Heterogen katalysierte Reaktivdestillation: Design und Scale‐up am Beispiel von Methylacetat

Reactive Distillation by Heterogeneous Catalysis: Design and Scale‐up Using Methyl Acetate as an Example Methyl acetate synthesis and hydrolysis is used to exemplify the design and scale‐up of heterogeneously catalyzed reactive distillations using Katapak‐S/‐SP. Different equilibrium and non‐equilibrium stage models and a rate‐based model are compared in order to clarify the level of complexity needed to predict the process behavior. An equilibrium stage model accounting for reaction kinetics is the best choice for methyl acetate reactive distillation. Reliable information on fluid dynamics of the used reactive distillation packing is needed for the fluid dynamic design in order to assure a wide operation range of the reactive distillation column. To verify the process model, experiments on the synthesis of methyl acetate have been performed in columns with different diameters. As a case study, the model‐based scale‐up is described for an industrial methyl acetate hydrolysis process.     

Exploring the Steady Operation of a Continuous Pilot Plant for the Di‐Nitration Reaction

Continuous‐flow synthesis of the selective herbicide pendimethalin was demonstrated in both a laboratory‐scale and a pilot‐scale reactor using only concentrated nitric acid as nitrating agent. The di‐nitration reaction follows second‐order kinetics where the reaction is first order with respect to both reactant and nitric acid. The pinched‐tube reactor was chosen for pilot‐scale reactor fabrication due to its excellent mixing and mass transfer characteristics compared to a straight‐tube reactor. The estimated mass transfer coefficient showed similar nature in the laboratory‐scale and the pilot‐scale pinched‐tube reactor, ensuring similar performance at the pilot scale. Di‐nitration in continuous flow, inline quenching, extraction, and phase separation are some of the salient features of the developed pilot plant. The importance of the start‐up time for achieving steady state in the flow system at the large scale is highlighted.     

分批操作条件下超滤过程膜面积的确定与放大

推导了在分批操作条件下确定膜面积的计算公式，利用小波实验结果，即可确定放大到中试以及生产规模所需膜面积，以红霉纱发酵滤液为例，利用外压式中空纤维膜和内压式中空纤维膜进行超滤，在１０～２０Ｌ规模取得实验数据，拟合出通量预测模型参数，然后计算出日处理８０吨发酵滤液时在不同情况下所需的膜面积，本文还讨论了影响膜面积的因素，并在１００Ｌ规模实验验证了计算是正确的。     

Scaling Up of the Geometrically Similar Unbaffled Circular Tank Surface Aerators

The present investigation is concerned with the development of scale‐up equations for the oxygen transfer coefficient, k, and the power number, P_O, for unbaffled circular tank surface aerators under geometrically similar conditions, with the purpose of designing energy efficient aerators. It has been found for the present aerators that k and P_O are uniquely related to a parameter, X, governing the theoretical power per unit volume and which is defined as Fr^4/3Re^1/3, where Fr and Re are the impellers' Froude and Reynolds numbers, respectively. Empirical correlations between k and X, as well as P_O with X are developed for the range of experiments conducted. Based on such experimental results, procedures to design energy efficient aeration systems have been demonstrated and it was found that smaller sized aerators are more energy efficient and economical when compared to bigger sized tanks, while aerating the same volume of water, by maintaining the same input power to the tanks irrespective of their size. It has been also demonstrated that substantial amounts of energy can be saved if the aeration tanks run at higher input power.     

Strategy for a Scale‐up Correlation in a Dissolved Air Flotation Chamber

Beginning with a laboratory‐scale physical model, a scale‐up correlation for a pilot unit project was determined based on the analysis of dynamic similarity correlations involving the predominant phenomena of a dissolved air flotation (DAF) chamber. The implantation costs of pilot units require special strategies due to the lack of correlations of this type, as novel flotation methods have been considered strictly from an economic standpoint. With the aid of computational fluid dynamics and videos of microbubble and floc flow, inertia and gravity were identified as the predominant phenomena in a DAF chamber. The strategy described herein is simple and reduces the likelihood of future risks in scale‐up investments.     

Design of a Flexible Pilot Plant Reactor for the Steam Cracking Process

A design technique for a pilot plant reactor of single diameter is presented to scale up or down steam cracking coils of different configurations like mono‐tubular, classical, and reversed splits. Using dimensional analysis, two criteria are selected in establishing partial similarity between different scales, the mean residence time, and the axial pressure profile in the reactor, in addition to preserving the flow pattern within the turbulent region. The sensitivity and accuracy of the proposed method is compared to another conceivable alternative that focuses on the lateral gradients. The pilot reactor coil is adapted for any large‐scale reactor by the adjustment of feed flow rate and the effective length exposed to the firebox heat flux. Simulation results for naphtha cracking in a commercial split coil and also the equivalent pilot plant reactors are used for verification and validation of this method.     

Removal of Cr(VI) from Aqueous Solutions by a Bacterial Biofilm Supported on Zeolite: Optimisation of the Operational Conditions and Scale‐Up of the Bioreactor

The aim of this study was to investigate the feasibility of a bioreactor system and its scale‐up to remove Cr(VI) from solution. The bioreactor is based on an innovative process that combines bioreduction of Cr(VI) to Cr(III) by the bacterium Arthrobacter viscosus and Cr(III) sorption by a specific zeolite. Batch studies were conducted in a laboratory‐scale bioreactor, taking into account different operating conditions. Several variables, such as biomass concentration, pH and zeolite pre‐treatment, were evaluated to increase removal efficiency. The obtained results suggest that the Cr removal efficiency is improved when the initial biomass concentration is approximately 5 g L^–1 and the pH in the system is maintained at an acidic level. Under the optimised conditions, approximately 100 % of the Cr(VI) was removed. The scale‐up of the developed biofilm process operating under the optimised conditions was satisfactorily tested in a 150‐L bioreactor.     

Schnelle,effiziente und kostengünstige Auslegung von Membranverfahren mit flexiblen Labormembrantestständen

When designing complex membrane processes, different aspects have to be considered. While fundamental questions are addressed in the laboratory phase, the real conditions in the technical process can only be investigated in the course of a complex and extensive pilot phase. To assure a fast, efficient and cost‐effective layout, modern and flexible laboratory membrane test units are necessary that can reproduce operational conditions even in the laboratory with small test quantities. The requirements for modern laboratory membrane test units, the design and the procedure for the laboratory tests are presented and illustrated using the recovery of process water during glycerine production as an example.     

Scale‐up of Mini‐Plant Extractors on Energy Dissipation‐Based Population Balances

The new scale‐up concept for extraction columns relies on three identities being kept idem, as is the total specific flow rate, energy dissipation, and mean droplet residence time in a compartment. The droplet population balance‐based model allows maintaining hydrodynamic similarity in different geometries, as is in a mini‐ or a pilot plant. This leads to similar breakage and coalescence probabilities giving comparable droplet size distributions, thus mass transfer area and extraction efficiency. A new breakage frequency term has been developed relying on the energy dissipation rate and is thus independent from geometric constraints. The traditional scale‐up rules are based either on a constant tip velocity (≈ N) or on a constant energy input (≈ N³), whereas here it follows a constant energy dissipation (≈ N²). A step‐by‐step approach to the new procedure proved by case samples is given. Data from literature pilot experiments could be verified by computer simulations, without using adaptable parameters. All parameters in the correlations where derived in a lab‐scale apparatus and the coalescence parameters were obtained in the mini‐plant experiments. Derivation between simulated and experimental pilot data for stage numbers was less than 14 %, operating parameters (rotational speed N, throughput) were underestimated by 4 % leading to a slightly smaller HETS (Height Equivalent of Transfer Stages) value as measured, affecting the column height with less than 1 %.     

Microwave‐Assisted Chemical Reactions

This article reviews the state of the art of microwave‐assisted reactions and the influence of microwaves on mass and heat transfer. The heating behavior of representative test reactions and single substances is compared for heating with microwaves and thermal energy. Similarities and differences between convective heating and dielectric irradiation methods are discussed with regard to the yield, the selectivity, and the enantiomeric purity of the reaction products. Furthermore, prevailing problems related to the scale‐up of microwave‐assisted reactions are discussed considering the energy absorption of the substances and mixtures to be heated, and their dependence on the energy consumption and the amount of substance.     

Separation von Starterkulturen nach Hochdruck‐Homogenisierung

The present work demonstrates how shearing through a high‐pressure homogenizer affects the separation properties of exopolysaccaride producing bacterial starter cultures. In addition to changes in medium viscosity and sedimentation velocity significant differences in the compactness of the cell sediment were observed. The scalability of the laboratory results obtained through analytical centrifugation in larger scale using a stack disc separator is also demonstrated.     

Pilot Development of Polygeneration Process of Circulating Fluidized Bed Combustion combined with Coal Pyrolysis

A pilot polygeneration process of a 75 t h^–1 circulating fluidized bed (CFB) boiler combined with a moving bed coal pyrolyzer was developed based on laboratory‐scale experimental results. The process operation showed good consistency and integration between boiler and pyrolyzer. Some critical operating parameters such as hot ash split flow from the CFB boiler to the pyrolyzer, mixing of hot ash and coal particles, control of pyrolysis temperature and solid inventory in the pyrolyzer, and pyrolysis gas clean‐up were investigated. Yields of 6.0 wt‐% tar and 8.0 wt‐% gas with a heating value of about 26 MJ m^–3 at 600 °C were obtained. Particulate content in tar was restrained less than 4.0 wt‐% by using a granular filter of the moving bed. Operation results showed that this pilot polygeneration process was successfully scaled up.     

PILOT PLANT STUDIES AND MODELLING OF A SEMI-BATCH POLYESTERIFICATION PROCESS

A novel unsaturated polyester formulation was developed recently in our laboratories. The polyester resin, which was designed as a green-house glazing material, exhibited excellent optical properties and superior resistance to weathering conditions. This study describes the scale-up procedure followed in preparing the resin in a 200 L pilot plant reactor starting from its preparation in a 1 L reactor. The paper analyzes the major variables affecting the polyesterification process and presents a semi-empirical model capable of predicting the pilot plant kinetic data from laboratory reactor data. The model is based on a recently developed third order kinetic equation for the reaction of non-stoichiometric amounts of hydroxyl and carboxylic groups. The model quantifies the effects of reaction temperature and inert gas flow rate on reaction rate and provides a basis for the polyesterification process scale-up. The reaction temperature dependence is assumed Arrhenius, whereas the gas flow rate dependence is empirically determined as a function of the molar ratio of reactants to inert gas. Application of the model to commercial sized reactors will be highlighted.     

Microwave and ultrasonic processing: Now a realistic option for industry

Environmentally friendlier preparations of chemical compounds and organic or inorganic materials are generally accompanied by the concept of saving resources by optimizing reaction conditions and/or introducing new process technologies. The use of ionic liquids and a solvent-free approach are among these technologies, but in terms of the minimisation of energy and optimization of reaction control both microwave and ultrasound irradiation have now proved to be real options. This review starts from the basic considerations on the separate interaction of microwaves and ultrasound with matter and goes on to explore some laboratory and industrial applications of each type of activation. It is also possible to enhance the effects of high frequency electromagnetic fields, typical of microwaves, or the cavitational energy associated with sonochemistry by combining them with other extreme conditions such as plasmas, high pressure and UV. Finally the simultaneous use of microwaves and ultrasound in a single reactor is described. This novel mixing of technologies has been implemented in order to combine the effects of enhanced energy with improved matter transportation.     

Influence of Spacing of Multiple Impellers on Power Input in an Industrial‐Scale Aerated Stirred Tank Reactor

Despite the fact that aerated stirred tank reactors are widely used in industry and often studied, their design and scale‐up still remains challenging. Especially the specific power input is a crucial and geometry‐dependent scale‐up parameter, usually calculated with the dimensionless power number Po. Within the scope of this study, the power number is measured for different stirrer types and configurations in a laboratory and an industrial‐scale aerated stirred tank reactor. Good agreements to literature are found for the unaerated case for the two‐stage stirrer configurations at different stirrer spacing for both scales. By literature only the aerated case in the laboratory scale can be predicted. Scale‐up of an aerated industrial‐scale reactor is challenging because of a specific influence of the aeration. In case of a three‐stage Rushton configuration, an asymmetrical distribution of the stirrers should be preferred to ensure a high power number as well as good power performance under aerated conditions.     

Continuous Transesterification with Acidic Ionic Liquids as Homogeneous Catalysts

Ionic liquids (ILs) are recyclable acid catalysts for transesterification reactions. In the present study, different acidic ILs were examined in this reaction, with special focus on their recyclability. Furthermore, the IL‐catalyzed transesterification reaction was realized in continuous operation. A miniplant reactor with technically representative design and operating characteristics was used for this study. The applied rig has a volume of 5 L and an external thermosyphon reboiler. The miniplant reactor can be operated in batch and in continuous mode. ILs functionalized with a sulfonic acid group were found to be the most suitable IL catalysts for the transesterification reactions under investigation. Using these ILs, reaction rates as high as for H₂SO₄ could be realized. Moreover, the IL catalyst was demonstrated to be active for at least 1000 h of operation time.     

淀粉基天然高分子重金属离子捕集剂放大试验

以乙二胺改性淀粉接枝甲基丙烯酸缩水甘油酯(AMS)小试工艺为依据,考察了pH、搅拌速度、反应时间和乙二胺用量对放大试验的影响,确定了AMS中间放大试验配方工艺,研究了产品氮含量对重金属捕集性能的影响,并采用傅氏转换红外线光谱分析仪(FTIR)表征产品结构。结果表明:放大试验结果与小试结果基本吻合,反应时间和搅拌速度影响显著,产品氮含量越高捕集重金属离子性能越好,改进后的工艺产品氮含量可达到11.46%;放大试验产品AMS被乙二胺改性。     

Advancement of Fischer‐Tropsch synthesis via utilization of supercritical fluid reaction media

The Fischer Tropsch Synthesis (FTS) reaction has been studied and for nearly a century for the production of fuels and chemicals from nonpetroleum sources. Research and utilization have occurred in both gas phase (fixed bed) and liquid phase (slurry bed) operation. The use of supercritical fluids as the reaction media for FTS (SCF‐FTS) now has a 20‐year history. Although a great deal of progress in SCF‐FTS has been made on the lab scale, this process has yet to be expanded to pilot or industrial scale. This article reviews the research activities involving supercritical FTS and published in open literature from 1989 to 2008. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Effect of scale on the draw down of floating solids

In this study, the draw down of floating solids from the liquid surface has been investigated using vessels of 0.61 and 2.67 m diameter. The importance of impeller type (mixed flow pitched blade turbine (PBT) and the narrow blade hydrofoil LE-20), pumping mode and position and the effect of varying liquid height have also been studied. Impeller speed and power consumption at which no solids remain at the surface for more than 2-4 s are determined by visual observations.Results from different scales are discussed in relation to the way in which solids are drawn down from the liquid surface. It has been shown that over a wide range of conditions the power required for drawing down solids can be reduced by operating in the upward rather than downward pumping mode and using an axial flow narrow blade hydrofoil rather than a mixed flow pitched blade turbine. Different scale up criteria, power per unit volume, tip speed and Froude number, are discussed for these systems. For scale up, specific power input is shown to be the most appropriate criterion for upward pumping impellers.