Optimal temperature profiles for tubular reactors implemented through a flow reversal strategy

Optimal steady-state reactor temperature profiles in classic jacketed tubular reactors often exhibit a (nearly) trapezoidal shape along the reactor, i.e., in a first part the temperature is raised, then a constant temperature interval follows, and (possibly) the temperature is lowered towards the outlet. The practical realisation of these optimal reactor temperature profiles is, however, complex because of the spatially varying jacket fluid temperature profile that is required for the constant reactor temperature part. Since similar trapezoidal temperature profiles are encountered in reverse flow configurations, this reactor type may be an alternative to implement the optimal profiles in practice. This article conceptually proves the feasibility of this concept and provides an optimisation procedure for its design and operation.     

Gas-phase residence time distribution in a falling-film microreactor

Industrial-scale performance of gas-liquid reactors can be difficult to optimise for very rapid or highly exothermic reactions. Microstructured reactors for laboratory measurements offer new opportunities for the study of these reactions by enabling precise heat management and fine control of reactor operating conditions. For accurate experimental study, characterisation of the flow conditions within these new reactor devices is essential.The present study examines experimental residence time distributions for the gas phase through a microstructured falling-film reactor, in order to develop an appropriate flow model for further study of gas-phase mass-transfer characteristics in the system. For the gas-phase residence time distribution experiments, the detection system involves a flow of oxygen containing ozone as a tracer gas with continuous monitoring of the concentration by UV-light absorption. The experimental results are used to model the flow behaviour in the gas volume over the gas-liquid contact zone as a series of continuous stirred tank reactors whose number is a simple function of the gas Reynolds number.The experimental results are compared with computational fluid dynamics calculations of the gas flow within the reactor. The comparison indicates a clear correlation of the flow model behaviour with the appearance of recirculation loops in the reaction chamber and the effect of the gas jet at the entrance of the gas-liquid contact zone.     

HYDRODYNAMIC MODELLING IN AN AIR-LIFT LOOP REACTOR

A simple hydrodynamic model is proposed for use in the design, scale-up and characterization of external loop air-lift reactors. The approach is based upon a momentum balance for the flow loop coupled with a drift-flux equation for the reactor riser and establishes a rational basis for a predictive model relating gas throughput to induced liquid flow and gas hold-up in a range of air-lift reactors. The effective resistance of the reactor, k, defined in terms of the total loss coefficients of the reactor and the aerated height of the two-phase riser, was identified to allow for the quantification of the influence of reactor design on the hydrodynamic variables. An extensive body of data for the air-water system, collected on two reactors with active volumes of 0·055 m³ and 0·3 m³, is presented and used, in conjunction with literature data encompassing a wide range of reactor geometries and flow conditions, to define a unique relationship between flow behaviour and reactor configuration. The model, which accounts for the prevailing flow regime in the reactor, provides a direct method of predicting hydrodynamic behaviour in relatively non-viscous systems.     

Methanol synthesis in a forced unsteady-state reactor network

The feasibility of carrying out the low-pressure methanol-synthesis process in forced unsteady-state conditions, using a network of three catalytic fixed bed reactors with periodical change of the inlet position, has been investigated; advantages and limitations in comparison with the previously proposed reverse-flow reactor have been highlighted. The effect of the main operating parameters—inlet temperature, switching time, inlet flow rate—has been studied. A cyclic-steady-state condition and auto-thermal behaviour are possible; nevertheless, they are attainable only for switching times varying in two narrow ranges. Out of these regions, complex steady-states of high periodicity, where conversion is low, or extinction of the reactors occur. For low values of the switching time, the establishing of optimal temperature profiles along the network allows higher conversions than in the reverse flow reactor. Furthermore, the performances of the network are weakly affected by wash-out, the removal of unconverted gas in correspondence of switching, which is in intrinsic disadvantage of reverse flow operation.     

Comparison between the Reverse‐Flow Reactor and a Network of Reactors for the Oxidation of Lean VOC Mixtures

Catalytic reactors in forced nonstationary operation enable autothermal VOC (volatile organic compounds) oxidation even when the adiabatic temperature rise of the combustible mixtures is extremely low. The simulated moving bed (or ring reactor), realized with a network of two or three reactors, has been suggested as an alternative to the well‐investigated reverse‐flow reactor. The behavior of these configurations has been compared, showing that the reactor network has a narrower stability range than the reverse‐flow reactor; the stability range is decreased if we increase the number of reactors. The maximum temperature of the catalyst is higher in the network than in the reverse‐flow reactor and in both configurations it is increased if part of the catalyst is substituted by inert material.     

Combustion of toluene-hexane binary mixtures in a reverse flow catalytic reactor

This work is focused on the application of reverse flow reactors to the combustion of lean mixtures of aliphatic and aromatic hydrocarbons in air. For this purpose, hexane and toluene were chosen as model compounds. The combustion of binary mixtures of these compounds (up to 500 ppmV total hydrocarbon concentration) over a commercial Pt/Al₂O₃ catalyst in reverse flow reactors has been studied both experimentally, in a bench-scale unit, and by simulations, using a heterogeneous mono-dimensional dynamic model, good correspondence being observed between both approaches.As general trend, it was observed that the behaviour of the reactor is determined mainly by the combustion enthalpies and reactivities of toluene and hexane. Hence, increasing total concentration and increasing fraction of toluene (the most reactive compound) lead to more stable operation. Regarding the kinetic inhibition effects, in the conditions studied no influence on the reactor performance was observed, probably because the hydrocarbons combust in different reactor zones. This behaviour can be extended to the combustion of aromatic and C₅-C₈ alkanes, characterised by their relatively low concentrations (determined by their vapour pressure) and high reaction rates.     

Validation of pressure drop prediction and bed generation of fixed-beds with complex particle shapes using discrete element method and computational fluid dynamics

Catalytic fixed-bed reactors with a low tube-to-particle diameter ratio are widely used in industrial applications. The heterogeneous packing morphology in this reactor type causes local flow phenomena that significantly affect the reactor performance. Particle-resolved computational fluid dynamics has become a predictive numerical method to analyze the flow, temperature, and species field, as well as local reaction rates spatially and may, therefore, be used as a design tool to develop new improved catalyst shapes. Most validation studies which have been presented in the past were limited to simple particle shapes. More complex catalyst shapes are supposed to increase the reactor performance. A workflow for the simulation of fixed-bed reactors filled with various industrially relevant complex particle shapes is presented and validated against experimental data in terms of bed voidage and pressure drop. Industrially relevant loading strategies are numerically replicated and their impact on particle orientation and bed voidage is investigated.     

Heterogeneous catalytic reactor design with optimum temperature profile I: application of catalyst dilution and side-stream distribution

A generic method for the design of reactors with optimal temperature profiles has been developed. This paper focuses on the use of side-streams and inert pellets to control the temperature profiles in addition to external cooling. These two aspects of reactor design have so far been developed separately and mainly applied to laboratory-scale reaction systems. In this work, a reactor design procedure is developed that considers the combination of these two aspects simultaneously. Nitrobenzene hydrogenation and ethylene oxidation in non-isothermal and non-adiabatic reactors are used as case studies. The results show that higher reactor performance, characterised by conversion, yield or selectivity, can be achieved with optimal temperature profiles manipulated by side-streams and inert pellets. Temperature can be effectively controlled to be below a certain maximum point that causes hot spots, or thermal run-away behaviour. Various reactor designs such as Packed-Bed Membrane Reactor (PBMR), Multi-Bed Multi-Tubular Reactor (MBMTR) with side-stream injection are considered and compared with typical fixed-bed reactors. Pseudo-homogeneous (1D) and heterogeneous (1D) reactor models are used for the modelling of the reactor with SQP (Successive Quadratic Programming) and stochastic methods applied for the optimisation.     

Effects of the gas/solids distributor on the local and overall solids distribution in a downer reactor

In the last few years, the downer has been proposed as a new reactor for gas/solids reactions. Compared to state-of-the-art riser reactors, the cocurrent downflow of gas and solids should lead to a more uniform flow structure, close to plug flow. Experimental studies showed, that the gas/solids distributor at the top of the reactor is significantly influencing the flow pattern in a downer reactor. Local information about the solids concentration is indispensable for a thorough characterization of the flow structure in gas/solids flows. To obtain this information, x-ray computed tomography has been used for the experimental investigations.     

径向移动床反应器流场特性及其数学模拟

本文票据主流道变质量流及颗粒床层气固体力学理论,建立了完整的径向移动床反应器流体力学数学模型,开发了模拟计算床层气相二维流场的一种新的数学方法及相应的计算程序。黛此可以模拟计算床层气相压力和轴径向速度的二维分布、内外主流道压力和流速分布以及布气孔道的过孔气速和压降。根据模拟计算结果,提出首先优化设计两主流道截面积分配,然后采用变开孔率设计消除开孔区端效应的两步设计方法。借此实现径向移动床反应器的优     

Modelling and design of thin-film slurry photocatalytic reactors for water purification

Photocatalytic oxidation processes are highly effective clean technologies for the degradation and mineralization of a wide variety of priority pollutants in water and wastewater. However, the application of heterogeneous photocatalysis for wastewater treatment on an industrial scale has been impeded by a lack of mathematical models that can be readily applied to reactor design and scale-up. As a results current photocatalytic reactors in research and development have been designed by empirical or semi-empirical methods only.In this paper, a simple and generic mathematical model for steady-state, continuous flow, thin-film, slurry (TFS) photocatalytic reactors for water purification using solar and UV lamps is presented. The model developed is applicable to TFS flat plate and annular photoreactors of (a) falling film design or (b) double-skin design, operating with three ideal flow conditions: (1) falling film laminar flow, (2) plug flow and (3) slit flow. The model is expressed in dimensionless form and scale-up of TFS photocatalytic reactors can be carried out by dimensional analysis. In addition, the model parameters can be estimated easily from real systems and model solutions can be obtained with little computational effort.Comparison of a number of ideal flow systems shows that both falling film laminar flow and plug flow operation modes give higher performance than the slit flow system. Slit flow operation mode results in lower conversions due to the non-correspondence of fluid-residence time and the transversal radiation field. The effect of optical thickness, on reactor performance and the evolution of radial profiles of a model pollutant with photoreactor length are presented for each of the operation modes. The falling film laminar flow system was found to be more efficient than the plug flow system when the reactor conversion is above 80%. For lower reactor conversion the plug flow system was found to be marginally more efficient than the falling film laminar flow system. A methodology for the optimal geometrical design of a highly efficient configuration of TFS photocatalytic reactors is also presented. The mathematical models presented may be used as a tool for the design, scale-up and optimization of these types of photocatalytic reactors.     

Flow visualization and modelling of a filter-press type electrochemical reactor

A study of flow visualization and residence time distribution is provided in order to model the flow between two electrodes in a commercial filter-press reactor, the ElectroSynCell® from Electrocell AB. Flow visualization indicates that both axial and lateral dispersion phenomena occur and a global plug flow behaviour is observed. The flow distribution is asymmetric due to the design of the inlet system in the active zone. The flow throughout the cell is described by a dispersed plug flow model for which the mean residence time and the Pe´clet number are determined. The reaction area and the inlet system are separately analysed by locating conductimetric probes inside the electrochemical cell. The reaction area is also well described by a dispersed plug flow model, and characterized by high dispersion. The inlet system is, respectively, described by a dispersed plug flow model and by a cascade of continuous stirred tank reactors. The high number of reactors in the cascade denotes a quasi plug flow behaviour. The results are confirmed by two cascades of continuously stirred tank reactors in series. The dispersion coefficients obtained throughout the reaction area of the cell are not constant. This shows that the flow is not well established at the entrance of the reaction zone and depends on the entrance conditions.     

Simulation of a Reverse Flow Reactor for the Catalytic Combustion of Lean Methane Emissions

This work is focused on the performance prediction of pilot scale catalytic reverse flow reactors used for combustion of lean methane-air mixtures. An unsteady one-dimensional heterogeneous model for t...     

STEADY-STATE MODELLING OF A LATEX REACTOR TRAIN FOR THE PRODUCTION OF STYRENE-BUTADIENE RUBBER

A mathematical model is developed for the emulsion copolymerization of styrene and butadiene carried out in a continuous train of stirred tank reactors. The model predicts copolymer composition, conversion, molecular weight averages, and long chain branching frequencies, as well as the latex particle size distribution for all reactors in the train. It is capable of simulating closely the behaviour of industrial SBR processes.

Several simulation studies are performed. Topics investigated include: process operating modifications to improve productivity; the effect of chain transfer agent flow rate and number of reactors on the molecular weight development; the effect of process modifications on the development of the particle size distribution down the reactor train; and the effect of reactor design on particle generation rates.     

Macro-mixing in a draft-tube airlift bioreactor

Airlift reactors are pneumatically agitated reactors that have been widely used in industries, particularly in bioprocesses. Extensive studies about the flow dynamics in airlift column reactors exist; however, most of these studies have focused on global hydrodynamic parameters using conventional techniques. The local flow characteristics, such as the macro-mixing and the turbulence intensity, are crucial for reliable design and scale-up, and they remain unclear. This work focuses on studying the macro-mixing in a draft-tube airlift bioreactor utilizing an advanced flow dynamic measurement technique, computer automated radioactive particle tracking (CARPT). True residence time distribution analyses for the overall column as well as individual regions, i.e., the riser, the downcomer, the top, and the bottom regions, are conducted for the first time based on CARPT measured particle trajectories. The effects of the superficial gas velocity and the top/bottom clearances on the macro-mixing are also discussed. The results suggest that although the flow structures in the overall draft-tube column reactor, as well as in the riser and in the downcomer, are close to plug flows, bypassing and stagnancy exist in the top and the bottom regions.     

Kinetics of a catalyzed semi-batch ethoxylation of nonylphenol

A combined experiments and mathematical modelling were carried out to study the kinetics of nonylphenol ethoxylation. Experiments were carried out in a well-stirred reactor used in an industrial research laboratory. The governing equations of the kinetic model were solved using Mathematica (2009). Results were validated against published kinetic data. The experiments and kinetics modelling were extended to account the presence of nitrogen in the vapour phase for a potassium hydroxide catalyzed ethoxylation of nonylphenol in a well-stirred reactor. The modelling results were successfully validated against the experimental data. This model has been successfully used (Chiu et al., 2008) for optimizing the productivity of the existing alkoxylation reactors and can be used as a tool for the exploration and design of innovative new reactor systems.     

A novel reverse flow reactor coupling endothermic and exothermic reactions. Part I: comparison of reactor configurations for irreversible endothermic reactions

A new reactor concept is studied for highly endothermic heterogeneously catalysed gas phase reactions at high temperatures with rapid but reversible catalyst deactivation. The reactor concept aims to achieve an indirect coupling of energy necessary for endothermic reactions and energy released by exothermic reactions, without mixing of the endothermic and exothermic reactants, in closed-loop reverse flow operation. Periodic gas flow reversal incorporates regenerative heat exchange inside the reactor. The reactor concept is studied for the coupling between the non-oxidative propane dehydrogenation and methane combustion over a monolithic catalyst.Two different reactor configurations are considered: the sequential reactor configuration, where the endothermic and exothermic reactants are fed sequentially to the same catalyst bed acting as an energy repository and the simultaneous reactor configuration, where the endothermic and exothermic reactants are fed continuously to two different compartments directly exchanging energy. The dynamic reactor behaviour is studied by detailed simulation for both reactor configurations. Energy constraints, relating the endothermic and exothermic operating conditions, to achieve a cyclic steady state are discussed. Furthermore, it is indicated how the operating conditions should be matched in order to control the maximum temperature. Also, it is shown that for a single first order exothermic reaction the maximum dimensionless temperature in reverse flow reactors depends on a single dimensionless number. Finally, both reactor configurations are compared based on their operating conditions. It is shown that only in the sequential reactor configuration the endothermic inlet concentration can be optimised independently of the gas velocities at high throughput and maximum reaction coupling energy efficiency, by the choice of a proper switching scheme with inherently zero differential creep velocity and using the ratio of the cycle times.In this first part, both the propane dehydrogenation and the methane combustion have been considered as first order irreversible reactions. However, the propane dehydrogenation is an equilibrium reaction and the low exit temperatures resulting from the reverse flow concept entail considerable propane conversion losses. How this ‘back-conversion’ can be counteracted is discussed in part II Chemical Engineering Science, 57, (2002), 855-872.     

Startup of an industrial adiabatic tubular reactor

The dynamic behaviour of an adiabatic tubular plant reactor during the startup is demonstrated, together with the impact of a feed-pump failure of one of the reactants. A dynamic model of the reactor system is presented, and the system response is calculated as a function of experimentally-determined, time-dependent, manipulated variables. The values of model parameters are estimated by using the SimuSolv (1991) computer program. The data set collected during the reactor start-up is used for the parameter estimation procedure. An excellent agreement is obtained between the experimental and the calculated system response. Many continuously-operated commercial reactors require a complete conversion of one of the main reactants at the reactor exit. It is shown that for an industrial tubular reactor a much higher initial reactor temperature is required during the startup, compared to the reactor inlet temperature during normal steady-state operation, to ensure a complete reactant conversion. Much more research is necessary to determine whether this is a generally valid rule.     

On a mathematical model for loop reactors—II. Estimation of parameters

Based on a model of loop reactors with sections of different mixing behaviour and on an approximation formula for its residence time distribution, a procedure is derived to determine the main model parameters, the mean circulation time, the circulation variance and the corresponding values of the individual sections. Finally the results of application of this procedure to RTD-measurements in a laboratory liquid jet loop reactor are presented.