偶氮二异庚腈的热分解动力学研究
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摘要
为获得准确的偶氮二异庚腈(ABVN)的热分解动力学模型及其动力学参数,利用差示扫描量热仪(DSC)和绝热量热仪(ARC)对ABVN在动态和绝热条件下的热分解特性进行测试。由于ABVN是一种吸放热耦合的物质,因而采用AKTS软件对其进行解耦。联合采用解耦后的动态和绝热两种量热模式下的试验数据对ABVN进行热分解动力学分析,建立了N级分解动力学模型,并采用Friedman方法和非线性拟合方法求算其热分解动力学参数。联合动态和绝热两种量热模式下试验数据的拟合结果表明:N级分解动力学模型拟合得到的拟合曲线与试验曲线基本吻合,说明该模型可以很好地反映ABVN的热分解过程,其活化能为98.31kJ/mol,指前因子为3.3×1015,反应级数为1.18。最后利用中断回扫法进一步验证了建立的ABVN热分解动力学模型的正确性。基于ABVN热分解动力学模型获得的热分解动力学参数对ABVN的生产、运输、存储等过程具有一定的安全指导意义。
In order to obtain accurate thermal decomposition kinetics model and kinetic parameters of 2,2'-Azobisisoheptonitrile(ABVN),this paper conducts the dynamic and adiabatic experiments by Differential Scanning Calorimeter(DSC)and Accelerating Rate Calorimeter(ARC).The paper uses AKTS software to decouple ABVN which has the phenomenon of heat absorption and generation.Combining decoupled dynamic and adiabatic data for kinetic analysis,the paper establishes"N-order"decomposition kinetics models,and calculates their kinetic parameters by Friedman method and the nonlinear fitting method.The curves obtained by simulating the N-order model are basically consistent with the experiments curves,which means that the decomposition process can be better reflected by the dynamic and adiabatic calorimetry mode at the same time.The activation energy is 98.31 kJ/mol,the pro-exponential factor is 3.3×1015,and reaction order is 1.18.It is further proved by the"interruption and re-scanning"method that the kinetic model of ABVN is correct.The thermal decomposition kinetics parameters of ABVN obtained based on the model have certain safety guiding significance for production,transportation and storage.
In order to obtain accurate thermal decomposition kinetics model and kinetic parameters of 2,2'-Azobisisoheptonitrile(ABVN),this paper conducts the dynamic and adiabatic experiments by Differential Scanning Calorimeter(DSC)and Accelerating Rate Calorimeter(ARC).The paper uses AKTS software to decouple ABVN which has the phenomenon of heat absorption and generation.Combining decoupled dynamic and adiabatic data for kinetic analysis,the paper establishes"N-order"decomposition kinetics models,and calculates their kinetic parameters by Friedman method and the nonlinear fitting method.The curves obtained by simulating the N-order model are basically consistent with the experiments curves,which means that the decomposition process can be better reflected by the dynamic and adiabatic calorimetry mode at the same time.The activation energy is 98.31 kJ/mol,the pro-exponential factor is 3.3×1015,and reaction order is 1.18.It is further proved by the"interruption and re-scanning"method that the kinetic model of ABVN is correct.The thermal decomposition kinetics parameters of ABVN obtained based on the model have certain safety guiding significance for production,transportation and storage.
引文
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[21]Kossoy A,Yu A.Identification of kinetic models for the assessment of reaction hazards[J].Process Safety Progress,2010,26(3):209-220.
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[23]杨庭,陈利平,陈网桦,等.分解反应自催化性质快速鉴别的实验方法[J].物理化学学报,2014,30(7):1215-1222.
[24]王凯,肖松,申孝立,等.六硝基六氮杂异戊兹烷自催化分解特性与热安全性研究[J].兵工学报,2018,39(1):57-62.
[25]胡荣祖.热分析动力学[M].2版.北京:科学出版社,2016.
[26]Friedman H L.Kinetics of thermal degradation of charforming plastics from thermogravimetry.Applications to phenolic plastic[J].Journal of Polymer Science Part C:Polymer Symposia,2010,6(1):183-195.
[27]Sergey V.Kinetic concepts of thermally stimulated reactions in solids:A view from a historical perspective[J].International Reviews in Physical Chemistry,2000,19(1):45-60.
[28]Vyazovkin S.On the phenomenon of variable activation energy for condensed phase reactions[J].New Journal of Chemistry,2000,24(11):913-917.
[28]Lu G B,Yang T,Chen L P,et al.Thermal decomposition kinetics of 2-ethylhexyl nitrate under non-isothermal and isothermal conditions[J].Journal of Thermal Analysis&Calorimetry,2016,124(1):471-478.
[29]岳越,陈利平,彭金华.Mg(BH4)2对钝化RDX安全性的影响[J].中国安全科学学报,2016,26(7):125-129.
[30]吕家育,陈网桦,陈利平,等.2,4-二氯过氧化苯甲酰的热分解及等温动力学模型[J].化工学报,2013,64(11):4054-4059.
[31]Chen J R,Cheng S Y,Yuan M H,et al.Hierarchical kinetic simulation for autocatalytic decomposition of cumene hydroperoxide at low temperatures[J].Journal of Thermal Analysis&Calorimetry,2009,96(3):751-758.
[32]施特塞尔.化工工艺的热安全:风险评估与工艺设计[M].陈网桦,彭金华,陈利平,译.北京:科学出版社,2009:250-283.
[33]Vyazovkin S,Burnham A K,Criado J M,et al.ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data[J].Thermochimica Acta,2011,520(1):1-19.
[34]Roduit B,Hartmann M,Folly P,et al.Prediction of thermal stability of materials by modified kinetic and model selection approaches based on limited amount of experimental points[J].Thermochimica Acta,2014,579(5):31-39.
[2]王麒,张森,陈惠芳,等.以偶氮二异庚腈为引发剂的丙烯腈的低温溶液共聚合[J].化学学报,2010,68(24):2609-2614.
[3]Liu S H,Yu Y P,Lin Y C,et al.Complex thermal evaluation for2,2′-azobis(isobutyronitrile)by non-isothermal and isothermal kinetic analysis methods[J].Journal of Thermal Analysis&Calorimetry,2014,116(3):1361-1367.
[4]Li X R,Wang X L,Koseki H.Study on thermal decomposition characteristics of AIBN[J].Journal of Hazardous Materials,2008,159(1):13-18.
[5]Alastair D,Lester E H,Thurecht K J,et al.Temperature dependence of the dielectric properties of 2,2′-azobis(2-methyl-butyronitrile)(AMBN)[J].Industrial&Engineering Chemistry Research,2010,49(6):3011-3014.
[6]Li X R,Koseki H.SADT prediction of autocatalytic material using isothermal calorimetry analysis[J].Thermochimica Acta,2005,431(1/2):113-116.
[7]Li X R,Koseki H.Study on the early stage of runaway reaction using Dewar vessels[J].Journal of Loss Prevention in the Process Industries,2005,18(4/5/6):455-459.
[8]杜晓燕,吴建华,朱庆明,等.我国危险化学品事故灰色残差马尔科夫预测模型的建立及应用研究[J].安全与环境工程,2018,25(3):125-129.
[9]王炎,陈利平,陈网桦.易燃易爆危险化学品DSC鉴别方法的研究[J].安全与环境工程,2018,25(2):143-149.
[10]国务院京珠高速河南信阳“7·22”特别重大卧铺客车燃烧事故调查组.京珠高速河南信阳“7·22”特别重大卧铺客车燃烧事故调查报告[J].劳动保护,2012(8):12-16.
[11]Idage B B,Vernekar S P,Ghatge N D.Decomposition rate studies of azo initiators in solution[J].Journal of Polymer Science Part A:Polymer Chemistry,2010,21(7):524-530.
[12]Hook J P V,Tobolsky A V.The thermal decomposition of 2,2'-azo-bis-isobutyronitrile[J].Journal of the American Chemical Society,1956,80(4):25-30.
[13]费轶,金满平,张帆.偶氮二异庚腈(ABVN)的安全性分析[J].安全、健康和环境,2015,15(11):42-46.
[14]张婷,谢传欣,金满平,等.偶氮二异庚腈(ABVN)热危险性及杂质对其影响研究[J].中国安全科学学报,2012,22(10):120-125.
[15]Liu S H,Chen Y C,Hou H Y.Thermal runaway hazard studies for ABVN mixed with acids or alkalines by DSC,TAM III,and VSP2[J].Journal of Thermal Analysis&Calorimetry,2015,122(3):1107-1116.
[16]Liu S H,Shu C M.Advanced technology of thermal decomposition for AMBN and ABVN by DSC and VSP2[J].Journal of Thermal Analysis&Calorimetry,2015,121(1):1-8.
[17]Zhang J,Xue B B,Rao G N,et al.Thermal decomposition characteristic and kinetics of DINA[J].Journal of Thermal Analysis&Calorimetry,2017(4):1-9.
[18]Zhang C X,Lu G B,Chen L P,et al.Two decoupling methods for non-isothermal DSC results of AIBN decomposition.[J].Journal of Hazardous Materials,2015,285:61-68.
[19]董泽,陈利平,陈网桦.40%DCP溶液的热分解模型[J].化工学报,2017,68(5):1773-1779.
[20]CISP site[EB/OL].[2017-02-02].http://www.cisp.spb.ru/tss.
[21]Kossoy A,Yu A.Identification of kinetic models for the assessment of reaction hazards[J].Process Safety Progress,2010,26(3):209-220.
[22]Svoboda R,Málek J.Importance of proper baseline identification for the subsequent kinetic analysis of derivative kinetic data[J].Journal of Thermal Analysis&Calorimetry,2016,124(3):1-9.
[23]杨庭,陈利平,陈网桦,等.分解反应自催化性质快速鉴别的实验方法[J].物理化学学报,2014,30(7):1215-1222.
[24]王凯,肖松,申孝立,等.六硝基六氮杂异戊兹烷自催化分解特性与热安全性研究[J].兵工学报,2018,39(1):57-62.
[25]胡荣祖.热分析动力学[M].2版.北京:科学出版社,2016.
[26]Friedman H L.Kinetics of thermal degradation of charforming plastics from thermogravimetry.Applications to phenolic plastic[J].Journal of Polymer Science Part C:Polymer Symposia,2010,6(1):183-195.
[27]Sergey V.Kinetic concepts of thermally stimulated reactions in solids:A view from a historical perspective[J].International Reviews in Physical Chemistry,2000,19(1):45-60.
[28]Vyazovkin S.On the phenomenon of variable activation energy for condensed phase reactions[J].New Journal of Chemistry,2000,24(11):913-917.
[28]Lu G B,Yang T,Chen L P,et al.Thermal decomposition kinetics of 2-ethylhexyl nitrate under non-isothermal and isothermal conditions[J].Journal of Thermal Analysis&Calorimetry,2016,124(1):471-478.
[29]岳越,陈利平,彭金华.Mg(BH4)2对钝化RDX安全性的影响[J].中国安全科学学报,2016,26(7):125-129.
[30]吕家育,陈网桦,陈利平,等.2,4-二氯过氧化苯甲酰的热分解及等温动力学模型[J].化工学报,2013,64(11):4054-4059.
[31]Chen J R,Cheng S Y,Yuan M H,et al.Hierarchical kinetic simulation for autocatalytic decomposition of cumene hydroperoxide at low temperatures[J].Journal of Thermal Analysis&Calorimetry,2009,96(3):751-758.
[32]施特塞尔.化工工艺的热安全:风险评估与工艺设计[M].陈网桦,彭金华,陈利平,译.北京:科学出版社,2009:250-283.
[33]Vyazovkin S,Burnham A K,Criado J M,et al.ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data[J].Thermochimica Acta,2011,520(1):1-19.
[34]Roduit B,Hartmann M,Folly P,et al.Prediction of thermal stability of materials by modified kinetic and model selection approaches based on limited amount of experimental points[J].Thermochimica Acta,2014,579(5):31-39.
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