碳钢在管流体系中的流动腐蚀动力学模型

针对管流体系 ,根据动量、能量和质量守恒原理 ,应用壁函数、k -ε湍流运动模型确立了管流体系中的计算流体力学模型和质量传递模型 ;结合必要的实验分析碳钢流动腐蚀过程中的主要控制因素及其影响程度 ,建立了碳钢在流动的 3.5 %NaCl溶液中的流动腐蚀动力学模型 .同时 ,采用数值计算方法计算了流动腐蚀速度 ,并与实验结果进行了验证 .揭示出腐蚀电化学因素在碳钢流动腐蚀过程中起着主导的作用.     

Numerical approximation of nonlinear and non-equilibrium two-dimensional model of chromatography

This article is concerned with the numerical approximation of a nonlinear model describing the two-dimensional non-equilibrium transport of multi-component mixtures in a chromatographic column of cylindrical geometry. In contrast to previous studies, the work includes joint analysis of deviations from equilibrium and the possibility that radial concentration profiles can develop. The considered radial gradients are typically ignored, which can be problematic in the case of non perfect injections. The model consists of nonlinear convection-diffusion partial differential equations coupled with some differential and algebraic equations. A high resolution finite volume scheme is applied to solve the model equations numerically. The considered case studies include single-component, two-component and three-component elution on fixed (non-movable) beds of liquid chromatography. The developed numerical algorithm is an efficient tool to study the effects of mass transfer kinetics on the elution profiles.     

Multiphase mass transport in mini/micro-channels microreactor

This paper describes a computational study of two-phase gas/liquid flow in mini/micro-scale reaction channels at low Reynolds numbers. The direct fluorination of toluene is used as a sample process. We consider two different configurations, a falling film and membrane microreactor. The detailed mathematical model of the processes in these configurations is based on mass and momentum conservation equations, which are solved numerically using the finite element method.

Gas-phase mass transport in both reactor configurations is analysed by means of the mathematical model. For fully developed gas flow a correlation for the gas-phase mass transport is developed in terms of the Sherwood and the relative Reynolds number. It is shown that the flow pattern in this regime and entrance effects strongly influence mass transport from the bulk flow to the reaction plane. The velocity profile for the falling film reactor yields higher Sherwood numbers compared to the membrane reactor. The latter has the advantage over the falling film reactor that the gas and liquid phases are decoupled and operating conditions and channel design can be freely chosen.     

Studies of the Kinetics of Reaction Between Iron Catalysts and Ammonia—Nitriding of Nanocrystalline Iron with Parallel Catalytic Ammonia Decomposition

Analysis of two parallel chemical reactions was performed using a flow differential tubular reactor with thermogravimetric measurement and analysis of the gas phase composition. The nitriding rate of the iron ammonia synthesis catalyst and the ammonia decomposition rate were investigated at 350–550 °C. Various gas-phase nitriding potentials were applied. Phase composition was analysed by X-ray diffraction. From a comparison with Lehrer diagram, the critical nitriding potentials for nanoiron were found to be higher than that for bulk materials. The rates of nitriding and ammonia decomposition on iron and various nitrides were determined. Ammonia decomposition was the most rapid on α-Fe and the slowest on γ′-Fe₄N. Results were interpreted on the basis of the adsorption range model and values of kinetics and thermodynamic parameters were assessed. A new method for the determination of crystallite mass distribution, using the results of iron catalyst nitriding process rate measurements, was proposed.     

Performance Optimization of a Brick Dryer Using Porous Simulation Approach

In the present study, an innovative method for an accurate simulation and design of a chamber dryer used in the brick/ceramic industry has been proposed. A thorough investigation of currently used dryers is conducted and optimization criteria are detected and discussed. Three-dimensional modeling of the chamber dryer has been performed. In the second step, from the result of 3D modeling, the critical values for heat transfer coefficient are obtained. The governing equations for a two-dimensional brick as a porous solid are derived by combining conservation laws and Fourier's law for heat conduction and Darcy's and Fick's laws for mass diffusion in porous material. The set of partial differential equations governing heat and mass transport in a single brick together with the respective temperature and humidity boundary conditions have been solved numerically based on finite difference method. Finally, an efficient scheme for the air circulation devices, inlet air temperature and humidity, burner characteristics, flow rates, and drying process control have been proposed for a typical industrial-scale brick dryer.     

Mathematical modeling and numerical simulation of ammonia removal from wastewaters using membrane contactors

This study investigates simulation of ammonia transport through membrane contactors. The system studied involves feed solution of NH₃, a dilute solution of sulfuric acid as solvent and a membrane contactor. The model considers coupling between equations of motion and convection-diffusion. Finite element method was applied for numerical calculations. The effect of different parameters on the removal of ammonia was investigated. The simulation results revealed that increasing feed velocity decreases ammonia removal in the contactor. The modeling findings also showed that the developed model is capable to evaluate the effective parameters which involve in the ammonia removal by means of contactors.     

Modeling and Simulation of a Co-Current Rotary Dryer Under Steady Conditions

A model which joins the overall design algorithm of a rotary dryer with the drying kinetics equations derived from experimental data and with a finite segment algorithm is implemented in order to verify the dryer dimensions obtained from a basic sizing procedure. Total energy and mass balances and well-known correlations for the overall heat transfer coefficient are employed to develop it. Moreover, a one-dimensional finite segment model is solved to obtain the length profiles of temperature and water content for the air and solid phases. An experimental correlation for the mass transfer coefficient between solid and air phases is included in the finite segment model. The chosen heat transfer unit number for the basic sizing is verified with the outlet temperature and water content calculated by the finite segment scheme.     

Falsification of Kinetic Parameters by Transport Limitations and Its Role in Discerning the Controlling Regime

Reactions occurring on the surface of a porous catalyst are accompanied by transport of heat and mass in the pores of the catalyst and across the boundary layer at the external surface. Under the conditions normally encountered in catalytic reactors, heat and mass fluxes can be large enough to cause finite gradients of concentration and temperature in the solid as well as in the film. In such instances the resulting rate of reaction is governed by both the kinetics of the reaction and the transport process (or processes) which gives rise to the gradient. Hence the dependence of the overall or global rate on temperature and the partial pressures of the reacting species can no more be expressed by the intrinsic kinetics of the reaction but is influenced also by the transport parameters of the system. In other words, in the presence of finite transport limitations the catalyst exhibits kinetics falsified by transport processes. This has been referred to as “disguised kinetics” by Wei [l]. Carberry [2] has examined the implications of this disguise in determining the operating regime of a process.     

Falsification of Kinetic Parameters by Transport Limitations and Its Role in Discerning the Controlling Regime

Reactions occurring on the surface of a porous catalyst are accompanied by transport of heat and mass in the pores of the catalyst and across the boundary layer at the external surface. Under the conditions normally encountered in catalytic reactors, heat and mass fluxes can be large enough to cause finite gradients of concentration and temperature in the solid as well as in the film. In such instances the resulting rate of reaction is governed by both the kinetics of the reaction and the transport process (or processes) which gives rise to the gradient. Hence the dependence of the overall or global rate on temperature and the partial pressures of the reacting species can no more be expressed by the intrinsic kinetics of the reaction but is influenced also by the transport parameters of the system. In other words, in the presence of finite transport limitations the catalyst exhibits kinetics falsified by transport processes. This has been referred to as “disguised kinetics” by Wei [l]. Carberry [2] has examined the implications of this disguise in determining the operating regime of a process.     

Reaction scheme and kinetic modelling for the MTO process over a SAPO-18 catalyst

A kinetic model for simulation of the MTO process over SAPO-18 catalyst in a wide range of operating conditions has been proposed. The kinetic model predicts the experimental evolution of reaction products with time on stream, which follows three consecutive periods: initiation (where olefin production increases), a period of maximum olefin production and a period in which this production decreases. The kinetic scheme takes into account these three steps that evolve with time on stream: formation of active intermediate compounds, an step where olefins are formed by reaction of oxygenates (methanol/DME) with these intermediates and deactivation of intermediates by degradation to coke. The presence of water in the reaction medium attenuates the reaction rate of these steps. Discrimination of kinetic equations and calculation of the parameters of best fit have been carried out by solving the mass conservation equations of the individual components of the kinetic scheme together with the kinetic equation for deactivation and taking into account the effect of water on the kinetics of each step.     

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     

Structural impact of honeycomb catalysts on hydrogen peroxide decomposition for micro propulsion

Hydrogen peroxide is under investigation with regard to its potential to replace the presently used highly toxic rocket propellants NTO and MON-3. Catalytically decomposed hydrogen peroxide results in a steam–oxygen mixture at elevated temperature and can be used either as a monopropellant or as an oxidizer in a bipropellant system. To guide the monolith catalyst design, a lumped parameter model of the decomposition implemented into a numerical thermal model has been developed. The one dimensional flow model includes decomposition and is coupled to a finite element structural domain of the decomposition chamber and catalyst to investigate the impact of the catalyst and the chamber structure on the decomposition behavior. Special focus is laid on the transitional behavior of hydrogen peroxide conversion to facilitate immediate start-up of the thruster system after valve opening command. The numerical results have been validated with experimental data. Major findings of the model such as the existence of a radial temperature gradient across the catalyst have been experimentally validated. The presented theoretical method predicted a strong impact of structural mass capacities of catalyst and decomposition chamber on the transient decomposition performance. This prediction has shown to be in good correlation with the experimental results.     

Modeling and Simulation of Laser‐Induced Ignition of RDX Using Detailed Chemical Kinetics

A laser‐induced ignition model of RDX is developed, in which a detailed chemical kinetics scheme, containing 45 species and 231 reactions, is employed to describe the reaction in the gas phase. The model is spatially one‐dimensional and includes the transient development of two regions: the condensed phase and the gas phase. The condensed phase is composed of solid RDX, liquid RDX, and some decomposition products. The main physicochemical processes include melting, decomposation, vaporization, and radiation absorption. The gas phase is composed of RDX vapor and reaction products and the main processes include convection, diffusion, heat conduction, chemical reaction, and radiation absorption. With interfacial boundary conditions, the governing parameters for the condensed phase are conservation equations of energy and species concentration, whereas those for the gas phase are the conservation equations of mass, momentum, energy, and species concentration. A finite difference program using FORTRAN is compiled and numerical simulation is carried out. The ignition process of RDX is discussed from the distribution and evolution of temperature and species concentration. The model can provide a reasonable prediction of the phenomenon that the flame moves towards the surface immediately after ignition, and then departed from the surface.     

SIMULATION OF OSCILLATIONS IN BOILING FLOW IN A NATURAL CIRCULATION EVAPORATOR

This article presents both experimental and theoretical investigations on the nature of oscillations of void fraction and temperature in a boiling natural circulation loop of a short-tube natural circulation evaporator at low pressure and low heat flux conditions. The experimental study includes online measurement of void fraction and temperature in the loop. The proposed moving boundary model equations for boiling channel in the loop have been solved by a finite volume scheme and subsequently nonlinear ODEs have been solved by Gear's method. The proposed model equations have been validated with experimental data and the data taken from literature. The periodic nature of the pulse-variation of both void fraction and temperature has been identified. A comparison has been made on the applicability of homogeneous flow model and nonhomogeneous flow model to predict the void-fraction pulses and the temperature pulses. Measurement uncertainties and model uncertainties have also been discussed.     

Electrochemical Impedance Modeling of a Solid Oxide Fuel Cell Anode

A simulation package for the impedance response of SOFC anodes is presented here. The model couples the gas transport in gas channels and within a porous electrode with the electrochemical kinetics. The gas phase mass transport is modeled using mass conservation equations. A transmission line model (TLM), which is suitably modified to account for the electrode microstructural details, is used for modeling the impedance arising from the electrochemical reactions. In order to solve the system of nonlinear equations, an in‐house code based on the finite difference method was developed. Some of the model constants have been calibrated against experimental data. It is demonstrated that the simulation tool is capable of predicting the impedance response of an experimental data set obtained on symmetrical cells with Ni/ScYSZ SOFC anodes. A parametric study is also carried out using the developed simulation tool and the results are further discussed.     

Drying of soybean seeds in a crossflow moving bed

The aim of this work was to investigate simultaneous heat and mass transfer between air and soybean seeds in a crossflow moving bed dryer. A model was developed from mass and energy conservation applied to the fluid and particulate phases. The equilibrium, heat transfer and mass transfer equations were taken from studies published earlier. Equations for drying kinetics were obtained from a thin layer study, and the equilibrium equation was chosen from rival model discrimination based on nonlinearity measures. The experimental part of this work involved the determination of air temperature distribution, grain moisture through the bed and air humidity at the bed outlet. The model equations were discretized by orthogonal collocation in the air flow direction. The resulting differential-algebraic equations were solved using a method based on backward differential formulas. Simulation results showed good agreement with experimental data.     

质子交换膜燃料电池阴极催化剂的位置效应

考虑局部几何效应,通过二维稳态数学模型研究了质子交换膜燃料电池阴极催化剂的位置与其表面传质和反应能力的关系。模型方程涉及氧气在催化层气孔的传输,氧气在气相和电解质相界面的分配以及氧气和质子在电解质中的传递和电化学反应过程。计算结果表明,催化剂表面的氧气扩散能力对催化剂的位置变化非常敏感,随催化剂深入电解质内部,其表面的氧气扩散能力经短暂上升后迅速下降。催化剂位置对质子传递阻力的影响与氧气扩散类似,但位置效应要弱些。性能比较确定最优的催化剂位置是恰好处于刚被电解质膜完全覆盖的位置。     

Systematic analysis of the direct methanol fuel cell

The dynamic operating behaviour of the direct methanol fuel cell (DMFC) is governed by several physico-chemical phenomena which occur simultaneously: double layer charging, electrode kinetics, mass transport inside the porous structures, reactant distributions in the anode and cathode flowbeds etc. Therefore it is essential to analyse the interactions of these phenomena in order to fully understand the DMFC. These phenomena were initially analysed independently by systematic experiments and model formulations. Electrode kinetics were determined by fitting models of varying complexity to electrochemical impedance spectroscopy (EIS) measurements. Reaction intermediates adsorbed on the catalyst seem to play a key role here. To describe mass transport across the DMFC a one-dimensional model was formulated applying the generalised Maxwell–Stefan equations for multi-component mass transport and a Flory–Huggins model for the activities of mobile species inside the membrane (PEM). Also swelling of the PEM as well as heat production and transport were considered. Finally, the anode flowbed was analysed by observing flow patterns in different flowbed designs and measuring residence time distributions (RTDs). Detailed CFD models as well as simpler CSTR network representations were used to compare to the experimental results. Even the simpler models showed good agreement with the experiments. After these investigations the results were combined: the electrode kinetics model was implemented in the mass transport model as well as in the CSTR network flowbed model. In both cases, good agreement, even to dynamic experiments, was obtained.     

Multiplicity of the steady state in fluidized bed reactors—IV. Fluid catalytic cracking (FCC)

A mathematical model for fluid catalytic cracking units is developed. The model takes into account the kinetics of the cracking reactions, as well as the kinetics of coke combustion in the regenerator. A numerical scheme is developed for the solution of the model equations. It is found that multiplicity of the steady states extends over a wide scope of operating variables and parameters. The model investigates the effects of catalyst circulation rate and gas oil flow rate, which have a strong effect on the reactor temperature and hence yield and selectivity. The phenomenon of hysteresis has been investigated. The model can be used for yield optimization and steady state control.     

Steady‐State Modeling and Simulation of an Axial‐Radial Ammonia Synthesis Reactor

A two‐dimensional model was developed for an axial‐radial ammonia synthesis reactor of the Shiraz petrochemical plant. In this model, momentum and continuity equations as well as mass and energy balance equations are solved simultaneously by orthogonal collocation on the finite element method to obtain pressure, velocity, concentration and temperature profiles in both axial and radial directions. For the catalyst particle, the effectiveness factor is calculated by solving a two‐point boundary value differential equation. The boundary conditions for the Navier‐Stokes and continuity equations are obtained by using equations representing the phenomena of gases splitting or joining in different streams and going through holes in a thin wall. The results of the mathematical model have been compared with the plant data and a good agreement is obtained.