不同溶剂辅助碱性过氧化氢脱除木质素的研究

doi:10.3969/j.issn.0253-2417.2023.04.011

林产化学与工业 ›› 2023, Vol. 43 ›› Issue (4): 74-80.doi: 10.3969/j.issn.0253-2417.2023.04.011

不同溶剂辅助碱性过氧化氢脱除木质素的研究

朱北平¹, 焦健¹, 梁芳敏¹, 邓拥军¹, 房桂干¹^,²^,*()

1. 中国林业科学研究院林产化学工业研究所; 江苏省生物质能源与材料重点实验室; 国家林业和草原局林产化学工程重点实验室; 林木生物质低碳高效利用国家工程研究中心; 江苏省林业资源高效加工利用协同创新中心, 江苏南京 210042
2. 山东华泰纸业集团, 山东东营 257335

收稿日期:2022-05-17 出版日期:2023-08-28 发布日期:2023-08-26
通讯作者: 房桂干 E-mail:fangguigan@icifp.cn
作者简介:房桂干，研究员，博士生导师，研究领域为制浆造纸清洁生产、环保和生物质利用；E-mail: fangguigan@icifp.cn
朱北平(1992—)，男，山东济宁人，硕士生，主要从事清洁制浆技术与生物质利用研究
基金资助:
中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2021ZI001-01);泰山产业领军人才工程专项经费资助项目(tscy20200213)

Delignification by Alkaline Hydrogen Peroxide Assisted with Different Solvents

Beiping ZHU¹, Jian JIAO¹, fangmin LIANG¹, Yongjun DENG¹, Guigan FANG¹^,²^,*()

1. Institute of Chemical Industry of Forest Products, CAF; Key Lab. of Biomass Energy and Material, Jiangsu Province; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; National Engineering Research Center of Low-carbon Processing and Utilization of Forest Biomass; Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing 210042, China
2. Shandong Huatai Paper Co., Ltd., Dongying 257335, China

Received:2022-05-17 Online:2023-08-28 Published:2023-08-26
Contact: Guigan FANG E-mail:fangguigan@icifp.cn

摘要/Abstract

摘要：

为了探究木质纤维原料在不同有机溶剂辅助碱性过氧化氢条件下脱除木质素的效果，以碱性过氧化氢体系(AHP)为参照，考察了乙醇碱性过氧化氢(EAHP)、二氧六环碱性过氧化氢(DAHP)对杨木机械浆脱除木质素后的组分变化。通过高效液相色谱(HPLC)、傅里叶变换红外光谱(FI-IR)、凝胶渗透色谱(GPC)、核磁共振磷谱(³¹P NMR)表征分析了碱木质素(AL)、碱性过氧化氢木质素(AHPL)、乙醇碱性过氧化氢木质素(EAHPL)和二氧六环碱性过氧化氢木质素(DAHPL)的化学结构、分子质量和羟基含量的变化。研究结果表明：3种反应体系均导致脱木质素后物料得率不同程度降低，并导致了大量半纤维素的溶出。与AHP、DAHP相比，EAHP更有利于保存纤维素和溶出较多的木质素，木质素脱除率最高达65%。与AL相比，AHPL、EAHPL、DAHPL红外光谱峰型基本一致，均属于GS型。制备的木质素数均分子质量(M_n)最小为4 672 g/mol，分散性较好，酚羟基的量较少，但是脂肪族羟基和羧基羟基的量较高，最高值分别为14.95和1.25 mmol/g。

关键词: 碱性过氧化氢, 脱木质素, 有机溶剂

Abstract:

In order to explore the effect of delignification under different organic solvent-assisted alkaline hydrogen peroxide treatment, the composition changes of poplar mechanical pulp after lignin removal by ethanol alkaline hydrogen peroxide(EAHP) and dioxane alkaline hydrogen peroxide(DAHP) were investigated using the alkaline hydrogen peroxide system(AHP) as a reference. The chemical structure, molecular weight, and hydroxyl content of alkali lignin(AL) and alkaline hydrogen peroxide lignin(AHPL), ethanol alkaline hydrogen peroxide lignin(EAHPL) and dioxane alkaline hydrogen peroxide lignin(DAHPL) were characterized by high-performance liquid chromatography(HPLC), Fourier transforms infrared spectroscopy(FT-IR), gel-permeation chromatography(GPC), and ³¹P nuclear magnetic resonance(³¹P NMR). The results showed that the three reaction systems led to the varying degradation degrees of the material yield and the dissolution of a large number of hemicellulose. Compared with AHP and DAHP, EAHP was more conducive to preserve cellulose and dissolve more lignin, and the highest lignin removal rate reached 65%. Compared with AL, AHP, EAHPL and DAHPL possessed basically the same infrared spectral peak type, both belonging to G-S type. The minimum M_n of the prepared lignin was 4 672 g/mol with low polydispersity and low phenolic hydroxyl content, while it had higher aliphatic hydroxyl group and carboxylic acid hydroxyl group contents, with the highest contents of 14.95 and 1.25 mmol/g, respectively.

Key words: alkaline hydrogen peroxide, delignification, organic solvent

中图分类号:

TQ35

朱北平, 焦健, 梁芳敏, 邓拥军, 房桂干. 不同溶剂辅助碱性过氧化氢脱除木质素的研究[J]. 林产化学与工业, 2023, 43(4): 74-80.

Beiping ZHU, Jian JIAO, fangmin LIANG, Yongjun DENG, Guigan FANG. Delignification by Alkaline Hydrogen Peroxide Assisted with Different Solvents[J]. Chemistry and Industry of Forest Products, 2023, 43(4): 74-80.

图/表 5

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表1

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样品 sample	酶解前before enzymolysis		酶解后after enzymolysis
样品 sample	葡萄糖/% glucose	木聚糖/% xylan	M_n/(g·mol^-1)	M_w/(g·mol^-1)	M_w/M_n	葡萄糖/% glucose	木聚糖/% xylan
AHPL	3.45	7.20	6 936	13 307	1.92	0.12	—
EAHPL	0.03	5.89	4 672	6 663	1.43	0.10	0.20
DAHPL	4.65	3.96	5 976	8 533	1.43	0.11	0.25

基团 group	化学位移(δ) chemical shift	不同样品中羟基的量content of OH groups in different samples/(mmol·g^-1)
基团 group	化学位移(δ) chemical shift	AL ^[23]	AHPL	EAHPL	DAHPL
脂肪族羟基aliphatic OH	145.5-150.5	0.48	14.95	14.93	13.76
S型结构羟基5-substituted OH	140.0-144.7	2.46	0.78	0.70	0.71
G型结构羟基guaiacyl OH	138.2-140.0	0.65	0.40	0.41	0.44
H型结构羟基p-hydroxyphenyl OH	137.3-138.2	0.06	0.28	0.21	0.37
羧基羟基carboxylic acid OH	133.6-136.6	0.07	1.25	1.25	1.17
酚羟基phenolic OH	137.3-144.7	3.17	1.47	1.32	1.52

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不同溶剂辅助碱性过氧化氢脱除木质素的研究

Delignification by Alkaline Hydrogen Peroxide Assisted with Different Solvents

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