腐殖酸热分解动力学

doi:10.3969/j.issn.0438-1157.2014.09.022

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

• 催化、动力学与反应器 • 上一篇下一篇

腐殖酸热分解动力学

程亮, 张保林, 徐丽, 侯翠红, 刘国际

郑州大学化工与能源学院, 河南郑州 450001

收稿日期:2014-01-16 修回日期:2014-04-11 出版日期:2014-09-05 发布日期:2014-09-05
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）。

Thermal decomposition kinetics of humic acid

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

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).

摘要/Abstract

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

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

中图分类号:

TQ013.1

程亮, 张保林, 徐丽, 侯翠红, 刘国际. 腐殖酸热分解动力学[J]. 化工学报, 2014, 65(9): 3470-3478.

CHENG Liang, ZHANG Baolin, XU Li, HOU Cuihong, LIU Guoji. Thermal decomposition kinetics of humic acid[J]. CIESC Journal, 2014, 65(9): 3470-3478.

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腐殖酸热分解动力学

Thermal decomposition kinetics of humic acid

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