubility in ethanol-water mixtures[J]. Journal of Applied Polymer Science, 1995, 57 (12): 1441- 1446. doi: 10.1002/app.1995.070571203
48	SUN Y C , WEN J L , XU F , et al. Structural and thermal characterization of hemicelluloses isolated by organic solvents and alkaline solutions from Tamarix austromongolica[J]. Bioresource Technology, 2011, 102 (10): 5947- 5951. doi: 10.1016/j.biortech.2011.03.012
49	SMIT A , HUIJGEN W . Effective fractionation of lignocellulose in herbaceous biomass and hardwood using a mild acetone organosolv process[J]. Green Chemistry, 2017, 19 (22): 5505- 5514. doi: 10.1039/C7GC02379K
50	SCHUTYSER W , RENDER T , BOSCH S V D , et al. Chemicals from lignin:An interplay of lignocellulose fractionation, depolymerisation, and upgrading[J]. Chemical Society Reviews, 2018, 47 (3): 852- 908. doi: 10.1039/C7CS00566K
51	CHEN B W , WANG X Z , LENG W Q , et al. Spectroscopic/microscopic elucidation for chemical changes during acid pretreatment on Arundo donax[J]. Journal of Bioresources and Bioproducts, 2019, 4 (3): 192- 199.
52	HAGE R E , PERRIN D , BROSSE N . Effect of the pre-treatment severity on the antioxidant properties of ethanol organosolv Miscanthus×giganteus lignin[J]. Natural Resources, 2012, 3 (2): 29- 34. doi: 10.4236/nr.2012.32005
53	安艳霞.基于胆碱离子液体的木质纤维素预处理酶解及其机制的研究[D].广州:华南理工大学, 2016.
54	SWATLOSKI R P , SPEAR S K , HOLBREY J D , et al. Dissolution of cellose with ionic liquids[J]. Journal of the American Chemical Society, 2002, 124 (18): 4974- 4975. doi: 10.1021/ja025790m
55	PU Y Q , JIANG N , ARTHUR J R . Ionic liquid as a green solvent for lignin[J]. Journal of Wood Chemistry and Technology, 2007, 27 (1): 23- 33.
56	闭帅珠, 彭林才, 陈克利. 蔗渣纤维素乙醇的预处理技术研究进展[J]. 生物质化学工程, 2016, 50 (2): 53- 60.
57	YAWALATA D , PASZNER L . Anionic effect in high concentration alcohol organosolv pulping[J]. Holzforschung, 2004, 58 (1): 1- 6. doi: 10.1515/HF.2004.001
58	ZHANG H D , FAN M S , LI X , et al. Enhancing enzymatic hydrolysis of sugarcane bagasse by ferric chloride catalyzed organosolv pretreatment and Tween 80[J]. Bioresource Technology, 2018, 258, 295- 301. doi: 10.1016/j.biortech.2018.03.004
59	ZHANG H D , ZHANG S S , YUAN H Y , et al. FeCl₃-catalyzed ethanol pretreatment of sugarcane bagasse boosts sugar yields with low enzyme loadings and short hydrolysis time[J]. Bioresource Technology, 2018, 249, 395- 401. doi: 10.1016/j.biortech.2017.10.053
60	TANG C L , SHAN J Q , CHEN Y J , et al. Organic amine catalytic organosolv pretreatment of corn stover for enzymatic saccharification and high-quality lignin[J]. Bioresource Technology, 2017, 232, 222- 228. doi: 10.1016/j.biortech.2017.02.041
61	WANG K , YANG H Y , GUO S H , et al. Organosolv fractionation process with various catalysts for improving bioconversion of triploid poplar[J]. Process Biochemistry, 2012, 47 (10): 1503- 1509. doi: 10.1016/j.procbio.2012.06.002
62	ZHONG L X , ZHANG X , TANG C L , et al. Hydrazine hydrate and organosolv synergetic pretreatment of corn stover to enhance enzymatic saccharification and co-production of high-quality antioxidant lignin[J]. Bioresource Technology, 2018, 268, 677- 683. doi: 10.1016/j.biortech.2018.08.063

预处理方式 pretreatment methods	原料 raw material	有机溶剂 organic solvent		温度/℃ temperature	酶解效率/% enzymatic digestibility	参考文献 references
预处理方式 pretreatment methods	原料 raw material	类型 type	用量/% dosage	温度/℃ temperature	酶解效率/% enzymatic digestibility	参考文献 references
自催化 auto-catalyzed	麦草wheat straw	甘油glycerinum	70	220	90	^[8]
	麦草wheat straw	丙酮acetone	50	205	87	^[9]
	麦草wheat straw	乙醇ethanol	50	210	85	^[10]
	毛竹Moso bamboo	丁二醇butanediol	20	200	82.3	^[11]
	蔗渣bagasse	甘油glycerinum	70	220	67	^[12]
酸催化 acid-catalyzed	麦草wheat straw	乙醇ethanol	50	190	89.5	^[10]
	玉米秸秆corn stover	乙醇ethanol	50	200	80.2	^[13]
	鹅掌楸yellow poplar	乙醇ethanol	50	130	77.3	^[14]
	松木pine	乙醇ethanol	50	180	57	^[15]
	椰壳Coir	丁二醇butanediol	80	200	79.4	^[16]
碱催化 alkali-catalyzed	玉米秸秆corn stover	乙醇ethanol	60	110	83.7	^[7]
	鹅掌楸yellow poplar	乙醇ethanol	50	160	65	^[14]
	松木pine	乙醇ethanol	50	210	85.4	^[15]
	芦竹giant reed	乙醇ethanol	70	90	49.4	^[17]
	玉米秸秆corn stover	甲醇methanol	60	50	83.7	^[18]
	稻草straw	丙酮acetone	80	80	93	^[19]
	蔗渣bagasse	甘油glycerinum	70	240	90	^[12]

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