树脂吸附-超滤协同分离甘蔗渣碱法半纤维素

doi:10.11949/0438-1157.20201172

化工学报 ›› 2021, Vol. 72 ›› Issue (4): 2139-2147.DOI: 10.11949/0438-1157.20201172

树脂吸附-超滤协同分离甘蔗渣碱法半纤维素

杜娟^1,²(),龚志强¹,黄曹兴³,梁辰^1,²(),姚双全^1,²,刘杨^1,²

^1.广西大学轻工与食品工程学院，广西南宁 530004
^2.广西清洁化制浆造纸与污染控制重点实验室，广西南宁 530004
^3.南京林业大学林业资源高效加工利用协同创新中心，江苏南京 210037

收稿日期:2020-08-17 修回日期:2020-08-29 出版日期:2021-04-05 发布日期:2021-04-05
通讯作者: 梁辰
作者简介:杜娟（1994—），女，硕士研究生，lfdj0722@163.com
基金资助:
国家自然科学基金项目(21968004);广西自然科学基金项目(2017GXNSFBA198119)

Resin adsorption - ultrafiltration synergistic separation of alkaline extracted hemicellulose from bagasse

DU Juan^1,²(),GONG Zhiqiang¹,HUANG Caoxing³,LIANG Chen^1,²(),YAO Shuangquan^1,²,LIU Yang^1,²

^1.School of Light Industry and Food Engineering, Guangxi University, Nanning 530004, Guangxi, China
^2.Guangxi Key Laboratory of Cleaning Pulp & Papermaking and Pollution Control, Guangxi University, Nanning 530004, Guangxi, China
^3.Co-Innovation Center for Efficient Processing and Utilization of Forest Products, Nanjing Forestry University, Nanjing 210037, Jiangsu, China

Received:2020-08-17 Revised:2020-08-29 Online:2021-04-05 Published:2021-04-05
Contact: LIANG Chen

摘要/Abstract

摘要：

针对碱法提取半纤维素中木质素含量高、纯化难的问题，通过疏水树脂吸附-超滤协同处理，探讨纯化分离方式的影响。利用离子色谱（IC）、紫外分光光度计（UV）、凝胶渗透色谱（GPC）和热重量分析（TGA），对半纤维素的化学组分、分子量、热稳定性等特性进行了分析。结果表明，树脂吸附-膜超滤处理能有效脱除木质素，获得较高分子量的半纤维素，分子主链结构没有发现明显变化，热稳定性略有提高。经树脂吸附后的半纤维素侧链单元有较为明显的变化，分子量较小的半纤维素带有更多侧链木质素单元，通过苯基糖苷键（PhGlc）与碳水化合物相连，可通过树脂吸附-超滤协同处理分离出来，从而达到分离不同侧链结构的半纤维素。

关键词: 半纤维素, 木质素, 膜分离, XAD树脂, 甘蔗渣, 分离纯化

Abstract:

Aiming at the problem of high lignin content in the hemicellulose extracted by alkaline method and difficult purification, the hydrophobic resin adsorption-ultrafiltration is used for cooperative treatment. In this study, the effect of different methods on the purification and separation of hemicellulose was explored through the method of macroporous resin adsorption and ultrafiltration technology. Ion chromatography (IC), ultraviolet spectrophotometer (UV), gel permeation chromatography (GPC) and thermogravimetric analysis (TGA) were used to analyze chemical composition, molecular weight, thermal stability and other characteristics of the separated and purified hemicellulose. The results show that the resin adsorption-membrane ultrafiltration treatment can effectively remove lignin and obtain hemicellulose with higher molecular weight. No significant changes are found in the molecular backbone structure, and the thermal stability is slightly improved. The side chain unit of hemicellulose after resin adsorption has obvious changes. The hemicellulose with smaller molecular weight has more side chain lignin unit structure, and is mostly connected to carbohydrates by phenyl glycosidic bonds (PhGlc). Through the cooperative treatment of resin adsorption and ultrafiltration, hemicellulose with different side chain units and lignin content can be obtained, which provides a basis for expanding the utilization value of hemicellulose.

Key words: hemicellulose, lignin, membrane separation, XAD resin, bagasse, separation and purification

中图分类号:

TQ 353

杜娟, 龚志强, 黄曹兴, 梁辰, 姚双全, 刘杨. 树脂吸附-超滤协同分离甘蔗渣碱法半纤维素[J]. 化工学报, 2021, 72(4): 2139-2147.

DU Juan, GONG Zhiqiang, HUANG Caoxing, LIANG Chen, YAO Shuangquan, LIU Yang. Resin adsorption - ultrafiltration synergistic separation of alkaline extracted hemicellulose from bagasse[J]. CIESC Journal, 2021, 72(4): 2139-2147.

图/表 11

图1 不同pH酸沉淀后的甘蔗渣提取液

Fig.1 Bagasse extracts after acid precipitation with different pH

图2 超滤后甘蔗渣提取液

Fig.2 Bagasse extracts after ultrafiltration

图3 吸附-超滤后提取液

Fig.3 Extracts after adsorption - ultrafiltration

图4 不同提取液中残余木质素含量

Fig.4 Residual lignin content in different extracts

表1 超滤后半纤维素组分

Table 1 Hemicellulose components after ultrafiltration

糖组分	Hu₂/%	Hu₃/%	Hu₄/%	Hu₅/%	Hu₆/%
木糖	62.81	56.14	53.16	50.25	39.56
阿拉伯糖	14.36	14.78	14.96	11.98	11.58
葡萄糖	3.74	2.76	3.03	3.14	2.44
半乳糖	3.81	4.17	3.38	3.32	3.39
甘露糖	2.01	1.43	1.58	2.14	1.29
木质素	1.51	2.39	3.77	5.82	17.06
糠醛	4.77	4.32	4.12	3.99	2.94
甲酸	10.05	12.58	10.05	9.27	8.68
乙酸	3.10	3.44	3.91	2.75	3.14

图5 半纤维素总糖含量

Fig.5 Total sugar content of hemicellulose

表2 吸附-超滤的半纤维素组分

Table 2 Hemicellulose components after adsorption-ultrafiltration

糖组分	Hau₂/%	Hau₃/%	Hau₄/%	Hau₅/%	Hau₆/%
木糖	56.97	56.93	51.61	52.96	38.70
阿拉伯糖	14.00	11.11	11.07	9.06	11.58
葡萄糖	3.49	2.46	3.63	2.86	2.54
半乳糖	3.78	1.70	3.69	1.94	3.39
甘露糖	1.92	1.86	2.66	2.27	1.69
木质素	1.39	1.86	2.18	2.53	14.86
糠醛	4.47	4.31	3.87	3.93	2.87
甲酸	11.49	15.47	11.37	14.51	9.36
乙酸	3.65	4.51	3.83	2.96	2.48

图6 半纤维素分支化程度

Fig.6 Degree of branching of hemicellulose

表3 半纤维素分子量

Table 3 Molecular weight of hemicellulose

Sample	M_w	M_n	M_w/M_n
Hu₂	4.57×10⁴	4.11×10⁴	1.11
Hu₆	6.78×10⁴	3.92×10⁴	1.73
Hau₂	8.54×10⁴	5.16×10⁴	1.65
Hau₆	6.47×10⁴	4.48×10⁴	1.44

图7 半纤维素的热重分析

Fig.7 Thermogravimetric analysis of hemicellulose

图8 半纤维素的二维核磁谱图

Fig.8 2D NMR spectrum of hemicellulose

参考文献 35

1	Sun S L, Wen J L, Ma M G, et al. Successive alkali extraction and structural characterization of hemicelluloses from sweet sorghum stem[J]. Carbohydrate Polymers, 2013, 92(2): 2224-2231.
2	Giummarella N, Pu Y Q, Ragauskas A J, et al. A critical review on the analysis of lignin carbohydrate bonds[J]. Green Chemistry, 2019, 21(7): 1573-1595.
3	孙世荣, 郭祎, 岳金权. 秸秆半纤维素的分离纯化及化学改性研究进展[J]. 天津造纸, 2016, 38(1): 7-12.
	Sun S R, Guo Y, Yue J Q. Straw hemicellulose research progress on isolation, purification and chemical modification[J]. Tianjin Paper Making, 2016, 38(1): 7-12.
4	Del Rio J C, Rencoret J, Prinsen P, et al. Structural characterization of wheat straw lignin as revealed by analytical pyrolysis, 2D-NMR, and reductive cleavage methods[J]. Journal of Agricultural and Food Chemistry, 2012, 60(23): 5922-5935.
5	Pandey A, Soccol C R, Nigam P, et al. Biotechnological potential of agro-industrial residues(Ⅰ): Sugarcane bagasse[J]. Bioresource Technology, 2000, 74(1): 69-80.
6	Sahlgren C, Meinander A, Zhang H, et al. Tailored approaches in drug development and diagnostics:from molecular design to biological model systems[J]. Advanced Healthcare Materials, 2017, 6(21): 1700258.
7	Berglund L, Forsberg F, Jonoobi M, et al. Promoted hydrogel formation of lignin-containing arabinoxylan aerogel using cellulose nanofibers as a functional biomaterial[J]. RSC Advances, 2018, 8(67): 38219-38228.
8	Chen G G, Qi X M, Guan Y, et al. High strength hemicellulose-based nanocomposite film for food packaging applications [J]. ACS Sustainable Chemistry & Engineering, 2016, 4(4): 1985-1993.
9	van Heiningen A. Converting a kraft pulp mill into an integrated forest biorefinery[J]. Pulp & Paper-Canada, 2006, 107(6): 38-43.
10	李亚辉, 雷以超, 周伦. 蔗渣碱抽提半纤维素的超滤浓缩及分离和表征[J]. 造纸科学与技术, 2018, 37(2): 32-37.
	Li Y H, Lei Y C, Zhou L. Isolation and characterization of hemicellulose obtained from alkali-extracted liquor of bagasse by ultrafiltration[J]. Paper Science & Technology, 2018, 37(2): 32-37.
11	雷以超, 王锐金, 蒋兴林, 等. 蔗渣的低固形物烧碱-AQ制浆[C]//中国造纸学会第十七届学术年会. 北京: 中国造纸学会, 2016:74-77.
	Lei Y C, Wang R J, Jiang X L, et al. Lo-solids soda AQ pulping of bagasse[C]//Proceedings of the 17th Annual Conference of CTAPI. Beijing: China Technical Association of the Paper Industry (CTAPI), 2016:74-77.
12	Arnaud B, Durand S, Fanuel M, et al. Imaging study by mass spectrometry of the spatial variation of cellulose and hemicellulose structures in corn stalks[J]. Journal of Agricultural and Food Chemistry, 2020, 68(13): 4042-4050.
13	Maki-Arvela P, Salmi T, Holmbom B, et al. Synthesis of sugars by hydrolysis of hemicelluloses—a review[J]. Chemical Reviews, 2011, 111(9): 5638-5666.
14	Peng F, Peng P, Xu F, et al. Fractional purification and bioconversion of hemicelluloses[J]. Biotechnology Advances, 2012, 30(4): 879-903.
15	Jiang H, Chen Q Q, Ge J H, et al. Efficient extraction and characterization of polymeric hemicelluloses from hybrid poplar[J]. Carbohydrate Polymers, 2014, 101: 1005-1012.
16	Farhat W, Venditti R, Quick A, et al. Hemicellulose extraction and characterization for applications in paper coatings and adhesives[J]. Industrial Crops and Products, 2017, 107: 370-377.
17	Sun J X, Sun X F, Sun R C, et al. Fractional extraction and structural characterization of sugarcane bagasse hemicelluloses[J]. Carbohydrate Polymers, 2004, 56(2): 195-204.
18	You X, Wang X, Liang C, et al. Purification of hemicellulose from sugarcane bagasse alkaline hydrolysate using an aromatic-selective adsorption resin[J]. Carbohydrate Polymers, 2019, 225: 115216.
19	Egüés I, Sanchez C, Mondragon I, et al. Separation and purification of hemicellulose by ultrafiltration[J]. Industrial & Engineering Chemistry Research, 2012, 51(1): 523-530.
20	Oriez V, Peydecastaing J, Pontalier P Y. Separation of sugarcane bagasse mild alkaline extract components by ultrafiltration – membrane screening and effect of filtration parameters[J]. Process Biochemistry, 2019, 78: 91-99.
21	Persson T, Jonsson A. Isolation of hemicelluloses by ultrafiltration of thermomechanical pulp mill process water—influence of operating conditions[J]. Chemical Engineering Research & Design, 2010, 88(12): 1548-1554.
22	Westerberg N, Sunner H, Helander M, et al. Separation of galactoglucomannans, lignin and lignin-carbohydrate complexes from hot-water-extracted Norway spruce by cross-flow filtration and adsorption chromatography[J]. BioResources, 2012, 7(4): 4501-4516.
23	Zhou Y F, Wang L L, Chen L C, et al. Enrichment and separation of steroidal saponins from the fibrous roots of Ophiopogon japonicus using macroporous adsorption resins[J]. RSC Advances, 2019, 9(12): 6689-6698.
24	Koivula E, Kallioinen M, Sainio T, et al. Enhanced membrane filtration of wood hydrolysates for hemicelluloses recovery by pretreatment with polymeric adsorbents[J]. Bioresource Technology, 2013, 143(17): 275-281.
25	Narron R H, Chang H M, Jameel H, et al. Soluble lignin recovered from biorefinery pretreatment hydrolyzate characterized by lignin-carbohydrate complexes[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(11): 10763-10771.
26	Peng F, Ren J L, Xu F, et al. Comparative study of hemicelluloses obtained by graded ethanol precipitation from sugarcane bagasse[J]. Journal of Agricultural and Food Chemistry, 2009, 57(14): 6305-6317.
27	Giummarella N, Lawoko M. Structural insights on recalcitrance during hydrothermal hemicellulose extraction from wood[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(6): 5156-5165.
28	Chen W J, Zhao B C, Cao X F, et al. Structural features of alkaline dioxane lignin and residual lignin from Eucalyptus grandis x E. urophylla[J]. Journal of Agricultural and Food Chemistry, 2019, 67(3): 968-974.
29	Thuvander J, Oinonen P, Jonsson A S. Enzymatic treatment of hemicelluloses and lignin isolated from thermomechanical pulp mill process water[J]. Chemical Engineering Journal, 2016, 296:141-145.
30	Naidu D S, Hlangothi S P, John M J. Bio-based products from xylan: a review[J]. Carbohydrate Polymers, 2018, 179: 28-41.
31	Bian J, Peng F, Peng X P, et al. Isolation of hemicelluloses from sugarcane bagasse at different temperatures: structure and properties[J]. Carbohydrate Polymers, 2012, 88(2): 638-645.
32	Yang H P, Yan R, Chen H P, et al. Characteristics of hemicellulose, cellulose and lignin pyrolysis[J]. Fuel, 2007, 86(12/13): 1781-1788.
33	Bhagia S, Pu Y, Evans B R, et al. Hemicellulose characterization of deuterated switchgrass[J]. Bioresource Technology, 2018, 269: 567-570.
34	Zhang X M, Meng L Y, Xu F, et al. Pretreatment of partially delignified hybrid poplar for biofuels production: characterization of organosolv hemicelluloses[J]. Industrial Crops and Products, 2011, 33(2): 310-316.
35	Sun R, Sun X F, Tomkinson J. Hemicelluloses and their derivatives[J]. ACS Symposium Series, 2003, 864: 2-22.

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树脂吸附-超滤协同分离甘蔗渣碱法半纤维素

Resin adsorption - ultrafiltration synergistic separation of alkaline extracted hemicellulose from bagasse

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