采用GC-MS分析玉米秸秆纤维素与亚/超临界乙醇液化产物,将产物划分酮类(KE)、酯类(ES)、醇类(AL)、液化残渣(RE)和其他(OT)五集总,初步探索反应网络,建立12条反应路径的5集总模型,运用遗传算法简化优化后得出计算结果和最佳条件。结果显...采用GC-MS分析玉米秸秆纤维素与亚/超临界乙醇液化产物,将产物划分酮类(KE)、酯类(ES)、醇类(AL)、液化残渣(RE)和其他(OT)五集总,初步探索反应网络,建立12条反应路径的5集总模型,运用遗传算法简化优化后得出计算结果和最佳条件。结果显示,反应级数n在0.1~1.2之间,指前因子A在1.23×10~7/h到1.78×10^(15)/h之间,活化能Ea在76.75~153.45 k J/mol。模拟结果与实验数据相吻合,证实该5集总模型是可靠的,用遗传算法计算动力学参数是可行的,为生物质转化为平台化合物提供基础数据。展开更多
Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla- tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode...Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla- tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode potential (e), the surface coverage of carbon monoxide (x), and adsorbed water (y). The chemical reactions and electrode potential were coupled together through the rate constant ki = exp(ai(e ? ei)). The analysis to the established model discloses the following: there are different kinetics be- haviors in different ranges of current densities. The chemical oscillation in methanol electrooxidation is assigned to two aspects, one from poison mediate CO of methanol electrooxidation, which is the in- duced factor of the chemical oscillation, and the other from the oxygen-containing species, such as H2Oa. The formation and disappearance of H2Oa deeply depend on the electrode potential, and directly cause the chemical oscillation. The established model makes clear that the potential oscillation in methanol electrooxidation is the result of the feedback of electrode potential e on the reactions in- volving poison mediates CO and oxygen-containing species H2Oa. The numerical analysis of the estab- lished model successfully explains why the potential oscillation in methanol galvanostatic oxidation on a Pt electrode only happens in a certain range of current densities but not at any current density.展开更多
文摘采用GC-MS分析玉米秸秆纤维素与亚/超临界乙醇液化产物,将产物划分酮类(KE)、酯类(ES)、醇类(AL)、液化残渣(RE)和其他(OT)五集总,初步探索反应网络,建立12条反应路径的5集总模型,运用遗传算法简化优化后得出计算结果和最佳条件。结果显示,反应级数n在0.1~1.2之间,指前因子A在1.23×10~7/h到1.78×10^(15)/h之间,活化能Ea在76.75~153.45 k J/mol。模拟结果与实验数据相吻合,证实该5集总模型是可靠的,用遗传算法计算动力学参数是可行的,为生物质转化为平台化合物提供基础数据。
基金National Key Research and Development Program（2017YFB0902302）National Natural Science Foundation of China（51477165）Fundamental Research Funds for the Central Universities（2017RC009）
基金Supported by the National Natural Science Foundation of China (Grant No. 20676156)the Chinese Ministry of Education (Grant No. 307021)+1 种基金China National 863 Program (Grant Nos. 2006AA11A141 and 2007AA05Z124)Chongqing Sci&Tech Key Project (Grant No. CSTC2007AB6012)
文摘Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla- tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode potential (e), the surface coverage of carbon monoxide (x), and adsorbed water (y). The chemical reactions and electrode potential were coupled together through the rate constant ki = exp(ai(e ? ei)). The analysis to the established model discloses the following: there are different kinetics be- haviors in different ranges of current densities. The chemical oscillation in methanol electrooxidation is assigned to two aspects, one from poison mediate CO of methanol electrooxidation, which is the in- duced factor of the chemical oscillation, and the other from the oxygen-containing species, such as H2Oa. The formation and disappearance of H2Oa deeply depend on the electrode potential, and directly cause the chemical oscillation. The established model makes clear that the potential oscillation in methanol electrooxidation is the result of the feedback of electrode potential e on the reactions in- volving poison mediates CO and oxygen-containing species H2Oa. The numerical analysis of the estab- lished model successfully explains why the potential oscillation in methanol galvanostatic oxidation on a Pt electrode only happens in a certain range of current densities but not at any current density.
