Analysis and optimization of cross-flow reactors with distributed reactant feed and product removal

A systematic and general model was proposed for the simulation of cross-flow reactors with product removal and reactant feed policies. Six types of cross-flow reactors were analyzed for reversible series-parallel reaction systems and their optimal feed distributions were determined by maximizing the desired product yield at the outlet of the reactor. The performances of reactors with different types of feed policies were compared at their optimal operating conditions. For irreversible reaction systems with lower order in distributed reactant for the desired reaction than those for undesired reactions, a higher yield and selectivity of the desired product could be achieved with the reactors with staged feed than with conventional co-feed reactors and a sufficiently high residence time was required by staged feed reactors to significantly improve the desired product yields and selectivities over those obtained by a co-feed reactor. However, for reversible reaction systems, the desired product yield always reached a maximum value, and then dropped down as the residence time increased. In addition to the kinetic order and residence time requirements, the rate constants of the reactions involved have to fall within certain ranges for the distributed feed reactor to obtain a higher maximum yield than one-stage co-feed reactors. Optimally distributed feed reactors always give higher maximum product yields than evenly distributed reactors with the same number of feed points. However, the improvement of yields is not as great as that between co-feed reactors and evenly distributed reactors. On the other hand, for reaction systems with higher order with respect to the distributed reactant in the desired reaction than the undesired reactions, co-feed reactors always give higher yield than staged feed reactors.     

Cyclic mass transport phenomena in a novel reactor for gas–liquid–solid contacting

This study introduces a novel reactor concept, referred to as the Siphon Reactor, for intensified phase contacting of gas–liquid reactants on heterogeneous catalysts. The reactor comprises a fixed catalyst bed in a siphoned reservoir, which is periodically filled and emptied. This serves to alternate liquid–solid and then gas–liquid mass transfer processes. As the duration of each phase can be manipulated, mass transfer can be deliberately harmonized with the reaction. Residence time experiments demonstrate that, in contrast to periodically operated trickle‐bed reactors, the static liquid hold‐up is exchanged frequently and uniformly due to the complete homogeneous liquid wetting. A mathematical model describing the siphon hydrodynamics was developed and experimentally validated. The model was extended to account for a heterogeneously catalyzed gas–liquid reaction and capture the influence of siphon operation on conversion and selectivity of a consecutive reaction. © 2016 American Institute of Chemical Engineers AIChE J, 63: 208–215, 2017     

Liquid‐Phase Aerobic Oxidation of Benzyl Alcohol Catalyzed by Pt/ZrO2

The oxidation of benzyl alcohol by molecular oxygen in the liquid phase and catalyzed by Pt/ZrO2 using n‐heptane as the solvent was studied. Pt/ZrO₂ was very active and 100 % selective for benzyl alcohol conversion to benzaldehyde. The catalyst can be separated by filtration and reused. No leaching of Pt or Zr into the solution was observed. Typical batch reactor kinetic data were obtained and fitted to the Langmuir‐Hinshelwood, Eley‐Rideal and Mars‐van Krevelen models of heterogeneously catalyzed reactions. The Langmuir‐Hinshelwood model was found to give a better fit. The rate‐determining step was proposed to involve direct interaction of an adsorbed oxidizing species with the adsorbed reactant or an intermediate product of the reactant. H₂O₂ was also proposed to be an intermediate product. n‐Heptane was found to be an appropriate solvent in this reaction system.     

Comprehensive Fischer–Tropsch reactor model with non-ideal plug flow and detailed reaction kinetics

This paper presents a detailed first principle Fischer–Tropsch reactor model including detailed heat transfer calculations and detailed reaction kinetics. The model is based on a large number of components and chemical reactions. The model is tuned to a fixed bed nearplug flow reactor but can also be applied to slurry and micro-channel reactors.The presented model is based on a cascade of ideally stirred reactors. This modelling approach is novel for Fischer–Tropsch reactors and has the advantage of being able to represent none-ideal reactors. Using a large number of components and reactions makes it possible to better represent the product slate than with conventional modelling based on distribution models.The results of the simulations emphasise that temperature control is important. Global conversion and product yields are dependent on operating conditions especially the temperature. The model is used to calculate the dimensions of an industrial reactor from a laboratory scale reactor.     

A Microfluidic Approach to the Rapid Screening of Palladium‐Catalysed Aminocarbonylation Reactions

The evaluation and selection of the most appropriate catalyst for a chemical transformation is an important process in many areas of synthetic chemistry. Conventional catalyst screening involving batch reactor systems can be both time‐consuming and expensive, resulting in a large number of individual chemical reactions. Continuous flow microfluidic reactors are increasingly viewed as a powerful alternative format for reacting and processing larger numbers of small‐scale reactions in a rapid, more controlled and safer fashion. In this study we demonstrate the use of a planar glass microfluidic reactor for performing the three‐component palladium‐catalysed aminocarbonylation reaction of iodobenzene, benzylamine and carbon monoxide to form N‐benzylbenzamide, and screen a series of palladium catalysts over a range of temperatures. N‐Benzylbenzamide product yields for this reaction were found to be highly dependent on the nature of the catalyst and reaction temperature. The majority of catalysts gave good to high yields under typical flow conditions at high temperatures (150 °C), however the palladium(II) chloride‐Xantphos complex [PdCl₂(Xantphos)] proved to be far superior as a catalyst at lower temperatures (75–120 °C). The utilised method was found to be an efficent and reliable way for screening a large number of palladium‐catalysed carbonylation reactions and may prove useful in screening other gas/liquid phase reactions.     

Miniaturization of screening devices for the combinatorial development of heterogeneous catalysts

The present work is focused on the determination of the advantages, bottlenecks and challenges of miniaturized screening systems which are essential to the success of combinatorial high-throughput methodologies in heterogeneous catalysis. Two different reactor configurations with different degrees of miniaturization were developed for the parallel and fast screening of heterogeneously catalyzed gas phase reactions: a monolithic reactor system acting as a multichannel reactor and a microreaction system based on microfabrication techniques. In both cases, a scanning mass spectrometry technique was successfully applied for quantitative product analysis within 60 s per catalyst. Due to its flexibility and high spatial resolution, this three dimensional scanning MS can be used with different and highly parallel reactor arrays. Many experiments were carried out to study the efficiency and reliability of the different screening systems, with the oxidation of methane, the oxidation of CO, and the oxidative dehydrogenation of i-butane as model reactions. Moreover, chip modules in silicon–glass technology having a number of parallel microchannels were developed, each of them containing a different catalyst. Using this approach, “catalysis-on-a-chip” proved in methane oxidation was possible. Finally, a multibatch reactor consisting of a number of parallel mini autoclaves was developed and tested in the liquid-phase hydrogenation of citral in order to overcome the lack of parallel and fast screening procedures for heterogeneously catalyzed gas–liquid reactions widely spread in the chemical industry.     

New advances in agitation technology for exothermic reactions in very large reactors

Organic reactions, such as polymerisations, often require precisely controlled homogeneous reaction conditions in order to achieve high product quality, minimise waste or rework, and therefore reduce environmental impact. Many such processes were originally manufactured in moderately sized reactors with a height-diameter ratio of around 1. Operators have subsequently driven up their production rates by intensifying the reaction and by increasing the reactor size (and often increased the reactor's height-diameter geometry) in response to the economic requirement for world-scale manufacturing plants.However, as reaction intensities and reactor sizes increase, product quality can be affected due to poorer homogeneity, since reaction rates are faster but bulk mixing is slower. This can lead to a “Limit to Scale” beyond which product quality is unacceptable. Better bulk mixing within very large reactors would increase the Limits to Scale.Laboratory trials were undertaken to compare the homogeneity achieved by different impeller configurations in a model of a typical large reactor. This leads to a new agitator design concept, which achieves rapid mixing in large vessels with high height-diameter ratios using a series of impellers that produce a narrowly confined axial flow, effectively a virtual draft tube, in the centre of the reactor. Fluid returns to the top of the reactor near the walls creating a loop flow pattern within the reactor, effectively an “internal loop reactor”. CFD simulations of the reactor were undertaken to better understand the hydrodynamics, and were validated against experimental results.     

Application of electrochemical oxidation for treatment of industrial wastewater — the influence of reactor hydrodynamics on direct and mediated processes

The influence of kinetic and hydrodynamic factors in electrochemical reactors used in the removal of pollutants from industrial wastewater is shown, distinguishing between the two main types of reactions, namely direct and mediated electro‐oxidation. The effect of stirring during treatment of four different types of wastewater is reported. Whilst for direct electro‐oxidation of pollutants, the influence of agitation on the performance of the reactor can be easily predicted from a mass transfer correlation, its effect during electro‐oxidation mediated in the homogeneous phase by a redox couple is not straightforward. The Hatta number can be a useful criterion to apply to electrochemical reactors performing mediated oxidation of compounds (in analogy to gas–liquid reactions), so as to define whether the reaction occurs in the bulk of the reactor or near the electrode, and thus can be affected differently by stirring. The hydrodynamic conditions in the reactor for treatment of industrial wastewater can affect the differential selectivity of the removal of pollutants and this can be used for optimising the performance of the reactor with respect to a target pollutant. Copyright © 2006 Society of Chemical Industry     

Organische Synthese mit mikrostrukturierten Reaktoren

Organic Synthesis with Microstructured Reactors This article describes the chances microstructured reactors offer for chemical plant engineering. This suitability for chemical production is commonly regarded to be the key to the market penetration. Seen in the long term, there is potential that new plants can be equipped with microstructured reactors. Only economic balances, however, which draw up profitability, will open the door to the usage of chemical micro process engineering for plant construction. Main arguments for using microstructured reactors are thus enhanced conversion and selectivity, increased space‐time yields, waste reduction and more safety via small reactor volumes. Credit‐card sized reaction systems allow one to perform the screening of multi‐phase reactions. More prominent, similar screening is carried out for single‐step reactions. Moreover, safe processing with microstructured reactors in the explosive regime enlarges the traditional range of processing. The reaction guidance by microstructured reactors can further influence subsequent processing steps such as product purification and, in this way, can lower the energy costs of processes.     

PERIODIC OPERATION OF ISOTHERMAL PLUG-FLOW REACTORS FOR AUTOCATALYTIC REACTIONS

The performance of isothermal plug-flow tubular reactors under periodic inlet concentration is theoretically analyzed for improvement in yield for liquid phase, homogeneous, autocatalytic reactions of both quadratic and cubic forms. The system of two hyperbolic partial differential equations describing the reactor is solved by the topological method suggested by Bailey (1977). The negligible yield of product obtained at steady-state operation is enhanced to 100 percent yield under periodic operation. The performance of the periodically forced reactor with autocatalytic reactions is compared with that of ordinary simple reactions. The improvement in the yield is much more (at least five times) than that of ordinary simple reactions. The effect of decay of autocatalyst to stable product and the effect of reversibility of reactions on the performance of the periodically forced reactor are evaluated. For irreversible reaction with decay, the yield shows a resonance with inlet pulse width. This is due to complete conversion of the reactant and further only the decay of the autocatalyst.     

Heterogeneously Catalyzed Epimerization of Menthol Stereoisomers – An Instructive Example to Account for Diffusion Limitations in Complex Reaction Networks

The heterogeneously catalyzed epimerization of menthol stereoisomers is an important step in the synthesis of (–)‐menthol by the Haarmann and Reimer process. For an accurate design of a technical reactor, the intrinsic kinetics as well as pore diffusion limitations have to be taken into account. The epimerization consists of a complex reaction network and so a simple approach using effectiveness factors based on Thiele moduli is not possible. In this work, a method is presented to simultaneously calculate the change in concentrations in the bulk phase as well as within the porous particles with time (fixed bed reactor) or local position (batch reactor). A commercially available numerical software was used to solve the differential equations.     

Scale-up of an electrochemical reactor for treatment of industrial wastewater with an electrochemically generated redox mediator

This paper presents the results of a study on the scale-up, from a batch to a continuous flow unit, of an electrochemical reactor applied for the treatment of textile wastewater. Decolourisation of the wastewater bearing a reactive dye Red Procion H-EXGL proceeded via indirect electro-oxidation, mediated by “active chlorine”. The kinetics of decolourisation in a single-cell reactor under different operating conditions were second order, with the highest apparent rate constant (k = 0.523 l mol⁻¹ s⁻¹) achieved at 40 °C. A low Hatta number (Ha = 0.03) indicated that the reaction occurred totally in the bulk solution, hence homogeneous reaction kinetics were used successively to scale-up a continuous flow electrochemical unit: a once-through filter-press reactor. Its hydrodynamic characteristics were defined by the residence time distribution (E(t)) function using a pulse injection method. The decolourisation efficiency experimentally determined in a continuous flow reactor was further compared with that predicted on the basis of the knowledge of the E(t) of the reactor and the homogeneous phase kinetic expression, obtained from the batch study and corrected for the geometric parameters of the reactors. A complete segregation of the fluid inside the flow reactor was assumed. For different applied flow rates, the experimentally defined conversion of the dye was close to the calculated value.     

Membrane reactors in chemical production processes and the application to the pervaporation-assisted esterification

When appropriate membrane was used for the assistance of chemical and biochemical equilibrium reactions, it is possible to enhance the yield and the purity of the reaction product by selectively adding educts or selectively removing products and to a lower the energy input and the reaction time compared to conventional process. In this paper a review on membrane reactors with special emphasis on membrane-assistance of esterification reactions and a continuous tube membrane reactor for the pervaporation-assistance of the esterification are presented. The heterogeneously catalyzed esterification of ethanol and acetic acid to ethyl acetate and water was investigated as a typical chemical equilibrium reaction. The selective and simultaneous water separation from the reaction mixture of the esterification with polyvinyl alcohol pervaporation membranes is considered to be an interesting process alternative to the conventional distillation process. Compared to the distillation process, for the pervaporation-assisted process a decrease of the energy input of over 75% and of the investment and operating coasts of over 50% each was calculated.     

Assessment of micro-structured fixed-bed reactors for highly exothermic gas-phase reactions

The application of micro-structured fixed-bed reactors for highly exothermic partial oxidation reactions and their comparison to established multi-tubular fixed-bed reactors was investigated by numerical simulation. As examples, the partial oxidations of butane to maleic anhydride and of o-xylene to phthalic anhydride were chosen. The simulation results revealed that the reactor productivity, i.e. the amount of product per unit of reactor volume, achievable in micro-structured fixed-bed reactors is between 2.5 and 7 times higher than in conventional multi-tubular fixed-bed reactors without the danger of excessive pressure drop. For the partial oxidation of butane to maleic anhydride this can be explained by the increased reactor efficiency caused by lower efficiency losses through heat and mass transfer limitations. In addition, maleic anhydride selectivities and yields are higher in micro-structured fixed-bed reactors. In the case of o-xylene oxidation to phthalic anhydride the main advantage is that egg-shell catalysts in the conventional fixed-bed reactor can be replaced by bulk catalysts in the micro-structured fixed-bed reactor. For this reaction, product selectivities are very similar for all reactor configurations. Thus the catalyst inventory and reactor productivity are strongly increased. This study underlines, that micro-structured fixed-bed reactors exhibit the potential to intensify large scale industrial processes significantly.     

Processability‐enhanced bimodal high‐density polyethylene with comb‐branched high‐density polyethylene

Two solution reactors in series were utilized to synthesize comb‐branched high‐density polyethylene (HDPE), cbHDPE, where the first reactor prepares vinyl‐terminated HDPE macromers catalyzed by an organometallic catalyst favoring beta hydride transfer and the second reactor copolymerizes HDPE macromers with ethylene using a different organometallic catalyst capable of incorporating macromers. A bimodal HDPE, biHDPE with bimodalities in molecular weight, and hexene content of the desired composition distribution was also prepared in a gas phase reactor using silica supported dual organometallic catalysts. By blending 3% solution‐made cbHDPE into the gas‐phase biHDPE, the resulting trimodal HDPE preserves the excellent stiffness and toughness of the bimodal HDPE while having exceptional melt strength and processability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45755.     

Heterogeneous Enantioselective Synthesis of a Dihydropyran Using Cu-Exchanged Microporous and Mesoporous Materials Modified by Bis(oxazoline)

The formation of dihydropyran from the Diels–Alder reaction between E-ethyl-2-oxo-3-pentenonate and vinyl ethyl ether is investigated using copper (II) bis(oxazoline) as catalyst. The homogeneously and heterogeneously catalyzed reactions are contrasted. Immobilization using mesoporous materials (Cu-MCM-41, Cu-AlSBA-15, Cu-MSU-2) and zeolite Y is found to produce an effective heterogeneous catalyst. Although the level of enantioselection is not high in this initial study, the CuH-zeolite Y/bis(oxazoline) catalyst gives the highest ee (41% ee), which is significantly higher than that observed for the Cu(OTf)₂ homogeneous catalyst (20% ee) under comparable conditions. In addition, with the heterogeneously catalyzed reaction, the enantioselection changes from the initial 2R,4S product to the 2S,4R diastereoisomer. This behavior is not observed with the homogeneously catalyzed reaction, which always yields the 2R,4S product. These results are discussed in terms of the confinement of the catalyst complex within the pores of the heterogeneous catalyst.     

Homogene oder heterogene Katalyse? Simultane Verwendung von basischen und sauren Zeolithen in der flüssigen Phase bei der Umesterung und Veresterung

Base catalyzed transesterification of triglycerides with methanol was studied in liquid phase on a K-LSX zeolite. The presence of free fatty acid results in its deactivation. Their esterification was catalyzed by an acidic H-Y zeolite. Surprisingly, in case of mixing of both catalysts, no catalytic activity was observed. Consequently, both reactions should proceed homogeneously because the formation of the intermediate methylat ion is suppressed. This could be explained in term of a fast ion exchange between the K⁺ ions of K-LSX and the H⁺ ions of Y-zeolite. On the other hand, the observed transport limitation indicates on a heterogeneously catalyzed reaction. Therefore, in case of even non-aqueous liquid phase reactions, a contribution of a homogeneous reaction path must be considered.     

Operating Characteristics and Performance of a Monolithic Downflow Bubble Column Reactor in Selective Hydrogenation of Butyne‐1,4‐diol

The effects of flow condition, bubble dispersion level, and liquid flow rate on the behavior of a novel monolithic downflow bubble column (M‐DBC) were investigated using a reaction model, the palladium‐catalyzed hydrogenation of butyne‐1,4‐diol. The stable and closely packed homogeneous bubble dispersion present in the bulk region of the M‐DBC allowed effective introduction of the gas‐liquid phase for formation of Taylor flow inside the monolith channels. The condition defined as the minimum level dispersion was required in order to obtain high selectivity towards the intermediate product, cis‐2‐butene‐1,4‐diol. Enhanced reaction rates were obtained at increasing the dispersion level and lowering the liquid flow rate. Comparison with the DBC employing 5 % Pd/C powder catalyst and 1 % Pd‐on‐Raschig‐ring revealed a better performance of the M‐DBC (1 % Pd loading) with the advantage of smaller reaction volume and intensified reaction rate. As an alternative to conventional three‐phase reactors, the M‐DBC was so simple due to its inherent characteristic operation and no specially designed device is required.     

Integrated thermodynamic and kinetic model of homogeneous catalytic N-oxidation processes

The homogeneous phosphotungstic acid catalyzed N-oxidation of alkylpyridines by hydrogen peroxide has important applications in pharmaceutical and fine chemical industries. Current industry practice is to employ a semibatch reactor with gradual dosing of hydrogen peroxide into an alkylpyridine/catalyst solution under isothermal conditions. However, due to lack of understanding of reaction mechanism and thermodynamic behavior, this system is subject to significant risk of flammability, fires and explosions due to hydrogen peroxide decomposition. In this study, we conducted semibatch N-oxidation process in an isothermal reaction calorimeter (RC1) over a wide range of temperature, catalyst amount and oxidizer dosing rates. Reactor pressure, reaction heat generation rate and in situ FTIR spectra of liquid phase species were recorded in real-time during experiments, and final product was quantified using HPLC and GC–MS analytical tools. We developed an integrated thermodynamic and kinetics model of homogeneous N-oxidation reaction based on experimental results and past literature findings. More specifically, Wilson excess Gibbs model was employed to estimate activity coefficients of highly nonideal liquid mixture. We found ideal gas law was satisfactory in calculating incondensable oxygen pressure. First principle reaction mechanism and kinetics parameters of (a) catalytic N-oxidation reaction; (b) catalytic hydrogen peroxide decomposition reaction; (c) noncatalytic N-oxidation reaction; (d) noncatalytic hydrogen peroxide decomposition reaction was derived based on experimental findings of this study and past literature. The proposed integrated thermodynamic model and kinetics model successfully predicted highly nonlinear reactor pressure, species concentration and reaction enthalpy generation rate profile of homogenous catalytic N-oxidation and H₂O₂ decomposition reaction. The optimal reactions conditions with maximum N-oxide product yield and minimum reactor pressure and catalyst usage was theoretically identified and further verified by experiments. The obtained model can be used for inherently safer reactor design and applied to other homogeneous tungstic acid catalytic hydrogen peroxide oxidation processes.     

From Mechanistic and Kinetic Understanding of Heterogeneously Catalyzed Reactions to Tuning Catalysts Performance

A number of strategies for tuning performance of heterogeneously catalyzed reactions are being explored. They comprise: (1) optimizing reactor operation based on the knowledge of reaction mechanism and kinetics, (2) application of well-defined nano-sized metal nanoparticles for preparation of supported catalysts, and (3) combining complementary reactions into one process via a proper reactor design. The present mini review demonstrates their potential for conversion of C₃–C₄ alkanes to the corresponding alkenes, oxidative functionalization of methane, Fischer–Tropsch reaction and HCl oxidation to Cl₂ (Deacon process).