Approximate design of loop reactors

A loop reactor (LR) is an N-unit system composed of a loop with gradually shifted inlet/outlet ports. This system was shown in our previous study [Sheintuch M., Nekhamkina O., 2005. The asymptotes of loop reactors. A.I.Ch.E. Journal 51, 224-234] to admit an asymptotic model for a loop of a fixed length with N→∞. Both the finite-unit and the asymptotic model exhibit a quasi-frozen or a frozen rotating pulse (FP) solution, respectively, within a certain domain of parameters that becomes narrower as feed concentration declines.In the present paper we derive approximate solutions of the ignited pulse properties in an LR as a function of the external forcing (switching) rate. Analysis of these solutions enable us to determine the maximal temperature in the system, as well as the boundaries of the FP domain. For the optimal solution we determine the maximal temperature and conversion dependencies on the reactor length and on N. The approximate solutions are verified by comparison with direct simulations of the asymptotic model and a good agreement was found. The obtained results can be successfully used for prediction of the finite unit LR.     

Structure of operating domains of loop reactors

A loop reactor (LR), composed as an N-unit loop with step-wise shifted inlet and outlet ports, is one of suggested technological solutions for low-concentration volatile organic compounds (VOC) combustion. Such a scheme ensures a sufficiently high temperature with autothermal behavior and nearly uniform catalytic utilization. The main drawback of the LR is a very narrow window of switching velocities that sustain a stable “frozen” solution that exists if the switching and the pulse velocity are synchronized. In the present work we show the existence of many “finger”-like domains of complex frequency-locked solutions that allow to significantly extend the operation domain, rendering the LR scheme more attractive for practical implementation. A brief comparison with the other heat recuperation technologies (reverse flow and circular loop reactors) is presented. © 2008 American Institute of Chemical Engineers AIChE J, 2008     

Mathematical modelling of a reverse flow reactor with catalytic surface dynamics

This paper studies a system of partial differential equations modelling the behaviour of a reverse flow reactor. For the parameters appropriate for the oxidation of ammonia on a Pt/Al₂O₃ catalyst in a typical laboratory set-up, the reactor may be split into regions where approximate formulas that determine its behaviour are deduced. Numerical calculations are presented and can be used to compare with the analytical formulas. The physical insight gained from the asymptotic analysis suggests a new switching strategy which is the subject of numerical experiments. The switching strategy is found to be efficient at minimising the ammonia exiting the reactor after reversal.     

Analysis of design sensitivity of flow-reversal reactors: Simulations, approximations and oxidation experiments

The analysis of a flow-reversal reactor, constructed from a catalytic bed imbedded within two inert beds and catalysing an instantaneous reaction, shows that the main parameters that determine the maximal reactor temperature are the thermodynamic parameters, heat loss through the walls and the conductivity and length of the inert zones. We show how these parameters can be easily extracted from the experimental data of very fast reactions, and demonstrate it for ethylene and for propane oxidation. We also derive an approximation for the maximal temperature for fast or slow reactions. These approximations are compared with experimental results obtained during propane (with low feed concentration) or methane oxidation.     

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.     

Experimental Simulation on Chemical-looping Combustion of Cold Model（英文）

The pressure profiles, gas velocities, solid circulation rate, solids flux, residence time distribution of gas and particles in chemical-looping combustion reactors and gas leakage were studied in a cold flow model unit. And these parameters in both air and fuel reactors were measured in the experimental stage. The experimental results show that gas fluidization velocity in the air reactor is 1.8 m/s, gas fluidization velocity in the fuel reactor 0.5 m/s, and the bed materials inventory of the two reactors between 1.2 to 3.15 kg. The first cold flow model results show that the solid circulation rates are sufficient. The appropriate operating conditions are optimized and the summary of final changes is made the on cold model. The proposed design solutions are currently being verified in a cold flow model simulating the actual reactor(hot) system. This paper presents an overview of the research performed on a cold flow model and highlights the current status of the technology.     

Experimental Simulation on Chemical-looping Combustion of Cold Model

The pressure profiles, gas velocities, solid circulation rate, solids flux, residence time distribution of gas and particles in chemical-looping combustion reactors and gas leakage were studied in a cold flow model unit. And these parameters in both air and fuel reactors were measured in the experimental stage. The experimental results show that gas fluidization velocity in the air reactor is 1.8 m/s, gas fluidization velocity in the fuel reactor 0.5 m/s, and the bed materials inventory of the two reactors between 1.2 to 3.15 kg. The first cold flow model results show that the solid circulation rates are sufficient. The appropriate operating conditions are optimized and the summary of final changes is made the on cold model. The proposed design solutions are currently being verified in a cold flow model simulating the actual reactor (hot) system. This paper presents an overview of the research performed on a cold flow model and highlights the current status of the technology.     

Dynamic responses of packed bed reactors

Amplification of process disturbances, wrong-way behavior, and extinction waves are responses to inlet disturbances of temperature, concentration or flow velocity in packed bed catalytic reactors. They can result in unexpected high temperatures that might compromise the reactor safety or performance. All of these responses are either manifestations of or are related to differential flow instability. The degree of amplification depends on the width of the reaction zone, which in turn depends on the diameter of catalyst particle. The ratio of the former and the latter determines the relative strength of convective (destabilizing) and diffusive (stabilizing) transport of heat. A modified Peclet number based on the length of the reaction zone is proposed as a criterion for the importance of disturbance amplification. Experiments and numerical analyses indicate that significant amplification under typical operating conditions of packed-bed reactors occurs for gaseous reaction systems at disturbance frequencies 0.0003-0.001 Hz and for liquid-phase reactions around 1 Hz. While simple estimates suggest that amplification that is large enough to threaten the reactor safety or to deactivate catalysts is infrequent, amplification and related responses to disturbance cannot be neglected in reactor design. Despite almost a decade of study, several questions persist about the prediction of these responses to inlet perturbations in industrial reactors.     

Assessment of the role of thermally induced gas flow inhomogeneities in fixed bed reactors

The paper presents results of a numerical solution of the equation of motion of gas in a fixed bed catalytic reactor. The equation was formulated so as to reflect the effects on the velocity field of variable local temperature in the bed through the temperature dependences of density and viscosity of the flowing gas. The temperature field used for the calculation was obtained from experiments with catalytic oxidation of ethane in a laboratory fixed bed reactor, 4 cm in diameter, packed with 0.4 cm catalyst particles.

The computed velocity field in the reactor is thus only approximate as, rigorously, the equation of motion is coupled with the heat and mass balances of the reacting species. Nevertheless, the estimated velocity field induced by the inhomogeneous temperature field indicated severe inhomogeneities of the axial velocity component which in the wall region exceeded the value on the reactor axis by about 50%. Additional convective heat fluxes induced by the temperature field amounted to as much as 20% of the radial heat dispersion flux. This contribution, however, must be expected to be substantially larger in reactors with larger reactor to particle diameter ratio and at higher gas velocities.

Rigorous forms of the model equations are suggested, accounting simultaneously for the thermally induced and variable void fraction induced flow inhomogeneities in the reactor as well as corresponding forms of heat and mass balances to be solved simultaneously.     

Flow-rate effects in flow-reversal reactors: experiments, simulations and approximations

Design and operation of a reactor with flow reversal requires accurate prediction of the domain of operating conditions, and especially the range of flow rates, where the ignited state exist. In this work we compare experimental observations of flow-rate effects during ethylene oxidation on Pt/Al₂O₃, with simulations of this reactor using a kinetic rate expression that was derived elsewhere and with approximate solutions based on instantaneous or very fast reactions. The oxidation of ethylene on supported Pt catalyst, that is employed here as a model reaction, is a complex reaction characterized by self-inhibition (expressed by Langmuir-Hinshelwood kinetics), by strong activation energy and by strong thermal effects that lead to a wide domain of steady-state multiplicity. The analysis of a flow- reversal reactor for such reactions can be approximated using the assumption of an instantaneous or fast reaction as the feed meets the catalyst layer. We suggest several approximations that capitalize on this property and apply them to the structure of our reactor, in which the catalytic bed is imbedded between two inert zones.Adequate agreement between the experimental results and simulations, using homogeneous or heterogeneous reactor model with no adjustable parameters, is demonstrated. The difference between the homogeneous and heterogeneous model predictions is usually small. The approximations show that the most important parameters for predicting the highest temperature are the inert zone properties (conductivity and length).     

A highway in state space for reactors with minimum entropy production

Thousands of numerical solutions of an optimal control problem for plug flow reactors were found to give, what we call a “highway in the reactors’ state space”. The problem was to find the heat transfer strategy which minimise the entropy production in reactors with fixed chemical conversion. The control variable was always the temperature of the heating/cooling medium along the reactor. The highway represents the most energy efficient way to travel far in state space. Such highways were studied for five reactor systems, endothermic and exothermic ones. Numerical analysis showed that the reactor highway is characterised by approximately constant thermodynamic driving forces/local entropy production for reasonable process intensities. Each solution represents a compromise between the entropy production of reactions, heat transfer and frictional flow (pressure drop). The solutions enter and leave the highway at different positions depending on how far from the highway their initial and final destinations are. Knowledge about the nature of the highway, e.g. when the reactor operates in a reaction mode or a heat transfer mode, may be important for energy efficient reactor design. The theoretical formulation of the optimisation problem is valid for plug flow as well as batch reactors. We showed that important results in literature like the Spirkl-Ries quantity, the theorems of equipartition of entropy production and equipartition of forces are contained in our general formulation. The numerical results showed that the analytical results are good approximations to the optimum also in problems where they do not apply in a strictly mathematical sense.     

Control of temperature wave trains in periodically forced networks of catalytic reactors for methanol synthesis

We study the stabilisation of travelling temperature wave trains in periodically forced networks of catalytic reactors where methanol synthesis takes place. Temperature wave train solutions reproduce the inter-stage cooling effect of multistage fixed bed reactors and are therefore particularly attractive in terms of methanol conversion. However, these solutions are generally stable within narrow operating windows and always coexist with solutions characterised by lower methanol conversion. We implement a feedback control strategy with the switching time as a manipulated variable to ensure the stability of temperature wave trains. The reaction front velocity is estimated during each cycle based on temperature measurements. This allows the switching time to be computed so that the reaction front does not cross a prescribed set-point position. Indications on how to place temperature sensors and to select the set-point and controller parameters are provided. Numerical simulations demonstrating the ability of the implemented control law to prevent the transition to undesired solutions in the presence of disturbances both in the operating regime and during start-up are reported.     

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.     

Highly efficient two-stage ring-opening of epichlorohydrin with carboxylic acid in a microreaction system

Ring-opening of epoxides with carboxylic acids has been widely used to prepare many high value intermediates in the polymer and pharmaceutical industries. Most of conventional processes proceeded in batch stirred reactors. As such they always suffer from low productivity and selectivity. Here we developed an advanced technology to perform the ring-opening reaction of epichlorohydrin with neodecanoic acid (NDA) for continuous production of 3-chloro-2-hydroxypropyl neodecanoate in a more efficient and safer way. A microreaction system where a microreactor connected to a stirred reactor was established. When the conversion of NDA rapidly reaching around 90% in a microreactor at 110°C, the reaction solution was transferred to a stirred reactor at 90°C. This two-stage operating mode can reduce the reaction time and improve the selectivity through free switching of temperature in the consecutive two reactors, thus substantially reducing the consumption of energy and materials.     

Homogeneous vs. catalytic combustion of lean methane—air mixtures in reverse-flow reactors

To carry out a comparative assessment of a recently proposed idea of using thermal flow-reversal reactors (TFRR) for mine ventilation air, the results for the catalytic flow-reversal reactor (CFRR) investigated within the European Project (2003) are briefly presented. Next, experimental investigations of thermal combustion are presented in this paper. These consisted of the kinetic study of homogeneous combustion in the pelletized bed and in the monolith. Kinetic equations for the two cases are derived and discussed. Experimental autothermal reverse-flow operation in a laboratory setup was performed. Due to the high heat capacity of the wall and insulation of the pelletized bed reactor, with considerable heat losses to the surroundings, autothermal operation was successful only in the monolithic reactor. It is finally concluded that the thermal combustion can be competitive compared with the catalytic oxidation.     

Optimizing the catalyst distribution for countercurrent methane steam reforming in plate reactors

Microscale autothermal reactors remain one of the most promising technologies for efficient hydrogen generation. The typical reactor design alternates microchannels where reforming and catalytic combustion of methane occur, so that exothermic and endothermic reactions take place in close proximity. The influence of flow arrangement on the autothermal coupling of methane steam reforming and methane catalytic combustion in catalytic plate reactors is investigated. The reactor thermal behavior and performance for cocurrent and countercurrent are simulated and compared. A partial overlapping of the catalyst zones in adjacent exothermic and endothermic channels is shown to avoid both severe temperature excursions and reactor extinction. Using an innovative, optimization‐based approach for determining the catalyst zone overlap, a solution is provided to the problem of determining the maximum reactor conversion within specified temperature bounds, designed to preserve reactor integrity and operational safety. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Characterization of an airlift reactor with helical flow promoters

The helical flow promoter (HFP), inserted in the downcomer of an airlift reactor (ALR), generates a helical flow pattern in the circulating gas–liquid (solid) mixture. Data on the fluidization capacity, gas holdup, liquid velocity and mass transfer rate for two- and three-phase systems with two different carboxymethylcellulose solutions collected in a 58 L ALR-HFP are presented and compared with those of common pneumatic reactors. Generally, an increasing solid concentration led to a slight decrease in gas holdup and liquid velocity but to a considerable decrease in mass transfer rates. Insertion of HFPs produced a significantly enhanced fluidization capacity of solid particles compared to the common systems.     

Comparison between simulated moving bed and reverse flow chromatographic reactors for equilibrium limited reactions

A staged linear model, containing five parameters, is developed to compare equivalent simulated moving bed chromatographic reactors (SMBCR) and reverse flow chromatographic reactors (RFCR). A first order reversible reaction and linear adsorption equilibrium, with preferential adsorption of the reactant is assumed. The analysis uses simple, easily computable analytical solutions that rigorously represents the transients in the cyclic steady state for both the RFCR and the SMBR. A comparison between the two types of reactors is carried out to determine the maximum conversion attainable and the range of operation where these systems have advantages over conventional steady state reactors. It is found that the maximum conversion of both reactors is similar. The range of operation in terms of amount of catalyst and range of switching times favors the RFCR, while the conversion at low separation factors favors the SMBCR.     

撞击流反应器用于甲醇合成反应

撞击流反应器用于气液固三相甲醇合成反应可以充分发挥其优良的传热、传质性能。在撞击流反应器内,催化剂浆料经喷嘴雾化后成微米尺度的液滴,气液相间接触面积远大于其他三相合成反应器。考察了温度、压力、气体流量、浆料循环量以及喷嘴个数对甲醇合成反应的影响,结果表明,当压力从3.8 MPa上升到5 MPa时,反应器的时空产率增长了近1倍,气体流量达22.4 L·min^-1后时空产率几乎不再变化,增加浆料循环量以及在同一循环量下采用多喷嘴对置都可以增加催化剂时空产率。同时,与固定床、搅拌釜和浆态鼓泡床甲醇合成进行了对比,结果表明,在低空速下撞击流反应器与其他反应器时空产率相当,而在高空速下要优于其他反应器。