Polymerization Kinetics of Fischer‐Tropsch Reaction on Iron Based Catalysts and Product Grade Optimization

The polymerization kinetics of Fischer‐Tropsch reactions on a K‐promoted Fe catalyst was studied. To represent the product distribution, a kinetic model was developed based on alkyl and alkenyl mechanisms for hydrocarbon chain propagation, which were assumed to occur simultaneously in the Fischer‐Tropsch synthesis. The conclusion was drawn that superimposed Anderson‐Schulz‐Flory (ASF) distributions with different chain growth probabilities, on iron catalysts, can be the result of different chain growth mechanisms. The polymerization mechanism was used to obtain the product distribution for several conditions, and the optimum conditions for the production of transportation fuels were found.     

PSI’s 1 kW imaging furnace—A tool for high-temperature chemical reactivity studies

A new experiment has been installed to conduct studies at temperatures as high as 2500 K on chemical reactions that involve solids or melts and the release of condensable gases. The sample is radiatively heated by a 1 kW xenon short arc lamp placed in the upper focus of a vertically oriented ellipsoid of revolution. The optimal optical configuration has been determined by a Monte-Carlo Ray tracing method. Several methods to machine the reflector have been evaluated by experimentally determining the optical quality of the surface of plane test pieces. In the imaging furnace the sample is placed on a water-cooled support and heated by the concentrated radiation. This arrangement allows for fast heating and impedes the reaction of the sample with crucible material. A remotely controlled hammer allows for freezing the high-temperature composition of the sample by a fast quench. Thus, the sample can be later analyzed by conventional methods such as XRD or TEM. To allow for measurements under defined atmospheres and to protect the ellipsoidal reflector from liberated condensable products, the entire sample stage is enclosed by a hemispherical glass dome. The dome itself is protected from condensable compounds by a laminar flow of inert gas. Experiments with an incense cone at the place of the sample to visualize the gas flow showed that a steady layer of inert gas protects the dome from smoke, if the inert gas flow is properly adjusted. Measured peak flux densities clearly exceed 500 W cm⁻² required to access temperatures of at least 2500 K. Decomposition experiments on copper sulfides confirmed the operation of the furnace. In the near future flash assisted multi-wavelength pyrometry (FAMP) will be implemented to measure sample temperatures online. Though the imaging furnace was developed to study the decomposition of metal sulfides it is obviously suited to conduct high-temperature studies on most materials relevant for high-temperature solar technology.     

Temperature dependence of kinetics and diffusion coefficients for ferrocene/ferricenium in ammonium-imide ionic liquids

The electrochemical behavior of ferrocene (Fc) and ferricenium (Fc⁺) was investigated by cyclic voltammetry with convolutional and semi-differential electroanalyses in the temperature range 298-373 K in the hydrophobic room temperature ionic liquid systems consisting of bis(trifluoromethanesulfone)imide anion with quaternary ammonium cation. The experimental results indicated that the redox reaction of Fc/Fc⁺ was reversible in this ionic liquid and the charge-transfer rate constant (k⁰) has been obtained. Mass transport towards the electrode is a simple diffusion process and the diffusion coefficient (D) for Fc/Fc⁺ has been also calculated. These results indicated that the k⁰ and D increased with increasing temperature in ionic liquids. The validity of the Arrhenius law was verified by investigating the temperature dependences of k⁰ and D.     

Valid parameter range analyses for chemical reaction kinetic models

The present work quantifies the relations between the structure of a chemical reaction kinetic model, its valid parameter range, and the truncation error tolerance of the model. General methods are presented to solve the three important problems of valid parameter range analysis: (1) identification of the valid parameter range of a kinetic model, (2) estimation of the error tolerance required when applying a kinetic model over a specified parameter range, and (3) improvement of existing model generation algorithms to construct more robust models. Finally, the relationship between a model's structure, its valid parameter range, and the truncation error tolerance are illustrated by the flexibility-tolerance-model graph. The new methods are applied to pyrolysis of methane/ethane mixtures.     

Kinetics of TSCD zinc oxide nano-layer growth by modified diffuse-interface model

Deposition of zinc oxide films from aqueous solutions containing complex Zn²⁺ ions on soda-lime substrates were studied by two-stage chemical deposition (TSCD) process. It was shown that the film thickness can be controlled by the number of dipping stages. Nano-layers were produced with less than nine times dipping stages. Greater dipping numbers resulted in film thickness exceeding 100 nm. The growth rate obeyed double-stage zeroth order with respect to the concentration and first order with respect to the temperature. This rate was proportional to the difference between the temperature of the hot water and the substrate. Overall activation energy of 17.20 ± 0.42 kJ mol⁻¹ and frequency factor of 2.81 ± 0.07 μm s⁻¹ was determined for ZnO deposition. These values were attributed to two resistances. One resistance corresponded with film heat transfer mechanism. The other was attributed to species attachment to the solid substrate. A modification to the diffuse-interface kinetic model was devised for explanation of the latter. EDAX (electron dispersive elemental analysis), XRD (X-ray diffraction) and SEM (scanning electron microscopy) were used to characterize the layer formed. These methods showed that the product consisted solely of pure elliptical ZnO grains.     

Influence of Drying Conditions on Ascorbic Acid during Convective Drying of Whole Persimmons

Degradation kinetics of food constituents may be related to the matrix molecular mobility by glass transition temperature. Our objective was to test this approach to describe ascorbic acid degradation during drying of persimmons in an automatically controlled tray dryer with temperatures (40 to 70°C) and air velocities (0.8 to 2.0 m/s) varying according a second order central composite design. The Williams-Landel-Ferry model was satisfactorily adjusted to degradation curves for both control strategies adopted—constant air temperature and temperature fixed inside the fruit. Degradation rates were higher at higher drying temperatures, independent of the necessary time to attain the desired moisture content.     

Leaching kinetics of Cs and Co radionuclides fixed in cement and cement-based materials

Leach characteristics of ¹³⁷Cs and ⁶⁰Co radionuclides from both ordinary Portland cement and cement mixed with two different ratios of silica fume and ilmenite have been studied using International Atomic Energy's (IAEA) standard leach method. A mathematical model has been simulated to predict the release rate of each nuclide from cubic geometry waste matrix and the predicted values are discussed in relation to experimentally observed leach rates to confirm the validity of the proposed mechanism in the model. The effect of temperature on the radionuclides leaching rates was also studied and the effective diffusion coefficients were obtained at different temperatures. The net fractional release of the two radionuclides from different waste forms showed a decreasing pattern as ¹³⁷Cs>⁶⁰Co, indicating the largest diffusion coefficient for cesium in all waste matrices.     

Gasification reactivity of charcoal with CO2. Part I: Conversion and structural phenomena

The gasification reaction of fir charcoal with CO₂ was studied by isothermal thermogravimetric analysis under kinetic control. The derived reaction rate (r=dX/dt) as a function of the converted carbon mass (X) was compared with random pore model predictions and found to be much higher at elevated conversion levels than predicted by theory. Similar enhanced reaction rate behaviour was evidenced after removing the natural alkali catalyst from the charcoal by acid washing, suggesting that with untreated charcoal the late reaction rate contribution stems from both, catalytic and additional structure effects. Literature attributes the unpredicted late reaction rate behaviour to the disintegration of the porous char particle into small fragments, which, in line with percolation theory predictions, seems to occur only after a critical conversion level has been reached. However, our gasification data reveal a gradual rise in the charcoal reactivity thereafter, suggesting a breaking up (embrittlement) of the solid phase accompanied by the exposure of fresh surface area from fracturing. The original random pore model derivation given by Bhatia and Perlmutter is extended to account also for these peculiarities and the resulting kinetic relation described our reaction rate data well over the entire conversion range.     

RELAP5程序与三维时空中子动力学模型的耦合以及改进研究

引入堆芯物理计算的两群三维时空中子动力学模型,对RELAP5程序的点堆中子动力学模型进行了改进,同时设计了可视化界面,可方便地实现人.机交互操作.计算结果与实际应用表明,改进后的RELAP5程序计算功能和精度得到提高,使用更加方便,在核动力装置的仿真方面有很好的应用前景.     

Macroscopic model for multispecies ion-exchange kinetics

A model for multispecies ion-exchange kinetics based on the Nernst-Planck equation is suggested. It is analyzed in comparison with the “locally-determinate” model described by Hwang and Helfferich [1]. The model makes possible simple computation. The conditions for the occurrence of unusual kinetic curves with a maximum are clarified. The proposed model is developed for different types of kinetic problems and verified by the experimental investigation of a kinetics in ternary systems.