乙酸对过氧化氢热稳定性的影响

Influence of acetic acid on the thermal stability of hydrogen peroxide

为了研究氧化脱硫工艺中以乙酸作催化剂为代表的过氧化氢/羧酸氧化体系的热稳定性,利用快速筛选仪和绝热加速量热仪对过氧化氢/乙酸体系的放热分解过程进行试验研究,得到其初始放热温度、最大温升速率等参数。结果表明,30%过氧化氢和乙酸在等体积配比时具有的危险性最大;乙酸的加入使过氧化氢的活化能、初始放热温度降低,体系的热稳定性降低。通过绝热相容性分析计算可知,30%H2O2和H2O2/CH3COOH的平均加速度分别为0.579 8和0.049 8,乙酸和过氧化氢的相容性较好,体系的危险性降低。

The paper is to introduce our analysis and experimental research on the thermal stability of the oxidation of hydrogen peroxide/acetic acid. For the above research purpose, we have laid out and conducted a series of preliminary analysis of hydrogen peroxide/acetic acid system in different ratios. Then we have carefully measured the probability of the relatively serious risk and the hydrogen peroxide of 30% at the same time by the adiabatic acceleration rate calorimeter （ARC）. And next we have worked out the curves between the temperature and pressure vs the time experienced and their reaction order n and the activation energy Ea by fitting the lnk-1/T curves under different reaction orders. At the same time, we have also obtained the thermal decomposition parameters through accounting the thermal inertia factor ＆Phi; under the fully adiabatic condition. The results gained by RSD indicate that when the ratio of acetic acid and hydrogen peroxide is equal, the system tends to face the likely most serious risks. And the testing done with the method of ARC proves that the initial exothermic temperature of H2O2/CH3COOH under adiabatic condition should be 38.4℃, lower than that of H2O2, which is 45.4℃. The results demonstrate that the thermal stability of hydrogen peroxide tends to decrease by the act of acetic acid. In the mean time, the initial temperature rising rate of the H2O2 and H2O2/CH3COOH should be 0.113 and 0.122. The maximal temperature rising rates turn to be 67.029 and 16.432, respectively. But, the average acceleration model of the compatibility criteria evaluation proves that the average acceleration rate of H2O2/CH3COOH should be 0.049, which is much lower than that of H2O2, that is, 0.579 8. The evaluation results have shown that both H2O2 and CH3COOH enjoy a nice compatibility, which can be inferred by adding acetic acid, with the decrease of the relative risk of H2O2/CH3COOH system. Hence, the results of this study suggest a great significance for the safety of production, usage, transportation and storage of hydrogen peroxide.