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 free-radical polymerization of styrene in the stirred tank reactor. Effect of inhibitors

The influence of inhibitors (p-benzoquinone) on the conversion and the molecular weight distribution (MWD) during free radical polymerization (AIBN) of styrene was examined. A continuous stirred tank reactor (CSTR) was used for the experiments. The concentration of the inhibitor and initiator, the mean residence time and the reaction temperature were modified. The measurement of the residence time distribution (macroscopic mixing) and the estimation of the segregation number showed an ideal mixing behaviour (HCSTR). The conversion and the MWD were calculated. As the results show, it is possible to calculate the reaction in a HCSTR by only using the kinetic constants measured in discontinuous runs.     

Experimental study and model simulation of a two-stage continuous polymerization process for polystyrene

Free radical solution polymerization of styrene in two stage polymerization process has been studied using a binary mixture of symmetrical bifunctional initiators. The continuous reactor system was composed of two reactor units; a prepolymerization reactor (e.g. stirred tank reactors) and a filled tubular reactor packed with static mixers. When the stirred tank reactor was used as a prepolymerizer, a feed stream to the filled tubular reactor was more viscous than the monomer/solvent mixture. It was of interest to investigate how the performance of the filled tubular reactor has been investigated by the feed of viscous prepolymer solution. A dynamic model of the continuous two stage polymerization process was presented by experimental data and model simulation. A reasonably good agreement between the model and the experimental data was obtained without using any adjustable parameters. The experimental results of the two stage polymerization were compared with the results without prepolymerization reactor. It was found that the addition of a prepolymerization reactor has almost no effect on the performance of the filled tubular reactor.     

Non-linear bifurcation analysis of the living nitroxide-mediated radical polymerization of styrene in a CSTR

In this paper, the non-linear behavior of the styrene nitroxide-mediated radical polymerization (NMRP) taking place in a continuous stirred tank reactor (CSTR) is studied. The cooling water flow rate, feed stream temperature, cooling water feed temperature, monomer feed stream concentration and residence time were chosen as the bifurcation parameters. Typical hysteresis behavior was found for this reactor, making necessary the use of a control scheme to operate in potential regions of interest. Input multiplicities, as well as disjoint bifurcations and isola behavior were found, making the reactor to be prone to operability and control problems.     

Saccharification of bagasse using a counter-current plug-flow reactor

A method for the simulation of a 3-stage counter-current plug-flow reactor (PFR) for the enzymic Saccharification of alkali-treated (a.t.) sugar cane bagasse is described. The PFR gave higher conversion than a conventional stirred-tank reactor (STR). The STR achieved 44.3% conversion while the PFR achieved 56.4% conversion using 11 % a.t. bagasse after 48 h. The PFR offers potential for more efficient mass transfer and enzyme utilisation, and reduced end product inhibition.     

Minimum tank volumes for CFST bioreactors in series

The primary reactor type currently used in the production of microorganisms or microbial products is the stirred tank reactor (STR). If operated on a continuous flow basis (CFSTR) they become similar in performance to the primary reactor configuration used in most of the chemical industry. In this work, microbial kinetics are considered in the design of CFSTRs in series. An equation is derived to predict the minimum possible total residence time to achieve any desired substrate conversion. The equation permits the use of a wide variety of growth kinetic models and is applied here to Monod, substrate inhibition and product inhibition cases. For the majority of cases, it is found that three optimally designed CFSTRs in series provide close to the minimum possible residence time for any desired substrate conversion. A comparison to the use of a PFR is made for cases of both no-recycle and biomass recycle to the CFSTR train. It is found that three CFSTRs, which are not equi-volume, provide the same required total mean residence time as a PFR for Monod kinetics, but are significantly superior (i.e., less total volume required) to a PFR for substrate-inhibited growth.     

Analysis of reactive trace contaminants in styrene by GC/MS

Summary The purity of the styrene monomer is critical since impurities influence the physical properties and appearance of the final polymerized product. It is particularly important to assess the content of the monomer for oxygenated compounds. In this study, two typical monomers were studied. One sample consisted of a one month old monomer that had been exposed to air. The other monomer was a recycle feedstock taken from a continuous polymerization reactor. Analysis was carried out by capillary column gas chromatography/mass spectrometry.In addition to dimers and trimers that have been reported in the literature, the presence of several classes of oxygenated impurities was established for the first time.     

Modelling of condensation polymerization of novolac-type phenol–formaldehyde in homogeneous,continuous-flow,stirred-tank reactors

A detailed kinetic model for the novolac-type phenol–formaldehyde polymerization has been proposed in terms of five reactive sites. These sites have been shown to have different reactivities. Mass-balance equations for homogeneous, continuous-flow, stirred tank reactors (HCSTR) for each of the species have been written, and these have been solved numerically. A comparison of the results with those for the batch reactor shows that, for a given residence time, smaller but more polydispersed and branched chains are formed.     

Die maximal durchmischte Zwillingsschlaufe. Ein erweitertes Schlaufenmodell für isotherme,homogene reaktionen

The total range of reactor performance, that is between the PFR and the whole reactor volume being a stagnant zone, may be represented by the three parameter twin loop model. The two basic assumptions made in the model—plug-flow with no longitudinal mixing in each loop, as well as immediate mixing of the two recycling streams and the inflow on the molecular scale (maximum mixedness)—are fairly well achieved in large-scale reactors. Consequently, such reactors are easy to calculate without scale-up problems. At constant mean residence time the three parameters—total recycle number, partial recycle number, ratio of recycle times—can be varied independently. Thus, the twin loop is rather adaptable and easy to control.     

Simulation of reversible nylon-66 polymerization in homogeneous continuous-flow stirred tank reactors

Experimental data of Ogata¹ has been curve-fitted to obtain the forward and reverse rate constants for nylon-66 polymerization. Its molecular weight distribution (MWD) has been simulated in homogeneous continuous-flow stirred tank reactors (HCSTR) for 11 h of residence time when the reaction mass is very close to equilibrium. The set of algebraic equations have been solved using Brown's algorithm,² which was found to be more efficient compared to the Gauss-Jordon techniques of solution. The MWD thus obtained is compared with our earlier simulation of the molecular weight distribution from batch reactors³ and was found to differ significantly. In HCSTR, the weight fraction distribution does not undergo a maximum and the polydispersity index ρ of the polymer formed is much higher than that obtained from batch reactors. The number and weight average of the polymer formed in HCSTR is found to be significantly lower.     

Differentiation criteria study for continuous stirred tank reactor and plug flow reactor

All reactors in reality are not ideal plug flow reactor (PFR) or ideal continuous stirred tank reactor (CSTR). They are difficult to differentiate. This study was to investigate the reactor analysis of PFR and CSTR through tracer response curves, residence time distributions (RTD) and several hydraulic performance indexes. We set up the differentiated value of each index. The tracer response curve showed that our lab-scale CSTR was close to ideal CSTR and got 99.9% recovery. In the RTD curves, the results could significantly recognize the PFR nature of high rate pond (HRP). With hydraulic performance indexes study, every selected index demonstrated that the studied HRP was closer to PFR than the studied CSTR. Based on the lab-scale study results, this study established the cutting point between the PFR and CSTR in each index; we were looking through the different types of reactors in literature and we confirmed the criteria with all literature reactors with the “graphic method”. The method helped us to establish those important values to help us to differentiate the reactor types in practice and to understand the designs better.     

In-line dielectric monitoring of monomer conversion in a batch polymerization reactor

In-line monitoring of monomer conversion is studied using a low-frequency dielectric sensor during solution polymerization of methyl methacrylate in a laboratory-scale batch reactor. It has been found that the induction period due to the presence of an inhibitor can be determined by the dielectric sensor to detect the starting point of polymerization. The dielectric loss factor that changes with the progress of polymerization is empirically correlated with monomer conversion measured by the off-line gravimetric method at different temperatures and initiator concentrations. It is demonstrated that dielectrometry can be used as an in-line monitoring method in free-radical polymerization. © 1995 John Wiley & Sons, Inc.     

The process design and simulation for the methanol production on the FPSO (floating production,storage and off-loading) system

A process for methanol production from 100 MM scfd of stranded gas and CO₂ is proposed and simulated using a commercial process simulator, PRO/II v.9.1, for a FPSO (floating production, storage, off-loading) system. The process consists of Steam-CO₂ Reforming (SCR), methanol synthesis, a Reverse Water-Gas Shift (RWGS) reaction and ancillaries with recycle streams to SCR and RWGS. All reactors were simulated using the Gibbs reactor model. Also, the Plug Flow Reactor (PFR) model with reaction rate equations was used for the methanol reactor and the result was compared to the Gibbs reactor model. To maximize the use of the carbon source in stranded gas and CO₂ while avoiding an undesirable increase in process size, the optimum recycle ratios were calculated with a satisfying constraint, a steam-to-carbon ratio ≥ 1 in the SCR. In the proposed Methanol-FPSO process the RWGS reactor can maximize CO₂ utilization and case studies were performed to analyze the influence of RWGS.     

An efficient algorithm of computation of molecular weight distributions and its moments for reversible step growth polymerization in homogeneous continuous flow stirred tank reactors

The reversible step growth polymerization in homogeneous continuous flow stirred tank reactors (HCSTRs), in which the condensation product (W) leaves the reactor through flashing, has been analyzed. The molecular weight distribution (MWD) of the polymer formed is governed by nonlinear coupled algebraic relations to be solved simultaneously. To find the MWD numerically a large number of these are normally solved simultaneously using a suitable iterative procedure. In this paper, these have been decoupled using the technique proposed in our earlier works (1, 2) and the MWD can now be obtained sequentially without any trial and error. This leads to considerable saving in computation time compared to methods currently used. To demonstrate the efficacy of the algorithm, the polycondensation step of the poly(ethylene terephthal-ate) (PET) formed in HCSTRs has been analyzed. The MWD, the average chain length and the polydispersity index of the polymer have been computed and it takes 0.1 CPU seconds on a DEC 1090 as opposed to the earlier method which would take seventy minutes for similar computations. The simple model of the HCSTR for the PET formation gives the effect of reactor temperature and pressure and the quantitative results have been presented in this paper.     

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.     

State multiplicity in PFR-separator-recycle polymerization systems

This article explores the non-linear behaviour of isothermal and non-isothermal plug-flow reactor (PFR)-separator-recycle systems, with reference to radical polymerization. The steady-state behaviour of six reaction systems of increasing complexity, from one-reactant first-order reaction to chain-growth polymerization, is investigated. In PFR-separator-recycle systems feasible steady states exist only if the reactor volume exceeds a critical value. For one-reaction systems, one stable steady state is born at a transcritical bifurcation. In case of consecutive-reaction systems, including polymerization, a fold bifurcation can lead to two feasible steady states. The transcritical bifurcation is destroyed when two reactants are involved. In addition, the thermal effects also introduce state multiplicity. When multiple steady states exist, the instability of the low-conversion branch sets a lower limit on the conversion achievable at a stable operating point. A low-density polyethylene process is presented as a real plant example.The results obtained in this study are similar to CSTR-separator-recycle systems. This suggests that the behaviour is dictated by the chemical reaction and flowsheet structure, rather than by the reactor type.     

Continuous tube-CSTR reactor system for emulsion polymerization kinetic studies

A plug-flow tubular reactor (PFT) was used to generate a latex feed stream for a CSTR. Measurements of monomer conversion, particle number, particle size distribution and molecular weight distribution in the effluent streams of both reactors were used to study transport of free radicals and chain transfer agents in the emulsion polymerization of styrene.     

Application of hydrogen-permselective Pd-based membrane in an industrial single-type methanol reactor in the presence of catalyst deactivation

This work presents application of palladium-based membranes in a conventional single-type methanol reactor. A novel reactor configuration with hydrogen-permselective Pd and Pd–Ag membrane are proposed. In this configuration the reacting synthesis gas is fed to the shell side of reactor while the high pressure product is routed from recycle stream through tubes of the reactor in a co-current mode with reacting gas. The reacting gas is cooled simultaneously with recycle gas in tube and saturated water in outer shell. The permselective palladium layer on inner tube allows hydrogen to penetrate from the tube side to the reaction side. In this work, the results of two types of novel membrane reactors are compared with a conventional methanol synthesis reactor at identical process conditions. Also the effect of key parameters such as membrane thickness, reaction and tube side pressure, ratio of tube side flow rate to reaction side flow rate on performance of reactor are investigated. The steady-state and quasi-steady-state simulations results show that there are favorable profiles of temperature and methanol mole fraction along the reactor in proposed reactor relative to conventional reactor system. Therefore using this novel configuration in industrial single-type methanol reactor improves methanol production rate.     

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.     

New concepts for the design of mass polymerization reactors

A novel reactor arrangement for the anionic polymerization of styrene described in this paper comprises alternating adiabatically operated plug-flow reactors and heat exchangers. A novel tube-bundle recycle reactor is presented for the bulk polymerization of styrene and acrylonitrile.