基于竞争因子的特戊酰氯光氯化反应宏观动力学

采用内环流反应器进行蓝色光源引发的特戊酰氯光氯化反应实验和动力学研究,测定不同温度下氯化反应液中各组分浓度与时间的变化关系,建立基于竞争因子的特戊酰氯光氯化连串反应的宏观动力学模型结果表明:加入竞争因子的连串反应动力学模型比拟一级模型能更准确地反映特戊酰氯光氯化的反应规律,通过参数估计得到特戊酰氯生成一氯代特戊酰氯的活化能为1.98 kJ/mol,一氯代特戊酰氯生成β,β-二氯代特戊酰氯和β,β′-二氯代特戊酰氯的活化能分别为2.40和1.42 kJ/mol,二氯代特戊酰氯生成对应三氯代特戊酰氟的活化能分别为4.83和4.82 kJ/mol。各步反应的表观活化能部较小,说明特戊酰氯的光氯化反应受Cl₂的气液传质影响明显

Macrokinetics of photo-chlorination for pivaloyl chloride based on competition factor

The pholo-chlorination and kinetics of pivaloyl chloride with blue light as catalyst were investigated in an internal loop reactor.The relationship between the concentration of chlorides and time at different temperatures was measured,and the consecutive reaction niacrokinetics model of pholo-chlorination for pivaloyl chloride was established based on competition factor.Results showed that the competition factor model reflected photo-chlorination dynamic features of pivaloyl chloride more accurate than the pseudo -first order model did.The activation energy of each reaction was obtained by parameter estimation.The activation energy ofβ-chloropivaloyl chloride from pivaloyl chloride was 1.98 kJ/mol,the reaction activation energy ofβ,β-dichloropivaloyl chloride andβ,β′-dichloropivaloyl chloride was 2.40 and 1.42 kJ/mol respectively,and the reaction activation energv of trichloropivaloyl chloride fromβ,β-diehloropivaloyl chloride andβ,β′-dichloropivaloyl chloride was 4.83 and 4.82 kJ/mol respectively.The activation energy of each reaction was very small,which indicated that the photo-chlorination of pivaloyl chloride was significantly affected by gas-liquid mass transfer of chlorine.