Guidance on Safety/Health for Process Intensification Including MS Design. Part IV: Case Studies

The new technology of process intensification by multiscale equipment can significantly contribute to the achievement of a safer design by switching from batch/semi‐batch to continuous operation combined with a reduction of the inventory of hazardous substances in critical stages. On the other hand, the shift to higher space‐time‐yields and temperatures comprises new risks (see Parts I and II). A tool was developed for preliminary risk assessment to cover characteristic features of micro‐designed equipment, called HAZOP‐LIKE study (see Part III). The generic case studies were applied to two demonstration projects within the IMPULSE project: sulfur dioxide oxidation and the alkylation reaction for the production of ionic liquids. The generic templates proved to be applicable and support comprehensive risk analysis studies on processes with hidden deviations not obviously following traditional HAZOP studies.     

Transition from Low Velocity to High Velocity in a Three Phase Fluidized Bed

The onset liquid velocity demarcating the conventional and the circulating fluidization regimes of three‐phase fluidized beds was determined by measuring the time required to empty all particles in a batch fluidized bed at various liquid and gas velocities. Experiments were performed in a gas‐liquid‐solid circulating fluidized bed of 2.7 m in height using glass beads of 0.508 mm in diameter as solid phase and air and tap water as the fluidizing gas and liquid, respectively. The results show that gas velocity is a strong factor on the onset liquid velocity. Higher gas velocity yields a lower onset liquid velocity. It is also demonstrated that the onset liquid velocity has the same value as particle terminal velocity in a gas‐liquid mixture. Within the gas‐liquid‐solid circulating fluidization regime, the solids circulation rate is increased with the total liquid velocity and the auxiliary liquid velocity.     

Titelbild Chem. Ing. Tech. 10/2016

The so‐called plug & play reactor is a novel reaction device with exchangeable reaction segments as well as modules for heating/cooling and mixing. The applications of the plug & play reactor include gas/solid, liquid/solid as well as gas/liquid/solid reactions. Commercially available HPLC columns, filled with catalyst particles, can be inserted in the reaction segment to act as fixed bed reactors. No external mixing device is needed, which leads to a high compactness of the reactor. The monitoring of the reaction progress and the reaction parameters can be carried out inline and online and an easy scale‐up by increasing the pipe diameter as well as simply numbering‐up by multiplying the modules is possible. Thus, the plug & play reactor is an attractive alternative to existing batch processes and can be easily implemented in existing processes. G. J. Lichtenegger, V. Tursic, H. Kitzler, K. Obermaier, J. G. Khinast, H. Gruber‐Wölfler*, Chem. Ing. Tech. 2016 , 88 (10), 1518 – 1523. DOI: 10.1002/cite.201600013     

Kinetics studies of ketazine formation: Effect of temperature and catalyst concentration

Formation of methyl ethyl ketazine is a distinct case of homogeneous catalyzed gas–liquid–liquid reactions. Kinetics studies of methyl ethyl ketazine formation has been carried out in a semi‐batch reactor. The effects of temperature and catalyst concentration on the percentage yield of ketazine have been studied extensively. The yield of ketazine is found to increase with increase in temperature and then levels off. Increase in catalyst concentration favours the formation of ketazine. The conversion of peroxide is found to increase with increase in temperature thus indicating that chemical reaction is rate‐limiting step in the system. The desired temperature for carrying out the reaction is found to be 60°C and the required catalyst to peroxide ratio is 2.5. The activation energy for the reaction is 24.5 kJ/mol.     

Kinetic Model of Gas‐Liquid‐Liquid Reactive Extraction for Production of Hydrogen Peroxide

The kinetic aspects of the gas‐liquid‐liquid reactive extraction process for the production of hydrogen peroxide were investigated in a batch reactor. It was observed that the gas‐liquid reaction rate is strongly affected by mass transfer of oxygen across the liquid film and the reaction can be simplified to pseudo‐first order. The extraction rate is governed by both reaction and liquid‐liquid mass transfer, and is slightly lower than the reaction rate. In addition, a kinetic model of the reactive extraction process for the production of hydrogen peroxide was developed. Kinetic parameters under different conditions were determined by experiments. The data calculated from the kinetic model match experimental data well under different conditions for hydrogen peroxide production in gas‐liquid‐liquid reactive extraction.     

间歇冶炼工艺烟气制酸装置的设计

对间歇冶炼工艺烟气制酸装置的设计和操作进行了论述。为解决气体流量和SO_2浓度的波动问题,确保硫酸装置稳定运行,提出了各种解决方案,其中包括增设焚硫炉或预干燥塔、注入液体SO_2、采用一转一吸装置加尾气洗涤塔等。     

Extraction of Anthocyanins Using a Laboratory Robot and Innovative Extraction Technologies

Solid‐liquid extraction using a laboratory robot, where anthocyanins are leached from dried red vine leaves, is evaluated with respect to precision and accuracy. The solid handling of the robot results in standard deviations between ± 0.6 and ± 1.8 depending on the particle size. For liquid handling the standard deviations are slightly higher depending on the volatility of the solvents. The validated, fully automated natural plant extraction robot achieves varying yields based on dry matter for methanol, water, and ethanol which are improved with increasing particle size. Manually performed extraction kinetics experiments are compared with the robot. With respect to process intensification, a comparison of yields obtained by microwave‐ and ultrasonic‐supported extraction compared to laboratory robot shaking and stirred single‐stage batch experiments was performed.     

Analysis of Flow Patterns in High‐Gravity Equipment Using Gamma‐Ray Computed Tomography

The capacity of today's gas‐liquid contacting equipment such as tray or packed columns is limited by the gravitational‐driven liquid flow. Intensified equipment applying centrifugal force offers great potential for enhancing the mass transfer and for reducing equipment size. Yet, detailed knowledge about the liquid flow inside rotating packings is scarce due to limited accessibility with conventional measurement systems. In this study, a gamma‐ray computed tomography is employed to quantify the liquid hold‐up and its distribution in the moving packing.     

The effect of gas‐liquid counter‐current operation on gas hold‐up in bubble columns using electrical resistance tomography

BACKGROUND: In order to improve the performance of a counter‐current bubble column, radial variations of the gas hold‐ups and mean hold‐ups were investigated in a 0.160 m i.d. bubble column using electrical resistance tomography with two axial locations (Plane 1 and Plane 2). In all experiments the liquid phase was tap water and the gas phase air. The superficial gas velocity was varied from 0.02 to 0.25 m s^?1, and the liquid velocity varied from 0 to 0.01 m s^?1. The effect of liquid velocity on the distribution of mean hold‐ups and radial gas hold‐ups is discussed. RESULTS: The gas hold‐up profile in a gas–liquid counter‐current bubble column was determined by electrical resistance tomography. The liquid velocity slightly influences the mean hold‐up and radial hold‐up distribution under the selected operating conditions and the liquid flow improves the transition gas velocity from a homogeneous regime to a heterogeneous regime. Meanwhile, the radial gas hold‐up profiles are steeper at the central region of the column with increasing gas velocity. Moreover, the gas hold‐up in the centre of the column becomes steeper with increasing liquid velocity. CONCLUSIONS: The value of mean gas hold‐ups slightly increases with increasing downward liquid velocity, and more than mean gas hold‐ups in batch and co‐current operation. According to the experimental results, an empirical correlation for the centreline gas hold‐up is obtained based on the effects of gas velocity, liquid velocity, and ratio of axial height to column diameter. The values calculated in this way are in close agreement with experimental data, and compare with literature data on gas hold‐ups at the centre of the column. Copyright © 2010 Society of Chemical Industry     

Gas‐Lift Reactors for Rapid Reactions with Appreciable Gas Consumption

Gas‐lift reactors offer important advantages for a number of gas/liquid and gas/liquid/solid reactions. However, the design and operation of these reactors can be complex when there is a substantial change in the molar gas flow rate along the length of the reactor, e.g., when a gaseous reactant is converted into a liquid product. In this situation, there is a strong coupling between reactor hydrodynamics and reaction kinetics, which arises from the fact that the rate of liquid circulation through the reactor and the longitudinal profile of gas holdup in the riser are mutually dependent. Several one‐dimensional models have been developed to describe kinetic/hydrodynamic coupling in gas‐lift reactors. These models offer useful insights into the parameters that affect reactor performance. The models can also be used to explore different approaches to scale‐up.     

Competition between hydrotreating and polymerization reactions during pyrolysis oil hydrodeoxygenation

Hydrodeoxygenation (HDO) of pyrolysis oil is an upgrading step that allows further coprocessing of the oil product in (laboratory‐scale) standard refinery units to produce advanced biofuels. During HDO, desired hydrotreating reactions are in competition with polymerization reactions that can lead to unwanted product properties. To suppress this polymerization, a low‐temperature HDO step, referred to as stabilization, is typically used. Small batch autoclaves have been used to study at near isothermal conditions the competition between hydrotreating and polymerization reactions. Although fast polymerization reactions take place above 200°C, hydrogen consumption was already observed for temperatures as low as 80°C. Hydrogen consumption increased with temperature and reaction time; however, when the end temperature exceeded 250°C, hydrogen consumption achieved a plateau. This was thought to be caused by the occurrence of fast polymerization reactions and the refractivity of the products to further hydrotreating reactions. The effect of the gas–liquid mass transfer was evaluated by using different stirring speeds. The results of these experiments (carried out at 300°C) showed that in the first 5 min of HDO, gas–liquid mass transfer appears to be limiting the overall rate of hydrotreating reactions, leading to undesired polymerization reactions and product deterioration. Afterward, intraparticle mass transfer/kinetics seems to be governing the hydrogen consumption rate. Estimations on the degree of utilization (effectiveness factor) for industrially sized catalysts show that this is expected to be much lower than 1, at least, in the early stage of HDO (first 30 min). Catalyst particle size should, thus, be carefully considered when designing industrial processes not only to minimize reactor volume but also to improve the ratio of hydrotreating to polymerization reactions. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Influences of top clearance and liquid throughput on the performances of an external loop airlift slurry reactor integrated mixing and separation

A new developed external loop airlift slurry reactor, which was integrated with gas–liquid–solid three-phase mixing, mass transfer, and liquid–solid separation simultaneously, was deemed to be a promising slurry reactor due to its prominent advantages such as achieving continuous separation of clear liquid from slurry and cyclic utilization of solid particles without any extra energy, energy-saving, and intrinsic safety design. The principal operating parameters, including gas separator volume, handling capacity, and superficial gas velocity, are systematically investigated here to promote the capabilities of mixing, mass transfer, and yield in the pilot external loop airlift slurry reactor. The influences of top clearance and throughput of the clear liquid on flow regime and gas holdup in the riser, liquid circulating velocity, and volumetric mass transfer coefficient with a typical high solid holdup and free of particles are examined experimentally. It was found that increasing the gas separator volume could promote the liquid circulating velocity by about 14.0% at most. Increasing the handling capacity of the clear liquid from 0.9 m~3·h~(-1) to 3.0 m~3·h~(-1) not only could increase the output without any adverse consequences, but also could enhance the liquid circulating velocity as much as 97.3%. Typical operating conditions investigated here can provide some necessary data and guidelines for this new external loop airlift slurry reactor to upgrade its performances.     

Multistage rotor‐stator spinning disc reactor

The scale up of a rotor‐stator spinning disc reactor by stacking single stage rotor‐stator units in series is demonstrated. The gas‐liquid mass transfer per stage is equal to the mass transfer in a single stage spinning disc reactor. The pressure drop per stage increases with increasing rotational disc speed and liquid flow rate. The pressure drop is more than a factor 2 higher for gas‐liquid flow than for liquid flow only, and is up to 0.64 bar at 459 rad s^?1. The high mass and heat transfer coefficients in the (multistage) rotor‐stator spinning disc reactor make it especially suitable for reactions with dangerous reactants, highly exothermic reactions and reactions where selectivity issues can be solved by high mass transfer rates. Additionally, the multistage rotor‐stator spinning disc reactor mimics plug flow behavior, which is beneficial for most processes. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Unified correlation for overall gas hold‐up in bubble column reactors for various gas–liquid systems using hybrid genetic algorithm‐support vector regression technique

The objective of this study is to collect the data on overall gas hold‐up (∈_G) for bubble column reactors handling various gas–liquid systems and further develop a unified data‐driven model for the estimation of the same. In this work, around 3300 experimental points for ∈_G have been collected from 85 open sources spanning the years 1963–2008. The data‐driven model for overall gas hold‐up has been established using hybrid Genetic Algorithm‐Support Vector Regression (GA‐SVR)‐based methodology. In the present study, GA has been used for nonlinear rescaling of the parameters. These exponentially scaled parameters are subsequently subjected for SVR training. The technique is an extension of conventional SVR technique, showing relatively enhanced results. The proposed hybrid model is based on various prominent design and operating parameters (15 in number) which includes superficial gas velocity, superficial liquid velocity, gas density, molecular weight of gas, sparger type, sparger hole diameter, number of sparger holes, liquid viscosity, liquid density, liquid surface tension, ionic strength of liquid, operating temperature, operating pressure, liquid height, and the column diameter. The estimations made by the SVR‐based unified model for ∈_G shows an excellent agreement with actual values with estimation accuracy of 98.5% and % AARE of 9.32%. For ease in applicability and ready reference of the practicing engineers, the hybrid GA‐SVR‐based model in the form of software and the entire database for ∈_G has been uploaded on the link http://www.esnips.com/web/UICT‐NCL .     

Primary and secondary gas penetration during gas‐assisted injection molding. Part I: Formulation and modeling

A theoretical study has been carried out on the transient gas‐liquid interface development and gas penetration behavior during the cavity filling and gas packing stage in the gas‐assisted injection molding (GAIM) of a tube cavity. A mathematical formulation describing the evolution of the gas/melt interface and the distribution of the residual wall thickness of skin melt along with the advancement of gas/melt front is presented. The physical model is put forward on the basis of Hele‐Shaw approximation and interface kinematics and dynamics. Numerical simulation is implemented on a fixed mesh covering the entire cavity. The model and simulation can deal with both primary and secondary gas penetrations. The predicted and measuredresults are compared in Part II of this study to validate the theoretical model. Polym. Eng. Sci. 44:983–991, 2004. © 2004 Society of Plastics Engineers.     

Kinetics of homogeneous 5‐hydroxymethylfurfural oxidation to 2,5‐furandicarboxylic acid with Co/Mn/Br catalyst

2,5‐furandicarboxylic acid (FDCA) is a potential non‐phthalate based bio‐renewable substitute for terephthalic acid‐based plastics. Herein, we present an investigation of the oxidation rate of 5‐hydroxymethylfurfural (HMF) to FDCA in acetic acid medium using Co/Mn/Br catalyst. Transient concentration profiles of the reactant (HMF), intermediates [2,5‐diformylfuran (DFF), 5‐formyl‐2‐furancarboxylic acid (FFCA)], and the desired product (FDCA) were obtained for this relatively fast reaction in a stirred semi‐batch reactor using rapid in‐line sampling. Comparison of the effective rate constants for the series oxidation steps with predicted gas–liquid mass transfer coefficients reveals that except for the FFCA → FDCA step, the first two oxidation steps are subject to gas–liquid mass transfer limitations even at high stirrer speeds. Novel reactor configurations, such as a reactor in which the reaction mixture is dispersed as fine droplets into a gas phase containing oxygen, are required to overcome oxygen starvation in the liquid phase and further intensify FDCA production. © 2016 American Institute of Chemical Engineers AIChE J, 63: 162–171, 2017     

Primary and secondary gas penetration during gas‐assisted injection molding. Part II: Simulation and experiment

Simulation and experimental studies have been carried out on the transient gas‐liquid interface development and gas penetration behavior during the cavity filling and gas packing stage in the gas‐assisted injection molding of a spiral tube cavity. The evolution of the gas/melt interface and the distribution of the residual wall thickness of skin melt along with the advancement of gas/melt front were investigated. Numerical simulations were implemented on a fixed mesh covering the entire cavity. The residual thickness of a polymer layer and the length of gas penetration in the moldings were calculated using both the simulation and model developed in Part I of this study and commercial software (C‐Mold). Extensive molding experiments were performed on polystyrene at different processing conditions. The obtained results on the gas bubble dynamics and penetration behaviors were compared with those predicted by the present simulation and C‐Mold, indicating the good predictive capability of the proposed model. Polym. Eng. Sci. 44:992–1002, 2004. © 2004 Society of Plastics Engineers.     

Polyurethane/clay nanocomposites with improved helium gas barrier and mechanical properties: Direct versus master‐batch melt mixing route

Thermoplastic polyurethane (TPU)/clay nanocomposite films were produced by incorporation of organo‐modified montmorillonite clay (Cloisite 30B) in TPU matrix by two different melt‐mixing routes (direct and master‐batch‐based mixing), followed by compression molding. In master‐batch mixing where the master‐batch was prepared by mixing of clay and TPU in a solvent, better dispersion of clay‐layers was observed in comparison to the nanocomposites produced by direct mixing. As a consequence, superior mechanical and gas barrier properties were obtained by master‐batch mixing route. The master‐batch processing resulted in 284 and 236% increase in tearing strength and tearing energy, respectively, with 5 wt % clay‐loading. Interestingly, in case of master‐batch mixing, the tensile strength, stiffness as well as breaking extension increased simultaneously up to 3 wt % clay‐loading. The helium gas permeability reduced by about 39 and 31% for the TPU/clay nanocomposites produced by mater‐batch and direct mixing routes, respectively, at 3 wt % loading of clay. Finally, the gas permeability results have been compared using three different gas permeability models and a good correlation was observed at lower volume fraction of clay. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46422.     

A Microfluidic Approach to the Rapid Screening of Palladium‐Catalysed Aminocarbonylation Reactions

The evaluation and selection of the most appropriate catalyst for a chemical transformation is an important process in many areas of synthetic chemistry. Conventional catalyst screening involving batch reactor systems can be both time‐consuming and expensive, resulting in a large number of individual chemical reactions. Continuous flow microfluidic reactors are increasingly viewed as a powerful alternative format for reacting and processing larger numbers of small‐scale reactions in a rapid, more controlled and safer fashion. In this study we demonstrate the use of a planar glass microfluidic reactor for performing the three‐component palladium‐catalysed aminocarbonylation reaction of iodobenzene, benzylamine and carbon monoxide to form N‐benzylbenzamide, and screen a series of palladium catalysts over a range of temperatures. N‐Benzylbenzamide product yields for this reaction were found to be highly dependent on the nature of the catalyst and reaction temperature. The majority of catalysts gave good to high yields under typical flow conditions at high temperatures (150 °C), however the palladium(II) chloride‐Xantphos complex [PdCl₂(Xantphos)] proved to be far superior as a catalyst at lower temperatures (75–120 °C). The utilised method was found to be an efficent and reliable way for screening a large number of palladium‐catalysed carbonylation reactions and may prove useful in screening other gas/liquid phase reactions.     

Process intensification of gas–liquid downflow and upflow packed beds by a new low‐shear rotating reactor concept

In the present work, a new low‐shear rotating reactor concept was introduced for process intensification of heterogeneous catalytic reactions in cocurrent gas–liquid downflow and upflow packed‐bed reactors. To properly assess potential advantages of this new reactor concept, exhaustive hydrodynamic experiments were carried out using embedded low‐intrusive wire mesh sensors. The effect of the rotational velocity on liquid flow patterns in the bed cross‐section, liquid saturation, pressure drop, and regime transition was investigated. Furthermore, liquid residence time and Péclet number estimated by a stimulus‐response technique and a macro‐mixing model were presented and discussed with respect to the prevailing flow patterns. The results revealed that the column rotation induces different flow patterns in the cross‐section of the packed bed operating in a concurrent downflow or upflow mode. Moreover, the new reactor concept exhibits a more flexible adjustment of pressure drop, liquid saturation, liquid residence time, and back‐mixing at constant flow rates. © 2016 American Institute of Chemical Engineers AIChE J, 63: 283–294, 2017