Measuring the particle size of a known distribution using the focused beam reflectance measurement technique

The accuracy of the focused beam reflectance measurement (FBRM) probe, which measures a chord length distribution, from Mettler-Toledo Lasentec^® has been explored. A particle video microscope (PVM) probe, which provides in situ digital images, was used as a direct visual method to test the reliability of the FBRM results. These probes can provide in situ particle characterization at high pressures. The FBRM has been used to study emulsions and ice and clathrate hydrate formation. The ability of the FBRM to accurately characterize unimodal and bimodal distributions of particles and droplets and to measure agglomeration events was investigated. It was found that while the FBRM can successfully identify system changes, certain inaccuracies exist in the chord length distributions. Particularly, the FBRM was found to oversize unimodal distributions of glass beads, but undersize droplets in an emulsion and was unable to measure full agglomerate sizes. The onset of ice and hydrate nucleation and growth were successfully detected by the FBRM, but quantitative analysis of the particle and agglomerate sizes required simultaneous PVM measurements to be performed.     

稠油包水乳状液的表观黏度

以渤海SZ36-1稠油、矿化水为工质配制了2组不同液滴直径的W/O型乳状液,研究了温度、含水率、剪切率和液滴直径对乳状液黏度的影响。结果表明,温度对乳状液表观黏度的影响非常明显,而对相对黏度的影响却较小;同时含水率、剪切率和液滴直径也是影响乳状液黏度的重要因素,低含水率下,剪切率、液滴直径对黏度的影响不明显,而当含水率较高时,剪切率、液滴直径的影响非常突出,乳状液呈现出强烈的剪切稀释特性。利用国内外现有的一些黏度模型对实验获得的黏度数据进行了预测分析,发现Brinkman(1952)模型具有较好的预测精度。     

Effect of solvent type on preparation of ethyl cellulose microparticles by solvent evaporation method with double emulsion system using focused beam reflectance measurement

The purpose of this study was to investigate the effect of solvent type on the solidification rate of ethyl cellulose (EC) microparticles and particle size/distribution of emulsion droplets/hardened microparticles during the solvent evaporation process using focused beam reflectance measurement (FBRM). EC microparticles were prepared with a water‐in‐oil‐in‐water solvent evaporation method using various solvents, including dichloromethane, dichloromethane–methanol (1:1), ethyl acetate and chloroform. The particle size/distribution of the emulsion droplets/hardened microparticles was monitored using FBRM. The morphology of EC microparticles was characterized using scanning electron microscopy (SEM). The transformation of the emulsion droplets into solid microparticles for all solvents occurred within the first 10–90 min. The square weighted mean chord length of EC microparticles prepared using chloroform was smallest, but the chord count was not the highest. The chord length distribution (CLD) measured by FBRM showed that a larger mean particle size gave longer CLD and a lower peak of particle number. SEM data revealed that the morphology of microparticles was influenced by the type of solvent. FBRM can be employed for online monitoring of the shift in the microparticle CLD and detect transformation of emulsion droplets into solid microparticles during the solvent evaporation process. The microparticle CLD and transformation process were strongly influenced by solvent type. © 2017 Society of Chemical Industry     

An investigation of the droplet size distributions in a cyclone reactor for liquid-liquid heterogeneous reactions using FBRM and PVM

A multi-element process coupled cyclone reactor for the liquid-liquid heterogeneous reaction was proposed. This paper presents the investigation of dispersed phase droplet size distributions near the wall surface using FBRM and PVM. To translate a chord length distribution (CLD) measured by the FBRM instrument into its droplet size distribution (DSD), a CLD-DSD transformation model was proposed. Moreover, the effects of operational parameters on the droplet size distributions were studied. The results show that the total inlet flow plays a decisive role on the dispersed phase droplet size distributions, while the influence of feed ratio is mainly reflected in inhibiting the probability of droplet coalescence. In comparison, the influence of overflow ratio on the droplet size distributions can be neglected.     

物性对油滴剪切变形影响的模拟分析

以简单线性剪切流为背景,采用VOF模型及若干自定义子程序进行模拟分析,探讨物性对油滴变形和破碎的影响关系。模拟表明:粘度对变形起到抑制作用,粘度越大,变形越难,更能耐受剪切流动;表面张力越小,油滴越容易发生变形和破碎,稳定性越差,表面张力阻止了油滴的变形;油滴粒径越大,越易变形、破碎,越不稳定。     

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。     

Methane hydrate formation and an inward growing shell model in water-in-oil dispersions

Significant factors controlling gas hydrate growth in water and water-in-oil dispersions have been tested. In particular, the influence of shear rate, presence of oil, and thermodynamic driving force (represented by pressure supersaturation) on hydrate growth rates is included. Formation rates in water show some discrepancy compared to previous work, which is likely caused by differences in the apparatus geometries. A model is proposed for growth of hydrate in oil, in which a hydrate shell forms on a water droplet, followed by additional conversion of the water core to hydrate.     

液液静电雾化特性

对水静电雾化弥散于玉米油的液-液雾化过程进行了实验研究。通过拍照对雾滴形态进行了观察。观察表明,不同电压下液-液雾化会呈现出滴状和云状雾化两种较为典型的雾化形态,在两种形态下液滴具有不同的形貌和运动特点,本文给出了两种雾化形态的出现条件及特征描述。通过Winner99颗粒图像分析仪及雾滴尺寸的分布理论,对不同静电电压下雾滴直径的分布规律进行了定量分析。研究结果表明,液-液静电雾化中雾滴的直径分布服从Rosin-Rammler分布规律。随着电压的升高,雾滴直径分布趋向均匀,雾化细度得到改善。与在空气中雾化有所不同,液-液雾化中雾滴分布的概率密度曲线峰值两边呈现出显著的不对称性,小液滴数尺寸分布较窄而大雾滴数的尺寸分布较宽。随着电压的升高,大雾滴尺寸分布有所变窄,概率密度曲线趋近对称。     

Modeling and Optimization of Two Stage AC Electrostatic Desalter

Electrostatic desalters are commonly used to separate water from crude oil emulsions. In this study, a novel mathematical model based on a bivariate population balance equation has been proposed to model the steady state distribution of water droplet sizes and salt concentration along an Alternative Current (AC) electrostatic desalter. Pilot plant data for two heavy crude oils are used to validate the model. Effect of different operational parameters on the outlet dehydration efficiency and salt content of crude oil have been studied. Furthermore, the effect of two-stage desalting on the outlet Basic Sediment and Water (BS&W) and salt content of oil have been studied and the optimized parameters of such configuration have been found by differential evolution method to get the best performance of the electrostatic desalters.     

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%.     

AN EXPERIMENTAL STUDY OF DISPERSED LIQUID/LIQUID TWO-PHASE UPFLOW IN A PIPE

This paper presents experimental data for dispersed liquid/liquid upflows. Water was the continuous phase and mineral oil was the dispersed droplet phase. For this flow regime reduced gravity bubbly flow phenomena was simulated because the mineral oil and water had almost the same density. The mean velocity and turbulence fields, the size distributions of the oil droplets, the volume fraction, and interfacial area density distribution were measured using fiber optic Laser Doppler Anemometer (LDA) and phase Doppler Anemometer (PDA) systems. Significantly, the results presented in this paper are similar to those for bubbly air/water flows in microgravity conditions (Kamp el at., 1995).     

A water droplet size distribution dependent modeling of hydrate formation in water/oil emulsion

Experimental data on chord length distributions and growth rate during methane hydrate formation in water‐in‐oil emulsions were obtained in a high pressure stirring reactor using focused beam reflectance measurement and particle video microscope. The experiments were carried out at 274.2 K for 10–30% water cuts and agitation rates ranging from 200 to 500 rpm initially at 7.72 MPa. Rapid growth was accompanied by gradually decrease in rate. Free water was observed to become depleted during rapid growth while some water remained encapsulated inside hydrate layers constituting a mass transfer barrier. The apparent kinetic constants of methane hydrate formation and free‐water fractions were determined using a newly developed kinetic model independent of the dissolution rate at the gas–oil interface. It was illustrated that continued growth depends on distribution and transfer of water in oil‐dominated systems. This perception accords with observations of hydrate film growth on suspended water droplet in oil and clarifies transfer limits in kinetics. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1010–1023, 2017     

Mathematical modelling of a hydrocyclone for the down-hole oil–water separation (DOWS)

In this study, a mathematical model is developed to predict the efficiency of a down-hole oil–water separation hydrocyclone. In the proposed model, the separation efficiency is determined based on droplet trajectory of a single oil droplet through the continuous-phase. The droplet trajectory model is developed using a Lagrangian approach in which single droplets are traced in the continuous-phase. The droplet trajectory model uses the swirling flow of the continuous-phase to trace the oil droplets. By applying the droplet trajectory, a trial and error approach is used to determine the size of the oil droplet that reaches the reverse flow region, where they can be separated. The required input for the proposed model is hydrocyclone geometry, fluid properties, inlet droplet size distribution and operational conditions at the down hole. The model is capable of predicting the hydrocyclone hydrodynamic flow field, namely, the axial, tangential and radial velocity distributions of the continuous-phase. The model was then applied for some case studies from the field tested DOWS systems which exist in the literature. The results show that the proposed model can predict well the split ratio and separation efficiency of the hydrocyclone. Moreover, the results of the proposed model can be used as a preliminary evaluation for installing a down-hole oil–water separation hydrocyclone system in a producing well.     

Interfacial phenomena and droplet size of particle stabilized emulsions in oscillatory shear

Production of particle stabilized oil in water emulsions has been investigated both theoretically and experimentally under oscillatory shear conditions using different stabilizing particles (SPs). The investigation included analysis of the interaction between particles interfacial stability and droplets breakage and coalescence. For hydrophobic SPs, droplets maintained their sizes as determined by torque balance (TB) without significant breakage or coalescence. For the more hydrophilic SPs, larger droplets formed that broke by eddies in the inertial subrange. At higher fluid shear stresses, loss of the SPs occurred during droplet formation leading to near bare droplet surface and coalescence to much larger sizes with subsequent fragmentation by capillary instabilities. The final droplet size in both cases was very different from TB model predictions. A modeling approach is proposed that combined both TB and droplet breakage and coalescence mechanisms. Comparison between the experimental results and the models predictions showed satisfactory agreement. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2902–2911, 2016     

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.     

Coalescence of Water Droplets in Crude Oil Emulsions: Analytical Solution

In petroleum refineries, water is used in desalting units to remove the salt contained in crude oil. Typically, 7 % of the volume of hot crude oil is water, forming a water‐and‐oil emulsion. The emulsion flows between two electrodes and is subjected to an electric field. The electrical forces promote the coalescence of small droplets of water dispersed in crude oil, and these form bigger droplets. This paper calculates the forces acting on the droplets, highlighting particularly the mechanisms proposed for droplet–droplet coalescence under the influence of an applied electric field. Moreover, a model is developed in order to calculate the displacement speed of the droplets and the time between droplet collisions. Thus, it is possible to simulate and optimize the process by changing the operational variables (temperature, electrical field, and water quantity). The main advantage of this study is to show that it is feasible to increase the volume of water recycled in desalting processes, thus reducing the use of freshwater and the generation of liquid effluents in refineries.     

A STUDY OF SILICONE OIL-IN-WATER EMULSIONS

Emulsions of silicone oil-in water were formed using a Brinkmann Polytron homogenizer with Igepal CO-530 as an emulsifier. Silicone viscosities ranged from 10 to 33,000 mPa.s at 25°C. Rheological characteristics and particle size analyses of silicone oil-in-water emulsions were studied. At high volume fraction of the dispersed phase (70%-75%), silicone oil-in-water emulsions were stable. At lower volume fractions (50%-60%), emulsions formed were less stable and the two phases easily separated in a few days. The emulsions formed with high volume fraction silicone oil show highly non-Newtonian behavior (shear thinning). Emulsions made with low viscosity oils had lower viscosities than those made from high viscosity oils. Relative viscosity-concentration data could be correlated by the Frankel and Acrivos Equation. Increasing the emulsifier concentration of 70% oil-in-water emulsions resulted in a decrease in mean droplet size and an increase in emulsion viscosity. Increasing the intensity of agitation also resulted in higher viscosity and smaller droplet size until a critical energy input above which droplet size increased. Emulsification with low shear mixing provides more control in decreasing mean droplet size with time.     

悬浮聚合法制备磁性微球的粒度分布特性

本文研究了含有微细铁黑颗粒的混合单体悬浮聚合产物的粒度分布特性。分析了分散剂、超声预分散和无机铁黑颗粒对形成粒度多峰分布的影响。结果表明,分散剂是体系中形成小颗粒的主要因素;超声波的预分散作用使悬浮体系的液滴破裂以“腐蚀破碎（erosive breakage)”为主;无机铁黑颗粒由于其表面亲水性,倾向于分布在油性单体液表面,不仅有利于悬浮液滴的“磨蚀破碎”,同时也对分散液滴具有良好的稳定作用。上述因素的共同作用使得聚合产物的粒度呈三峰分布。     

油水乳化液流变性研究进展

综述了油水乳化液流变性研究进展，介绍了目前国内外乳化液流变性的研究情况、乳化液的流变模式及乳化液流变性的评价方法。乳化液的剪切应力-剪切速率关系明显受油滴尺寸的影响，在含油量一定时，表观黏度随油滴尺寸的减小而增加。绝大多数乳化液在低剪切速度下(低于50s^-1)，呈现剪切变稀行为；在剪切速率超过1000s^-1时呈现牛顿行为。高含水原油的视黏度是温度、含水率以及剪切速率的函数。介绍了乳化液的3种流变模式，并给出了流变性评价方法实例。提出了油水乳化液流变性研究的发展方向。     

Droplet Generation and Nanoparticle Formation in Low-Pressure Spray Pyrolysis

In the present study, we found that pressure-dependent droplet-to-particle formation is important for the control of both droplet and particle characteristics during the production of particles with enhanced properties. Using experimental and simulation approaches, the present study investigated the droplet-to-particle formation of zinc oxide as a model material that was synthesized via low-pressure spray pyrolysis. The size distributions of both the droplets generated under low-pressure and the synthesized particles were measured and compared. The effects of operating conditions, i.e., operating pressure, carrier gas-, and liquid-flow rates, reactor temperature, and precursor concentration, on the characteristics of the generated droplets and synthesized zinc oxide particles were systematically investigated. We found that broad and bimodal droplet size distributions shifted to narrow and monodispersed distributions as chamber pressures were reduced. The low-pressure-synthesized zinc oxide nanoparticles were highly crystallized with unimodal distributions and sizes of approximately 8 nm. Droplet temperature decreased with decreasing chamber pressure, which confirmed both the evaporative cooling of droplets and the formation of smaller droplet sizes. The chamber temperature and droplet size simulation results were in accordance with the experimental results. In conclusion, we found that the chamber pressure is the primary determinant of monodispersity with respect to droplet size distribution and to the size and morphology of the synthesized particles.