Suspension polymerization of styrene with circular loop reactor

A circular loop reactor was devised and applied to the suspension polymerization of styrene. The transient droplet diameter distribution and the final particle size distribution are measured by changing widely the impeller speed, the dispersed phase volume fraction, and the stabilizer concentration. The effects of these conditions on the size distribution and mean size of the final polymer particle are investigated. An expression correlating the mean particle size with the operating conditions is derived. The circular loop reactor is found to be superior to the production of the polymer particle of uniform size.     

Effect of double agitation on particle size in suspension polymerization of styrene with a loop reactor

Suspension polymerization of styrene was performed in the loop reactor. In order to allow wide change to the polymer particle size, a sub impeller was included within the main impeller. The sub impeller served to increase the fluid velocity and to uniformly disperse the polymer droplets during polymerization. It was investigated how the double agitation method by the main and the sub impellers affected the transient droplet diameter distribution and the final particle size distribution. The particle size could be changed widely by the double agitation method without the decrease in degree of the uniformity of the particle size.     

Dispersing behaviour of droplets in suspension polymerization of styrene in a loop reactor

Suspension polymerization of styrene was performed using a loop reactor. The dispersing behaviour of the droplets in the course of the reaction was observed. The mean droplet diameter was determined by the energy level at the impeller region. Moreover, the final particle size distribution and mean particle size were also determined after an elapsed time of 1-2 hrs. An expression which correlated the final mean particle size with the operating conditions, such as the mixing conditions at the impeller region and the initial physical properties of the suspension system, was derived. The deposition of polymers on the reactor wall was found to be prevented due to the high fluid velocity.     

CFD analysis of turbulence non-homogeneity in mixing vessels: A two-compartment model

A two-compartment model has been developed for calculating the droplet/particle size distribution in suspension polymerization reactors by taking into account the large spatial variations of the turbulent kinetic energy and its dissipation rate in the vessel. The two-compartment model comprised two mixing zones, namely an impeller zone of high local energy dissipation rates and a circulation zone of low kinetic energy. Computational fluid dynamics (CFD) was employed for generating the spatial distribution of energy dissipation rates within an unbaffled mixing vessel agitated by a flat two-blade impeller. A general methodology was developed for extracting, from the results of the CFD simulations, the volume ratio of the impeller over the circulation zone, the ratio of the average turbulent dissipation rates in the two zones, and the exchange flow rate between the two compartments. The effect of agitation rate, continuous phase viscosity, impeller diameter, and mixing vessel scale on the two-compartment model parameters was elucidated. The two-compartment model was then applied to a non-homogeneous liquid-liquid dispersion process to calculate the time evolution of the droplet size distribution in the mixing vessel. An excellent agreement was obtained between theoretical and experimental results on droplet size distributions obtained from a laboratory-scale reactor operated over a wide range of experimental conditions.     

Effect of impeller diameter on mean droplet diameter in circular loop reactor

Experiments in liquid-liquid dispersion were performed using a circular loop reactor designed for suspension polymerization. In order to vary widely differences in physical properties such as the viscosity, density, and interfacial tension between the two liquids concerned, polystyrene pellets were dissolved into the dispersed phase which consisted of a styrene monomer liquid. The diameter distributions and mean diameters of droplets formed were measured by stepwise changes in the impeller diameter. From these results, the effect of the impeller diameter on the breakup of droplets was determined. Correlations relating the mean droplet diameter to the operational conditions were derived.     

甘露醇喷雾干燥过程中液滴粒度分布变化的群体粒数衡算模拟和实验研究

利用群体粒数衡算（population balance，PB）计算机模拟和实验研究了甘露醇水溶液的喷雾干燥过程中液滴的粒度分布的变化规律。液滴干燥过程中的颗粒粒度的萎缩速率，在群体粒数衡算模型中描述为液滴的逆（或负）生长项，通过单个液滴反应动力学方法（reaction engineering approach，REA）获得。基于单个液滴干燥的反应工程方法模型REA和群体粒数衡算模型PB集成建立了PBREA模型。PBREA 模型的求解是通过高分辨率数值方法。本文模拟研究了不同工况下，不同粒径液滴的干燥时间、液滴平均含湿量以及液滴粒度分布随时间的变化。结果显示，液滴粒径越大，干燥时间越长，模型预测的颗粒平均粒径为实验值的1.0~1.5倍，粒度分布跨度是实验值的0.61~0.89倍。模拟误差主要来源于液滴及颗粒粒径分布统计精度、单个静止液滴与群体运动液滴干燥的差异、热导率及扩散系数是经验值3个方面。在使用Buchi 290 小型喷雾干燥仪进行的实验中，使用了图像采集和分析方法得到了液滴及颗粒的数密度分布，并和模拟结果做了对比。结果表明该模型可以有效地预测喷雾干燥过程中干燥颗粒的平均粒度及分布跨度。     

Local drop size variation in an agitated vessel

The local droplet diameters were measured at two positions inside the circulation region of a stirred tank. The Sauter mean diameter near the top of the vessel was always 1.4 times greater than the one just outside the impeller region for rotational speeds of 250, 300, 350 and 400 rpm and for hold-up fractions of 0.01, 0.025 and 0.05. The drop size distributions at a hold-up fraction 0.01 had one mode for all impeller speeds studied and at both positions. At higher hold-up fractions the distributions usually were bimodal.     

自由基聚合反应器中多尺度流场的模拟进展

自由基聚合过程中,由于混合、传递及聚合反应的相互作用使得反应器内部存在复杂的多尺度流场,例如宏观尺度的速度、浓度、温度分布,介观尺度的液滴粒径分布,微观尺度的聚合反应速率、聚合物分子量和多分散性指数分布。这些复杂的多尺度流场分布使得聚合反应器的模型化研究成为难题。本文较为系统地介绍了自由基聚合反应器中存在的多尺度现象;简述了微观尺度聚合物性质流场分布的模型化与模拟研究方法;从悬浮聚合和乳液聚合两个方面介绍了介观尺度液滴粒径分布的模拟研究进展;从非理想混合的角度阐述了宏观尺度多相流流场分布的研究进展。最后,本文分析了多尺度模型的耦合求解方法。本综述也有本文作者对这个领域的初步观点,可为聚合反应器的设计、优化和放大提供参考。     

Droplet Size Distributions of Liquid-Liquid Dispersions in Centrifugal Pumps

The generation of liquid-liquid dispersions with defined droplet size distributions is an important aspect for process equipment design. In this work, two centrifugal pumps with different impeller diameters were used to generate dispersions at selected operating points for a paraffin oil-water system. The droplet break-up phenomena within the centrifugal pumps were analyzed using a transparent pump design in combination with high-speed imaging. Droplet size distributions at centrifugal pump discharge nozzle were recorded with optical probe measurement technologies and evaluated by means of image processing using a neural network. The influence of impeller diameter, rotational speed, volumetric flow rate and dispersed phase fraction are discussed. Experimental data is correlated using fluid properties, operating data as well as centrifugal pump dimensions. The correlations developed from results of this work serve as a basis for the equipment design of centrifugal pumps.     

Preparation of Spherical SnO2 Powders by Ultrasonic Spray Pyrolysis

Spherical SnO₂ powders were prepared from SnCl₄ aqueous solution by ultrasonic spray pyrlysis. The particle size distributions normalized by mean diameters are almost identical in spite of the variation in the concentration of the source solution. The mean diameter of SnO₂ particles increases with the concentration of the source solution and it is in the range of 0.2 to 0.8 μm. Each spherical particle is composed of many primary particles and has a solid, microporous structure.     

Effect of Ultrasonication on Droplet Size in Biodiesel Mixtures

Biodiesel fuels have become more attractive recently because of their environmental benefits and cost competitiveness compared to diesel fuel. Many processing improvements have been proposed to increase the conversion rates and the yields of vegetable oil in order to lower production costs and improve biodiesel product quality. In conventional biodiesel production chemistries, alkaline transesterifications of alcohol/oil dispersions should occur primarily near the interface. Ultrasonic mixing has already been shown to increase overall conversion rates for alcohol/vegetable oil mixtures. Our data show that ultrasonic mixing produced smaller droplet sizes than conventional agitation, leading to more interfacial area for the reaction to occur. Droplet size distributions have been measured for conventional impeller and ultrasonic mixing systems using methanol/soybean oil as a model system. The dispersions were stabilized by surfactant in order to obtain droplet size distribution for mixture samples. Ultrasonic mixing produced dispersions with average droplet sizes 42% smaller than those generated using standard impellers.     

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.     

Droplet breakage and coalescence models for the flow of water-in-oil emulsions through a valve-like element

An experimental and theoretical study was carried out regarding the evolution of droplet size distributions for the flow of water in oil emulsions through a valve-like element that simulates a mixing valve. The water droplets had diameters in the 0.1–100 μm range, which includes droplets that are either smaller or larger than the Kolmogorov length scale for the experimental conditions. Droplet breakage and coalescence models that can be used for this size range were proposed. A simplified population balance model was developed to interpret the experimental data and solved by the method of classes. The model parameters were estimated by the orthogonal distance regression method. The simplifying assumption of the model was verified by global optimization using a parallel implementation of the particle swarm optimization method. The agreement between simulated and experimental droplet volume size distributions was good. The predictions of the DeBroukere mean diameter, d₄₃, were unbiased with mean errors of 8%.     

Role of mixing in copolymerizations of styrene and n-butyl acrylate

The effect of agitation speed and impeller type on the kinetics of emulsion copolymerization of styrene and n-butyl acrylate was investigated. It was shown that the solids content was an important variable in these studies. At low solids (30%), the impeller type and speed did not have any significant effect on the final number of particles and the overall rate of polymerization. Particle size distributions were unimodal in all the cases. At high solids (50%), some differences were observed when 2 different impellers (Rushton and A310 fluidfoil) were used. The polymerization carried out with the Rushton impeller was faster. Bimodal particle size distributions were obtained for both cases; however, the bimodality was more significant when the A310 fluidfoil impeller was used. Greater numbers of particles and unimodal particle size distributions with high rates of polymerization at 30% solids contrasted the lower numbers of particles and bimodal particle size distributions with lower rates of polymerization seen at 50% solids. These differences were attributed to the partitioning behavior of the surfactant (Triton X-405; octylphenoxy polyethoxy ethanol; Union Carbide, Danbury, CT). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2277–2289, 1998     

Preparation of hemolysate-filled hexamethylene sebacamide microcapsules with controlled diameter

Hemolysate-filled hexamethylene sebacamide microcapsules (nylon-6, 10 membranes) were prepared by interfacial polymerization. Sheet lattice, frame lattice, turbine and marine impellers were tested to control the microcapsule mean diameter and size distribution parameters. Mean diameters ranging from 40 to 200 μm were obtained depending on the impeller type, rotational speed and emulsifier concentration. The size dispersion of microcapsule preparations was best controlled with a frame lattice impeller, achieving standard deviation values less than 40% of the mean diameter. The wire diameter and mesh dimensions of the impeller lattice had little effect on the distribution parameters.     

Effect of dispersed phase feed time on the droplet size of Pickering emulsions produced in a stirred tank

The aim of this study was to investigate the effect of feed time of the oil phase on the average droplet size of Pickering emulsions produced in stirred tanks. Three types of impellers were tested: RT, up-pumping PBT (PBTU), and down-pumping PBT (PBTD). All the impellers were tested at two sizes, T/3 and T/2. All configurations were compared at constant tip speed, power per mass, and impeller Reynolds number. The droplet diameters were measured in Mastersizer® 3,000 (Malvern). The results showed that an increase in feed time causes a reduction in the average droplet size. At lower impeller speeds and higher feed times, the effect is more pronounced. It was found that some other geometric parameters also have an impact on the average droplet size.     

Effect of an unsteady agitation method on drop coalescence characteristics in suspension polymerization of styrene

A tracer dye technique was used to investigate the effect of the co‐reverse rotational of impeller method, the agitation speed and periodic time interval on the coalescence rate in the suspension polymerization of styrene. The results showed that the extent of coalescence decreased with the use of the co‐reverse rotational method and with the decrease in the periodic time interval or agitation speed. The results also showed that the final particle sizes became small and the particle size distributions became uniform with the use of the co‐reverse rotational method and with a decrease in the periodic time interval.     

Effects of Sand Fraction on Toluene‐diluted Heavy Oil in Water Emulsions in Turbulent Flow

The impact of the presence of sand on emulsification of toluene‐diluted heavy oil in simulated process water was systematically studied as a function of agitation time, in a stirred tank. Droplet size distributions were measured by light scattering technique. Optical microscopy and high‐speed video micrography were used to visually monitor agitation and emulsion stability. Results showed that the Sauter mean diameters of the droplets decreased with increasing sand content. Droplet breakage followed a first‐order kinetic model for all mixing speeds. Plots of droplet volume percent frequency versus droplet size followed lognormal distribution. The distribution span broadened into lower sizes with increased sand content. Emulsions were stable for over 48 h after formation.     

湍流搅拌槽中原油-水分散体系的液滴破碎

对搅拌槽内原油-水分散体系中液滴的破碎过程进行了实验和理论分析。实验测定了在不同温度和转速条件下油滴的粒径分布以及最大稳定粒径,并采用以Voigt模型为基础的理论对最大稳定粒径进行了计算。在温度较低时,原油表现出了具有触变性的流变学性质,经过计算和数量级分析,液滴破碎时间与粘度达到平衡的时间相比非常短,可认为在破碎过程中液滴的粘度始终为初始粘度。实验结果与以初始粘度计算的理论值吻合较好。     

不溶液-液分散在搅拌槽内的CFD模拟

液滴平均尺寸和液滴尺寸分布是描述不溶液-液分散程度的2个重要参数,决定着两相接触面积的大小,进而决定着相间的传质、传热和化学反应速率。利用CFD方法详细研究了水-油两相在搅拌槽内的分散过程,发现叶轮转速、分散相体积分数和连续相黏度对分散效果有显著影响。当两相组成一定时,增大叶轮转速和连续相黏度均有利于两相的分散。在一定范围内,液滴平均直径与叶轮转速、分散相体积分数均为对数线性关系,相关系数高达0.999。基于个数的液滴尺寸分布在不同转速和连续相黏度条件下出现了双峰分布,而基于体积的液滴尺寸分布则始终为单峰分布。