The decomposition kinetics of glucose and 5-hydroxymethylfurfural catalyzed by copper chloride were measured in small volume high-pressure vessel batch reactors,at various temperatures from 423.15 K to 463.15 K and ca...The decomposition kinetics of glucose and 5-hydroxymethylfurfural catalyzed by copper chloride were measured in small volume high-pressure vessel batch reactors,at various temperatures from 423.15 K to 463.15 K and catalyst concentration from 0 to 0.08 mol·L-1.The results showed that their conversion went up with the increase of reaction temperature and catalyst concentration,resulting in higher yield of levulinic acid.By comparing the correlation coefficients,it was confirmed that both glucose and 5-hydroxymethylfurfural decomposition are first order reaction.By using first order kinetics equation,the activation energies of desired and undesired reaction were estimated,134.65 kJ·mol-1 and 144.1 kJ·mol-1 for glucose decomposition,131.97 kJ·mol-1 and 135.18 kJ·mol-1 for 5-hydroxymethylfurfural decomposition,respectively.This work would provide important basic data not only for the exploration of reaction mechanism of glucose decomposition,but also for the development of high activity and high selectivity catalyst.展开更多
文摘为提高2,6-二氨基-3,5-二硝基吡啶^(-1)-氧化物(ANPyO)Pb(Ⅱ)(Pb-ANPyO)含能配合物能量水平,获得安全性能和热分解特性参数。以ANPy O和醋酸铅为原料,N,N-二甲基甲酰胺(DMF)为溶剂,合成了ANPy OPb(Ⅱ)含能配合物。采用红外光谱(FTIR),元素分析和X射线光电子能谱分析(XPS)表征其结构,测试了其撞击感度和摩擦感度,采用差热分析-热重法(DSC-TG)研究其在不同升温速率下的热分解行为,利用Kissinger公式,Ozawa公式,热力学关系式和Zhang-Hu-Xie-Li公式分别计算了配合物热分解反应的表观活化能和热力学参数,以及配合物的热安全性参数。结果表明,配合物分子式为Pb(C5H3N5O5),特性落高和摩擦感度分别为238 cm和0。配合物在25~500℃范围内的热分解过程由一个吸热熔融峰和一个分解放热峰组成,相应峰温分别为265.0℃和332.6℃。用Kissinger法和Ozawa法所得配合物放热分解反应的活化能分别为202.42 k J·mol^(-1)和197.40 k J·mol^(-1),放热分解反应的活化熵,活化焓和活化自由能分别为149.5 J·mol^(-1)·K^(-1),197.7 k J·mol^(-1),112.1 kJ·mol^(-1),热爆炸临界温度和自加速分解温度分别为586.6 K和572.4 K。
文摘The decomposition kinetics of glucose and 5-hydroxymethylfurfural catalyzed by copper chloride were measured in small volume high-pressure vessel batch reactors,at various temperatures from 423.15 K to 463.15 K and catalyst concentration from 0 to 0.08 mol·L-1.The results showed that their conversion went up with the increase of reaction temperature and catalyst concentration,resulting in higher yield of levulinic acid.By comparing the correlation coefficients,it was confirmed that both glucose and 5-hydroxymethylfurfural decomposition are first order reaction.By using first order kinetics equation,the activation energies of desired and undesired reaction were estimated,134.65 kJ·mol-1 and 144.1 kJ·mol-1 for glucose decomposition,131.97 kJ·mol-1 and 135.18 kJ·mol-1 for 5-hydroxymethylfurfural decomposition,respectively.This work would provide important basic data not only for the exploration of reaction mechanism of glucose decomposition,but also for the development of high activity and high selectivity catalyst.
