Performance of hollow fiber supported liquid membrane on the extraction of mercury(II) ions

The extraction and recovery or stripping of mercury ions from chloride media using microporous hydrophobic hollow fiber supported liquid membranes (HFSLM) has been studied. Tri-n-octylamine (TOA) dissolved in kerosene was used as an extractant. Sodium hydroxide was used as a stripping solution. The transport system was studied as a function of several variables: the concentration of hydrochloric acid in the feed solution, the concentration of TOA in the liquid membrane, the concentration of sodium hydroxide in the stripping solution, the concentration of mercury ions in the feed solution and the flow rates of both feed and stripping solutions. The results indicated that the maximum percentages of the extraction and recovery of mercury ions of 100% and 97% were achieved at the concentration of hydrochloric acid in the feed solution of 0.1 mol/l, the concentration of TOA at 3% v/v, the concentration of sodium hydroxide at 0.5 mol/l and the flow rates of the feed and stripping solutions of 100 ml/min. However, the concentration of mercury ions from 1–100 ppm in the feed solution had no effect on the percentages of extraction and recovery of mercury ions. Thus, these results have identified that the hollow fiber supported liquid membrane process has high efficiency on both the extraction and recovery of mercury (II) ions. Moreover, the mass transfer coefficients of the aqueous phase (k _i ) and membrane or organic phase (k _m ) were calculated. The mass transfer coefficients of the aqueous phase and organic phase are 0.42 and 1.67 cm/s, respectively. The mass transfer coefficient of the organic phase is higher than that of the aqueous phase. Therefore, the mass transfer controlling step is the diffusion of the mercury ions through the film layer between the feed solution and the liquid membrane.     

Permeation and modeling studies on Ge(IV) facilitated transport using trioctylamine through supported liquid membrane

Germanium transport from a solution containing tartaric acid by a flat sheet supported liquid membrane (FSSLM) using trioctylamine (TOA) as a carrier and polytetrafluoroethylene (PTFE) as a membrane was investigated. A mass transfer model was developed to monitor the transport process based on experimental results. The effect of parameters such as feed solution pH, TOA concentration, initial germanium concentration, and strip hydrochloric acid concentration on the germanium flux and the transport percentage were studied. A high permeation was observed at a feed solution pH of 3.00, 40%v/v TOA and 5 mg/dm³ Ge⁴⁺. At HCl concentrations of 1–3 mol/dm³, the germanium transport was complete. Finally, based on the mass transfer model, the aqueous and organic resistance values were 11,802 and 860.85 h/cm, respectively. The validity of the model was investigated by fitting the model and experimental data. The correlation coefficient of 0.99 showed the validity of the model.     

Selective enantioseparation of levocetirizine via a hollow fiber supported liquid membrane and mass transfer prediction

The enantioselective separation of levocetirizine via a hollow fiber supported liquid membrane was examined. O,O′-dibenzoyl-(2R,3R)-tartaric acid ((?)-DBTA) diluted in 1-decanol was used as a chiral selector extractant. The influence of concentrations of feed and stripping phases, and extractant concentration in the membrane phase, was also investigated. A mathematical model focusing on the extraction side of the liquid membrane system was presented to predict the concentration of levocetirizine at different times. The extraction and recovery of levocetirizine from feed phase were 75.00% and 72.00%, respectively. The mass transfer coefficients at aqueous feed boundary layer (k _f ) and the organic liquid membrane phase (k _m ) were calculated as 2.41×10² and 1.89×10² cm/s, respectively. The validity of the developed model was evaluated through a comparison with experimental data, and good agreement was obtained.     

Separation of As(III) and As(V) by hollow fiber supported liquid membrane based on the mass transfer theory

Separation of As(III) and As(V) ions from sulphate media by hollow fiber supported liquid membrane has been examined. Cyanex 923 was diluted in toluene and used as an extractant. Water was used as a stripping solution. The extractability of As(V) was higher than As(III). When the concentration of sulphuric acid in feed solution and Cyanex 923 in liquid membrane increased, more arsenic ions were extracted into liquid membrane and recovered into the stripping solution. The mathematical model was focused on the extraction side of the liquid membrane system. The mass transfer coefficients of the aqueous phase (k _i ) and organic phase (k _m ) are 7.15×10⁻³ and 3.45×10⁻² cm/s for As(III), and 1.07×10⁻² and 1.79×10⁻² cm/s for As(V). Therefore, the rate-controlling step for As(III) and As(V) in liquid membrane process is the mass transfer in the aqueous film between the feed solution and liquid membrane. The calculated mass transfer coefficients agree with the experimental results.     

Extraction and pertraction of phenol through bulk liquid membranes

The extraction and pertraction of phenol through a bulk liquid membrane (BLM) with Cyanex^® 923, Amberlite^® LA‐2 and trioctylamine (TOA) as carriers were studied. Cyanex^® 923 was selected as the best carrier for pertraction. The distribution coefficient of phenol for solvents with carrier and pure n‐alkanes, the individual mass‐transfer coefficient at the extraction interface and the initial flux of phenol through the extraction interface (J_Fo) decreased in the order: Cyanex^® 923 > Amberlite^® LA‐2 > TOA ? pure n‐alkanes. The opposite order was observed for the value of the mass‐transfer coefficient in BLM and the maximum flux of phenol through the stripping interface (J_Rmax). At constant driving forces the maximum fluxes through the extraction and stripping interfaces were similar when amine carriers were used. However, J_Rmax was lower than J_Fo for Cyanex^® 923. Although the kinetics of stripping was the rate‐determining step, the flux of phenol was significantly higher than in pertraction with amine carriers. The adsorption of the carrier at aqueous phase/membrane interfaces was probably responsible for the rapid and slow transfer of phenol through the extraction and stripping interface, respectively. Copyright © 2004 Society of Chemical Industry     

REACTIVE EXTRACTION OF LEVULINIC ACID FROM AQUEOUS SOLUTIONS WITH TRI-n-OCTYLAMINE (TOA) IN 1-OCTANOL: EQUILIBRIA,KINETICS, AND MODEL DEVELOPMENT

Levulinic acid, a carboxylic acid containing a ketone structure, can be used as an acidulant in foods and beverages. Reactive extraction is a promising alternative for the recovery of carboxylic acids from aqueous streams. The design of an amine extraction process requires kinetic data for the acid-amine + solvent system used. In this study, equilibrium and kinetic data on the extraction of levulinic acid from aqueous solutions using tri-n-octylamine (TOA) in 1-octanol have been determined. The mass transfer coefficients of levulinic acid, TOA, and 2:1 levulinic acid-amine complex in 1-octanol were calculated from the acetic acid mass transfer coefficient, which was determined by measuring its fluxes of simple diffusion from kerosene to water. Based on the Hatta number and the criterion given by Doraiswamy and Sharma, the reaction regime has been found to be instantaneous reaction regime occurring at the interface on the organic phase side. An extraction model comprising equilibrium complexation constant w.r.t 2:1 levulinic acid-TOA complex formation, K_E2i (14.794 (m³ kmol^?1)²), and complex mass transfer coefficient, k_B2A (2.193 × 10^?6 m s^?1), has been developed.     

Removal of H2S and volatile organic sulfur compounds by silicone membrane extraction

BACKGROUND: This study explores an alternative process for the abatement and/or desulfurization of H₂S and volatile organic sulfur compounds (VOSC) containing waste streams, which employs a silicone‐based membrane to simultaneously remove H₂S and VOSC. An extractive membrane reactor allows the selective withdrawal of VOSC and H₂S simultaneously from the waste stream, while preventing direct contact between the waste stream and the absorbing solution and/or the biological treatment system. The influence of the sulfur compounds, membrane characteristics, extractant and pH was studied. RESULTS: Sulfide and the VOCS studied, i.e. methanethiol (MT), ethanethiol (ET) and dimethylsulfide (DMS) were removed from the synthetic wastewater using a silicone rubber membrane. Methanethiol showed the highest (8.72 × 10^?6 m s^?1) overall mass transfer coefficient (k_ov) and sulfide the lowest k_ov value (1.23 × 10^?6 m s^?1). Adsorption of the VOCS into the silicone membrane reduced the overall mass transfer coefficient. The k_ov when using Fe(III)EDTA^? as extractant (5.81 × 10^?7 m s^?1) for sulfide extraction was one order of magnitude lower than with anaerobic water (2.54 × 10^?6 m s^?1). On the other hand, the sulfide removal efficiency with Fe(III)EDTA^? was higher (84%) compared with anaerobic water (60%) as extractant. An additional mass transfer resistance was formed by elemental sulfur which remained attached to the membrane surface. CONCLUSIONS: Extraction of sulfide and VOCS from a synthetic wastewater solution through a silicone rubber membrane is a feasible process as alternative to the techniques developed to treat VOSC emissions. Optimizing the aqueous absorption liquid can increase the efficiency of extraction based processes. Copyright © 2008 Society of Chemical Industry     

Transport of cobalt(II) through a hollow fiber supported liquid membrane containing di-(2-ethylhexyl) phosphoric acid (D2EHPA) as the carrier

This work presents experimental, modeling and simulation studies for Co²⁺ ion extraction using hollow fiber supported liquid membrane (HFSLM) operated in a recycling mode. Extractant di-(2-ethylhexyl) phosphoric acid (D2EHPA) diluted with kerosene has been used as the membrane phase. The Co²⁺ ion concentration in the aqueous feed phase was varied in the range of 1–3 mM. Also, D2EHPA concentration was varied in the range of 10–30% (v/v). A mass transfer model has been developed considering the complexation and de-complexation reactions to be fast and at equilibrium. Equations for extractant mass balance and counter-ion (H⁺) transport have also been incorporated in the model. Extraction equilibrium constant (K_ex) for cobalt–D2EHPA system has been estimated from equilibration experiments and found to be 3.48 × 10⁻⁶. It was observed that the model results are in good agreement with the experimental data when diffusivity of metal-complex (D_m) through the membrane phase is 1.5 × 10⁻¹⁰ m²/s. Feed phase pH and strip phase acidity had negligible effect on the extraction profiles of Co²⁺ ions. An increase in D2EHPA concentration increased extraction rates of Co²⁺ ions. The membrane phase diffusion step was found to be the controlling resistance to mass transfer.     

Influence of Pressure on the Hydrodynamics and Mass Transfer Parameters of an Agitated Bubble Reactor

The present study deals with the pressure effects on the hydrodynamic flow and mass transfer within an agitated bubble reactor operated at pressures between 10⁵ and 100 × 10⁵ Pa. In order to clarify the flow behavior within the reactor, liquid phase residence time distributions (RTD) for different operating pressures and gas velocities ranging between 0.005 m/s and 0.03 m/s are determined experimentally by the tracer method for which a KCl solution is used as a tracer. The result of the analysis of the liquid‐phase RTD curves justifies the tank‐in‐series model flow for the operating pressure range. Good agreement is obtained between theoretical and experimental results assuming the reactor is operating as perfectly mixed. Two parameters characterizing the mass transfer are identified and investigated in respect to pressure: the gas‐liquid interfacial area and volumetric liquid‐side mass transfer coefficient. The chemical absorption method is used. For a given gas mass flow rate, the interfacial area as well as the volumetric liquid mass transfer coefficient decrease with increasing operating pressure. However, for a given pressure, a and k_La increase with increasing gas mass flow rates. The mass transfer coefficient k_L is independent of pressure.     

Liquid-solid mass transfer in a rotating packed bed reactor with structured foam packing

A rotating packed bed (RPB) reactor has substantially potential for the process intensification of heterogeneous catalytic reactions. However, the scarce knowledge of the liquid–solid mass transfer in the RPB reactor is a barrier for its design and scale-up. In this work, the liquid–solid mass transfer in a RPB reactor installed with structured foam packing was experimentally studied using copper dissolution by potassium dichromate. Effects of rotational speed, liquid and gas volumetric flow rate on the liquid–solid mass transfer coefficient (k_LS) have been investigated. The correlation for predicting k_LS was proposed, and the deviation between the experimental and predicted values was within ± 12%. The liquid–solid volumetric mass transfer coefficient (k_LSa_LS) ranged from 0.04–0.14 1⁻¹, which was approximately 5 times larger than that in the packed bed reactor. This work lays the foundation for modeling of the RPB reactor packed with structured foam packing for heterogeneous catalytic reaction.     

Study of the mechanism of pore diffusion in batch adsorption systems

In this study the film-pore diffusion model was applied to describe system transport kinetics of three basic dye-carbon systems, namely Basic Blue 69, Basic Red 22 and Basic Yellow 21. The mass transfer parameters evaluated were the external mass transfer coefficient k_f (cm s^?1) and the effective diffusivity D_eff (cm² s^?1). A single k_f value was sufficient to describe each dye system: these were 0.15 × 10^?2, 0.20 × 10^?2 and 0.50 × 10^?2 cm s^?1 for BB69, BR22 and BY21, respectively. The effective diffusivity was found to have values much larger than those of pore diffusivities calculated from liquid diffusivities and its value decreased with increasing initial dye concentration. This was attributed to the effect of surface diffusion, hence pore diffusivity was exchanged by the effective pore diffusivity in the model. The present model was solved by the exponential curve fit technique; results were expressed in the form of experimental and theoretical Sherwood Numbers compared in terms of the residual.     

Modeling and Optimization of Reactive Extraction of Gallic Acid Using RSM

Reactive extraction was experimentally investigated for recovery of gallic acid (GA) from the aqueous solution using tri-n-octylamine (TOA) as extractant in hexanol. All experiments were carried out according to statistical design in order to develop a regression model used to optimize the extraction of GA. Two independent variables were selected as: initial concentration of GA (C_GA0) in aqueous phase and concentration of TOA (C_TOA) in organic phase. The statistical analysis showed that both the independent variables had significant effect on response value, followed by the quadratic and interactive effect on response. A five-level central composite rotatable design (CCRD) was employed. Analysis of variance (ANOVA) showed a high coefficient of determination (R²?=?99.0%). The optimal extraction conditions of GA were determined as: C_GA0?=?2.01?g/L, C_TOA?=?6.8% v/v. At the optimum conditions, the experimental yield of GA was 91.9%, which was in close agreement with the predicted value of 93.2%.     

Ozone Mass Transfer in the Mixing Zone of a Confined Plunging Liquid Jet Contactor

In a Confined Plunging Liquid Jet Contactor (CPLJC) a jet of liquid is introduced into an enclosed cylindrical column (downcomer) that generates fine gas bubbles that are contacted with the bulk liquid flow. The region where the liquid jet impinges the receiving liquid and expands to the wall of the downcomer is called the Mixing Zone (MZ). In the MZ, the energy of the liquid jet is dissipated by the breakup of the entrained gas into fine bubbles, and the intense recirculation of the two-phase mixture. The study presented here was undertaken to quantify the ozone-water mass transfer performance of the MZ through the determination of the volumetric mass transfer coefficient, k_La (s^?1), and to produce a model for predicting k_La based on the specific energy dissipation rate. It was found experimentally that k_La in the MZ increased with increasing superficial gas velocity. A maximum experimental k_La value of 0.84 s^?1 was achieved which compares well to other contactors used in water treatment. Such a large k_La value combined with the small volume of the reactor, favorable energy requirements and safety features of the system, suggests that the CPLJC provides an attractive alternative to conventional ozone contactors. The relatively large mass transfer rates were found to be a function of the high gas holdup and fine bubble size generated in the MZ, which results in an almost froth-like consistency. A model based on the specific energy dissipation rate of the water jet, E (kg · m^?1· s^?3), and MZ bubble size was used to predict k_La in the MZ. Using E, the number average bubble size was predicted which was then used to calculate the liquid phase mass transfer coefficient k_L. The bubble size was also used with the predicted mixing zone gas holdup to calculate the specific interfacial area, a (m^?1), which was then combined with k_L to determine a predicted value of k_La. The average deviation between experimental and predicted k_La was 6.2%.     

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.     

Gas hold-up and oxygen transfer in three-phase external-loop airlift bioreactors: Non-Newtonian fermentation broths

The effects of solids loading on gas hold-up and oxygen transfer in external-loop airlift bioreactors with non-Newtonian fermentation media are discussed. Experiments were performed in two model external-loop airlift bioreactors with aqueous solutions of carboxymethyl cellulose (CMC) and xanthan gum representing non-Newtonian flows. Low-density plastic particles of 1030 and 1300 kg m⁻³ were used and the solids loading was varied in the range 0–20% (v/v). For the inelastic non-Newtonian CMC aqueous solutions, the presence of low-density solid particles slightly increased the riser gas hold-up, ϕ_gr, but decreased the volumetric mass transfer coefficient, k_La. On the other hand, ϕ_gr decreased but k_La increased with solids loading in the viscoelastic non-Newtonian xanthan gum aqueous solution. The extent of these effects depended on non-Newtonian flow behavior. Theoretical models of riser gas hold-up and volumetric mass transfer coefficient have been developed. The capability of the proposed models was examined using the present experimental data obtained in the model external-loop airlift bioreactors and the available data in the literature. The data were successfully correlated by the proposed correlations except the results for k_La coefficient in the xanthan gum solution.     

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.     

Enhancing CO2 absorption efficiency using a novel PTFE hollow fiber membrane contactor at elevated pressure

The internal structure design of membrane module is very important for gas removal performance using membrane contactor via physical absorption. In this study, a novel membrane contactor developed by weaving polytetrafluoroethylene (PTFE) hollow fibers was applied to remove CO₂ from 60% N₂ + 40% CO₂ mixture (with CO₂ concentration similar to that of biogas) at elevated pressure (0.8 MPa) using water as absorbent. Compared with the conventional module with randomly packed straight fibers, the module with woven PTFE fibers exhibited much better CO₂ absorption performance. The weaving configuration facilitated the meandering flow or Dean vortices and renewing speed of water around hollow fibers. Meanwhile, the undesired influences such as channeling and bypassing were also eliminated. Consequently, the mass transfer of liquid phase was greatly improved and the CO₂ removal efficiency was significantly enhanced. The effects of operation pressure, module arrangement, feed gas, and water flow rate on CO₂ removal were systematically investigated as well. The overall mass‐transfer coefficient (K_OV) varied from 1.96 × 10^?5 to 4.39 × 10^?5 m/s (the volumetric mass‐transfer coefficient K_La = 0.034–0.075 s^?1) under the experimental conditions. The CO₂ removal performance of novel woven fiber membrane contactor matched well with the simulation results. © 2017 American Institute of Chemical Engineers AIChE J, 64: 2135–2145, 2018     

Combined Absorption and Self-Decomposition of Ozone in Aqueous Solutions with Interfacial Resistance

A theoretical analysis is performed employing the film model for the isothermal absorption and self-decomposition of ozone in aqueous solutions with interfacial resistance, which is inversely proportional to the interfacial mass transfer coefficient k_s. A closed-form solution has been obtained. The effects of system parameters on the ozone mass transfer rate are examined. These parameters include the interfacial resistance (1/k_s), the acidic and basic self-decomposition reaction rate parameters (M_m ^0.5, M_n ^0.5.; M_m = [2D_Ak_mC_Ai ^m-1/(m+1)]/(k_L ⁰)², M_n=(2D_Ak_nC_Ai ^n-1/(n+1))/(k_L ⁰)², the reaction orders (m,n), the pH value of solution, and the liquid-phase mass transfer coefficient (k_L ⁰). The results indicate that the reduction effect of the interfacial resistance on the absorption rate is most significant for the situation with the larger values of M_m and M_n as well as with higher pH values. Also, for any particular finite value of k_L ⁰/k_s, the reduction effect encountered is greater for a gas liquid contactor with a lower k_L ⁰. The reduction effect should be avoided in order to maintain a higher mass transfer rate of ozone in aqueous solution. This analysis is of importance for the efficient use of ozone in water/wastewater treatment processes in the presence of interfacial resistance substances such as surface active agents. For some known special cases (for example, cases with no interfacial resistance), the present solution reduces to the previous works of other investigators.     

Effect of surfactants on liquid-side mass transfer coefficients

In the present paper, the effect of liquid properties (surfactants) on bubble generation phenomenon, interfacial area and liquid-side mass transfer coefficient was investigated. The measurements of surface tension (static and dynamic methods), of critical micelle concentration (CMC) and of characteristic adsorption parameters such as the surface coverage ratio at equilibrium (s_e) were performed to understand the effects of surfactants on the mass transfer efficiency. Tap water and aqueous solutions with surfactants (cationic and anionic) were used as liquid phases and an elastic membrane with a single orifice as gas sparger. The bubbles were generated into a small-scale bubble column. The local liquid-side mass transfer coefficient (k_L) was obtained from the volumetric mass transfer coefficient (k_La) and the interfacial area (a) was deduced from the bubble diameter (D_B), the bubble frequency (f_B) and the terminal bubble rising velocity (U_B). Only the dynamic bubble regime was considered in this work (Re_OR=150-1000 and We=0.002-4).This study has clearly shown that the presence of surfactants affects the bubble generation phenomenon and thus the interfacial area (a) and the different mass transfer parameters, such as the volumetric mass transfer coefficient (k_La) and the liquid-side mass transfer coefficient (k_L). Whatever the operating conditions, the new k_La determination method has provided good accuracy without assuming that the liquid phase is perfectly mixed as in the classical method. The surface coverage ratio (s_e) proves to be crucial for predicting the changes of k_L in aqueous solutions with surfactants.