Mass transfer from nanofluid drops in a pulsed liquid–liquid extraction column

Mass transfer in gas–liquid systems has been significantly enhanced by recent developments in nanotechnology. However, the influence of nanoparticles in liquid–liquid systems has received much less attention. In the present study, both experimental and theoretical works were performed to investigate the influence of nanoparticles on the mass transfer behaviour of drops inside a pulsed liquid–liquid extraction column (PLLEC). The chemical system of kerosene–acetic acid–water was used, and the drops were organic nanofluids containing hydrophobic SiO₂ nanoparticles at concentrations of 0.01, 0.05, and 0.1 vol%. The experimental results indicate that the addition of 0.1 vol% nanoparticles to the base fluid improves the mass transfer performance by up to 60%. The increase in mass transfer with increased nanoparticle content was more apparent for lower pulsation intensities (0.3–1.3 cm/s). At high pulsation intensities, the Sauter mean diameter (d₃₂) decreased to smaller sizes (1.1–2.2 mm), leading to decreased Brownian motion in the nanoparticles. Using an analogy for heat and mass transfer, an approach for determining the mass diffusion coefficient was suggested. A new predictive correlation was proposed to calculate the effective diffusivity and mass transfer coefficient in terms of the nanoparticle volume fraction, Reynolds number, and Schmidt number. Finally, model predictions were directly compared with the experimental results for different nanofluids. The absolute average relative error (%AARE) of the proposed correlation for the mass transfer coefficient and effective diffusivity were 5.3% and 5.4%, respectively.     

第三相的加入对气液传质过程的影响

系统地介绍了气液传质过程中,固体小颗粒或第二分散液相(有机相)所形成的第三相的加入对传质过程的影响.分别论述了在不同的气-液接触器(搅拌釜、鼓泡塔)中,固体小颗粒和第二分散液相的加入对体系的传质系数、传质速率及界面面积等的影响,叙述并讨论了传质机理及模型的最新进展.     

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.     

The Effect of Size and Concentration of Nanoparticles on the Mass Transfer Coefficients in Irregular Packed Liquid–Liquid Extraction Columns

This investigation explored the effects of nanofluids on mass transfer enhancement using an irregularly packed liquid–liquid extraction column and the chemical systems of water–acetic acid–toluene. SiO₂ nanoparticles with sizes of 10, 30, or 80 nm are dispersed in toluene–acetic acid to produce nanofluids with different volume fractions of 0, 0.01, 0.05, and 0.1 vol.%. The effects of nanoparticle size and concentration on dispersed phase mass transfer coefficient were discussed based on the experimental data. This is for the first time that the effect of nanoparticle size is studied in liquid–liquid extraction systems. It was found that the mass transfer enhancement was more significant in nanofluids with smaller particles. It was also observed that mass transfer coefficient is larger in nanofluids compared to that in dispersed phase without nanoparticles, with a peak enhancement at a nanoparticle volume fraction of 0.05 vol.% for 10-nm particles and 0.01 vol.% for 30- and 80-nm particles. The maximum mass transfer coefficient enhancement was approximately 42% at 0.05% concentration of nanoparticles using smaller particles (10 nm). Finally, a novel correlation for prediction of effective diffusivity in the presence of nanoparticles has been proposed, which is a function of nanoparticle size and its concentration. The main advantage of this approach is that the principal effect of these two parameters is considered in correlation without which the experimental data could not be fitted with an acceptable accuracy.     

Mass transfer into/from nanofluid drops in a spray liquid‐liquid extraction column

The performance of a spray liquid‐liquid extraction column at two mass‐transfer directions was experimentally studied in the presence of silica nanoparticles. Toluene‐based nanofluid drops containing 0.0005–0.01 vol % silica nanoparticles were dispersed in aqueous phase and acetic acid (AA) transfer between phases was investigated. The experiments were performed at fixed volumetric flow rates of dispersed and continuous phases. Maximum enhancement of 47.4% and 107.5% in overall mass‐transfer coefficient, respectively, for mass‐transfer direction of dispersed to continuous phase and vice versa were achieved for drops with 0.001 vol % silica nanoparticles. These enhancements can be referred to Brownian motion of nanoparticles and induced microconvection. The results showed that nanoparticles are more effective in augmenting AA transfer from continuous to dispersed phase. Probable reason is that smaller diameter and lower internal turbulence of drops in this transfer direction increase dispersed phase resistance potential to be manipulated by Brownian motion of nanoparticles. © 2015 American Institute of Chemical Engineers AIChE J, 62: 852–860, 2016     

Brownian diffusion effect on nanometer aerosol classification in electrical mobility spectrometer

A multi-channel differential mobility analyzer (MCDMA) or aerosol spectrometer is widely used for classifying and measuring nanometer aerosol particles in the size range from 1 nm to 1 μm because of its better time response than a typical differential mobility analyzer. In the present study, the effect of Brownian diffusion on electrical mobility classification and trajectory of nanometer aerosol particles in an electrical mobility spectrometer developed at Chiang Mai University has been analytically investigated. Th Brownian diffusion of particles inside the spectrometer increased with decreasing particle size and flow rates of aerosol and clean sheath air, and with increasing inner electrode voltage, and also decreased with decreasing operating pressure. The particle trajectories considering Brownian diffusion motion inside the spectrometer were found to be broader than those under no Brownian diffusion. Smaller particles were found to have higher degree of broadening of trajectory than the larger particles. Brownian diffusion effect was found to be significant for particles smaller than 10 nm.     

液-液微尺度混合体系的传质模型

针对微尺度液-液混合体系,考察了流量对膜分散萃取过程的影响,并根据传质过程方程,计算了各种条件下的传质系数和传质速率;采用现有的传质模型分别计算分散相和连续相的分传质系数,然后根据传质阻力的加合性得到总传质系数;应用理论传质系数计算传质效率,与实验值进行了比较.研究结果表明,在微尺度混合条件下,直接影响传质系数的因素是停留时间和液滴直径,传质系数随着停留时间的减小而增大.膜分散萃取的传质系数可以达到1.2×10^-4m•s^-1,比传统的萃取方式大10～100倍;不能像塔式萃取设备一样,用简单地忽略某一相的传质阻力或用总体平均的简化计算公式来计算微尺度混合的传质性能;考虑滴内滴外传质系数,并考虑时间的影响,利用现有公式分别计算滴内滴外传质系数,并采用阻力加合,可以较为准确地计算微混合条件下的总传质系数,计算值与实验值符合很好.     

Modelling of batch fluidised bed drying of pharmaceutical granules

This paper presents a mathematical model based on a three-phase theory, which is used to describe the mass and heat transfer between the gas and solids phases in a batch fluidised bed dryer. In the model, it is assumed that the dilute phase (i.e., bubble) is plug flow while the interstitial gas and the solid particles are considered as being perfectly mixed. The thermal conductivity of wet particles is modelled using a serial and parallel circuit. The moisture diffusion in wet particles was simulated using a numerical finite volume method. Applying a simplified lumped model to a single solid particle, the heat and mass transfer between the interstitial gas and solid phase is taken into account during the whole drying process as three drying rate periods: warming-up, constant rate and falling-rate. The effects of the process parameters, such as particle size, gas velocity, inlet gas temperature and relative humidity, on the moisture content of solids in the bed have been studied by numerical computation using this model. The results are in good agreement with experimental data of heat and mass transfer in fluidised bed dryers. The model will be employed for online simulation of a fluidised bed dryer and for online control.     

Photocatalytic degradation rate of oxalic acid on the semiconductive layer of n-TiO2 particles in the batch mode plate reactor Part I: Mass transfer limits

Organic compounds dissolved in water can be decomposed on a layer of n-TiO2 particles irradiated by u.v. light, which generates holes and electrons in the TiO2 material. Dissolved oxygen was used as electron scavenger and holes reacted with water to give OH radicals. The rate of degradation of the dissolved organic compounds by OH radicals is limited by the transfer of either oxygen or of theorganic compounds to the surface of n-TiO2 particles. The consequence of these limits is that, in the batch mode reactor with recirculation of the liquid, the dependence of the concentration of an organic compound on time has either a linear or an exponential form. Experiments with decomposition of oxalic acid in aqueous solutions using a plate reactor (60 cm × 120 cm) confirmed the analysis. Equations for evaluation of the mass transfer coefficient of the dissolved species to the surface of the plate reactor with a moving liquid fil m were developed for the case of the thickness of the Nernst diffusion layer being thinner than the thickness of the liquid. The experimentally obtained decomposition rate of oxalic acid was about 60 to 80% of the theoretical decomposition rate limited by oxygen flux through the film of a moving liquid. The present theory neglects the diffusion of oxygen into the porous layer of n-TiO2.     

Mass transfer and selectivity of ozone reactions

The present research concerns the behavior of mass transport in absorption of ozone accompanied by decomposition and ozonation reactions in aqueous solutions. On the basis of the film theory, a mathematical model has been formulated for the transport process taking into account molecular diffusion and the simultaneous decomposition and ozonation reactions of different orders. Analytical approximate and finite difference methods have been employed to predict concentration profiles, enhancement factor and selectivity of the chemical mass transfer in gas-liquid systems. The rate of mass transfer is enhanced by the chemical reactions as well as the availability of liquid reactant in the aqueous phase. When the ozonation reaction is much faster than the decomposition reaction, a large fraction of the absorbed ozone is utilized effectively in reacting with the liquid constituent and a high selectivity of the gas-liquid reactions can be obtained. Calculated results indicate that removal of certain organic pollutants by the oxidation process may be effective only in acidic or neutral solutions where a high mass transfer rate and selectivity is achieved.     

The mechanism model of gas–liquid mass transfer enhancement by fine catalyst particles

In order to present the enhancement of gas–liquid mass transfer by heterogeneous chemical reaction near interface, the mechanism model has been proposed to describe the mass transfer rate for a gas–liquid–solid system containing fine catalyst particles. The composite grid technique has been used to solve the model equations. With this model the effect of particle size, first-order reaction rate constant, distance of particle to gas–liquid interface and residence time of particle near gas–liquid interface on the mass transfer enhancement have been discussed. The particle–particle interaction and slurry apparent viscosity can be considered in the model. The experimental data have been used to verify the model, and the agreement has been found to be satisfied.     

直接甲醇燃料电池阴极水的传输特性

利用COMSOL Multiphysics软件对直接甲醇燃料电池（DMFC）阴极模型进行计算,获得压力、速度、水、氧气和液态饱和度分布情况,研究扩散层在不同物理参数（如厚度、孔隙率、孔径大小和亲憎水性）下电池阴极水和氧气的传输情况,进一步建立扩散层孔隙率梯度的数学模型,研究扩散层孔隙率梯度以及支撑层参数对直接甲醇燃料电池性能和物质传输的影响。结果表明,扩散层具有大孔隙率、薄扩散层时均有利于氧气传质,可以使电池性能提高;扩散层孔隙率梯度的存在可以减轻氧气传输阻力,提高电池性能。     

内循环生物流化床曝气过程氧传质特性研究

针对水-空气-高分子颗粒三相体系,测试了内循环好氧生物流化床曝气过程中气-液相间氧传递的体积传质系数KLa,分析了操作参数(进气量QG、固含率εs和升降流区截面积比Ar/Ad)对氧传质系数KLa的影响。结果表明,KLa随着进气量的提高呈线性增加趋势;固含率对KLa有正反两方面的作用,存在一个较适宜的固含率使氧传质效率达到最高;随升降流区截面积比Ar/Ad的增大,KLa随之提高。基于KLa影响因素的分析对实验数据进行拟合,建立了关于体积传质系数KLa的关联式:Kd=2.23×10-6Reb0.582Ab0.976εs0.016。该关联式预测结果与实验数据吻合良好,对类似流化床反应器的设计有一定参考价值。     

Importance of sample intraparticle diffusivity in investigations of the mass transfer mechanism in liquid chromatography

The effective diffusivity of a nonretained (thiourea) and of a strongly retained (phenol) compounds were measured with the peak parking method in two different columns (both 150 × 4.6 mm) packed with two types of porous particles having different mesopore sizes [5 μm Jupiter‐C₁₈, 320 Å and Luna(2)‐C₁₈, 100 Å]. The eluent was a methanol–water mixture (10/90 v/v) and the temperature 294 K. The effective diffusivity data acquired were used to determine the intraparticle diffusivity, D_p, based on two different diffusion models. The first one assumes that the diffusion fluxes across the particles and in the interparticle volume are additive (parallel diffusion model). The second model was rigorously derived on the basis of the effective medium theory of diffusion (diffusion model) in a binary composite medium (particles + interparticle volume). In both models, it was assumed that the rate of equilibrium between the liquid and the solid phases was infinitely faster than the rate of axial diffusion along the column at zero flow rate. Both models provide physically meaningful intraparticle diffusivity coefficients that take into account the average mesopore size of the particles, their specific surface area, and the retention factor of the analyte. Although the actual effective intraparticle diffusivity remains unknown, these result confirm that the mass transfer resistance due to diffusion through the porous particles has almost negligible effects in reversed phase liquid chromatography due to the importance of surface diffusion. Combining the results of the peak parking method with the h data measured at high linear velocities allows the unambiguous measurement of the film mass transfer and the surface diffusion coefficients. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

New liquid membrane technology for simultaneous extraction and stripping of copper(II) from wastewater

In this paper, a new liquid membrane technique, hollow fiber renewal liquid membrane (HFRLM), is presented, which is based on the surface renewal theory, and integrates the advantages of fiber membrane extraction, liquid film permeation and other liquid membrane processes. The results from the system of CuSO₄+D2EHPA in kerosene+HCl show that the HFRLM process is very stable. The liquid membrane is renewed constantly during the process, the direct contact of organic droplets and aqueous phase provides large mass transfer area. These effects can significantly reduce the mass transfer resistance in the lumen side. Then the mixture of feed phase and organic phase flowing through the lumen side gives a higher mass transfer rate than that of stripping phase and organic phase, because the aqueous layer diffusion of feed phase is the rate-controlling step. The overall mass transfer coefficient increases with increasing flow rates and D2EHPA concentration in the organic phase, and with decreasing initial copper concentration in the feed phase. The overall mass transfer coefficient also increases with increasing pH in the feed phase, and reaches a maximum value at pH of 4.44, then decreases. Also, there is a favorable w/o volume ratio of 20:1 to 30:1 for this process. Compared with hollow fiber supported liquid membrane and hollow fiber membrane extraction processes, HFRLM process has a high mass transfer rate. Mathematical model for the HFRLM process based on the surface renewal theory is developed. The calculated results are in good agreement with experimental results under the conditions studied.     

Investigations of mass transfer with chemical reactions in two-phase liquid–liquid systems

A new method based on experimental determination of the product distribution of a set of complex test reactions has been introduced and applied to study mass transfer in liquid–liquid systems. The test reactions consist of two parallel reactions, one of them being instantaneous and the second fast relative to mass transfer. Two reactants are transferred from the dispersed, organic phase (phase volume 1% vol) to the continuous aqueous phase, where the third reactant is present. Experiments were carried out in a batch system agitated with either a six-blade paddle impeller or a high-shear rotor–stator LR4 Silverson mixer to disperse drops and increase the mass transfer rate. The product distribution and the drop size distribution were measured using gas chromatography–mass spectroscopy and Malvern MasterSizer, respectively with pH variation recorded during the process. The results show that the focused supply of energy in the Silverson mixer is effective for the short term irreversible drop break-up process producing smaller droplets than the six-blade paddle impeller. However for the long term mass transfer process the paddle impeller is more effective due to more uniform supply of energy and better mixing throughout the tank compared to the more localized mixing of the Silverson.     

Hydrodynamics and local mass transfer characterization under gas–liquid–liquid slug flow in a rectangular microchannel

Gas–liquid–liquid three-phase slug flow was generated in a glass microreactor with rectangular microchannel, where aqueous slugs were distinguished by relative positions to air bubbles and organic droplets. Oxygen from bubbles reacted with resazurin in slugs, leading to prominent color changes, which was used to quantify mass transfer performance. The development of slug length indicated a film flow through the corner between bubbles and the channel wall, where the aqueous phase was saturated with oxygen transferred from bubble body. This film flow results in the highest equivalent oxygen concentration within the slug led by a bubble and followed by a droplet. The three-phase slug flow subregime with alternate bubble and droplet was found to benefit the overall mass transfer performance most. These results provide insights into a precise manipulation of gas–liquid–liquid slug flow in microreactors and the relevant mass transfer behavior thereof.     

Residence time distribution in a packed bed bioreactor containing porous glass particles: Influence of the presence of immobilized cells

An experimental investigation of the liquid phase residence time distribution (RTD) in a packed bed bioreactor containing porous glass particles is presented. For Re < 1, intraparticle forced convection is negligible and only diffusion, characterized by an effective diffusion coefficient, must be considered to describe the mass transfer process between the extraparticle and the intraparticle fluid phase. For Re > 1, the mass transfer rate becomes dependent on the liquid flow rate, indicating the existence of intraparticle convection. A model including axially dispersed flow for the external fluid phase and an ‘apparent’ effective diffusivity that combines diffusion and convection, predicts experimental RTD data satisfactorily. Yeast cells immobilized inside the porous glass beads did not affect the mass transfer rate at low biomass loading. At high biomass loading (0·02 g yeast cells g^?1 carrier), the mass transfer rate between the extraparticle and intraparticle fluid phase was significantly decreased. Comparison of the RTD data from experimets performed in the presence and absence of cells in the external fluid phase revealed that the mass transfer rate is influenced by the cells immobilized inside the porous particles and not by the cells present in the external fluid phase.     

The Effect of Nanoparticles on the Mass Transfer in Liquid–Liquid Extraction

This article investigates the effect of nanoparticles on mass transfer in the liquid–liquid extraction for the chemical system of n-butanol–succinic acid–water. For this purpose, nanofluids containing various concentrations of ZnO, carbon nanotubes (CNT), and TiO₂ nanoparticles in water, as base fluid, were prepared. To examine the flow mode effect on mass transfer rate, different fluid modes including dropping and jetting were employed in the process. Results show that mass transfer rate enhancement depends on the kinds and the concentration of nanoparticles and the modes of flow. It was observed that after adding nanoparticles, the mass transfer rate significantly increases up to two-fold for ZnO nanoparticles. Furthermore, the results indicate that under the circumstances in which the mass flow rate is high enough, the effect of nanoparticles on the mass transfer phenomenon is too slight.