Advancements in droplet reactor systems represent new opportunities in chemical reactor engineering: A perspective

Traditional chemical reactors, such as batch reactors, continuous reactors, and semi-batch reactors, have been extensively studied and frequently act as central components of modern chemical plants. Recently, various advances in reaction times, surface-to-volume ratios, required amounts of reagents, and throughput have led to new directions in the design of miniaturized chemical reactors. In this Perspective, we provide an overview of the progress from traditional to miniaturized chemical reactors by summarizing the characteristics and applications of different types of reactors. Furthermore, we compare classical chemical reactors and miniaturized droplet reactors to highlight advancements in the design of droplet reactor systems based on open functional surfaces. Finally, we provide an outlook on the research directions of miniaturized droplet reactors.     

Measurement and control of polymerization reactors

The measurement and control of polymerization reactors is very challenging due to the complexity of the physical mechanisms and polymerization kinetics. In these reactors many important variables, which are related to end-use polymer properties, cannot be measured on-line or can only be measured at low sampling frequencies. Furthermore, end-use polymer properties are related to the entire molecular weight, copolymer composition, sequence length, and branching distributions. This paper surveys the instrumentation technologies, which are of particular interest in polymerization reactors with emphasis on, for example, measurement of viscosity, composition, molecular weight, and particle size. This paper presents a hierarchical approach to the control system design and reviews traditional regulatory techniques as well as advanced control strategies for batch, semibatch, and continuous reactors. These approaches are illustrated by focusing on the control of a commercial multiproduct continuous emulsion polymerization reactor. Finally, the paper captures some of the trends in the polymer industry, which may impact future development in measurement and reactor control.     

Continuous reactor preparation of thermoplastic modified epoxy‐amine prepolymers

This paper describes a new continuous reactor method to prepare thermoplastic modified epoxy prepolymers for aerospace prepregs with the aim of replacing traditional batch reactors. Compared with batch reactors, the continuous reactor is capable of producing epoxy prepolymers through simultaneous dissolution of polyethersulfone (PES) and 4,4′‐diaminodiphenylsulfone in tetraglycidyl‐4,4′‐ diaminodiphenylmethane (TGDDM). In addition, concurrent chain extension reactions advance prepolymer molecular weights to desired viscosities in less than 2 min of mean residence time. Optical micrographs were used to define how process temperature influences PES dissolution in TGDDM in a continuous reactor. Kinetic studies confirmed that the chain extension reaction in a continuous reactor is similar to that in a batch reactor, and the molecular weights and viscosities of prepolymers were readily controlled through reaction kinetics. Atomic force microscopy was used to confirm similar cured network morphologies for formulations prepared from batch and continuous reactors. Additionally tensile strength, tensile modulus and fracture toughness analyses concluded that mechanical properties of cured epoxy matrices produced from the two reactors were equivalent. © 2014 Society of Chemical Industry     

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.     

Temperature Control of a Bench‐Scale Batch Polymerization Reactor for Polystyrene Production

Batch polymerization reactors commonly use optimal temperature control as the strategic operation parameter. This strategy allows for better operability and a more economic process. The main objective of the batch polymerization reactor control is to obtain acceptable product quality. Direct measurement of polymer quality is rarely achievable, which makes the online control of the reactor difficult. Temperature is the most controllable operational variable in the polymer reactor, which is seen to have a direct effect on the polymer properties. Temperature is chosen as the set point by using either the isothermal temperature or optimal temperature trajectory. Online control of the optimal temperature profile of a bench‐scale batch polymerization reactor was experimentally investigated in this study. The temperature trajectory was used as the target for controllers to follow. The time‐profile temperature was obtained with the objective of obtaining the desired conversion and number‐average chain length within the minimum time. Two advanced controls of fuzzy logic control and generic model control were applied to the polymer reactor. A comparison of the controllers reveals that both performed better than conventional controllers.     

Transition from Batch to Continuous Operation in Bio‐Reactors: A Model Predictive Control Approach and Application

This work considers the problem of determining the transition of ethanol‐producing bio‐reactors from batch to continuous operation and subsequent control subject to constraints and performance considerations. To this end, a Lyapunov‐based non‐linear model predictive controller is utilized that stabilizes the bio‐reactor under continuous mode of operation. The key idea in the predictive controller is the formulation of appropriate stability constraints that allow an explicit characterization of the set of initial conditions from where feasibility of the optimization problem and hence closed‐loop stability is guaranteed. Additional constraints are incorporated in the predictive control design to expand on the set of initial conditions that can be stabilized by control designs that only require the value of the Lyapunov function to decay. Then, the explicit characterization of the set of stabilizable initial conditions is used in determining the appropriate time for which the reactor must be run in batch mode. Specifically, the predictive control approach is utilized in determining the appropriate batch length that achieves stabilizable values of the state variables at the end of the batch. Application of the proposed method to the ethanol production process using Zymomonas mobilis as the ethanol producing micro‐organism demonstrates the effectiveness of the proposed model predictive control strategy in stabilizing the bio‐reactor.     

BATCH AND SEMIBATCH REACTORS MODELLING AND VALIDATION BASED ON ON-LINE pH MEASUREMENT

Based on on-line pH measurement, a comparative study between batch and semibalch reactors performance has been carried out in a glass-jacketed reactor of 51 provided with the measuring, data acquiring and controlling system. The reaction system chosen was an acid-base reaction, the concentrations of the species in the reactor were obtained simply by measuring the pH of reaction solution. Based on the conductivity profiles of the solution at different temperatures, the kinetic equation of this acid-base reaction was established. The thermal behaviors of batch reactor were investigated by heating and cooling water in the reactor. The dynamic behavior of batch reaction could be described by a set of differential equations resulting from the mass and energy balance of the reaction mixture, the energy balance of the jacket wall and the circulating fluid inside the jacket. This model has been validated with experimental results, and could be applied to the complex control situations.     

ADAPTIVE LINEAR QUADRATIC CONTROL OF BATCH AND SEMI-BATCH CEHMICAL REACTORS WITHIN THE DELTA OPERATOR FORMULATION

Batch and semi-batch chemical reactors are extensively used in polymer, fine chemical and pharmaceutical industries. The temperature control is of fundamental importance from product quality and reproductibility points of view. It is then necessary to improve the automation of these plants which are typically controlled using standard PID controllers. An autotuning PID controller is proposed and evaluated by application to a batch and semi-batch pilot plant reactor to investigate advanced control techniques. The involved control design is derived in the spirit of the partial state reference model adaptive control (PSRMAC) approach within the delta operator formulation. PSRMAC is mainly motivated by its suitable tracking capability when only a crude knowledge about the plant to be controlled is available. The delta operator formualtion is particularly motivated by the convergence of the performances to their continuous time counterpart as well as its numerical robustness when the sampling is required to be fast.     

Characterization and use of a penicillin acylase biocatalyst

A complete characterization of a penicillin acylase biocatalyst is presented, including the determination of physicochemical and kinetic parameters. Stability studies are detailed in terms of both storage temperature and pH as well as operational stability after 150 batch reactions of two hours duration each. An Arrhenius-type model was used to simulate the effect of pH on biocatalyst stability. A kinetic model is proposed to describe batch and continuous stirred tank reactors and to predict the long-term behavior of the process.     

Application of coal conversion technology to tire processing

Tire recycling has been carried out using technology most commonly developed for coal conversion processes trying to take advantage of well-known reactors. Two different batch reaction systems (tubing bomb reactors and magnetically stirred autoclave) and a continuous reactor (swept fixed bed reactor) were tested. In addition, the influence of hydrogen pressure (ranging from 1 to 10 MPa) was assessed together with the influence of an inert or a hydrogenating atmosphere. Independently of the reactor used (tubing bomb reactors or magnetically stirred autoclave), the initial hydrogen pressure and the atmosphere, the 100% of the organic matter conversion was obtained in all the runs when batch reactors were used. When the semicontinuous reactor was used, slightly lower conversions were obtained, probably due to the deposition of products on the surface of the solid products. In all the experiments, conversion products were always oils and gases (comprised mainly of light hydrocarbons) plus a rich in carbon black solid residue. It was observed that the distribution between oils and gases was a function of the reactor type and in some cases a function of the hydrogen pressure. Oils were characterised by thin layer chromatography coupled to a flame ionisation detector (TLC-FID) and by simulated distillation. Different results in oils composition were obtained as a function of the reactor type and hydrogen pressure.     

Gas-phase residence time distribution in a falling-film microreactor

Industrial-scale performance of gas-liquid reactors can be difficult to optimise for very rapid or highly exothermic reactions. Microstructured reactors for laboratory measurements offer new opportunities for the study of these reactions by enabling precise heat management and fine control of reactor operating conditions. For accurate experimental study, characterisation of the flow conditions within these new reactor devices is essential.The present study examines experimental residence time distributions for the gas phase through a microstructured falling-film reactor, in order to develop an appropriate flow model for further study of gas-phase mass-transfer characteristics in the system. For the gas-phase residence time distribution experiments, the detection system involves a flow of oxygen containing ozone as a tracer gas with continuous monitoring of the concentration by UV-light absorption. The experimental results are used to model the flow behaviour in the gas volume over the gas-liquid contact zone as a series of continuous stirred tank reactors whose number is a simple function of the gas Reynolds number.The experimental results are compared with computational fluid dynamics calculations of the gas flow within the reactor. The comparison indicates a clear correlation of the flow model behaviour with the appearance of recirculation loops in the reaction chamber and the effect of the gas jet at the entrance of the gas-liquid contact zone.     

A highway in state space for reactors with minimum entropy production

Thousands of numerical solutions of an optimal control problem for plug flow reactors were found to give, what we call a “highway in the reactors’ state space”. The problem was to find the heat transfer strategy which minimise the entropy production in reactors with fixed chemical conversion. The control variable was always the temperature of the heating/cooling medium along the reactor. The highway represents the most energy efficient way to travel far in state space. Such highways were studied for five reactor systems, endothermic and exothermic ones. Numerical analysis showed that the reactor highway is characterised by approximately constant thermodynamic driving forces/local entropy production for reasonable process intensities. Each solution represents a compromise between the entropy production of reactions, heat transfer and frictional flow (pressure drop). The solutions enter and leave the highway at different positions depending on how far from the highway their initial and final destinations are. Knowledge about the nature of the highway, e.g. when the reactor operates in a reaction mode or a heat transfer mode, may be important for energy efficient reactor design. The theoretical formulation of the optimisation problem is valid for plug flow as well as batch reactors. We showed that important results in literature like the Spirkl-Ries quantity, the theorems of equipartition of entropy production and equipartition of forces are contained in our general formulation. The numerical results showed that the analytical results are good approximations to the optimum also in problems where they do not apply in a strictly mathematical sense.     

Über die Auswahl von Polymerisationsreaktoren

Choice of polymerization reactors . Industrial syntheses of polymers always yield a highly complex product whose adequate characterization often requires application-oriented tests in addition to chemical and physical parameters. In contrast to the synthesis of low-molecular mass substances subsequent corrections, e. g. by distillation or crystallization, are usually impossible. Extremely detailed reaction control is of paramount importance. Polyreactions can be classified according to kinetic aspects (monomer linkage with and without termination reaction, linkage of polymers). Apart from homogeneous bulk polymerization, there are the heterogeneous processes of precipitation-, bead-, and emulsion-polymerization. The polymerization reactors can be assigned to the known ideal types (batch reactor, continuous plug flow reactor, series of stirred tanks, and continuous stirred tank reactor). High viscosity often thwarts thorough mixing in bulk polymerization and segregation may occur. The article surveys the variants of the reactor types used for various polyreactions and polymerization processes in industry and examines the reasons for this choice. Most commonly used is the batch reactor, followed by the cascade of stirred tanks. Continuous polymer-linkage (polycondensation, polyaddition) is frequently performed in a series of several different kinds of reactors.     

Glycerolysis of Fatty Acid Methyl Esters: 2. Simulation and Experiments in Continuous Reactors

The glycerolysis of methyl ester was investigated in flow reactors. This reaction represents a liquid two-phase reaction with changing reaction rates in a batch reactor. A semi-empirical model tested earlier with batch reactor data was used to simulate different continuous processes for this reaction. Among the processes simulated, a single continuous-flow stirred tank reactor (CSTR) without recycling was considered most appropriate for experimental implementation, although simulations showed that a faster reaction rate is possible with the application of a CSTR followed by a tubular reactor with certain associated residence times. The CSTR simulations were verified experimentally. A good agreement was found between the experimental data and simulation results.     

Emulsion polymerisation in continuous reactor systems

Continuous reactor systems find important applications in the production of sythetic polymer latexes and increased production rates are providing additional incentives for the development of new continuous systems. The fundamental factors that should be considered in the development of continuous processes are reviewed in this paper. Particular emphasis is placed on exploring the differences between batch and continuous reactors and why these difference can lead to different latex product, even if the same recipe is employed. These factors make the task of designing continuous reactor systems based on batch research and development very difficult and risky. Thus it is recommended that small-scale continuous reactors be employed early in a product/process development effort if that effort is likely to lead to a continuous commercial process. The published literature on continuous emulsion polymerization reactors has been reasonably active in the past ten years. Our understanding of the chemistry and reactor modelling has been advanced but a number of areas for fruitful research remains. Some of these problems are reviewed and directions for new efforts are suggested.     

Emulsion polymerization and copolymerization in continuous reactor systems

Continuous reactors are important for commercial production of latex products and they can be useful tools for fundamental polymerization kinetics studies. Results are presented for four projects: (i) elimination of conversion oscillations in continuous stirred-tank reactors (CSTR) by use of a tubular prereactor; (ii) use of a seed-fed CSTR to measure free radical transport from monomer-swollen latex particles; (iii) development of a continuous process as an alternative to a commercial batch process; and (iv) determination of copolymerization kinetic parameters with a steady-state CSTR system.     

Continuous flow operation in emulsion polymerization of styrene

The kinetics of continuous emulsion polymerization of styrene were studied theoretically on the basis of the authors' batch reaction model, and a new reaction model was proposed for continuous operation. The validity of the model was tested by experiments conducted with stirred tank reactors in series. The characteristics of the first reactor used to generate polymer particles were studied in particular detail. It was found that there was an optimum residence time for the first reactor, the value of which was quantitatively predictable from the operating variables. The most suitable combinations of several types of reactors for continuous emulsion polymerization are also discussed.     

Blocking and copolymer heterogeneity in anionic copolymerization in industrial reactors

An analysis is given of the effect of reactor design on the variation of composition and extent of blocking in anionic copolymerization. Batch, pipeline, continuous stirred tank (CSTR), and recycle reactors are contrasted. Specifically, alkyl lithium-polymerized butadiene–styrene and alkyl sodium-polymerized p-methylstyrene–styrene are contrasted to the products of copolymerization of the same monomers by free-radical mechanism. It is shown for both systems that considerably more extensive blocking occurs in a batch reactor when the anionic polymerization mechanism is used. The free-radical copolymers, unlike the anionic copolymers, exhibit compositional heterogeneity in a batch reactor. Carrying out the polymerization reaction in a pipeline reactor gives results equivalent to the batch reactor if there is plug flow. However, if a parabolic profile exists in the reactor, there will be significantly increased compositional drift in the copolymer product and a broadened molecular weight distribution, with little effect on blocking. Recycle reactors, including the recirculating loop variety, seem effective in decreasing blocking. The extent of blocking may be considerably decreased in a wellmixed continuous stirred tank reactor. However, poor mixing will greatly increase both the extent of blocking and the compositional heterogeneity of the product.     

Photocatalytic reactors for treating water pollution with solar illumination. I: A simplified analysis for batch reactors

Usual applications of photocatalytic reactors for treating wastewater exhibit the difficulty of handling fluids having varying composition and/or concentrations; thus, a detailed kinetic representation may not be possible. When the catalyst activation is obtained employing solar illumination an additional complexity always coexists: solar fluxes are permanently changing with time.For comparing different reacting systems under similar operating conditions and to provide approximate estimations for scaling up purposes, simplified models may be useful. For these approximations the model parameters should be restricted as much as possible to initial physical and boundary conditions such as: initial concentrations (expressed as such or as TOC measurements), flow rate or reactor volume, irradiated reactor area, incident radiation fluxes and a fairly simple experimental observation such as the photonic efficiency.A combination of a new concept: the “actual observed photonic efficiency” with ideal reactor models and empirical kinetic rate expressions can be used to provide rather simple working equations that can be efficiently used to describe the performance of practical reactors. In this paper, the method has been developed for the case of a photocatalytic batch reactor.     

A comparative study of residence time distribution and selectivity in a monolith CDC reactor and a trickle bed reactor

A comparative study of the performance of a trickle bed reactor (TBR) and a monolith cocurrent downflow contactor (CDC) reactor in terms of selectivity and residence time distribution was conducted for the hydrogenation of 2-butyne-1,4-diol (B). Selectivity (S) towards 2-butene-1,4-diol was investigated with the solvent 2-propanol and a 30% (v/v) 2-propanol/water mixture (M) in batch recycle mode. Liquid residence time distribution (RTD) curves were obtained for both reactors. Although both reactors presented almost identical hydrodynamic behaviour, i.e. RTD, significant differences regarding selectivity towards the alkene were observed in both solvents. The use of 2-propanol gave lower selectivities in both reactors, but even then the monolith reactor was superior. In the monolith CDC, the liquid RTD curve was also obtained at different radial positions. RTD profiles across the monolith showed that from the centre to the column wall there is possibly an increased retention of material and despite this, overall selectivity does not appear to be considerably depressed by the backmixing that the above result implies in 2-propanol/water where the selectivity was found to be 100% towards the intermediate (C).

Modelling of the monolith CDC reactor was also conducted to predict RTD. The models tested were tanks-in-series, piston exchange and piston dispersion exchange; from which, piston exchange model was found to best predict and fit the experimental data.