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。     

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。     

Review on the effect of heat exchanger tubes on flow behavior and heat/mass transfer of the bubble/slurry reactors

Bubble/Slurry bubble column reactors(BCR/SBCR) are intensively used as multiphase reactors for a wide range of application in the chemical, biochemical and petrochemical industries. Most of these applications involve complicate gas–liquid/gas–liquid–solid flow behavior and exothermic process, thus it is necessary to equip the BCR/SBCR with heat exchanger tubes to remove the heat and govern the performance of the reactor. Amounts of experimental and numerical studies have been carried out to describe the phenomena taking place in BCR/SBCRs with heat exchanger tubes. Unfortunately, little effort has been put on reviewing the experiments and simulations for examining the effect of internals on the performance and hydrodynamics of BCR/SBCR. The objective of this work is to give a state-of-the-art review of the literature on the effects of heat exchanger tubes with different types and configurations on flow behavior and heat/mass transfer, then provide adequate information and scientific basis for the design and the development of heat exchanger tubes in BCR/SBCR, ultimately provide reasonable suggestions for better comprehend the performance of different heat exchanger tubes on hydrodynamics.     

Tomography measurements of gas holdup in rotating foam reactors with Newtonian, non-Newtonian and foaming liquids

Rotating solid foam reactors have already proven to show high mass transfer rates and to be a potential alternative to slurry reactors. The rotation of a foam block stirrer results in a high mass transfer and in the development of different reactor sections showing specific hydrodynamics and gas holdup distributions. In order to optimize the reactor system the hydrodynamics in a lab scale reactor are studied using γ-ray tomography, a powerful method to measure the gas holdup in three-phase reactors. The influence of liquid properties, such as viscosity and surface tension, and the rotational speed on the gas/liquid distribution in the different reactor sections is investigated. Especially the viscosity has a strong effect on the entrapment of gas bubbles in the foam block structure, while the surface tension is the dominant parameter in the outer reactor section. The influence of these parameters on the inset of foaming and the collapse of the gas/liquid dispersion is investigated. Conclusions on the mass transfer performance are drawn and recommendations for further optimizations of the reactor design and the operational conditions depending on the liquid properties are developed.     

Methanol synthesis from CO2 and H2 in multi-tubular fixed-bed reactor and multi-tubular reactor filled with monoliths

This work investigates the impact of catalyst structuring into particles or monoliths on methanol production from only CO₂ and H₂ at a large scale. Methanol synthesis in multi-tubular reactors is evaluated using packed-bed and monolithic reactors by modeling heat and mass transfer in each reactor. The obtained simulation results show that, at low gas hourly space velocity (GHSV = 10,000 h⁻¹), the performances of both reactor technologies are similar. In this case, the packed-bed reactor technology is the most appropriate technology due to its simplicity of installation and operation. At high GHSV (25,000 h⁻¹), the packed-bed reactor technology is limited by a considerable pressure drop that causes an important loss in productivity due to thermodynamic equilibrium, whereas the monolithic reactors exhibit negligible pressure drop and achieve far better performances.     

Characterization of a Modular,Scalable Millistructured Plate Reactor

Micro‐ and millistructured reactors offer significant advantages compared to conventional reactors, e.g., in terms of heat and mass transfer as well as safety. For the substitution of larger batch reactors by continuously operated millireactors a comprehensive reactor characterization is required. The heat transfer and hydrodynamics of the millistructured plate reactor PR37 are studied. The meandering of the process channel and its periodically changing cross‐sectional area increase the heat transfer significantly and lead to a dependency of the heat transfer coefficient on the Reynolds and Prandtl number that is not found in straight channels at Reynolds numbers below 2300.     

蒽醌法制过氧化氢用氢化反应器的研究进展

综述了近年来蒽醌法生产过氧化氢用悬浮氢化反应器和固定床氢化反应器的研究进展。着重介绍了管式和鼓泡床 悬浮氢化反应器的改进和泡沫固定床三相反应器用于蒽醌氢化过程可显著提高反应时空收率和选择性的优势。指出泡沫固定 床是蒽醌氢化反应器研究开发中的新思路,也是气-液-固三相反应器研究的新方向。     

多相光催化反应器的研究进展

介绍了多相光催化反应器的类型、特点和研究现状.围绕光传递限制和传质限制两方面的问题,结合反应器的新型设计和应用情况展开讨论.通过比较悬浮型和负载型光催化反应器,阐明了研究可分离悬浮型和负载型流化床光催化反应器是实现光催化技术工业化的关键所在,指出了光催化反应器设计中存在的问题和今后的研究重点.     

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.     

MULTIPHASE HYDRODYNAMICS AND SOLID-LIQUID MASS TRANSPORT IN AN EXTERNAL-LOOP AIRLIFT REACTOR—A COMPARATIVE STUDY

The solid-solid mass transfer performance of an external-loop airlift reactor was measured by dissolution of benzoic acid coated on nylon-6 particles, and the hydrodynamics of the gas-liquid-solid multiphase system in the airlift reactor were investigated. The solid-liquid system was designed to simulate the micro-carrier culture of animal cells, and some typical suspensions of immobilized enzyme particles.

The solid-liquid mass transfer coefficient remained constant below a superficial air velocity of 0.04 ms^-1 for the particles examined, but increased rapidly with further increase in gas velocity. Solids loading (0.3-3.5% w/w) did not affect the mass transfer coefficient in turbulent flow.

The mass transfer coefficient was correlated with energy dissipation rate in the airlift reactor. The mass transfer coefficient in stirred vessels, bubble columns, fluidized beds, and airlift reactors was compared.

Over an energy dissipation Reynolds number of 4-400, the solid-liquid mass transfer coefficient in the airlift device was comparable to that obtainable in fluidized beds. The performance of the airlift was distinctly superior to that of bubble columns and stirred tanks.     

微型气液固三相等温微分浆态床反应器的优化

针对气液固三相浆态床催化反应中,传递、反应、催化剂的原位表征均比较复杂的问题,为了有利于气、固相均匀分散于液相和反应温度在反应器中实现等温,通过对气液固三相反应工艺特性和反应器性能要求的分析,对微型气液固三相浆态床反应器进行了优化。根据微型浆态床对气液固三相反应分析的要求,采用图像法研究了分布器为G1、G2、G3,砂板直径为2、2.5、3 cm反应器中的流体力学性能特征,考察了气体流速、温度、反应器直径及气体分布器对气含率、气泡尺寸、气泡上升速率以及气泡分布的影响,并进行流体动力学模拟计算,确定了微型浆态床反应器的直径为2 cm,气体分布器为G3砂板的反应器结构,该反应器可以应用于反应过程中间态及液体产物生成过程的测试。     

多相流搅拌反应器研究进展

综述了近五年冷态气液固三相搅拌反应器的研究成果,阐明近期研究热点已转为热态多相流搅拌反应器的流体力学行为。概述了热态气液两相体系中通气功率、混合时间、局部及总体气含率的研究结果。指出今后研究重点应为热态的固液悬浮、气液传质过程及其机理,同时说明用计算流体力学（CFD）对气液固三相搅拌反应器的数值模拟仍属起步阶段。     

偶氮染料在气-液-固循环浆态光催化反应器中的降解脱氮

偶氮染料废水是一种集中量大的重要污染物,其中的偶氮键可被环境微生物降解生成具有毒性的芳香胺类化合物。本文从光量子效率、脱氮速率、脱氮能耗等方面,对比研究了一种新设计的气-液-固循环浆态光催化反应器和环隙式光催化反应器对偶氮染料降解脱氮的性能。结果表明,由于空气的引入,使气-液-固循环浆态光催化反应器的量子收率有一定程度下降,同时造成单位数量级脱氮能耗也有一定增大,但偶氮染料脱氮速率比在环隙式反应器中的情况有大幅度提高,表明气-液-固循环浆态反应器在偶氮染料废水光催化降解脱氮方面具有较大应用前景。     

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.     

Fast gas–liquid–solid reactions in monoliths: A case study of nitro-aromatic hydrogenation

Monolith catalyst supports are attractive as fixed bed reactors that, at the scale of the catalyst dimension, exhibit the mass transfer characteristics of slurry reactors. This paper presents a reactor design study for the single-pass conversion of dinitrotoluene in a loop configuration with an external heat exchanger. The advantage of such a loop system is the elimination of a solvent, which in turn allows more reaction heat to be recovered. The advantages of using a monolith are the low pressure drop at high recycle ratio, while maintaining good mass transfer characteristics. The modelling includes internal diffusion limitation, external mass transfer characteristics, heat effects, maldistribution and flow stability. The optimal design is found at the lowest hydrodynamic stable flow rates, where the mass transfer is fastest and the residence time in the column maximal.     

Measurement and enhancement of gas-liquid mass transfer in milliliter-scale slurry reactors

Due to the limited availability of chemical reactants in the early process development of pharmaceuticals and fine chemicals, and sometimes the high-cost of catalyst, it is increasingly popular to use milliliter-scale slurry reactors with reaction volumes of 20 ml or less to screen catalyst candidates for three-phase reactions. To ensure the success of catalyst screening, it is advantageous to run reactions under kinetically controlled conditions so that the activities of different catalysts can be compared. Because catalysts with small particle sizes are used in slurry reactors, the reactions are susceptible to gas-liquid mass transfer limitations. This work presents an efficient way of enhancing gas-liquid mass transfer in milliliter-scale reactors through the use of magnetically driven agitation with complex motion. In the reactor described here, gas-liquid mass transfer coefficients can be doubled over those obtained with the agitation technique used in commercial milliliter-scale units. In addition, the reactor can achieve the top range of mass transfer coefficients obtained in a full-scale reactor. This work also presents the first measurements of gas-liquid mass transfer coefficients in milliliter-scale reactors, which are two orders-of-magnitude smaller than systems for which mass transfer coefficients have been reported earlier. Both physical and chemical absorption techniques are used.