Semibatch anionic ring‐opening polymerization of octamethylcyclotetrasiloxane in emulsions: effect of the amount of seed polymer particles

Semibatch anionic ring‐opening polymerization of octamethylcyclotetrasiloxane with the use of seed polymer particles in emulsions was studied. The concentration of the emulsifier was set above the critical micelle concentration. We investigated the effect of the amount of seed polymer particles on the chemical kinetics and the average particle size and distribution. During monomer starving conditions the polymerization rate strongly depended on the monomer feed rate and not on the amount of seed particles. Throughout the entire monomer feed period the average particle size increased. This increase depended on the number and the size of seed particles. In emulsions with higher particle sizes higher equilibrium conversions were obtained. In our opinion, a greater extent of backbiting reactions is responsible for lower equilibrium conversions during and at the end of the process. The seeded semibatch process seems a reasonable choice for designing emulsion products with high monomer conversion and desired particle size. © 2012 Society of Chemical Industry     

Continuous inverse microemulsion polymerization

The inverse microemulsion polymerization of 2‐methacryloyl oxyethyl trimethyl ammonium chloride (MADQUAT) in a continuous stirred tank reactor is investigated. The effect of removing the oxygen from the feed tank, initiator concentration, aqueous phase volume/emulsifier volume ratio, and residence time on the monomer conversion, particle size, and molecular weight was investigated. The removal of the oxygen allowed high conversions with moderate amounts of initiator to be obtained. In general, the process did not present oscillations. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1341–1348, 1999     

Effect of multiple feeds on a termination-free polymerization in continuous stirred tank reactors

The effect of monomer and initiator feeds to each of a series of continuous stirred tank reactors (CSTR) on the molecular weight distributions, average molecular weight, polymer production rate, and initiator and monomer conversions is studied for the termination-free polymerization system. For initiator feed concentrations less than 0.001 mole/liter, the distribution becomes narrower as the polymer progresses from reactor 1 to reactor 3. But for concentrations of initiator of 0.01 mole/liter, the distribution may be broadened from reactor 1 to reactor 3. The broadening of the distribution results in the production of a lower molecular weight polymer.     

Feasible compositions for random copolymerizations

Using the attainable region approach, feasible compositions and conversions for random copolymers are determined, along with altermatives for the related reactor configurations. This analysis attempts to find all of the possible compositions that can be produced by any system of reactros and mixing. The average copolymer compositions are bounded by the feed composition and the instantaneous copolymer composition produced at the initial conditions. Since the instantaneous copolymer composition can be found through the Mayo‐Lewis equation, that case and the feed composition mark the limiting feasible compositions. The results can also be used to determine the range of feed compositions for which a specific copolymer product composition is possible. If the addition of monomer at any point in the reactor system is possible, e.g., by side‐feeding, the analysis indicates that any desired copolymer composition can be obtained.     

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.

     

Dynamic behaviour of a continuous-flow polymerisation reactor

The polymerisation of a vinyl monomer, which is promoted by an added free-radical generator, is considered. When the polymerisation occurs in a continuous-flow reactor, the dynamic behavior of the reactor is shown to depend on the generator concentration. Reactor stability can depend on the start-up procedure. In the case of styrene polymerisation, start-up procedures which are safe when initiation is purely thermal may be unsafe when a generator is present. The importance of small changes in physical properties of the reaction fluid is demonstrated and the behavior of monomers other than styrene is discussed.     

Modeling of molecular weights in industrial autoclave reactors for high pressure polymerization of ethylene and ethylene‐vinyl acetate

We have incorporated mass balances of monomer, radical and polymer species to a previously developed mixing model for high pressure autoclave polymerization reactors. The customary quasi steady state approximation is not used, and the method of moments is used to simplify the mass balance calculations. The resulting moment model is able to calculate conversions, average molecular weights, long chain branching and melt flow indexes at any point in the reactor. It may also calculate concentration and temperature profiles along the reactor. Results for two base cases are presented in detail. Model predictions were compared with experimental data obtained at the industrial reactor; excellent agreement was obtained. The moment balance equations are presented in a modular way so that they may be easily adapted to be used with any other mixing model for this type of reactor.     

Operation of semi-batch emulsion polymerisation reactors: Modelling, validation and effect of operating conditions

A detailed dynamic model was developed for a styrene emulsion polymerisation semi-batch reactor to predict the evolution of the product particle size distribution (PSD) and molecular weight distribution (MWD) over the entire range of monomer conversion. A system exhibiting zero-one kinetics was employed, with the model comprising a set of rigorously developed population balance equations to predict monomer conversion, PSD and MWD. The modelling equations included diffusion-controlled kinetics at high monomer conversion where the transition from the zero-one regime to a pseudo-bulk regime occurs. The model predictions were found to be in good agreement with experimental results. Both particle growth and the PSD were found to be strongly affected by the monomer feedrate. Reactor temperature had a major influence on the MWD which was, however, insensitive to changes in the monomer feedrate. These findings were confirmed experimentally. As a result, it seems reasonable to propose that the use of the monomer feedrate to control the PSD and the reactor temperature to control the MWD are appropriate in practical situations. Consequently, an optimal monomer feed trajectory was developed off-line (using the validated reactor simulation) and verified experimentally by producing a polymer with specific PSD characteristics.     

Anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion above critical micelle concentration

Batch anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion using nonionic and cationic emulsifiers was studied. The concentration of emulsifiers was set above their critical micelle concentration. Effects of emulsifier concentration, nonionic/cationic emulsifier ratio and cationic emulsifier/initiator (KOH) ratio on the kinetics, average particle size and distribution and on the average molecular weight and distribution were investigated and discussed. At the beginning of the polymerization, empty micelles, active micelles (polymer particles) and monomer droplets co-exist in emulsion. The transport of monomer from monomer droplets toward empty micelles was confirmed by monomer droplets and empty micelles disappearance and by formation of smaller particles. The transport of monomer from monomer droplets toward polymer particles was not confirmed, since the average polymer particle size did not increase during polymerization. It was proposed, that at lower conversions, monomer diffuses from polymer particle interior to particle surface, while at higher conversions, the monomer diffuses from larger to smaller polymer particles. Emulsifier concentration, nonionic/cationic emulsifier ratio and cationic emulsifier/KOH ratio have an evident effect on the kinetics and on the average molecular weight, thus demonstrating that cationic emulsifier participates to the initiation reaction.     

Suspension,bulk, and emulsion polymerization of vinyl chloride—mechanism,kinetics, and reactor modelling

A review of relevant microscopic processes, both chemical and physical, which occur during suspension, bulk and emulsion polymerization (both before and after pressure drop) is given. The state of the art of kinetic modelling of monomer consumption rate, reactor pressure, molecular weight and short and long chain branching development and polymer chain microstructure is illustrated. The effects of diffusion-controlled termination and propagation reactions and the significant decrease in initiator efficiency and decomposition rate constant at high monomer conversions on the relative rates of various chemical reactions are discussed. The application of temperature programming and semibatch operation are emphasized. Finally, attempts to model polymer particle morphology are described.     

Simulation of nylon 6 polymerization in tubular reactors with recycle

In the hydrolytic polymerization of ?-caprolactam, the ring opening of the monomer is much slower than the polyaddition reaction. Hence, the mixing of aminocaproic acid to the feed results in a faster conversion of the monomer. Industrially, this fact is exploited by using a recycle stream. An isothermal plug flow reactor (PFR) with a recycle is simulated in this study, using two techniques: the method of successive substitutions and Wegstein's method. It is found that, under certain operating conditions, the use of a recycle stream gives higher monomer conversions and lower cyclic dimer concentrations than either a PFR or a homogeneous continuous-flow stirred-tank reactor (HCSTR), with the degree of polymerization almost the same as that obtained in an HCSTR, and thus offers a considerable advantage. However, when a recycle reactor is coupled with a subsequent flashing operation and a finishing reactor, these advantages are considerably reduced.     

Advanced modelling and optimal operating strategy in emulsion copolymerization: Application to styrene/MMA system

A model-based framework for advanced optimal operation of copolymerization processes was developed and tested experimentally in conjunction with a distributed control system (DCS) suitable for industrial application. A test case of emulsion copolymerization of styrene (Sty) and methyl-methacrylate (MMA) was investigated for predicting and optimizing key product properties including molecular weight distribution (MWD), particle size distribution (PSD), copolymer composition and conversion. The model equations include diffusion-controlled kinetics at high monomer conversions, where transition from a ‘zero-one’ to a ‘pseudo-bulk’ regime occurs. The reactor mass and energy balances describe the system transients for batch and semi-batch operations. Population balance equations, describe the particle evolution and comprise sets of integro-partial differential and nonlinear algebraic equations. The models were solved using an efficient numerical scheme suitable for on-line monitoring and control. The model predictions were found to be in good agreement with experimental results for measurements carried out with variable monomer feed rates, variable temperature and variable composition of styrene-MMA, from 25/75 to 75/25 proportions. The manipulation of these variables was found to affect the PSD significantly. The experimental results confirmed the accuracy of our optimization scheme for the desired conversion, MWD and PSD.     

Semibatch anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion

The semibatch anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion was studied under the condition of no seed particles used in polymerization system. Concentration of emulsifier was set above critical micelle concentration. Effect of monomer feed rate on the chemical kinetics, average particle size and distribution and on the polymer molar mass and distribution was investigated. During monomer addition, polymerization rate was constant and controlled by the monomer feed rate. According to the proposed mechanism for anionic polymerization in emulsion, it was assumed that also the number of active polymerization sites and monomer concentration at the particle surface, where propagation occurs, remain constant. A continuous increase of average particle size and absence of extensive condensation reactions at high conversion suggested that the freshly added monomer diffuses toward hydrophobic polymer particles, where it is consumed in propagation reaction and/or accumulated in the particle core.     

Coal hydrogenation: Quality of start-up solvents and partially process-derived recycle solvents

The performance of three sets of start-up solvents and one set of partially process-derived recycle solvents was studied in small autoclave coal hydrogenation tests. The start-up solvents were obtained by catalytically hydrotreating anthracene oils or creosote oils. It is shown that this preparation procedure converts polynuclear aromatics and two-ring aromatics to hydroaromatics and, ultimately, to alicyclics. Coal conversions using start-up solvents are found to reach a maximum at intermediate degrees of solvent hydrogenation which is believed to correspond to a maximal abundance of hydroaromatic solvent hydrogen donors. A solvent hydrogen donor index (SHDI), simply derived from ¹H n.m.r. spectral data, was devised and is found to successfully correlate coal conversions obtained using different start-up solvents, especially where N₂ gas rather than H₂ gas is employed in the autoclave tests. A set of partially process-derived recycle solvents were produced in multiple cycle continuous coal hydrogenation experiments. These were tested under relatively severe hydrogenation conditions in the presence of hydrogen gas, using the small autoclave unit. Substantial donation of solvent hydrogen was found to occur and coal conversions to hexane — and toluene-soluble products are found to be a smooth function of the solvent hydrogen donor index. It is concluded that the hydrogen donor capacity of a solvent is a major factor governing coal conversion, especially when the demand for solvent hydrogen is high. The SHDI parameter is useful in rationalizing the behaviour of start-up solvents. Also, at least in the first few cycles of a continuous two stage coal hydrogenation process, the SHDI parameter allows solvent quality to be monitored, and consequently optimized.     

Study on the enzymatic hydrolysis of racemic methyl ibuprofen ester

The hydrolysis of racemic methyl ibuprofen ester in the presence of lipase from Candida rugosa was investigated in shake flasks. Experiments were performed to study the effect of temperature, pH and shaking speed on the reaction rate. Different hydrophobic co‐solvents were screened for the highest reaction rate and the presence of enzyme inhibition by substrate and products was examined. A kinetic expression was then proposed to describe the reaction. Kinetic parameters were determined for the optimum operating conditions and the proposed model was verified with the experimental results. Next, this reaction was scaled up to a fed batch stirred tank reactor. Batch reactor and fed batch reactor configurations were compared for better conversions. The effects of aqueous phase hold‐up, substrate concentration and feed flow rate on the conversion of the reaction were also studied. Higher conversions were obtained in a fed batch reactor when compared with the batch reactor. In the fed batch reactor, increased conversions were observed with lower feed flowrates and high aqueous phase hold‐up. © 2001 Society of Chemical Industry     

Modeling the effects of micromixing and start-up procedures on bulk copolymerization and copolymer in a tubular reactor

The combined effects of micromixing and start-up procedures on free radical, bulk copolymerization of styrene and acrylonitrile in an isothermal, premixed-feed tubular reactor have been theoretically analyzed. An axial dispersion model, which takes into account the entire range of backmixing, froms the basis of this analysis. Model predictions show that the overall conversion decreases with the increase of initial styrene content in the reactor, and is not affected by the degree of micromixing. However, for the nonazeotropic feed, the copolymer composition distribution becomes wider with the increase of initial acrylonitrile content in the reactor. For the azeotropic feed, broadening occurs with the decrease of initial acrylonitrile content in the reactor. Average copolymer composition is not affected either by micromixing or start-up procedure.     

Operating strategies for Fischer-Tropsch reactors: A model-directed study

A comprehensive parametric study for a Fischer-Tropsch (FT) synthesis process has been conducted to investigate the relation between process parameters and reactor characteristics such as conversion, selectivity, multiplicity, and stability. A flexible model was employed for this purpose, featuring the dependence of Anderson-Shultz-Flory (ASF) factor on composition and temperature. All variable process parameters in industrial FT reactors were subject to variation, including reaction temperature, reactor pressure, feed ratio, inlet mass flux, feed temperature, heat transfer coefficient, catalyst concentration, catalyst activity, etc. While typical trade-off was encountered in most cases, i.e., the change of a parameter in one direction enhances one aspect but deteriorating another, the change of feed conditions gave some promising results. It has been found that decreasing the feed rate (or increasing the residence time) and/or lowering the feed concentration can successfully enhance the conversion up to more than 90% for our specific case, without hurting the product selectivity as well as effectively condense the region of multiple steady states. The benefits and limitations accompanied with the variation of the parameters were discussed in detail and a rational start-up strategy was proposed based on the preceding results. It is shown that the decrease of inlet mass flux (say, 85% decrease of the feed rate or 60% decrease of the feed concentration from the nominal condition chosen here) or the decrease of H₂/CO ratio (specifically, below about 0.25), or their combination can eliminate multiple steady states. The resulting unique relation between temperature and manipulated variable (i.e., coolant flow rate) appears to assure a safe arrival at the target condition at the start-up stage. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

START-UP TIME IN TUBULAR REACTORS WITH AXIAL DISPERSION

In the modeling of nonideal reactors the axial dispersion model is one of the most used (Butt, 1980). Boundary conditions for a tubular reactor with axial dispersion were extensively analyzed (Danckwerts, 1953, Wehner and Wilhelm, 1965, Van Cauwen-berghe, 1966, Choi and Perlmutter, 1976, Deckwer and Mahlmann, 1976) Similarly, the steady state behaviour of the reactor when simple or complex reactions take place was also studied by several authors (Deckwer et al. 1972, Wan and Ziegler, 1973). However, the transient behaviour was only analyzed for simple kinetics expressions (Fan and Ahn, 1963, Sawinsky artd Hunek, 1977, Godslave and Chang, 1980)

In the present work, the time necessary to reach the steady state or start-up time is determined for single and complex reversible reactions. The analysis presented is also valid in case there is a change in feed concentration (feed upset, etc.)     

Analysis and performance of a countercurrent moving-bed chromatographic reactor

A theoretical and experimental investigation of a countercurrent moving-bed chromatographic reactor is the subject of this paper. In this reactor a reversible heterogeneous reaction takes place on catalyst particles passing downward through an upcoming gas stream. The behaviour of an ideal reactor model was examined for different values of feed concentrations and reactor length. It is predicted that reaction and separation can be achieved simultaneously and that under appropriate operating conditions, a reactor fed at the bottom with the species more favoured by thermodynamic equilibrium can lead to 100% product purity with overall conversions lower than a conventional fixed bed reactor. The effect of nonidealities on the reactor performance is also discussed. Finite adsorption and axial dispersion have a generally deteriorating effect on overall conversion and product purity. An improved reactor configuration with a bottom stripping section is suggested. Its operating conditions can be tailored so that predicted performance exceeds that of a fixed bed both in yield and product purity. The hydrogenation of mesitylene with excess hydrogen over a Pt on alumina catalyst was used for an experimental investigation of the reactor. The experiments, performed in a 1/2″ i.d., 7′ long column, resulted in products of higher purity than the equilibrium prediction, and overall conversions comparable to a fixed bed reactor.     

Dynamics and stability of ethylene polymerization in multizone circulating reactors

Multizone circulating bed reactors (MZCR) have the exclusive characteristics of producing polymers of different molecular weights in a single particle. Traditional fluidized bed reactors, on the other hand, can produce only one kind of molecular weight with relatively narrow distribution. A dynamic model for the MZCR is used to illustrate the basic dynamic behavior of the new reactor design used for polyethylene production. The model is used to study the copolymerization of ethylene with butene. Several parameter sensitivity analyses are performed to show the computer-simulated time responses for reactor temperature, number-average molecular weight, weight-average molecular weight, catalyst feed rate and the monomer/comonomer concentration along the reactor length. At certain operating conditions dynamic instability is observed and the results for the effect of cooling water temperature, catalyst feed rate, monomer and comonomer initial feed concentration on the reactor temperature and polymer molecular weight reveal that the system is very sensitive to disturbances in the heat exchanger coolant temperature. Also, at some operating conditions, the reactor temperature oscillates above the polymer melting temperature. Temperature runaway above polymer softening point is a serious problem which may cause polymer melting and hence reactor shutdown. The oscillatory behavior of the reactor temperature necessitates a suitable temperature control scheme to be installed.