欢迎访问林业科学,今天是

林业科学 ›› 2022, Vol. 58 ›› Issue (3): 139-148.doi: 10.11707/j.1001-7488.20220315

•   • 上一篇    下一篇

自发泡方法制备木质素基高比表面积泡沫炭

桂有才,左宋林*,金凯楠   

  1. 南京林业大学化学工程学院 林产化学与材料国际创新高地 江苏省农林生物质资源国家重点实验室培育建设点 南京 210037
  • 收稿日期:2021-04-06 出版日期:2022-03-25 发布日期:2022-06-02
  • 通讯作者: 左宋林
  • 基金资助:
    国家重点研发计划课题"木质素高值功能材料创制技术"(2019YFB1503804)

Preparation of High-Surface-Area Carbon Foam by Self-Bubbling Method of Lignin

Youcai Gui,Songlin Zuo*,Kainan Jin   

  1. College of Chemical Engineering, Nanjing Forestry University International Innovation Center for Forest Chemicals and Materials State Key Laboratory of Chemistry and Utilization of Agriculture and Forestry Biomass in Jiangsu Province Nanjing 210037
  • Received:2021-04-06 Online:2022-03-25 Published:2022-06-02
  • Contact: Songlin Zuo

摘要:

目的: 根据木质素结构特点, 探究一种木质素基泡沫炭制备方法, 为木质素制备新型炭材料提供新的技术方法和产品。方法: 以酶解木质素为碳质前驱体, 以氯化锌和酚醛树脂为催化剂和增强剂, 在未添加发泡剂的情况下, 经混合塑化、发泡、固化、炭化等工艺制备木质素基高比表面积泡沫炭; 采用热重分析、扫描电子显微镜和氮气吸附等方法分析木质素发泡机理、过程以及制备的泡沫炭结构; 通过测试泡沫炭的密度、机械性能、开孔率等质量指标, 探讨发泡温度、氯化锌和酚醛树脂用量对泡沫炭结构的影响。结果: 热重分析结果表明, 氯化锌显著催化并降低木质素热分解温度, 使木质素发生热分解的温度与发生软化/塑化的温度重合, 为木质素热分解产生的挥发性物质发挥发泡功能提供合适温度区域, 酚醛树脂与木质素之间形成的三维网状结构赋予发泡前驱体较好的韧性和强度, 为木质素自发泡提供基础。160~180 ℃是合适的发泡温度; 氯化锌用量显著影响泡沫炭的密度和孔隙率, 酚醛树脂用量主要影响泡沫炭的孔泡尺寸和开孔率。在未添加发泡剂的情况下, 采用自发泡方法制备出体积密度为0.26~0.46 g·cm-3、孔隙率为74%~85%、开孔率为82%~94%以及比表面积为524~1 055 m2·g-1的孔泡结构较均匀的高比表面积木质素基泡沫炭。结论: 利用氯化锌催化木质素的热分解作用和木质素塑化等特性, 可实现木质素自发泡, 制备出发达孔泡结构的木质素泡沫炭, 为木质素工业化利用提供一条新的技术路线。

关键词: 木质素, 泡沫炭, 自发泡, 酚醛树脂, 氯化锌

Abstract:

Objective: In order to develop a novel approach of preparing lignin-based carbon materials, this paper has exploited a self-bubbling approach of industrial lignin for the preparation of carbon foams based on the physicochemical properties of lignin. Method: A self-bubbling process of lignin was realized using enzymatic hydrolysis lignin as the carbonaceous precursor, zinc chloride as a catalyst and phenolic formaldehyde resin as enhancer in the absence of additional foaming agents. The lignin-based carbons with a high surface area could be prepared from the mixture of lignin, zinc chloride and resoles through the steps of kneading, foaming, curing and carbonization. A thermogravimetric analysis, scanning electron microscope observation and nitrogen adsorption were employed to elucidate the mechanisms of lignin self-bubbling, the foaming processes and the texture of the resultant carbon foams. The effects of the dosage of zinc chloride and phenolic resin on the structure of carbon foams were studied by measuring the density, mechanical properties and porosity of the carbon foams. Result: The thermogravimetric analysis revealed that in the process of lignin self-bubbling, zinc chloride catalyzed the thermal decomposition of lignin leading to an obvious decrease in the temperature of lignin pyrolysis. As a result, the thermal decomposition and softening/plasticizing of lignin could simultaneously take place in the same temperature range, which allows lignin derived volatile pyrolysis products to work as a foaming agent in the softening/plasticizing lignin precursors. Meantime, phenolic resin provided the lignin-based foaming precursors with a higher tenacity and strength by crosslinking with lignin forming a three-dimensional network structure. The results showed that 160-180 ℃ is the suitable temperature range for lignin self-bubbling. The dosage of zinc chloride produced a significant effect on the density and porosity of carbon foams, and the dosage of phenol formaldehyde resin had a main effect on the cell size and open porosity. The self-bubbling process of lignin developed here produced lignin-based carbon foams with a relatively homogeneous cell bubble texture and high surface area, which had a bulk density of 0.26-0.46 g·cm-3, porosity of 74%-85%, open porosity of 82%-94% and specific surface area of 524-1 055 m2·g-1. Conclusion: The self-bubbling of lignin might be feasible to prepare lignin-based carbon foams with developed cell structure by regulating the temperature of thermal decomposition and softening/plasticizing of lignin. Therefore, it may be a graat potential to become a novel technology for the preparation of lignin-based carbon material.

Key words: lignin, carbon foam, self-bubbling, phenolic formaldehyde resin, zinc chloride

中图分类号: