RDX热分解研究

为了更加全面的探究黑索今(RDX)热安全性,利用绝热加热法及DSC-TG-DTG法两种实验方法分析了RDX的热分解过程。通过对比两种实验方法可以总结出RDX在密闭条件下热分解初始速度比在开放系统中低5.4℃,实验条件对分解过程及相关参数影响较大。     

含氨典型废气净化及工程示范装置运行总结

采用吸收/吸附-催化有氧分解耦合工艺净化合成氨及尿素生产过程中产生的含氨废气。介绍了净化合成氨弛放气的工程示范装置的工艺操作条件、工艺流程及运行效果。氨含量约3%的弛放气经过离子液吸收塔处理后,气体中的氨平均浓度降到45×10-6以下,再经4级蒸馏后,回收氨的浓度可达95%;氢氨回收膜分离装置含少量氨的工艺尾气经催化反应器处理后,排放氨浓度小于1.4×10-6;弛放气中氨的净化率达到99.99%。     

Numerical investigation on the number of active surface sites of carbon catalysts in the decomposition of methane

The number of active sites on the surface of carbon catalysts is an important factor in determining their activity in the decomposition of methane. Although several studies have been performed to identify the nature of these sites, no method has been established to estimate their number. A method is presented to estimate this value, and its effect on hydrogen production is evaluated, along with that of temperature and residence time. For this purpose, the thermocatalytic decomposition of methane is modeled with the inclusion of the number of active sites of the catalyst in the kinetics. The results of the model indicate the high influence of variations of small residence times in this process, and the reduction of this effect at high temperatures. Also, the effect of the number of surface sites is shown to be more prominent at low residence times and temperatures. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2228–2234, 2014     

Formic acid decomposition on Au catalysts: DFT,microkinetic modeling,and reaction kinetics experiments

A combined theoretical and experimental approach is presented that uses a comprehensive mean‐field microkinetic model, reaction kinetics experiments, and scanning transmission electron microscopy imaging to unravel the reaction mechanism and provide insights into the nature of active sites for formic acid (HCOOH) decomposition on Au/SiC catalysts. All input parameters for the microkinetic model are derived from periodic, self‐consistent, generalized gradient approximation (GGA‐PW91) density functional theory calculations on the Au(111), Au(100), and Au(211) surfaces and are subsequently adjusted to describe the experimental HCOOH decomposition rate and selectivity data. It is shown that the HCOOH decomposition follows the formate (HCOO) mediated path, with 100% selectivity toward the dehydrogenation products (CO₂ + H₂) under all reaction conditions. An analysis of the kinetic parameters suggests that an Au surface in which the coordination number of surface Au atoms is ≤4 may provide a better model for the active site of HCOOH decomposition on these specific supported Au catalysts. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1303–1319, 2014     

Steam reforming of ethanol over skeletal Ni‐based catalysts: A temperature programmed desorption and kinetic study

An investigation on reaction scheme and kinetics for ethanol steam reforming on skeletal nickel catalysts is described. Catalytic activity of skeletal nickel catalyst for low‐temperature steam reforming has been studied in detail, and the reasons for its high reactivity for H₂ production are attained by probe reactions. Higher activity of water gas shift reaction and methanation contributes to the low CO selectivity. Cu and Pt addition can promote WGSR and suppress methanation, and, thus, improve H₂ production. A reaction scheme on skeletal nickel catalyst has been proposed through temperature programmed reaction spectroscopy experiments. An Eley‐Rideal model is put forward for kinetic studies, which contains three surface reactions: ethanol decomposition, water gas shift reaction, and methane steam reforming reaction. The kinetics was studied at 300–400°C using a randomized algorithms method and a least‐squares method to solve the differential equations and fit the experimental data; the goodness of fit obtained with this model is above 0.95. The activation energies for the ethanol decomposition, methane steam reforming, and water gas shift reaction are 187.7 kJ/mol, 138.5 kJ/mol and 52.8 kJ/mol, respectively. Thus, ethanol decomposition was determined to be the rate determining reaction of ethanol steam reforming on skeletal nickel catalysts. © 2013 American Institute of Chemical Engineers AIChE J 60: 635–644, 2014     

红土镍矿分解实验研究

提出了酸碱交替分解、互为活化的工艺思路,通过实验确定了优化工艺条件和工艺流程。在优化工艺条件下,红土镍矿中Fe2O3、NiO、MgO、Co、SiO2分解率分别达到96.78%、99.62%、94.39%、100%和98.60%,从而为实现对红土镍矿的全元素综合利用奠定了基础。     

阻燃POM的热降解动力学研究

采用双螺杆挤出机制备了APP/MC/DPER/novolak阻燃POM材料,对材料进行了TGA测试,采用Flynn-WallOzawa方法、Starink方法两种动力学方法研究了阻燃POM的热降解动力学。由这两种方法计算得到的结果较为吻合,结果表明,阻燃剂的添加使POM材料的热降解活化能先下降后升高,说明阻燃剂先于POM分解并生成耐热性好的残炭。     

含氰基聚酰亚胺薄膜的制备及其热分解动力学

以4-[3,5-双(4-氨基苯氧基)苯氧基]邻苯二甲腈和3,3′,4,4′-联苯四甲酸二酐为原料,经聚酰胺酸热酰亚胺化制备含氰基的聚酰亚胺(CN-BP-PI)薄膜。采用傅里叶变换红外光谱、热重分析、差示扫描量热法对CN-BP-PI薄膜进行了分析。采用动态热重法研究了CN-BP-PI的分解动力学,用积分法结合常见固相热分解反应动力学函数来判断热分解的动力学函数。由Ozawa,KAS,Kissinger,Achar,Coats-Redfern,MacCallum-Tanner,van Krevelen方程求热分解反应的动力学参数。转化率为0.2~0.8时所得CN-BP-PI在氮气中热分解反应的表观活化能为119.68~215.61 kJ/mol,平均活化能为136.35 kJ/mol,指前因子平均值为8.52×107 s-1。     

Recursive State-space Model Identification of Non-uniformly Sampled Systems Using Singular Value Decomposition☆

In this paper a recursive state-space model identification method is proposed for non-uniformly sampled systems in industrial applications. Two cases for measuring all states and only output(s) of such...     

羧酸盐配合物的热分解研究进展

羧酸盐配合物具有非常广泛的用途,热稳定性作为其非常重要的一种性质而被深入研究。本文对稀土、碱土和过渡金属羧酸盐配合物的热分解反应过程,以及芳香族羧酸盐配合物的热分解过程的动力学分析方面的研究进展进行了综述,以期为该类物质的实际应用提供更全面的参考数据。