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林业科学 ›› 2023, Vol. 59 ›› Issue (11): 85-94.doi: 10.11707/j.1001-7488.LYKX20220081

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基于TG-FTIR的竹材细胞壁主要组分热解特性

代琳心1,王智辉1,李振瑞1,王佳军1,刘杏娥1,文甲龙2,马建锋1,*   

  1. 1. 国际竹藤中心竹藤科学与技术重点实验室 北京100102
    2. 北京林业大学材料科学与技术学院 北京 100083
  • 收稿日期:2022-02-15 出版日期:2023-11-25 发布日期:2023-12-08
  • 通讯作者: 马建锋
  • 基金资助:
    国际竹藤中心基本科研业务费项目(1632022008)

Pyrolysis Characteristics of the Main Components of Bamboo Cell Wall Using TG-FTIR

Linxin Dai1,Zhihui Wang1,Zhenrui Li1,Jiajun Wang1,Xing’e Liu1,Jialong Wen2,Jianfeng Ma1,*   

  1. 1. Key Labatory of Bamboo and Rattan Science & Technology, International Center for Bamboo and Rattan Beijing 100102
    2. College of Materials Science and Technology, Beijing Forestry University Beijing 100083
  • Received:2022-02-15 Online:2023-11-25 Published:2023-12-08
  • Contact: Jianfeng Ma

摘要:

目的: 探究不同热解条件下竹纤维细胞和薄壁细胞中主要组分的热解规律,分析热解过程对固体残余量和挥发分组成的影响,为竹材热解转化为高品质气体燃料和炭材料提供理论参考和借鉴,为开发清洁高效的梯度炭化及物理活化工艺提供技术支撑。方法: 选取3年生毛竹,利用热重—红外联用分析仪(TG-FTIR)对竹粉、水选分离出的竹纤维和薄壁细胞以及化学法分离获得的细胞壁纤维素、半纤维素和木质素在10、20和30 ℃·min?1升温速率条件下进行热解特性与气体相对含量的半定量分析。结果: 10 ℃·min?1、N2气氛条件下,竹粉、竹纤维细胞和薄壁细胞的主热解阶段发生在180~400 ℃之间,三者固体残余量分别为19.8%、21.3%和17.5%。竹纤维素、半纤维素和木质素的主热解阶段分别发生在250~400 ℃、190~365 ℃和100~500 ℃之间,纤维细胞和薄壁细胞中纤维素的固体残余量分别为9.9%和6.3%,半纤维素的固体残余量分别为20.2%和18.3%,木质素的固体残余量分别为30.4%和25.8%。热重—红外光谱分析表明,热解产生的气体主要由CO2、CO和CH4等组成。纤维素热解产物中含C=O和C—O—C等官能团化合物的相对含量最高为65.8%,半纤维素中CO2的相对含量最高为42.7%,木质素气体产物中合成气(CH4、CO)含量最高为27.6%。提高升温速率,纤维素热解产物中含C=O和C—O—C等官能团化合物和木质素中合成气的相对含量减少约5%,半纤维素中CO2含量增加近10%。结论: 1) 竹粉、不同类型细胞及其三组分的热解特性各异,其中薄壁细胞-纤维素的固体残余量最低,纤维细胞-木质素的固体残余量最高;2) 竹粉、竹纤维和薄壁细胞及其3种主要组分的热解气体组成类型基本相同,但相对含量存在明显差异,纤维素主要热解气体产物为含C=O、C—O—C等官能团化合物,半纤维素主要热解产物为CO2和含C=O官能团化合物,木质素主要热解产物为CO2和含C—O—C官能团化合物;3) 随升温速率增加,竹粉、不同类型细胞及其3种主要组分的TG/DTG曲线整体向高温一侧移动,热解气体产物的红外吸收峰强度增加,CO和含C=O官能团化合物的相对含量有所降低。

关键词: 毛竹, 纤维素, 半纤维素, 木质素, 热重-红外联用, 半定量

Abstract:

Objective: In order to provide guidance and reference for the pyrolysis and utilization of bamboo to become high-quality gas fuel and carbon materials, the pyrolysis properties of the cellulose, hemicellulose and lignin extracted from bamboo fiber and parenchyma under different pyrolysis conditions were explored. The effects of pyrolysis process on solid residues and volatiles composition were analyzed to provide technical guidance for the development of clean and efficient gradient carbonization and physical activation processes. Method: The pyrolysis characteristics and relative gas content of 3-year-old moso bamboo powder, bamboo fiber and parenchyma separated by water separation and three main components extracted by chemical method were analyzed semi quantitatively by TG-FTIR at heating rates of 10, 20 and 30 ℃·min?1. Result: Under 10 ℃·min?1 and N2 atmosphere, the main pyrolysis stage of bamboo powder, bamboo fiber and parenchyma were 180-400 ℃, and the final solid residues were 19.8%, 21.3% and 17.5%. The main pyrolysis stages of cellulose, hemicelluloses and lignin in bamboo fiber and parenchyma occurred at 250-400 ℃, 190-365 ℃ and 100-500 ℃ respectively. The solid residues of cellulose, hemicelluloses and lignin in the two cells were 9.9% and 6.3%, 20.2% and 18.3%, 30.4% and 25.8%. TG-FTIR analysis showed that the gases produced by pyrolysis of all samples were mainly composed of CO2, CO and CH4. The highest relative content of functional group compounds such as C=O and C—O—C in cellulose pyrolysis products was 65.8%. The highest relative content of CO2 in hemicelluloses was 42.7%. The content of combustible gas (CH4, CO) in the gas products of lignin was the highest, which was 27.3%. With the increase of heating rate, the relative content of functional group compounds such as C=O and C—O—C in cellulose pyrolysis products and syngas in lignin decreased by about 5%, and the content of CO2 in hemicellulose increased by nearly 10%. Conclusion: 1) Bamboo powder, different types of cells and their three components had different pyrolysis characteristics. The solid residue of parenchyma-cellulose was the lowest and that of fiber-lignin was the highest. 2) The pyrolysis gas composition types of bamboo powder, bamboo fiber and parenchya and three main components were basically the same, but the relative contents were obviously different. The main gas products of the cellulose pyrolysis were compounds containing C=O and C—O—C functional groups, the main products of hemicellulose pyrolysis were CO2 and compounds containing C=O functional groups, and the main products of lignin pyrolysis were CO2 and compounds containing C—O—C functional groups. 3) With the increase of heating rate, the TG/DTG curves of bamboo powder, different types of cells and three main components moved to the high temperature side as a whole. The FTIR absorption peak intensity of pyrolysis gas products increased, in which the relative content of CO and compounds containing C=O functional groups decreased gradually.

Key words: moso bamboo, cellulose, hemicelluloses, lignin, TG-FTIR, semi quantitative calculation

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