醇对过氧化氢热危险性的影响研究

Effect of alcohol on the thermus of hydrogen peroxide

为了防止过氧化氢在生产、储存、运输和使用过程中因为混入杂质导致火灾爆炸事故,利用绝热加速量热仪对过氧化氢及其掺杂醇类物质后的放热分解过程进行了试验研究。结果表明,醇使过氧化氢的初始放热分解温度、活化能和SADT均降低,热危险性增加;正丙醇对过氧化氢热分解的促进作用大于无水甲醇和无水乙醇。

The paper is to introduce our analysis and experimental research on the effect of alcohol on the thermos of hydrogen peroxide. As is known, hydrogen peroxide is a kind of widely used chemical material, whose production and transportation often leads to dangerous explosion accidents during the production, storage, transportation and practical application. In order to prevent aecidents of fire and explosion caused by the mixture of hydrogen peroxide, we have studied the exothermic decomposition process of hydrogen peroxide and its mixtures with alcohol by means of Accelerating Rate Calorimeter. As a result, we have gained the thermodynamic parameters, kinetic parameters of hydrogen peroxide and hydrogen peroxide mixed with alcohol. Then, we have analyzed the decomposition characteristics and the effect of aleohol on hydrogen peroxide. The results we have gained shown that the activation energy Ea of hydrogen peroxide turned to be 119.61 kJ·mol^-1, whereas the initial exothermic decomposition temperature of hydrogen peroxide was 41.27 ℃ . While the highest heating rate was 37.291 ℃/min, the highest reaction temperature could reach 242.89 ℃ . On the other hand, as the high- est reaction pressure reached 25.66 MPa, the maximum pressure rate was just 4.4 MPa/min. The above data prove that the hydrogen peroxide and hydrogen peroxide mixed with alcohol tends to be explosive by nature with great explosive power. Actually, alcohol may exert great influence on the decomposition reaction of the hydrogen peroxide. Our experiments also prove that the initial exothermic decompo- sition temperature of hydrogen peroxide can be reduced by 8.26%, 10.32% and 13.41% respectively, whereas the exothermic decom- position activation energy may decrease by 12.09%, 21.18% and 28.80%. At the same time, the SADT tends to decrease by 20.13%, 22.35% and 25.04% for the addition of methanol, alcohol and n-propanol. The strongest reaction temperature would be so remarkably raised by 5.78% , 23.10% and 21.29%, and so would the thermal; the promotion effect of n-propanol on the thermal de- composition of hydrogen peroxide was bigger than that of anhydrous methanol and anhydrous alcohol. So the contact thermal between the hydrogen peroxide and the alcohol should be prevented in the process of production, storage, transportation and application of the hydrogen peroxide so as to get rid of any unhappy accidents.