Mass transfer effects on hydroformylation catalyzed by a water soluble complex

The rate of hydroformylation of 1-octene catalyzed by a water soluble catalyst is measured in mechanically agitated batch reactor at various stirrer speeds and organic phase holdups. The data have been analyzed by coupling reaction kinetics to a pseudo-homogeneous gas–liquid–liquid model based on Higbie's penetration theory which takes into account the presence of the dispersed organic phase. A rapid liquid–liquid mass transfer of the reactants is assumed leading to an equilibrium between the continuous and the dispersed phases. The predicted values of the rate are in good agreement with the experimental one. The depletion of the organic substrate in the continuous phase is found negligible.     

Euler–Lagrange modeling of a gas–liquid stirred reactor with consideration of bubble breakage and coalescence

Simulations of a gas–liquid stirred reactor including bubble breakage and coalescence were performed. The filtered conservation equations for the liquid phase were discretized using a lattice‐Boltzmann scheme. A Lagrangian approach with a bubble parcel concept was used for the dispersed gas phase. Bubble breakage and coalescence were modeled as stochastic events. Additional assumptions for bubble breakup modeling in an Euler–Lagrange framework were proposed. The action of the reactor components on the liquid flow field was described using an immersed boundary condition. The predicted number‐based mean diameter and long‐term averaged liquid velocity components agree qualitatively and quantitatively well with experimental data for a laboratory‐scale gas–liquid stirred reactor with dilute dispersion. Effects of the presence of bubbles, as well as the increase in the gas flow rate, on the hydrodynamics were numerically studied. The modeling technique offers an alternative engineering tool to gain detailed insights into complex industrial‐scale gas–liquid stirred reactors. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Hydrodynamics of slurry bubble column during dimethyl ether (DME) synthesis: Gas-liquid recirculation model and radioactive tracer studies

Radioactive tracer measurements, using impulse injections of Ar⁴¹, powdered oxide of Mn⁵⁶ and real catalyst particles doped with an oxide of Mn⁵⁶, conducted at the Advance Fuels Development Unit (AFDU) slurry bubble column (BC) reactor during dimethyl ether (DME) synthesis (reactor pressure of 5.27 MPa, reactor temperature of , inlet superficial gas velocity of 17.1 cm/s, and a catalyst loading of 36 wt%) at LaPorte, Texas, are interpreted. The differences in the responses obtained by the catalyst and fine powdered Mn₂O₃ tracer injections are minimal indicating the validity of the pseudo-homogeneous assumption for the liquid plus solid (catalyst) phase mixtures. The gas-liquid recirculation model [Gupta et al., 2001a. Comparison of single- and two-bubble class gas-liquid recirculation models—application to pilot-plant radioactive tracer studies during methanol synthesis. Chemical Engineering Science 56(3), 1117-1125. 2001b. Hydrodynamics of churn turbulent bubble columns: gas-liquid recirculation and mechanistic modeling. Catalysis Today 64(3-4), 253-269], based on a constant bubble size, describing gas-liquid mass transfer superimposed on turbulent mixing of the gas and liquid phases, is used to simulate the gas, liquid and catalyst tracer responses acquired at the AFDU. The model is able to predict the characteristic features of the experimental responses observed for gas, slurry powder and catalyst tracers at different reactor elevations. The fact, that the same model was previously shown capable of predicting both gas and liquid radioactive tracer responses during methanol and Fischer-Tropsch (FT) synthesis, indicates that this model offers a relatively simple tool for assessing mixing and transport in bubble (BCs) for a variety of gas conversion processes and provides a phenomenologically based framework for BC reactor modeling.     

Liquid back-mixing in packed-bubble column reactors: a state-of-the-art correlation

The extent of liquid back-mixing in gas–liquid concurrent upflow packed-bubble column reactors is quantified in terms of an axial dispersion coefficient or its corresponding dimensionless Péclet number. Effects of reactor operating conditions on the axial dispersion coefficient are not properly accounted for by the available literature correlations, wherein most often the Péclet number is expressed solely in terms of the gas and liquid Reynolds numbers or superficial velocities. Based on the broadest experimental databank (1322 measurements, 11 liquids, four gases, 28 packing materials, 14 columns diameters, Newtonian, non-Newtonian, aqueous, organic, coalescing and non-coalescing liquids, high pressure, bubble and pulsing flow regime conditions), a state-of-the-art liquid axial dispersion coefficient correlation is obtained by combining neural network modeling and dimensional analysis. Thorough qualitative and quantitative analyses of the constructed databank demonstrate the robustness of the proposed correlation to restore the variety of trend variations of liquid Péclet numbers reported in the literature.     

Dehydration of ortho-boric acid in a three-phase bubble column reactor operating at low pressure

This study investigates the applicability of the bubble column as a reactor to perform the dehydration of ortho-boric acid efficiently and economically. The effects of operating conditions such as reaction time, temperature, gas flow rate, particle size and solid content in the slurry phase on the fractional conversion of the reaction have been determined, and the performance of the three-phase bubble column reactor operating at low pressure (92 kPa) has been discussed. It can be noted from this study that the reaction time has been reduced and the particle size and solid content which are required in the slurry phase for favourable fractional conversion have been increased in the bubble column reactor in comparison with those in the continuous stirred tank reactor. The reaction could be described by means of a fluid–solid heterogeneous reaction model.     

Liquid circulation hydrodynamics in an external loop airlift reactor

The radial profiles of axial liquid velocity and gas hold‐ups are investigated in the riser of a pilot plant scale external loop airlift reactor (ELAR) using a modified Pavlov tube and differential pressure technique. The experimental investigation reveals that there exist two different kinds of liquid circulation structures in an ELAR, which has rarely been reported in the literature, namely internal liquid circulation, which exists only in the riser and external liquid circulation, which circulates through the downcomer. A power–law relationship is used to correlate the gas hold‐up and superficial gas velocity, which gives good agreement with experimental data. Experiments for axial liquid velocity profiles are analysed in analogy to a model described for a conventional bubble column. The results predicted by the model are in excellent agreement with the experimental data obtained under various operating conditions. © 2011 Canadian Society for Chemical Engineering     

The ejector-driven monolith loop reactor — experiments and modeling

A novel catalytic gas–liquid reactor configuration, consisting of a monolithic reactor with a liquid-motive ejector as gas–liquid distributor is introduced as a retrofit or alternative to an agitated slurry reactor. The ejector distributes gas and liquid to the channels of a monolith reactor at velocities greater than those attainable with gravity-driven flow, intensifying mass transfer and reaction in a compact reactor. Pressure drops measured using this configuration do not conform to models from the literature. A strong effect of liquid coalescence properties was observed. Until fully predictive pressure drop and gas–liquid distribution models become available, successful scale-up will depend on pressure-drop data measured with industrial process conditions and fluids. Current literature models for mass transfer underpredict laboratory autoclave reaction results, indicating a need for further model development, and in the interim requiring pilot-scale testing for scale-up purposes.     

The mechanism model of gas–liquid mass transfer enhancement by fine catalyst particles

In order to present the enhancement of gas–liquid mass transfer by heterogeneous chemical reaction near interface, the mechanism model has been proposed to describe the mass transfer rate for a gas–liquid–solid system containing fine catalyst particles. The composite grid technique has been used to solve the model equations. With this model the effect of particle size, first-order reaction rate constant, distance of particle to gas–liquid interface and residence time of particle near gas–liquid interface on the mass transfer enhancement have been discussed. The particle–particle interaction and slurry apparent viscosity can be considered in the model. The experimental data have been used to verify the model, and the agreement has been found to be satisfied.     

Axial mixing in a novel pilot scale gas–liquid reciprocating plate column

Axial mixing in a novel pilot scale landau reciprocating plate column (LRPC) has been investigated for counter-current gas–liquid contacting over a wide range of operating conditions. The experimental results obtained using the dynamic response method were analysed using both the dispersion and compartment models under different boundary conditions and using both the method of moments and the direct time domain parameter estimation techniques. Based on the results, it was identified that axial mixing in this column can be best described using the back flow and the dispersion models solved with “closed–closed” boundary conditions. A general correlation describing the effect of operating parameters on the extent of axial mixing was developed with a mean absolute relative residuals of 6.8%. Similar to other RPC designs, axial mixing in LRPC increases with increasing both phase flows and plates oscillatory velocity. Values of axial dispersion coefficient in this work ranged from 10⁻⁴ to over 3 × 10⁻³ m²/s, which are comparable or less than those in other RPC designs under similar phase velocities and oscillatory conditions, but an almost order of magnitude lower than those measured in bubble columns under similar operating flow rates.     

气液两相流摆动特性实验的数值模拟

为了给鼓泡塔反应器设计提供依据,运用计算流体力学(CFD)软件模拟了鼓泡塔气液两相流动态行为。采用双欧拉法对鼓泡塔矩形反应器内不同曝气量下气液两相流的摆动特性进行了模拟考察,液相采用标准κ-ε紊流模型,气相采用分散相零方程模型,分析了网格尺寸、时间步长以及相间作用力对模拟结果的影响,模拟的曝气量为42.5~237 m L/s。结果表明,当相间作用力仅考虑阻力时,气液两相流呈现周期性摆动规律;随着气流量的增加,气泡羽流的摆动幅度和频率增大,同时液体的气含率也在增加;模拟的气液两相流摆动频率数据与实验值吻合较好,两者的相对误差为7.2%~12.9%。     

Computation of plate columns for NOx absorption by a new stage-to-stage method

A new stage-to-stage method has been developed for the calculation of NX_x absorption columns. Each stage of the absorption column is simulated as a combination of a bubble column reactor (absorption) and an adiabatic plug for reactor (oxidation). The bubble column reactor is modelled as two single stirred tank reactors, one as a gas-phase and one as a liquid-phase reactor, both coupled by mass and heat transfer. In this hydrodynamic model, a dynamic approach is adopted, in which the gas-phase transport of N₂O₄ is the limiting step for the absorption. A gas-phasepseudo-enhancement for factor for N₂O₄ is therefore introduced. The balance equations for a single phase of the bubble column are solved with a Newton-Raphson algorithm. The entire column calculation is divided into a gas and a liquid side. On both sides, the stage-to-stage method is applied in such way that the overall calculation is performed as a loop process. The direction of the loop calculation follows that of the flow: gas-side upwards and liquid-side downwards.     

CFD modeling of slurry bubble column reactors for Fisher-Tropsch synthesis

Industrial bubble column reactors for Fischer-Tropsch (FT) synthesis include complex hydrodynamic, chemical and thermal interaction of three material phases: a population of gas bubbles of different sizes, a liquid phase and solid catalyst particles suspended in the liquid. In this paper, a CFD model of FT reactors has been developed, including variable gas bubble size, effects of the catalyst present in the liquid phase and chemical reactions, with the objective of predicting quantitative reactor performance information useful for design purposes. The model is based on a Eulerian multifluid formulation and includes two phases: liquid-catalyst slurry and syngas bubbles. The bubble size distribution is predicted using a Population Balance (PB) model. Experimentally observed strong influence of the catalyst particles concentration on the bubble size distribution is taken into account by including a catalyst particle induced modification of the turbulent dissipation rate in the liquid. A simple scaling modification to the dissipation rate is proposed to model this influence in the PB model. Additional mass conservation equations are introduced for chemical species associated with the gas and liquid phases. Heterogeneous and homogeneous reaction rates representing simplified FT synthesis are taken from the literature and incorporated in the model.Hydrodynamic effects have been validated against experimental results for laboratory scale bubble columns, including the influence of catalyst particles. Good agreement was observed on bubble size distribution and gas holdup for bubble columns operating in the bubble and churn turbulence regimes. Finally, the complete model including chemical species transport was applied to an industrial scale bubble column. Resulting hydrocarbon production rates were compared to predictions made by previously published one-dimensional semi-empirical models. As confirmed by the comparisons with available data, the modeling methodology proposed in this work represents the physics of FT reactors consistently, since the influence of chemical reactions, catalyst particles, bubble coalescence and breakup on the key bubble-fluid drag force and interfacial area effects are accounted for. However, heat transfer effects have not yet been considered. Inclusion of heat transfer should be the final step in the creation of a comprehensive FT CFD simulation methodology. A significant conclusion from the modeling results is that a highly localized FT reaction rate appears next to the gas injection region when the syngas flow rate is low. As the FT reaction is exothermal, it may lead to a highly concentrated heat release in the liquid. From the design perspective, the introduction of appropriate heat removal devices may be required.     

Effect of backmixing on the performance of bubble column reactors

The dispersion model was used to account for the effect of backmixing in the liquid phase on the performance of a bubble column reactor. It was assumed that gas phae moves in the plug flow and gas absorption is accompanied by a fast general order reaction. An analytical solution can be obtained when the liquid phase is assumed to move in plug flow. However, for a general case the relevant differential equations were solved numerically. The effect of pertinent variables is discussed.     

GAS-PHASE CONTROLLED MASS TRANSFER IN A FOAM-BED REACTOR

Gas-phase controlled absorption of ammonia in foams made of solutions of sulphuric acid has been studied experimentally. Effects of gas-phase concentration of ammonia and type of surfactant on the performance of the foam-bed reactor are investigated. Gas-phase controlled absorption from a spherical bubble is anaylzed using the asymptotic value of Sherwood number (Sh = 6·58), for both negligible as well as significant changes in the volume of the bubble. The experimental data are shown to be in good agreement with the single-stage model of the foam-bed reactor using these asymptotic sub-models, as well as the diffusion-in-sphere analysis available in literature. Influence of effective diffusivity on the time dependence of fractional gas absorption has been found to be unimportant for foam columns with large times of contact. The asymptotic sub-models have been compared and use of the rigid-sphere asymptotic sub-model is recommended for foam columns of practical relevence.     

Numerical simulation of the gas–liquid flow in a laboratory scale bubble column: Influence of bubble size distribution and non-drag forces

In the present work, a computational model based on an Eulerian–Eulerian approach was used for the simulation of the transient two-phase flow in a rectangular partially aerated bubble column. Superficial gas velocities (U_G) ranging from 0.24 to 2.30 cm/s were used throughout both the experiments and the simulations. The calculated results were verified by comparing them with experimental data including measurements of gas hold-up, plume oscillation period (POP) and Sauter mean bubble diameter. The study shows the effect of mesh refinement, time-step and physical model selection, the latter regarding the role of bubble size distribution and non-drag forces, on the computational results. According to the results presented here, the representation of bubble populations using multiple size groups (MUSIG model) instead of a single group improves the prediction of the experimental parameters under study. Additionally, the results obtained after including the virtual mass force term do not differ considerably from those obtained including only the drag force. On the contrary, as a consequence of introducing the lift force term into the model, the gas hold-up is overestimated and a non-symmetric bubble plume oscillation appears, a fact that is not experimentally observed.     

第二液相的加入对气液传质系数的影响

以搅拌罐中的水吸收CO2为研究体系,分别采用异戊醇、苯和正己烷为第2液相,通过实验考察了第2液相的加入对气液传质的影响.实验结果表明:第2液相的加入对气液体积传质系数KLa有很大的影响,且不同的第2液相的影响程度也不同.在一定的操作条件下,KLa均随搅拌速度和第2液相体积分数的增加呈先增大后减小的趋势,随表观气速(在一...     

Two-phase modeling of a gas phase polyethylene fluidized bed reactor

A two-phase model is proposed for describing the behavior of a fluidized bed reactor used for polyethylene production. In the proposed model, the bed is divided into several sequential sections where flow of the gas is considered to be plug flow through the bubbles and perfectly mixed through the emulsion phase. Polymerization reactions occur not only in the emulsion phase but also in the bubble phase. Voidages of the emulsion and bubble phases are estimated from the dynamic two phase structure hydrodynamic model. The kinetic model employed in this study is based on the moment equations. The hydrodynamic and kinetic models are combined in order to develop a comprehensive model for gas-phase polyethylene reactor. The results of the model are compared with the experimental data in terms of molecular weight distribution and polydispersity of the produced polymer. A good agreement is observed between the model predictions and actual plant data. It has been shown that about 20% of the polymer is produced inside the bubble phase and as such cannot be neglected in modeling such reactors.     

三相鼓泡淤浆床环氧乙烷合成反应器数学模拟及工程分析

建立了加压三相鼓泡淤浆床环氧乙烷合成反应器的数学模型 ,计入了催化剂颗粒在床层中沉降形成沿床高浓度分布对反应的影响以及由于惰性液相载体部分返混对传递的影响 ,进一步利用经实验验证的上述数学模型模拟不同表观气速、床高、反应器直径 (扣除传热元件截面积 )、进口乙烯摩尔分数等参数对床层中催化剂浓度随床高的分布、出口环氧乙烷摩尔分数、环氧乙烷选择率以及单位质量催化剂环氧乙烷年产量的影响 .通过模拟分析预示了工业三相床环氧乙烷反应器的合理尺寸、表观气速、环氧乙烷选择率以及时空产率 ,为工业化提供必要的设计依据     

Hydrodynamic Modelling of Internal Loop Airlift Reactor Applying Drift‐Flux Model in Bubbly Flow Regime

A new model for the liquid circulation rates in airlift reactor (ALR) is presented. The model is based on the energy balance for the flow loop (riser, turn riser‐downcomer, downcomer, and turn downcomer‐riser) coupled with a drift flux theory of two‐phase flow gas‐liquid system, considering a bubbly flow regime. The predicted values of the liquid circulation rates by the developed model are compared with experimental results performed in a 22 dm³ internal loop airlift reactor and with the results obtained in the literatures. The proposed model predicted the experimental results very well. Slip velocity relationship based on the drift flux model was proposed; including the gas holdup, bubble size and the liquid physical properties. The predicted slip velocity was similar to that obtained from the literature. The study revealed that appropriate arrangements of internal bioreactor parts can positively influence the liquid circulation velocity at the same energy consumption. The proposed models are useful in the design; scale up and characterization of the internal loop airlift reactors, and provides a direct method of predicting hydrodynamic behaviour in gas‐liquid airlift reactors.     

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.