Yu Hai, Kennedy Eric M, Uddin Md Azhar, Sullivan Simon P, Dlugogorski Bogdan Z
Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, New South Wales 2308, Australia.
Environ Sci Technol. 2005 May 1;39(9):3020-8. doi: 10.1021/es049372o.
The gas-phase reaction of halon 1211 (CBrClF2) with hydrogen has been studied experimentally at atmospheric pressure in a plug flow, isothermal reactor over the temperature range of 673 to 973 K, at residence times ranging from 0.5 to 2.5 s with an input ratio of N2:H2:halon 1211 of 19:10:1. The major carbon containing products include CHClF2, CHBrF2, CH2F2, and CH4. Gas-phase reactions of CHClF2, CCl2F2, and CH2F2 with hydrogen are also investigated under the conditions similar to those for halon 1211 hydrodehalogenation, and the results are used to assist in understanding the mechanism of the reaction of halon 1211 with hydrogen. A kinetic reaction scheme involving 90 species and 430 reaction steps is developed and used to model the halon 1211 hydrodehalogenation reaction. Generally, satisfactory agreement between experimental and computational results is obtained for the production of major species. Using the software package AURORA, the reaction pathways leading to the formation of major products are elucidated. It has been found that the reaction steps involving CF2 are responsible for the formation of CH4.
在活塞流等温反应器中,于673至973K的温度范围内、停留时间为0.5至2.5秒、氮气:氢气:哈龙1211(CBrClF₂)输入比为19:10:1的条件下,对哈龙1211与氢气的气相反应进行了常压实验研究。主要含碳产物包括一氯二氟甲烷(CHClF₂)、一溴二氟甲烷(CHBrF₂)、二氟甲烷(CH₂F₂)和甲烷(CH₄)。还在与哈龙1211加氢脱卤反应类似的条件下,研究了一氯二氟甲烷、二氯二氟甲烷(CCl₂F₂)和二氟甲烷与氢气的气相反应,其结果用于辅助理解哈龙1211与氢气的反应机理。开发了一个包含90种物质和430个反应步骤的动力学反应方案,并用于模拟哈龙1211加氢脱卤反应。总体而言,主要物质生成的实验结果与计算结果取得了令人满意的一致性。使用AURORA软件包,阐明了导致主要产物形成的反应途径。已发现涉及CF₂的反应步骤是甲烷形成的原因。