丁醇醛和丁醇酸热解形成CO和CO<sub>2</sub>机理的密度泛函理论研究

黄金保; 童红; 曾桂生; 谢宇; 李伟民

丁醇醛和丁醇酸热解形成CO和CO₂机理的密度泛函理论研究

1.
贵州民族大学理学院, 贵州贵阳 550025;
2.
南昌航空大学环境与化学工程学院, 江西南昌 330063;
3.
华南理工大学制浆造纸工程国家重点实验室, 广东广州 510640

基金项目: 贵州省科技厅、贵州民族学院联合基金(黔科合J字LKM[2011]22号); 华南理工大学制浆造纸工程国家重点实验室开放基金(200928); 贵州省"模式识别与智能系统"重点实验室建设项目(黔科合计[2009]4002)。

详细信息

通讯作者:
黄金保, E-mail: huangjinbao76@126.com.

中图分类号: TK6;O642
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- 文章访问数: 2011
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- PDF下载量: 705
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出版历程
- 收稿日期: 2011-11-03
- 修回日期: 2012-02-19
- 刊出日期: 2012-08-31

Density functional theory studies on the formation mechanism of CO and CO₂ in pyrolysis of hydroxyl butyraldehyde and butyric acid

1.
School of Science, Guizhou University for Nationalities, Guiyang 550025, China;
2.
School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063, China;
3.
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China

摘要

摘要: 采用密度泛函理论方法B3LYP/cc-pVTZ,对模型化合物2,3,4-羟基丁醛的脱羰基和2,3,4-羟基丁酸的脱羧基反应机理进行了量子化学理论研究。对两种模型化合物分别设计了三种热解反应途径,计算了不同温度下各热解反应途径的标准热力学及动力学参数。计算结果表明,纤维素热解过程中CO₂和CO的逸出分别与脱羧基和脱羰基反应相对应,脱羧基和脱羰基反应均为分子内氢原子转移的协同过程。脱羰基反应是吸热反应,而脱羧基反应是放热反应。饱和丁醇醛的脱羰基反应反应能垒为288.8 kJ/mol,脱水后的不饱和烯醇醛的脱羰基反应能垒增大;饱和丁醇酸的脱羧基反应能垒较高,为303.4 kJ/mol,脱水后的不饱和烯醇酸的脱羧基反应能垒明显减小,这说明脱水有利于CO₂的生成。
- 2,3,4-羟基丁醛 /
- 2,3,4-羟基丁酸 /
- 脱羰基反应 /
- 脱羧基反应 /
- 密度泛函理论
Abstract: The pyrolysis of 2,3,4-hydroxyl-butyraldehyde and 2,3,4-hydroxyl-butyric acid as model compounds was investigated by using B3LYP/cc-pVTZ methods to reveal the decarbonyl and decarboxyl mechanism. Three possible pathways for the pyrolysis of each model compound were designed and the standard thermodynamic and kinetic parameters of each reaction path at different temperatures were determined. The results showed that the release of CO and CO₂ during the cellulose pyrolysis is related to the decarbonyl and decarboxyl reactions, respectively; both involve a concerted process via intra-molecular hydrogen transfer. Decarboxyl reaction is endothermic while decarbonyl reaction is exothermic. The activation energy of decarbonyl reaction of 2,3,4-hydroxyl-butyraldehyde is 288.8 kJ/mol, while the activation energy of decarbonyl reaction of undersaturated olefine aldehyde after dehydration is higher than that for saturated aldehyde. The activation energy of decarboxyl reaction of 2,3,4-hydroxyl-butyric acid is 303.4 kJ/mol, while the activation energy of decarboxyl reaction of undersaturated olefine acid after dehydration is much lower, indicating that the dehydration favors the release of CO₂.
- 2,3,4-hydroxyl-butyraldehyde /
- 2,3,4-hydroxyl-butyricacid /
- decarbonyl reaction /
- decarboxyl reaction /
- density functional theory (DFT)

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参考文献(12)

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黄金保, 刘朝, 曾桂生, 谢宇, 童红, 李伟民. 左旋葡聚糖热解机理的密度泛函理论研究[J]. 燃料化学学报, 2012, 40(7): 807-815. (HUANG Jin-bao, LIU Chao, ZENG Gui-sheng, XIE Yu, TONG Hong, LI Wei-min. A density functional theory study on the mechanism of levoglucosan pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2012, 40(7): 807-815.)

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黄金保, 刘朝, 魏顺安, 黄晓露. 纤维素热解形成左旋葡聚糖机理的理论研究[J]. 燃料化学学报, 2011, 39(8): 590-594. (HUANG Jin-bao, LIU Chao, WEI Shun-an, HUANG Xiao-lu. A theoretical study on the mechanism of levoglucosan formation in cellulose pyrolysis [J]. Journal of Fuel Chemistry and Technology, 2011, 39(8): 590-594.)

GAUSSIAN 03, REVISION A. 1, FRISCH M J, et al . Gaussian, Inc., Pittsburgh PA, 2003.

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丁醇醛和丁醇酸热解形成CO和CO₂机理的密度泛函理论研究

通讯作者:
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Density functional theory studies on the formation mechanism of CO and CO₂ in pyrolysis of hydroxyl butyraldehyde and butyric acid

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丁醇醛和丁醇酸热解形成CO和CO2机理的密度泛函理论研究

通讯作者: 黄金保, E-mail: huangjinbao76@126.com.

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Density functional theory studies on the formation mechanism of CO and CO2 in pyrolysis of hydroxyl butyraldehyde and butyric acid

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出版历程

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2023年《燃料化学学报（中英文）》评优结果公布！

丁醇醛和丁醇酸热解形成CO和CO₂机理的密度泛函理论研究

通讯作者:
黄金保, E-mail: huangjinbao76@126.com.

Density functional theory studies on the formation mechanism of CO and CO₂ in pyrolysis of hydroxyl butyraldehyde and butyric acid