木质素衍生介孔碳固体酸制备及催化木聚糖制备糠醛  

Preparation of lignin-derived mesoporous carbon solid acid and its catalytic synthesis of furfural from xylan

作　　者：周翠瑶 朱沛雯 邓晓雅 陶昱恒 王利群[1] 卿青[1] ZHOU Cuiyao;ZHU Peiwen;DENG Xiaoya;TAO Yuheng;WANG Liqun;QING Qing(School of Biological and Food Engineering,Changzhou University,Changzhou 213164,Jiangsu,China)

机构地区：[1]常州大学生物与食品工程学院,江苏常州213164

出　　处：《精细化工》2024年第10期2258-2265,共8页Fine Chemicals

基　　金：江苏省青蓝工程项目(2022);江苏省自然科学基金项目(BK20230636);常州市科技计划项目(CJ20220217)。

摘　　要：以丙酮/水混合溶剂提取玉米秸秆得到的木质素和间苯三酚为碳前体、乙二醛为交联剂,采用溶剂蒸发诱导自组装法制备了介孔碳(MC),再经磺化合成了木质素衍生介孔碳固体酸(MC-SO_(3)H)。采用SEM、XPS、元素分析仪、N2吸附-脱附和酸度测定对催化剂进行了表征,以木聚糖转化率和糠醛产率为指标,考察了MC-SO_(3)H催化降解木聚糖制备糠醛的反应条件,探究了MC-SO_(3)H失活的原因。结果表明,MC-SO_(3)H具有120.74 cm^(2)/g的介孔比表面积和4.15 nm的平均孔径;在1.0 g木聚糖、1.0 g MC-SO_(3)H、30 mLγ-戊内酯为溶剂、反应温度180℃、反应时间10 min的最佳反应条件下,木聚糖转化率和糠醛产率分别为90.0%和79.5%。MC-SO_(3)H的总酸度(2.06 mmol/g)和—SO_(3)H酸度(0.82 mmol/g)是其催化活性的主要来源,未反应的木聚糖及反应过程中形成的降解物等在催化剂上附着造成了MC-SO_(3)H的总酸度和—SO_(3)H酸度的下降,是其失活的主要原因。在以木糖代替木聚糖评价MC-SO_(3)H稳定性的实验中,重复使用4次后,木糖转化率和糠醛产率仍可达89.5%和66.8%。Lignin-derived mesoporous carbon(MC-SO_(3)H)solid acid was synthesized from sulfonation of mesoporous carbon,which was prepared by solvent evaporation-induced self-assembly method using lignin and phloroglucinol obtained from corn stalk extracted with acetone/water as carbon precursors and glyoxal as crosslinking agent,and characterized by SEM,XPS,elemental analyzer,N_(2)adsorption-desorption and acidity determination.With xylan conversion and furfural yield as indexes,the reaction conditions for MC-SO_(3)H catalytic degradation of xylan to produce furfural were investigated,while the reason for MC-SO_(3)H inactivation was further explored.The results showed that MC-SO_(3)H exhibited a mesoporous surface area of 120.74 m^(2)/g and an average pore size of 4.15 nm.Under the optimal reaction conditions of 1.0 g xylan,1.0 g MC-SO_(3)H,30 mLγ-valerolactone as solvent,reaction temperature 180℃and reaction time 10 min,the xylan conversion and furfural yield reached 90.0%and 79.5%,respectively.The total acidity of MC-SO_(3)H(2.06 mmol/g)and—SO_(3)H acidity(0.82 mmol/g)were the main sources of its catalytic activity.The main reason for the catalyst inactivation was attributed to the adhesion of unreacted xylans and degraded substances formed during the reaction on the catalyst,resulting in the decrease of total acidity and—SO_(3)H acidity.When xylose instead of xylan was used,the xylose conversion and furfural yield could still reach 89.5%and 66.8%after repeated use for 4 times,indicating the good stability of MC-SO_(3)H.

关 键 词：木质素 介孔碳 固体酸 木聚糖 糠醛 催化技术 

分 类 号：TQ032.4[化学工程] TQ251.1