CIESC Journal ›› 2014, Vol. 65 ›› Issue (9): 3470-3478.DOI: 10.3969/j.issn.0438-1157.2014.09.022

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Thermal decomposition kinetics of humic acid

CHENG Liang, ZHANG Baolin, XU Li, HOU Cuihong, LIU Guoji   

  1. School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, Henan, China
  • Received:2014-01-16 Revised:2014-04-11 Online:2014-09-05 Published:2014-09-05
  • Supported by:

    supported by the "Twelfth Five-Year" Plan of National Science and Technology Project (2011BAD11B05) and the Science and Technology Hall of Henan Province Foundation and Frontier Project (2011A530008).

腐殖酸热分解动力学

程亮, 张保林, 徐丽, 侯翠红, 刘国际   

  1. 郑州大学化工与能源学院, 河南 郑州 450001
  • 通讯作者: 刘国际
  • 基金资助:

    “十二五”国家科技计划项目(2011BAD11B05);河南省科技厅基础与前沿项目(2011A530008)。

Abstract: Process and kinetics of thermal decomposition of humic acid were studied with TG-DTG techniques. Thermal decomposition temperature of humic acid was in the range of 284.65-417.16℃. The structure of humic acid was characterized with FT-IR, 1H NMR and 13C NMR. The kinetic parameters, including activation energy and pre-exponential factor of the thermal decomposition process of humic acid were calculated with the Flynn-Wall-Ozawa (FWO), Kissinger and Šatava-Šesták method respectively. Activation energy and logarithmic value of pre-exponential factor were found to be 210.83 kJ·mol-1 and 17.55, respectively. Moreover, reaction order and mechanism of thermal decomposition and thermodynamic parameters were also studied. Thermal decomposition of humic acid was a second-order reaction, and the mechanism of the decomposition process was obtained. The maximal used temperature of humic acid maintaining one-minute lifetime in N2 atmosphere was 278℃. Meanwhile, the thermodynamic paramaters of ΔH, ΔS and ΔG were calculated as 67.99 kJ·mol-1, -164.83 J·(mol·K)-1 and 176.36 kJ·mol-1, respectively.

Key words: humic acid, thermal decomposition, kinetics, mechanism, enthalpy, NMR

摘要: 采用热重分析法(DTA-TGA)研究了腐殖酸的热分解过程及其动力学,分析其DTA-TGA曲线可得:热分解反应发生在284.65~417.16℃; 用红外光谱(FT-IR)、核磁氢谱(1H NMR)、核磁碳谱(13C NMR)对腐殖酸结构进行表征,用Flynn-Wall-Ozawa(F-W-O)法、Kissinger法及Šatava-Šesták法计算出腐殖酸热分解反应的表观活化能为210.83 kJ·mol-1,指前因子对数为17.55;确定了其热分解反应的级数和动力学参数,且热分解反应机理为二级反应;腐殖酸在氮气氛围下维持1min寿命的最高使用温度为278℃;同时,计算出腐殖酸样品热力学参数焓变、熵变及摩尔自由能变分别为67.99 kJ·mol-1、-164.83 J·(mol·K)-1 和176.36 kJ·mol-1

关键词: 腐殖酸, 热分解, 动力学, 机理, 焓, 核磁共振

CLC Number: