Separation of Picric Acid with Trioctyl Amine (TOA) Extractant in Diluents

Separation of 2,4,6-trinitrophenol (Picric acid) from aqueous solution by trioctyl amine (TOA), which is a long-chain aliphatic amine, has been studied at 298 K. Diluents (alcohols) (isoamyl alcohol, octan-1-ol, decan-1-ol) have been used to dissolve TOA. Experimental results of batch extraction are calculated and reported as distribution coefficients (K_D), loading factors (Z), and extraction efficiency (E). The most effective diluent has been found to be isoamyl alcohol with a distribution coefficient value of 19.333. In this article, the linear solvation energy relationship (LSER) modeling (included Hidebrand-Hansen solubility parameters) has been done on the reactive extraction of picric acid to obtain the model parameters. Modeling using an LSER model predict a close resemblance of experimental data.     

Reactive Extraction of Formic Acid by using Tri Octyl Amine (TOA)

Abstract

Distribution of formic acid (methanoic acid) between water and tri octyl amine (TOA) dissolved in various alcohols (isoamyl alcohol, hexan-1-ol, octan-1-ol, nonan-1-ol, decan-1-ol) as diluents, as well as the extraction capacity of pure diluent alone have been studied at isothermal conditions. All measurements were carried out at 298.15 K. The difference between the physical extraction and reactive extraction was studied. The loading factor, T _T, extraction efficiency, D _E, modified separation factor, S _F, and, distribution coefficients, K _D were calculated. The isoamylalcohol was found most effective solvent with maximum distribution value of 14.521. Possible equilibrium complexation constants for (acid:amine) (5:1), (6:1), and (7:1) have been determined as values of about 21.8 × 10³, 15.6 × 10⁴, and 11.1 × 10⁵ for K₅₁, K₆₁, and K₇₁, respectively with isoamylalcohol. Furthermore, Linear Solvation Energy Relationship (LSER) model equation has been obtained to calculate distribution coefficients for alcohols with regression coefficient of 0.981.     

Extraction of Gibberellic Acid from Aqueous Solution by Trioctyl Amine (TOA)

Gibberellic acid (GA) extraction from fermentation broth by trioctyl amine (TOA), which is a long chain aliphatic amine was studied. Initial concentration of GA was 0.65 g · L^?1. This was performed using the fungi Gibberella fujikuroi in fermentation. Alcohols (isoamyl alcohol, n-octanol, n-decanol) have been used to dissolve TOA for preparing organic phases. All experiments were studied as batch extraction. Distribution coefficients (K_D), loading factors (Z), and extraction efficiency (E) were calculated. The highest extraction efficiency, distribution coefficient, and loading factor were achived with isoamyl alcohol diluent as value of 80.6, 98.7, and 4.58, respectively. Furthermore, the linear solvation energy relationship (LSER) model including Hansen solubility parameters regressed to experimental results. The LSER model predicts a close resemblance of experimental data.     

Separation of Penicillin G from Fermentation Broth Using N,N-Dioctyloctan-1-amine Extractant in Different Diluents

The extraction of penicillin G was investigated using N,N-Dioctyloctan-1-amine (TOA) with different diluents having distinct functional groups. Nine diluents were used in the study, namely, octan-1-ol, nonan-1-ol, isoamyl alcohol, ethyl ethanoate, propyl ethanoate, methyl iso butyl ketone(MIBK), octan-2-one, octane, and decane. The measurements were performed at a temperature of 298.2 K. The experimental results of batch extractions were used to calculate distribution coefficients (K_D), loading factors (Z), and extraction efficiency (E). The highest distribution coefficient (K_D = 5.79) was obtained with isoamyl alcohol, and its extraction efficiency was 85.27%. Further, the highest loading factor was reached to a value of 0.130 at 0.374 mol.kg^?1 amine concentration. Overloading was not observed at any amine concentration. Solvatochromic model (Linear solvation Energy Relationship (LSER)) for data which obtained from alcohols experiments gives the good results as near as same to experimental results. Suitability of data between experiments and model predictions have been tested with root main square deviation (RMSD) with 0.99.     

Investigations on the Reactive Extraction of Glyoxylic Acid by Amberlite-LA2 Dissolved in Alcoholic Diluents

In this study, reactive extraction of glyoxylic acid (0.93 kmol·m^?3) using Amberlite-LA2 (0.24 to 1.67 kmol·m^?3) in five different alcoholic diluents is performed at 298 K. The extraction ability of Amberlite-LA2 is found to be in the order of isoamylalcohol (IAA) > nonan-1-ol > octan-1-ol > decan-1-ol > dodecanol. Maximum extraction efficiency, 98.92% is obtained at 1.67 kmol·m^?3 of Amberlite-LA2 in IAA. The values of stoichiometric coefficient (m), overall equilibrium constant (K_E) and individual constants (K₁₁, K₂₁, and K₁₂) are estimated. The effect of diluent on K_D is also quantified by applying LSER model using solvatochromic parameters of diluents.     

Reactive Extraction of Levulinic Acid Using TPA in Toluene Solution: LSER Modeling,Kinetic and Equilibrium Studies

Abstract

Levulinic acid, a carboxylic acid containing ketone structure, is a clear to brownish semi‐solid melting at 37°C; soluble in alcohol, ether, and chloroform, levulinic acid can be used as an acidulant in foods and beverages. Organic solutions of amines are being used increasingly to separate organic acids from aqueous mixture solutions by reactive extraction. The design of an amine extraction process requires kinetic data for the acid–amine+solvent system used. Kinetic studies for the extraction of levulinic acid from aqueous solution with tripropylamine (TPA) diluted in toluene were carried out using a stirred cell for kinetic studies. Equilibria for levulinic acid extraction by TPA in toluene as a diluent have been determined. All measurements were carried out at 298.15 K. The equilibrium data were also interpreted by a proposed mechanism of complexation by which (1∶1) and (2∶1) acid‐amine complexes are formed. Kinetics of extraction of levulinic acid by TPA in toluene has also been determined. The results of the liquid‐liquid equilibrium measurements were correlated by a linear solvation energy relationship (LSER).     

Estimation of equilibrium parameters using differential evolution in reactive extraction of propionic acid by tri-n-butyl phosphate

The graphical and conventional optimization methods, used for the estimation of equilibrium parameters, do not guarantee the global optimum values. In this study, the equilibrium parameters are estimated using a well proven evolutionary based optimization routine [differential evolution (DE)]. For the estimation of stoichiometry and equilibrium constants, experiments are carried out for the reactive extraction of propionic acid using tri-n-butyl phosphate (TBP) dissolved in n-decane (inert diluent) and 1-decanol (modifier). The number of TBP molecules (n) in the acid:TBP complex and equilibrium extraction constant (K_E) using 1:1 volume ratio of 1-decanol and n-decane as a diluent, are determined through proposed mathematical model using graphical methods as well as the differential evolution algorithm (DE, an optimization routine) and found that the predicted values of distribution coefficient (K_D) using DE are closely matching with the experimental values of K_D. 1:1 complexes between TBP and acid are formed in most of the cases. The enthalpy and entropy of reactive extraction of propionic acid using TBP are also determined and found to be −12.47 kJ mol⁻¹ and −32.42 J mol⁻¹ K⁻¹, respectively. The results of present study will be useful to intensify the recovery of propionic acid from fermentation broth (bio-separation) and aqueous waste stream.     

A Study on Glutaric Acid Extraction by Tridodecylamine: Equilibria and Models

The extraction of glutaric acid was studied using tridodecyl amine (TDA) with respect to the functional groups of the diluent. The diluents studied were 1‐octanol (alcohol), methyl isobuthyl ketone, MIBK (ketone), and toluene (aromatic hydrocarbon) and these were used to dilute the TDA. The experimental results of batch extraction experiments are reported as distribution coefficients, D_C, loading factors, Z, and extraction efficiency, E. All measurements were carried out at 298.15 K. The results of the liquid‐liquid equilibrium measurements are correlated by a linear solvation energy relationship (LSER) model that takes into account physical interactions and modified Freundlich and Langmuir equations. The experimental results are compared with model results.     

Synthesis and characterization of temperature-responsive copolymer of PELGA modified poly(N-isopropylacrylamide)

Novel amphiphilic PELGA modified temperature-responsive copolymer, [(poly(methoxyethylene glycol)-co-poly(lactic acid)-co-poly-(glycolic acid))acrylate-co-poly(N-isopropylacrylamide)-co-poly(N-hydroxymethylacrylamide)] (PELGAA-co-PNIPAAm-co-PNHMAAm) was synthesized by incorporating PELGA as the amphiphilic moiety into poly(N-isopropylamide) with various LA/GA ratios. Polymers obtained were characterized by FT-IR, GPC, ¹H-NMR and DSC. The lower critical solution temperature (LCST) of the copolymeric nanoparticles was 40±0.6 °C, the critical aggregation concentration (CAC) was 18 mg L⁻¹, and reversible change in nanoparticle size related to temperature was fluctuated between 210±10 and 109±26 nm, while change in zeta potential of the nanoparticles was between −36±6 and −26±4 mV. The transmission electron microscopy (TEM) images of nanoparticles were also presented.     

Optimization of total alkannin yields of Alkanna tinctoria by using sub- and supercritical carbon dioxide extraction

The effects of supercritical carbondioxide extraction was investigated to compare previously validated extraction methods on total alkannin yield with Alkanna tinctoria collected form Antalya, Turkey. A two-step process was used; extraction of alkannin derivatives with supercritical CO₂ followed by alkaline hydrolysis of alkannin derivatives. A Box-Behnken exprerimental design was used to evaluate the effect of three variables, pressure (50-350 bar), temperature (30-80 °C) and CO₂ flow (5-20 g min⁻¹) at 1:30 ratio of alkanna root:CO₂ amount. Response surface analysis revealed that the data were adequately fitted to a second-order polynomial model with R² 0.9665 and the most effective variable was pressure (P ≤ 0.05). Optimum conditions were determined as 80 °C, 175 bar, 5 g min⁻¹ CO₂ flow yielding the highest total alkannins (1.47%) which was higher than conventional hexane extraction (1.24%) providing a solvent-free alternative for industrial production.     

Reactive Extraction of Pyridine Carboxylic Acids with N,N-Dioctyloctan-1-Amine: Experimental and Theoretical Studies

The paper represents the equilibrium study on reactive extraction of pyridine-3-carboxylic acid (NA) and pyridine-4-carboxylic (iNA) acid from aqueous solution by N, N-dioctyloctan-1-amine (TOA) dissolved in five different diluents [dodecane, methyl benzene, decan-1-ol, 4-methylpentan-2-one (MIBK), and chloroform] at constant temperature of 298 ± 1 K. According to an experimental study, the extraction ability of diluents with TOA is found to be in the order of chloroform > decan-1-ol > MIBK > methyl benzene > dodecane for both acids. The highest extraction efficiency in terms of the distribution coefficient (K _D) is found to be 45.15 and 25.79 for NA (0.12 mol · dm^?3) and iNA (0.03 mol · dm^?3), respectively. The values of loading ratio, Z (between 0.194 and 0.512) for both acids indicate the formation of 1:1 acid-TOA complexes in the organic phase. The values of the equilibrium constants (K ₁₁) are determined from the experimental data using mass action law. These estimated values of K ₁₁ are compared with the predicted values of K ₁₁ from relative basicity and linear solvation energy relationship (LSER) models. The LSER model predicts the K ₁₁ with an error limit of ±3% for NA and ±2% for iNA.     

Extraction and separation of D/L-lactic acid in simulated fermentation broth

The recovery of lactic acid from fermentation broth plays an important part in production of lactic acid. In this case, the extraction of lactic acid from simulated fermentation broth was processed by tri-n-octylamine dissolved in oleyl alcohol. The extraction efficiency was investigated with several variables, and the optimal condition of extraction of lactic acid (10 mg mL⁻¹) from aqueous solution was tri-n-octylamine/oleyl alcohol (30/70, v/v) and solvent phase/ fermentation (1/2, v/v) stirred for 60 min under room temperature. The optimal back extraction of lactic acid was obtained by hot water (∼90 °C) with solvent phase/water (1/4, v/v). The back extracted racemic lactic acid was direct enantiomeric analyzed and separated by chiral ligand chromatography due to strict requirement of absolute configuration in pharmaceutical field and food science. The effect of various parameters on enantioselectivity was discussed and the (L)-phenylalaninamide·HCl (6.0 mmol L⁻¹) and CuSO⁴·5H₂O (3.0 mmol L⁻¹) dissolved in methanol/water (5/95, v/v) at pH=6.0 was the suitable mobile phase for chiral ligand exchange separation of (D, L)-lactic acids. By the investigations, a convenient systemic method was established for extraction and separation of (D, L)-lactic acid.     

Melting parameters of poly(glycolic acid)

Equilibrium melting temperature T_m⁰, heat of fusion ΔH_f, and entropy of fusion ΔS_f of poly(glycolic acid) (PGA) was determined by using Clapeyron-Clausius equation. Equilibrium melting temperature T_m⁰ was 504.6 K which was determined by Hoffman-Weeks plots. The pressure dependence of T_m⁰ was determined by high pressure DTA up to 150 MPa. Volume change ΔV_f at melting was determined by using dilatometer. Heat of fusion in PGA was 183.2 (J g⁻¹), which is very close to the value reported by Chujo et al. who determined it by using T_m depression in copolymer with poly(lactic acid). ΔS_f of PGA was 0.363 (J g⁻¹ K⁻¹), which is about twice that of PLA, and the reason was discussed on the basis of the elastic modulus below T_m.     

Poly(vinyl alcohol)-based polymer electrolyte membranes for direct methanol fuel cells

We have prepared polymer electrolyte membranes (PEMs) from poly(vinyl alcohol) (PVA) and modified PVA polyanion containing 2 or 4 mol% of 2-methyl-1-propanesulfonic acid (AMPS) groups as a copolymer. The PEMs of various AMPS content and cross-linking conditions were prepared to determine the effect of AMPS content and cross-linking conditions on PEM properties. Proton conductivity and permeability of methanol through the PEMs increased with increasing AMPS content, C_AMPS, and with decreasing cross-linker concentration, C_GA, because of the increase in the water content. The permeability coefficient of methanol through the PEM prepared under the conditions of C_AMPS = 2.7 mol% and C_GA = 0.35 vol% was about 30 times lower than that of Nafion^®117 under the same measurement conditions. The proton permselectivity of the PEM, which is defined as the ratio of the proton conductivity to the permeability coefficient of methanol, gave a maximum value of 66 × 10³ S cm⁻³ s. The value is about three times higher than that of Nafion^®117.     

Extraction of metal ions with non-fluorous bipyridine derivatives as chelating ligands in supercritical carbon dioxide

Three new non-fluorous bipyridine derivatives, bis(2-(2-butoxyethoxy)ethyl)-2,2′-bipyridine-4,4′-dicarboxylate (ligand 1), bis(2-(2-ethoxyethoxy)ethyl)-2,2′-bipyridine-4,4′-dicarboxylate (ligand 2), and bis(2-butoxyethyl)-2,2′-bipyridine-4,4′-dicarboxylate (ligand 3), were synthesized as chelating ligands to remove metal ions from solid matrix into supercritical CO₂ (scCO₂). These produced compounds 1-3 showed considerable solubilities in scCO₂ (8.0 g/l, 4.8 g/l, 7.8 g/l for ligands 1-3 at 313 K, respectively) and the tested solubility data were then calculated and correlated with semiempirical model at different pressures and temperatures, which showed satisfactory agreement with each other and the average absolute relative deviation were in the range of 0.1-28.3%. The effects of pressure, temperature, time, and ligand to metal ratio (5:1 to 75:1) on the extraction efficiency of metal ions were also systematically investigated. The extraction efficiency was 100% for Ni²⁺ and 95.9% for Cu²⁺ in scCO₂ with the system of ligand 1, ultrapure water, and perfluoro-1-octanesulfonic acid tetraethylammonium salt (PFOAT) under the optimized conditions (25 MPa, 313 K, 90 min, and ligand to metal ratio of 10). Although all ligands exhibited good efficiency for Ni²⁺ (>85%) and Cu²⁺ (>70%) extraction, the extraction of mixed metal ions indicated that the bipyridine derivatives had low selectivity. Finally, the detailed calculation results exhibited that the extraction constants (K_ex) of the metal ions increased with the increase of the extraction efficiency in the same extraction system for each same metal ion.     

Oxidative desulfurization of Gas oil by polyoxometalates catalysts

Several polyoxometalates: Na₂HPM₁₂O₄₀, H₃PM₁₂O₄₀, Na₂HPM₁₂O₄₀, (VO)H[PM₁₂O₄₀] and (n-Bu₄N)₃[PM₁₂O₄₀] (M = Mo and W) as well as (n-Bu₄N)_3 + x[PW_12−xV_xO₄₀] (x = 0–3) were synthesized and characterized. Benzothiophene, dibenzothiophene and 4,6-dimethyl-dibenzothiophene were used as model sulfur compounds in gas oil. The oxidation reaction was performed using different polyoxometalates as catalyst and H₂O₂/acetic acid. The experimental results show that the W-based polyoxometalate catalysts are more active than the Mo catalysts. The oxidation reactivity of the catalysts depends on the type of countercation: Na⁺ > H⁺ > (VO)⁺ > (n-Bu₄N)⁺. In a series of (n-Bu₄N)_3 + x [PW_12−xV_xO₄₀] (x = 0–3) the order of catalytic activity is V₃ > V₂ > V₁ > V₀. The reactivity order of the sulfur compounds is: dibenzothiophene > 4,6-dimethyldibenzo-thiophene > benzothiophene. The catalytic system in this work was used for the oxidation of gas oil combined with solvent extraction to remove sulfur content in gas oil. Under mild reaction condition, high sulfur removal up to 98% can be achieved with high oil recovery (90%).     

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.     

Growth and kinetics of Lactobacillus plantarum in the fermentation of edible Irish brown seaweeds

The aim of the present study was to see the applicability of using brown edible seaweeds as a sole source of nutrition for the growth of lactic acid bacteria. Growth kinetics of lactic acid bacteria (LAB; Lactobacillus plantarum) was studied using three species of edible Irish brown seaweeds Himanthalia elongata, Laminaria digitata and Laminaria saccharina. As part of the screening process, growth of the LAB was carried out on raw and heat treated forms of seaweeds. The seaweed species in their raw state could not support the growth of L. plantarum. Heat treatment resulted in almost 4 times increase in the total sugar content in L. digitata and L. saccharina broth which allowed the growth of L. plantarum for 24 h after which the cell number started decreasing. The Laminaria spp. contains a high content of laminaran polysaccharide which can be fermented by LAB. In case of H. elongata, neither raw nor heat treated forms could be fermented; even though the total sugar content increased 4.6 times upon the application of heat. Kinetics of cell growth, lactic acid and acetic acid production was evaluated at different agitation rates in heat treated seaweeds. A maximum log CFU/ml of 10 was achieved at the end of 16-24 h of fermentation for L. saccharina and L. digitata, respectively. The cell growth increased and lactic acid accumulation decreased as the agitation speed was increased from 0 to 100 rpm. Maximum lactic acid accumulation of 2.5 g/l was achieved under static (0 rpm) conditions. The production of acetic acid was very minimal during the entire course of fermentation. Experimental data was mathematically modelled to optimize the cell growth and lactic acid production with respect to the different rotation conditions. The results of this study present an indication of the potential of fermentation of seaweeds using LAB with a possibility towards the development of a range of functional foods.     

Kinetic model of solute aqueous extraction from Fennel (Foeniculum vulgare) treated by pulsed electric field, electrical discharges and ultrasonic irradiations

This work investigates the aqueous extraction from Fennel (Foeniculum vulgare) assisted by pulsed electric field (PEF), electrical discharges (ED) and ultrasound irradiations (UI). It aims the improvement of the solutes yield and the extraction kinetics at room temperature.Fennel gratings of size (1.5 × 0.75 × 30-50 mm³; width × height × length), were treated by PEF (intensity: 50-1200 V/cm and number of pulses: 50-1000), ED (voltage: 40 kV and number of discharges: 10-60) and ultrasound (intensity: 400 W/cm² and treatment duration: 10-350 min). The liquid-to-solid (weight/weight) ratio equal to 2. All tests were carried out at room temperature (20 °C), under stirring at 250 rpm. The extraction kinetics was modelled using a simplified two-exponential kinetic model, which corresponds to mass transfer in two stages (rapid washing and slow diffusion).The optimal parameters of PEF, ED and UI, giving the maximal juice yield, were determined and the effect of these three treatments on the mass transfer rate was studied.     

Extraction kinetics of Fe(III) by di-(2-ethylhexyl) phosphoric acid using a Y–Y shaped microfluidic device

The extraction kinetics of Fe^III by di-(2-ethylhexyl) phosphoric acid (D2EHPA) were investigated using a Y–Y shaped microfluidic device. Finite-volume simulations were used to examine the accuracy of a single-step dimeric reaction mechanism in fitting the experimental data. Results demonstrate the validity of the proposed mechanism and show that Fe^III extraction occurred at a slow rate (second-order forward rate constant of k₁ = (3.0 ± 0.1) × 10⁻⁶ m⁴/mol s) under a mixed reaction–diffusion resistance regime. The present study provides insight for the control of Fe^III extraction rates in hydrometallurgical processes.