Separation of Molybdenum(VI) and Tungsten(VI) through a Supported Liquid Membrane Impregnated with Trioctylmethylammonium Chloride

Abstract

Transport separation of molybdenum(VI) through a supported liquid membrane (SLM) was investigated by employing trioctylmethylammonium chloride (TOMAC) as a mobile carrier. The transport behavior of Mo(VI) and W(VI) was greatly dependent on hydrochloric acid and chloride ion concentrations in the feed solution. Molybdenum(VI) was effectively transported together with W(VI) from dilute HCl solutions in the presence of 0.1 M tartaric acid into NaOH stripping solutions. Molybdenum(VI) in high HCl concentration was transported in preference to W(VI). Addition of NaCl to the feed solution reduced the W(VI) transport, and this enhanced the separation of Mo(VI) from W(VI). Lower TOMAC concentration in SLM was favorable for the separation of the two metal ions, and a separation factor (α_Mo/W) of 46 was obtained with 0.1 M TOMAC-SLM.     

大块液膜技术处理含六价铬废水

以磷酸三丁酯(TBP)为载体,煤油为稀释剂,NaOH为反萃剂,采用大块液膜技术处理含95~100mg/LCr(VI)的模拟废水。考察了液膜相用量、载体体积分数及反萃剂浓度对大块液膜过程中Cr(VI)传质过程的影响。结果表明,大块液膜技术对废水中Cr(VI)的去除效果较好。Cr(VI)迁移速率随TBP体积分数的提高而加快。当反萃剂NaOH浓度大于0.5mol/L时,反萃剂浓度对Cr(VI)传质过程的影响较小。处理后废水中Cr(VI)含量降至0.5mg/L以下,达到国家排放标准。     

LONG-TERM PERFORMANCE OF HOLLOW FIBRE MEMBRANE SOLVENT EXTRACTION MODULES USED FOR Cr(VI) RECOVERY FROM ELECTROPLATING RINSE WATER

ABSTRACT

The long-term performance of a hollow fibre membrane solvent extraction unit has been investigated for the recovery of Cr(VI) from plating rinse water. A pilot scale experiment was performed in a local electro-plating plant using-membrane modules with an area of 0·17 m². The separation of Cr(VI) from the rinse liquor was carried out in two hollow fibre membrane modules, and is compared with a single module supported liquid membrane (SLM) which was also used in the same service. The Cr(VI) flux declined gradually to half the initial value after 25 days. This was found to be due to the membrane fouling combined with the degradation of organic solvent. The loss of organic solution was initially severe but stabilized after a few days and became negligible. The flux in the SLM mode appeared similar but the life time was very short, less than a day, however continuous operation was attainable by periodic replenishment of the membrane. Using both designs, it has been shown that Cr(VI) could be extracted from dilute feed into the stripping solution with an enrichment factor of 10 – 20 times using this technique.     

Application of Supported Liquid Membranes for Removal of Uranium from Groundwater

Abstract

The separation of uranium from Hanford site groundwater was studied by hollow-fiber supported liquid membranes, SLM. The carrier bis(2,4,4-trimethylpentyl)phosphinic acid, H[DTMPeP], contained in the commercial extractant Cyanex^TM 272 was used as membrane carrier, because of its selectivity for U over calcium and magnesium. The water soluble complexing agent, 1-hydroxyethane-1,1-diphosphonic acid, HEDPA, was used as stripping agent. Polyproylene hollow-fibers and n-dodecane were used as polymeric support and diluent, respectively. Laboratory scale hollow-fiber modules were employed in a recycling mode, using as feed synthetic groundwater at pH 2, to confirm the capability of the proposed SLM system to separate and concentrate U(VI) in the strip solution. Information was obtained on the U(VI) concentration factor and on the long-term performance of the SLMs. Encouraging results were obtained both with a conventional module and with a module containing a carrier solution reservoir. Industrial scale modules were used at Hanford to test the SLM separation of U(VI) from real contaminated groundwater. The uranium concentration was reduced from approximately 3,500 ppb to about 1 ppb in a few hours.     

Transport of Chromium(VI) through a Supported Liquid Membrane Containing Tri-n-octylphosphine Oxide

ABSTRACT

In this study the transport of chromium(VI) from aqueous solutions of pH 2–4 through a supported liquid membrane (SLM) with tri-n-octylphosphine oxide (TOPO) dissolved in kerosene as a mobile carrier was investigated. The transport flux of Cr(VI) increased with an increase in the concentrations of Cr(VI) in the feed phase and of TOPO in the membrane phase, but with a decrease in pH of the feed phase. Considering the equilibria of various Cr(VI) species in the aqueous phase and of the Cr(VI)—TOPO complexes formed in the membrane phase, a permeation model including the aqueous film diffusion of HCrO₄ ^? and Cr₂O₇ ^2? toward the membrane, the interfacial chemical reaction between them and TOPO, and the membrane diffusion of the Cr(VI)—TOPO complexes (H₂CrO₄(TOPO) and H₂Cr₂O₇(TOPO)₃) was proposed to describe the transport of Cr(VI) through the SLM. By best fitting the transport flux equations of Cr(VI) with the experimental data using the Rosenbrock method, the apparent mass-transfer coefficients of HCrO₄ ^? and Cr₂O_7^. across the aqueous film, and those of H₂CrO₄(TOPO) and H₂Cr₂O₇(TOPO)₃ across the membrane phase, were obtained. This work helps to clarify the transport mechanism of Cr(VI) through an SLM.     

Transport of Cr(VI) from HCl Media Using (PJMTH+Cl−) Ionic Liquid as Carrier by Advanced Membrane Extraction Processing

The transport of Cr(VI) from acidic media through pseudo-emulsion based membrane strip dispersion (PEMSD) containing the ionic liquid (PJMTH⁺Cl^?) as carrier in the form of a pseudo-emulsion with sodium hydroxide has been investigated. The ionic liquid was generated in situ by reaction of the primary amine Primene JMT and HCl. The transport of Cr(VI) is evaluated as a function of various experimental variables: stirring speed in the feed phase, concentration of Cr(VI) and HCl in the feed phase, carrier concentration, and organic diluents in pseudo-emulsion, and NaOH concentration in pseudo-emulsion as strippant. In PEMSD, pseudo-emulsion is an emulsion that is formed temporarily between the organic and the stripping solutions. Both solutions are separated when the stirring device is stopped. The value of the overall permeation coefficient obtained under standard experimental conditions was 3.1 × 10^?3 cm s^?1, whereas the transport process is controlled by diffusion of chromium species in the stagnant film of the feed phase. The performance of the system against other carriers (amines, quaternary phosphonium salt and quaternary ammonium salt) was also evaluated.     

Application of Cr(VI) transport across the polymer inclusion membrane with calixresorcin[4]arene derivative as ion carrier

ABSTRACT

In this study, the experiments were performed to evaluate the Cr(VI) removal efficiency by transport across the polymer inclusion membrane with calixresorcin[4]arene derivative as ion carrier. The several influence factors such as carrier concentration, the amount of plasticizer in the membrane as well the effect of acid type and its concentration in source phase and the membrane stability were investigated. It was found that the immobilized calixresorcin[4]arene derivative in membranes effectively extracted chromium from acidic media. Under optimized conditions, the Cr(VI) removal efficiency was 98.4%.     

Efficient hollow fiber supported liquid membrane system for the removal and preconcentration of Cr(VI) at trace levels

A hollow fiber supported liquid membrane (HFSLM) system for the removal and preconcentration of Cr(VI) has been developed and characterized using Aliquat 336 as carrier. The influence of the chemical composition on the efficiency of the membrane system has been investigated, such as the organic solvent and the stripping composition. Among the stripping reagents tested, a solution of 0.5 M HNO₃ was found to be the most effective to strip Cr(VI) from the loaded organic phase. Moreover, physical parameters such as the stability of the membrane and the operation mode of the module were also evaluated. The results demonstrated the effectiveness of the HFSLM system during 8 non-stop days’ operation. This membrane-based separation system has effectively been used to remove Cr(VI) from different aqueous samples, such as industrial waters and spiked natural waters at μg L⁻¹ levels. Moreover, the system has allowed both the separation and enrichment of the metal and, thus, facilitating the detection of chromate contained in aqueous samples and reducing the volume of polluted water to be treated.     

Carrier-Mediated Transport of Molybdenum(VI) through Supported Liquid Membranes

Abstract

The liquid membrane transport of Mo(VI) from an acidic solution into an alkaline stripping solution was carried out by using a mobile carrier, 5,8-diethyl-7-hydroxy-dodecan-6-one oxime (LIX 63). Further transport of MoO₄ ^2? from the alkaline solution was performed by using another carrier, trioctylmethylammonium chloride (TOMAC). Molybdenum(VI) was effectively transported through double membranes composed of LIX 63/dilute NaOH solution/TOMAC from a feed solution (10^?3 M HNO₃) into a product solution (1 M NaOH). Molybdenum(VI) was concentrated with high recovery into a small volume of product solution. The separation of Mo(VI) from several ions was performed by means of the double membranes.     

Efficient transport and selective extraction of Cr(VI) from waste pickling solution of the stainless steel-cold rolled plate process using Aliquat 336 via HFSLM

The selective extraction of Cr(VI) from waste pickling solution of the stainless steel-cold rolled plate process by hydrophobic hollow fiber supported liquid membrane (HFSLM) was investigated. The effects of various parameters— types of organic extractants, i.e., metyl trioctylammonium chloride (Aliquat 336), tri-n-octylamine (TOA), tri-n-butyl phosphate (TBP) and the mixture of Aliquat 336 and TBP, concentration of the selected extractant, types of stripping solutions (NaCl and NaOH), pH and concentration of the selected stripping solution, and the operating temperature—were studied. The feed and stripping solutions flowed countercurrently. The results showed that the coexisting contamination in spent pickling solution of Fe(II) and Ni(II) ions had no significant effect on Cr(VI) extraction. Among the extractants used in this study, Aliquat 336 was a specific carrier to attain the highest percentage of Cr(VI) extraction. About 70% extraction was achieved by using 0.11 M Aliquat 336 and 0.5 M NaCl at pH 7. The percentage of stripping slightly increased when the concentration of NaCl increased. In addition, it was found that the operating temperature of 20, 30, 40, and 50 °C had almost no influence on the percentages of extraction and stripping of Cr(VI). The calculated diffusion energy of Cr(VI) extraction was 15.14 kJ/mol.     

Development of Liquid Membrane Pertraction for the Removal and Recovery of Chromium from Aqueous Effluents

Abstract

Liquid membrane pertraction combines the loading and stripping steps of solvent extraction into a single unit operation, allowing the continuous removal and concentration of a given species. In this paper the feasibility of applying liquid membrane pertraction to the recovery of chromium (Cr(VI) from aqueous effluents with the objective of reducing levels to below allowable discharge limits has been examined. A continuous laboratory-scale liquid membrane pertractor was constructed to solve a variety of problems associated with the treatment of Cr(VI)-bearing streams. Various operational factors such as feed velocity, strip velocity, membrane velocity, and composition of the inlet feed were then examined. Satisfactory continuous runs lasting up to 22 days were achieved. Chromium levels in synthetic waste could be reduced from 200–300 mg/L down to 1 mg/L, well within most allowable discharge limits. Experiments showed that the strip phase can be concentrated with inlet Cr(VI) concentrations of 2000 ppm Cr(VI), with indications that it should be possible at even higher concentrations.     

Study on Competitive Transport of Heavy Metal Ions Through Liquid Surfactant Membrane

Abstract

In the present work an attempt has been made to develop a mathematical model for competitive transport of Cr(VI) and Mo(VI) through liquid surfactant membrane from acidic solution using Alamine‐336 and Caustic Soda as extractant and stripping reagent respectively. A reaction front has been assumed to exist within the emulsion globule in the proposed model. It has been assumed that, an instantaneous and irreversible reaction takes place at the membrane‐internal stripping phase interface between the solute and internal stripping reagent. Experiments on simultaneous extraction of Cr(VI) and Mo(VI), in batch mode, from aqueous solutions of Potassium Dichromate and Ammonium Molybdate have been carried out with the initial concentration of the solutes between 50–100 mg/l. Experiment on emulsion stability has also been performed to arrive at a reasonably stable emulsion composition. Effect of initial solute concentration on distribution coefficient has also been found experimentally and fitted by a semiemperical model that has been used in the computer simulation of the simultaneous extraction process. It has been found that the experimental results are within reasonably close proximity with the simulated curves.     

Studies on the Recovery of Uranium from Phosphoric Acid Medium by D2EHPA/n-Dodecane Supported Liquid Membrane

Abstract

Present studies deal with the application of supported liquid membrane (SLM) technique for the separation of uranium (VI) from phosphoric acid medium using Di-2 ethyl hexyl phosphoric acid (D2EHPA)/n-dodecane as a carrier and ammonium carbonate as a receiving phase. The studies involve the investigation of process controlling parameters like feed acidity of phosphoric acid, carrier concentration, stripping agents, and the effect of thickness and the pore size of the membrane. The transport of uranium decreases with increase in the concentration of phosphoric acid in feed solution whereas it increases with increase in carrier concentration in supported liquid membrane. More than 90% uranium (VI) is recovered in 360 minutes using 0.5 M D2EHPA/dodecane as carrier and 0.5 M ammonium carbonate as stripping phase from the 0.001 M H₃PO₄ feed. Lower concentration of phosphoric acid and higher carrier concentration is found to be the most suitable condition for maximum transport of uranium (VI) from its lean sources like commercial phosphoric acid and analytical wastes generated from the analysis of uranium by Volumetric (Davis-Gray) method.     

Use of bulk liquid membrane for the removal of chromium (VI) from aqueous acidic solution with tri-n-butyl phosphate as a carrier

Tri-n-butyl phosphate (TBP) was used as carrier for the transport of chromium (VI) through a hexane bulk liquid membrane. The transport efficiency of chromium (VI) by TBP was investigated under various experimental conditions such as pH of the feed phase (Cr (VI) solution), concentration of the receiving phase (NaOH solution), concentration of TBP in membrane, rate of stirring, effect of transport time, type of solvent, Cr (VI) concentration in feed phase, and effect of temperature. The transport efficiency increased with increasing carrier concentration from 7.5 × 10^− 2 to 2.25 × 10^− 1 mol/L. At high pH (donor phase) the transport rate of chromate ions decreased. At high stirring speed (300 rpm) the Cr (VI) transport from the feed phase to the strip phase was completed within 5 h at 27 °C. Under optimum conditions: donor phase 4.8 × 10^− 4 mol/L K₂Cr₂O₇ solution at pH 1.0 ± 0.1, acceptor phase 1.0 mol/L NaOH solution, membrane phase 2.25 × 10^− 1 mol/L, stirring speed 300 rpm, and temperature 27 °C, the flux rate was found to be 2.90 × 10^− 7 mol/m² s.     

Permeation of Chromium(VI) and Rhenium(VII) Oxyanions through Liquid Organic Membranes Facilitated by Quaternary Ammonium Chlorides

Abstract

An experimental investigation is presented on the facilitated transport of Cr(VI) and Re(VII) oxyanions from aqueous solution into and through organic solutions of quaternary ammonium chlorides as mobile carriers of anions. Trimethyl tallow ammonium chloride (Aliquat 26), dimethyl dicoco ammonium chloride (Aliquat 221), and methyl tricapryl ammonium chloride (Aliquat 336) from General Mills Chemicals have been investigated. Effects of both anions and mobile carriers as well as the pH of feed aqueous solution and mixing rate on the course of metal permeation have been established. The hydrophobicity and nucleophilicity of a quaternary ammonium chloride were found to be the key factors influencing the transport of Cr(VI) and Re(VII) anions through bulk and emulsified liquid organic membranes. The permeation of perrhenates was much faster than that of chromates. Fast and effective separation was determined to be possible for rhenium from chromium in aqueous solution by means of facilitated transport of their oxyanions across liquid surfactant membranes.     

Removal of Chromium(VI) and Chromium(III) from Aqueous Solution by Grainless Stalk of Corn

Abstract

Grainless stalk of corn (GLSC) was tested for removal of Cr(VI) and Cr(III) from aqueous solution at different pH, contact time, temperature, and chromium/adsorbent ratio. The results show that the optimum pH for removal of Cr(VI) is 0.84, while the optimum pH for removal of Cr(III) is 4.6. The adsorption processes of both Cr(VI) and Cr(III) onto GLSC were found to follow first-order kinetics. Values of k _ads of 0.037 and 0.018 min^?1 were obtained for Cr(VI) and Cr(III), respectively. The adsorption capacity of GLSC was calculated from the Langmuir isotherm as 7.1 mg g^?1 at pH 0.84 for Cr(VI), and as 7.3 mg g^?1 at pH 4.6 for Cr(III), at 20°C. At the optimum pH for Cr(VI) removal, Cr(VI) reduces to Cr(III). EPR spectroscopy shows the presence of Cr(V) + Cr(III)-bound-GLSC at short contact times and adsorbed Cr(III) as the final oxidation state of Cr(VI)-treated GLSC. The results indicate that, at pH ≈ 1, GLSC can completely remove Cr(VI) from aqueous solution through an adsorption-coupled reduction mechanism to yield adsorbed Cr(III) and the less toxic aqueous Cr(III), which can be further removed at pH 4.6.     

Transport of Iron and Cobalt Complex Ions through Liquid Membrane Mediated by Methyltrioctylammonium Ion with the Aid of Redox Reaction

Abstract

A new type of carrier-mediated metal transport through liquid membrane is presented. The system involves redox reactions rather than acid-base reactions which have often been utilized in metal transport systems. Iron ion was selectively transported and concentrated through the membrane via a chloride complex by use of a lipophilic quaternary ammonium ion, methyltrioctylammonium (MTOA, Q⁺), as a carrier. The two aqueous solutions of different redox potentials were separated by a polymer-supported liquid membrane in which MTOA · chloride (Q⁺·CI^?) was dissolved as the carrier. Iron(III) ion in hydrochloric acid media formed a FeCl₄ ^? type complex which was readily extracted to the organic membrane phase as an ion-pair complex Q⁺·FeCl₄ ^?. On contact with a reducing agent on the other side of the membrane, iron(III) was reduced to iron(II) and liberated into aqueous solution; the chloride complexes of iron(II) are too hydrophilic to stay in the membrane phase. On the other hand, cobalt ion was transported via nitrilotriacetic acid (NTA) complex by MTOA carrier in a similar manner to the iron transport. The nature of the transport reactions was studied under various operational conditions (redox agents, carrier and ligand concentration, pH, coexisting metals, etc.). The extension of these transport reactions to a water-in-oil-in-water type emulsion system as well as to a photoassisted transport system was studied.     

The comprehensive investigation of the room temperature ionic liquid additives in PVC based polymer inclusion membrane for Cr(VI) transport

This study is to perform the comprehensive investigation of PVC based ionic plasticized membrane (IPM) production by using room temperature ionic liquid (RTIL)‐based additives and the membrane application of selective Cr(VI) removal. Some significant parameters related to membrane structures that are membrane thickness, plasticizer rate, and type, RTILs rate, and type, the average molecular weight of PVC were studied to define the excellent polymeric membrane film composition. After that, the PVC based polymeric film used in the Cr(VI) transport and initial mass transfer coefficient (J_o) were about 3.57 × 10^?7 mol s^?1 m^?2 by decyl substituted RTIL as an additive. Also, optimized membrane transport process has been considered as selective enough for Cr(VI) in the presence of the other heavy metal ions. Surface characterizations of the membranes have been performed to clarify the structural and the morphological assessment of IPMs at initial and end of Cr(VI) transport by SEM‐EDX, AFM, contact angle measurement and found a good relationship between the molecular structure of RTIL additive and membrane morphology. As we know that lots of researchers are still trying to find environmentally friendly, inexpensive and straightforward processes to remove toxic substances from industrial effluents or natural sources. At that point, our results can open a gate for cheap, novel and environmentally friendly Cr(VI) removal by PVC based membrane. J. VINYL ADDIT. TECHNOL., 25:E107–E119, 2019. © 2018 Society of Plastics Engineers     

Removal of Cr(VI) From Aqueous Solution by Turkish Vermiculite: Equilibrium,Thermodynamic and Kinetic Studies

Abstract

The adsorption of Cr(VI) from aqueous solution by Turkish vermiculite were investigated in terms of equilibrium, kinetics, and thermodynamics. Experimental parameters affecting the removal process such as pH of solution, adsorbent dosage, contact time, and temperature were studied. Equilibrium adsorption data were evaluated by Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models. Langmuir model fitted the equilibrium data better than the Freundlich model. The monolayer adsorption capacity of Turkish vermiculite for Cr(VI) was found to be 87.7 mg/g at pH 1.5, 10 g/L adsorbent dosage and 20°C. The mean free energy of adsorption (5.9 kJ/mol) obtained from the D–R isotherm indicated that the type of sorption was essentially physical. The calculated thermodynamic parameters (ΔG ^o , ΔH ^o and ΔS ^o ) showed that the removal of Cr(VI) ions from aqueous solution by the vermiculite was feasible, spontaneous and exothermic at 20–50°C. Equilibrium data were also tested using the adsorption kinetic models and the results showed that the adsorption processes of Cr(VI) onto Turkish vermiculite followed well pseudo-second order kinetics.     

Effect of Recycling of Feed Solution on the Efficiency of Supported Liquid Membrane Module

Abstract

The effect of recycling of a feed solution from the outlet to the inlet of the feed channel of a plate-and-frame type supported liquid membrane module on the recovery of zinc was investigated under the condition that the feed side mass transfer resistance is predominant. Di(2-ethylhexyl)phosphoric acid was used as the carrier. It was found that at a given feed flow rate, recycling of the feed solution is effective for improving the recovery of zinc since recycling brings about an increase of the flow rate in the feed channel and also the mass transfer coefficient in the feed side. The experimental data could be satisfactorily simulated by a proposed theoretical model.