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 to a drop stream from a field liquid

Mass transfer from a stream of drops falling freely in a stagnant liquid was investigated. Drop streams were produced by a dripping method and by a jet breakup method. Water and isobutanol, mutually saturated, were used as the dispersed and the continuous phases. Sodium hydroxide was transferred from isobutanol to water drops which were initially free of solute. The mass transfer resistance is on the continuous phase side. The mass transfer coefficient and terminal velocity of drop streams were measured experimentally. The experimental results show that the mass transfer coefficient in the drop stream is affected by the shielding effect of the previous drops. The experimental data have been correlated as K_t/U_t^0.5 versus interdrop distance l, a relationship describing the effect of the interdrop distance on the mass transfer coefficient in the continuous phase.     

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.     

Liquid–liquid–solid mass transfer and phase behavior of heterogeneous etherification of glycerol with isobutene

Previous experiments observed auto‐acceleration in the etherification of glycerol with isobutene. This article engaged to uncover the reason for this phenomenon via investigating the heterogenicity, including liquid–liquid phase equilibrium and liquid–liquid–solid mass transfer, of the reaction system. Phase behavior analysis showed that the reaction mixture separates into two liquid phases during the whole course of the reaction. The produced mono ethers of glycerol thermodynamically promote the homogenization of the two liquid phases. The modeling results of liquid–liquid–solid mass transfer indicated that the resistance of mass transfer is insignificant during the reaction. The bulk compositions of the two liquid phases are very close to their corresponding equilibrium compositions. An increase of isobutene concentration in the reaction phase is believed to lead all reactions speeding up. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2526–2535, 2018     

Use of axial dispersion and plug flow models for determination of axial mixing and mass transfer coefficient in an l‐shaped pulsed packed extraction column

In this study, the volumetric overall mass transfer and phases axial mixing coefficients have been investigated in a pilot plant of an L‐shaped pulsed packed extraction column by using two liquid systems of toluene/acetone/water and n‐butyl/acetone/water. The mass transfer performance has been evaluated using two methods of axial dispersion and a plug flow model. The effect of the operational variables and physical properties, including the dispersed and continuous phases flow rates, pulsation intensity, and interfacial tension, on mass transfer and phases axial mixing coefficients have been considered. It has been found that the pulsation intensity and the continuous phase flow rate seriously affect the mass transfer coefficient, however, the dispersed phase flow rate has a weaker effect. Also, the axial mixing of a phase is strongly affected by the pulsation intensity and the flow rate of the phase itself and it is not affected by the second phase flow rate. Finally, new correlations are proposed to accurately predict the mass transfer and axial mixing coefficients.     

Enhancement of oxygen mass transfer rate in the presence of nanosized particles

Absorption of gases into a liquid is essentially important for two- or three-phase reactions, because the diffusion of a sparingly soluble gas, like oxygen, across a gas-liquid interface generally limits the reaction rates. Using a third, dispersed phase, the mass transfer rate could be significantly increased. The question arises how the absorption rate can be described in the presence of very fine, nanometer size particles or droplets. Its mathematical model should take into account the specific properties of the nanoparticles, e.g. the Brownian motion of particles, its effect on the diffusion of the bulk phase molecules, the mass transfer rate into the nanoparticles, its dependency on the particle size, etc. The mass transfer rate of oxygen, in the presence of nanometer size, organic droplets, has been investigated both experimentally, using organic submicron n-hexadecane droplets, and theoretically. The effect of the Brownian motion of the nanoparticles as well as its effect on the diffusivity in the nanofluid has been discussed. Accordingly, the enhanced diffusion coefficient, due to the convective motion of the continuous liquid phase induced by the moving particles, has been predicted and its effect on the mass transfer enhancement has been calculated using both homogeneous and heterogeneous mathematical models. The predicted data were compared to the measured ones.     

Bubble/droplet formation and mass transfer during gas–liquid–liquid segmented flow with soluble gas in a microchannel

Microchannels have great potential in intensification of gas–liquid–liquid reactions involving reacting gases, such as hydrogenation. This work uses CO₂–octane–water system to model the hydrodynamics and mass transfer of such systems in a microchannel with double T‐junctions. Segmented flows are generated with three inlet sequences and the size laws of dispersed phases are obtained. Three generation mechanisms of dispersed gas bubbles/water droplets are identified: squeezing by the oil phase, cutting by the droplet/bubble, cutting by the water–oil/gas–oil interface. Based on the gas dissolution rate, the mass transfer coefficients are calculated. It is found that water droplet can significantly enhance the transfer of CO₂ into the oil phase initially. When bubble‐droplet cluster are formed downstream the microchannel, droplet will retard the mass transfer. Other characteristics such as phase hold‐up, bubble velocity and bubble dissolution rate are also discussed. The information is beneficial for microreactor design when applying three‐phase reactions. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1727–1739, 2017     

Mass‐transfer enhancement in single drop extraction in the presence of magnetic nanoparticles and magnetic field

Magnetite nanoparticles with an average particle size of 28.8 nm were synthesized, coated with oleic acid, and characterized using various techniques such as DLS, FT‐IR, SEM, XRD, VSM, and UV‐Vis analysis. A nanofluid consisting of synthesized nanoparticles and 5 wt % acetic acid in toluene as the dispersed phase was prepared and used in the chemical test system, Toluene‐Acetic Acid‐Water, for the single drop extraction in the presence and absence of an external oscillating magnetic field. Influences of various operating and design parameters such as nanoparticle concentration, drop diameter, and the applied current and frequency on the overall mass‐transfer coefficients for the mass‐transfer direction from d→c were investigated carefully. The obtained results were used to propose a general correlation for the mass‐transfer enhancement. It was found that the maximum mass‐transfer enhancement compared with that obtained in the absence of nanoparticles and the oscillating magnetic field is about 259%. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4466–4479, 2016     

Mass transfer in centrifugal extractors

This contribution presents the methods of measuring the mass transfer in centrifugal extractors and of determining it during the individual life stages of a fluid element of the dispersed liquid, i.e. drop formation, motion, coalescence and stay in the stationary layer of the dispersed phase. The experimental mass transfer coefficients of the dispersed and continuous phases are compared with well-known theoretical models developed for extraction columns in gravitational field. Due to the fast motion and coalescence of the fluid particles at high centrifugal field intensities, mass transfer in centrifugal extractors takes place during short contact times. Nevertheless, this contribution shows that mass transfer in a centrifugal field can be calculated with selected theoretical models of the gravitational field. The investigations on mass transfer are completed by a classification of the strongly deformed fluid particles in centrifugal field into regimes of circulating and oscillating drops. In addition, data on the performance of centrifugal extractors, undergoing several exchange steps, are given.     

Study of droplet behaviour along a pulsed liquid–liquid extraction column in the presence of nanoparticles

In this article, droplet size and its distribution along a pulsed liquid–liquid extraction column, is studied where SiO₂ nanoparticles with concentrations of 0.01, 0.05 and 0.1 vol.% and different hydrophobicities are applied to the dispersed phase. Using ultrasonication, nanoparticles were dispersed in kerosene as the base fluid. Nanofluids' stability was ensured using a UV–vis spectrophotometer. Some 22,000 droplets were measured by photographic technique and results were compared with systems containing no‐nanoparticles (Water–Acetic acid–Kerosene). Addition of nanoparticles changed the droplet shape from ellipsoidal to spherical. Also, there was a marked influence on droplet breakage and droplet coalescence at 0.01 vol.%, and 0.05 vol.% or higher volume fractions, respectively. © 2012 Canadian Society for Chemical Engineering     

Investigation of reactive extraction on single droplets

Extraction of dichlorphenol from freely suspended single drops into a continuous phase enhanced by an instantaneous chemical reaction was investigated using NaOH solutions of different concentrations. Also, the reverse mass transfer direction from the continuous phase into the dispersed phase was studied by extracting salicylic acid with the liquid ion exchanger LA-2. Concentrations were measured continuously without taking samples by means of a modified liquid scintillation technique. For appropriate concentrations of NaOH the continuous phase side mass transfer resistance vanishes with increasing extraction time and hence, for the first time, the individual mass transfer coefficients in the dispersed and continuous phase were determined from the overall value for exactly the same fluiddynamical conditions. Experimentally determined enhancement factors are larger than those predicted by the film theory.     

Numerical study of turbulent liquid‐liquid dispersions

A numerical approach is developed to gain fundamental insight in liquid‐liquid dispersion formation under well‐controlled turbulent conditions. The approach is based on a free energy lattice Boltzmann equation method, and relies on detailed resolution of the interaction of the dispersed and continuous phase at the microscopic level, including drop breakup and coalescence. The capability of the numerical technique to perform direct numerical simulations of turbulently agitated liquid‐liquid dispersions is assessed. Three‐dimensional simulations are carried out in fully periodic cubic domains with grids of size . The liquids are of equal density. Viscosity ratios (dispersed phase over continuous phase) are in the range 0.3–1.0. The dispersed phase volume fraction varies from 0.001 to 0.2. The process of dispersion formation is followed and visualized. The size of each drop in the dispersion is measured in‐line with no disturbance of the flow. However, the numerical method is plagued by numerical dissolution of drops that are smaller than 10 times the lattice spacing. It is shown that to mitigate this effect it is necessary to increase the resolution of the Kolmogorov scales, such as to have a minimum drop size in the range 20–30 lattice units [lu]. Four levels of Kolmogorov length scale resolution have been considered , 2.5, 5, and 10 [lu]. In addition, the numerical dissolution reduces if the concentration of the dispersed phase is increased. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2618–2633, 2015     

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.     

A study on hydrodynamic characteristics in a Φ38 pulsed extraction column by four‐sensor optical fiber probe

Accurate prediction of dispersed phase droplet behavior is crucial to the design and scaling‐up of an extraction column. In this article, the dispersed droplet velocity algorithm and the diameter algorithm in a liquid–liquid two‐phase flow have been developed based on the bubble velocity model in gas–liquid two‐phase flow of Lucas [Measurement Science & Technology. 749, 758(2005)] and Shen [International Journal of Multiphase Flow. 593, 617(2005)]. Hydrodynamic characteristics, including droplet diameter, holdup and droplet velocity, were measured using a self‐made four‐sensor optical fiber probe in a 38 mm‐diameter pulsed sieve‐plate extraction column. Water and kerosene were used as continuous and dispersed phases, respectively. The influences of the pulsed intensity, the continuous and dispersed phase superficial velocities on the hydrodynamic characteristics were investigated. The experimental results show that it is reliable to use a four‐sensor optical probe to measure the hydrodynamic characteristics of a pulsed extraction column. © 2016 American Institute of Chemical Engineers AIChE J, 63: 801–811, 2017     

Phase distribution in dispersed liquid–liquid flow in vertical pipe: Mean and turbulent contributions of interfacial force

We applied an Eulerian–Eulerian two‐fluid model on an upward dispersed oil–water flow in vertical pipe with 80 mm diameter and 2.5 m length. The numerical profiles of the radial distribution of the oil drops at 1.5 m from the inflow are compared to the experimental data of Lucas and Panagiotopoulos (Flow Meas Instrum. 2009;20:127–135) This article analyzes the roles of turbulence and interfacial forces on the phase distribution phenomenon. In liquid–liquid flow the relative velocity is low and the distribution of the dispersed phase is mainly governed by the turbulence. This work highlights the important role of the turbulent contribution obtained by averaging the added mass force on the radial distribution profiles of the oil drops. The numerical results present improved profiles of the dispersed phase comparing to the experimental data when this turbulent contribution is taken into account in the momentum balance. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4214–4223, 2017     

Corrosion inhibition of carbon steel under two‐phase flow (water‐petroleum) simulated by turbulently agitated system

The corrosion of carbon steel in single‐phase (water with 0.1N NaCl) and two immiscible phases (kerosene‐water) using turbulently agitated system was investigated. The experiments were carried out for Reynolds number (Re) range of 38 000 to 95 000 using circular disc turbine agitator at 40°C. In two‐phase system, test runs were carried out in aqueous phase (water) concentrations of 1% vol, 5% vol, 8% vol, and 16.4% vol mixed with kerosene at various Re. The effect of Re, percent of dispersed phase, dispersed droplet diameter, and number of droplets per unit volume on the corrosion rate were investigated and discussed. Test runs were carried out using two types of inhibitors: sodium nitrite of concentrations 20, 40, and 60 ppm and sodium hexapolyphosphate of concentrations 485, 970, and 1940 ppm in a solution containing 8% vol aqueous phase (water) mixed with kerosene (continuous phase) at 40°C for the whole range of Re. It was found that increasing Re increased the corrosion rate and the presence of water enhanced the corrosion rate by increasing the solution electrical conductivity. For two‐phase solution containing 8% vol and 16% vol of water, the corrosion rate was higher than single phase (100% vol water). The main parameters that play the major role in determining the corrosion rate in two phases were concentration of oxygen, solution electrical conductivity, and the interfacial area between the two phases (dispersed and continuous). Sodium nitrite and sodium hexapolyphosphate were found to be efficient inhibitors in two‐phase solution for the investigated range of Re.     

Performance improving with temperature in liquid–liquid extraction using cumene–isobutyric acid–water chemical system

The performance of single drops was investigated in liquid–liquid extraction while temperature was changed within the range of 15–40 °C. The recommended system of cumene–isobutyric acid–water with mass transfer resistance mainly in aqueous phase was used. An average enhancement of 75.6% in the rate of transfer was revealed. The extraction efficiency is the most influencing term due to molecular diffusivity enhancement. For modeling, a simple correlation was proposed for the effective diffusivity in Newman's equation, while continuous phase mass transfer coefficient was directly included. Using this model, relative deviation of the overall mass transfer coefficient was within only ±5.6%.     

Mass Transfer during Solute Extraction from a Droplet with Internal Circulation in the Presence of a Constant Uniform Electric Field

Mass transfer, under the influence of an constant uniform electric field in a ternary system, comprised of a transformed solute, a liquid dielectric continuous phase, and a stationary dielectric droplet, was considered in this study. The solubilities of the solute in the dispersed and continuous phases have the same order of magnitude, and the resistance to mass transfer in both phases is taken into account. The applied electric field causes Taylor circulation around the droplet, while the droplet deformation under the influence of the electric field is neglected. The problem is solved in the approximations of a thin concentration boundary layer in the dispersed and continuous phases. The bulk of a droplet, beyond the diffusion boundary layer, is completely mixed and the concentration of solute is homogeneous and time‐dependent in the bulk. The system of transient coupled equations of convective diffusion for solute transport in the dispersed and continuous phases with time‐dependent boundary conditions is solved by combining a generalized similarity transformation method with Duhamel's theorem; the solution is obtained in the form of a Volterra integral equation of the second kind. Numerical calculations essentially show an enhancement of the rate of mass transfer for dispersed liquid‐liquid systems, under the influence of an electric field.     

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.     

Methanol synthesis in a three‐phase catalytic bed under nonwetted condition

To overcome the heat removal problem encountered in methanol synthesis at high syngas concentrations in the gas phase, a three‐phase nonwetted catalytic system was established by introducing an inert liquid medium into a fixed‐bed reactor. To form a repellent interface between the liquid and the catalyst, the catalyst was modified into hydrophobic, while the liquid medium was chosen as a room temperature ionic liquid with hydroxyl groups. The liquid‐solid contact angle was measured to be 115°, and only 20% of the catalyst external surface was wetted by the liquid. Under three‐phase condition, the reaction rate was measured to be 60%–70% of gas‐phase reaction, while it was merely 10%–20% for the fully wetted catalyst. From the resistance analysis on the mass transfer and reaction steps, the overall reaction rate is expected to increase further if the surface could be more wet proofed. © 2016 American Institute of Chemical Engineers AIChE J, 63: 226–237, 2017