Comparison of a contactor catalytic membrane reactor with a conventional reactor: example of wet air oxidation

A wet air oxidation reaction was carried out in a gas/liquid catalytic membrane reactor of the contactor type. The oxidation of formic acid was used as a model reaction. The mesoporous top-layer of a ceramic tubular membrane was used as catalyst (Pt) support, and was placed at the interface of the gas (air) and liquid (HCOOH solution) phases.

A similar reaction was carried out in a conventional batch reactor, using a steering rate high enough to avoid gas-diffusion limitations, and exactly identical conditions than for the CMR (amount of catalyst, pressure, etc.). At room temperature, the CMR showed an initial activity three to six times higher than the conventional reactor. This activity increase was attributed to an easier oxygen access to the catalytic sites. Nevertheless, the catalytic membrane gradually deactivated after a few hours of operation. Different deactivation mechanisms are presented.     

金鸡纳-铂催化2-氧代-4-苯基丁酸乙酯的不对称加氢

Enantioselective hydrogenation of ethyl 2-oxo-4-phenylbutyrate to ethyl （R）-2-hydroxy-4-phenyl- bu- tyrate on Pt/γ-Al2O3 modified by 10,11-dihydrocinchonidine was studied by investigating the influences of the amount of modifier, initial concentration of reactant, pressure and temperature on conversion and enantiometric excess in a stirred autoclave and the effects of the liquid velocity, gas velocity, modifier concentration and various catalytic beds in a trickle-bed reactor. The maximum optical yields were about 50% and 60% in the two types of reactors, respectively. It was assumed that the total hydrogenation rate included the reaction rates over the unmodified and modified active sites on platinum surface and a kinetic model, which fitted the experimental data well in autoclave, was obtained. A simplified plug-flow model was proposed to describe the bed average efficiency of trickle-bed reactor.     

A comparative simulation analysis of propane dehydrogenation in composite and microporous membrane reactors

Propane dehydrogenation has been simulated for a composite membrane reactor and a microporous membrane reactor using plug‐flow reactor models, in which both were packed with Pt/Al₂O₃ catalyst in the tube‐side. The reaction kinetics employed in the analysis were obtained from experimental data produced in an integral fixed bed reactor with the same catalyst. Comparative studies were carried out to analyse the performances of reactors containing the different membranes in terms of contact time, flow pattern and flow rate of sweep gas, and pressure. In general, the composite membrane reactors gave the better performance for all cases investigated. © 2002 Society of Chemical Industry     

Catalytic wet air oxidation of phenol in concurrent downflow and upflow packed-bed reactors over pillared clay catalyst

An experimental study is presented for comparing the behavior of a packed bed reactor in the catalytic liquid-phase oxidation of aqueous phenol with two modes of operation, downflow and upflow. The operating parameters investigated included temperature, reactor pressure, gas flowrate, liquid hourly space velocity and feed concentration. Because of the completely wetted catalyst, the upflow reactor generally performs better for high pressures and low feed concentrations when the liquid reactant limitation controls the rate. The interaction between the reactor hydrodynamics, mass transfer, and reaction kinetics is discussed. For both operation modes, complete phenol removal and significant total organic carbon (TOC) reduction can be achieved at rather mild conditions of temperature (150-170 °C) and total pressure (1.5-3.2 MPa). The results show that the phenol and TOC conversion are considerably affected by the temperature, while the air pressure only has minor influence. Total elimination of TOC is difficult since acetic acid, as the main intermediate, is resistant to catalytic wet oxidation. All tests were conducted over extrudates of Fe-Al pillared clay catalyst, which is stable and maintains its activity during the long-term experimental process. No significant catalyst deactivation due to metal ion leaching and polymer deposition was detected.     

Investigation of a rotating disc reactor for acetone stripping and asymmetric transfer hydrogenation: Modelling and experiments

Asymmetric transfer hydrogenation of acetophenone with isopropanol as hydrogen donor in the presence of a homogeneous catalyst was investigated in a rotating disc reactor. Initially, acetone stripping from binary mixtures acetone-isopropanol with nitrogen as inert gas was studied, since its removal is a key issue in improving reaction performance. The reactor consisted of a stainless steel disc mounted on a horizontal shaft, accommodated in a cylindrical shell. The disc was partially immersed in the liquid phase. Its rotation generated a thin liquid film on its upper part, which could be brought in contact with a gas phase used for stripping. A mathematical model was formulated to simulate the reactor and showed good agreement with experimental data for acetone stripping. It was observed that the efficiency of acetone removal from the liquid phase increased with the gas flowrate per initial liquid volume ratio. The effect of disk rotation was found to be small when the stripping gas was introduced in the liquid bulk. The reactor model agreed well with experimental data of the asymmetric transfer hydrogenation. An advantage of the rotating disk reactor is that the hydrodynamics of the phases can be decoupled and the gas flowrate can be increased without constraints in the liquid phase, unlike conventional agitated reactors that are limited by flooding. Simulations using high stripping gas flowrate per initial liquid volume, unachievable in stirred reactors, showed significant reduction of the residence time required to achieve >99% conversion.     

硫回收装置的内冷式催化反应器

改良Claus工艺和相应的尾气处理工艺在不断地优化,以达到更高的硫回收率。如今的技术已可满足环保部门提出的最严格的要求,但是,这类工艺的投资和操作成本在很大程度上取决于硫回收装置必须达到的回收率。利用新一代催化反应器,即所谓的“催化热板反应器”,可优化投资和操作成本。这种创新反应器的特点是以生产蒸汽的方式在催化剂床内直接移走反应热。通过这种方式,流过催化剂床的工艺气体的温度可控制在很窄的范围内。这对Claus反应有很大的益处,因为较低的工艺气体温度将使反应进行得更加完全。论述新一代催化反应器的特点和它们在硫回收方面的应用。     

Multiphase catalytic reactors: a perspective on current knowledge and future trends

ABSTRACT

Conventional and emerging processes that require the application of multiphase reactors are reviewed with an emphasis on catalytic processes. In the past, catalyst discovery and development preceded and drove the selection and development of an appropriate multiphase reactor type. This sequential approach is increasingly being replaced by a parallel approach to catalyst and reactor selection. Either approach requires quantitative models for the flow patterns, phase contacting, and transport in various multiphase reactor types. This review focuses on these physical parameters for various multiphase reactors. First, fixed-bed reactors are reviewed for gas-phase catalyzed processes with an emphasis on unsteady state operation. Fixed-bed reactors with two-phase flow are treated next. The similarities and differences are outlined between trickle beds with cocurrent gas–liquid downflow, trickle-beds with countercurrent gas–liquid flow, and packed-bubble columns where gas and liquid are contacted in cocurrent upflow. The advantages of cyclic operation are also outlined. This is followed by a discussion on conventional reactors with mobile catalysts, such as slurry bubble columns, ebullated beds, and agitated reactors. Several unconventional reactor types are reviewed also, such as monoliths for two-phase flow processing, membrane reactors, reactors with circulating solids, rotating packed beds, catalytic distillation, and moving-bed chromatographic reactors.

Numerous references are cited throughout the review, and the state-of-the-art is also summarized. Measurements and experimental characterization methods for multiphase systems as well as the role of computational fluid dynamics are not covered in a comprehensive manner due to other recent reviews in these areas. While it is evident that numerous studies have been conducted to elucidate the behavior of multiphase reactors, a key conclusion is that the current level of understanding can be improved further by the increased use of fundamentals.     

DIRECT OXIDATION OF ETHYLENE TO ACETALDEHYDE IN A HOLLOW FIBER MEMBRANE REACTOR†

A hollow fiber membrane reactor, which resembles a tube-and-shell heat exchanger, was developed for homogeneous catalytic reactions with gas reactants and products. The gas stream flows through the tube side while the reaction takes place in the catalyst solution which fills the shell side. The separation load of product from the catalyst solution can be reduced by using a hollow fiber membrane reactor instead of a conventional bubble column reactor. The reactor operates in a plug-flow pattern with a large mass transfer area per unit volume of catalyst solution

This concept was investigated experimentally using the direct oxidation of ethylene to acetaldehyde reaction in an aqueous solution of palladium (H) chloride-cupric chloride with a silicone rubber membrane reactor and a polypropylene membrane reactor. It was experimentally demonstrated that membrane reactors could achieve higher production rates per unit volume of catalyst than the conventional sparged reactor. The experimental data were in good agreement with the predictions by the mathematical model. The conditions under which the membrane reactor will be more advantageous than the conventional sparged reactors can be readily ascertained with the analytical solution of the simplified membrane reactor model.     

Mass transfer in trickle-bed reactors at low reynolds number

Mass transfer rates were determined in a 3.4 cm i.d. trickle-bed reactor in the absence of reaction by absorption measurements and in presence of reaction. Gas flow rates were varied from 0-100 l/h and liquid flow rates from 0-1.5 l/h. The catalyst particles were crushed to an average diameter of 0.054 and 0.09 cm. Mass transfer coefficients remained unaffected by change in gas flow rate but increased with liquid rate. The data from absorption measurements were evaluated with predictions based upon plug-flow and axial dispersion model. Mass transfer coefficients were found greater in case of axial dispersion model than that of plug-flow model specially at low Reynolds number (Re₁ < 1).Hydrogenation of α-methylstyrene to cumene using a Pd/Al₂O₃ catalyst was taken as a model reaction. Intrinsic kinetic studies were made in a laboratory-stirred-autoclave. Mass transfer coefficients were determined using these intrinsic kinetic data from the process kinetic measurements in trickle-bed reactor. Mass transfer coefficients under reaction conditions were found to be considerably higher than those obtained by absorption measurements.Correlations were suggested for predicting mass transfer coefficients at low Reynolds number.The gas to liquid mass transfer coefficients for lower gas and liquid flow rates were determined in a laboratory trickle-bed reactor. The effect of axial dispersion on mass transfer was considered in order to evaluate the experimental data. Three correlations were formulated to calculate the mass transfer coefficients, which included the effect of liquid loading, particle size and the properties of the reacting substances. The gas flow rate influences the gas to liquid mass transfer only in the region of low gas velocities. In the additional investigations of gas to liquid mass transfer without reaction in trickle-bed reactor, the mass transfer coefficients were determined under reaction conditions and the intrinsic kinetics was studied in a laboratory scale stirred autoclave with suspended catalyst. A few correlations are formulated for the mass transfer coefficients. A comparison with the gas-liquid mass transfer coefficient obtained by absorption measurements showed considerable deviations, which were illustrated phenomenologically.     

A porous carbon membrane reactor for the homogeneous catalytic hydration of propene

A porous carbon membrane contactor was studied to determine whether such a reactor could be used for homogeneous catalytic reactions. The hydration of propene, catalysed by an aqueous solution of phosphoric acid, was selected as a suitable model reaction. Experiments at high pressure and temperature were conducted in a laboratory-scale gas phase continuous reactor equipped with a flat carbon membrane contactor. It was shown that reasonably stable operation of the reactor could be achieved at high operating pressures by tailoring the porous structure of the carbon membrane and coupling the reactor with an on-line feedback pressure controller. The reactor operated in a mass transfer limited regime due to mass transfer resistance in the liquid filled membrane pores. Periodic oscillation of transmembrane pressure was shown to reduce mass transfer resistance and considerably improve the overall reactor performance.A dynamic model of the reactor was developed and the results of simulations compared favourably with experiments and the performance of a commercially operated conventional reactor employing a supported liquid phase (SLP) catalyst.     

多孔膜反应器中丙烷催化脱氢制丙烯的模拟研究

针对丙烷高效脱氢制丙烯的多孔膜反应器构建了无量纲数学模型并进行了模拟研究,考察了催化剂活性、透氢膜性能、操作条件对多孔膜反应器中丙烷脱氢的转化率、丙烯收率、氢气收率和纯度的影响。结果表明,移走产物氢气可以有效提升膜反应器的性能,其性能的提升程度由不同温压条件下催化剂和透氢膜性能共同决定。高活性催化剂是丙烷高效转化的基础,催化剂活性越高,膜反应器内的产氢速率越快;其次,膜的选择性和渗透通量越高,氢气的移除效率越高,可在最大程度上打破热力学平衡的限制,使反应向生成丙烯的方向移动。当多孔透氢膜的氢气渗透率在10^-7~10^-6 mol·m^-2·s^-1·Pa^-1,H₂/C₃H₈选择性达到100时,其丙烷转化率可以与Pd膜反应器内的转化率相当,但分离的氢气纯度低于Pd膜反应器。与传统的固定床反应器相比,膜反应器由于促进了化学平衡的移动,可以在较低的反应温度下获得相当高的丙烷转化率,且丙烷转化率随着反应压力的增加呈现出一个最大值。该模拟研究可为实际生产过程中膜反应器用于PDH反应的高效强化提供有益的技术指导。     

Catalytic membrane structure influence on the pressure effects in an interfacial contactor catalytic membrane reactor applied to wet air oxidation

This paper deals with the influence of catalytic membrane structure on the way the gas pressure affects the efficiency of a catalytic membrane reactor (CMR). The CMR is an interfacial contactor, used for wet air oxidation, formic acid solution and air being fed separately from both sides of the catalytic membrane. The gas overpressure can shift the gas–liquid interface into the membrane wall, closer to the catalytic zone, and therefore greatly increase the reaction rate. It has been confirmed that this was not an oxygen partial pressure effect. When compared to a conventional slurry reactor, the contactor CMR showed a reaction rate more than three times higher.     

Progress in membrane gas–liquid reactors

Gas–liquid reactions are crucially important in chemical synthesis and industries. In recent years, membrane gas–liquid reactors have attracted great attentions due to their high selectivity, productivity and efficiency, and easy process control and scale‐up. Membrane gas–liquid reactors can be divided into three categories: dispersive membrane reactor, non‐dispersive membrane reactor and pore flowthrough reactor. The progress in membrane gas–liquid reactors, including features, applications, advantages and limits, is briefly reviewed. © 2012 Society of Chemical Industry     

A sequential approach to modeling catalytic reactions in packed-bed reactors

A sequential modeling approach is proposed to simulate catalytic reactions in packed-bed reactors. The hydrogenation of alpha-methylstyrene and wet oxidation of phenol are selected as studied cases. The modeling scheme combines a reactor scale axial dispersion model with a pellet scale model. Without involving any fitting parameters, such an approach accounts for the non-linear reaction kinetics expression and different types of pellet-liquid wetting contact. To validate the developed modeling scheme and the parallel approach reported in the literature, the experimental observations for hydrogenation of alpha-methylstyrene to cumene have been employed. The predicted results by both approaches agree reasonably with the experimental data for both gas- and liquid-limited reaction. The proposed sequential approach was also used to simulate the dynamic performance of the reactor and pellets for the catalytic wet oxidation of aqueous phenol over a newly developed but rapidly deactivated catalyst (MnO₂/CeO₂). The simulation results for the catalytic wet oxidation process by both approaches were compared. The simulation describes the time evolution of the catalyst stability at different pellet points along the reactor axis. The performance of trickle beds and packed bubble columns over a range of operating conditions were also investigated, and packed bubble columns were found to achieve higher phenol conversion at the cost of more rapid catalyst deactivation.     

对苯二酚生产技术研究进展

概述了苯胺氧化法、对二异丙苯过氧化法、双酚A法和苯酚羟基化法等对苯二酚的生产方法,指出苯酚羟基化法由于产品质量好、无污染等优点,将具有良好的发展前景。分析比较了其催化剂——无机酸、无机盐、分子筛、杂多化合物和复合金属氧化物等的性能与特点,认为铁基复合氧化物价格低廉、催化效果好是今后工艺开发的重点。介绍了焦油的形成和脱除及综合利用、催化剂与其相应反应器的开发、以及连续串联搅拌釜反应器能使铁基复合氧化物催化剂保持较高的活性等研究进展。     

Optimal design of n membrane reactors in series using michaelis-menten kinetics

Exact analytical expressions are derived for the optimal design (minimum overall reaction volume) of N perfectly mixed membrane reactors in series carrying out an enzyme catalysed reaction with Michaelis-Menten kinetics. These equations enable the direct calculation of the smallest total reactor volume (holding time) needed for a given overall conversion degree, as well as the individual reactor volume and conversion degrees. Results are compared with the ones obtained with a series of N CSTRs and with a plug flow reactor. The theoretical superiority of membrane reactors versus CSTRs is demonstrated.     

Computational fluid dynamics in the development of catalytic reactors

Computational fluid dynamics is becoming an important tool in the study of chemical engineering processes and apparatuses (in particular, the share of works with the application of this method is nearly 6% of the total number of all chemical engineering works issued by Elsevier Science Publishers in 2010). The possibilities of computational fluid dynamics are demonstrated using examples from three different chemical engineering fields: developing a method for loading a tubular reactor for the steam conversion of natural gas, studying heat transfer in a reactor for the hydrogenation of vegetable oils upon the replacement of a catalyst, and investigating the transitional processes in an automobile neutralizer. The results from computational fluid dynamics are verified by comparing them with experimental data in developing a method for loading a tubular reactor, using the problem of decelerating a catalyst particle with a flow of air as an example. The obtained data are compared with classical measurement data on the aerodynamic drag of a ball and a cylinder and represent the further development of works on the flow around particles of complex shape. In this work, the results from inspecting a reactor for the hydrogenation of oils with allowance for the possible heating and uniform distribution of a flow before its entering the catalyst bed are presented. It is shown that the construction of the reactor does not ensure homogeneity of the reaction flow at the desired level and requires modification of heating elements. The efficiency of computational fluid dynamics for investigating fast processes with a chemical reaction is exemplified by studying the transitional processes in an catalytic automobile neutralizer (the effect of flow dynamics and heat transfer on the thermal regime in a honeycomb catalyst particle is very difficult to study by experimental methods). The application of computational fluid dynamics allows us to reduce considerably the time and cost of developing and optimizing the designs of efficient catalytic fixed-, fluidized-, or moving-bed reactors (particularly multiphase stirred (slurry) reactors), along with mixers, adsorbers, bubblers, and other chemical engineering apparatuses with moving media.     

Modelling of catalytic reactors containing core–shell pellets with various morphologies for series reactions

Modelling of series reactions was performed for core–shell catalysts. Mathematical solutions of concentrations inside the pellets were derived from reaction–diffusion equations considering inert-core thickness (ξ_c) for first-order kinetics. Transient behaviours of catalytic reactors containing core–shell pellets were predicted, assuming pseudo-steady state approximation. In a batch reactor, the removal rate of reactants increased with increasing Thiele modulus and decreasing ξ_c in the order of sphere > cylinder > slab. The transient concentration of the intermediate product was maximum and affected by the distribution coefficient, diffusivity ratio, particle shape, and ξ_c. In a continuously stirred tank reactor, the concentration was affected by feed rate and catalyst loading, and conversion could be enhanced by a cascade connection. In a fixed-bed reactor, the concentration increased with increasing ξ_c due to an insufficient catalyst volume. Péclet number and particle shape also affected the concentration, implying that axial dispersion and interfacial area are important design parameters.     

Optimal design of continuously stirred membrane reactors in series using Michaelis-Menten kinetics with competitive product inhibition: theoretical analysis

Analytical expressions were derived for the optimal design (based on the minimum of the volume of the total number of reactors) of N continuously stirred membrane reactors (CSMRs) performing the enzyme-catalyzed reaction described by Michaelis-Menten kinetics with competitive product inhibition. The influence of membrane selectivity for both substrate and product on the total dimensionless residence time of the reactors (overall volume) was determined. The optimal design of N CSMRs (variable volume reactors) was compared with equal volume membrane reactors required to achieve the same degree of substrate conversion. The effect of kinetic and operating parameters on the performance of membrane reactors was determined. Optimization results show that membrane reactors are superior to continuously stirred tank reactors (CSTRs) in series at a high substrate rejection coefficient and low product rejection coefficient, high substrate conversion and using a small number of reactors. Also a high dimensionless Michaelis-Menten constant, high dimensionless inhibition constant and low substrate concentration in the feed to the first reactor improved the performance of the membrane reactors vs. CSTRs in series. The reduction in total volume of the optimal membrane reactors compared to CSTRs in series was up to 86% for the conditions in this work. A comparison between the optimum and equal volume design of membrane reactors in series showed no major difference in total volume between the two design criteria at a practical range of operating conditions. A volume reduction up to 16% was observed for the conditions in this work.     

Exploration of cinnamaldehyde hydrogenation in Co–Pt/γ‐Al2O3 catalytic membrane reactors

The feasibility of Co–Pt/γ‐Al₂O₃ catalytic membrane reactors for cinnamaldehyde hydrogenation has been explored. The results of hydrogenation in four membrane reactors with different configurations indicate that the effect of the gas transport limitation is more important than the liquid diffusion limitation. The membrane with the catalytic layer situated on the gas side shows the highest activity due to the minimized gas transport limitation. This revised version was published online in July 2006 with corrections to the Cover Date.