木质素制备燃料电池阴极电催化炭材料研究(Ⅰ)——改性酶解木质素的热解过程

doi:10.3969/j.issn.0253-2417.2021.06.001

林产化学与工业 ›› 2021, Vol. 41 ›› Issue (6): 1-9.doi: 10.3969/j.issn.0253-2417.2021.06.001

木质素制备燃料电池阴极电催化炭材料研究(Ⅰ)——改性酶解木质素的热解过程

金凯楠¹, 左宋林¹^,*(), 桂有才¹, 申保收²^,³^,*()

1. 南京林业大学化学工程学院, 江苏南京 210037
2. 陕西省地表系统与环境承载力重点实验室, 陕西西安 710127
3. 西北大学城市与环境学院/地表系统与灾害研究院, 陕西西安 710127

收稿日期:2021-03-18 出版日期:2021-12-28 发布日期:2021-12-31
通讯作者: 左宋林,申保收 E-mail:zslnl@njfu.edu.cn;bsshen@nwu.edu.cn
作者简介:申保收, 副教授, 硕士生导师, 研究领域为环境及储能材料与环境水化学, E-mail: bsshen@nwu.edu.cn
左宋林, 教授, 博士生导师, 研究领域为生物质热化学转化与炭材料, E-mail: zslnl@njfu.edu.cn
金凯楠(1996-), 男, 江苏南京人, 硕士生, 从事木质素的改性与应用研究
基金资助:
国家重点研发计划资助项目(2019YFB1503804);江苏省自然科学基金青年项目(BK20170928)

Studies on Lignin-based Carbon Materials as Electrocatalysts of Fuel Cells Cathode Ⅰ: Pyrolysis Process of Modified Enzymatic Hydrolysis Lignin

Kainan JIN¹, Songlin ZUO¹^,*(), Youcai GUI¹, Baoshou SHEN²^,³^,*()

1. College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China
2. Shaanxi Key Laboratory of Earth Surface System and Environmental Carrying Capacity, Xi'an 710127, China
3. College of Urban and Environmental Sciences/Institute of Earth Surface System and Hazards, Northwest University, Xi'an 710127, China

Received:2021-03-18 Online:2021-12-28 Published:2021-12-31
Contact: Songlin ZUO,Baoshou SHEN E-mail:zslnl@njfu.edu.cn;bsshen@nwu.edu.cn

摘要/Abstract

摘要：

为了制备高性能的木质素基燃料电池用电催化炭材料，以酶解木质素为原料制备尿素、三聚氰胺改性酶解木质素，采用TG和DSC分析了酶解木质素、尿素和三聚氰胺改性酶解木质素的热解过程；同时采用立式管式炉在不同热解温度下对3种木质素进行热解，计算了固体产物得率，并采用元素分析仪测试了固体产物的碳、氮、氢元素含量。研究结果显示：尿素或三聚氰胺改性酶解木质素显示出与未改性酶解木质素显著不同的热解过程，其中尿素改性酶解木质素的热解过程主要发生在180~360 ℃之间，三聚氰胺改性酶解木质素的主要热解反应发生在温度范围较窄的280~350 ℃之间。尿素改性和三聚氰胺改性木质素都能制备得到含氮量较高的木质素基炭。尽管三聚氰胺在400 ℃就完全热分解，但三聚氰胺改性酶解木质素能在900 ℃下制备得到含氮量超过10%、炭得率与未改性木质素得率相当的产物炭，三聚氰胺的改性效果显著。进一步的对比分析揭示，三聚氰胺改性酶解木质素在热解过程中产生了化学活性高的含氮有机化合物，大大提高了三聚氰胺改性木质素在较低温度下发生二次热解的几率，从而显著影响最终固体产物的得率及其含氮量。

关键词: 木质素, 炭材料, 电催化, 尿素, 三聚氰胺, 热解

Abstract:

In order to prepare lignin-based high-performance electrocatalytic carbon materials for fuel cells, enzymatic hydrolysis lignin was used as raw material to prepare urea or melamine modified enzymatic hydrolysis lignin. TG and DSC were used to study the pyrolysis process of these three kinds of lignin. Meantime, lignin pyrolysis experiments were conducted by a vertical tube furnace at different pyrolysis temperatures. The yield of solid products was calculated, and the carbon, nitrogen, and hydrogen content of these solid products were tested by elemental analyzer. The results show that urea or melamine modified enzymatic hydrolysis lignin exhibit a significantly different pyrolysis process from unmodified enzymatic hydrolysis lignin. The pyrolysis of urea modified enzymatic hydrolysis lignin mainly take place in the temperature range of 180-360 ℃, and melamine modified enzymatic hydrolysis lignin in a narrower temperature range of 280-350 ℃. Although melamine is basically thermally decomposed at 400 ℃, melamine modified enzymatic hydrolysis lignin produce a carbon product with a nitrogen content of more than 10% at 900 ℃. Moreover, the yield of char derived from melamine-modified lignin is equivalent to that of unmodified lignin. Conclusively, the melamine modification produces a significant effect on the pyrolysis of lignin. Further comparative analysis revealed that melamine modification result into the formation of a large amount of nitrogen-containing organic compounds with high chemical activity during the lignin pyrolysis, which greatly increased the probability of secondary pyrolysis reactions of melamine modified lignin at a lower temperature, thus significantly affecting the yield and nitrogen content of the final solid products.

Key words: lignin, carbon material, electrocatalysis, urea, melamine, pyrolysis

中图分类号:

TQ35

金凯楠, 左宋林, 桂有才, 申保收. 木质素制备燃料电池阴极电催化炭材料研究(Ⅰ)——改性酶解木质素的热解过程[J]. 林产化学与工业, 2021, 41(6): 1-9.

Kainan JIN, Songlin ZUO, Youcai GUI, Baoshou SHEN. Studies on Lignin-based Carbon Materials as Electrocatalysts of Fuel Cells Cathode Ⅰ: Pyrolysis Process of Modified Enzymatic Hydrolysis Lignin[J]. Chemistry and Industry of Forest Products, 2021, 41(6): 1-9.

图/表 6

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木质素制备燃料电池阴极电催化炭材料研究(Ⅰ)——改性酶解木质素的热解过程

Studies on Lignin-based Carbon Materials as Electrocatalysts of Fuel Cells Cathode Ⅰ: Pyrolysis Process of Modified Enzymatic Hydrolysis Lignin

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