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

Germanium transport across supported liquid membrane with Cyanex 923: Mathematical modeling

A mathematical model was developed to monitor the facilitated transport of germanium(IV) from oxalic acid solutions through a flat sheet supported liquid membrane (FSSLM) containing four trialkylphosphine oxides (Cyanex 923). The FSSLM modeling was based on the extraction constant (Kext) calculated from the liquid-liquid extraction (LLX) modeling. The LLX model presented a reliable calculation of the extraction constant (Kex= 2.057×103 L/mol4). The FSSLM model was solved using Matlab® software according to extraction constant, Fick's law, and diffusional principles. The model predicts the overall mass transfer coefficient (Korg) to be 3.84 cm/s. Using this value, diffusion coefficients (Dm) for various Cyanex 923 concentrations of 0.126, 0.252, 0.378, 0.505, 0.631 and 0.757 mol/L are found to be 8.50×10-4, 4.30×10-4, 1.87×10-4, 5.87×10-5, 2.57×10-5, 2.09×10-5 cm2/s, respectively. The results show that the diffusion rate of the current study is approximately more than that of similar FSSLM systems containing Cyanex 923 used to transport various metals. The modeling values are in good agreement with the experimental data, showing the good reliability of the mathematical model.Peer ReviewedPostprint (author's final draft

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

Non-dispersive extraction of ge(IV) from aqueous solutions by cyanex 923: Transport and modeling studies

Transport process of germanium from an aqueous solution containing oxalic acid and 100 mg/L Ge was studied. Cyanex 923 immobilized in a polytetrafluoroethylene membrane was employed as a carrier in a flat-sheet supported liquid membrane (FSSLM) system. The speciation of the germanium ion in the oxalic acid medium and related diagrams were applied to study the transport of germanium. The effective parameters such as oxalic acid, carrier concentration, and strip reagent composition were evaluated in this study. Based on the experimental data, the oxalic acid and carrier concentrations of 0.075 mol/L and 20% v/v were the condition in which the efficient germanium transport was achieved, respectively. The concentration range of 0.04–0.1 mol/L was selected for sodium hydroxide (NaOH) as a strip reagent providing the best efficiency to transport germanium through the supported liquid membrane (SLM) system. Furthermore, the permeation model was obtained to calculate the mass transfer resistance of the membrane (¿m) and feed (¿f) phases. According to the results, the values of 1 and 1345 s/cm were found for ¿m and ¿f, respectivelyPeer ReviewedPostprint (published version

Facilitated transport of germanium from acidic medium through supported liquid membrane using Cyanex 301 as mobile carrier

In this research, a flat sheet supported liquid membrane (FSSLM) system was used to transfer germanium from the acidic medium. The poly-tetra fluoro ethylene (PTFE) membrane filter with the hydrophobic nature and Cyanex 301 were selected as the support and the mobile carrier, respectively. The influence of various parameters being pH of the feed solution (1.5-5), germanium concentration (10-40 mg/dm3), carrier concentration in the solid membrane (10-40 vol%), and sulfuric acid concentration of the receiving phase (100-400 g/dm3) was investigated on the transport of germanium. Under the optimum condition being pH of 1.5, the germanium concentration of 40 mg/dm3, the carrier concentration of 1.18 mol/dm3, and the sulfuric acid concentration of 400 g/dm3, a mass transfer model was developed. Based on this model, the transport mechanism, diffusion of species to the feed-membrane interface, the chemical reaction of species and Cyanex 301, and diffusion of germanium-Cyanex 301 complexes across SLM were explained. According to the obtained model, the values of 6.57 and 738.6 s/cm were achieved for the aqueous and organic diffusion resistances, respectively

Recovery of germanium from leach solutions of fly ash using solvent extraction with various extractants

The solvent extraction of germanium and some heavy metals by commercial tri-octyl/decyl amine (Alamine 336), N-methyl-N, N-dioctyl chloride (Aliquat 336) and phosphine oxide (Cyanex 923) has been studied. In each extraction system, germanium was only extracted from a solution containing nickel, cadmium, cobalt, and zinc, which had a composition similar to gasification coal fly ash aqueous leach solutions. Under a comparable condition, the germanium extraction efficiency by the aforementioned extractants was in the order Aliquat 336 > Alamine 336 > Cyanex 923. The slope analysis method showed that 2 moles of Alamine 336 and Aliquat 336, as well as 4 moles of Cyanex 923, participated in the extraction of germanium. In amine extraction systems, tartaric acid was required as a complexant used to convert germanium to anionic species. As a result, the ratio of 2 (mole ration of tartaric acid to Ge) was required to complete anionic complexation. On the other hand, oxalic acid with a concentration of 0.1 M was chosen as a proper solvated complexant in the Cyanex 923 system. HCl solutions with concentrations of 1 and 2 M can properly strip germanium from the loaded Alamine 336 and Aliquat 336, respectively. In addition, 0.1 M NaOH was sufficient for germanium stripping from Cyanex 923. Consequently, it can be concluded that Aliquat 336 can be an economical and industry-friendly extractant for germanium solvent extraction from a mixed solution.Peer ReviewedPreprin

Germanium transport across supported liquid membrane with Cyanex 923: Mathematical modeling

A mathematical model was developed to monitor the facilitated transport of germanium(IV) from oxalic acid solutions through a flat sheet supported liquid membrane (FSSLM) containing four trialkylphosphine oxides (Cyanex 923). The FSSLM modeling was based on the extraction constant (Kext) calculated from the liquid-liquid extraction (LLX) modeling. The LLX model presented a reliable calculation of the extraction constant (Kex= 2.057×103 L/mol4). The FSSLM model was solved using Matlab® software according to extraction constant, Fick's law, and diffusional principles. The model predicts the overall mass transfer coefficient (Korg) to be 3.84 cm/s. Using this value, diffusion coefficients (Dm) for various Cyanex 923 concentrations of 0.126, 0.252, 0.378, 0.505, 0.631 and 0.757 mol/L are found to be 8.50×10-4, 4.30×10-4, 1.87×10-4, 5.87×10-5, 2.57×10-5, 2.09×10-5 cm2/s, respectively. The results show that the diffusion rate of the current study is approximately more than that of similar FSSLM systems containing Cyanex 923 used to transport various metals. The modeling values are in good agreement with the experimental data, showing the good reliability of the mathematical model.Peer Reviewe

Non-Dispersive Extraction of Ge(IV) from Aqueous Solutions by Cyanex 923: Transport and Modeling Studies

Transport process of germanium from an aqueous solution containing oxalic acid and 100 mg/L Ge was studied. Cyanex 923 immobilized in a polytetrafluoroethylene membrane was employed as a carrier in a flat-sheet supported liquid membrane (FSSLM) system. The speciation of the germanium ion in the oxalic acid medium and related diagrams were applied to study the transport of germanium. The effective parameters such as oxalic acid, carrier concentration, and strip reagent composition were evaluated in this study. Based on the experimental data, the oxalic acid and carrier concentrations of 0.075 mol/L and 20% v/v were the condition in which the efficient germanium transport was achieved, respectively. The concentration range of 0.04–0.1 mol/L was selected for sodium hydroxide (NaOH) as a strip reagent providing the best efficiency to transport germanium through the supported liquid membrane (SLM) system. Furthermore, the permeation model was obtained to calculate the mass transfer resistance of the membrane (Δm) and feed (Δf) phases. According to the results, the values of 1 and 1345 s/cm were found for Δm and Δf, respectively

Selective separation of Germanium(IV) from simulated industrial leachates containing heavy metals by non-dispersive ionic extraction

Germanium can be found in industrial leachates of coal gasification fly ashes or zinc plant residues, containing various heavy metals. In this research, the selective separation of germanium from simulated water coal gasification fly ash leach liquors containing Zn(II), Ni(II), Cd(II), and Co(II) through the flat sheet and hollow fiber supported ionic liquid membrane (FSSLM & HFSLM) systems was developed using an ionic liquid Aliquat 336 as a carrier. As a result, Aliquat-336 was a very fast and effective carrier for the selective transport from these types of solutions. The selective transport of germanium through the mentioned FSSLM system was carried out from a simulated zinc acidic leach liquor containing the aforementioned metals and 0.5 mol/L of H2SO4 under the condition found for the neutral solutions. As a result, an insignificant difference was observed between the germanium transports from both solutions. The germanium transport from both types of solutions was selective and its efficiency reached >98%. Finally, a facilitated transport of germanium was conducted in an HFSLM under the same condition obtained for the FSSLM system. It was observed that this system could transport major amounts of germanium species in the first 30 min showing faster transport than the FSSLM system.Peer ReviewedPreprin