The hydrogenolysis of n-Butane on a nickel on silica catalyst: II Fluidized bed studies

This study was undertaken to obtain experience in developing steady-state mathematical models of full-scale chemical reactors through the use of a combination of bench-scale experiments and actual plant operating data. In this case, the hydrogenolysis of n-butane on a nickel on silica gel catalyst was studied in a %inch diameter pilot plant fluidized bed reactor. The kinetic parameters in a mechanistic reaction model were obtained in a bench-scale integral reactor and these rate equations were included in a simple two-phase fluidized bed model. The parameter relating to interchange of gas between bubbles and emulsion was determined from the fluidized bed data. A comparison of the predicted and observed selectivities suggested a weakness in the kinetic model. This shortcoming was then partially corrected by using the fluidized bed data. In this way, a reactor model was achieved which was satisfactory for overall plant simulations.     

A simplified mathematical modeling for thermo-catalytic decomposition of methane over carbon black catalyst in a fluidized bed reactor

A mathematical model for thermo-catalytic decomposition of methane over carbon black catalysts in a fluidized bed was proposed. The simplified isothermal, uniform flow model was considered and implemented into a computer code to predict the reactor performance. The experiment of methane decomposition into hydrogen and carbon was carried out in a fluidized bed of I.D of 0.055 m and height of 1.0 m. The range of reaction temperature was 850–900 °C, gas velocity was 1.0–3.0 U _mf , and catalyst loading was 50–200 g. The reaction parameters for model equation were determined from the curve fittings and the comparison of experimental data with simulation results showed good agreement for fluidized bed reactor system. From the simulation results, the fluidized bed performance with different operating conditions were obtained, and this simple model can be used to predict the performance of a larger scale fluidized bed reactor and also in determining the optimum operating conditions.     

Simulation of a catalytic turbulent fluidized bed reactor using the sequential modular approach

Combustion of natural gas in fluidized bed reactors is considered as an economical way for producing energy and food-grade CO₂ largely needed in food and chemical industries. Therefore, their simulation and modeling could be of great industrial importance. In this study, a model is developed based on the sequential modular approach for combustion of natural gas in a catalytic turbulent fluidized bed (TFB) reactor. The proposed model integrates hydrodynamic parameters, reaction model and kinetic data necessary to simulate the combustion of natural gas in the catalytic turbulent fluidized bed reactor. For the purpose of this study and based on hydrodynamic considerations, a number of ideal reactors have been considered to simulate the overall performance of the reactor. The validity of the proposed model was demonstrated using the pilot plant experimental data from the literature. The agreement between the simulation results and the experimental data was found to be satisfactory.     

Modelling and simulation of an oxychlorination reactor in a fluidized bed

Taking 1,2‐dichloroethane from the oxychlorination reaction is a commercially very important process due to the large application of the 1,2‐dichloroethane in the chemical industry of PVC production. This work presents the modeling and simulation of an oxychlorination reactor with a fluidized bed. The pseudo‐homogeneous model with one‐dimensional flow in steady state was applied based on the theory of fluidized bed in two phases. It allows the sensitivity analysis of the operational and project parameters of the reactor. The ordinary differential equations system that represents the mathematical model of the reactor was solved through the application of the numerical method of Newton–Raphson's. The results obtained have proved that the developed model represents the system suitably, in spite of the one‐dimensional model. The effect of different parameters was investigated through the sensitivity analysis, and the results show that the parameters that have the largest influence on the reactor performances are: fluidized bed height, bubble diameter, residence time, cupric chloride weight in the catalyst, and emulsion phase temperature.     

A two‐phase model for variable‐density fluidized bed reactors with generalized nonlinear kinetics

A model based on the classical two‐phase concept is developed for the simulation of variable‐density reaction with generalized nonlinear kinetics in a bubbling fluidized bed. The influence of reaction density parameter on the fluidodynamics and performance of the reactor for four general types of reactions was explored. The results show that the expansion factor has a significant effect on both fluidodynamic characteristics and reaction conversion. In all types of reactions, higher values of hydro‐dynamic variables were obtained when ? ≥ 0. Reaction conversion, however, dropped as the expansion factor increased. This trend was more pronounced for reaction orders higher than unity. This suggests that bubbling fluidized operations are probably not optimal and applicable for certain types of reactions. Comparative analysis between reaction type and implications for optimum fluidized bed reactor are discussed.     

Simulation of catalytic fluidized bed reactors by a transient axial dispersion model with invariant physical properties and nonlinear chemical reactions

This paper presents a transient axial dispersion model for an isothermal, catalytic fluidized bed reactor, which is frequently employed in synthetic production processes including coal gasification and liquefaction. A non-linear chemical reaction is considered to occur in the reactor. This model of a fluidized bed reactor takes into account the axial dispersion in the three phases, bubble, cloud-wake and emulsion. The physical properties along the axial coordinate are invariant in the model. Transient characteristics of the gas reactant, and the length of the transient period have been examined based on the model. The model compares favorably with experimental data in the steady state condition.     

Model study of the direct causticization reaction between sodium trititanate and sodium carbonate

The solid state reaction between sodium tri‐titanate and sodium carbonate, forming mainly sodium pentatitanate, was investigated. Experiments were carried out in a micro‐differential reactor made of quartz glass at various temperatures between 800°C and 880°C and in a pilot fluidized bed reactor operated in a semi‐batch mode. In the former reactor, basic kinetic data was obtained by measuring the release of carbon dioxide. Different kinetic models were considered to describe the conversion, such as the Valensi‐Carter model for diffusion controlled reaction rates and the phase‐boundary model for first‐order reaction kinetics. Furthermore, a model that included both diffusion in the solid material and the chemical kinetics was derived. This model described the experimental data obtained in the micro‐differential reactor very well. However, for the fluidized bed experiments, these different kinetic models did not accurately describe the experimental data. Therefore, an improved model was developed, which also took into account the time taken for the reactants to achieve physical contact. This model gave good agreement with the experimental data.     

The influence of catalyst dilution by inert particles on the effectivity of a catalytical process in a fluidized bed

The method of the increasing a selectivity of catalytic processes in fluidized bed reactor by decreasing local chemical reaction rates together with increasing a reactive volume is discussed.Based on the two-phase model of a fluidized bed it is shown that the dilution of a catalyst by inert particles leads to an increasing of effective inteRestrictions to applications of the method connected with local features of a bed structure are discussed.     

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).     

SOME ASPECTS OF THEORETICAL COMPARISON OF FISCHER-TROPSCH REACTORS

The reactor systems used for the Fischer-Tropsch synthesis, fixed bed, fluidized bed and slurry bed, are compared on the basis of space time yield (STY) and level of conversion obtainable under the same set of feed and operating conditions. The slurry bed and fluidized bed reactor were compared on the basis of a first order reaction model. The performance of these two reactors was found to be comparable at low values of WHSV, but at higher values of WHSV, the fluidized bed reactor gave higher conversions and STY. A power law kinetic expression was used to compare the performance of the slurry bed and fixed bed reactors. Higher conversions and STY were obtained from the fixed bed with varying WHSV. This may be due to the omission of the intra and inter phase mass transfer resistances in the modelling of the fixed bed reactor.     

有内构件工业湍动流化床反应器的模型化——反应器模型的开发

引　言湍动流化床反应器因具有良好的气固接触氛围和传热性能、高固含率以及有限的轴向返混等优点 ,在工业生产中被普遍采用 ,但对于湍动流化床的模型化工作和反应器性能的报道较少[1] .Thompson等在 1999年提出的一般性鼓泡 /湍动流化床模型最有特色 ,该模型实现了从鼓泡区域到湍动区域的平滑过渡 ,与其他模型相比模型预测值与Sun于 1991年报道的实验数据能更好地吻合[2 ] .但是对于这些模型都缺少更多的工业数据去检验它们应用于工业模拟时的可靠性[1,3] ,对于具有垂直内构件的工业湍动流化床的模型化文献中未见报道 .秦霁光等人[4 ] 提…     

微型流化床内混合特性的数值模拟

微型流化床反应分析仪是中国科学院过程工程研究所研制的具有等温微分反应特性,且适合于气固反应分析的新仪器。细微样品与高温流化介质的瞬间混合是该仪器实现等温微分的必要条件。针对如何满足该要求,基于欧拉多流体模型对连接不同进样器的微型反应器本体进行了三维数值模拟,得到了不同喷口结构和位置下的流动图景及混合区浓度的相对标准偏差曲线,定量表征了各种进样器的混合质量。同时采用高速摄像手段获得了冷态实验中颗粒流动的快照,验证了模拟计算结果的可靠性。模拟结果对脉冲射流微量进样器结构的优化提出了如下建议：进样细管应避免采用弯角喷口,弯角结构会导致脉冲进样载流气喷出方向与流化气流相逆,使得细微颗粒试样堆积滞留,影响混合效果。     

Modeling a fluidized bed reactor by integrating various scales: Pore,particle, and reactor

This work proposes a novel population-balance based model for a bubbling fluidized bed reactor. This model considers two continuum phases: bubble and emulsion. The evolution of the bubble size distribution was modeled using a population balance, considering both axial and radial motion. This sub-model involves a new mathematical form for the aggregation frequency, which predicts the migration of bubbles from the reactor wall toward the reactor center. Additionally, reacting particles were considered as a Lagrangian phase, which exchanges mass with emulsion phases. For each particle, the variation of the pore size distribution was also considered. The model presented here accurately predicted the experimental data for biochar gasification in a lab-scale bubbling fluidized bed reactor. Finally, the aggregation frequency is shown to serve as a scaling parameter.     

甲醇制烯烃反应动力学及反应器模型研究进展

甲醇制烯烃（MTO）工艺是现代煤化工领域的研究热点,MTO反应动力学及其反应器模型研究是高效反应器开发和工业装置操作优化的基础。本文综述了甲醇制烯烃反应动力学研究进展,详细论述了机理型动力学模型、八集总动力学模型、五集总动力学模型,指出集总动力学模型适用于描述MTO反应过程,如何考虑水、积炭等因素的影响是MTO动力学研究的难点和关键。结合现有动力学模型,评述了MTO反应过程在工业规模的固定床反应器、提升管反应器、循环流化床反应器、湍动流化床反应器中产物分布和转化率模拟情况,结果表明：循环流化床反应器和湍动流化床反应器适合MTO工业过程。最后指出,甲醇制烯烃反应动力学下一步研究方应集中于工业规模流化床反应器气固两相流动模拟,以及与动力学模型结合获得准确预测工业反应结果的MTO反应器模型。     

Experiments and modeling on the deacidification of agglomerates of nanoparticles in a fluidized bed

The deacidification of the fumed silica AEROSIL® 200 was studied experimentally in a batch fluidized bed in the temperature range from 250 °C to 400 °C. For a well fluidized bed, the temperature and the steam concentration in the fluidizing gas are the determining parameters for the overall rate of deacidification. If the bed is not well fluidized, e.g. because it is too shallow, or it is fluidized near the point of minimum fluidization velocity, the rate of deacidification drops because channeling and bypassing occur. The adsorption equilibrium of steam and HCl on AEROSIL® 200 was measured for a wide temperature range and the temperature dependency of the Henry coefficient for steam is given. A mathematical reactor model was developed for the adsorption and for the surface reaction on highly agglomerated nanoparticles in a fluidized bed. In applying this model to the experimental data for the deacidification, a simple kinetic rate expression could be derived for the deacidification reaction, which is otherwise not obtainable. The temperature dependency of the rate constant was also determined. All other parameters for the model can either be found through independent measurements (e.g. adsorption equilibrium or fluidizing characteristics) or in literature. The model can be used for sizing and optimizing of fluidized bed reactors in the production of fumed oxides.     

基于变分贝叶斯算法的线性变参数系统辨识

线性变参数系统（LPV）将多阶段、非线性的过程建模转化为线性多模型的辨识问题,是解决非线性过程建模的一个有效手段。由于实际工业过程存在各种干扰因素,导致被建模系统呈现随机性及模型参数的不确定性。针对这一问题,考虑采用变分贝叶斯（VB）算法对LPV模型进行辨识。该算法首先给定参数相应的先验分布,通过最大化目标函数的下界,从而估计得到参数的后验分布。不仅可实现对参数的点估计,同时量化了估计值的不确定性。针对典型二阶过程和连续搅拌反应釜（CSTR）,运用提出的算法进行仿真实验,表明了该贝叶斯估计方法的优越性。     

LIQUID-SOLID MASS TRANSFER IN A THREE PHASE DRAFT TUBE FLUIDIZED BED REACTOR

Liquid-solid mass transfer coefficients in a three phase draft tube fluidized bed reactor have been measured using spherical ion exchange particles. The particle diameters ranged from 655 to 1119μm and solids volume fractions of approximately 5 and 10% were employed in water at 28°C. The experimental data can be successfully correlated using a Reynolds number derived using Kolmogoroffs theory of isotropic turbulence, although it is doubtful whether isotropic turbulence actually prevails in the fluidized bed over the range of conditions employed. Comparison with correlations determined for bubble columns and gas-liquid fluidized beds is performed. A model which considers the draft tube reactor as comprising two distinct fluid mechanical regions is developed to explain the apparently lower values of mass transfer coefficients obtained in a draft tube as opposed to conventional fluidized bed reactor.     

A fluidized bed kinetic model for the fluorination of dissociated zircon

A reaction kinetic model for the fluorination of plasma dissociated zircon (PDZ, or ZrO₂.SiO₂) with hydrogen fluoride was developed. The model uses reaction as rate‐limiting step, with a shrinking core of PDZ in a porous matrix of zirconia (ZrO₂). This model was used to develop models for a multi‐stage fluidized bed reactor. These models facilitated the determination and design of an optimally configured multi‐stage fluidized bed reactor for the fluorination of PDZ. It was shown that a combination cross‐/countercurrent multi‐stage fluidized bed reactor could yield significant improvement over the conventional countercur‐rent multi‐stage fluidized bed reactor for certain reaction kinetic conditions.     

Modeling of biomass devolatilization in a fluidized bed reactor

A simple model that simulates a single biomass particle devolatilization is described. The model takes into account the main physical and chemical factors influencing the phenomenon at high temperatures (>700 K), where the production of gaseous components far outweighs that of liquids. The predictions of the model are shown to be in good agreement with published data. The model is then applied to the devolatilization of biomass in a fluidized bed, in which attention is focused on heat transfer, particle mixing and elutriation, and gas production. Predictions on the overall devolatilization time for a biomass particle are compared with experimental results obtained in a fluidized bed reactor in which the process was monitored by continuous measurement of the bed pressure. Good correspondence of predicted with calculated values was obtained, supporting the validity of the many approximations made in the derivation of the governing relationships for the pyrolysis process.     

Precise parameter estimation for chemical batch reactions in heterogeneous medium

A sequential experimental strategy for precise parameter estimation has been used in the case of liquid-liquid dispersions in batch-stirred tank reactors where slow chemical reactions take place. The mathematical model for a batch reaction in a stirred tank reactor is formulated as a system of non-linear differential equations standing for the mass balance of each component. Physical kinetic parameters and chemical kinetic parameters which arise from this model are estimated simultaneously. The estimation problem is posed as a weighted least squares problem and solved by using a standard Levenberg-Marquardt algorithm. In this work, we intend to show how it is possible to develop efficient experimental design strategies that lead to an accurate estimation of the parameters involved in phenomenological models and most particularly in kinetic models. Three design criteria for designing the experiments have been employed in order to increase the precision on the parameter estimates of the model. A standard non-linear sequential quadratic programming method ensures the determination of the operating conditions which define the experimental design. The well-known alkaline hydrolysis of esters in aqueous phase has been treated as a numerical application example.