Kinetic study for the production mechanism of halo-dibenzo-p-dioxin

卤代二苯并对二恶英生成机理的动力学研究

• 批准号: 13650827
• 负责人: FUJII Nobuyuki
• 金额: $ 2.3万
• 依托单位: Nagaoka University of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650827/
• 关键词: dibenzo-p-dioxin; production; shock-tube; phenoxy radical; gas chromatography; mechanism; high-temperature; combustion; ダイオキシン骨格; 生成反応機構; シクロペンタジエニルラジカル; 脱水素付加反応; 衝撃波管実験; 原子共鳴分光法; メトキシベンゼン

In order to confirm that the dibenzo-p-dioxin production channel in combustion is 2C_6H_5O→C_6H_4O_2C_6H_4+2H, high temperature reactions of phenoxy radicals (C_6H_5O) were investigated over the temperature range 1250 - 1700 K using shock-tube techniques. Methoxybenzene (C_6H_5OCH_3) and trifluromethoxybenzene (C_6H_5OCF_3) were used as sources of C_6H_5O radicals. By comparing the experimental results with those by computer simulations, high temperature reactions of C_6H_5O radicals including the dibenzo-p-dioxin production channel were discussed. Reaction products of C_6H_5O decomposition were also analyzed with gas chromatography by sampling the final products behind the reflected shock of C_6H_5OCH_3 and C_6H_5OCF_3 diluted with Ar mixtures. We found that not only the linear hydrocarbons but also aromatic compounds such as phenol were produced behind the shock. However the dibenzo-p-dioxin was not detected as the final products behind the shockwaves of C_6H_5OCH_3 and C_6H_5OCF_3 diluted with Ar mixtures. To simulate the temperature dependence of the yield of dibenzo-p-dioxin production, kinetic model for dibenzo-p-dioxin formation was proposed and compared with the experimental observations.

为了证实燃烧过程中二苯并对二恶英的生成途径是2C_6H_5O→C_6H_4O_2C_6H_4+2H，利用激波管技术研究了苯氧基自由基(C_6H_5O)在1250 - 1700 K温度范围内的高温反应。甲氧基苯(C_6H_5OCH_3)和三氟甲氧基苯(C_6H_5OCF_3)被用作C_6H_5O自由基的来源。通过将实验结果与计算机模拟结果进行比较，讨论了C_6H_5O自由基包括二苯并-对-二恶英生成通道的高温反应。还通过对用Ar混合物稀释的C_6H_5OCH_3和C_6H_5OCF_3的反射冲击后的最终产物进行取样，用气相色谱法分析了C_6H_5O分解的反应产物。我们发现，冲击后不仅产生了直链烃，还产生了苯酚等芳香族化合物。然而，在Ar混合物稀释的C_6H_5OCH_3和C_6H_5OCF_3冲击波后，并未检测到二苯并对二恶英作为最终产物。为了模拟二苯并-对-二恶英产量的温度依赖性，提出了二苯并-对-二恶英形成的动力学模型，并与实验观察结果进行了比较。

项目成果

Fujii, N., Saejung, T., Sugimoto, K., Watanabe, N., Kobayashi, T., Murakami, Y.: "Kinetic Study on High Temperature Decomposition of Phenoxy Radical"29th International Symposium on Combustion. 217 (2002)

Fujii, N.、Saejung, T.、Sugimoto, K.、Watanabe, N.、Kobayashi, T.、Murakami, Y.：“苯氧基高温分解的动力学研究”第29届国际燃烧研讨会。

藤井 信行: "衝撃波管を用いたフェニルラジカルの高温酸化反応機構の研究"平成14年度衝撃波シンポジウム(講演論文集). 289-291 (2003)

Nobuyuki Fujii：“使用激波管研究苯基自由基的高温氧化反应机理”2002年冲击波研讨会（论文集）289-291（2003）。

Y.Murakami et al.: "Kinetics and oxidation of cyclopentadiene behind shock waves"Shock Waves. 13. 149-154 (2003)

Y.Murakami 等人：“冲击波后环戊二烯的动力学和氧化”冲击波。

大橋知可子 他: "フェノキシラジカルの高温反応の検討"平成14年 衝撃波シンポジウム(講演論文集). 291 (2003)

Chikako Ohashi 等人：“苯氧基自由基的高温反应的研究”2002 年冲击波研讨会（论文集）291（2003 年）。

大橋 知可子: "フェノキシラジカルの高温酸化反応の検討"平成14年度衝撃波シンポジウム(講演論文集). 291-293 (2003)

Chikako Ohashi：“苯氧基自由基的高温氧化反应的研究”2002年冲击波研讨会（论文集）291-293（2003）。