对二甲苯液相氧化过程中燃烧副反应动力学

During the liquid-phase oxidation of p-xylene, over-oxidation of reactant, intermediates and solvent to carbon dioxide and carbon monoxide is generally known as the burning side reaction. Batch and semi-continuous experiments were carried out, and the experimental data of the burning side reaction were analyzed and reported in this paper. The results showed that the rates of burning side reactions were proportional to the rates of the main re-action, but decreased with the increasing concentrations of reactant and intermediates. The inter-stimulative and competitive relationship between the burning side reaction and the main reaction was confirmed, and the rates of the burning side reaction could be described with some key indexes of the main reaction. According to the mecha-nism of the side reactions and the kinetics model of main reaction which were proposed and tested in the previous papers, a kinetic model of the burning side reactions involving some key indexes of the main reaction was devel-oped, and the parameters were determined by data fitting of the COx rate curves. The obtained kinetic model could describe the burning side reactions adequately.     

用于甲烷偶联的SrCe0.95Yb0.05O3-α中空纤维膜反应器建模

Proton-hole mixed conductor, SrCe0.95Yb0.05O3-α(SCYb), has the potential to be used as a membrane for dehydrogenation reactions such as methane coupling due to its high C2-selectivity and its simplicity for fabricating reactor systems. In addition, the mixed conducting membrane in the hollow fibre geometry is capable of providing high surface area per unit volume. In this study, mechanism of methane coupling reaction on the SCYb membrane was proposed and the kinetic parameters were obtained by regression of experimental data. A mathematical model describing the methane coupling in the SCYb hollow fibre membrane reactor was also developed.With this mathematical model, various operating conditions such as the operation mode, operation pressure and feed concentrations affecting performance of the reactor were investigated. The simulation results show that the cocurrent flow in the reactor exhibits higher conversion of methane and higher yield of ethylene compared to the countercurrent flow. In order to achieve the highest C2 yield, especially of ethylene, pure methane should be used as feed and the operating pressure be 300 kPa. Air can be used as the source of oxygen for the reaction and it soptimum feed velocity is twice of the methane feed velocity. The air pressure in the lumen side should be kept the same as or slightly lower than the vressure of shell side.     

合成气制二甲醚三相淤浆床反应器的数学模型研究

A mathematical model for a bubble column slurry reactor is presented for dimethyl ether synthesis from syngas. Methanol synthesis from carbon monoxide and carbon dioxide by hydrogenation and the methanol dehydration are considered as independent reactions, in which methanol, dimethyl ether and carbon dioxide are the key components. In this model, the gas phase is considered to be in plug flow and the liquid phase to be in partly back mixing with axial distribution of solid catalyst. The simulation results show that the axial dispersion of solid catalysts, the operational height of the slurry phase in the bubble column slurry reactor, and the reaction results are influenced by the reaction temperature and pressure, which are the basic data for the scale-up of reactor.     

矿物均相酸催化剂催化甲醇和乙酸酯化反应动力学(英文)

In this work, esterification of acetic acid and methanol to synthesize methyl acetate in a batch stirred reactor is studied in the temperature range of 305.15–333.15 K. Sulfuric acid is used as the homogeneous catalyst with concentrations ranging from 0.0633 mol·L?1 to 0.3268 mol·L?1. The feed molar ratio of acetic acid to methanol is varied from 1:1 to 1:4. The influences of temperature, catalyst concentration and reactant concentration on the reaction rate are investigated. A second order kinetic rate equation is used to correlate the experimental data. The forward and backward reaction rate constants and activation energies are determined from the Arrhenius plot. The developed kinetic model is compared with the models in literature. The developed kinetic equation is useful for the simulation of reactive distillation column for the synthesis of methyl acetate.     

Application of kinetics and computational fluid dynamics in pinene isomerization

A reliable kinetic model to describe the effects of various factors on the reaction rate and selectivity of pinene isomerization is developed. Furthermore, computational fluid dynamics(CFD) is applied to simulate the solid–liquid dispersion in reactor. The catalyst Ti M is obtained by improving the composition and structure of hydrated titanium dioxide. The kinetic equation of pinene isomerization is deduced based on reaction mechanism and catalyst deactivation model. The kinetic equation of pinene isomerization reaction is fitted, and the results show that the fitted equation is correlated with the experimental data. The rate and selectivity of pinene isomerization reaction are affected by the amount of catalyst, deactivation of catalyst, structure of catalyst, reaction temperature and water content of catalyst. The solid–liquid distribution of the reactor is calculated by computational fluid dynamics numerical simulation, and the solid–liquid dispersion in commercial scale reactor is more uniform than that in lab-scale reactor.     

Polyethoxylation and polypropoxylation reactions: Kinetics,mass transfer and industrial reactor design

Ethoxylation and propoxylation reactions are performed in the industry to produce mainly non-ionic surfactants and ethylene oxide(EO)–propylene oxide(PO) copolymers.Both the reactions occur in gas–liquid reactors by feeding gaseous EO,PO or both into the reactor containing a solution of an alkaline catalyst(KOH or Na OH).Non-ionic surfactants are produced by using liquid starters like fatty alcohols,fatty acids or alkyl-phenols,while when the scope is to prepare EO–PO copolymers the starter can be a mono-or multi-functional alcohol of low molecular weight.Both reactions are strongly exothermic,and EO and PO,in some conditions,can give place to runaway and also to explosive side reactions.Therefore,the choice of a suitable reactor is a key factor for operating in safe conditions.A correct reactor design requires:(i) the knowledge of the kinetic laws governing the rates of the occurring reactions;(ii) the role of mass and heat transfer in affecting the reaction rate;(iii) the solubility of EO and PO in the reacting mixture with the non-ideality of the reacting solutions considered;(iv) the density of the reacting mixture.All these aspects have been studied by our research group for different starters of industrial interest,and the data collected by using semibatch well stirred laboratory reactors have been employed for the simulation of industrial reactors,in particular Gas–Liquid Spray Tower Loop Reactors.     

EFFECT OF FLOW PATTERNS ON EPOXIDATION OF PROPYLENE WITH ETHYLBENZENE HYDROPEROXIDE

The process of producing propylene oxide by epoxidation of propylene with ethylbenzene hydroper-oxide is one of the most promising methods in recent years.In order to select an optimum reaction equip-ment technologically,the mathematical models of epoxidation reactor for plug flow,single-stage andmultistage perfect mixing have been founded in this paper by means of the kinetic model on epoxidationand the effects of various flow patterns on the reaction are also discussed.The analyses show that themultistage reactor is a more ideal one for industrial equipment,and its optimum operating conditions aresuggested.     

MATHEMATICAL MODELING OF NON-CATALYTIC LIQUID-SOLID REACTION AND ITS SOLUTION BY ORTHOGONAL COLLOCATION

The mathematical model of non-catalytic liquid-solid diffusion reactions discussed in this paper can be applied to quite different cases. The models in the literature such as unreacted shrinking core model, two stage model and homogeneous model can be considered as special cases of the above model which has been derived for leaching vanadium from steel slag with sodium carbonate and]or sodium bicarbonate solution reacting with two components in the slag simultaneously. The vanadium leaching reaction is inhibited by the solid product formed during the reaction. The power law equation can be used to represent the kinetic experimental data of leaching reaction. The model equations have been solved by orthogonal collocation and semi-implicit Runge-Kutta method. The parameters of the model have been estimated by the complex method. The calculated results based on this model is in good agreement with experimental data.     

Detailed kinetics of methylphenyldichlorosilane synthesis from methyldichlorosilane and chlorobenzene by gas phase condensation

Methylphenyldichlorosilane (MPDS, CH3C6H5SiCl2) is an important silicone monomer for the synthesis of high-performance polymethylphenylsiloxane polymers. In this work, the mechanism of the synthesis of MPDS from methyldichlorosilane and chlorobenzene by gas phase condensation was studied, and a kinetic model with 35 species and 58 elementary reactions was established. Experiments were carried out in a tubular reactor under a wide range of reaction conditions. The calculated mole fractions of the reactants and products were in a good agreement with the experimental results. A mechanism of the insertion of chloromethylsilylene into the C-Cl bond of chlorobenzene was proposed, which was proved to be the main pathway of MPDS production. The established kinetic model can be used in design and optimization of the industrial reactor for MPDS synthesis.     

Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies

The kinetic behavior of esterification between methacrylic acid and methanol catalyzed by NKC-9 resin was studied in a fixed bed reactor. The reaction was conducted in the temperature range of 323.15 to 368.15 K with the molar ratio of reactants from 0.8 to 1.4 under certain pressure. The measurement data were regression with the pseudo-homogeneous(P-H), Eley-Rideal(E-R), and Langmuir-Hinshelwood(L-H) heterogeneous kinetic models. Independent adsorption experiments were implemented to gain the a...     

环氧乙烷合成银催化剂宏观动力学及失活分析

在工业生产的条件下用无梯度反应器研究了工业颗粒银催化剂上乙烯氧化合成环氧乙烷宏观动力学 ,得到了能反映该系统主副反应特性的双速率方程 .建立了二维非均相反应器模型 ,模拟并比较了工业生产操作数据 ,获得了该种催化剂的活性校正因子随使用时间变化的经验关联式和主副反应失活速率方程     

Performance Enhancement by Unsteady‐State Reactor Operation: Theoretical Analysis for Two‐Sites Kinetic Model

Theoretical analysis of the reactor performance under unsteady‐state conditions was carried out. The reactions are described by two kinetic models, which involve the participation in catalytic reaction of two types of active sites. The kinetic model I assumes the blocking of one of the active sites by a reactant, and the kinetic model II suggests a transformation of active sites of one type into another under the influence of the reaction temperature. The unsteady‐state conditions on the catalyst surface are supposed to be created (i) by forced oscillations of temperature and concentration in the reactor inlet (periodic operation of reactor) and (ii) by catalyst circulation between two reactors in a dual‐reactor system (spatial regulation). The influence of various parameters like concentration of reactant, cycle split, length of period of forced oscillations, temperatures and the ratio of catalyst volumes in the dual‐reactor was investigated with respect to the yield of the desired product. It is shown that for both cases of unsteady‐state conditions (periodic reactor operation as well as in a dual‐reactor system), a mean reaction rate predicted by the kinetic model I was up to two times higher than the steady‐state value. The kinetic model II shows a 20 % increase of the selectivity towards the desired product.     

Gas‐Lift Reactors for Rapid Reactions with Appreciable Gas Consumption

Gas‐lift reactors offer important advantages for a number of gas/liquid and gas/liquid/solid reactions. However, the design and operation of these reactors can be complex when there is a substantial change in the molar gas flow rate along the length of the reactor, e.g., when a gaseous reactant is converted into a liquid product. In this situation, there is a strong coupling between reactor hydrodynamics and reaction kinetics, which arises from the fact that the rate of liquid circulation through the reactor and the longitudinal profile of gas holdup in the riser are mutually dependent. Several one‐dimensional models have been developed to describe kinetic/hydrodynamic coupling in gas‐lift reactors. These models offer useful insights into the parameters that affect reactor performance. The models can also be used to explore different approaches to scale‐up.     

EXPERIMENTAL STUDY OF A COMPLEX CATALYTIC REACTION NETWORK IN A TRICKLE-BED REACTOR

In the present report a relatively complex reaction system including several side reactions to the desired main reaction has been studied in a trickle-bed reactor. In addition the experimental part—which showed very good reproducibility of the results—an attempt to a reasonable modelling of the reactor was tried. The starting point was the differential equation system describing the kinetics of the reactions as well as the corresponding kinetic parameters, which had been established earlier in a slurry-reactor. It was possible to demonstrate that the behaviour of a trickle-bed reactor can be simulated by a relatively simple approach containing the basic kinetic equations, the wetting efficiency of the catalyst particles and a one-dimensional, pseudohomogeneous reactor model, the cell model. The so calculated concentration curves of the different reactants and products fitted the experimental values very closely. For those reasons, and especially for the reasonable effort needed for very satisfactory modeling, the results and proceeding steps outlined here might be of particular interest for further applications of trickle-bed reactors.     

Kinetic study of propane dehydrogenation and side reactions over Pt–Sn/Al2O3 catalyst

The kinetics of reactions involved in dehydrogenation of propane to propylene over Pt–Sn/Al₂O₃ catalyst was studied. The simultaneous deactivation of individual dehydrogenation, hydrogenolysis and cracking sites was also studied. A model was developed to obtain the transient conversion of propane, product selectivity and catalytic site activity. The dehydrogenation reaction was considered as the main reaction governing propane and hydrogen concentrations along the reactor. Catalytic test runs were performed in a fixed-bed quartz reactor. The kinetic expressions developed for the main and side reactions were verified by integral and a combination of integral–differential analysis of reactor data, respectively, and the kinetic parameters were obtained. The deactivation of the active sites for the three reactions was found to follow a first-order independent decay law. The rate constants of deactivation were found to decrease in the order of dehydrogenation, hydrogenolysis and cracking. Noncatalytic thermal cracking was found to be comparable to the catalytic route resulting in a very low apparent deactivation rate constant for cracking reaction.     

Optimal reaction conditions for the minimization of energy consumption and by‐product formation in a poly(ethylene terephthalate) process

We determined the optimal reaction conditions to minimize the energy cost and the quantities of by‐products for a poly(ethylene terephthalate) process by using the iterative dynamic programming (IDP) algorithm. Here, we employed a sequence of three reactor models: the semibatch transesterification reactor model, the semibatch prepolymerization reactor model, and the rotating‐disc‐type polycondensation reactor model. We selectively chose or developed the reactor models by incorporating experimentally verified kinetic models reported in the literature. We established the model for the entire reactor system by connecting the three reactor models in series and by resolving some joint problems arising when different types of reactor models were interconnected. On the basis of the simulation results of the reactor system, we scrutinized the cause and effect between the reaction conditions and the final quality of the polymer product. Here, we set up the optimization strategy by using IDP on the basis of the integrated reactor model, and the process variables with significant influence on the properties of polymer were selected as control variables with the help of a simulation study. With this method, we could refine the reaction conditions at the end of each iteration step by contracting the spectra of control regions, and the iteration process finally stopped when the profile of the optimal trajectory converged. We also took the constraints on the control variables into account to guarantee polymer quality and to suppress side reactions. Constituting six different strategies by setting weighting vectors differently, we examined the differences in optimal trajectories, the trend of optimality, and the quality of the final polymer product. For each of the strategies, we conducted the optimization to examine whether the number‐average degree of polymerization approached the desired value. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 993–1008, 2002     

Modeling of a Methanol Synthesis Reactor for Storage of Renewable Energy and Conversion of CO2 – Comparison of Two Kinetic Models

The storage of renewable energy over a long time period, via methanol synthesis, will become very important to reach a greenhouse gas‐free energy supply. A steady‐state methanol synthesis flowsheet, containing a 2D pseudo‐homogeneous reactor, flash, and recycle, is modeled in MATLAB. With the kinetic models of Graaf and Bussche & Froment, two frequently used kinetic models for conventional methanol synthesis are compared and evaluated for applicability regarding methanol synthesis from CO₂/H₂. The results are presented for different cases of synthesis gas compositions. Both kinetic models produce similar results when the system is limited by thermodynamic equilibrium. However, differences in reaction rates are observable from the reactor axial molar component profiles of the reaction products.     

邻二甲苯液相氧化动力学的研究

在搅拌釜（φ107×350mm）中进行邻二甲苯液相氧化动力学的研究,其结果表明,在本试验条件下（搅拌釜转速为1200rpm空釜线速≥1.5cm/s,氧化温度在130℃以下）可以消除传质影响。 本研究建立了邻二甲苯（OX）氧化的动力学方程式（在 OX的转化率<50％时适用）,为气液反应器放大提供计算氧化速度的动力学 模型。 本工作还对邻二甲苯氧化七组分的主副反应动力学进行研究,测定了不同温度下各反应的速率常数和活化能。其数值与采用鼓泡塔氧化的结果相一致,再次表明邻二甲苯氧化为串、并联一级反应。     

Overall effectiveness factor of heterogeneous-homogeneous chain reactions with one limited species in a catalytic slurry reactor

The analysis of the overall effectiveness factor for the reaction system involving heterogeneous-homogeneous chain reactions at low concentration of one species is studied. A more general theoretical analysis for estimating the overall effectiveness factor of reaction systems which can be a heterogeneous-homogeneous chain reaction system at low concentration of one species in a slurry reactor is presented, incorporating all the transport parameters. The concepts of overall effectiveness factors for reactions have been extended from the traditional heterogeneous reaction system to the heterogeneous-homogeneous chain reaction system. The effects of reaction mechanism and kinetic models on the overall effectiveness factor are also proposed. Comparisons of the overall effectiveness factor for a slurry reactor with or without considering the reaction mechanism are also obtained.     

A Novel Fluidized‐Bed Membrane Dual‐Type Reactor Concept for Methanol Synthesis

A novel fluidized‐bed membrane dual‐type methanol reactor (FBMDMR) concept is proposed in this paper. In this proposed reactor, the cold feed synthesis gas is fed to the tubes of the gas‐cooled reactor and flows in counter‐current mode with a reacting gas mixture in the shell side of the reactor, which is a novel membrane‐assisted fluidized bed. In this way, the synthesis gas is heated by heat of reaction which is produced in the reaction side. Hydrogen can penetrate from the feed synthesis gas side into the reaction side as a result of a hydrogen partial pressure difference between both sides. The outlet synthesis gas from this reactor is fed to tubes of the water‐cooled packed bed reactor and the chemical reaction is initiated by the catalyst. The partially converted gas leaving this reactor is directed into the shell of the gas‐cooled reactor and the reactions are completed in this fluidized‐bed side. This reactor configuration solves some drawbacks observed from the new conventional dual‐type methanol reactor, such as pressure drop, internal mass transfer limitations, radial gradient of concentration, and temperature in the gas‐cooled reactor. The two‐phase theory of fluidization is used to model and simulate the proposed reactor. An industrial dual‐type methanol reactor (IDMR) and a fluidized‐bed dual‐type methanol reactor (FBDMR) are used as a basis for comparison. This comparison shows enhancement in the yield of methanol production in the fluidized‐bed membrane dual‐type methanol reactor (FBMDMR).