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.     

浆态床费托合成技术研究进展

综述了近年来浆态床费托合成反应的研究进展。重点评述了浆态床F-T工艺特点,分析了铁基催化剂和钴基催化剂以及工艺条件对浆态床F-T合成反应的影响,介绍了浆态床上费托合成的一些数学模型,概述了浆态床中催化剂与液相产物分离的一些方法。     

Modeling and optimization of a large-scale slurry bubble column reactor for producing 10,000 bbl/day of Fischer-Tropsch liquid hydrocarbons

A user-friendly simulator based on a comprehensive computer model for slurry bubble column reactors (SBCRs) for Fischer-Tropsch (F-T) synthesis, taking into account the hydrodynamics, kinetics, heat transfer, and mass transfer was developed. The hydrodynamic and mass transfer data obtained in our laboratories under typical F-T conditions along with those available in the literature were correlated using Back Propagation Neural Network and empirical correlations with high confidence levels. The data used covered wide ranges of reactor geometry, gas distributor, and operating conditions. All reactor partial differential equations, equation parameters and boundary conditions were simultaneously solved numerically.The simulator was systematically used to predict the effects of reactor geometry (inside diameter and height) as well as superficial gas velocity and catalyst concentration on the performance of a large-scale SBCR provided with cooling pipes and operating under F-T conditions with cobalt-supported catalyst and H₂/CO = 2. The performance of the SBCR was expressed in terms of CO conversion, liquid hydrocarbon yield, catalyst productivity, and space time yield. The simulator was also used to optimize the reactor geometry and operating conditions in order to produce 10,000 barrels/day (bbl/day) of liquid hydrocarbons.     

高温高压浆态鼓泡床反应器中的气-液传质

The gas-liquid mass transfer of H2 and CO in a high temperature and high-pressure three-phase slurry bubble column reactor is studied. The gas-liquid volumetric mass transfer coefficients kLa are obtained by measuring the dissolution rate of H2 and CO. The influences of the main operation conditions, such as temperature, pressure,superficial gas velocity and solid concentration, are studied systematically. Two empirical correlations are proposed to predict kLa values for H2 and CO in liquid paraffln/solid particles slurry bubble column reactors.     

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.     

浆态鼓泡床反应器气液传质特性的研究进展

本文总结了有关浆态鼓泡床反应器气液传质特性的研究成果。详细地阐述了主要影响因素如系统压力、温度、气体表观气速、液体性质,固体浓度及其物性等对传质特性的影响,并对浆态鼓泡床传质模型进行了归纳介绍,最后对反应器未来的研究方向进行了预测。     

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.     

Modeling gas absorption accompanied by chemical reaction in bubble column and foam-bed slurry reactors

The published data in the literature and the reported models on foam-bed reactors have been reanalyzed. It is observed that the models have been developed assuming negligible conversion in the storage section although the storage constitutes 65–85% of the total volume of liquid/slurry charged into the reactor. For confirmation of the reported information, in the present work, experiments have been performed in foam-bed and bubble column slurry reactors for carbonation of hydrated lime slurry using carbon-dioxide gas under identical conditions. A comparison of the relative performances of the two reactors has been made. Storage section is found to be the main section governing the performance of the foam-bed slurry reactor. New mathematical models have been developed for both the reactors. The model predictions agree well with the experimental data.     

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 size fractal dimension,gas holdup,and mass transfer in a bubble column with dual internals

As the scale of residual oil treatment increases and cleaner production improves in China, slurry bubble column reactors face many challenges and opportunities for residual oil hydrogenation technology. The internals development is critical to adapt the long-term stable operation. In this paper, the volumetric mass transfer coefficient, gas holdup and bubble size in a gas-liquid up-flow column are studied with two kinds of internals. The gas holdup and volumetric mass transfer coefficient increase by 120% and 42% when the fractal dimension of bubbles increases from 0.56 to 2.56, respectively. The enhanced mass transfer processing may improve the coke suppression ability in the slurry reactor for residual oil treatment. The results can be useful for the exploration of reacting conditions, scale-up strategies, and oil adaptability. This work is valuable for the design of reactor systems and technological processes.     

Bubble size fractal dimension,gas holdup,and mass transfer in a bubble column with dual internals

As the scale of residual oil treatment increases and cleaner production improves in China, slurry bubble column reactors face many challenges and opportunities for residual oil hydrogenation technology. The internals development is critical to adapt the long-term stable operation. In this paper, the volumetric mass transfer coefficient, gas holdup and bubble size in a gas–liquid up-flow column are studied with two kinds of internals. The gas holdup and volumetric mass transfer coefficient increase by 120% and 42% when the fractal dimension of bubbles increases from 0.56 to 2.56, respectively. The enhanced mass transfer processing may improve the coke suppression ability in the slurry reactor for residual oil treatment. The results can be useful for the exploration of reacting conditions, scale-up strategies, and oil adaptability. This work is valuable for the design of reactor systems and technological processes.     

三相鼓泡淤浆床环氧乙烷合成反应器数学模拟及工程分析

建立了加压三相鼓泡淤浆床环氧乙烷合成反应器的数学模型 ,计入了催化剂颗粒在床层中沉降形成沿床高浓度分布对反应的影响以及由于惰性液相载体部分返混对传递的影响 ,进一步利用经实验验证的上述数学模型模拟不同表观气速、床高、反应器直径 (扣除传热元件截面积 )、进口乙烯摩尔分数等参数对床层中催化剂浓度随床高的分布、出口环氧乙烷摩尔分数、环氧乙烷选择率以及单位质量催化剂环氧乙烷年产量的影响 .通过模拟分析预示了工业三相床环氧乙烷反应器的合理尺寸、表观气速、环氧乙烷选择率以及时空产率 ,为工业化提供必要的设计依据     

撞击流反应器用于甲醇合成反应

撞击流反应器用于气液固三相甲醇合成反应可以充分发挥其优良的传热、传质性能。在撞击流反应器内,催化剂浆料经喷嘴雾化后成微米尺度的液滴,气液相间接触面积远大于其他三相合成反应器。考察了温度、压力、气体流量、浆料循环量以及喷嘴个数对甲醇合成反应的影响,结果表明,当压力从3.8 MPa上升到5 MPa时,反应器的时空产率增长了近1倍,气体流量达22.4 L·min^-1后时空产率几乎不再变化,增加浆料循环量以及在同一循环量下采用多喷嘴对置都可以增加催化剂时空产率。同时,与固定床、搅拌釜和浆态鼓泡床甲醇合成进行了对比,结果表明,在低空速下撞击流反应器与其他反应器时空产率相当,而在高空速下要优于其他反应器。     

MODELING OF THREE PHASE NONCATALYTIC BUBBLE COLUMN REACTORS

Mathematical models have been developed for the design of bubble column slurry reactors wherein the particles with nonuniform distribution of solid reactant take part in the reaction and follow the shrinking core model. The cases of external mass transfer control, ash layer diffusion control and chemical reaction control have been analyzed using solid distribution functions presented by Dudukovic (1984). It was found that the nonuniformity of solid reactant can strongly affect the reactor performance. Correction factors for modifying the performance charts of Joshi el al. (1981) who considered only uniform solid reactant distribution are presented for design and scale-up purposes.     

MODELING OF THREE PHASE NONCATALYTIC BUBBLE COLUMN REACTORS

Mathematical models have been developed for the design of bubble column slurry reactors wherein the particles with nonuniform distribution of solid reactant take part in the reaction and follow the shrinking core model. The cases of external mass transfer control, ash layer diffusion control and chemical reaction control have been analyzed using solid distribution functions presented by Dudukovic (1984). It was found that the nonuniformity of solid reactant can strongly affect the reactor performance. Correction factors for modifying the performance charts of Joshi el al. (1981) who considered only uniform solid reactant distribution are presented for design and scale-up purposes.     

高温高压下浆态鼓泡床气液传质系数的测定

采用气体动态吸收法,对高温高压下浆态鼓泡床中气液传质系数进行了测定,考察了系统压力、温度、表观气速及固含量等操作条件对传质系数的影响. 结果表明,在温度298~473 K、气体压力1.0~3.0 MPa、表观气速0.03~0.10 m/s、固含量0%~20%(w)的实验条件下,体积传质系数随着压力、温度及表观气速的增加而增大,随固含量的增加而减小. 同时对不同塔径的传质系数进行了比较,表明在相同的操作条件下,大塔的传质系数略高于小塔.     

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。     

MASS TRANSFER EFFECTS IN LIQUEFACTION OF COAL BY SRC-II PROCESS PART II STUDY OF BUBBLE COLUMN REACTORS

The effects of hydrogen mass transfer resistance in large-scale SRC-II bubble column reactors (BCR), over large ranges of process variables, are studied. Due to the interactive effects of mass transfer resistance and gas hold up, the hydrogen consumption or liquid yield in a BCR has a maximum with respect to the specific mixing power. Under normal SRC-II process conditions a superficial gas velocity of about 0.01 m/s represents the optimum with respect to the hydrogen consumption or liquid yield. In general, the product quality requirement rather than the rate of hydrogen consumption determines the minimum specific mixing power requirement. Increase in hydrogen partial pressure can be used to reduce the level of mixing power required to maintain the desired product quality. Interrelations between mass transfer and gas hold effects and the variations in hydrogen concentration in slurry over large ranges of process conditions are also illustrated. This work provides some bases for the selection of reactor dimensions and process conditions for an SRC-II bubble column reactor (BCR).