生物油重质组分模型物热解行为及其动力学研究

吕微; 张琦; 王铁军; 李伯松; 马隆龙

生物油重质组分模型物热解行为及其动力学研究

中国科学院广州能源研究所可再生能源与天然气水合物重点实验室, 广东广州 510640

基金项目: 国家自然科学基金青年基金(51106166); 国家科技支撑计划(2011BAD22B07); 国际科技合作项目(246772)。

详细信息

通讯作者:
张琦(1976-)女,吉林省吉林市人,博士,从事生物质能转化利用研究。Email:zhangqi@ms.giec.ac.cn。

中图分类号: TQ517.4
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出版历程
- 收稿日期: 2012-06-23
- 修回日期: 2012-09-26
- 刊出日期: 2013-02-28

Thermal degradation behaviors and pyrolysis kinetics of model compounds of bio-oil heavy fractions

Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China

摘要

摘要: 采用TG-FT-IR在非等温条件下对生物油重质组分酚、醛和糖类模型代表物(丁香酚、香草醛、左旋葡聚糖)进行热解特性及其热解动力学分析。TG-DTG曲线和FT-IR测试数据显示,重质组分模型物热解的先后次序是酚类、醛类、糖类物质。香草醛、丁香酚均为一个主热解阶段,主要产物为水、烷烯烃、CO₂、CO和小分子酚、芳香醛。左旋葡聚糖热解分两阶段进行,热解发生在较高温区(180~370℃),主要热解产物有CO₂、烷烯烃、醛、酮和环醚,少量的CO和水。混合物热解分为三个阶段,产物与单一模型物热解产物相似,但有少量缩醛低聚物。对比单一组分,混合物中羰基和羟基组分在较高温区(≥300℃)存在相互作用,生成难分解的缩聚物。其中,糖类是影响重质组分热解速率的主要物质。根据热重数据对热解各阶段进行动力学拟合,确定了模型物热解反应动力学三因素。平均表观活化能和反应级数分别为:E_{左旋葡聚糖}第一、第二阶段分别为115.80 kJ/mol(0.5级)、141.19 kJ/mol(2/3级); E_混合物第一阶段为54.46 kJ/mol(1级)、第二阶段为50.67 kJ/mol(2/5级); E_丁香酚为42.29 kJ/mol(0.7级); E_香草醛为36.53 kJ/mol(0.95级)。
- 生物油重质组分 /
- 模型物 /
- 热解特性 /
- 动力学
Abstract: Eugenol, vanillic aldehyde and levoglucosan were selected as the model compounds of bio-oil heavy fractions for phenols, aldehydes and saccharides, respectively; their thermal degradation behaviors and pyrolysis kinetics were investigated by thermogravimetric and Fourier transform infrared spectrometer analyses (TG-FT-IR) under non-isothermal conditions. The results indicated that the hydroxylbenzenes exhibits the greatest tendency to decompose, followed by the aldehydes and carbohydrate. One stage thermal degradation is identified for eugenol and vanillic aldehyde, with the formation of water, CO₂, CO, alkanes, alkenes, as well as small molecules of phenols and aromatic aldehydes. Levoglucosan pyrolysis proceeds slowly in two stages at medium-high temperature (180~370℃); the products are mainly composed of CO₂, aldehydes, ketones, cyclic ethers, and a small amount of water and CO. As for the mixture of the model compounds, there are three stages in the pyrolysis process; the pyrolysis products evolved share the same compositions of three model samples besides the formation of some low molecular acetal polymers. Compared with the single model compounds, the interaction between the carbonyl groups and hydroxyl groups in the mixture of model compounds may produce polycondensates at high temperature (≥ 300℃), which makes a complete pyrolysis of the mixture more difficult. The saccharide should be the key substance that dominates the pyrolysis rate of heavy fractions. By fitting the dynamic profiles of each stage, kinetic parameters of thermal degradation were determined. For the pyrolysis of levoglucosan, the apparent activation energy and reaction order are 115.80kJ/mol and 0.5 (first stage) and 141.19kJ/mol 2/3 (second stage), respectively; for eugenol, the apparent activation energy is 42.29kJ/mol, with the reaction order of 0.7; for vanillic aldehyde, the apparent activation energy is 36.53kJ/mol, with the reaction order of 0.95; for the mixture of model compounds, the apparent activation energy and reaction order are 54.46kJ/mol and 1 (first stage) and 50.67kJ/mol 2/5 (second stage), respectively.
- heavy fraction of bio-oil /
- model compound /
- pyrolysis character /
- kinetic dynamic

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