铂催化剂上乙烯和一氧化碳同时氧化反应多定态特性的实验研究

对铂催化剂上乙烯和一氧化碳同时氧化反应多定态特性的实验研究结果表明：在实验条件下体系最多存在有两个稳定的定态,随乙烯和／或一氧化碳浓度的增加,系统的点火温度升高,熄火温度下降,存在多定态的操作参数区域增大;在较高的乙烯和／或一氧化碳浓度条件下,系统将出现自持,实验观测不到熄火现象。通过对体系多定态特性的分析可知,同时氧化反应体系的多定态特性并不等于两个单独氧化反应体系多定态特性的简单迭加,在两个反应之间,除了热量的相互作用外,还存在着动力学抑制作用。     

在铂催化剂上-氧化碳氧化反应的多定态特性

对铂催化剂上一氧化碳氧化反应的多定态特性进行了实验研究,借助于奇异理论和突变理论,对实验结果进行了分析,找出了系统可能存在的定态数目,并预测出在定态数目不同的操作参数区域内,描述系统状态变量与操作参数的分岔图型式,最后,尝试利用系统的多定态特性识别反应的动力学模型,取得了满意的效果.     

在铂催化剂上-氧化碳氧化反应的多定态特性

对铂催化剂上一氧化碳氧化反应的多定态特性进行了实验研究,借助于奇异理论和突变理论,对实验结果进行了分析,找出了系统可能存在的定态数目,并预测出在定态数目不同的操作参数区域内,描述系统状态变量与操作参数的分岔图型式,最后,尝试利用系统的多定态特性识别反应的动力学模型,取得了满意的效果.     

单颗粒催化剂多定态特性的理论分析

借助于奇异理论和突变理论,本文对单颗粒催化剂的多定态特性进行了分析。得到了反应为一级不可逆放热反应时系统定态模型方程解的结构以及可能具有的歧化图型式;对非一级反应系统,利用区域搜索算法得到了其系统定态模型方程突变集合在操作参数平面上的投影图,分析了反应动力学表达式及动力学参数的变化对体系多定态特性的影响。     

B-O2催化剂上丁烯氧化脱氢动力学研究

本文利用内循环无梯度反应器,在320～420℃及较宽的各组分分压范围内研究了B-02工业催化剂用于丁烯氧化脱氢反应的本征动力学.按照串-并联反应网络,依据Redox机理、L-H机理和幂函数型规律构想出28个动力学模型;应用模型参数的物理特征、参数估值中的残差平方和相对大小以及非本征参数法筛选模型;采用模式探测法和马垮特法相结合的综合方法进行模型参数估值,从而求得适宜的本征动力学模型.最后对所定动力学模型进行显著性检验,证明该模型对实验数据确有较好的表现力.文中还讨论了水/烯比值对模型参数的影响、丁二烯的阻碍作用及催化剂的选择性等问题.     

B-O2催化剂上丁烯氧化脱氢动力学研究

本文利用内循环无梯度反应器,在320～420℃及较宽的各组分分压范围内研究了B-02工业催化剂用于丁烯氧化脱氢反应的本征动力学.按照串-并联反应网络,依据Redox机理、L-H机理和幂函数型规律构想出28个动力学模型;应用模型参数的物理特征、参数估值中的残差平方和相对大小以及非本征参数法筛选模型;采用模式探测法和马垮特法相结合的综合方法进行模型参数估值,从而求得适宜的本征动力学模型.最后对所定动力学模型进行显著性检验,证明该模型对实验数据确有较好的表现力.文中还讨论了水/烯比值对模型参数的影响、丁二烯的阻碍作用及催化剂的选择性等问题.     

挥发性有机化合物催化氧化技术

基于环境友好,对使用催化氧化法去除挥发性有机化合物(VOCs)的原理、特点以及催化剂、工艺流程等研究进行综述。挥发性有机化合物完全催化氧化机理分为:Mars-van Krevelen(MVK)模型、Langmuir-Hinshelwood(L-H)模型和Eley-Rideal(E-R)模型。复合金属氧化物催化剂是研究的热点,去除VOCs的核心是使反应温度降低,即具有低温和高活性的催化剂。延长催化剂寿命、提高去除效率也可以带来良好的节能效果和降低投资成本。对于低浓度和大体积VOCs排放,可通过吸附+催化混合法先进技术实现去除,且成功应用于实践。     

纳米材料的应用

１　工业催化纳米材料的比表面积大,表面活性中心多,为做催化剂提供了必要条件。同时纳米材料的表面效应和体积效应决定了它具有良好的催化活性和催化反应选择性。目前在高分子聚合物氧化、还原及合成反应中可直接用纳米态铂黑、银、氧化铝、氧化铁等做催化剂,大大提高了反应效率;利用纳米镍作为火箭固体燃料反应催化剂,燃烧效率可提高１００倍。纳米材料催化剂的催化反应选择性还表现出特异性,如用硅载体纳米镍催化剂对丙醛的氧化反应研究表明,镍粒径在５ｎｍ以下时,反应选择性发生急剧变化——醛分解得到控制,生成乙醇的选择性迅…     

完全液相制备催化剂上合成二甲醚动力学研究

采用浆态床反应器,研究了用完全液相法制备的Cu-Zn-A l双功能催化剂上CO加氢直接合成二甲醚(DME)的反应动力学。按CO加氢先合成CH3OH,再由CH3OH脱水生成DME二步串联的反应机理,根据不同的中间产物及控制步骤分别建立了动力学模型,以反应物的平衡浓度代替逸度进行计算,最终选取的模型计算值和实验值吻合较好,说明采用L-H型动力学模型可以合理地描述催化剂表面的反应过程,模型参数计算结果表明,催化剂表面对CO2的弱吸附是该催化剂在浆态床中稳定性较好的主要原因之一。     

甲醇在耐高温磺酸树脂催化下的脱水反应动力学

为了开发反应精馏合成二甲醚新工艺,实验在2MPa(G)、120℃～155℃、初始甲醇摩尔分数100%～30%、液空速0.10mL/(min·g催化剂)～0.15mL/(min·g催化剂)条件下,以耐高温磺酸树脂作催化剂,在等温积分反应器内,系统地测定了甲醇脱水生成二甲醚的反应动力学数据。分别用L-H及E-R模型建立了反应动力学方程,并对实验数据进行了拟合。拟合结果表明:在实验范围内,按E-R模型拟合的反应动力学方程与实验结果更吻合。通过对动力学方程进行分析,发现随着反应温度的升高以及甲醇活度与水活度比值的增大,甲醇脱水反应速率都会增大。实验工作可为开发反应精馏合成二甲醚新工艺提供重要的反应动力学数据。     

STEADY STATE MULTIPLICITY FEATURES OF ETHYLENE OXIDATION ON PLATINUM FOIL

The catalytic oxidation of ethylene to carbon dioxide in excess air has been studied atsteady state.The catalyst temperature was measured for various feed temperature and concentration.The bifurcation diagrams Which describe the dependence of the catalyst temperature on the feed gastemperature were obtained for different ethylene concentrations in the feed gas.The ignition and ex-tinction temperatures were found out and the unique and multiple steady state regions could bedetermined from these diagrams.The experimental results can be satisfactorily explained by thecatastrophe theory and singularity theory.According to the steady state multiplicity features an at-tempt to discriminate the competitive kinetic models was made for the reaction.     

The kinetics and mechanism of the oxidation of carbon monoxide over an industrial vanadium oxide catalyst

The rate of catalytic oxidation of carbon monoxide was studied in a fixed bed reactor over the following range of conditions: 325 to 396°C, 0.11 to 1.75 mole % oxygen, 9.50 to 10.20 mole % carbon monoxide. Oxygen was the limiting component, most of the runs were taken to greater than 10% oxygen conversions, and therefore an integral approach was taken in the data analysis. The catalyst was vanadium oxide/potassium sulfate on silica, an industrial preparation which had been used in previous kinetic studies. The data were correlated successfully by the steady state adsorption model with Arrhenius activation energies of 22.1 k.cal/g. mole for the oxygen chemisorption step and 18.0 k.cal/g. mole for the reaction step. The rate constants obtained provide further support for the steady state adsorption model, previously used to evaluate the oxidation kinetics of naphthalene, toluene, benzene and orthoxylene on the same catalyst. The integrated rate equation appears to well describe the relationship between the various parameters with the conversion of the limiting component varying from less than 5% to over 50%. A brief comparison is reported between the steady state adsorption model and the more complex triangular mechanism postulated by Hirota and co-workers.     

In situ XAS with high-energy resolution: The changing structure of platinum during the oxidation of carbon monoxide

The catalytically active species during the oxidation of carbon monoxide over a real alumina-supported platinum catalyst under atmospheric pressure are determined by combining in situ high-energy resolution fluorescence detection X-ray absorption spectroscopy (HERFD XAS) at the Pt L₃ edge and kinetic measurements. Catalysts were prepared by incipient wetness impregnation. The oxidation of carbon monoxide occurred in two distinctive regimes, a high-activity regime and a low-activity regime, which have high and low rates of reaction respectively. In the low-activity region, the catalyst is poisoned by carbon monoxide, limiting the dissociative adsorption of oxygen. In the high-activity regime, all CO is desorbed from the surface, increasing the rate of reaction. The low carbon monoxide concentration enables oxygen to react to the surface in this reaction regime generating a more reactive surface. HERFD showed that different phases are active depending on the reaction conditions in nano-sized catalyst particles.     

Poisoning and inhibition of catalytic oxidations: I. The effect of silicone vapour on the gas-phase oxidations of methane,propene, carbon monoxide and hydrogen over platinum and palladium catalysts

The influence of hexamethyldisiloxane (HMDS) on the catalytic oxidations of methane, propene, carbon monoxide and hydrogen has been studied. The oxidations of methane and carbon monoxide were studied over platinum wire and platinum and palladium supported on alumina, silica and 13X zeolite. The rates of oxidation both in the absence and presence of HMDS were found to be influenced by the nature of the catalyst support. For carbon monoxide oxidation, the presence of HMDS revealed that three types of oxidation were occurring. These results, taken with those obtained for the oxidation of hydrogen and propene, show that in general the relative importance of the three types of oxidation depends on the nature of the reaction and the catalyst support.     

Reaction pathways and poisons—II: The rate controlling step for electrochemical oxidation of hydrogen on Pt in acid and poisoning of the reaction by CO

The reaction mechanism for hydrogen molecule oxidation on platinum electrocatalysts in acid solutions is deduced by comparing kinetic rate parameters obtained electrochemically, to those rate parameters obtained in the gas phase from H₂—D₂ exchange. The electrochemical rate parameters were obtained from potentiodynamic scanning of smooth platinum and from polarisation curves of porous platinum black flooded electrode structures. The rate controlling step for hydrogen molecule oxidation on Pt is the dual site dissociative chemisorption of the hydrogen molecule H₂ → 2H (known as the Tafel reaction). Specific poisons for this reaction are chemisorbed carbon monoxide and adsorbed hydrogen, producing a simple site elimination for dissociative chemisorption of the hydrogen molecule and confirm the dual site mechanism. The electrochemical reaction rate parameters are the same on smooth platinum, unsupported platinum black and platinum crystallites supported on graphitised carbon, correlating with the H₂-H₂ exchange in the gas-phase, both with and without chemisorbed carbon monoxide and are dependent only upon the surface areas of platinum catalysts.     

Adsorption kinetics for carbon monoxide on platinum in hot phosphoric acid

The availability and activity of platinum electrocatalyst sites for oxidation of the hydrogen in reformed natural gas has been one of the problems associated with efficient utilization of the platinum-anode catalyst. The major anode catalyst poison is carbon monoxide and the mechanism of poisoning of the hydrogen reaction by carbon monoxide has been reported.The equilibrium adsorptions and the rates of adsorption of CO on platinum surfaces were studied at a series of p_co values between 0·01 and 0·10 atm in 96 per cent H₃PO₄ between 105 and 148°C. This range of partial pressures of CO is expected within an operating fuel cell.The adsorption isotherms are explicable in terms of single-site adsorption of the carbon monoxide molecule on the platinum surface atoms, causing a slow anion adsorption at the unpoisoned platinum sites. The equilibrium coverages for carbon monoxide on the platinum surfaces are independent of temperature in the range studied. Adsorption equations are used to describe the coverages of the platinum surface by carbon monoxide so that extrapolation of the data to both higher and lower carbon monoxide partial pressures gives reliable estimates of the resultant surface coverages.