丙酮连氮催化水解制肼反应动力学拟合

Kinetics of catalyzed hydrolysis of hydrazine hydrate by acetone azine

以自制丙酮连氮和蒸馏水为原料,研究在催化剂条件下丙酮连氮水解制水合肼的不同工艺条件;考察了催化剂种类,催化剂用量,丙酮连氮与水的摩尔比以及温度对水解反应的影响。实验可得较佳的工艺条件是选用C106弱酸阳离子交换树脂为催化剂,催化剂用量为全部溶液质量的5%,n(水)∶n(丙酮连氮)=7∶1,温度90℃,此时丙酮连氮的转化率可达到34.6%。在上述条件下,采用幂函数动力学模型拟合得到了丙酮连氮水解反应的宏观动力学方程。结果表明,丙酮连氮与水反应生成水合肼和丙酮的正反应的活化能为2 067.57 J/mol,指前因子为5.957 8;逆反应的活化能为125.07 J/mol,指前因子为4.146 3;丙酮连氮、水、水合肼、丙酮的反应级数分别为0.099 8,0.110 8,0.113 2,0.114 5。

With self-made acetone azine and distilled water as raw materials, the different process conditions of acetone azine and water to hydrazine hydrate were studied in the presence of catalyst. The influence of catalyst, catalyst dosage, mole ratio of acetone azine to water, temperature on the hydrolysis reaction is investigated. The optimal process conditions obtained are as follows： C106 weak-acid ion exchange resin was selected as catalyst, the mass fraction of catalyst is 5 %, molar ratio of water to acetone azine is 7 ： 1, and temperature is 90 ~C. In this condition, the conversion of acetone azine is 34.6%. On that basis, a power-law function kinetic model was used to describe the macrokinetics of the reaction of acetone azine. The results show that the apparent activation energy and pre-exponential factor of forward reaction are 2 067.57 J/mol and 5. 957 8, respectively ; the apparent activation energy and pre-exponential factor of the reverse reaction are 125.07 J/mol and 4. 146 3, respectively; the reaction orders with respect to acetone azine, water, hydrazine hydrate and acetone are 0. 099 8,0. 110 8,0.113 2 and 0.1145.