Effect of transfer on droplet size in liquid-liquid dispersions

Mean droplet diameter of the dispersed phase in pulsed plate extraction columns was measured for binary and ternary systems. A change in the droplet size in the presence of solute, dependent on such factors as the direction of mass transfer, droplet size in the binary system, radio of diffusion coefficients, viscosity of the continuous phase, interfacial tension and driving force for extraction was observed. Two new empirical correlations of mean droplet sizes in mass transfer conditions are proposed. These correlations have been successfully applied to other extraction columns.     

萃取柱内液-液两相流CFD-PBM模拟研究进展

对萃取柱内CFD-PBM模拟研究进行了较详细的综述,包括其基本理论、不同的求解方法及模拟研究现状等. CFD-PBM模拟的基本方程包括流动方程和群体平衡方程,其相互耦合,群体平衡方程涉及破碎与聚并2个关键模型. 群体平衡模型的求解方法包括直接离散化方法、矩量法、正交矩量法、直接正交矩量法、分段正交矩量法等,对这些方法的原理、优点和缺点进行了综述. 目前国际上关于萃取柱内CFD模拟采用较多的是简单的欧拉-欧拉两相流模拟,考虑液滴尺寸分布和进一步的浓度分布的群体平衡模型应用较少. 完善伴随传质的液-液分散体系的群体平衡模型,并将其应用于不同类型的萃取柱中,是萃取分离学科的重要任务.     

An experimental study of immiscible liquid–liquid dispersions in a pump–mixer of mixer–settler

Drop size distribution(DSD) or mean droplet size(d32) and liquid holdup are two key parameters in a liquid–liquid extraction process. Understanding and accurately predicting those parameters are of great importance in the optimal design of extraction columns as well as mixer–settlers. In this paper, the method of built-in endoscopic probe combined with pulse laser was adopted to measure the droplet size in liquid–liquid dispersions with a pump-impeller in a rectangular mixer. The dispersion law of droplets with holdup range 1% to 24% in batch process and larger flow ratio range 1/5 to 5/1 in continuous process was studied. Under the batch operation condition, the DSD abided by log-normal distribution. With the increase of impeller speed or decrease of dispersed phase holdup, the d32 decreased. In addition, a prediction model of d32 of kerosene/deionized system was established as d_(32)/D = 0.13(1 + 5.9φ)We~(-0.6). Under the continuous operation condition, the general model for droplet size prediction of kerosene/water system was presented as d_(32)/D = C_3(1 + C_4φ)We~(-0.6). For the surfactant system and extraction system, the prediction models met a general model as d_(32)/D = bφ~nWe~(-0.6).     

The Droplet Population Balance Model – Estimation of Breakage and Coalescence

A droplet population balance model is employed in order to describe the hydrodynamic behavior of solvent extraction columns. This model describes the axial change of local column holdup and local droplet size distributions due to the basic phenomena, like droplet rising, axial dispersion, droplet breakage and coalescence. In order to reduce experimental efforts, single and swarm droplet experiments in small lab‐scale devices were performed. For this, a rotating disc contactor (RDC) with one compartment and a Venturi tube were used to investigate droplet breakage and droplet coalescence. In case of breakage the experiments were made for different droplet sizes at different rotor speeds for the EFCE system toluene/water, whereas the investigations of the coalescence phenomena depending on droplet size and holdup were done with the EFCE system n‐butylacetate/water.     

一体式陶瓷外膜直接乳化法制备单分散水包油乳液

膜乳化法是靠膜两侧的压差使分散相通过微孔膜,以小液滴的形式分散在连续相中而形成乳状液的方法．与转一定体系、高压均化等传统制乳方法相比,膜乳化法所制得的乳液具有液滴尺寸均一、节能、剪应力小等特点,可应用于食品、医药、聚合物工业等领域．过去的十几年中,尽管在膜乳化方面进行了大量的工作,过程参数对乳滴尺寸的影响并未完全研究清楚．甚至在一些研究中,仅仅把平均乳滴直径作为分布参数．     

Turbulent liquid–liquid dispersion in SMV static mixer at high dispersed phase concentration

The aim of this paper is to investigate the influence of physico-chemical parameters on liquid–liquid dispersion at high dispersed phase concentration in Sulzer SMV™ mixer. Four different oil-in-water systems involving two different surfactants are used in order to evaluate the effect of interfacial tension, densities and viscosities ratio on mean droplets size diameters. Moreover the influence of the dispersed phase concentration on the pressure drop as well as on the droplet size distribution is investigated. Two different droplets size distribution analysis techniques are used in order to compare the resulting Sauter mean diameters. The comparison between residence time in the mixer and surfactants adsorption kinetics leads to take into account the evolution of the interfacial tension between both phases at short times. Finally experimental results are correlated as a function of dimensionless Reynolds and Weber numbers.     

An improved dynamic combined model for evaluating the mass transfer performances in extraction columns

Dispersed phase droplet behavior research is very important for the design and scaling up of extraction columns. Recently, the droplet velocities at high holdup were found to be uniform, which means the conventional concept of forward mixing needs correction. The drop size distribution only influences the mass transfer coefficients and not the residence time distribution of droplets. In this work, an improved dynamic combined model considering the influence of drop size distribution has been developed, by which the axial mixing can be easily evaluated using a one-dimension search. A typical experimental system of 30% tributyl phosphate (TBP) (in kerosene)-nitric acid-water with interfacial tension of 0.00995 N/m was used to investigate the mass transfer performances in a coalescence-dispersion pulsed-sieve-plate extraction column (CDPSEC) with 150 mm in diameter. The two-point dynamic method was used to obtain the stimulus-response curves. With these results, the axial mixing in the CDPSEC was evaluated. The calculated results showed that the response curves could be predicted by the dynamic combined model with a deviation less than 0.001. This model has marked advantages over previous models in literature because of its accuracy, simple boundary conditions, and single parameter optimization.     

Rotor‐Stator and Disc Systems for Emulsification Processes

Emulsions now find a wide range of applications in industry and daily life. In the pharmaceutical industry lipophilic active ingredients as well as many nutritional products such as vitamins are often formulated in the dispersed phase of oil‐in‐water emulsions. Emulsions can be produced with different mechanical emulsification techniques. In the following review, the process of rotor‐stator systems and disc systems are compared to other popular mechanical emulsification systems. On the basis of experimental results from the authors' laboratory, a discontinuous gear‐rim dispersing system, discontinuous disc system, and a continuous high pressure system are compared with regard to their attainable mean droplet diameter and drop size distribution in an oil‐in‐water emulsion. It can be shown that dissolver discs with a very simple geometry attain very small mean droplet diameters and a very narrow droplet size distribution, comparable to the emulsions obtained with established rotor‐stator systems such as gear‐rim dispersers.     

A dynamic forward mixing model for evaluating the mass transfer performances of an extraction column

It is well known that the droplet behavior of the dispersed phase in extraction equipments has a strong influence on the mass transfer performances. It is, and will continuously be a key project for design and scaling up of extraction columns. In this work, a dynamic mass transfer model, considering the effect of forward mixing led by the drop size distribution and the axial mixing of the continuous phase, has been developed, by which the axial mixing characteristic can be easily evaluated when a stimulus-response dynamic curve is obtained. In order to test the mass transfer model and to study in the effect of droplet coalescence on mass transfer performance, a typical experimental system of 30% tributyl phosphate (in kerosene)-nitric acid-water with interface intension of 0.00995 N/m was chosen to investigate the mass transfer in a coalescence-dispersion pulsed-sieve-plate extraction column (CDPSEC) with 150 mm in diameter. The two-point dynamic method was applied to get the stimulus-response curves. With these results the axial mixing of the CDPSEC were evaluated. The calculated results showed that the response curves could be predicted with the new mass transfer model very well. The model has marked advantages over the traditional diffusion model. It is closer to the practice, easier to solve for the mathematical equations and boundary conditions, and has only one parameter to be optimized. The calculated results also showed that the influence of local coalescence of droplets on mass transfer performances is obvious.     

Reaktive extraction of salicylic acid and D, L-phenylalanine in a bench-scale pulsed sieve plate column

The reactive (ion pair) extraction of salicylic acid with a secondary amine (Amberlite LA-2) in xylene and, for comparison, its physical extraction with xylene alone were investigated in a bench-scale pulsed sieve tray column. Also, the reactive (ion exchange) extraction of an amino acid (D,L-phenylalanine) with a quaternary ammonium salt (Adogen 464) in xylene was investigated in the same column. To characterize the two-phase system, the holdup and the droplet size distribution of the dispersed phase as well as the residence time distributions of both phases were measured.

The influence of the volumetric flow rate of the dispersed phase, the stroke frequency and the carrier concentration on the holdup, Sauter diameter, specific interfacial area, mean residence time and numbers of equivalent stages in the cascade, as well as on the degree of extraction and the longitudinal concentration profile of the solute in the column, were investigated. The degree of extraction and the longitudinal concentration profiles of the solute were calculated by means of a countercurrent cascade model and the measured kinetics for the extraction of salicylic acid. For physical extraction, satisfactory agreement between measured and calculated values was found. For reactive extraction, the measured and calculated degrees of extraction agree well. However, the longitudinal concentration profiles of the solute are not in agreement. The cause of this has not been evaluated yet.     

AI-Based Supervision for a Stirred Extraction Column Assisted with Population Balance-Based Simulation

Solvent extraction as environmental benign separation technique can be modeled in physical detail by population balance of the droplet size distribution. However, much information on the droplet generation and coalescence is necessary for representative results. In this contribution, we present a comparison of AI-evaluated experimental and simulated data on the behavior of a stirred solvent extraction column with an inner diameter of 32 mm. Lab experiments were performed using the standard test system with n-butyl acetate, acetone, and deionized water. A digital camera is placed in front of the middle section as well as the head of the column. Droplet size evaluation is performed using a retrained neural net (Mask R-CNN). The stirred DN32 extraction column is modeled and simulated using a 1D CFD population balance software. The simulation allows for behavior analysis, trends comparison, and validation of the hydrodynamics and mass transfer performances.     

Hydrodynamics and Mass Transfer in a Lab‐Scale Stirred‐Pulsed Extraction Column

An extraction column with energy input through simultaneous stirring and pulsation allows for efficient countercurrent extraction on lab‐scale. While stirring generates small droplets with a narrow droplet size distribution, pulsation supports the axial transport of the dispersed phase, enabling countercurrent flow on this small scale. By studying the influence of several operating parameters, fundamental mechanics and characteristics of the column are revealed. Increasing the stirrer speed leads to smaller droplets and higher extraction performance as well as lower maximum throughput. The maximum throughput is increased by raising the pulsation intensity.     

Separation of Submicron Particles in Packed Columns – Optimization and Scale-up of the Process

Particle enlargement by heterogeneous condensation and – based on it – separation of submicron particles in packed columns of technical scale are investigated. The activation of submicron particles and droplet growth by heterogeneous condensation is briefly described. Calculations of the droplet growth are performed and compared with experimental results. The enlargement and the separation of submicron particles by cascading packed columns trickled with water which is alternately colder or warmer than the gas is experimentally studied in a technical scale pilot plant consisting of three packed columns with a diameter of 300 mm. Droplet size distributions are measured by means of an optical particle sizer at the outlet of the columns. In order to optimize the separation process, the influence of different parameters on the separation of the submicron particles is investigated. These are the gas and the water temperature, the gas and the water flow rate, and the particle concentration. Moreover, the supersaturation of the air stream in the column is calculated by means of a rate-based nonequilibrium process model as a function of different parameters.     

Agitation of aerated emulsions

Aerated emulsions are gaining significance in fermentation as well as in inorganic and organic chemistry. In these processes, liquid-liquid mass transfer can be the limiting step. Therefore, the effect of gassing rate on droplet size was investigated as a function of dispersed liquid phase concentration and power input in different vessels. At high power inputs, the droplet size decreased. With increasing dispersed phase concentration and gassing rate, the droplet size increased and its dependence on power input subsided.     

乳化萃取中乳状液的重力沉降和搅拌破乳研究

乳化萃取是强化溶剂萃取的有效方法,可大大缩短反应时间、减小设备占地面积、提高萃取效率,但技术瓶颈是形成的乳状液破乳困难。采用了重力沉降和搅拌剪切法对乳化过程形成的油包水乳状液破乳,研究了2种方法的破乳机理、破乳率及破乳前后乳液微观粒径、显微镜图像的演变过程。结果表明：2种破乳方法结合可取得良好的破乳效果,破乳后两相间有明显的相界面,连续相内悬浮液滴数量急剧减少且液滴粒径显著变大,分布变窄。实验确定适宜的操作条件：搅拌速度为180 r/min、搅拌时间为5 min、静置时间为8 min,在此条件下破乳率可达到96%,临界液滴粒径为15 μm。     

Microspheres and microcapsules,a survey of manufacturing techniques: Part III: Solvent evaporation

A methodological survey of microsphere formation and microencapsulation techniques based on solvent extraction/evaporation techniques is presented. Thus, basic features of solvent extraction and solvent evaporation processes, including droplet formation, droplet/particle stabilization, and solvent removal, are outlined. Preparation of a wide range of microspherical and microcapsular products based on biodegradable polyesters, polysaccharides, and nonbiodegradable polymers are discussed. Dependence of microcapsule characteristics on manufacturing parameters, as well as performance evaluation of microspherical and microcapsular products, are also briefly covered.     

New Approach in the Prediction of RDC Liquid‐Liquid Extraction Column Parameters

The liquid‐liquid extraction process is well‐known for its complexity and often entails intensive modeling and computational efforts to simulate its dynamic behavior. This paper presents a new application of the Genetic Algorithm (GA) to predict the modeling parameters of a chemical pilot plant involving a rotating disc liquid‐liquid extraction contactor (RDC). In this process, the droplet behavior of the dispersed phase has a strong influence on the mass transfer performance of the column. The mass transfer mechanism inside the drops of the dispersed phase was modeled by the Handlos‐Baron circulating drop model with consideration of the effect of forward mixing. Using the Genetic Algorithm method and the Numerical Analysis Group (NAG) software, the mass transfer and axial dispersion coefficients in the continuous phase in these columns were optimized. In order to obtain the RDC column parameters, a least‐square function of differences between the simulated and experimental concentration profiles (SSD) and 95 % confidence limit in the plug flow number of the transfer unit prediction were considered. The minus 95 % confidence limit and sum of square deviations for the GA method justified it as a successful method for optimization of the mass transfer and axial dispersion coefficients of liquid‐liquid extraction columns.     

Experimental investigation on the mean drop size and drop size distribution in an L-shaped pulsed sieve-plate column

Vertical pulsed extraction columns cannot be employed in applications with height limitations. On the other hand, the horizontal extraction columns have low throughput, which affects their applicability in industrial applications. Therefore, there is a need to design a new type of extractors for such circumstances. In this paper, an experimental study on drop sizes has been implemented in a novel L-shaped pulsed sieve-plate extraction column in the absence and presence of mass transfer. Moreover, new correlations are developed for prediction of the mean drop size and size distribution using the log-normal probability density function.     

Impact of fluid path geometry and operating parameters on l/l-dispersion in interdigital micromixers

The dispersion of two immiscible fluids in interdigital micromixers was investigated using silicon oil/water and n-heptane/water as test systems. The experiments revealed the dependence of the average droplet size and size distribution on geometrical parameters of the micromixer and operating conditions. The mean droplet size was found to be correlated with total volume flow, volume flow ratio and corresponding pressure drop of the two liquids for a given micromixer geometry, which could be explained in light of the energy input. As a major focus, the effect of mixing chamber geometry and feeding system geometry was investigated with regard to droplet size distribution by systematically varying decisive dimensions in the mixer and by changing the feeding structure. It was shown that reducing the slit height and the number of feeding channels had a significant effect on droplet size distribution, leading to a smaller mean droplet size. Furthermore, the dispersion efficiency was also investigated by an extraction process.     

Comparison of the Hydrodynamic Performance of Pulsed Solvent Extraction Columns with Tenova Pulsed Column Kinetics Internals and Standard Disc and Doughnut Internals for Copper Extraction Using the LIX 84 System

The dispersed phase holdup and droplet size are important parameters for understanding the hydrodynamic performance of pulsed solvent extraction columns. This study provides a comparison of the hydrodynamic performance between a Tenova Pulsed Column with Kinetics Internals (TPC-KI) and a pulsed column with standard disc and doughnut internals. The TPC-KIs are designed to improve the performance of systems with slow reaction kinetics, such as copper extraction with LIX 84, which was the focus of the current study. Holdup and drop size have been measured as a function of pulsation intensity and phase velocities for both types of column internals. Lower holdup and larger drop sizes were obtained with the TPC-KI, which indicates a higher flood point and a higher throughput. Correlations have been developed to predict the performance of these internals over a range of operating conditions.