Page 61 - 《精细化工》2020年第3期

第 37 卷第 3 期 精 细 化 工 Vol.37, No.3
202 0 年 3 月 FINE CHEMICALS Mar. 2020

功能材料
酶解秸秆残渣中木质素的提取及应用

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白毓黎，张 通 ，白富栋，李澜鹏，彭绍忠，乔 凯
（中国石油化工股份有限公司 大连石油化工研究院，辽宁 大连 116045）

摘要：采用碱性乙醇法从酶解玉米秸秆残渣原料中提取木质素，考察了乙醇体积分数、温度、固液比和碱质量
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分数对木质素提取率的影响；对提取的木质素进行了 FTIR、 CNMR 及 HNMR 表征，并探索了木质素部分替
代聚己内酯二醇用于聚氨酯薄膜的合成及降解性能研究。结果表明，在体积分数 50%乙醇溶液、220 ℃、m(固)∶
V(液)(固指固体酶解残渣原料，单位 g；液指乙醇溶液体积，单位 mL)=1∶20 和质量分数 1% NaOH 溶液条件下，
提取产物中木质素质量分数为 94.1%，木质素提取率达到 93.5%；产物的羟基含量为 66.5 mg KOH/g。当添加质
量分数 27%的木质素和质量分数 44%的聚己内酯二醇与异氰酸酯制备聚氨酯薄膜时，薄膜的拉伸强度为
24.0 MPa，断裂伸长率为 224%，降解率为 3.3%。进一步添加适量葡萄糖提高聚氨酯薄膜的降解性能和耐水性
能，降低薄膜透气性，葡萄糖质量分数为 3%时薄膜 60 d 内的降解率达到 11%。
关键词：生物质；木质素；碱性乙醇；降解；聚氨酯薄膜；功能材料
中图分类号：TQ353.6 文献标识码：A 文章编号：1003-5214 (2020) 03-0479-07

Extraction and application of lignin from corn stalks
residue by enzymatic hydrolysis

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BAI Yuli, ZHANG Tong , BAI Fudong, LI Lanpeng, PENG Shaozhong, QIAO Kai
（Dalian Research Institute of Petroleum and Petrochemicals, SINOPEC, Dalian 116045, Liaoning, China）

Abstract: Lignin was extracted from fermentation residue of corn stalks by alkaline-ethanol method. The
effects of volume fraction of ethanol, temperature, residue/solvent ratio and mass fraction of alkaline on the
extraction yield of lignin were studied. The obtained lignin was characterized by Fourier transform infrared
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spectroscopy (FTIR), carbon-13 nuclear magnetic resonance ( CNMR) and proton nuclear magnetic
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resonance ( HNMR) spectroscopies. The synthesis and degradation properties of polyurethane films were
investigated by means of partial substitution of lignin for polycaprolactone glycol. The results showed that
the extraction yield of lignin reached 93.5% and the mass fraction of lignin was up to 94.1% under the
conditions of volume fraction of ethanol 50%, temperature 220 ℃, m(fermentation residue): V(solvent)=
1∶20 (g∶mL)and mass fraction of NaOH 1%. In addition, the product obtained a hydroxyl content of 66.5
mg KOH/g. When the polyurethane film was prepared from 27% (mass fraction, the same below) lignin and
44% polycaprolactone diol and isocyanate, its tensile strength, elongation at break and degradation rate
were 24.0 MPa, 224% and 3.3%, respectively. Furthermore, the appropriate addition of glucose into the
lignin-based polyurethane film could increase its biodegradation rate and water resistance, reduce
membrane permeability. The degradation rate of the film containing 3% glucose was 11.0% within 60 days.
Key words: biomass; lignin; alkaline-ethanol; degradation; polyurethane film; functional materials

木质素是由许多苯基丙烷（C9）单元结构通过 具有绿色、环保和原料可再生等优势受到广泛关注，
醚键或碳碳键连接的具有三维结构的天然高分子材 但玉米秸秆酶解发酵制备生物乙醇过程中产生大量
料，具有较好的生物降解性能。目前，生物乙醇因 废渣，如果采用适当的提取方法对残渣中的木质素

收稿日期：2019-06-05; 定用日期：2019-09-16; DOI: 10.13550/j.jxhg.20190512
基金项目：中国石油化工集团公司资助项目（SH1601、SH1711）
作者简介：白毓黎（1991—），男，助理工程师，硕士。联系人：张 通（1988—），男，工程师，E-mail：zhangtong.fshy@sinopec.com。