40%DCP溶液的热分解模型

发布时间：2018-04-03 07:53

  本文选题：热分解　切入点：量热模式　出处：《化工学报》2017年05期

【摘要】：准确的热分解动力学模型有助于人们采取各种安全措施预防和控制物料热失控导致的燃烧爆炸事故。以40%过氧化二异丙苯(DCP)的2,2,4-三甲基戊二醇二异丁酯(DIB)溶液为研究对象,运用差示扫描量热仪(DSC)和绝热量热设备(VSP2)进行了量热实验,并采用TSS软件(Thermal Safety Software)对数据进行动力学分析,建立了两种分解模型:"N级+N级"模型(模型1)和"N级+自催化"模型(模型2),采用Friedman法和非线性拟合方法求算其动力学参数。在运用所建立的两种模型拟合曲线时,发现两种模型对同种量热模式数据拟合的相关系数非常接近,说明单一量热模式在求算动力学上存在局限性。联合采用基于动态扫描模式的DSC数据及基于绝热模式的VSP2数据共同求算动力学,发现相对于模型2,模型1可以更好地反映分解过程,其两步反应的活化能分别为115.5 kJ·mol~(-1)和135.7 kJ·mol~(-1),指前因子的对数分别为28.3和31.6,反应级数分别为0.40和0.84。研究结果表明采用基于不同量热模式的数据求算动力学有助于确定正确的动力学模型,从而获得准确的动力学参数,并克服单一量热模式下动力学求算的局限性。
[Abstract]:Accurate kinetic model of thermal decomposition is helpful to take various safety measures to prevent and control combustion explosion caused by heat runaway of materials.Two decomposition models were established: "N-order N-order" model (model 1) and "N-order autocatalytic" model (model 2). The kinetic parameters were calculated by Friedman method and nonlinear fitting method.When the two models are used to fit the curves, it is found that the correlation coefficients of the two models are very close to the data of the same calorimetric model, which indicates that the single calorimetric model is limited in computing dynamics.The DSC data based on dynamic scanning mode and VSP2 data based on adiabatic mode are used to calculate the dynamics together. It is found that model 1 can better reflect the decomposition process compared with model 2.The activation energy of the two-step reaction is 115.5 kJ / mol ~ (-1) and 135.7 kJ / mol ~ (-1) respectively. The logarithm of the preexponential factor is 28.3 and 31.6, and the reaction order is 0.40 and 0.84, respectively.The results show that the use of data based on different calorimetric models is helpful to determine the correct kinetic model and to obtain accurate kinetic parameters, and to overcome the limitation of dynamic calculation under a single calorimetric model.
【作者单位】： 南京理工大学化工学院;索尔维投资有限公司(中国);
【分类号】：O645.11
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本文编号：1704277