本文選題：熱分解　切入點：量熱模式　出處：《化工學(xué)報》2017年05期

【摘要】：準(zhǔn)確的熱分解動力學(xué)模型有助于人們采取各種安全措施預(yù)防和控制物料熱失控導(dǎo)致的燃燒爆炸事故。以40%過氧化二異丙苯(DCP)的2,2,4-三甲基戊二醇二異丁酯(DIB)溶液為研究對象,運用差示掃描量熱儀(DSC)和絕熱量熱設(shè)備(VSP2)進(jìn)行了量熱實驗,并采用TSS軟件(Thermal Safety Software)對數(shù)據(jù)進(jìn)行動力學(xué)分析,建立了兩種分解模型:"N級+N級"模型(模型1)和"N級+自催化"模型(模型2),采用Friedman法和非線性擬合方法求算其動力學(xué)參數(shù)。在運用所建立的兩種模型擬合曲線時,發(fā)現(xiàn)兩種模型對同種量熱模式數(shù)據(jù)擬合的相關(guān)系數(shù)非常接近,說明單一量熱模式在求算動力學(xué)上存在局限性。聯(lián)合采用基于動態(tài)掃描模式的DSC數(shù)據(jù)及基于絕熱模式的VSP2數(shù)據(jù)共同求算動力學(xué),發(fā)現(xiàn)相對于模型2,模型1可以更好地反映分解過程,其兩步反應(yīng)的活化能分別為115.5 kJ·mol~(-1)和135.7 kJ·mol~(-1),指前因子的對數(shù)分別為28.3和31.6,反應(yīng)級數(shù)分別為0.40和0.84。研究結(jié)果表明采用基于不同量熱模式的數(shù)據(jù)求算動力學(xué)有助于確定正確的動力學(xué)模型,從而獲得準(zhǔn)確的動力學(xué)參數(shù),并克服單一量熱模式下動力學(xué)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.
【作者單位】： 南京理工大學(xué)化工學(xué)院;索爾維投資有限公司(中國);
【分類號】：O645.11
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本文編號：1704277