Extraction and recovery of lignosulfonate from its aqueous solution using bulk liquid membrane

The paper presents an experimental study on the coupled transport of lignosulfonate (LS) through bulk liquid membrane (BLM) and thereby to identify the best set of solvent, operating conditions and mode of transport that would yield optimum performance of the BLM. Trioctylamine (TOA) is used as carrier. Among various solvents, tested for the above purpose, dichloroethane is found to be the best. The effects of operating condition, viz. pH, temperature, and carrier concentration, on the equilibrium distribution of LS are investigated. The effects of temperature, stirring of aqueous and organic phases, stirring speed, carrier concentration, initial feed and strip phase concentration on the separation of LS using BLM are also studied. It is observed that transport of LS can be enhanced by increasing the temperature and stirring speed of feed phase. Stirring of strip phase has no appreciable effects on the transport of LS. With increase in initial feed concentration the initial rate of the transport of LS is higher but continues for a longer time. Recovery of LS is much higher in co-transport mode in comparison to counter transport mode. Application of 1.25 M NaOH as stripping solution gives high recovery (70%) and high strip flux (70% of feed flux).     

Separation of lignosulfonate from its aqueous solution using supported liquid membrane

This paper presents an experimental and theoretical study on facilitated transport of lignosulfonate (LS) through a flat sheet supported liquid membrane using trioctylamine (TOA) as carrier and dichloroethane as diluent. The studies were carried out with various support materials and operating conditions (viz. carrier concentration, strip phase concentration, salt concentration, etc.) and their effects on the transport of LS. The results were analyzed to identify a suitable combination of support and operating condition that would yield best performance of the supported liquid membrane (SLM) in terms of fast and efficient transport of LS. The stability of the SLM was assessed in terms of loss of liquid from the pores of membrane support. The SLM is found to be stable till 10 h. Co-transport mechanism has been adopted in this work by using NaOH as the strip phase. It was observed that extraction of LS is increased with increase in concentration of NaOH up to a limiting value of 0.5 M NaOH. Difference of salt concentration between feed and strip phase considerably affect the separation process. The diffusional resistances of organic membrane (Δorg) and aqueous solution (Δaq) calculated from the permeation model, which is again a combination of three unique mechanisms viz., diffusion through a feed aqueous layer, a fast interfacial chemical reaction, and diffusion of carrier–complex through the organic membrane, are found to be 609.9 and 176.6 s cm⁻¹, respectively. The values of the diffusion coefficient in the membrane (D_org) and in the bulk organic phase (D_complex) are 1.67×10⁻⁹ and 6.68 × 10⁻⁸ m²s⁻¹, respectively. The extraction of LS is about 90%. Nearly 43% of LS can be recovered at optimum condition.     

Extraction of penicillin G from aqueous solution using a membrane contactor: Numerical investigation

In the current study, the treatment of pharmaceutical wastewater containing penicillin G treatment using a hollow fibre membrane contactor was investigated. A mathematical model based on the finite element method was developed. The extraction was performed using Shellsol TK as organic solvent containing 5% Aliquat 336. The effect of feed pH, flow rate and temperature were examined for the extraction of penicillin G from aqueous solution. The results showed that there is reasonable good agreement between experimental data and modelling values. It was found that increasing temperature from 10 °C to 30 °C increases the penicillin G extraction from 33% to 54%. Also, penicillin G extraction was decreased from 34.7% to 25.1% with increasing pH from 5.5 to 6.5 while it grew to 45.8% when the pH of feed solution was 7. Furthermore, the results showed the diffusive flux is favourable for the system and penicillin G extraction but the convective flux has negative impact on the system in terms of penicillin G extraction. It was concluded that a hollow fibre membrane contactor has the potential for use in wastewater treatment through it is important to improve diffusive flux in the system to enhance penicillin G extraction.     

Simultaneous separation of mercury and lignosulfonate from aqueous solution using supported liquid membrane

This paper presents an experimental investigation on facilitated and simultaneous transport of mercury and lignosulfonate (LS) through a flat sheet supported liquid membrane (SLM) having Nylon 6,6 as support, trioctylamine (TOA) as carrier and dichloroethane as solvent. The experiments were performed at various operating conditions such as strip phase concentration, feed pH, carrier concentration and feed concentration to find the best set of parameters that would yield the maximum separation of pure mercury as well as its mixture with LS. The experiments were performed in co-transport mode using NaOH as the strip phase. It was observed that extraction of mercury as well as its mixture increases with increase in concentration of NaOH up to a certain limit 0.1 M NaOH in case of pure solution and 0.2 M NaOH in case of mixture). Feed phase pH significantly affects the mercury separation process. However, initial feed concentration does not affect the extraction process appreciably. Separation of mixture of mercury and LS behaves in a similar way as their pure solution; however the extraction is low in comparison to pure solution. The extraction of mercury from its pure solution is about 81% in 1 h. The extraction of mercury and LS from their mixture is about 52.6% and 50.2%, respectively at optimum condition and in a period of 2 h.     

Extraction of lanthanides from aqueous solution by using room-temperature ionic liquid and supercritical carbon dioxide in conjunction

For the first time, the study of a three-step extraction system of water/ionic liquid/supercritical CO2 has been performed. Extraction of trivalent lanthanum and europium from an aqueous nitric acid solution to a supercritical CO2 phase via an imidazolium-based ionic liquid phase is demonstrated, and extraction efficiencies higher than 87 % were achieved. The quantitative extraction is obtained by using different fluorinated beta-diketones with and without the addition of tri(n-butyl)phosphate. The complexation phenomenon occurring in the room-temperature ionic-liquid (RTIL) phase was evidenced by using luminescence spectroscopy.     

Adsorption of cadmium from aqueous solutions on manganese dioxide

Journal of Radioanalytical and Nuclear Chemistry - The adsorption of cadmium on manganese dioxide has been investigated from different media in relation to shaking time, pH, composition and...     

Extraction and preconcentration of salbutamol and terbutaline from aqueous samples using hollow fiber supported liquid membrane containing anionic carrier

This paper presents a new three-phase liquid-phase microextraction (LPME) strategy for extraction and preconcentration of salbutamol (SB) and terbutaline (TB) from aqueous samples, including urine. The drugs were extracted from 11 ml of aqueous sample (source phase; SP) into an organic phase with microliter volume located inside the pores of a polypropylene hollow fiber, and then back-extracted into 24 microl of a second aqueous solution as the receiving phase (RP), located in the lumen of the hollow fiber. In preliminary experiments, we tried to transport the drugs using a pH gradient between the two sides of the hollow fiber. Due to the existence of both amine and phenolic groups on the drugs, very little transport occurred and enrichment factors (EF) less than one were obtained. Further experiments were done in the presence of bis(2-ethylhexyl) monohydrogenphosphoric acid (D2EHPA) or methyltrioctylammonium chloride (Aliquat 336) in the organic phase, to extract drugs from acidic and basic matrices, respectively. Results showed that transport of drugs from alkaline solution into 1M of sodium bromide occurred when the membrane was impregnated with dihexyl ether containing 20% Aliquat 336. To optimize the EF, the effects of different parameters such as the nature of organic solvent used to impregnate the membrane, compositions and volumes of SP and RP, type and concentration of carrier, extraction time and stirring rate were investigated. Optimal results were obtained in the presence of 0.005 M of NaOH (pH 11.70) in the SP, 1M of NaBr in the RP, 20% of Aliquat 336 in dihexyl ether as membrane impregnation solvent, stirring rate of 500 rpm and extraction time of 60 min. Under these conditions, enrichment factors of 52.9 and 213.1, dynamic linear ranges of 20-5000 and 10-5000, and limits of detection of 2.5 and 0.5 ng/ml were obtained for salbutamol and terbutaline, respectively. Also determination of drugs in environmental water and urine samples in the range of nanograms per millilitre with RSDs<10% was possible using HPLC-photodiode array detection or HPLC-MS.     

Extraction of cadmium from aqueous solutions by emulsion liquid membrane (ELM) using three different carriers dissolved in a 70:30 ratio of sunflower oil to kerosene

This study explores the use of novel green emulation liquid membranes (GELMs) for the simultaneous extraction and stripping of Cd (II) from aqueous solutions. A solute is transported through the membrane due to the presence of the carrier and then concentrated in the internal phase. Soybean, sunflower, corn, and canola oils were used to form green substitutes to petroleum-based organic diluents for use as GELMs. Bis-(2-ethylhexyl) phosphate (D2EHPA), tri-butyl- phosphate (TBP), and trioctylamine (TOA) were the extractants, span 80 was the emulsifier, and HCl or H₂SO₄ was used as the stripping agent. The best conditions for maximum extraction efficiency (98.68%), stripping efficiency (97.14%), and lowest membrane breakage (0.9%) were achieved using a mixture of sunflower oil and kerosene in the ratio of 70:30. The other optimum values of the variables were: 2% (v/v) Span 80, 10 min emulsification time, 12700 rpm emulsification speed, 400 rpm of agitation speed, 5% (v/v) D2EHPA, an external phase pH was 3.5, an internal phase of 0.25 M HCl, and 5:1 of the treat ratio (external phase to emulsion) at 10 min contact time. The synthesized membrane was reused eight times, with approximately the same efficiency and no significant breakage during the first seven cycles.     

Extraction and preconcentration of toxic metal ions from aqueous solution using benzothiazole-based chelating resins

Polystyrene-divinylbenzene resin (PS-DVB) was functionalized with a benzothiazole group. PS-DVB with amino group was initially prepared by nitration and reduction reactions and subsequently treated with ethyl 2-benzothiazolylacetate (BA) to obtain the chelating resin with an amide linkage (BA-PS-DVB). Meanwhile, the amino-PS-DVB was diazotized and coupled with BA to obtain the chelating resin with an azo linkage (azo-BA-PS-DVB). The resins were characterized by elemental analysis and infrared spectroscopy and evaluated for their extraction of Cd(II), Cu(II) and Pb(II) ions in water before their determinations by flame atomic absorption spectrometry (FAAS). Extraction conditions were optimized for batch method such as the pH of the solution, the extraction time and the adsorption isotherm. The optimum pH for the extraction of Cd(II), Cu(II) and Pb(II) are 8.0, 7.0 and 6.0, respectively, while the equilibrium time of all ions was reached within 10-20 min. The adsorption behavior of all the metal ions followed the Langmuir adsorption isotherm. In the column method, the optimum flow rates of metal sorption onto BA-PS-DVB and azo-BA-PS-DVB columns were 2.5 and 4.0 mL min^− 1. Metal ions sorbed onto columns were eluted by 0.5 to 2.0 M HNO₃. The preconcentration factors of Cd(II) and Cu(II) on azo-BA-PS-DVB and Cu(II) on BA-PS-DVB were 50, 50, and 20, respectively. The present column method gave acceptable validation results: 71.2 and 74.0% recovery for Cd(II) and Cu(II) and an overall relative standard deviation (R.S.D) less than 10% (n = 15). The proposed method was applicable for determining Cu(II) in drinking water.     

Extraction and preconcentration of manganese(II) from biological fluids (water, milk and blood serum) using supported liquid membrane and membrane probe methods

A supported liquid membrane (SLM) technique was investigated to extract and preconcentrate Mn(II) from water, milk and blood serum. Di-2-ethylhexyl phosphoric acid (DEHPA) with kerosene as diluent was used as a carrier in the membrane to transport Mn(II) from the donor side to acceptor side. The membrane was modified with tri-n-octylphosphine oxide (TOPO) to increase its polarity. Various parameters were investigated to optimise the extraction efficiency: pH of the donor and acceptor phase, dilution factor, donor flow rate. Scanning electron microscope images of the membranes revealed that some matrix compounds were deposited on the surface, thus limiting the extraction process. The optimum conditions found were: pH 3 in the donor phase, 0.2 M nitric acid in the acceptor phase, donor flow rate between 1.0 and 0.3 ml min⁻¹, 15% (w/v) DEPHA and 10% TOPO in kerosene as a carrier in membrane, and dilution factors of 20 times for blood serum and 30 times for milk. The extraction efficiencies were found to be low but constant and highly reproducible showing, strong dependence on sample matrix. The new SLM extraction probe was developed and optimised for Mn(II) extraction. Compared to traditional SLM configurations, this is the simplest configuration. The use of stirring allows the same sample to be extracted many times giving higher extraction efficiency and to minimise the sample size. Adsorptive stripping voltammetry (AdSV) was applied to measure Mn(II) concentration. The optimised method was used to determine the concentration of Mn(II) in water, milk and blood serum samples.     

Isotopic exchange between manganese hydroxide and manganese ions in aqueous solution

Heterogeneous isotopic exchange between manganese hydroxide and manganese ions in aqueous solutions tagged with radioactive⁵⁴Mn has been studied at different values of α, the ratio of the quantity of exchangeable ions in the solid phase to that in the liquid phase. The aging of the precipitate in its mother liquor prior to the exchange has a significant effect on both the extent and rate of the exchange reaction. A marked feature of great interest is the appearance of two aging-times, one at about 10² and the other at about 10⁴ min. The overall reaction appears to be of the consecutive type. In the case of a fresh precipitate, “complex-surface-exchange” and “self-diffusion” mechanisms are the most probable rate-determining steps in the initial and final stages of the reaction, respectively. “Complex-surface-exchange” is a new suggested mechanism. In the case of a well-aged precipitate, “surface-exchange” and ‘self-diffusion” mechanisms are the most probable-determining steps in the initial and final stages of the reaction, respectively.     

Pertraction of cadmium and zinc ions using a supported liquid membrane impregnated with different carriers

An experimental study on the removal of Cd²⁺ and Zn²⁺ through a supported liquid membrane using a mixture of mono-(2-etylhexyl) ester of phosphoric acid (M2EHPA) and bis-(2-etylhexyl) ester of phosphoric acid (D2EHPA) as carriers is presented. Parameters affecting the Cd²⁺ and Zn²⁺ pertraction such as feed concentration, carrier concentration, pH of the stripping phase, and TBP (tributyl phosphate) concentration were analyzed using the Taguchi method. Optimal experimental conditions for Cd²⁺ and Zn²⁺ pertraction were obtained using the analysis of variance (ANOVA) after a 6 h separation with the initial feed concentration of 8.9 × 10^?4 mol L^?1, carrier concentration of 20 vol. %, TBP concentration of 4 vol. %, and pH of 0.5. Then, under optimum conditions, a comparison of M2EHPA, D2EHPA, and bis-(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex 302) was performed. Effective pertraction of Cd²⁺ and Zn²⁺ using these carriers was observed in the following order: mixture of M2EHPA and D2EHPA, D2EHPA, Cyanex 302. It was also found that the presence of one metal ion in the feed solution reduces the pertraction rate of the other one.     

Removal and enrichment of copper ions from aqueous solution by 1,8-diaminonapthalene polymer

Microparticles of poly(1,8-diaminonapthalene) (PDAN) were prepared by chemically oxidative polymerization by (NH₄)₂S₂O₈. The effect of pH on the sorption of Cd(II), Cu(II), Ni(II), Mn(II), Zn(II) and Pb(II) on PDAN was examined by the batch procedure. PDAN showed good sorption capacity and high selectivity towards Cu(II) in comparison with the very popular chelating sorbent Chelex 100 containing iminodiacetic functional groups. The on-line preconcentration system containing the knotted reactor with the obtained polymer was examined for the sorption and desorption processes of copper ions. The applicability of this system was checked by analysis of Cu(II) content in standard reference material (NIST 1643e) and some natural water samples.     

Extraction of lutetium(III) from aqueous solutions by employing a single fibre‐supported liquid membrane

Transport behaviour of Lu(III) across a polypropylene hollow fibre‐supported liquid membrane containing di(2‐ethylhexyl)phosphoric acid (DEHPA) in dihexyl ether as a carrier has been studied. The donor phase was LuCl₃ in the buffer solution consisting of 0.2 M sodium acetate at pH 2.5–5.0. A miniaturised system with a single hollow fibre has been operated in a batch mode. The concentration of Lu(III) was determined by indirect voltammetric method using Zn–EDTA complex. The effect of pH and volume of the donor phase, DEHPA concentration in the organic (liquid membrane) phase, the time of extraction and the content of the acceptor phase on the Lu(III) extraction and stripping behaviour was investigated. The results were discussed in terms of the pertraction and removal efficiency, the memory effect and the mean flux of Lu(III). The optimal conditions for the removal of ¹⁷⁷Lu(III) from labelled ¹⁷⁷Lu‐radiopharmaceuticals were discussed and identified. The removal efficiency of Lu(III) greater than 99% was achieved at pH of the donor phase between 3.5 and 5.0 using DEHPA concentration in the organic phase of 0.47 M and the ratio of the donor to the acceptor phase of 182.     

Recovery of pyridine from aqueous solution by membrane pervaporation

Three different membranes, based on poly(dimethylsiloxane) (PDMS), cation-exchange material and poly(vinyl alcohol) (PVA) respectively, were tudied for the separation of pyridine-water mixtures by pervaporation. The PDMS membrane was preferentially permeable to pyridine and the other two were selective towards water. Three membranes showed different permeation performance, allowing the application of the technique to the separation of feeds of different composition. The temperature profile of the permeability suggests that it is possible to carry out the operation at an elevated temperature in order to achieve high productivity. A combination of the three types of membranes was designed for the production of anhydrous pyridine from dilute pyridine aqueous solution by pervaporation.     

Tritium enrichment from aqueous solutions using cryosublimation of mono- and polysaccharides

Cryosublimation is one technique, which allows the accumulation of tritium from aqueous solutions using certain chemical compounds. After studying several inorganic compounds such as zeolites and metal salts,¹ as well as some humic substances,² we have now investigated several mono-and polysaccharides, such as glucose, maltose, galactose, starch, agar, and gelatine. Except for starch all of the above mentioned compounds showed a clear enrichment of tritium. The highest value was reached for Agartine, which gave an enrichment factor of 6.2. Since mono-and polysaccharides form weak hydrogen bonds, these results prove again our theory that tritium is preferably accumulated in exchangeable hydrogen bonds.     

Applicability of a liquid membrane in enrichment and determination of nickel traces from natural waters

In this work, a bulk liquid membrane method has been applied for Ni enrichment and separation from natural waters. The carrier-mediated transport was accomplished by pyridine-2-acetaldehyde benzoylhydrazone dissolved in toluene as a complexing agent. The preconcentration was achieved through pH control of source and receiving solutions via a counterflow of protons. The main variables were optimized by using a modified simplex technique. High transport efficiencies (101.2 ± 1.8–99.7 ± 4.2%) were provided by the carrier for nickel ions in a receiving phase of 0.31 mol L⁻¹ nitric acid after 9–13 h depending on sample salinity. The precision of the method was 2.05% (without a saline matrix) and 4.04% (with 40 g L⁻¹ NaCl) at the 95% confidence level and the detection limit of the blank was 0.015 μg L⁻¹ Ni for detection by atomic absorption spectroscopy. The applicability of the method was tested on certified reference and real water samples with successful results, even for saline samples. The relative errors were −0.60% for certified reference materials and ranged from −0.39 to 2.90% and from 0.3 to 11.05% for real samples, obtained by comparison of inductively coupled plasma mass spectrometry and adsorptive cathodic stripping voltammetry measurements, respectively.     

Amoxicillin removal from aqueous solutions using hollow fibre supported liquid membrane: kinetic study

Amoxicillin was removed from aqueous solutions using hollow fibre supported liquid membrane system (HFSLM). After evaluation of the influencing variables, the highest permeation coefficient of amoxicillin reached 2.778 × 10^?4 ms^?1 when the length of hollow fibres was 15 cm and the operating time was 60 min. Then, the reaction flux models of extraction and stripping were calculated. Thereafter, the modelling results were compared with the experimental data at standard deviations of 2.07 and 3.19%. In the comparison of carrier and diluent, the best conditions were achieved when Aliquat 336 and 1-Decanol were used. Results showed that amoxicillin extraction and stripping were of first and zero reaction orders; their reaction rate constants were 0.0344 min^?1 and 0.0445 mg/L·min, respectively.     

Recovery of acetaminophen from aqueous solutions using a supported liquid membrane based on a quaternary ammonium salt as ionophore

A flat sheet-supported liquid membrane (FSSLM) system, consisting of an ionic liquid, tricapryl-methylammonium chloride (Aliquat 336®) in octan-2-ol, is proposed as a means of recovering acetaminophen (Ac) from aqueous solutions; Ac is an active ingredient widely used in many pharmaceutical preparations. Several parameters which could affect the transport efficiency were examined, i.e., the strippant nature and concentration in the receiving solution, the diluent nature, carrier concentration, initial acetaminophen concentration in the feed solution, and the polymeric support type. A facilitated transport was obtained by impregnating the polymeric support with 10 vol. % of Aliquat 336® in octan-2-ol, 1 M NaOH as a receiving solution, and a feed solution of Ac dissolved in ultrapure water. The study was completed by using the FSSLM thus developed for extracting Ac from some drugs in frequent use in Tunisia (Analgan®, Doliprane®, and Fervex®).