过氧丙酸的制备及热危害研究

Study on preparation of perpropionic acid and its thermal hazard

利用过氧化氢氧化丙酸制备出过氧丙酸,并考察了过氧丙酸的热危害特性:利用等转化率法计算得到过氧丙酸分解的热动力学;利用绝热时到达最大反应速率所需时间(TMRad)判断了过氧丙酸在不同温度存储时的失控可能性;利用泄放尺寸实验仪(VSP2)实测出过氧丙酸绝热分解特性。研究结果表明:过氧丙酸TMRad为1 h、8 h及24 h时的初始温度分别为51℃、6℃及-12.5℃,绝热条件下分解时最高温升速率及最高压升速率分别可达130℃.s-1及80 MPa.s-1。因此,过氧丙酸潜在热危害较大,为使过氧丙酸稳定存储,存储温度应低于-10℃,若在常温下存储,则应增加冷却系统。

In order to promote the application of perpropionic acid(PPA) in fine chemicals,PPA is prepared through oxidation of propionic acid by peroxide hydrogen.The thermal hazard of PPA is deeply studied:thermal decomposition kinetic parameters of PPA is obtaind by iso-conversional method.The probability of runaway reaction of PPA under different storage temperature is judged by TMRad(time to maximum rate under adiabatic condition) assessment criteria.Decomposition characteristics of PPA under adiabatic condition are measured by Vent Size Package 2.The results show that:under storage temperature of 51℃,6℃,-12.5℃,TMRad of PPA is 24 h,8 h and 1 h respectively.The maximum temperature and pressure rise rate are 130℃·s-1 and 80 MPa·s-1 within the region of self-decomposition of PPA under approximately adiabatic conditions.Therefore,PPA has high thermal hazard.The storage temperature of PPA must be kept below-10℃ to avoid its decomposition.The cooling system must be configured when PPA is stored at ambient temperature.