Continuous emulsion polymerization of styrene in a single Couette–Taylor vortex flow reactor

The effect of the geometrical and operational parameters on the mixing characteristics of a Couette–Taylor vortex flow reactor (CTVFR) were investigated and were correlated with the same parameters by using the tank‐in‐series model. Continuous emulsion polymerization of styrene was conducted at 50°C in a CTVFR to clarify the effects on kinetic behavior and reactor performance of operational parameters such as rotational speed of inner cylinder (Taylor number), reactor mean residence time, and emulsifier and initiator concentrations in the feed streams. It was found that steady‐state monomer conversion and particle number could be freely varied only by varying the Taylor number. In order to explain the observed kinetic behavior of this polymerization system, a mathematical model was developed by combining the empirical correlation of the mixing characteristics of a CTVFR and a previously proposed kinetic model for the continuous emulsion polymerization of styrene in continuous stirred tank reactors connected in series (CSTRs). On the basis of these experimental results, it was concluded that a CTVFR is suitable for the first reactor (prereactor) of a continuous emulsion polymerization reactor system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1931–1942, 2001     

Continuous emulsion polymerization of vinyl acetate. II Operation in a single Couette–Taylor vortex flow reactor using sodium lauryl sulfate as emulsifier

Continuous emulsion polymerizations of vinyl acetate were conducted at 50°C in a single continuous Couette–Taylor vortex flow reactor (CCTVFR) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. The polymerization can be carried out very smoothly and stably, but the steady‐state monomer conversion attained in a CCTVFR is not as high as that in a plug flow reactor (PFR), but only slightly higher than that in a continuous stirred tank reactor (CSTR), even if the Taylor number is adjusted to an optimum value. Also, the effects of operating variables, such as the emulsifier, initiator, and monomer concentrations in the feed and the mean residence time on the kinetic behaviors were almost the same as those observed in a CSTR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2755–2762, 2002     

Continuous polymerization of methyl methacrylate in a taylor‐couette reactor. II. influence of fluid dynamics on polymer properties

In this work, the free radical continuous polymerization of methyl methacrylate (MMA) with the solvent xylene and 2,2‐Azoisobutyronitrile (AIBN) as initiator was studied in a laboratory Taylor‐Couette reactor. It was found that the property of the polymerized product (molecular weight distribution) is affected by the fluid dynamic conditions (mean residence time, rotational speed, diameter of the inner cylinder, and gap width). The weight average molecular weight decreases with an increase of the mean residence time, is strongly dependent on the geometry of the reactor, and was found to be independent on the shear rate in the gap. The width of the molecular weight distribution decreases weakly with increasing residence time, increases with increasing shear rate, and weakly depends on the diameter of the inner cylinder. A correlation was developed to describe the weight‐average molecular weight as a function of the Taylor number and the Damköhler number. This correlation is dimensionless and may be used for scaling‐up purposes. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Polynomial ARMA model identification for a continuous styrene polymerization reactor using on‐line measurements of polymer properties

The multiinput–multioutput identification for a continuous styrene polymerization reactor using a polynomial ARMA model is carried out by both simulation and experiment. The pseudorandom multilevel input signals are applied for model identification in which input variables are the jacket inlet temperature and the feed flow rate, whereas the output variables are the monomer conversion and the weight‐average molecular weight. The use of a polynomial ARMA model for identification of the multivariable polymerization reaction system is validated by simulation study. For the experimental corroboration, correlations are developed to convert the on‐line measurements of density and viscosity of the reaction mixture to the monomer conversion and the weight‐average molecular weight. The on‐line values of the conversion and weight‐average molecular weight turn out to be in good agreement with the off‐line measurements. Despite the complex and nonlinear features of the polymerization reaction system, the polynomial ARMA model is found to satisfactorily describe the dynamic behavior of the polymerization reactor. Therefore, one may apply the polynomial ARMA model to the optimization and control of polymerization reactor systems. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1889–1901, 2000     

Modeling and simulation of an industrial slurry phase ethylene polymerization reactor: effect of reactor operating variables

A hierarchical and computationally efficient mathematical model was developed to explain the polymerization of high-density polyethylene (HDPE) in an isothermal, industrial, continuous stirred tank slurry reactor (CSTR). A modified polymeric multi-grain model (PMGM) was used. Steady-state macroscopic mass balance equations were derived for all species (namely, monomer, solvent, catalyst and polymer) to obtain the final particle size and the required monomer and solvent input rates for a given catalyst input and the reactor residence time. The interphase mass transfer coefficients were calculated for the industrial CSTR using the operating data on the reactor. The present model was tuned with some data on an isothermal industrial reactor and the simulation results were compared with data on another set of industrial reactor. The comparison revealed that the present tuned model is capable of predicting the productivity and the polymer yield at various catalyst feed rates and the mean residence times. The effects of variation of two operating variables (catalyst feed rate and mean residence time) on the productivity, the polymer yield, the polydispersity index (PDI) and the operational safety were analyzed. The present study indicated that an optimal value of the reactor residence time (for maximum productivity per catalyst particle) exists at any catalyst feed rate.

     

Influence of Shear‐Thinning Rheology on the Mixing Dynamics in Taylor‐Couette Flow

Non‐Newtonian rheology can have a significant effect on mixing efficiency, which remains poorly understood. The effect of shear‐thinning rheology in a Taylor‐Couette reactor is studied using a combination of particle image velocimetry and flow visualization. Shear‐thinning is found to alter the critical Reynolds numbers for the formation of Taylor vortices and the higher‐order wavy instability, and is associated with an increase in the axial wavelength. Strong shear‐thinning and weak viscoelasticity can also lead to sudden transitions in wavelength as the Reynolds number is varied. Finally, it is shown that shear‐thinning causes an increase in the mixing time within vortices, due to a reduction in their circulation, but enhances the axial dispersion of fluid in the reactor.     

Emulsion polymerization kinetics and reactor design. IV. Continuous-flow operation with recycling

A new mathematical model with a correction for radical capturing efficiency in a continuous emulsion polymerization with recycle flow has been proposed. These performance equations predict the conversion as well as molecular weight distribution of the polymer product during the continuous-flow operation. Experimental results obtained with vigorous mixing associated with a premixer are in best agreement with the theoretical prediction. In certain situations, the recycling provides a means for obtaining a higher degree of back-mixing with a normal flow reactor. However, it is difficult to obtain a high conversion of monomer by a continuous emulsion polymerization operation even with a long residence time. Theoretical and experimental average degrees of polymerization of polymer leaving the reactor are progressively displaced toward smaller values with greater mean residence time. According to the calculations based on our kinetic model the ratio M?_w/M?_n in the continuous emulsion polymerization remains constant regardless of mean residence time.     

Computational Fluid Dynamics Study of a Styrene Polymerization Reactor

The computational fluid dynamics (CFD) approach was adopted to simulate benzoyl peroxide (BPO)‐initiated styrene polymerization in a laboratory‐scale continuous stirred‐tank reactor (CSTR). The CFD results revealed the effects of non‐homogeneity and the short‐circuiting of the unreacted styrene and initiator on the reactor performance. The study also investigated the effects of the impeller speed and the residence time on the conversion and the flow behavior of the system. The CFD simulation showed that intense mixing remained confined to a small region near the impeller. With increasing impeller speed, it was found that the perfectly mixed region near the impeller expanded, thus reducing non‐homogeneity. Different contours were generated and exhibited the effect of the mixing parameters on the propagation rate and styrene conversion. The monomer and initiator conversions predicted with the CFD model were compared to those obtained with a CSTR model. The CFD model accounts for the non‐ideality behavior of the polymerization reactor, and hence conversion predictions are more realistic.     

Non-Newtonian and non-isothermal analysis of flow during polymerization of methyl methacrylate in a model twin screw extruder. Part II

The flow analysis network (FAN) method was modified to analyze the flow during polymerization of methyl methacrylate (MMA) in a model counter-rotating nonintermeshing screw extruder. The shear viscosity of the reactive mixture in the twin screw extruder was considered as a mixture of polymer and monomer. Thus, the reaction viscosity of the mixture of polymer and monomer was taken to be an explicit function dependent on the shear rate, temperature, conversion, and molecular weight. A new flow path method was developed to calculate the residence time distribution, which related to the degree of conversion. The numerical prediction of the velocity, temperature, viscosity, and pressure profiles during reaction in the model twin screw extruder is described.     

Numerical Simulation of Sterilization Processes for Shear‐Thinning Food in Taylor‐Couette Flow Systems

The performance of the Taylor‐Couette flow apparatus as a heat sterilizer is numerically investigated. The destruction of Clostridium botulinum and thiamine (vitamin B1) was selected as model reaction. When Taylor vortices were formed in the annular space, the heat transfer significantly enhanced as compared to the case without vortex flow. As a result, the equivalent lethality calculated from the temperature field increased, which is regarded as a quantum leap. Conversely, the improvement of heat transfer induced destruction of thiamine. These results suggest that there is a trade‐off relationship between the enhancement of heat transfer and the avoidance of thermal destruction of nutritional components. In conclusion, the Taylor‐Couette flow sterilizer has the potential for process intensification in heat sterilization processes.     

Experimental study and simulation of the polymerization of methyl methacrylate at high temperature in a continuous reactor

The bulk polymerization of MMA at high temperature (120–180°C) in a continuous pilot‐plant reactor has been studied. The polymerization is initiated by diterbutyle peroxide and the chain transfer agent is 1‐butanethiol. A simulation program has been developed to predict the steady state behavior of the reactor. The particular features of the kinetic at above‐T_g temperature are included in the model, especially the thermal initiation of the reation and the attenuation of the autoacceleration effect. For the flow and mixing model, the actual vessel cannot be approximated to a single ideal reactor because of its design and of the moderate agitation imposed by the high viscosity of the reacting fluid. A tanks in series model with a recycle stream between tanks is proposed to evaluate the backmixing caused by the special design of the agitator. The parameters of the model are determined with the help of the experimental residence time distribution measured on the reactor. The data collected on the actual reactor, i.e., operation, conversion, molecular weight, temperature, are compared to the calculated one. The agreement is satisfactory but the tendencies are slightly underestimated. The program is a tool to evaluate the effect of modifications of the design of the reactor or changes on the operation parameters like input rate, temperature, and agitation on its behavior. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2038–2051, 2001     

Increasing PVC suspension polymerization productivity by using temperature‐programmed reactions

Vinyl chloride polymerizations are known to be autoaccelerating. The reaction rate increases with conversion. Because of this phenomenon, substantial reactor productivity at early conversion can be lost because the heat‐removal capacity of the reactor is not fully utilized until near the end of the polymerization. For this reason it is desirable to speed up the polymerization at the beginning and slow it down near the end. This rate adjustment can be achieved by running the polymerization hotter in the beginning and then cooling. We have written a scientifically based computer model of the polymerization designed specifically to simulate such temperature‐programmed reactions. The model does a complete heat balance on the polymerization, has a molecular weight predictor, and will be described and demonstrated for a polymerization at 50°C using sec‐butyl peroxydicarbonate (SBP) as initiator. By using this single initiator and a very simple straight‐line temperature‐programmed reaction, the time to 80% conversion can be reduced from 335 minutes to 240 minutes. This is a substantial increase in productivity.     

Finite volume method as the numerical method for new emulsion polymerization tubular reactor with internal angle baffles

A finite volume method is used to solve a determinist mathematical model and to analyze the performance of an alternative design for an emulsion polymerization reactor with internal angular baffles as static mixer. It is assumed to be a steady‐state, cylindrical one‐dimensional model having a fully developed laminar plug flow. The Smith‐Ewart model is used to estimate the monomer conversion, the kinetics is of Arrhenius type, and laminar finite‐rate model is assumed to compute chemical source terms. The objective of this work is to develop the finite volume method for the new emulsion polymerization tubular reactor with internal angle baffles. The performance of the alternative reactor is compared with continuous tubular reactor with constant reaction temperature. The simulations were validated with experimental results for the isothermal and tubular reactor, with a good concordance. The results with baffles were better than without baffles in relation to desired properties such as particle size and viscosity. The problem is sufficiently well solved by finite volume method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6037–6048, 2006     

Optimal policies for BMA polymerization in nonisothermal batch reactor

In this paper, the optimal policies for bulk polymerization of n‐butyl methacrylate (BMA) are determined in a nonisothermal batch reactor. Four objectives are realized for BMA polymerization based on a detailed process model. The objectives are: (i) maximization of monomer conversion in a specified operation time, (ii) minimization of operation time for a specified, final monomer conversion, (iii) maximization of monomer conversion for a specified, final number average polymer molecular weight, and (iv) maximization of monomer conversion for a specified, final weight average polymer molecular weight. For each objective, the optimal temperature policy of heat‐exchange fluid inside reactor jacket is determined. The temperature of the heat‐exchange fluid is considered as a function of a specified variable. Necessary equations are provided to suitably transform the process model in terms of a specified variable other than time, and to evaluate the elements of Jacobian to help in the accurate solution of the process model. A genetic algorithm‐based optimal control method is applied to realize the objectives. The resulting optimal policies of this application reveal considerable improvements in the batch production of poly(BMA). © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2799–2809, 2006     

Poly(dimethylsiloxane‐b‐styrene) diblock copolymers prepared by reversible addition‐fragmentation chain transfer polymerization: Kinetic model

Well‐defined polydimethylsiloxane‐block‐polystyrene (PDMS‐b‐PS) diblock copolymers were prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization using a functional PDMS‐macro RAFT agent. The RAFT polymerization kinetics was simulated by a mathematical model for the RAFT polymerization in a batch reactor based on the method of moments. The model described molecular weight, monomer conversion, and polydispersity index as a function of polymerization time. Good agreements in the polymerization kinetics were achieved for fitting the kinetic profiles with the developed model. In addition, the model was used to predict the effects of initiator concentration, chain transfer agent concentration, and monomer concentration on the RAFT polymerization kinetics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

低温液相甲醇合成鼓泡浆态反应器数学模拟

建立了经由甲酸甲酯的低温液相甲醇合成鼓泡浆态反应器的数学模型 ,模拟了实验室鼓泡浆态反应器的行为 ,并利用模型考察了工艺参数如表观气速、催化剂浓度对反应的影响 ,对改进和提高低温液相浆态床反应器甲醇合成提供了信息 ,以便对开发低温甲醇合成工艺提供参考和指导     

Experimental investigation of vinyl chloride polymerization at high conversion—reactor dynamics

A series of suspension polymerizations of vinyl chloride monomer (VCM) was carried out in a 5-L pilot plant reactor over the temperature range, 40–70°C. The reactor pressure and monomer conversion were monitored simultaneously every 7–8 min. The critical conversion X_f, at which the liquid monomer phase is consumed, was considered to occur when the reactor pressure fell to 98% of the vapor pressure of VCM for suspension at the polymerization temperature. The reactor model predictions of pressure are in excellent agreement with the experimental data over the entire conversion and temperature ranges studied. The mechanism of reactor pressure development for VCM suspension polymerization is discussed herein in some detail. For isothermal batch polymerization, the reactor pressure falls in two stages due to the effect of polymer particle morphology on pressure drop. The first stage is due to the volume increase of the vapor phase as a result of volume shrinkage due to conversion of monomer to polymer. The monomer phase is not yet consumed at this stage, but it is trapped in the interstices between primary particles creating a mass transfer resistance; therefore, the reactor pressure drops slowly. The second stage is due to both the volume increase of the vapor phase and to the monomer in the vapor phase diffusing into the polymer phase because of the subsaturation condition with respect to monomer in the polymer phase. The reactor pressure drops dramatically with an increase in monomer conversion at this stage. The present model can be used to predict reactor dynamics during suspension polymerization under varying temperature and pressure conditions.     

Experimental validation of the optimal trajectory of initiator concentration in a batch MMA polymerization reactor

This article presents a method to determine the trajectory of initiator concentration that will produce polymer with desired number‐ and weight‐average molecular weights at a prespecified level of monomer conversion. The optimal control theory is applied to the mathematical model for a batch methymethacrylate (MMA) solution polymerization reactor system. By imposing the constraint that initiator concentration should decrease within the range of self‐consumption by the initiation reaction, one can obtain the initiator concentration trajectory that can be tracked by feeding the initiator alone. A control scheme is constructed with a cascade proportional‐integral‐derivative (PID) control algorithm for temperature control and a micropump is installed to manipulate the initiator feed rate. The experimental results show satisfactory tracking control performance despite the nonlinear features of the polymerization reactor system. Also, the monomer conversion and the average molecular weights measured are found to be in fairly good agreement with those of model prediction, respectively. In conclusion, the polymer having desired molecular weight distribution can be produced by operating the batch reactor with the initiator supplement policy calculated from the model. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1256–1266, 2000     

Hexafluoropropylene plasmas: Polymerization rate–reaction parameter relationships

Plasma polymerization generates thin, pinhole-free, and highly adhering films and is often described by the ratio of power to mass flow rate (energy per mass). This research explores the relationships between plasma reactor parameters such as monomer flow rate, plasma power, and reactor pressure and the rates of polymerization, etching, and deposition. The chemical structure of the amorphous, crosslinked plasma polymerized hexafluoropropylene consists largely of similar amounts of C*-CF, CF, CF₂, and CF₃ groups and some C-C groups. A dimensionless plasma parameter (E) proportional to power and inversely proportional to flow rate cubed was derived. E, reflecting both plasma energy and residence time, was used to describe various aspects of the plasma reactions. A dimensionless exponential expression successfully described the dependence of pressure on E with a master curve. An expression for polymerization efficiency (polymer conversion) derived in part through a mass balance was also successfully related to E using an exponential master curve. The rate of deposition was described as the difference between the rates of polymerization and etching. The deposition efficiency maximum and plateau were successfully described by the difference between polymerization and etching efficiencies, each related exponentially to E. The technique used to derive parameters to describe the dependence of plasma reactions on plasma operating conditions can be applied to any monomer/reactor system.