汽车催化转化器数学模型的修正

催化转化器涂层和孔道之间存在着质量传递,由于涂层和孔道中物质的能量不同,在质量传递的同时必然伴随着能量传递。首先对这种伴随质量传递的能量传递进行分析,从理论上研究了这部分能量交换对计算结果的影响,得出这部分能量交换不可忽视的结论,据此对当前应用的催化转化器模型进行了改进,使计算模型在理论上更加完善,又结合试验对模型改进前后的预测结果进行了分析,验证了改进模型的有效性。     

汽车排气催化转化器中的现象分析

催化转化器己广泛用于汽车排放控制,深入了解其中发生的现象对改进催化剂和转化器的设计以及建立合理的转化器模型都具有重要意义。本文分析了整装催化转化器中发生的现象,其中主要物理、化学过程包括传热、传质、气流分布、化学动力学过程、储放氧和催化剂中毒等。     

微通道内液-液两相流流型及传质的研究进展

微通道内液-液两相流流动在微化工系统中占有重要的地位,了解微通道内液-液两相流体流动和传质规律对推动其工业化应用有重要作用。本文以微通道内液-液两相流系统为研究对象,简述了不同工况下微通道内液-液两相流流型和混合传质效率,分析了微通道特征、流体性质和流体流动速度等对流型形成和传质效率的影响。指出目前对于微通道内液-液两相流的研究多处于定性研究,定量研究仅针对某一体系展开,所得结果具有一定的局限性。关于微通道内液-液两相流传质研究实验较多而数值模拟方法相对较少,接下来的研究工作中应该考虑建立微通道内液-液两相流基础研究的数据库,通过分析大量的数据获得有效的流型划分准则和相关经验式以此推动微通道内液-液两相流的工业化应用。同时在传质研究过程中应研究开发相应的数值模拟模型,保证实验和数值模拟相结合,提出有效的传质效率评价机制。     

聚合物膜催化接触器研究进展

对聚合物膜催化接触器的特点、所用催化膜材料及其制备方法进行归纳总结。与传统催化反应器相比,聚合物膜催化接触器具有结构紧凑,工艺及操作流程简单,催化活性、反应速率及转化率高等特点。所用聚合物膜材料分子主链和侧链具有丰富的功能基团,以便引入活性纳米粒子或基团,得到高活性的催化膜。聚合物催化膜制备方法主要有杂化法、浸渍法及化学接枝法。扩散过程为聚合物膜接触器催化反应过程的控制步骤,整个过程包括内扩散和外扩散两个步骤。文中最后提出聚合物膜催化接触器应用中存在的问题,即催化效率和使用寿命有待进一步提高;新型聚合物催化膜材料亟需开发,膜污染和催化膜失活问题亟待解决;膜催化反应动力学模型的建立和研究等关键性、基础性问题还需要更加深入地研究。     

Mathematical Modeling of Drying Kinetics for Apricots: Influence of the External Resistance to Mass Transfer

The drying curves of halved and deseeded apricots obtained during convective drying at different temperatures (from 50 to 90°C) have been examined, and a diffusional model, solved by a finite elements method, has been proposed to simulate the drying kinetics. The importance of taking into account both the internal and the external resistances to mass transfer when modeling the drying curves is discussed. Due to the geometry of halved apricots as a hemisphere losing water only through the flat section, the mass transfer coefficient (k_c) was not correctly estimated through an empirical correlation. Only the identification of this coefficient from the experimental results allowed an accurate simulation, decreasing the mean relative error from 12.3±3.8% when k_c was calculated through the Pasternak and Gauvin correlation to 2.9±1.0% when k_c was identified.     

Mathematical Modeling of Drying Kinetics for Apricots: Influence of the External Resistance to Mass Transfer

The drying curves of halved and deseeded apricots obtained during convective drying at different temperatures (from 50 to 90°C) have been examined, and a diffusional model, solved by a finite elements method, has been proposed to simulate the drying kinetics. The importance of taking into account both the internal and the external resistances to mass transfer when modeling the drying curves is discussed. Due to the geometry of halved apricots as a hemisphere losing water only through the flat section, the mass transfer coefficient (k_c) was not correctly estimated through an empirical correlation. Only the identification of this coefficient from the experimental results allowed an accurate simulation, decreasing the mean relative error from 12.3±3.8% when k_c was calculated through the Pasternak and Gauvin correlation to 2.9±1.0% when k_c was identified.     

On the use of internal mass transfer coefficients in modeling of diffusion and reaction in catalytic monoliths

We utilize the recently developed concept of internal or intraphase mass transfer coefficient to simplify the problem of diffusion and reaction in more than one spatial dimension for a washcoated monolith of arbitrary shape. We determine the dependence of the dimensionless internal mass transfer coefficient (Sh_i) on washcoat and channel geometric shapes, reaction kinetics, catalyst loading and activity profile. It is also reasoned that the concept of intraphase transfer coefficient is more useful and fundamental than the classical effectiveness factor concept. The intraphase transfer coefficient can be combined with the traditional external mass transfer coefficient (Sh_e) to obtain an overall mass transfer coefficient (Sh_app) which is an experimentally measurable quantity depending on various geometric and transport properties as well as kinetics. We present examples demonstrating the use of Sh_app in obtaining accurate macro-scale low-dimensional models of catalytic reactors by solving the full 3-D convection-diffusion-reaction problem for a washcoated monolith and comparing the solution with that of the simplified model using the internal mass transfer coefficient concept.     

汽车尾气催化净化过程中的水煤气反应和蒸汽转换反应

本研究主要考察了不同组成的汽车尾气净化催化剂在无氧条件下对ＣＯ水煤气反应和ＨＣ蒸汽转换反应的催化性能。结果表明,在催化剂中添加一定量的稀土金属氧化物（Ｌａ_２Ｏ_３、ＣｅＯ_２）和过渡金属氧化物（ＮｉＯ）,均有利于改善催化剂对ＣＯ水煤气反应和ＨＣ蒸汽转换反应的催化性能。此外还考察了水蒸汽含量以及空速的变化对反应的影响。     

Mass Transfer of Ozone to Water: A Fundamental Study

The authors review mass transfer of ozone to water with or without chemical reaction. In order to calculate the dimensions of an ozone-water contactor, it is necessary to know its characteristics without chemical reaction (K_L) and with chemical reaction.     

Effect of oxygen mobility in solid catalyst on transient regimes of catalytic reaction of methane partial oxidation at short contact times

Mathematical modeling of the effect of the oxygen mobility in a solid oxide catalyst on the dynamics of transients of fast catalytic reactions has been carried out. The analysis was based upon the redox mechanistic scheme with a due regard for diffusion of oxygen from the bulk of catalyst to its surface. Parameters of kinetic and mathematical models were selected via fitting of the experimental data for methane selective oxidation into syngas on 1.4%Pt/Gd_0.2Ce_0.4Zr_0.4O _x catalyst. The range of the Thiele parameter (φ) where the oxygen bulk diffusion affects the most strongly reaction transients corresponds to φε [0.3 ÷ 7]. For high-surface-area oxide catalysts, the bulk oxygen diffusion coefficients corresponding to this range of the Thiele parameter are in the range of 10^–18 ÷ 10^–13cm²/s.     

Homotopy analysis of heat and mass transfer boundary layer flow through a non‐porous channel with chemical reaction and heat generation

This paper describes the two‐dimensional flow of an incompressible viscous fluid through a non‐porous channel with heat generation and a chemical reaction. Employing similarity transformations the governing non‐linear partial differential equations are solved both analytically and numerically. Analytically, we used the homotopy analysis method and numerically, we used the Matlab in‐built boundary value solver bvp4c. The effects of the Reynolds number Re, the Eckert number Ec, heat generation parameter δ, chemical reaction parameter γ, and the local Grashof number Gc on the velocity, temperature, and concentration fields are shown through tables and graphs and discussed.     

Controlling reaction rate of phase transfer hydrogenation of acetophenone by application of low external electric field

The controllable mass transfer and reaction rate for phase transfer hydrogenation of acetophenone across a well-defined boundary were investigated. The effect of solvent was found important and 1-butanol exhibited the best performance among the five investigated homologous alcohol solvents, consistent with its higher solubility in water and greater dielectric constant. Initial reaction rates increased with increasing electric potential, consistent with enhanced mass transfer across the aqueous/organic boundary. At longer reaction times, deactivation was apparent. It correlated with increasing voltage and is ascribed to lower equilibrium concentration of reactive species at the interface. External control over reaction rate was demonstrated by switching the applied electric potential over the course of the reaction. Effects of external electric field on enantioselectivity were also explored with reversal field direction. The changes correlate with catalyst decomposition.     

伴有瞬时化学反应微溶固体颗粒的气液传质

为研究瞬时化学反应性固体颗粒对气液传质过程的影响,对伴有瞬时反应性固体颗粒/水浆料体系吸收气体过程进行了理论分析。考虑了固体颗粒在气液界面附近的溶解,以及固体颗粒尺寸对传质的影响,将cell模型融入溶质渗透理论,建立了气液二相间传质模型,并对模型进行了解析求解,得到了液相传质系数的解析表达式。结果显示:固含率、固体颗粒尺寸和溶解度对气液传质过程具有重要影响,液相传质系数随固含率和固体颗粒在液相中饱和浓度的增加而增大,随固体颗粒粒径增大而减小。在搅拌式反应器中利用Mg(OH)2/水浆料吸收SO2气体,对传质模型进行了实验验证。模型计算结果与实验值吻合良好。     

A study of mass transfer behaviour in a catalytic distillation column

Catalytic distillation (CD) is a process where reaction and separation take place simultaneously in a distillation column. Recently, a new CD process for the aldol condensation of acetone to diacetone alcohol and mesityl oxide was developed in our laboratory. Owing to the unique structure used to support catalysts in the CD column, mass transfer data are needed to model the CD process. The mass transfer behaviour in the CD column has been studied both for the reactive and non-reactive sections of the column in our laboratory. Based on the experimental results, general correlations for the mass transfer coefficients have been established and the 95% confidence intervals for the associated parameters were obtained. The experimental results indicated that the catalyst bags did not play a significant role for the separation between the vapour and liquid phases. The mass transfer correlations developed in this study have been used successfully to model the CD process for the aldol condensation of acetone carried out in our laboratory.     

Importance of sample intraparticle diffusivity in investigations of the mass transfer mechanism in liquid chromatography

The effective diffusivity of a nonretained (thiourea) and of a strongly retained (phenol) compounds were measured with the peak parking method in two different columns (both 150 × 4.6 mm) packed with two types of porous particles having different mesopore sizes [5 μm Jupiter‐C₁₈, 320 Å and Luna(2)‐C₁₈, 100 Å]. The eluent was a methanol–water mixture (10/90 v/v) and the temperature 294 K. The effective diffusivity data acquired were used to determine the intraparticle diffusivity, D_p, based on two different diffusion models. The first one assumes that the diffusion fluxes across the particles and in the interparticle volume are additive (parallel diffusion model). The second model was rigorously derived on the basis of the effective medium theory of diffusion (diffusion model) in a binary composite medium (particles + interparticle volume). In both models, it was assumed that the rate of equilibrium between the liquid and the solid phases was infinitely faster than the rate of axial diffusion along the column at zero flow rate. Both models provide physically meaningful intraparticle diffusivity coefficients that take into account the average mesopore size of the particles, their specific surface area, and the retention factor of the analyte. Although the actual effective intraparticle diffusivity remains unknown, these result confirm that the mass transfer resistance due to diffusion through the porous particles has almost negligible effects in reversed phase liquid chromatography due to the importance of surface diffusion. Combining the results of the peak parking method with the h data measured at high linear velocities allows the unambiguous measurement of the film mass transfer and the surface diffusion coefficients. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

外场作用下多组分质量传递Maxwell-Stefan方程及其应用：电场作用下球形颗粒中的扩散

Fick扩散定律只能用于没有外场作用下的二组分扩散过程,Maxwell-Stefan（MS）方程适用于外场作用下多组分系统中的质量传递过程。阐述了MS方程的物理意义,并由此将外场作用下普遍化MS方程的表达式改写为清晰且易于使用的形式。给出了在MS方程中常用的外场作用力的数学形式。Fick扩散定律是MS方程在没有外场作用下对二元理想流体扩散的应用;MS方程对离心分离和电解质扩散等过程的描述比传统的描述方法更全面。利用MS方程导出了欧姆定律,利用该结论可以通过测量电导率计算带电粒子的扩散系数。利用MS方程研究了电场作用下球形颗粒中的扩散过程,结果表明,该方程可以对电场强化质量传递过程给出有效描述。MS方程为外场作用下的质量传递过程提供了一种有效的理论研究方法。     

Organosilane surfactant-assisted synthesis of mesoporous SSZ-39 zeolite with enhanced catalytic performance in the methanol-to-olefins reaction

SSZ-39 zeolite with AEI framework structure is a good catalyst candidate for the methanol-to-olefins (MTO) reaction. However, the diffusion limitation and coke formation often results in fast deactivation of the SSZ-39 zeolite catalyst. One solution for this challenge is to introduce mesoporosity in the SSZ-39 zeolite. Herein, we report the synthesis of mesoporous SSZ-39 zeolite using an organosilane surfactant, N,N-dimethyl-N-(3-(trimethoxysilyl)propyl)octan-1-aminium chloride, as a mesopore template and N,N-dimethyl-cis-2,6-dimethylpiperidinium as a micropore template. The obtained zeolites were characterized by X-ray diffraction, N₂ sorption, scanning electron microscopy, temperature programmed desorption of ammonia, and magic angle spinning nuclear magnetic resonance of ²⁷Al. The results show that the mesoporous SSZ-39 zeolite has high crystallinity, meso/microporosity, high surface area, cuboid morphology, and abundant acidic sites. More importantly, this mesoporous SSZ-39 zeolite exhibits enhanced catalyst lifetime in the MTO reaction due to the presence of mesoporosity for fast mass transfer, compared with a conventional SSZ-39 zeolite without mesoporosity.     

汽车尾气三效催化器排气系统冷启动阶段数值模拟

发动机冷启动状态汽车尾气的排放情况对尾气排放控制起着关键的作用,建立了发动机冷启动状态排气系统传热、传质的非稳态单通道数学模型,通过对模型的数值求解,分析了汽车尾气排气系统温度、浓度的演变,经与实验结果对比,模型拟和与实验值能很好吻合,所建模型和选择参数正确.模拟了催化器内尾气温度场、浓度场的分布情况,对催化器的研究、设计具有重要意义.