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林产化学与工业 ›› 2016, Vol. 36 ›› Issue (3): 43-52.doi: 10.3969/j.issn.0253-2417.2016.03.007

• 研究报告 • 上一篇    下一篇

在Ru/C和甲酸(甲酸盐)体系中碱木质素水热解聚特性研究

李霄虹, 武书彬   

  1. 华南理工大学制浆造纸工程国家重点实验室, 广东 广州 510640
  • 收稿日期:2015-06-16 出版日期:2016-06-25 发布日期:2016-07-07
  • 通讯作者: 武书彬(1965-),男,教授,博士生导师,从事纤维高效回用与高值化利用方向研究;E-mail:shubinwu@scut.edu.cn。 E-mail:shubinwu@scut.edu.cn
  • 作者简介:李霄虹(1988-),女,河北石家庄人,硕士生,主要从事生物质资源转化与利用方向的研究
  • 基金资助:
    国家自然科学基金项目(31270635);国家973计划项目(2013CB228101);中央高校基本科研业务费资助(2014ZP14)

Hydrothermal Depolymerization Characteristics of Alkali Lignin in Ru/C and Formic Acid/Formate System

LI Xiao-hong, WU Shu-bin   

  1. State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China
  • Received:2015-06-16 Online:2016-06-25 Published:2016-07-07

摘要: 在Ru/C和甲酸(甲酸盐)的共同作用下, 275~350℃的亚临界水中,进行碱木质素的水热解聚反应。通过GC-MS定性分析和GC-FID定量分析,探究了供氢试剂及用量、反应温度、木质素分子级分对木质素水热解聚的影响。结果表明:在甲酸和Ru/C条件下,木质素解聚液相产物得率最高,组成较简单,具有较好催化降解效果;在甲酸添加量为0.8 mol/L,反应30 min时,木质素解聚液相产物最多,其中含量最高的单酚类物质为4-甲基愈创木酚,在主要单酚类物质中占32.77%,木质素水热解聚液相产物得率随温度升高而先增后减,并在325℃时取得峰值;L1、L2和L3是碱木质素的3个不同的分子级分,L1级分对木质素解聚液相产物得率贡献最大,达61.80%,且产物中单酚类物质总得率最高,为112.71 mg/g。其中,愈创木酚与4-甲基愈创木酚所占比例最高,可分别为35.38和35.52 mg/g;对木质素进行分级分离处理后再进行水热转化反应,有利于液相产物和单酚类物质得率的进一步提高。

关键词: 木质素, 亚临界水, 催化, 解聚, 酚类化合物

Abstract: Hydrothermal depolymerization of lignin were conducted in catalytic system of formic acid/formate and Ru/C at 275-350℃. The effects of hydrogen donator type and dosage, temperature, different fractions of alkali lignin on hydrothermal depolymerization were investigated by GC-MS and GC-FID. The results showed that the best catalytic effect with highest liquid product yield was realized when the degradation was conducted in the co-catalyst system of formic acid and Ru/C, and the component of liquid product (LP) was relatively simple. The yield of LP achieved the maximum when the dosage of formic acid was 0.8 mol/L. Furthermore, as the most monomer phenols in LP, 4-methyl guaiacol gained a 32.77% share. With the rising reaction temperature, the yield of LP increased at first and then decreased, and peaked at 325℃. L1, L2 and L3 were three different fractions of alkali lignin. Among them, L1 made the 61.80% contribution to the yields of LP , and the maximum total yield of main monomer phenols, i.e., 112.71 mg/g, was achieved. Among the monomers, guaiacol and 4-methy-guaiacol were dominant components, and represented 35.38 and 35.52 mg/g, respectively. Proper isolation of lignin before hydrothermal conversion was benefit for the liquefaction reaction.

Key words: lignin, subcritical water, catalyst, depolymerization, phenols

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