Transversal patterns in three‐dimensional packed bed reactors: Oscillatory kinetics

Formation of transversal patterns in a 3D cylindrical reactor is studied with a catalytic reactor model in which an exothermic first‐order reaction of Arrhenius kinetics occurs with a variable catalytic activity. Under these oscillatory kinetics, the system exhibits a planar front (1D) solution with the front position oscillating in the axial direction. Three types of patterns were simulated in the 3D system: rotating fronts, oscillating fronts with superimposed transversal (nonrotating) oscillations, and mixed rotating–oscillating fronts. These solutions coexist with the planar front solution and require special initial conditions. We map bifurcation diagrams showing domains of different modes using the reactor radius as a bifurcation parameter. The possible reduction of the 3D model to the 2D cylindrical shell model is discussed. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Transversal thermal patterns in packed‐bed reactors with simple kinetics: Bifurcation criterion and simulations

We derive a new criterion for transversal instability of planar fronts based on the bifurcation condition dV_f/dK|_K=0 = 0, where V_f and K are the front velocity and its curvature, respectively. This refines our previously obtained condition, which was formulated as α = (ΔT_adPe_T)/(ΔT_mPe_C) > 1 to α > 1 + |δ|, where ΔT_ad and ΔT_m are the adiabatic and maximal temperature rise, respectively, Pe_C and Pe_T are the axial mass and the heat Pe numbers, respectively, and δ is a small parameter. The criterion is based on approximate relations for ΔT_m and V_f, which account for the local curvature of a propagating front in a packed bed reactor with a first‐order activated kinetics. The obtained relations are verified by linear stability analysis of planar fronts. Simulations of a simplified 2D model in the form of a thin cylindrical shell are in good agreement with the critical parameters predicted by dispersion relations. Three types of patterns were detected in simulations: “frozen” multiwave patterns, spinning waves, and complex rotating–oscillating patterns. We map bifurcation diagrams showing domains of different modes using the shell radius as the bifurcation parameter. The possible translation of the 2D cylindrical shell model results to the 3D case is discussed. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

工业环管反应器结构对非均匀流动的影响

工业环管反应器的结构参数对管内液固两相流动及装置的平稳高效运行具有重要的影响。对工业聚丙烯环管反应器进行CFD模拟,发现环管反应器中存在明显的非均匀流动现象--弯管处的颗粒偏析和直管处的颗粒带。进而引入非均匀度定量表征非均匀流动,研究直管段长度和直管段数量对非均匀流动的影响。研究发现,对直管段数量为2的环管反应器,当直管段高径比超过43时,出口截面上颗粒分布的非均匀度不随高径比增加而变化;对直管段数量为4的环管反应器,直管段高径比越大,出口截面上颗粒分布越均匀;对直管段长度为39 m、高径比为65的环管反应器,直管段数量越多,出口截面上颗粒分布越均匀;与直管段数量相比,直管段长度（高径比）对出口处非均匀度的影响更显著。研究结果可为工业环管反应器的设计和优化提供指导。     

固定化氨基酰化酶载体结构及在拆分中的应用

对采用大孔弱碱性阴离子树脂DEAE-D/H为载体制备得到的高活性固定化氨基酰化酶的载体的结构进行了扫描电镜分析,具有这种结构的DEAE-D/H固定化酶活力接近1 400 U/g。采用自制的固定床反应器连续拆分乙酰DL-蛋氨酸,根据对停留时间的测量,在反应器的液体流动为全混流、液体流速低于25 mL/h时,转化率接近100%。固定化酶具有良好的连续操作稳定性和贮藏稳定性。     

Design and operational considerations of catalytic membrane reactors for ammonia synthesis

Production of ammonia using hydrogen derived from renewable electricity instead of hydrocarbon reforming would dramatically reduce the carbon footprint of this commodity chemical. Novel technologies such as catalytic membrane reactors (CMRs) may potentially be more compatible with distributed ammonia production than the conventional Haber–Bosch process. A reactor model is developed based on integrating a standard industrial iron catalyst into a CMR equipped with an inorganic membrane that is selective to NH₃ over N₂/H₂. CMR performance is studied as functions of wide ranges of membrane properties and operating conditions. Conversion and ammonia recovery are dictated principally by the ammonia permeance, and the benefits by using membranes become significant above 100 GPU = 3.4 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹. To be effective, the CMR requires a minimum selectivity for ammonia of 10 over both nitrogen and hydrogen and purity scales with the effective selectivity. Increasing the pressure of operation significantly improves all metrics, and at P = 30 bar with a quality membrane, ammonia is almost completely recovered, enabling direct recycle of unreacted hydrogen and nitrogen without need for recompression. Temperature drives conversion and scales monotonically without thermodynamic limitations in a CMR. Alternatively, the temperature may be reduced as low as 300°C while achieving conversion levels surpassing equilibrium limits at T = 400°C in a conventional reactor.     

Global-coupling induced temperature patterns on top of packed-bed reactors

Infrared thermography was used to study the formation and dynamics of hot zones on top of a shallow packed bed reactor in which CO was oxidized by spherical Pd/Al₂O₃ catalytic pellets. The impact of global coupling between the gas on top of the bed and the catalyst was studied by changing the residence time of the gas. The global coupling had a strong impact on the selection, dynamics and stability of the observed hot zone motions (breathing, anti-phase and rotation).     

喷射环流反应器性能与模化

评述国内外近１０年来有关喷射环流反应器性能及其模化研究的现状及进展，分析了研究中存在的薄弱环节，并对今后的工作提出建议和展望。     

三种反应器微观混合性能的对比

介绍了撞击流、旋转填料床和撞击流-旋转填料床三种反应器的原理;采用化学偶合法,对三种反应器的微观混合性能进行了实验测定与研究,结果表明,撞击流-旋转填料床反应器的微观混合性优于其它两种反应器。     

Are 3‐D models necessary to simulate packed bed reactors? analysis and 3‐D simulations of adiabatic and cooled reactors

Simulations and analysis of transversal patterns in a homogeneous three‐dimensional (3‐D) model of adiabatic or cooled packed bed reactors (PBRs) catalyzing a first‐order exothermic reaction were presented. In the adiabatic case the simulation verify previous criteria, claiming the emergence of such patterns when (ΔT_ad/ΔT_m)/(Pe_C/Pe_T) surpasses a critical value larger than unity, where ΔT_ad and ΔT_m are adiabatic and maximal temperature rise, respectively. The reactor radius required for such patterns should be larger than a bifurcation value, calculated here from the linear analysis. With increasing radius new patterned branches, corresponding to eigenfunction of the problem emerge, whereas other branches become unstable. The maximal temperature of the 3‐D simulations may exceed the 1‐D prediction, which may affect design procedures. Cooled reactor may exhibit patterns, usually axisymmetric ones that can be characterized by two anomalies: the peak temperature may exceed the corresponding value of an adiabatic reactor and may increase with wall heat‐transfer coefficient, and the peak temperature in a sufficiently wide reactor need not lie at the center but rather on a ring away from it. In conclusions, we argue that transversal patterns are highly unlikely to emerge in practical adiabatic PBRs with a single exothermic reaction, as in practice Pe_C/Pe_T > 1. That eliminates patterns in stationary and downstream‐moving fronts, whereas patterns may emerge in upstream‐moving fronts, as shown here. This conclusion may not hold for microkinetic models, for which stationary modes may be established over a domain of parameters. This suggests that a 1‐D model may be sufficient to analyze a single reaction in an adiabatic reactor and a 2‐D axisymmetric model is sufficient for a cooled reactor. The predictions of a 2‐D cylindrical thin reactor with those of a 3‐D reactor were compared, to show many similarities but some notable differences. © 2012 American Institute of Chemical Engineers AIChE J, 2012     

Numerical determination of fluid-to-particle mass and heat transfer coefficients in packed bed reactors

A method based on particle-resolved CFD is built and validated, to calculate the fluid-to-particle mass and heat transfer coefficients in packed beds of spheres with different tube-to-particle diameter ratios (N) and of various particle shapes with N = 5.23. This method is characterized by considering axial dispersion. The mass and heat transfer coefficients increase by 5%–57% and 9%–63% after considering axial dispersion, indicating axial dispersion should be included in the method. The mass and heat transfer coefficients are reduced as N decreases. The catalyst particles without inner holes show higher mass and heat transfer coefficients than the ones with inner holes, because of unfavorable fluid flow in inner holes. The bed of trilobes has the highest mass and heat transfer coefficients, being 85% and 95% higher than the one of spheres. This work provides a versatile method and some useful guidance for the design of packed bed reactors.     

Optimal design and control of non-adiabatic loop reactors

Loop reactors may compete with other heat recuperating technologies, like reverse-flow reactors, for catalytic abatement of low-concentration volatile organic compounds (VOC). Their main drawback, the narrow domain of operating parameters, can be resolved with a proper control system.The main goal of this research is to extend the optimal loop-reactor design conditions derived earlier to non-adiabatic units and to reactions with non-monotonic reaction kinetics and to suggest a systematic design of control. By optimal design we imply design that expands the envelope of operation in the parameters space, and specifically one that extends the operation into lower feed concentrations. A simple analytical approximation for pulse velocity in the non-adiabatic one-dimensional (1-D) model has been derived and compared with the numerical results     

Simulation and thermodynamic analysis of conventional and oxygen permeable CPO reactors

A one-dimensional steady-state heterogeneous model has been used to simulate the conventional CPO reactor. With the mechanism of O₂ permeable membrane, the model has been developed to simulate O₂ membrane reactor. The output temperature and the mole flow rates of different species in the tube side and the shell side can be calculated. They are the basis for the exergy analysis of the conventional CPO reactor with air, the conventional CPO reactor with pure O₂, and the O₂ permeable membrane CPO reactor. The simulation and exergy analysis results indicate that when the inlet conditions are the same, for a given methane conversion, the exergy efficiencies η₂ and η₁ of conventional CPO reactor with pure oxygen is lowest among the three reactors, because of the large amount of accumulative exergy required for obtaining pure oxygen.The exergy efficiencies η₁ and η₂ of membrane reactor are comparable with conventional CPO reactor with air and much higher than conventional CPO reactor with pure oxygen. As the membrane reactors can carry out simultaneous separation and reaction, in the mean time, removal of nitrogen from the product stream can be accomplished; the membrane reactor has advantages compared to other types of reactors.The operation of the membrane CPO reactor is more favourable when the inlet temperature is increased and the operation pressure is decreased from a thermodynamic point of view.     

气升式环流反应器的特性及应用

综述了气升式环流反应器的特性及其主要影响因素研究,简要介绍了这种反应器的应用情况,并提出了今后研究工作的方向。     

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.     

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.     

Modeling and simulation of non-isothermal catalytic packed bed membrane reactor for H2S decomposition

The recovery of H₂ from H₂S is an economical alternative to the Claus process in petroleum and minerals processing industries. Previous studies [React. Kinet. Catal. Lett. 62 (1997) 55; Catal. Lett. 37 (1996) 167] have demonstrated that catalytic decomposition of H₂S over bimetallic sulfide can proceed at relatively higher rates than over mono-metallic systems due to chemical synergism although conversions are still thermodynamically limited. In the present study, the performance of a catalytic membrane reactor containing a packed bed of Ru–Mo sulfide catalyst has been investigated with a view to improving H₂ yield beyond the equilibrium ceiling. A system of differential equations describing the non-isothermal reactor model has been solved to examine the effect of important hydrodynamic and transport properties on conversion. The results were obtained using a Pt-coated Nb membrane tube as the catalytic reactor enclosed in a quartz shell cylinder. Reynolds number for shell and tube side (Re^s and Re^t) as well as the modified wall Peclet number, Pe_m, dramatically affect H₂S conversions. Membrane reactor conversion rose monotonically with axial distance exceeding the equilibrium conversion by as much as eight times under some conditions.     

Spectral properties and low‐dimensional description of loop and recycle reactors

The spectral properties of the discrete and continuous convection and convection‐diffusion operators with loop or recycle boundary condition are analyzed. It is shown that the spectral properties of these nonsymmetric operators are closely related to the theory of circulant (Toeplitz) matrices and the complex Fourier series, respectively. Although there may be many complex eigenvalues, the smallest eigenvalue is real and approaches zero as the loop circulation or recycle ratio increases. This property is used to simplify nonlinear diffusion‐convection‐reaction models of loop and recycle reactors to obtain two‐mode low‐dimensional averaged models that are accurate in the limit of large recycle ratio. Explicit expressions for the two mixing coefficients that relate the two concentration modes and their dependence on various inlet conditions are also derived. Finally, the application of the low‐dimensional models to determine the impact of macromixing on the conversion, yield, and selectivity for the case of nonlinear kinetics is illustrated. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3365–3377, 2013     

新型连续乳液聚合反应器

介绍了4种主要连续乳液聚合反应器的研究新进展,包括连续搅拌釜式反应器、连续环管式反应器、脉冲填料塔式反应器及库爱特-泰勒旋流式反应器。提出了连续乳液聚合反应器的发展方向。     

Operational stability of Thermomyces lanuginosa lipase during interesterification of fat in continuous packed‐bed reactors

The operational stability of a commercial immobilized lipase from Thermomyces lanuginosa (“Lipozyme TL IM”) during the interesterification of two fat blends, in solvent‐free media, in a continuous packed‐bed reactor, was investigated. Blend A was a mixture of palm stearin (POS), palm kernel oil (PK) and sunflower oil (55 : 25 : 20, wt‐%) and blend B was formed by POS, PK and a concentrate of triacylglycerols rich in n‐3 polyunsaturated fatty acids (PUFA) (55 : 35 : 10, wt‐%). The bioreactor operated continuously at 70 °C, for 580 h (blend A) and 390 h (blend B), at a residence time of 15 min. Biocatalyst activity was evaluated in terms of the decrease of the solid fat content at 35 °C of the blends, which is a key parameter in margarine manufacture. The inactivation profile of the biocatalyst could be well described by the first‐order deactivation model: Half‐lives of 135 h and 77 h were estimated when fat blends A and B, respectively, were used. Higher levels of PUFA in blend B, which are rather prone to oxidation, may explain the lower lipase stability when this mixture was used. The free fatty acid content of the interesterified blends decreased to about 1% during the first day of operation, remaining constant thereafter.