A stochastic treatment of unimolecular reactions in an unsteady state continuous flow system

A stochastic approach, namely a continuous time Markov chain (Markov process), is employed to analyze and model, in a unified fashion, both the kinetics of unimolecular reactions and mixing accompanied by flow in a continuous flow reactor under an unsteady state operation; the results reduce to those under the corresponding steady state operation in the limit as t→∞. This approach can be applied to both the time homogeneous and heterogeneous processes. The transitional distributions of the number of molecules of each type inside the reactor as well as at the exit are formulated. The treatment leads to the general expressions for the transient internal and exit age distributions of molecules in the flow reactor. The life time distribution of molecules under steady state is also derived. The statistical basis of the residence time distribution theory for flow reactors is clarified. The approach is illustrated with two examples.     

下行床反应器内催化裂化过程的CFD模拟

耦合湍流气粒多相流模型和催化裂化集总动力学模型,建立了描述下行床内多相流动和催化裂化过程的反应器数学模型,并利用计算流体力学单元模拟软件CFX4.3对下行床内的催化裂化过程进行了数值模拟及分析.模型能预测出在工业应用中反应器内最受关注的诸多参数,如固含率、相间滑移速度、压降、气固相的加速区以及各组分浓度的分布情况.预测结果表明,气相反应的进行将导致反应器内的气粒流动行为发生较大变化,充分考虑反应与流动行为的耦合十分重要;而反应器床径的增大将导致转化率和各产物收率的下降.     

Experience in the application of the CHEMCAD program to the modeling of reactor processes

A computer simulation strategy that is focused on the application of modeling programs for the simulation of multistage chemical technology processes with a large number of equipment units, including reactor ones, is suggested for chemical transformation processes in reactors. The submitted strategy allows for the modeling of homogeneous and heterogeneous processes in reactors of any complexity on the basis of experimental data processing. The simulation of reactor processes has been performed with the use of the CHEMCAD program for the multistage syntheses of methanol and synthetic liquid fuel from natural gas at the following stages: synthesis gas production by steam-oxygen conversion, syntheses of hydrocarbons by the Fischer-Tropsch reaction and methanol, and the hydrocracking of heavy hydrocarbons.     

Simulation of nanoparticle synthesis in an aerosol flame reactor using a coupled flame dynamics–monodisperse population balance model

Flame aerosol synthesis is one of the commonly employed techniques for producing ultra fine particles of commodity chemicals such as titanium dioxide, silicon dioxide and carbon black. Large volumes of these materials are produced in industrial flame reactors. Particle size distribution of product powder is the most important variable and it depends strongly on flame dynamics inside the reactor, which in turn is a function of input process variables such as reactant flow rate and concentration, flow rates of air, fuel and the carrier gas and the burner geometry. A coupled flame dynamics–monodisperse population balance model for nanoparticle synthesis in an aerosol flame reactor is presented here. The flame dynamics was simulated using the commercial computational fluid dynamics software CFX and the particle population dynamics was represented using a monodisperse population balance model for continuous processes that predicts the evolution of particle number concentration, particle volume and surface area. The model was tested with published experimental data for synthesis of silica nanoparticles using different burner configurations and with different reactor operating conditions. The model predictions for radial flame temperature profiles and for the effects of process variables like precursor concentration and oxygen flow rate on particle specific surface area and mean diameter are in close agreement with published experimental data.     

A Novel Radial‐Flow,Spherical‐Bed Reactor Concept for Methanol Synthesis in the Presence of Catalyst Deactivation

A radial‐flow, spherical‐bed reactor concept for methanol synthesis in the presence of catalyst deactivation, has been proposed. This reactor configuration visualizes the concentration and temperature distribution inside a radial‐flow packed bed with a novel design for improving reactor performance with lower pressure drop. The dynamic simulation of spherical multi‐stage reactors has been studied in the presence of long‐term catalyst deactivation. Model equations were solved by the orthogonal collocation method. The performance of the spherical multi‐stage reactors was compared with a conventional single‐type tubular reactor. The results show that for this case study and with similar reactor specifications and operating conditions, the two‐stage spherical reactor is better than other alternatives such as single‐stage spherical, three‐stage spherical and conventional tubular reactors. By increasing the number of stages of a spherical reactor, one increases the quality of production and decreases the quantity of production.     

A stochastic flow model for a tubular solution polymerization reactor

Residence time distributions were evaluated experimentally for three tubular solution polymerization reactors to analyze aspects of the fluid‐dynamic behavior of these reactors. The analysis of the available experimental data indicates that the flow characteristics of these reactors may be subject to stochastic perturbations. A stochastic flow model is then proposed by assuming that a viscous polymer layer is formed in the proximities of the reactor walls and that plugs of polymer material are released at random during the operations. This model is able to represent the available experimental data fairly well for three tubular reactors with different configurations. POLYM. ENG. SCI., 47:1839–1846, 2007. © 2007 Society of Plastics Engineers     

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.     

浆态床反应器流体力学行为研究及工业应用

浆态床是一种重要的气-液-固三相反应器,具有结构简单,传热、传质性能好以及催化剂可在线补加和更换等优点,在学术研究和工业应用上备受关注。对浆态床反应器的流型、气含率、气泡行为、传质、传热等研究进行了总结,并对温度、压力、液体性质等参数对于流体力学性质的影响进行了分析。介绍了多级浆态床和构件式浆态床新型反应器,对浆态床在大化工、精细化工及环保等重要过程中的工业应用进行了总结,并对浆态床反应器的应用前景和研究趋势进行了展望。     

Bubble Column Reactors and Fischer-Tropsch Synthesis

Three-phase slurry bubble column reactors have been used extensively in a number of chemical, petrochemical, and biochemical process engineering applications. For the success of these operations and their large scale industrial exploitation, it is essential that their transport and chemical characteristics be adequately understood on a mechanistic basis so that appropriate design criteria and optimum operating conditions can be established. It is the purpose of this review to present such available knowledge in relation to chemical catalytic operations. The mass transfer characteristics, catalytic activity, and mixing patterns of different phases necessitate a detailed understanding of the hydrodynamic behavior and catalyst dispersion in slurry bubble column reactors. The current status of these aspects is presented, discussed, and assessed in this review. Chemical and biochemical reactions are exothermic in nature and hence efficient heat removal devices must be installed in the reactor to preserve its isothermal behavior and chemical catalytic activity by avoiding temperature runaway. Extensive work recently conducted from this heat transfer viewpoint is reviewed and appraised. The bubble dynamics, and slurry mixing and movement characteristics of such baffled bubble columns are significantly different from those of unbaffled bubble columns. Very limited information is available on baffled bubble column operations and this is reviewed and critically examined. An important application of the slurry bubble column is in the synthesis of fuel gases on suspended catalyst particle surface to produce chemicals. One such example is the Fischer-Tropsch synthesis of hydrogen and carbon monoxide in what is referred to as indirect coal liquefaction technology. Pilot plant efforts of this nature and their successes are briefly mentioned. Mathematical details and models developed from time to time to characterize catalytic bubble column operations are briefly described and discussed. In the context of available information and its integration presented here, the specific needs for future experimental and theoretical research work are pointed out.     

INVESTIGATION OF A NOVEL MICROREACTOR FOR ENHANCING MIXING AND CONVERSION

A novel microreactor with a network of omega-shaped microchannels has been designed, fabricated, and tested for enhanced chemical species mixing and reaction conversion. Fluidic and mixing properties of the omega channel reactor have been investigated by means of computational fluid dynamic (CFD) simulation. Also, a stochastic model describing particle transport in the axial direction was applied to characterize the residence time distribution or the cumulative probability of a particle exiting the microreactor over time. Both fluidic simulation and stochastic model approaches revealed the advantage of the omega-shaped microchannels as compared to straight or zigzag-shaped microchannels. Fischer-Tropsch reactions were carried out using sol-gel encapsulated iron and cobalt catalysts in the omega-shaped microchannels. The experimental results showed that the conversion rate for the omega-shaped microchannels was considerably higher than that for the conventional straight microchannel or for the zigzag-shaped microchannels. These results were consistent with the fluidic simulation and the stochastic modeling results.     

浆态相费托合成技术的化工研究进展

本文评述了费托合成用的BCSR在水力学、相际传递过程、动力学和反应器数学模型等方面的研究现状和问题,并推荐了对若干反应器设计有用的工程数据和关联式。     

Design and optimisation of batch and semi-batch reactors

This paper addresses a systematic methodology for batch and semi-batch reactor design and optimisation for both ideal and non-ideal mixing. It can be applied to non-isothermal and multiphase systems. The method starts from a general representation in the form of a temporal superstructure based on the similarity of between plug flow reactors and ideal batch reactors. The temporal superstructure of a batch reactor exists in both the space and time dimensions. For non-ideal mixing, this paper addresses a mixing compartment network model to represent mixing inside reactors. The mixing compartment network is then included into the temporal superstructure to model non-ideally mixed batch reactors and the mixing pattern optimised with the other variables. Besides the operation variables for batch reactors, this method can also suggest the optimum mixing pattern and promising reactor configurations for mechanical design. A profile-based approach is proposed to make a search of the profiles for temperature, pressure and feed addition. This approach starts from a set of initial profiles of temperature, pressure and feed addition. Then the performance of the batch reactor is evaluated against the objective function under different profiles. An optimal set of profiles is then found by this profile searching process. A stochastic optimisation technique based on simulated annealing is employed to obtain optimal solutions. This method is also extended to multiphase reaction systems based on the concept of shadow reactor compartments. A number of case studies are presented to illustrate the use of the proposed methodology.     

INVESTIGATION OF A NOVEL MICROREACTOR FOR ENHANCING MIXING AND CONVERSION

A novel microreactor with a network of omega-shaped microchannels has been designed, fabricated, and tested for enhanced chemical species mixing and reaction conversion. Fluidic and mixing properties of the omega channel reactor have been investigated by means of computational fluid dynamic (CFD) simulation. Also, a stochastic model describing particle transport in the axial direction was applied to characterize the residence time distribution or the cumulative probability of a particle exiting the microreactor over time. Both fluidic simulation and stochastic model approaches revealed the advantage of the omega-shaped microchannels as compared to straight or zigzag-shaped microchannels. Fischer-Tropsch reactions were carried out using sol-gel encapsulated iron and cobalt catalysts in the omega-shaped microchannels. The experimental results showed that the conversion rate for the omega-shaped microchannels was considerably higher than that for the conventional straight microchannel or for the zigzag-shaped microchannels. These results were consistent with the fluidic simulation and the stochastic modeling results.     

SOME ASPECTS OF THEORETICAL COMPARISON OF FISCHER-TROPSCH REACTORS

The reactor systems used for the Fischer-Tropsch synthesis, fixed bed, fluidized bed and slurry bed, are compared on the basis of space time yield (STY) and level of conversion obtainable under the same set of feed and operating conditions. The slurry bed and fluidized bed reactor were compared on the basis of a first order reaction model. The performance of these two reactors was found to be comparable at low values of WHSV, but at higher values of WHSV, the fluidized bed reactor gave higher conversions and STY. A power law kinetic expression was used to compare the performance of the slurry bed and fixed bed reactors. Higher conversions and STY were obtained from the fixed bed with varying WHSV. This may be due to the omission of the intra and inter phase mass transfer resistances in the modelling of the fixed bed reactor.     

Remarks on random residence time distributions

A discrete stochastic mixing model for chemical reactor; is presented here. The turbulent flow system has been modeled as a network of ideally mixed compartments with interconnecting flows that are random variables. The model is particularly useful for studying the statistics of RTD and of the output concentration in a chemical reactor. Some computations of confidence intervals of concentration using information about the stochastic nature of flows are presented.     

联合两段氧化制合成气/F-T合成的GTL工艺和催化剂

A novel process for catalytic oxidation of methane to synthesis gas (syngas),which consists of two consecutive fixed-bed reactors with air introduced into the reactors,integrated Fischer-Tropsch synthesis,was investigated.At the Same time,a catalytic combustion technology has been investigated for utilizing the F-T offgas to generate heat or powr energy.The results show that the two-stage fixed reactor process keep away from explosion of CH4/O2.The integrated process is fitted to produce diesel oil and lubricating oil in remote gas field.