CFD modeling of slurry bubble column reactors for Fisher-Tropsch synthesis

Industrial bubble column reactors for Fischer-Tropsch (FT) synthesis include complex hydrodynamic, chemical and thermal interaction of three material phases: a population of gas bubbles of different sizes, a liquid phase and solid catalyst particles suspended in the liquid. In this paper, a CFD model of FT reactors has been developed, including variable gas bubble size, effects of the catalyst present in the liquid phase and chemical reactions, with the objective of predicting quantitative reactor performance information useful for design purposes. The model is based on a Eulerian multifluid formulation and includes two phases: liquid-catalyst slurry and syngas bubbles. The bubble size distribution is predicted using a Population Balance (PB) model. Experimentally observed strong influence of the catalyst particles concentration on the bubble size distribution is taken into account by including a catalyst particle induced modification of the turbulent dissipation rate in the liquid. A simple scaling modification to the dissipation rate is proposed to model this influence in the PB model. Additional mass conservation equations are introduced for chemical species associated with the gas and liquid phases. Heterogeneous and homogeneous reaction rates representing simplified FT synthesis are taken from the literature and incorporated in the model.Hydrodynamic effects have been validated against experimental results for laboratory scale bubble columns, including the influence of catalyst particles. Good agreement was observed on bubble size distribution and gas holdup for bubble columns operating in the bubble and churn turbulence regimes. Finally, the complete model including chemical species transport was applied to an industrial scale bubble column. Resulting hydrocarbon production rates were compared to predictions made by previously published one-dimensional semi-empirical models. As confirmed by the comparisons with available data, the modeling methodology proposed in this work represents the physics of FT reactors consistently, since the influence of chemical reactions, catalyst particles, bubble coalescence and breakup on the key bubble-fluid drag force and interfacial area effects are accounted for. However, heat transfer effects have not yet been considered. Inclusion of heat transfer should be the final step in the creation of a comprehensive FT CFD simulation methodology. A significant conclusion from the modeling results is that a highly localized FT reaction rate appears next to the gas injection region when the syngas flow rate is low. As the FT reaction is exothermal, it may lead to a highly concentrated heat release in the liquid. From the design perspective, the introduction of appropriate heat removal devices may be required.     

A scale-up strategy for low-temperature methanol synthesis in a circulating slurry bubble reactor

Slurry bubble column reactors are being increasingly utilized in the large-scale conversion of coal or natural gas to liquid hydrocarbons and alcohols. A new suite of tools for developing low-temperature methanol synthesis in circulating slurry bubble reactors is explored in this study. The scale-up strategy consisting of hydrodynamics in cold flow units, catalyst performance evaluation in an autoclave, and process investigation in a pilot-scaled circulating slurry bubble reactor is presented. This methodology should be helpful for designing and scaling-up the low-temperature methanol synthesis and other related processes in slurry bubble column reactors, which will enhance and speed them towards commercial application.     

Comparison of different reactor types for low temperature Fischer-Tropsch synthesis: A simulation study

The commercially established slurry bubble column and fixed-bed reactors for low temperature Fischer-Tropsch synthesis were compared with novel micro- and monolith-reactors by mathematical modeling. Special attention was paid to the influence of catalytic activity on the reactor efficiency and the losses by mass and heat transfer resistances. The simulation results show that a micro-structured reactor exhibits the highest productivity per unit of catalyst volume followed by slurry bubble column reactor and monolith reactor. The fixed-bed reactor that was assumed to operate in the trickle-flow regime has a particularly low catalyst specific productivity due to severe mass transfer resistances. However, caused by a very low ratio of catalyst and reactor volume the micro-reactor has only a similarly low productivity per unit of reactor volume as the fixed-bed reactor. In contrast, the reactor specific productivity of slurry bubble column reactor and monolith reactor is up to one order of magnitude higher.     

Operating characteristics of special bubble column reactors

In chemical technology, bubble column reactors are often used to carry out gas-liquid conversions. Thus hydrogenation, hydroformylation, oxidation, sulphoxidation and chlorination are carried out in bubble columns, as are also fermentations and sewage water treatment processes. A considerable advantage of bubble column reactors as against other gas-liquid contact apparatus is their simplicity of construction without mechanically moving parts or parts subject to high wear and tear.The purpose of this paper is to report on the possible applications and on the behaviour in operation of specially designed and constructed bubble column reactors, for example, cascade bubble columns, bubble columns with internal or external loops and downflow bubble columns.The designs of bubble column reactor described here are used in the chemical industry for various process (Table 2).In the development of new process, there are often several different competing designs. The ultimate choice will depend on the operating characteristics discussed here.     

Multicompartment hydrodynamic model for slurry bubble columns

A core-annulus multicompartment two-dimensional two-bubble class model accounting for slurry recirculation and coupled with catalyst transport was developed as a part and parcel of the analysis of the behavior of slurry bubble column reactors at high gas throughputs corresponding to the churn turbulent flow regime. The model analyzed the contributions of bubble-induced turbulence closures, bubble coalescence and breakup phenomena, and catalyst axial distribution as the resultant of sedimentation, advection via liquid-solid slip, per-compartment axial dispersion and core-annulus lateral exchange of catalyst by bubble-induced turbulence. The model was also used to analyze the effects of catalyst loading, gas density and superficial velocity, and column diameter and vessel aspect ratio on the hydrodynamics of slurry bubble column reactors, namely, the per-compartment phase holdups and interstitial velocities, pressure gradient, bubble coalescence and break-up rates, and loci of velocity inversion for the gas and slurry profiles.     

A structured catalytic bubble column reactor: hydrodynamics and mixing studies

This paper reports the results of a comprehensive experimental study of the hydrodynamics and mixing in two bubble column reactors of 0.1 and 0.24 m in diameter with KATAPAK-S^® as packing material. Total gas hold up and axial dispersion coefficients were measured in the structured bubble columns and the values were compared with experimental results obtained in the same work with empty bubble columns. The results reveal that the gas hold up in structured bubble columns is practically the same as in empty bubble columns when compared at the same superficial gas velocity based on open area available for gas–liquid dispersion. The presence of the structured elements in the bubble column reactor reduces the liquid phase backmixing by one order of magnitude.     

Catalytic wet oxidation: micro–meso–macro methodology from catalyst synthesis to reactor design

Compared to alternative mature wet oxidation technologies that have tremendously proliferated in industry, heterogeneously mediated catalytic wet oxidation (CWO) has achieved, thus far, poor commercial penetration. The two factors that are likely responsible for this situation are (i) the lack of efficient and robust catalysts that pass with success the acid-test for commercial exploitation remote from the aseptic academic conditions, (ii) and the lack of a comprehensive reactor design framework and methodology for scale-up, reactor selection and operation inherent to the multiphase nature of the CWO reactors. This synthetic review summarizes the recent research and development work conducted at Laval University on the CWO from both the perspectives of catalyst development and testing, and multiphase reactor simulations and selection. Specific emphasis was put, on the one hand, on the development brought to some manganese oxide–ceria composites against deactivation, and on the other hand, on the formulation of multidimensional unsteady–steady non-isothermal mass-energy transport/reaction models, embedding catalyst deactivation or not, for trickle bed reactors, packed bubble column reactors, three-phase fluidized beds and slurry bubble columns. A micro–Meso–macro scale methodology was adopted from the materials synthesis up to reactor selection in which the catalyst performance (conversion, selectivity, and deactivation), the intrinsic chemical kinetics, the fluid phase thermodynamics, the pellet scale transport, and the reactor scale physical phenomena (heat, mass transport and hydrodynamics) were integrated. As a result, several aspects relevant to reactor behaviour such as solvent evaporation due to CWO reaction exothermic effects, catalyst partial wetting and catalyst deactivation, and back-mixing effects were covered, and recommendations were formulated.     

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.     

Two‐Phase Flow with Mass Transfer in Bubble Columns

Bubble columns are widely used in the chemical and biochemical industries. In these reactors a gaseous phase is dispersed into a continuous liquid phase thus the rising bubble swarm induces a circulating flow field. For the dimension of these reactors the local interfacial area and the residence time of the liquid and the gaseous phase are key parameters. In this paper an Euler‐Euler approach is used to calculate the flow field in bubble columns numerically. Therefore a transport equation for the mean bubble volume based on a population balance equation approach is coupled with the balance equations for mass and momentum. The calculations are performed for three‐dimensional, instationary flow fields in cylindrical bubble columns considering the homogeneous and the heterogeneous flow regime. For the interphase mass transfer the physical absorption of the gaseous phase into the liquid is assumed. The back mixing in the gaseous and liquid phase is calculated from the local and time dependent concentration of a tracer.     

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.     

Bubble column research in Japan

Many experimental studies on the bubble column have been reported by Japanese researchers since around 1960. They include studies of bubble behaviour, bubble size distribution, transition from the homogeneous bubbly flow regime to the heterogeneous liquid circulation regime, liquid velocity distribution, longitudinal liquid mixing, hydrodynamic modelling, the gas holdup, and the volumetric coefficient of gas-liquid mass tranfer k_La. Studies covered various modified bubble columns, such as the airlift reactor with an external or internal loop, the packed bubble column, and others. Performance of three-phase bubble columns, which deal with suspensions or emulsions, and their use as bioreactors or chemical reactors were also studied.     

Multiphase fluidization in large-scale slurry jet loop bubble columns for methanol and or dimethyl ether production

A solution methodology is proposed for the process development and process engineering of a continuously operated jet loop bubble column including integrated external or internal steam generation for, e.g., a high-efficiency large-scale medium pressure methanol and or dimethyl ether production, or other gas to liquid Fischer-Tropsch applications.A jet loop bubble column is defined in the present process development to study the combined integration of a jet-eductor draft tube system with an upper bubble column. The major advantages resulting from the integrated jet-eductor draft tube system in large-scale bubble columns are the guidance and good mixing efficiency of the multiphase flow up to the upper part of the bubble column. Reducing the bubble column operating liquid level at about 2.5-3.0 times of the column diameter above the upper end of the draft tube results in a classical jet-eductor draft tube reactor suitable for small and or medium-scale industrial applications.Methanol synthesis is usually executed catalytically in multistage packed beds at higher pressure, e.g. 26 MPa, and about 350-, resulting in a higher plant installation and operating cost. The successful scale-up of a slurry jet loop bubble column can achieve a higher catalytic selectivity at a lower pressure and temperature , and therefore reduce the overall plant investment and production cost [Toseland, 1999. Three phase flows under extreme conditions of pressure and temperature, Part II: industrial applications, Air products and Chemicals, Inc. Presented at the A.I.Ch.E. Annual Meeting, Dallas, TX; Fan, 1999. Three phase flows under extreme conditions of pressure and temperature, Part I: fundmental characteristics, Department of Chemical Engineering, The Ohio State University. Presented at the A.I.Ch.E. Annuxal Meeting, Dallas, TX]. In addition, the separate slurry production of dimethyl ether, or even coproduction with methanol, can be a more cost-effective process than the classical methanol dehydration process.The new Modified Slurry Process^© for large-scale methanol and or dimethyl ether production is presented including internal or external heat exchanger location for steam production.A process concept is developed of a Large Scale Slurry Jet Loop Bubble Column^© with external separator, auxiliary internal heat exchanger equipment and high-efficiency gas-liquid slurry jet-eductor mixing system including draft tubes and an upper bubble column. In addition, as comparison a simplified concept is discussed for a small-to-medium-scale slurry jet loop reactor including external steam production and bottom nozzle jet-eductor installation without the presence of an upper bubble column.The basic geometrical parameters of the proposed slurry jet loop bubble column and jet loop reactor are discussed. The influence of the selected geometrical parameters on the gas holdup, interfacial area and mixing is analyzed. Information about catalyst type and particle size distribution is also presented.The definition of optimal operating conditions related to the influence of the fluid dynamics and mixing on mass transfer efficiency and also information for the minimum required power input per unit volume for startup or stable reactor operation are discussed.A simplified estimation method is presented for the expected axial temperature difference across the overall length of the jet bubble column, and also the required heat transfer area of a new construction-type internal compact heat exchanger for efficient reactor cooling and operation.Scale-up is possible for large diameter jet loop bubble columns, typically up to 5 m diameter and 60 m height, including continuous three-phase slurry operation at higher power input and interfacial area, for more efficient synthesis gas absorption and reaction than in classical slurry bubble columns. Integration of suitable designed sieve trays can further guarantee an efficient operation of the lower jet loop draft tube system at higher column diameters and also achieve an efficient reactor operation in the upper bubble column section.     

Modeling of bubble column slurry reactor for reductive alkylation of p-phenylenediamine

A bubble column slurry reactor (BCSR) model has been developed for the reductive alkylation of p-phenylenediamine (PPDA) with methyl ethyl ketone (MEK) to N,N^′-di-secondary-alkyl-p-phenylenediamine (Di-amine). This particular reaction system is commercially relevant and involves a combination of parallel and consecutive reactions comprising equilibrium non-catalytic (homogeneous) and catalytic (heterogeneous) steps. The proposed model is based on the ‘mixing cell approach’. In this work the mixing cell approach has been extended by including a liquid backflow stream from all but the bottommost mixing cell. The model incorporates the contributions of gas-liquid and liquid-solid mass transfer, heat effects, and complex multistep reaction kinetics. CFD model is used to estimate the extent of backflow among mixing cells and its dependence on operating parameters. The effect of gas and liquid velocities, catalyst loading, inlet PPDA concentration, and temperature on the conversion, selectivity, global rate of hydrogenation, and temperature rise is discussed. The comparison of the current approach with the traditional mixing cell model is discussed. The BCSR model presented here will be useful to provide guidelines for designing and improving overall performance of bubble column reactors.     

Scale effects in fluidized multiphase reactors

It is shown that the two-phase model for bubbling gas—solid fluidized beds can be extended to bubble column slurry reactors operating in the heterogeneous flow regime by proper definition of the ‘dilute’ and ‘dense’ phases. The ‘dilute’ phase in a bubble column slurry reactor is to be identified with the fast-rising ‘large’ bubbles. The ‘dense’ phase consists of the slurry phase in which ‘small’ bubbles are finely dispersed. With the aid of extensive experimental data obtained in columns of 0.1, 0.19 and 0.38 m diameter it is shown that the rise velocity of the ‘dilute’ phase for gas—solid fluid beds and slurry reactors show analogous scale dependencies and can be modelled in a similar manner. It is also demonstrated that fluidized multiphase reactors can be modelled in a common manner using Computational Fluid Dynamics (CFD) within the Eulerian framework. It is concluded that CFD is an invaluable tool for scaling up of fluidized multiphase reactors.     

A PROBABILISTIC MODEL OF THE FISCHER-TROPSCH SYNTHESIS IN A FLOW REACTOR

The Fischer-Tropsch synthesis is usually carried out in flow reactors, such as fluidized-bed and bubble column slurry reactors. The nature of multiphase flow together with the well-known random nature of chemical reactions renders the performances of such flow reactors stochastic. In this work, stochastic processes, more specifically continuous time Markov chains, are employed for analyzing and modeling both the dispersive mixing and chemical kinetics in a flow reactor for the Fischer-Tropsch synthesis. The model predicts the distributions of products inside as well as outside the reactor at any time Under a steady state operation, the model gives rise to the Flory equation. Other results include expressions for predicting the mole fraction of chains with j carbon atoms inside and outside the reactor. This approach can be applied to both time homogeneous and heterogeneous processes.     

Classification and characterization of hydrodynamic and transport behaviors of three-phase reactors

According to axial profile of solid concentration, the cocurrent upward threephase reactors with liquid as continuous phase can be classified into three types (a) gassparged slurry reactors, (b) threephase bubble columns, and (c) threephase fluidized beds Comparative study shows that the gas hold up, bubble characteristics and mass transfer are significantly dependent on the type of threephase reactors Three types of reactors exhibit the different hydrodynamic and transport behaviors with particle size, solid concentration and gas holdup The structural analysis of the axial solid distribution indicates the bubble and bubble wake dynamics are the key factors to the hydrodynamic and transport behaviors of three-phase reactors.     

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

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.     

Effect of bubble deformation on stability and mixing in bubble columns

The paper deals with hydrodynamics in bubble columns. The objective of the paper is to study stability and mixing in a bubble column. The modeling of parameters such as stationary drag and added mass is addressed. In addition, the effect of bubble deformation in terms of eccentricity is highlighted. In a previous paper, the transition between homogeneous and heterogeneous regimes in bubble column without liquid flow has been shown to be driven by the deformation of the bubbles associated to drag and added mass. In the present paper, this work is generalized to bubble column with liquid flow and to the transition from bubble flow to slug flow in a vertical pipe. Numerical simulations of gas-liquid reactors are presented. The numerical simulations are validated in the case of gas plume after the Becker et al. data (Becker, S., Sokolichin, A., & Eigenberg, G. (1994) Gas-liquid flow in bubble columns and loop reactors: Part II. Comparison of detailed experiments and flow simulations. Chemical Engineering Science, 49 (24B), 5747-5762. The numerical simulations are finally applied to a bubble column. The simulations of residence time distribution coupled to transient hydrodynamics are shown to be very sensitive to the modeling of interfacial transfer of momentum from the bubbles to the liquid in terms of drag and added mass, including the effect of bubble deformation.