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离子液体[BMIM]Cl与H5PV2Mo10O40双效催化降解麦草碱木质素的研究

刘晓乐 任世学 侯莲霞 李淑君

刘晓乐, 任世学, 侯莲霞, 李淑君. 离子液体[BMIM]Cl与H5PV2Mo10O40双效催化降解麦草碱木质素的研究[J]. 北京林业大学学报, 2017, 39(5): 117-124. doi: 10.13332/j.1000-1522.20160399
引用本文: 刘晓乐, 任世学, 侯莲霞, 李淑君. 离子液体[BMIM]Cl与H5PV2Mo10O40双效催化降解麦草碱木质素的研究[J]. 北京林业大学学报, 2017, 39(5): 117-124. doi: 10.13332/j.1000-1522.20160399
LIU Xiao-le, REN Shi-xue, HOU Lian-xia, LI Shu-jun. Experimental evaluation on the ionic liquid [BMIM]Cl and H5PV2Mo10O40 dual function catalytic degradating wheat straw alkali lignin[J]. Journal of Beijing Forestry University, 2017, 39(5): 117-124. doi: 10.13332/j.1000-1522.20160399
Citation: LIU Xiao-le, REN Shi-xue, HOU Lian-xia, LI Shu-jun. Experimental evaluation on the ionic liquid [BMIM]Cl and H5PV2Mo10O40 dual function catalytic degradating wheat straw alkali lignin[J]. Journal of Beijing Forestry University, 2017, 39(5): 117-124. doi: 10.13332/j.1000-1522.20160399

离子液体[BMIM]Cl与H5PV2Mo10O40双效催化降解麦草碱木质素的研究

doi: 10.13332/j.1000-1522.20160399
基金项目: 

黑龙江省自然科学基金项目 C2015056

中央高校基本科研业务费专项 2572017EB07

详细信息
    作者简介:

    刘晓乐。主要研究方向:木质素化学应用。Email: liuxiaole1990@163.com   地址:150040 黑龙江省哈尔滨市香坊区和兴路26号东北林业大学材料科学与工程学院

    责任作者:

    任世学,副教授。主要研究方向:木材化学。Email: renshixue@nefu.edu.cn   地址:同上

  • 中图分类号: TQ351

Experimental evaluation on the ionic liquid [BMIM]Cl and H5PV2Mo10O40 dual function catalytic degradating wheat straw alkali lignin

  • 摘要: 采用常规合成法制备了杂多酸H5PV2Mo10O40,并通过FT-IR、XRD、SEM对其进行表征。研究了[BMIM]Cl单催化与{H5PV2Mo10O40+[BMIM]Cl}双效催化体系中,反应时间、温度以及H5PV2Mo10O40用量对麦草碱木质素降解的影响,并初步探讨了木质素的降解机理。结果表明:H5PV2Mo10O40中P、V、Mo相对原子质量满足1:2:10关系,并具有典型的Keggin结构;木质素降解反应中,仅离子液体[BMIM]Cl降解木质素的最佳条件为140 ℃下反应3 h,降解后固体产物中总羟基由3.49 mol/kg增加到10.92 mol/kg,液体产物中有香草醛与丁香醛生成,分别占2.00%和2.15%;{H5PV2Mo10O40+[BMIM]Cl}双效催化体系中,最佳反应条件为加入20%的H5PV2Mo10O40 120 ℃下反应6 h,降解后固体产物中总羟基由3.49 mol/kg增加到14.12 mol/kg,摩尔质量由7.691 kg/mol降为1.589 kg/mol;液体产物中无丁香醛生成,香草醛占6.97%。初步认为:当单独[BMIM]Cl催化木质素时,H+首先进攻木质素中β-O-4键上的氧原子,正电荷转移到β位,然后水分子中氧原子向带有正电荷的β位进攻,从而催化剂的H+被消除,最后实现了β-O-4键水解断裂,生成愈创木酚,进而侧链发生氧化生成香草醛与丁香醛;当添加H5PV2Mo10O40时,[PV2Mo10O40]5-中的VO2+由V(V)→V(IV),故使模型化合物得以单电子的氧化,使木质素脱甲氧基,由紫丁香基木质素转变成愈创木基木质素,液体产物中无丁香醛生成,且香草醛质量分数升高。

     

  • 图  1  H5PV2Mo10O40的XRD谱

    Figure  1.  XRD spectrum of H5PV2Mo10O40

    图  2  催化剂纯磷钼酸(a)和H5PV2Mo10O40 (b) FT-IR光谱

    Figure  2.  FT-IR spectra of phosphomolybdic acid hydrate (a) and H5PV2Mo10O40 (b)

    图  3  H5PV2Mo10O40SEM形貌图

    Figure  3.  SEM photos of H5PV2Mo10O40

    图  4  H5PV2Mo10O40的EDS能谱图

    Figure  4.  EDS spectra of H5PV2Mo10O40

    图  5  反应时间、温度对单效催化降解产物中总羟基(a)和酚羟基(b)的影响

    Figure  5.  Effects of reaction time and temperature on total hydroxyl (a) and phenolic hydroxyl (b) in the single function catalytic degradation products

    图  6  反应时间、温度对双效催化降解产物中总羟基(a)和酚羟基(b)的影响

    Figure  6.  Effects of reaction time and temperature on total hydroxyl (a) and phenolic hydroxyl (b) in the dual function catalytic degradation products

    图  7  反应时间、温度对固体降解产物摩尔质量的影响

    Figure  7.  Effects of temperature and time on the molar mass of solid degradation products

    图  8  原木质素(a)、未加杂多酸降解产物(b)和添加杂多酸催化后降解产物(c)的FT-IR光谱

    Figure  8.  FT-IR spectra of original lignin (a), degradation products without heteropolyacid catalyze (b) and degradation products with heteropolyacid catalyze (c)

    图  9  [BMIM]Cl与H5PV2Mo10O40催化降解木质素反应机理

    Figure  9.  Reaction mechanism of [BMIM]Cl and H5PV2Mo10O40 catalytic degradation of lignin

    表  1  不同H5PV2Mo10O40质量分数对双效催化降解产物羟基的影响

    Table  1.   Effects of H5PV2Mo10O40 mass fraction on the dual function catalytic degradation product hydroxyl

    H5PV2Mo10O40质量分数
    H5PV2Mo10O40 mass fraction
    总羟基质量摩尔浓度
    Mass molar concentration of total hydroxyl/(mol·kg-1)
    酚羟基质量摩尔浓度
    Mass molar concentration of phenolic hydroxyl/(mol·kg-1)
    醇羟基质量摩尔浓度
    Mass molar concentration of alcohol hydroxyl/(mol·kg-1)
    5% 4.48 2.25 2.23
    10% 8.66 4.38 4.28
    20% 14.12 9.12 7.90
    40% 13.98 6.22 5.77
    60% 10.64 6.87 3.77
    100% 7.27 4.96 2.31
    下载: 导出CSV

    表  2  液体降解产物中香草醛、丁香醛质量分数

    Table  2.   Mass fraction of vanillin and syringaldehyde in liquid degradation productions

    催化剂Catalyst 时间
    Time/h
    温度
    Temperature/℃
    香草醛质量分数
    Vanillin mass fraction
    丁香醛质量分数
    Syringaldehyde mass fraction
    [BMIM]Cl 3 120 2.08% 2.02%
    [BMIM]Cl 3 140 2.00% 2.15%
    [BMIM]Cl+ H5PV2Mo10O40 3 140 4.25% 0
    [BMIM]Cl+ H5PV2Mo10O40 3 120 6.97% 0
    下载: 导出CSV
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  • 收稿日期:  2016-12-08
  • 修回日期:  2017-03-19
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