Mathematical modeling for facilitated transport of Ge(IV) through supported liquid membrane containing Alamine 336

A mathematical model was developed for the germanium facilitated transport from a medium containing tartaric acid using Alamine 336 as a carrier. Modeling was carried out based on the extraction constant (Kext) obtained from the liquid-liquid extraction (LLX) modeling. The LLX data was achieved from experiments with conditions being Alamine 336 concentrations of 0.1-10 %v/v from a solution containing about 1.378 mmol/L Ge (100 mg/L) and tartaric acid as an anionic complexant. The LLX model was attained using the equilibrium-based procedure and fitted to extraction experimental data for various carrier concentrations. This model presented an accurate extraction constant (Kext=0.02) used in the facilitated transport modeling. The flat sheet supported liquid membrane (FSSLM) experiments were conducted in the condition of 1.378 mmol/L Ge (100 mg/L), tartaric acid concertation of 2.760 mmol/L, 1 M HCl as a stripping phase and various Alamine 336 concentrations in the range of 0 to 35 %v/v. The FSSLM model was developed according to the Fick’s law, the diffusional transport, and equilibrium equations. According to the model, mass transfer and diffusion coefficients for various concentrations of the carrier were found. In addition, the calculated and experimental values had a good correlation with together showing the validity of the model. This model can be used in the further process simulation such as hollow fiber SLMs.Peer ReviewedPostprint (author's final draft

Fenton coupled with nanofiltration for elimination of Bisphenol A

Bisphenol A (BPA) is a typical Endocrine Disrupting Chemical (EDC), which is potentially harmful during wastewater reclamation. In this study, its degradation during Fenton's process under different operational conditions was investigated in combination with subsequent nanofiltration of low concentration remnant BPA and compounds derived from oxidation. The results indicate that BPA could be degraded efficiently in aqueous phase by Fenton, even at very low hydrogen peroxide doses. The treatment of up to 300 mg/L solutions of BPA with Fenton liquor at optimal conditions resulted in its complete removal in less than 2 min. The optimal conditions were found to be pH, = 3, H2O2/BPA = 020 and Fe2+/BPA = 0.012. Five NF polymeric membranes having different properties were used for the nanofiltration of treated and non-treated solutions. The nanofiltration of BPA solutions showed that rejection is related to adsorption ability of BPA on the membrane and size exclusion mechanism. In the nanofiltration of the effluent after Fenton oxidation, high TOC, COD, colour and Fe2+ (>77%) removal were achieved, although significant membrane fouling was also observed. The normalised water flux after membrane flushing with water was lower than 60% in almost all used membranes, which indicates significant non-easily removable fouling. (C) 2014 Elsevier B.V. All rights reserved.Peer ReviewedPostprint (author’s final draft

Neodymium recovery by chitosan/iron(III) hydroxide [ChiFer(III)] sorbent material: Batch and column systems

A low cost composite material was synthesized for neodymium recovery from dilute aqueous solutions. The in-situ production of the composite containing chitosan and iron(III) hydroxide (ChiFer(III)) was improved and the results were compared with raw chitosan particles. The sorbent was characterized using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy-energy dispersive X-ray analyses (SEM-EDX). The equilibrium studies were performed using firstly a batch system, and secondly a continuous system. The sorption isotherms were fitted with the Langmuir, Freundlich, and Sips models; experimental data was better described with the Langmuir equation and the maximum sorption capacity was 13.8 mg g-1 at pH 4. The introduction of iron into the biopolymer matrix increases by four times the sorption uptake of the chitosan; the individual sorption capacity of iron (into the composite) was calculated as 30.9 mg Nd/g Fe. The experimental results of the columns were fitted adequately using the Thomas model. As an approach to Nd-Fe-B permanent magnets effluents, a synthetic dilute effluent was simulated at pH 4, in order to evaluate the selectivity of the sorbent material; the overshooting of boron in the column system confirmed the higher selectivity toward neodymium ions. The elution step was carried out using MilliQ-water with the pH set to 3.5 (dilute HCl solution).Peer ReviewedPostprint (published version

Non-dispersive selective extraction of germanium from fly ash leachates using membrane-based processes

Non-dispersive selective extraction of Ge(IV) tartrates was carried out from simulated fly ash solutions containing heavy metals through supported liquid membranes (SLM). The optimum transport was obtained using a PTFE membrane containing Alamine 336 5%v/v in the condition of tartaric acid 2.76 mmol/L and HCl 1 mol/L in feed and strip phases, respectively. Under this condition, a hollow fiber (HF) SLM experiment was conducted. The results showed that this system could transport germanium from the feed to the strip phase so much faster than the flat sheet (FS) SLM system. The rate of transport through HFSLMs is comparable to dispersive extractions.Peer ReviewedPostprint (author's final draft

Transport of Zn(II), Fe(II), Fe(III) across polymer inclusion membranes (PIM) and flat sheet supported liquid membranes (SLM) containing phosphonium ionic liquids as metal ion carriers

This is an Accepted Manuscript of an article published by Taylor & Francis Group in Separation Science and Technology on 18/04/2016, available online: http://www.tandfonline.com/doi/full/10.1080/01496395.2016.1174265In this work transport of Zn(II), Fe(II) and Fe(III) ions from chloride aqueous solutions across polymer inclusion membranes (PIMs) and supported liquid membranes (SLMs) containing one of three phosphonium ionic liquids: trihexyl(tetradecyl)phosphonium chloride (Cyphos IL 101), trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate (Cyphos IL 104) and tributyl(tetradecyl)phosphonium chloride (Cyphos IL 167) as an ion carrier was reported. The results show that Zn(II) and Fe(III) are effectively transported through PIMs and SLMs, while Fe(II) transport is not effective. The highest values of initial flux and permeability coefficient of Zn(II) were noticed for SLM containing Cyphos IL 167. Cyphos IL 101-containing SLM is more stable than PIM.Peer ReviewedPostprint (author's final draft

Mathematical modelling of neodymium, terbium and dysprosium solvent extraction from chloride media using methyl-tri(octyl/decyl)ammonium oleate ionic liquid as extractant

This paper collects experimental data and mathematical modelling of Nd(III), Tb(III) and Dy(III) solvent extraction with an ionic liquid prepared from Aliquat 336 (Methyl-tri(octyl/decyl)ammonium chloride) and Oleic Acid (AliOle). Extraction experiments were carried out to evaluate the effect of chloride anion in aqueous phase, AliOle and REE concentrations over the extraction extension. Mathematical models computed with Matlab software were derived from the mass balances and chemical equilibria involved in the extraction system of Neodymium(III), Terbium(III) and Dysprosium(III) individually. The optimized equilibria parameters proposed fit accurately the experimental data and allowed us to predict the extraction extension of each metal from an aqueous mixture.Postprint (author's final draft

Solvent extraction modeling of Ce/Eu/Y from chloride media using D2EHPA

End-of-life fluorescent lamps are becoming essential in the rare earths (REEs) field and suppose a feasible secondary source for getting them, reducing thus their supply risk. Considering the proved viability of the cationic extractants, the present study aims at establishing a solvent extraction model using di-(2-ethylhexyl)phosphoric acid (D2EHPA) not only based on the individual Ce, Eu, and Y behavior in chloride media, but also bearing in mind the competitive extraction of these metals in Ce/Eu/Y mixtures, depending on the media variables. Furthermore, the model allow determining the optimal REEs separation conditions. The results disclose that Y could be separated from the mixture using 0.1 mol/L D2EHPA, acidity above of 3 mol/L of protons and chloride concentrations higher than 4 mol/L.Peer ReviewedPreprin

Neodymium recovery from NdFeB magnet wastes using Primene 81R·Cyanex 572 IL by solvent extraction

The necessity of Rare Earth Elements (REEs) recycling is crucial to minimizing their supply risk and provide an alternative to greener technologies. Hence, the REEs recovery from NdFeB magnet wastes using cationic extractants by solvent extraction technique has been investigated in this research. Due to the difficulty in maintaining the aqueous pH in the industrial counter-current devices when extractants like Cyanex 272 or Cyanex 572 are used, the Primene 81R·Cyanex 572 ionic liquid has been synthesised to overcome this. 99.99% Nd(III) recovery with a purity of 99.7% from an aqueous mixture of Nd/Tb/Dy in chloride medium, the three representative REEs present in the NdFeB magnets wastes, has been achieved after two stages counter-current extraction process using 0.30¿M of Primene 81R·Cyanex 572 ionic liquid (1:4 A:O ratio) diluted in Solvesso 100, without any aqueous pH conditioning.Peer ReviewedPostprint (author's final draft

Rare earths separation from fluorescent lamp wastes using ionic liquids as extractant agents

Processing of end-of-life products has become essential in the rare earth elements (REEs) recovery field because the demand for these metals has increased over the last years due to their intensive use in advanced technologies. Fluorescent lamp wastes are considered one of the most interesting end-of-life products for investigation due to their high REEs content, mainly yttrium and europium. As a result, red phosphors (Y2O3:Eu3+ – YOX) have been chosen for evaluating their REEs’ recovery potential. The REEs from a YOX reach liquor, coming from a soft leaching process have been precipitated adding oxalic acid and calcined to get the REEs in oxide form. Cyanex 572, D2EHPA and the ionic liquids, Primene 81R·Cyanex 572 IL and Primene 81R·D2EHPA IL, have been chosen to investigate the efficiency of REEs separation in chloride media. Yttrium, europium and cerium have been individually recovered by a four stages cross-flow solvent extraction process using the Primene 81R·D2EHPA IL and the Primene 81R·Cyanex 572 IL as extractants. Ce(III), Eu(III) and Y(III) have been obtained at high purities >= 99.9%. 4 mol/L HCl has been used to recover the yttrium and the europium from the organic phases.Peer ReviewedPostprint (author's final draft

Supported liquid membranes for the removal of pharmaceuticals from aqueous solutions

In the following study, the extraction of three pharmaceutical compounds: Diclofenac (DCF), ibuprofen (IBP), and carbamazepine (CBZ) by liquid-liquid extraction and their transport by supported liquid membrane (SLM) using different commercial extractants (Cyanex 923 (Cy923), trioctylamine (TOA), tributylphosphate (TBP), and Versatic Acid 10 (neodecanoic acid)) were evaluated. Cy923 was demonstrated to be an efficient extractant for diclofenac and ibuprofen removal through a facil- itated transport mechanism from the aqueous feed phase to the aqueous stripping phase using hydroxide ions as stripping agent. Around 80 % of these pharmaceuticals were extracted in 4 h with 10 % of Cy923 and without extreme alteration in the pH. As for carbamazepine, the stripping conditions were achieved with 10 % of Versatic Acid 10. Variation of concentration of different extractants indicates that a higher transport of diclofenac can be obtained by using 40 % of Cy923. In addition, two commercial polymeric supports (PTFE and PVDF) were compared for the selected operational conditions. Finally, the lifetime of the membrane was extended by soaking the polymeric material in the organic solution under vacuum for 24 h and compared with the membrane pre- pared with an ultrasound-assisted method. Supported liquid membranes present many advantages and can easily be manipulated and integrated for the treatment of persistent pharmaceutical contaminants from water.This project has been supported by the grant RTI2018-096467-B-I00 funded by MCIN/AEI/10.PK039/501100011033 and “ERDF A way of making Europe”. The authors research group is recognized by the Comissionat per a Universitats i Recerca, DIUE de la Generalitat de Catalunya (2017 SGR 396), and supported by the Universitat Rovira i Virgili (2021PFR-URV-87) and Marti Franques grant 2019PMF-PIPF-81.Peer ReviewedPostprint (published version