化学学报 ›› 2016, Vol. 74 ›› Issue (1): 81-88.DOI: 10.6023/A15080548 上一篇    下一篇

研究论文

植物焦炭氧化中的平行反应及其动力学解析

陶骏骏, 陈帅, 姚奉奇, 王海晖   

  1. 中国科学技术大学火灾科学国家重点实验室 合肥 230027
  • 投稿日期:2015-08-17 发布日期:2015-10-29
  • 通讯作者: 王海晖 E-mail:HHWang4@ustc.edu.cn
  • 基金资助:

    项目受中央高校基本科研业务费专项资金(No. WK2320000032)资助.

A Study of Plant Char Oxidation: the Parallel Reactions and Their Chemical Kinetics

Tao Junjun, Chen Shuai, Yao Fengqi, Wang Haihui   

  1. State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230027
  • Received:2015-08-17 Published:2015-10-29
  • Supported by:

    Project supported by the Research grant from the Fundamental Research Funds for the Central Universities (No. WK2320000032).

通过建立多组分平行反应模型和开展非线性动力学解析, 理论上探索植物焦炭氧化中的平行反应以及其对焦炭氧化反应活性影响的机制. 运用高温管式炉并通入高纯氮气制备植物焦炭, 热处理温度分别设定为450、520和800 ℃. 运用同步热分析仪开展空气气氛中植物焦炭线性升温氧化实验, 并通过对热重和质量损失速率实验数据进行拟合以获取焦炭氧化动力学参数值. 解析结果证实, 对于低中热处理温度(450和520 ℃)制得的焦炭, 其质量损失速率及对应的热流率曲线的变化特征主要是由残留木质素、无定形碳及粗脂肪和粗蛋白等其它反应物质的平行氧化反应叠加而成; 当热处理温度达到800 ℃时, 焦炭中活性物质基本为无定形碳, 氧化则可简化为无定形碳的单步反应. 残留木质素氧化反应的活化能最低, 范围为86~147 kJ·mol-1, 相应的温度作用区间为300~480 ℃; 无定形碳的活化能为174~208 kJ·mol-1, 反应温度在370~520 ℃之间; 其它物质的反应活化能为214~225 kJ·mol-1, 温度作用区间在420~510 ℃之间. 焦炭的氧化活性主要由残留木质素含量决定. 随着热处理温度升高, 残留木质素含量降低, 同时另两个反应组分的氧化活化能均有所增大, 导致焦炭的氧化反应活性下降.

关键词: 植物焦炭, 氧化反应, 动力学解析, 反应温度, 反应活性

The present work explores the effects of the parallel reactions on the oxidation reactivity of plant chars formed at various heat treatment temperatures by using a multi-component parallel reaction model in conjunction with the non-linear kinetic analysis technique. Four plant species were selected. A plant char was prepared in a programme-controlled horizontal tube furnace under the atmosphere of N2 at a purity of 99.999%, and its heat treatment temperature was set at 450, 520 and 800 ℃, respectively. The aerial oxidation characteristics of plant chars were analyzed by using a simultaneous thermo-gravimetric analyzer and differential scanning calorimeter, and the kinetic data of the parallel reactions were then retrieved by fitting both the mass change and mass loss rate data obtained during the oxidation measurements. It was confirmed that for the oxidation of the chars formed at moderate heat treatment temperatures (i.e. 450 and 520 ℃), the variation patterns of mass loss rate and the heat flow rate curves are contributed by the parallel oxidation reactions of lignin residue, amorphous carbon and the other reactive substances such as crude fat and protein, etc. When the heat treatment temperature reaches 800 ℃, the reactive substances stored in the char produced are mainly amorphous carbon, and the char oxidation can be simplified to an one-step reaction. Compared with the other two reaction components, lignin residue has the lowest activation energy for oxidation with the range between 86 and 147 kJ·mol-1, and its reaction temperatures vary between 300 and 480 ℃. The activation energy for the amorphous carbon fluctuates between 174 and 208 kJ·mol-1 with its reaction temperatures altering between 370 and 520 ℃. The other reactive substances undergo oxidation with the activation energy between 214 and 225 kJ·mol-1 and the corresponding reaction temperatures are between 420 and 510 ℃. It is obvious that the oxidation reactivity of plant chars mainly relies on the performance of lignin residue. With the increase in the heat treatment temperature for making a char, the oxidation reactivity of the plant char essentially reduces, which is essentially attributed to the decrease in the content of lignin residue and the increase in the activation energies for the other two components to oxidize. The established understanding lays the foundation for developing more effective methodologies for making use of the energy stored in plant chars and paves the way for identifying the role of plant chars in the spread of a wildland fire.

Key words: plant char, oxidation, kinetic analysis, reaction temperature, reactivity