Intensification of cavitational activity in sonochemical reactors using different additives: Efficacy assessment using a model reaction

Sonochemical reactors offer excellent promise for the intensification of different chemical processing applications. The current work deals with intensification of cavitational activity using different additives with an objective of decreasing the processing cost as well as enhancing the applicability of sonochemical reactors for different applications. Potassium iodide oxidation has been used as a model reaction. Experiments have been carried out in a laboratory scale ultrasonic horn reactor. The effects of different additives such as air, solid particles (cupric oxide and titanium dioxide), salts (sodium chloride and sodium nitrite) and radical promoters (hydrogen peroxide, ferrous sulphate, iron metal, carbon tetrachloride and t-butanol) on the degradation of potassium iodide have been investigated. Combination of additives has also been investigated for examining the possible synergistic effects in comparison to the use of individual additions. It has been observed that based on the type of additive, optimum concentration needs to be selected and it may not be desirable always to use different additives in combination. It is desirable to select an additive which can give additional reaction mechanism in the system to aid the desired application under question.     

Flow regime maps and optimization thereby of hydrodynamic cavitation reactors

Hydrodynamic cavitation reactors are known to intensify diverse physical and chemical processes. In this article, flow regime maps have been proposed that give an overview of the operation of hydrodynamic cavitation reactor for different combinations of design and process parameters. These maps are based on simulations of cavitating flow using mathematical model that couples continuum mixture model with diffusion limited model. Specific flow regimes have been identified depending on the energetics of the collapse of cavitation bubble as sonophysical, sonochemical, and stable oscillatory (no physical or chemical effect). The radial motion of the bubble in the cavitating flow is governed by the mean and turbulent pressure gradients, which in turn, are decided by the design parameters. An analysis of variations in the pressure gradients in the cavitating flow with design parameters has been given. The flow regime maps form a useful tool for identification of most optimum set of design parameters for hydrodynamic cavitation reactor for a physical or chemical process. © 2012 American Institute of Chemical Engineers AIChE J, 58: 3858–3866, 2012     

Large‐scale sonochemical reactors for process intensification: design and experimental validation

Acoustic cavitation results in substantial enhancement in the rates of various chemical reactions but the existing knowledge about the application of reactors based on acoustic cavitation is limited to very small capacities (of the order of few millilitres). In the present work, an overview of the application of acoustic cavitation for the intensification of chemical reactions has been presented briefly, discussing the causes for the observed enhancement and highlighting some of the typical examples. A novel reactor has been developed operating at a capacity of 7 dm³ and tested with two reactions, ie liberation of iodine from aqueous potassium iodide and degradation of formic acid. The energy efficiency of the reactor has been calculated and compared with the conventional sonochemical reactors. The effect of frequency of irradiation on the percentage conversion of the reactants has been studied. Due to quite low conversions in the case of formic acid degradation, further intensification was attempted using aeration, addition of hydrogen peroxide, and the presence of solid particles (TiO₂). Compared with conventional reactors the novel reactor gives excellent results and it can be said that the future of using acoustic cavitation for process intensification lies in the development of large‐scale multiple frequency multiple transducer reactors. Copyright © 2003 Society of Chemical Industry     

Advancements in droplet reactor systems represent new opportunities in chemical reactor engineering: A perspective

Traditional chemical reactors, such as batch reactors, continuous reactors, and semi-batch reactors, have been extensively studied and frequently act as central components of modern chemical plants. Recently, various advances in reaction times, surface-to-volume ratios, required amounts of reagents, and throughput have led to new directions in the design of miniaturized chemical reactors. In this Perspective, we provide an overview of the progress from traditional to miniaturized chemical reactors by summarizing the characteristics and applications of different types of reactors. Furthermore, we compare classical chemical reactors and miniaturized droplet reactors to highlight advancements in the design of droplet reactor systems based on open functional surfaces. Finally, we provide an outlook on the research directions of miniaturized droplet reactors.     

Design of monolithic catalysts for multiphase reactions

Monolith reactors are emerging as an attractive alternative for gas-liquid-solid reactor applications. The use of monolithic catalysts in new reactors as well as in retrofit designs should be based on an optimal choice of monolith geometry and operating conditions.In this contribution, we illustrate through fundamental modeling of the transport-kinetic interactions in a monolith catalyst how such an optimal design may be evolved. We also highlight the potential benefits a monolith catalyst has as compared to a pellet-based trickle bed reactor.     

Some general considerations of reversible chemical reactions in batch and tubular reactors

The possibility of change in the algebraic sign of the net reaction rate of a single reversible reaction occurring in adiabatic or non-adibatic batch and tubular reactors is investigated. This change is shown not to occur for adiabatic reactors; it may depending on the operating conditions and the system parameters for non-adiabatic reactors. These and the related aspects of approach to system equilibrium are analyzed by an examination of the mathematical models describing these chemical reactors. Important results are summarized throughout the paper as Conclusions 1 - 10. The results have direct applications in reactor design and operation. From a practical point of view it means that yield may be reduced in some cases by allowing too long a residence time even for a single reaction. Numerical examples are given to illustrate the results.     

Estimation of heating time in tubular supercritical water reactors

Reactor efficiency and product distribution in supercritical water (SCW) reactors is greatly influenced by the design of the heating section of these reactors. However, little experimental or theoretical work is available to estimate the rate of heat transfer in such systems. In the present study, CFD modeling of the heat transfer in tubular SCW reactors has been performed. Effects of various operating parameters; i.e. reactor temperature and pressure, flow rate, reactor diameter, and the external heating mechanism, on the heating time constant, the temperature profile along the reactor, and reactor residence time are investigated. Based on numerical simulations, a semi-theoretical model is proposed to estimate the heating time constant as a function of reactor operating conditions. Results of this study provide useful insights for designing continuous supercritical water reactors as well as for the analysis of experimental data obtained from such systems.     

Novel Gas-Liquid-Solid Reactors

Multiphase reactors involving gas, liquid, and solid phases have several important applications in the chemical industry, particularly in catalytic processes. Some of the well-known examples are: hydrogenation and oxidation of organic compounds, hydro-processing coal-derived and petroleum oils, Fischer-Tropsch synthesis, and methanation reactions. Due to the presence of three phases, the problem of reactor design is often important to achieve effective mass and heat transfer as well as a mixing pattern favorable to the particular process. The reactors are mainly of two types: (a) solid catalyst is suspended either by mechanical agitation or gas-induced agitation and (b) solid catalyst is in a fixed bed with concurrent or countercurrent feed of gas and liquid re-actants. The reactor types conventionally used in industry are: (a) mechanically agitated or bubble column slurry reactors and (b) trickle-bed or packed-bed bubble reactor. The various design and modeling aspects of these reactors have been reviewed by Satterfield [1], Chaudhari and Ramachandran [2], Shah [3,4], Ramachandran and Chaudhari [5], Shah et al. [6], and Herskowitz and Smith [7]. In several industrial processes these reactor designs are modified to achieve a certain specific objective, such as better heat or mass transfer, higher catalyst efficiency, better reactor performance and selectivity, etc. Similarly, specially designed reactors are often used for laboratory kinetic studies or to understand a certain phenomenon. Thus, novel multiphase reactors are becoming important from both academic and industrial viewpoints. Some of the recently introduced novel gas-liquid-solid reactor types are: (a) loop recycle slurry reactors, (b) basket-type reactors, (c) ebullated-bed reactors, (d) internal or external recycle reactors, (e) multistage slurry or packed-bed reactors, (f) column reactors with sieve trays or multiple agitators, (g) gas-induced agitated reactors, and (h) horizontal-packed-bed reactors. are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed. These novel reactor designs are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed.     

Novel Gas-Liquid-Solid Reactors

Multiphase reactors involving gas, liquid, and solid phases have several important applications in the chemical industry, particularly in catalytic processes. Some of the well-known examples are: hydrogenation and oxidation of organic compounds, hydro-processing coal-derived and petroleum oils, Fischer-Tropsch synthesis, and methanation reactions. Due to the presence of three phases, the problem of reactor design is often important to achieve effective mass and heat transfer as well as a mixing pattern favorable to the particular process. The reactors are mainly of two types: (a) solid catalyst is suspended either by mechanical agitation or gas-induced agitation and (b) solid catalyst is in a fixed bed with concurrent or countercurrent feed of gas and liquid re-actants. The reactor types conventionally used in industry are: (a) mechanically agitated or bubble column slurry reactors and (b) trickle-bed or packed-bed bubble reactor. The various design and modeling aspects of these reactors have been reviewed by Satterfield [1], Chaudhari and Ramachandran [2], Shah [3,4], Ramachandran and Chaudhari [5], Shah et al. [6], and Herskowitz and Smith [7]. In several industrial processes these reactor designs are modified to achieve a certain specific objective, such as better heat or mass transfer, higher catalyst efficiency, better reactor performance and selectivity, etc. Similarly, specially designed reactors are often used for laboratory kinetic studies or to understand a certain phenomenon. Thus, novel multiphase reactors are becoming important from both academic and industrial viewpoints. Some of the recently introduced novel gas-liquid-solid reactor types are: (a) loop recycle slurry reactors, (b) basket-type reactors, (c) ebullated-bed reactors, (d) internal or external recycle reactors, (e) multistage slurry or packed-bed reactors, (f) column reactors with sieve trays or multiple agitators, (g) gas-induced agitated reactors, and (h) horizontal-packed-bed reactors. are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed. These novel reactor designs are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed.     

A novel approach to the design and operation scheduling of heterogeneous catalytic reactors

A number of studies have been conducted to reduce the overall level of catalyst deactivation in heterogeneous catalytic reactors, and improve the performance of reactors, such as yield, conversion or selectivity. The methodology generally includes optimization of the following: (1) operating conditions of the reaction system, such as feed temperature, normal operating temperature, pressure, and composition of feed streams; (2) reactor design parameters, such as dimension of the reactor, side stream distribution along the axis of the reactor beds, the mixing ratio of inert catalyst at each bed; and (3) catalyst design parameters, such as the pore size distribution across the pellet, active material distribution, size and shape of the catalyst, etc. Few studies have examined optimization of the overall catalyst reactor performance throughout the catalyst lifetime, considering catalyst deactivation. Furthermore, little attention has been given to the impact of various configurations of reactor networks and scheduling of the reactor operation (i.e., online and offline-regeneration) on the overall reactor performance throughout the catalyst lifetime. Therefore, we developed a range of feasible sequences of reactors and scheduling of reactors for operation and regeneration, and compared the overall reactor performance of multiple cases. Furthermore, a superstructure of reactor networks was developed and optimized to determine the optimum reactor network that shows the maximum overall reactor performance. The operating schedule of each reactor in the network was considered further. Lastly, the methodology was illustrated using a case study of the MTO (methanol to olefin) process.     

多孔陶瓷膜反应器用于非均相超细纳米催化的研究进展(英文)

Heterogeneous catalysts with ultrafine or nano particle size have currently attracted considerable attentions in the chemical and petrochemical production processes, but their large-scale applications remain challenging because of difficulties associated with their efficient separation from the reaction slurry. A porous ceramic membrane reactor has emerged as a promising method to solve the problem concerning catalysts separation in situ from the reaction mixture and make the production process continuous in heterogeneous catalysis. This article presents a review of the present progress on porous ceramic membrane reactors for heterogeneous catalysis, which covers classification of configurations of porous ceramic membrane reactor, major considerations and some important industrial applications. A special emphasis is paid to major considerations in term of application-oriented ceramic membrane design, optimization of ceramic membrane reactor performance and membrane fouling mechanism. Finally, brief concluding remarks on porous ceramic membrane reactors are given and possible future research interests are also outlined.     

Precise parameter estimation for chemical batch reactions in heterogeneous medium

A sequential experimental strategy for precise parameter estimation has been used in the case of liquid-liquid dispersions in batch-stirred tank reactors where slow chemical reactions take place. The mathematical model for a batch reaction in a stirred tank reactor is formulated as a system of non-linear differential equations standing for the mass balance of each component. Physical kinetic parameters and chemical kinetic parameters which arise from this model are estimated simultaneously. The estimation problem is posed as a weighted least squares problem and solved by using a standard Levenberg-Marquardt algorithm. In this work, we intend to show how it is possible to develop efficient experimental design strategies that lead to an accurate estimation of the parameters involved in phenomenological models and most particularly in kinetic models. Three design criteria for designing the experiments have been employed in order to increase the precision on the parameter estimates of the model. A standard non-linear sequential quadratic programming method ensures the determination of the operating conditions which define the experimental design. The well-known alkaline hydrolysis of esters in aqueous phase has been treated as a numerical application example.     

SCALE-UP OF HOLLOW FIBER REACTOR SYSTEMS

Hollow fiber reactors have been developed for many biochemical and biomedical applications. In the study of these reactor systems, we have used single fiber reactors as a prototype for the larger hollow fiber cartridges. Experiments using single fibers have been conducted to obtain conversion data for reactor scale-up. We present a model for predicting conversions in bench-scale hollow fiber cartridges using these single fiber data. The model is compared to experimental conversion data and is shown to be a valuable design tool.     

Optimization of Hydrodynamic Cavitation Using a Model Reaction

The decomposition of potassium iodide to liberate iodine, the model reaction to study cavitational effects, has been carried out under different cavitational conditions. The effect of various parameters (inlet pressure, flow geometry of orifice plates) on the iodine liberation rate has been studied. It is found that the flow geometry of the orifice plates considerably affects the rate of the iodine liberation. Recommendations are given for the arrangement of the holes in order to achieve maximum benefits from the hydrodynamic cavitation. The experimental results obtained in the present work are very much consistent with the results based on the theoretical model developed for the hydrodynamic cavitation. Due to this fact, it can be said that the model can be extended to any geometry of construction in the hydrodynamic cavitation setup and will be helpful in designing cavitational reactors.     

Microwave‐Assisted Continuous‐Flow Reactor Based on a Ridged Waveguide

Microwave‐assisted continuous‐flow reactors (MCFRs) are a valuable alternative to conventional reactors for accelerating chemical reactions. However, despite several interesting applications, only little quantitative research has been conducted on the temperature uniformity of the heating load. With water as a common inorganic solvent, a novel MCFR type based on a special ridged waveguide for heating water is studied by optimizing some parameters of micropipes in order to achieve better temperature uniformity. Compared to the original reactor, the standard deviation of the electric field decreased significantly when using the optimized reactor under the same heating conditions while the average electric field density increased. The optimized results were verified by experiments.     

Distributional uncertainty analysis and robust optimization in spatially heterogeneous multiscale process systems

Multiscale models have been developed to simulate the behavior of spatially‐heterogeneous porous catalytic flow reactors, i.e., multiscale reactors whose concentrations are spatially‐dependent. While such a model provides an adequate representation of the catalytic reactor, model‐plant mismatch can significantly affect the reactor's performance in control and optimization applications. In this work, power series expansion (PSE) is applied to efficiently propagate parametric uncertainty throughout the spatial domain of a heterogeneous multiscale catalytic reactor model. The PSE‐based uncertainty analysis is used to evaluate and compare the effects of uncertainty in kinetic parameters on the chemical species concentrations throughout the length of the reactor. These analyses reveal that uncertainty in the kinetic parameters and in the catalyst pore radius have a substantial effect on the reactor performance. The application of the uncertainty quantification methodology is illustrated through a robust optimization formulation that aims to maximize productivity in the presence of uncertainty in the parameters. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2374–2390, 2016     

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.     

Comparison of effectiveness of acoustic and hydrodynamic cavitation in combined treatment schemes for degradation of dye wastewaters

Cavitation has shown promising applications but individually it cannot prove to be an energy efficient approach for wastewater treatment. The present study reports the use of combined treatment strategies based on cavitation and different oxidizing agents (H₂O₂, Na₂S₂O₈ and NaOCl). Decolorization of two biorefractory dye pollutants viz. orange acid-II (OA-II) and brilliant green (BG) has been investigated as model systems for comparison of the effectiveness of cavitating conditions generated by acoustic and hydrodynamic modes. The optimum conditions for temperature, pH and power dissipation in the case of acoustic cavitation and inlet pressure in the case of hydrodynamic cavitation have been established initially. At the optimum operating conditions, the effect of combination of different oxidizing agents has been examined with an objective of obtaining the maximum decolorization. Basic extent of decolorization due to the use of oxidizing agents has also been quantified by performing experiments in the absence of cavitating conditions. The obtained results for cavitational yields indicate that the decolorization is most efficient for the combination of hydrodynamic cavitation and chemical oxidation as compared to chemical oxidation and acoustic cavitation based combination for both the dye effluents.     

Modeling hydrodynamic cavitation in venturi: influence of venturi configuration on inception and extent of cavitation

Hydrodynamic cavitation (HC) is useful for intensifying a wide variety of industrial applications including biofuel production, emulsion preparation, and wastewater treatment. Venturi is one of the most widely used devices for HC. Despite the wide spread use, the role and interactions among various design and operating parameters on generated cavitation is not yet adequately understood. This article presents results of computational investigation into the cavitation characteristics of different venturi designs over a range of operating conditions. Influence of the key geometric parameters such as the length of venturi throat and diffuser angle on the inception and extent of cavitation is discussed quantitatively. Formulation and solution of multiphase computational fluid dynamics (CFD) models are presented. Appropriate turbulence and cavitation models are selected and solved using a commercial CFD code. Care was taken to eliminate the influence of numerical parameters like mesh density, discretization scheme, and convergence criteria. The computational model was validated by comparing simulated results with three published data sets. The simulated results in terms of velocity and pressure gradients, vapor volume fractions and turbulence quantities, and so on, are critically analyzed and discussed. Diffuser angle was found to have a significant influence on cavitation inception and evolution. The length of the venturi throat has relatively less impact on cavitation inception and evolution compared to the diffuser angle. The models and simulated flow field were used to simulate detailed time–pressure histories for individual vapor cavities, including turbulent fluctuations. This in turn can be used to simulate cavity collapse and overall performance of HC device as a reactor. The presented results offer useful guidance to the designer of HC devices, identifying key operating and design parameters that can be manipulated to achieve the desired level of cavitational activity. The presented approach and results also offer a useful means to compare and to evaluate different designs of cavitation devices and operating parameters. © 2018 American Institute of Chemical Engineers AIChE J, 65: 421–433, 2019