Investigation of the effect of delayed reflux on PVC grain properties produced by suspension polymerization

The effects of the condenser operation on properties of polyvinyl chloride (PVC) particles produced by suspension polymerization process were investigated in a pilot scale reactor. It was observed that delaying reflux operation increased the cold plasticizer absorption of the final resin. Both bulk density and K‐value of the PVC powder decreased by increasing time delay in the reflux operation. It was also found that commencement of refluxing before 20% conversion resulted in bimodal particle size distribution (PSD), while monomodal PSD was obtained for longer delays in refluxing. SEM micrographs showed that surface of produced particles were rough and smooth when reflux started before and after 20% conversion, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dehydration of ortho-boric acid in a three-phase bubble column reactor operating at low pressure

This study investigates the applicability of the bubble column as a reactor to perform the dehydration of ortho-boric acid efficiently and economically. The effects of operating conditions such as reaction time, temperature, gas flow rate, particle size and solid content in the slurry phase on the fractional conversion of the reaction have been determined, and the performance of the three-phase bubble column reactor operating at low pressure (92 kPa) has been discussed. It can be noted from this study that the reaction time has been reduced and the particle size and solid content which are required in the slurry phase for favourable fractional conversion have been increased in the bubble column reactor in comparison with those in the continuous stirred tank reactor. The reaction could be described by means of a fluid–solid heterogeneous reaction model.     

Studies on solid mean residence time in a three-stage gas-solid fluidized bed with downcomer

Fluidized bed reactors behave as a continuously stirred tank reactor having wide residence time of solids, which is not desirable if a homogeneous product is required. The multi-stage fluidized bed reactors narrow the solids residence time, making it useful for various operations. A three-stage fluidized reactor was designed, fabricated and operated under stable operating condition to investigate the mean particle residence time in the system. The materials taken for the study were lime and sand. In the particle residence time experiments, the results revealed that at a particular solids velocity, mean residence time decreased with increase in gas velocity and increased with decrease in gas velocity. Based on the data, a correlation has been presented for predicting mean residence time.     

Dynamic modelling of the continuous emulsion polymerization of vinyl chloride

A dynamic model for the continuous emulsion polymerization of vinyl chloride (VCM) in a train of stirred tank reactors has been developed. This model can predict monomer conversion, polymer particle size distribution (PSD), molecular weight distribution and long and short chain branching frequencies under non-steady reactor operation during startup, reactor switching and during unstable operation when conversion and polymer and polymer particle properties oscillate with time. The model has been used to design a flexible reactor train configuration which operates in a stable mode and can produce latexes with a wide range of properties including a bimodal polymer particle size distribution.     

Agitation scale-up effects during VCM suspension polymerization

Experimental data are presented showing the effect of reactor agitation intensity and reactor size on final resin properties during VCM suspension polymerization. Experiments were carried out in three stirred batch polymerization reactors covering a broad range of vessel sizes (bench scale, pilot plant, and commercial production units). Reactors' shapes were geometrically similar. The same charge recipe and operating procedure was also used for all three reactors. The effects of major agitation parameters such as impeller diameter, width, and speed are correlated against resin properties using the Weber number. The same characteristic U-shaped curve is found for all three reactors when mean particle diameter is plotted versus Weber number. However, the curves do not lie on top of one another but are spread apart, the larger reactors having a higher Weber number. Another interesting feature is that the coefficient of variation (particle size standard deviation divided by mean diameter) decreases dramatically as reactor size is increased. Other resin properties also show improvement upon scale-up. In summary, resin properties continue to improve as reactor size is increased over the range studied (bench-to-commercial large reactor scale), but a correct application of the complex scale-up technology must be employed to take advantage of this observation.     

催化剂颗粒形状对甲烷水蒸气重整反应的影响及工业反应器模拟

甲烷水蒸气重整工艺是现阶段最主要的工业制氢技术,催化剂颗粒形状和反应器操作条件是影响重整反应器性能和产物组成的重要因素。首先从颗粒尺度研究催化剂形状对甲烷水蒸气重整反应的影响,在不同的反应温度和压力下,计算并比较了球形、柱形和环形催化剂的效率因子,其大小顺序为:柱形 < 球形 < 环形。其次,将反应器床层的质量、热量和动量传递与环形催化剂颗粒的扩散-反应方程相结合,建立了用于描述甲烷水蒸气重整工业反应器的一维轴向数学模型。计算并分析了反应器进口温度和压力对反应器床层的温度和压力分布、催化剂效率因子以及甲烷转化率和各组分浓度分布的影响,确定了适宜的工业反应器进口温度和压力,分别为773 K和3 MPa。     

Multiple Analysis in a Reactive Distillation Column for the Synthesis of tert‐Amyl Methyl Ether

tert‐Amyl methyl ether (TAME) is produced via reactive distillation. A simulation is set up and controlled on Aspen HYSYS v 8.0 for generating the highest purity of TAME. This simulation includes a plug‐flow reactor and a reactive distillation column. Emphasis was put on finding the optimal operating conditions of the reactive distillation column in order to get the maximum purity of TAME. The operational parameters were reflux ratio, number of reactive stages in the distillation column, and condenser pressure. The results indicated the optimal reflux ratio and condenser pressure which could be adapted to industrial scale.     

Conversion of hydrocarbon fuels to syngas in a short contact time catalytic reactor

Some results of the theoretical and experimental research on the oxidative production of syngas from hydrocarbon fuels in catalytic reactors which operate at high temperatures and short contact times are presented. Pilot scale tests of the partial oxidation of methane, isooctane and gasoline have been carried out in nearly adiabatic conditions on structured catalysts developed at the Boreskov Institute of Catalysis and characterized by a low (≤0.5 wt./wt.%) content of noble metals. High yield of syngas and stable performance of the catalysts were revealed in the experiments. The details of interaction between chemical and physical processes inside adiabatic monolith reactor have been elucidated by mathematical modeling of the partial oxidation reaction on the base of catalyst detailed chemistry. The problems that emerged from the short contact time reactor operating on a pilot scale are also discussed.     

The SCOPE dynamic model for emulsion polymerization I. Theory

The SCOPE dynamic process model has been developed to treat batch and semibatch emulsion copolymerizations. This computer-based model treats jacketed reactors of arbitrary size. It consists of a coupled set of ordinary differential and algebraic equations that describe material balances for the reacting species and energy balances for both the reactor and the cooling water jacket. The model also includes a feature that allows for proportional integral derivative (PID) control of the monomer emulsion and cooling water feed rates to a reactor temperature set point. The model is based largely upon the kinetic theories developed by Smith, Ewart, and Harkins to treat emulsion homopolymerizations. The SCOPE model improves upon and expands the classic theories by taking advantage of recent theoretical developments in emulsion polymerization. Such phenomena as diffusion-controlled termination and radical desorption—important for predicting accurate polymerization rates—are included in the model. More modern theories of particle nucleation, including both homogeneous and micellar mechanisms, have been incorporated into the model to predict accurate particle size distributions. SCOPE also extends the classic theories to treat the emulsion copolymerization of an arbitrary number of monomers. Output from the model includes species concentrations, residual monomer levels, particle size distributions, molecular weight distributions, instantaneous and cumulative copolymer compositions, and reactor temperatures as a function of time. The SCOPE model can be used to evaluate various process control strategies and to study the effects of process dynamics on polymer properties. In Part II, SCOPE model predictions are compared with experimental data for styrene-methyl methacrylate copolymerizations.     

The influence of the riser exit on the particle residence time distribution in a circulating fluidised bed riser

This paper reports measurements of the influence of riser exit geometry upon the particle residence time distribution in the riser of a square cross section, cold model, circulating fluidised bed. The bed is operated within the fast fluidisation regime. The fast response particle RTD technique developed by Harris et al. (Chem. Eng. J. 89 (2002) 127-142) was used to measure the residence time distribution.The geometry of the riser exit is shown to have a modest but consistent influence upon the particle RTD; the influence of operating conditions, i.e. superficial gas velocity and solids flux is more significant.Increasing the refluxing effect of the riser exit increases the mean, variance and breakthrough time and decreases the coefficient of variation of the residence time distribution. Changes in reflux do not have a systematic effect upon the skewness of the RTD.     

Turbulent Modeling of the Production of Ultra Fine Aluminum Particles: Scale-Up

A convenient way to synthesize aluminum nanoparticles is to evaporate the metal, direct this vapor into a tubular reactor and quench it with a radial flow of cold gas. The supersaturated vapors nucleate and grow into the desired nanoparticles. For small-scale operations, because of the high temperatures and relatively low flow rates involved, the conditions of operation are usually laminar. As the units are scaled up to higher production rates, the flows become transitional or even fully turbulent. This work reports on the use of a Low Reynolds Number (LRN) turbulent model to simulate this system and its scale up for the synthesis of pure aluminum powders. Coagulation was identified as the dominating mechanism in particle growth for the conditions and scales studied. Scale up with dynamic similitude results in increased residence time which significantly changes the particle properties during scale-up. In scale-up with constant residence time, the flow field regime changes from laminar to turbulent. These changes in the flow regime affect the particle characteristics significantly for reactors of small length to diameter ratio (L/D = 6), but are almost insignificant for large length to diameter ratios (L/D = 12). Turbulent reactors showed small changes in the particle characteristics, plus a better percentage of metal vapor recuperated as particles at the end of the reactor.     

Experimental and numerical investigation of the precipitation of barium sulfate in a rotating liquid film reactor

Precipitation of nanosized barium sulfate in a rotating liquid film reactor (RLFR) has been investigated experimentally and through simulations based on the computational fluid dynamics technique including the population balance equation coupled with the Navier–Stokes equations, renormalization group k–ε model equations, and species transport equations. A comparative experiment was carried out involving conventional precipitation in a flask. The structure of the precipitate was identified by powder X‐ray diffraction (PXRD), which showed that the crystals obtained using the RLFR were smaller in size than those obtained in the flask. Transmission electron microscopy (TEM) images demonstrated that the crystals produced by the two different processes had different morphologies. Further detailed experiments involving varying the operating parameters of the RLFR were performed to investigate the effects on crystal size distribution (CSD). Increasing the speed of the rotor in the RLFR in the range 1000–5000 rpm or increasing the rotor‐stator gap in the range 0.1–0.5 mm resulted in a decrease in particle size and narrower particle size distributions. The simulation results suggested that turbulent effects and reaction processes in the effective reactor space were directly related to rotor speed and rotor‐stator gap. The simulated volume weighted mean diameter and CSD of particles of barium sulfate were almost identical to the corresponding experimental results obtained using TEM and laser particle size analyzer. The effects of other parameters such as the Kolmogorov scale and competition between induction time and mixing time are also discussed. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Combustion of methane lean mixtures in reverse flow reactors: Comparison between packed and structured catalyst beds

The scope of this work is to compare systematically the performance of particle beds and monolithic beds in catalytic reverse flow reactors used for combustion of lean methane/air mixtures, using alumina-supported palladium as catalyst. Different values of gas surface velocity (0.1–0.3 m/s), particle diameter (3–6 mm, for particle bed), cell density (200–400 cpsi, for structured bed) and catalyst/inert ratio (0.4–1) were used for the simulation of the combustion of 3500 ppm methane in both kinds of reverse flow reactor. An unsteady one-dimensional heterogeneous model has been developed and solved using a MATLAB code. The model, physical parameters and transport properties used had been experimentally validated in a previous work, operating with a particle bed reverse flow reactor. Results obtained indicate that the reverse flow reactor is more stable when the catalyst particle beds are use, although the difference with the monolith bed decreases as surface velocity increases. In contrast, pressure drops in the bed are higher for the particle bed.     

Effect of Polymer Growth Rate and Diffusion Resistance on the Behavior of Industrial Polyethylene Fluidized Bed Reactor

The two‐phase model developed for the UNIPOL polyethylene process is improved by introducing polymer diffusion resistance, this means modelling of polyethylene fluidized bed reactors has been examined on two levels, at small scale of individual polymer particle, and macroscale of the whole reactor. The model utilizes the multigrain model that accounts for the reaction rate at catalyst surface to explore the static and dynamic bifurcation behavior of the fluidized bed catalytic reactor. Detailed bifurcation diagrams are developed and analyzed for the effect of polymer growth factor and Thiele modulus (the significance of the porous medium transport resistance is characterized by Thiele modulus) on reactor dense phase monomer concentration and reactor temperature as well as polyethylene production rate and reactor single pass conversion for the safe temperature region. The observations reveal that significant diffusion resistance to monomer transport exists, and this can mask the intrinsic rate constants of the catalyst. The investigation of polymer growth factor indicates that, the nascent stage of polymerization is highly gas phase diffusion influenced. Intraparticle temperature gradients would appear to be negligible under most normal operating conditions.     

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.

     

A numerical investigation of aerosol dynamics in a wall-less reactor

This paper describes a numerical investigation of aerosol formation during silane decomposition in a wall-less reactor. The wall-less reactor is amenable to numerical investigation because the homogeneous chemical reactions leading to the formation of solid particles are isolated from heterogeneous effects, such as occur at the walls of a laminar flow aerosol reactor. The flow/heat transfer and gas-phase chemical kinetics are simulated utilizing separate one-way coupled models. The aerosol dynamics model is based on a simplified sectional model originally developed by Okuyama et al. This model is modified to allow for the simulation of particle growth via condensation. Simulations have been performed which indicate that particle growth via condensation may be an important process. Additionally, the effects of total reactor pressure, temperature and inlet silane concentration on the dynamics of the aerosol population have been investigated. Conditions which result in the formation of larger and more numerous particles have been identified.     

Semi-empirical modeling of carbonator with the physico-chemical characteristics of sorbent activity parameterized by the partial least squares method

We developed an evaluation module to calculate the carbon capture efficiency of a fluidized bed carbonator via the semi-empirical modeling of the solvent activity of lime particles. Since the solvent activity is affected by regeneration cycle number, reactor temperature, and particle size, two design parameters for the particle activity model, i.e., the characteristic time (t*) and the maximum conversion of particles (X _N ), were determined as functions of the carbonator operating conditions by applying the partial least square (PLS) method to experimental data reported in the literature. The validity of the proposed approach was shown, and the effects of reactor design factors on the carbonator performance are discussed by means of appropriate simulation studies.     

Transient behaviour of encapsulated enzyme reactor systems

Mathematical models are developed for the transient behaviour of encapsulated enzyme reactor systems such as the continuous stirred tank reactor (CSTR) and the packed bed tubular reactor. The rate processes taking place in the encapsulated enzyme bed are approximated by using a combined rate control model of enzyme reaction and membrane diffusion. The change in transient substrate concentration is obtained by using the developed rate expression in the material balance over the substrate as a function of time for the CSTR and as a function of time and position for the packed bed tubular reactor. The effects of various parameters such as the enzymic reaction rate constant, Michaelis constant, diffusional resistance of membranes, and Peclet number on the substrate concentration distribution, which varies with respect to operating time, are investigated. This study affords insight into the transient operating characteristics of the encapsulated enzyme reactor system. The results should be useful in understanding the start-up performance of the reactor systems and to control such reactor systems at desired operating conditions.     

聚硅氧烷/聚丙烯酸酯共聚乳液的合成与表征

合成了含氢聚甲基硅氧烷／聚丙烯酸酯共聚乳液。研究了聚合工艺，配组成及操作方式对聚合稳定性，动力学，乳液的粒径分布和产物性能的影响。采用部分预乳化单体滴加法（工艺A）的部分纯单体滴加法（工艺B）两种工艺，聚硅氧烷采用高速预乳化滴加进料方式。用COULTER LS粒径仪和Nicolet傅立叶变换红外光谱仪分别测定共取乳液的粒径分布和产物的结构。研究结果表明，采用A，B两种工艺均能得到平均粒径为0.101-0.103μm的单峰窄分布共聚乳液，并能有效地将含氢聚硅氧烷引入了到共取物大分子中。含氢聚硅氧烷的引入量为3％（质量）时，共聚物涂膜具有柔软，滑爽和强度高等优点。     

A new two-impinging-streams heterogeneous reactor

The characteristics of a new heterogeneous reactor of the “two impinging streams” type, suitable for gas-solid heat and mass-transfer operations, were investigated. The operating limits of the reactor, with respect to gas and solid particles mass flow rate and pressure drop, were determined; scale-up criteria with respect to the hydrodynamics of the reactor were also established. It has been found that, under certain conditions, the introduction of solid particles into the gas stream lowers the pressure drop on the reactor. In addition, the maximal pumping energy per kg of solids transported through the reactor by the air is much lower than in a fluidized-bed-type reactor. A stochastic model based on Markov processes was developed which closely describes the behavior of the solid particles in the reactor. A technique based on this model was employed for determining the residence time distribution of the particles in the reactor.