Integration of CFD and polymerization for an industrial scale cis-polybutadiene reactor

A computational fluid dynamics (CFD) approach, coupled with anionic polymerization kinetics, was used to investigate the solution polymerization in a 12?m³ industrial scale cis-polybutadiene reactor. The kinetic model with double catalytic active sites was integrated with CFD by a user-defined function. The coupled model was successfully validated by the plant data and then used to investigate the key operating variables. Also, predictions of CFD model were compared with those of continuous stirred tank reactor (CSTR) model. Although the reaction mixture is well mixed in the middle and at the top of the reactor, there exists a poor mixing feeding zone at the bottom, which leads to serious deviations from the ideal CSTR. The polymerization process with nonideal mixing is very sensitive to the inlet temperature and the feeding rate. Enhancing the mixing performance in the feeding zone could be an effective way to improve the product quality.     

Mass transfer in emulsion polymerization: An experimental and modelling study

A model is proposed to describe the impact of interphase monomer transfer on the emulsion polymerization of vinylidene fluoride (VDF). The model is validated with experimental data of the rate of polymerization and particle size distribution (PSD). During a typical emulsion polymerization process, the VDF monomer is in a gas or supercritical state, and thus much lighter than the aqueous phase in which the polymerization takes place. For this reason, the flux of monomer into the aqueous phase can depend on the type, number, and distribution of agitators on the shaft, as well as the rotation rate. The new model incorporates the interphase mass transfer coefficient into a standard emulsion polymerization model to demonstrate the impact of the agitation (in the broadest sense) on the rate of polymerization and the PSD.     

Synthesis of submicron barium carbonate using a high-gravity technique

The purpose of this study was to build a platform for producing fine particles by applying a high-gravity (higee) technique to achieve reactive precipitation. Barium carbonate was chosen as a model compound and was produced in a spinning disk reactor (SDR), which is one type of higee equipment, via a carbonation route and a once-through mode. For size measurement, a suitable dispersion method was developed to obtain reproducible particle size data, using a laser-light analyzer. Several factors that affected the particle size of barium carbonate, including the CO₂ flow rate, the feed rate of Ba(OH)₂ slurry, the rotation speed, and the solid-content of feed slurry, were investigated. A high rotating speed and low feeding rate of slurry yielded small particles. The optimum solid-content of feeding slurry for obtaining small particles was also determined. However, the effect of the CO₂ flow rate on the particle size of the product was not significant.     

Pressurised flash drying of Yallourn lignite

A previously developed 1D model of lignite drying for pulverised lignite feeding into a conventional pulverised fuel boiler during the coal milling process is applied to lignite in an entrained flow configuration at elevated pressure. A combustor fired with diesel and air was used to produce a flue gas at 800 °C and 10 atm to flash dry Yallourn lignite at a nominal feed rate of 725 kg/h along a 50 m duct. A coal feeder arrangement was also developed which provides a simple positive feeding device for feeding against a back pressure. The feeder takes as an input coal which is nominally <50 mm and discharges it as a finely divided product with a mean particle size of approximately 1.0-1.5 mm. The comparison between model predictions and measured temperature profiles for the flue gas and final moisture content of the dried coal product showed excellent agreement. Coal moisture was reduced from 67 wt% to between 30 and 40 wt%, depending upon on the coal feed rate and particle size. The small variation in the final outlet temperature observed between the model and experimental results is due to heat losses from the exposed duct work to the environment.     

Online polymer molecular weight and conversion monitoring via calorimetric measurements in RAFT emulsion polymerization

BACKGROUND: Online measurements of key emulsion polymerization attributes, such as conversion and molar mass distribution, are unavailable. Costly offline measurements at low sampling frequencies with time delays usually lead to insurmountable challenges in real‐time product quality monitoring and process/product control. RESULTS: We developed an online calorimetric method monitoring the evolution of conversion and molecular weight in complex polymerization reactors. Our experiments were carried out in a 1 L reactor to produce polystyrene homopolymer. Monomer conversion was obtained in real time from polymerization rate, which was estimated from temperature measurements using platinum thermal transducers. The calorimetric model was validated offline for batch and semi‐batch emulsion polymerization of styrene with and without transfer agents. The conversion was validated using offline gravimetry. The molecular weights measured offline via size exclusion chromatography with multiple detectors compared well with those estimated online using the calorimetric method. CONCLUSION: We found that a semi‐batch emulsion polymerization process can be controlled online to approach living polymerization involving transfer agents. Thus our model is suitable as a ‘soft‐sensor’ for real‐time control applications. Copyright © 2009 Society of Chemical Industry     

Study of different types of monomer emulsion feedings to semibatch emulsion polymerization reactors

Semibatch emulsion polymerization processes with a monomer emulsion feed are of great importance in both academia and industry. Monomer emulsion feeds can be applied to semibatch reactors using either a stream of an emulsified monomer or two streams of a neat monomer feed and an aqueous solution of an emulsifier. The effect of the feeding policy on the rate of polymerization and on the secondary particle formation was studied for a seeded semibatch emulsion polymerization of styrene. When a single-stream monomer emulsion feed is applied to a semibatch process, the monomer-swollen micelles formed in the feed might become the locus of initiation upon entering the reaction vessel. Under the conditions of this study, the application of monomer emulsion feed in either one stream or two streams did not result in secondary particle formation. The incoming monomer-swollen micelles were disintegrated to supply emulsifier molecules for the stability of growing particles, before they can capture radicals and become polymer particles. The rate of polymerization was found to be independent of the way that the monomer emulsion feed is added. In the absence of nitrogen, the rate of polymerization decreased more appreciably for the monomer emulsion feed, due to the oxygen dissolved in the emulsified monomer. The number of particles, however, was not affected by the purging policy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2472–2477, 2001     

Preparation of polystyrene/poly(methyl methacrylate) core‐shell composite particles by suspension‐emulsion combined polymerization

Suspension‐emulsion combined polymerization process, in which methyl methacrylate (MMA) emulsion polymerization constituents (EPC) were drop wise added to styrene (St) suspension polymerization system, was applied to prepare polystyrene/poly(methyl methacrylate) (PS/PMMA) composite particles. The influences of the feeding condition and the composition of EPC on the particle feature of the resulting composite polymer particles were investigated. It was found that PS/PMMA core‐shell composite particles with a narrow particle size distribution and a great size would be formed when the EPC was added at the viscous energy dominated particle formation stage of St suspension polymerization with a suitable feeding rate, whereas St‐MMA copolymer particles or PS/PMMA composite particles with imperfect core‐shell structure would be formed when the EPC was added at the earlier or later stage of St suspension polymerization, respectively. It was also showed that the EPC composition affected the composite particles formation process. The individual latex particles would exist in the final product when the concentrations of MMA monomer, sodium dodecyl sulfate emulsifier, and potassium persulfate initiator were great in the EPC. Considering the feature of St suspension polymerization and the morphology of PS/PMMA composite particles, the formation mechanism of PS/PMMA particles with core‐shell structure was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Experimental Validation of the Explicit Radical-Particle Size Distribution Approach for Modeling Emulsion Polymerization: The Seeded Emulsion Polymerization of Styrene

Abstract:

The objective of the present paper is to demonstrate that the explicit radical-particle size distribution approach correctly predicts the effect of compartmentalization on the overall reaction rates and therefore chain length averages. Modeling results for the seeded emulsion polymerization of styrene were compared with experimental results. Several experiments were carried out with systematically varied compartmentalization of radicals by varying seed latex particle numbers and the amount of initiator. The overall polymerization rate was measured using reaction calorimetry and the final particle size distribution was measured using Transmission Electron Microscopy. The results demonstrated that the model is able to predict successfully the rate of polymerization and particle size distributions as a function of time for all recipes. This proves that the model deals correctly with the effect of compartmentalization on overall reaction rates and thus on chain length averages. The work described in this paper demonstrates that the explicit radical particle size distribution approach is a powerful method for predicting emulsion polymerization kinetics and product properties, such as particle size distributions and chain length distributions.     

Combined single particle growth and population balance modeling in stereoregular polymerization of styrene

Modeling and experimental analysis for syndiospecific polymerization of styrene over silica-supported metallocene catalyst was carried out. A detail model was developed by coupling the single particle growth model (PGM) with particle population balance equation. The model was employed to predict the effects of intraparticle mass transfer limitations and the initial catalyst particle size on the rate of polymerization and the particle size distribution (PSD) of syndiotactic polystyrene (sPS). The single PGM, based on a modified polymeric multigrain model, was first utilized to calculate the single particle growth rate and polymerization rate under intraparticle mass transfer limitations and different initial catalyst particle sizes. Then, the model was solved simultaneously with particle population balance equation to estimate the PSD of sPS under the same limitations. The single PGM results showed a significant radial distribution of styrene concentration across polymer growth. It was further noticed that the diffusion resistance was most intense at the beginning of the polymerization reaction and the effects of polymerization rate were stronger. Moreover, it appeared that increasing the initial catalyst particle size led to lower rate of polymerization. The PSD simulation results revealed that the mass transfer limitation, as well as the initial catalyst particle size made a strong impact on the PSD of sPS. In addition, the simulation results obtained from this model showed good agreement results with experimental data of sPS.     

Zur kinetik und teilchenbildung der fällungspolymerisation von acrylsäure in gegenwart von polystyrol-block-polyethylenoxid-copolymeren

A surfactant system containing polystyrene-block-poly(oxyethylene) and water was used for the free radical precipitation polymerization of acrylic acid in toluene. The use of this stabilizing system makes it possible to produce poly(acrylic acid) dispersions with a particle diameter ranging from 50 to 300 nm and solid contents up to 40 wt.-%, which remain stable for months. The rate of polymerization, which was measured on-line in a reaction calorimeter shows a strong autocatalytic behavior. The maximum of the polymerization rate and the corresponding time of appearance depend strongly on the water content. The influence of the composition of the surfactant (block length), its concentration and the concentration of initiator and monomer on the polymerization rate and the particle diameter were studied. Especially by varying the block length of the copolymer, the number of particles, respectively the particle diameter, can be controlled. To describe the course of the polymerization process, a model based on the theory of homogeneous particle nucleation is suggested. The influence of water on the swelling equilibrium of the poly(acrylic acid) particles is taken into account.     

氧化还原引发丙烯酸正丁酯乳液聚合

选用过氧化氢二异丙苯-硫酸亚铁氧化还原体系引发丙烯酸正丁酯的乳液聚合,研究了单体进料时间和反应温度对聚合反应速度、乳胶粒子尺寸和分子量的影响。结果表明,固定聚合条件,单体加料时间延长至3h时,粒径由90 nm减小至65nm,分子量降低了38%;当反应温度由20℃升高至70℃时,粒子粒径由95nm减小至65nm,表观聚合反应活化能为29.80kJ/mol。     

Modelling and simulation of batch and semi-batch emulsion copolymerization of styrene and butyl acrylate

This work deals with modelling of emulsion polymerization processes using batch and semi-batch reactors. Specific attention is paid to copolymerization of the system styrene/butyl acrylate.The main key parameters of the model are identified on the basis of batch experimental data in order to describe the complete sketch of emulsion polymerization. The model is then used to simulate, under several operating conditions, the polymerization rate, the global monomers conversion, the number and weight average molecular weights as well as the particle size distribution and the glass transition temperature. Then, the model is generalized to the use of semi-batch processes and validated for this application.     

Monitoring inverse‐phase emulsion polymerization using electrical impedance spectroscopy

Inverse‐phase emulsion polymerization (IEP) is a widely used technique for synthesizing polyacrylamide, a product in demand for water treatment and in food industries. Despite its extensive application, challenges exist in controlling and monitoring IEP due to the relatively high polymerization rate and high viscosity of polyacrylamide. We investigated IEP of acrylamide with an industrial solvent, D80, as the oil phase, azobisisobutyronitrile as an oil‐soluble initiator, and a mixture of sorbitan monooleate (Span 80) and poly(oxyethylene sorbitan trioleate) (Tween 85) as emulsifier. Our study showed that electrical impedance spectroscopy (EIS) is an efficient tool for monitoring the progress and characteristics of IEP in real time. The results revealed that the monomer conversion and polymerization rate correlate well with on‐line capacitance measurements using EIS at an appropriate frequency, while changes in conductance correlate well with changes in particle diameter which was validated using an off‐line dynamic light scattering method. © 2014 Society of Chemical Industry     

Free radical desorption in continuous emulsion polymerization

A mathematical model for continuous emulsion polymerization which accounts for the desorption of radicals from polymer particles is presented. The desorption factor has been incorporated into the Sato-Taniyama model and the resulting systems of equations solved iteratively. The effects of desorption on variables such as concentration of particles, polymerization rate, and average number of radicals per particle are illustrated. Fit of the model to experimental data is presented and discussed.     

First-principles calculation of particle formation in emulsion polymerization: pseudo-bulk systems

Kinetic behavior in emulsion polymerization can be conveniently assigned as either ‘zero-one’ or ‘pseudo-bulk’. Sufficiently small particles in emulsion polymerizations obey zero-one kinetics, where entry of a radical into a particle which contains a growing radical leads to instantaneous termination. Pseudo-bulk kinetics applies to particles in which more than one free radical can co-exist for a significant period; while this is commonly applicable to large particles for any monomer, it also applies to very small particles for monomers which propagate very rapidly, such as acrylates. A methodology is developed to enable particle sizes and rates to be calculated for systems in which pseudo-bulk kinetics are important during particle formation. This takes account of all significant reactions involving radical species in the water and particle phases, including the chain-length dependence of the termination rate coefficient. A ‘cross-over radius’ r_co is used to describe the particle size where termination of radicals within the particles is no longer instantaneous. The model is applied to the emulsion polymerization of butyl acrylate. All parameters are available from the literature, except for r_co and k_p¹, the rate coefficient for propagation of a monomeric radical formed from transfer. These were determined from experiments on seeded emulsion polymerizations of this monomer, involving the steady-state rate with chemical initiator and non-steady-state rate in a system initiated by γ radiolysis, after removal from the radiation source (‘relaxation’ mode). Particle sizes and rates in unseeded butyl acrylate emulsion polymerizations at 50 °C, over a range of concentrations of persulfate as initiator and sodium dodecyl sulfate as surfactant, are predicted by the model with acceptable accuracy.     

Miniemulsion polymerisation in pseudo-bulk regime: Mathematical modelling, prediction and optimal strategy of operation

A dynamic mathematical model based on pseudo-bulk kinetics was developed for styrene miniemulsion polymerisation and validated using experimental data. Key findings are that the developed model match reasonably with experimental data and is able to predict the polymerisation attributes and product properties such as fractional conversion, average molecular weight, molecular weight distribution (MWD), average particle size and particle size distribution (PSD) in miniemulsion polymerisation. Optimal strategy of semibatch operation was developed using reaction temperature and monomer feed rate as process variables with specified initial conditions.     

Modeling the free radical solution and bulk polymerization of methyl methacrylate

This paper reviews our current understanding of the kinetics and mechanisms of free-radical chain polymerization of methyl methacrylate. A mathematical model previously proposed to describe the bulk polymerization of MMA is here extended to cover solution polymerization. This extended model is validated by comparing its predictions with experimental data over a range of conversions and product molecular weights.     

硬泡用蔗糖型聚醚多元醇的合成研究

以蔗糖、甘油和环氧丙烷为原料合成了蔗糖聚醚多元醇,讨论了反应温度、进料速率、原材料品质等对蔗糖反应性的影响,提出了提高蔗糖反应程度的措施。结果表明,选择合适的初期聚合温度、PO进料速率、降低蔗糖粒径、增加蔗糖熔融时间,可有效降低蔗糖单体在聚醚中的残留,提高蔗糖型硬泡聚醚的质量。     

Influence of Operating Conditions for Fast Pyrolysis and Pyrolysis Oil Production in a Conical Spouted‐Bed Reactor

Fast pyrolysis experiments of larch sawdust were conducted in a conical spouted‐bed reactor to study the influences of reaction temperature, inlet gas velocity, feeding rate, and particle size on the product yield and pyrolysis oil quality. For the first time, the optimal conditions were determined for various pyrolysis operations of such reactor to increase the yield and quality of pyrolysis oil. The results demonstrate that the biomass particle size, reaction temperature, biomass feeding rate, and inlet gas velocity all affected the quality and yield of the pyrolysis oil, in this order.     

In situ syntheses of a suspension agent based on a styrene–acrylic acid copolymer for the suspension polymerization of styrene

We carried out the suspension polymerization of styrene, initiated with benzoyl peroxide at 80°C, in the presence of the simultaneous polymerization of acrylic acid in the water phase, initiated by potassium peroxidisulfate (KPS) at the same temperature. The polymerization in the water phase was started at certain times after the beginning of the polymerization of styrene. Then, a continuous addition of KPS was carried out at a given landing rate and during variable feeding times. The water‐phase polymerization actually produced a copolymer of styrene and acrylic acid, which displayed surface‐active properties. The particle size distribution depended on the variables mentioned earlier (starting time, KPS feeding rate, and addition time), being controlled by the molecular weight, and on the composition of the copolymer produced and its availability at the increasing conversion of styrene. A second distribution of submicronic particles was produced. Both families of particles had about the same molecular weight. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3271–3285, 2002