Extraction of citric acid from aqueous solutions with Alamine 336: equilibrium and kinetics

Citric acid is one of the organic acids for which the world market is growing every year. This article describes equilibria and kinetic studies for the extraction of citric acid by Alamine 336 with methyl‐iso‐butylketone (MIBK) as diluent. The theory of extraction accompanied by a chemical reaction has been used to obtain the intrinsic kinetics of extraction of citric acid by Alamine 336 in MIBK. The reaction has been found to be first order in both Alamine 336 and citric acid with a rate constant of 0.013 m³ kmol^?1 s^?1. Copyright © 2004 Society of Chemical Industry     

Transport of Thorium(IV) Across a Supported Liquid Membrane Containing N,N,N′,N′-Tetraoctyl-3-oxapentanediamide (TODGA) as the Extractant

The transport behavior of Th⁴⁺ was investigated from a feed containing 3.0 M HNO₃ into a receiver phase containing 0.1 M oxalic acid across a PTFE flat sheet supported liquid membrane (SLM) which contained TODGA (N,N,N′,N′-Tetraoctyl-3-oxapentanediamide) in n-dodecane as the extractant. Effects of the nature of the strippant, extractant concentration, Th concentration in the feed, and feed acidity on the transport rates were investigated. The transport behavior apparently depended on the rate of extraction of the metal ion at the feed-membrane interface and was not diffusion controlled. Influence of Th concentration on flux was also investigated. Transport mechanism was elucidated and the diffusion coefficient was calculated to be 2.13 × 10^?7 cm²/s. Solvent extraction studies at varying feed acidity and TODGA concentration were also carried out.     

Separation of zirconium from hafnium by ion exchange

This work aimed at separating Zr(IV) from Hf(IV) from an acid solution using cationic resin through column experiments. The influence of different inorganic acids in the loading of the resin as well as different organic and inorganic eluents such as hydrochloric, sulfuric, citric and oxalic acids were evaluated. The loading of Zr varied from 1.14 to 1.26 mmol g^?1 and for Hf it varied from 0.041 to 0.140 mmol g^?1. Elution with 0.5 M oxalic acid was the best option for the separation of these elements. The elution removed 100% of the Zr and 70% of the Hf. The final product contains 1% Hf and 99% Zr.     

Reactive extraction of itaconic acid using tri‐n‐butyl phosphate and aliquat 336 in sunflower oil as a non‐toxic diluent

Itaconic acid finds a place in various industrial applications. It can be produced by biocultivation in a clean and environment friendly route but recovery of the acid from the dilute stream of the bioreactor is an economic problem. Reactive extraction is a promising method to recover carboxylic acid but suffers from toxicity problems of the diluent and extractant employed. So there is need for a non‐toxic extractant and diluent or a combination of less toxic extractants in a non‐toxic diluent that can recover acid efficiently. Effect of different extractants: tri‐n‐butylphosphate (TBP) (an organophosporous compound) and Aliquat 336 (a quaternary amine) in sunflower oil was studied to find the best extractant–sunflower oil combination. Equilibrium complexation constant, K_E, values of 1.789 and 2.385 m³ kmol^?1, respectively, were obtained for itaconic acid extraction using TBP and Aliquat 336 in sunflower oil. The problem of toxicity in reactive extraction can be reduced by using a natural non‐toxic diluent (sunflower oil) with the extractant. Copyright © 2010 Society of Chemical Industry     

Comparative study of solvent extraction and supported liquid membrane for the extraction of gallium (III) from chloride solution using organophosphorus acids as extractants

ABSTRACT

The transport of Ga(III) from chloride solution by supported liquid membrane (SLM) using organophosphorus acids as carriers was studied and compared with solvent extraction results. The diffusion coefficient, permeability coefficient and mass transfer resistance for both processes were analyzed by investigating various parameters, such as flow pattern, flow rate, pH, Ga(III)/extractant concentration and temperature. Under optimized conditions, the extraction percentage of 97.0% and permeability coefficient of 9.22 × 10^?6 m/s was achieved for SLM process. Kinetic modeling was proposed to determine the mass diffusion coefficient of Ga(III) complex across the membrane and stability of this SLM system was also examined.     

Cobalt removal from waste‐water by means of supported liquid membranes

BACKGROUND: Supported liquid membranes (SLM) are an alternative technique to remove and recover metals from diluted process solutions and waste‐water. In the present work, the removal of Co(II) from a synthetic CoSO₄ solution containing initial amounts of cobalt(II) in the range 100–200 ppm (0.1–0.2 g dm^?3) has been studied on a pilot scale. By performing batch equilibrium experiments, the optimal settings, i.e. the composition of the organic phase, the pH of the feed, the type and concentration of the stripping agent were determined. RESULTS: It is shown that the equilibrium characteristics of a synergistic extractant mixture containing di‐2‐ethyl‐hexylphosphoric acid (D2EHPA) and 5‐dodecylsalicylaldoxime (LIX 860‐I) are superior to D2EHPA. Both hydrochloric acid and sulfuric acid have been evaluated as stripping solutions in liquid–liquid extraction tests and as the receiving phase in a SLM configuration. Although equilibrium tests showed no difference in stripping characteristics between both chemicals, it was observed that in a SLM configuration the stability of the system when hydrochloric acid is used is poor. With a commercially available SLM module (Liqui‐Cel Extra‐Flow 4 × 28) having a surface area of 19 m², a steady Co(II) flux of 0.140 gm^?2h^?1 has been obtained at influent concentrations of cobalt between 100 and 200 ppm with 3 mol dm^?3 sulfuric acid as stripping phase. CONCLUSIONS: The results obtained show that a supported liquid membrane containing a synergistic mixture of LIX 860‐I and D2EHPA gives the possibility of recovering cobalt from dilute solutions. Copyright © 2008 Society of Chemical Industry     

Extraction of Rhodium Chlorocomplexes and Acid through a Supported Liquid Membrane of Kelex 100

Abstract

The supported liquid membrane (SLM) technique was employed to effect the separation of Rh Chlorocomplexes from hydrochloric acid solutions. The liquid membrane consisted of an alkylated 8-hydroxyquinoline extractant (Kelex 100), tridecanol, and kerosene. The nonaquated Rh complexes were transported through the membrane upon ion-pair formation with protonated Kelex 100 molecules. The ion-pair was then dissociated at the strip side of the membrane, releasing the Rh values. The main driving force for this transport process was the acid activity gradient across the membrane. The permeation of acid and water, which were cotransported with the Rh complexes, was partially prevented upon addition of NaCl to the strip phase. However, the accumulation of Cl^? ions in the strip phase, in turn, slowed down the extraction of Rh. Optimum Rh extraction performance was obtained when a feed of 2.5 M HC1 and a strip solution of pH 1 were used. Under these conditions the membrane was found to be very stable for at least a period of 72 hours (maximum period tested) while the rate of extraction was found to be 2.8 × 10^?6 mol·s^?1·m^?2.     

Liquid-Liquid Extraction Studies of Trivalent Yttrium from Phosphoric Acid Solutions Using TOPS 99 as an Extractant

Liquid-liquid extraction studies of trivalent yttrium (Y) from phosphoric acid solutions have been carried out with commercial organophosphoric acid based extractant TOPS 99 (Talcher Organo phosphorus solvent, an equivalent of di-2-ethylhexyl phosphoric acid). The parameters studied include equilibration time, acid concentration, extractant concentration, diluent, metal concentration, temperature, stripping, and regeneration of the extractant. Increase of phosphoric acid concentration in the range from 0.01 to 0.5 M on the extraction of trivalent Y with 6 × 10^?3 M TOPS 99 (Talcher Organo phosphorus solvent) decreases the percentage extraction, indicating the transfer of metal follows ion exchange type reaction. The plot of log D vs. equilibrium pH gave a straight line with a slope of 3.1 indicating the exchange of three moles of hydrogen ions for every mole of trivalent Y extracted into the organic phase. Stripping of metal from the loaded organic with mineral acids indicate sulphuric acid as the best stripping agent. The extraction behavior of associated elements clearly follows their ionic radii with a maximum separation factor of 414 for Lu-Tb.     

Equilibria and Kinetics of Extraction of Citric Acid from Aqueous Solutions in Alamine 336–Cyclohexanone System

Abstract

Equilibria and kinetics for the extraction of citric acid by Alamine 336 in cyclohexanone as diluent are reported. The theory of extraction accompanied by a chemical reaction has been used to obtain the intrinsic kinetics of extraction of citric acid by Alamine 336 in cyclohexanone. The reaction has been found to be first order in both Alamine 336 and citric acid with a rate constant of 8.8×10^?3 m³ kmol^?1 s^?1.     

Supported Liquid Membrane Separation of Aluminum from Copper Leaching Liquors

Abstract

The Bureau of Mines, U.S. Department of the Interior, investigated the separation of aluminum from copper dump leaching liquors using a supported liquid membrane. Aluminum was selectively transported through porous polypropylene impregnated with di(2-ethylhexyl) phosphoric acid in an aliphatic diluent. The effects of variables, such as solution composition, temperature, and extractant concentrations, were measured using a three-level fractional factorial experimental design. Experimental results were used to derive equations for predicting transport rates for aluminum, iron, and copper. The major variables influencing aluminum transport were solution temperature, feed solution pH, aluminum concentration in the feed solution, and extractant concentration. Copper and iron transport rates were almost zero when aluminum transport rates were high. Measured aluminum transport rates under the best conditions of 55[ddot] C, pH 3.0, 16 g/L A1³⁺ and 65 pet extractant solution confirmed the predicted value of 210 μg/(cm²·h). Transport rates for iron and copper were less than 5 μg/(cm²·h) under these conditions.     

Effect of an electric field on the transport of Th(IV) in the presence of Eu(III) and U(VI) through supported liquid membrane containing di‐2‐ethylhexylphosphoric acid

This paper investigates the transport of Th(IV) ions in nitric acid media through a supported liquid membrane (SLM) impregnated with di‐2‐ethylhexylphosphoric acid (HDEHP) in kerosene using an electric field. The transport was carried out in a three compartment cell fitted with microporous cellulose nitrate (SLM) and cation exchange membrane (Nafion). The effect of different parameters including nitric acid concentration in the feed solution, HDEHP concentration in the membrane, and HCl concentration were studied. The optimal conditions for Th(IV) transport were 0.1 mol dm^?3 HDEHP, 10^?3 mol dm^?3 HNO₃ in the feed solution, 1 mol dm^?3 HCl in compartment 2 and 1 mol dm^?3 HCl in compartment 3 at 25 °C. Under the optimal conditions of Th(IV) transport the recovery factor after 90 min was 0.25 without applying an electrostatic field, compared with 0.9 when the electric field was applied. The effect of electric current on the flux of Th(IV) through the membrane was also studied. The flux increased as the current density increased from 10 to 30 mA cm^?2 to reach a maximum value at 30 mA cm^?2 (8 × 10^?9 g eq cm^?2 s^?1). The transport percentages of 0.3 g dm^?3 Th(IV) in the presence of 0.1 g dm^?3 Eu(III) and 1 g dm^?3 U(VI) were 66, 84 and 15%, respectively. The determined selectivities of U(VI)–Th(IV) and Th(IV)–Eu(III) were 0.12 and 0.3, respectively, after 90 min. Therefore, the order of selectivity of this system is Eu(III) > Th(IV) > U(VI). © 2001 Society of Chemical Industry     

Chemical structure of poly(β‐cyclodextrin‐co‐citric acid)

We synthesized water‐insoluble polymers, poly(β‐cyclodextrin‐co‐citric acid)s, by heating a mixture of citric acid, cyclodextrin (CD), and Na₂HPO₄ as a catalyst with a 6 : 1 : 2 molar ratio at 160, 170, and 180°C for 10 and 20 min. The chemical composition of the polyesters was determined by high pressure liquid chromatography (HPLC) analysis of the polymer hydrolysates. The crosslinking mechanisms and thermal degradation of the polymers were also investigated. The polyesters contained 30–35% citric acid, 1–4% unsaturated carboxylic acids (i.e., itaconic, cis‐aconitic, trans‐aconitic, and mesaconic acids), and 60–70% CD, whereas about 40% of them were able to form inclusion complexes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

THE SOLVENT EXTRACTION OF SELECTED ORGANIC COMPLEXANTS BY TRUEX PROCESS SOLVENT∗

The extraction by TRUEX solvent of ¹⁴C-labelled acetic, glycolic, and citric acids, and ¹⁴C-labelled glycine, EDTA, and ethylenediamine has been studied from aqueous solutions having different nitric acid concentrations. Only acetic and citric acids are extracted to a significant extent. Their behavior can be compared to that of oxalic acid. If the aqueous phase contains a high concentration of aluminum and iron(III) species, as in some nuclear waste solution, the extraction of aqueous complexants into the organic phase is strongly suppressed. By measuring distribution ratios of irradiated ¹⁴C-labelled acetic acid, citric acid and EDTA, it has been demonstrated that the radiolytic degradation of these compounds leads, at least in part, to oxalic acid. A scrub procedure, utilizing basic aluminum nitrate, has been successfully tested in order to remove any co-extracted oxalic acid from the TRUEX solvent.     

Removal of Organic Acids from Wine by Adsorption on Weakly Basic Ion Exchangers: Equilibria for Single and Binary Systems

Abstract

In order to remove or reduce the organic acids from wine and liqueur, we investigated their adsorption on weakly basic resins. CC-S, WA-10, and WA-30, which were made from chitosan, acryl, and styrene, respectively, appeared technically feasible. The concentration of the fixed amino group in CC-S, WA-10, and WA-30 is 3.31, 2.37, and 2.81 kmol/m³, respectively. These resins adsorbed citric acid and malic acid from wine selectively. The equilibrium isotherms for single component systems of citric acid or malic acid were little affected by the initial concentration (C ₀ = 0.01, 0.02, and 0.03 kmol/m³) and by ethanol. The equilibrium data were correlated by the Langmuir equation. The equilibrium data were correlated by the Langmuir equation. The equilibrium isotherms for the binary system of citric and malic acids were affected by the initial concentration (C _A0 = 0.02, C _B0 = 0.03 kmol/m³; C _A0 = 0.014, C _B0 = 0.004 kmol/m³). The equilibrium data were correlated reasonably well by the Markham-Benton equation. The equilibrium constants for citric acid were much larger than those for malic acid. By using these constants, the equilibrium data for adsorption of citric and malic acids from wine could be adequately correlated by the Markham-Benton equation.     

Recovery of aconitic and lactic acids from simulated aqueous effluents of the sugar‐cane industry through liquid–liquid extraction

The recovery of aconitic and lactic acids from dilute aqueous effluents of the sugar‐cane industry by a solvent extraction technique has been investigated in order to reduce environmental pollution and in view of the possible uses of pure solutes in the field of foods and pharmaceuticals. Reactive extraction of carboxylic acids with tributylphosphate dissolved in dodecane was examined. Experiments were performed at 25 °C for three extractant concentrations of 50%, 60% and 70% (mass %) in dodecane. The decrease of specific gravity and viscosity of solvent resulting from the presence of an inert diluent was favourable to the phase settling and the mass transfer. The percentage of acids recovered in the organic phase for a volumetric solvent ratio varying from 0.5 to 5.0 was determined. Taking into account the difference between the partition coefficients for the carboxylic acids under consideration, the selectivity of solvent with regard to aconitic acid also was quantified. Moreover, owing to its water‐insolubility, its availability and its low cost, tributylphosphate can be considered as a promising extractant for large‐scale applications. © 2000 Society of Chemical Industry     

巯基乙酸萃取工艺的研究

通过对若干种有机溶剂的比较,选定磷酸三丁酯(TBP)作为萃取剂,甲基异丁基甲酮(M IBK)作为稀释剂,对巯基乙酸(TGA)的萃取进行研究。同时考察了TGA浓度、萃取温度、pH等条件对TGA萃取分配系数的影响。实验结果表明,采用V(M IBK)∶V(TBP)=1∶9的混合萃取剂,控制V(有机相)∶V(水相)=1∶2,在室温下萃取TGA合成液两次,TGA萃取率达98.31%。萃取后有机相中含有无机酸杂质H2SO4和有机酸杂质二硫代二乙酸(DTDGA),可采用w(NaOH)=20%的水溶液洗涤去除。洗涤时控制n(NaOH)/n(DTDGA)=7,洗涤后无机酸杂质H2SO4去除率达100%,有机酸杂质DTDGA去除率达80.3%,TGA损失率2.6%,有机相中m(杂质)/m(TGA)=0.007 3。     

Transport of mercury(II) ion through a supported liquid membrane containing a triisobutylphosphine sulfide (Cyanex 471X) as a mobile carrier

Carrier‐facilitated transport of mercury(II) against its concentration gradient from aqueous 0.1 mol dm^?3 hydrochloric acid solution across a flat‐sheet supported liquid membrane (SLM) containing triisobutylphosphine sulfide (Cyanex 471X) as the mobile carrier in kerosene as diluent has been investigated. Dilute sodium thiocyanate solution (0.11 mol dm^?3) was the most efficient stripping agent among several aqueous reagents tested. Various parameters such as stirring rate, concentration of HCl in the feed solution, concentration of NaSCN in the strippant, concentration of Cyanex 471X in the membrane, and contact time were investigated. Under optimum conditions the transport of Hg(II) across the liquid membrane is about 100% after 6 h. The carrier, Cyanex 471X, selectively and efficiently transported Hg(II) ions in the presence of other associated metal ions. The method has been demonstrated to recover selectively mercury from waste samples and mercurochrome solution. © 2002 Society of Chemical Industry     

Organic acids: old metabolites,new themes

Fumaric, L ‐malic and citric acids are intermediates of the oxidative tricarboxylic acid (TCA) cycle which in eukaryotes is localized in mitochondria. These organic acids are synthesized and accumulated in the medium to very high concentrations by filamentous fungi such as Aspergillus spp. and Rhizopus sp. This article reviews basic research on the unusual acid production capability and the associated metabolic pathways operating under defined stress conditions in these specific fungi. In particular, we describe and discuss the importance of the cytosolic reductive TCA pathway, which includes the cytosolic activities of pyruvate carboxylase, malate dehydrogenase and fumarase, for production of fumaric and L ‐malic acids. This article also describes the differences between fumaric acid, L ‐malic acid and citric acid production by different organisms (filamentous fungi, yeast, and higher eukaryotes), and the possible application of novel technologies (genetic engineering and bioinformatics) to fungal systems which may offer new industrial potential of filamentous fungi for the production of valuable metabolites. Copyright © 2006 Society of Chemical Industry     

Performance improvement of direct methanol fuel cells via anodic treatment using various organic acids

Performance improvement of direct methanol fuel cells (DMFCs) was achieved via an anodic treatment technique. Previously, anodic treatment was performed using sulfuric acid as acidic media, but various organic acids including formic, acetic, oxalic, and citric acids were employed in this study to avoid the use of toxic sulfuric acid. By replacing sulfuric acid to organic acids, a potential damage to catalyst layers and other components such as polymer electrolyte membrane and bipolar plates are expected to be minimized. The anodic treatment was performed by applying 0.7 V (vs. reversible hydrogen electrode) at the anode of DMFCs flowing the organic acid solutions for 30min. After the anodic treatment, peak power densities of DMFCs were increased by +7, +32, +23, and ?2.6% when formic, acetic, oxalic, and citric acid solutions were employed, respectively. The enhanced catalytic activity of the DMFCs in the acetic and oxalic acid solutions was confirmed by analyzing electrochemical impedance spectroscopy data.     

Experimental and Theoretical Studies of Actinide and Lanthanide Ion Transport Across Supported Liquid Membranes

In this work, we propose a new transport mechanism for metal ions relevant for used nuclear fuel separation processes by a supported liquid membrane (SLM). Two SLM extraction systems were investigated where the membrane was impregnated with either di-(2-ethylhexyl)phosphoric acid (HDEHP) or tributyl phosphate (TBP). A HDEHP impregnated membrane was used to extract neodymium (III), representative of a typical trivalent lanthanide. Cerium, which was oxidized by sodium bismuthate from trivalent to tetravalent state, was extracted by TBP. Oxidized cerium was used as a surrogate for oxidized americium to investigate the kinetics and possibility of americium and curium separation by membrane extraction. Both extraction systems were operated at varying nitric acid concentrations, and changes in the kinetics and extraction efficiency of metal ions were investigated. The proposed transport mechanism that was chosen for our studies was modified from the previous works by Danesi et al.^[1,2] and Cussler et al.^[3] The mechanism was selected due to the ability to accommodate and describe transport phenomena across a SLM when formation of extractant nano-channels in the membrane may exist. We were able to obtain acceptable fit of the models to our overall data trends although chemical and physical conditions must be well established and purity and homogeneity of the membrane are critical. A reverse transport of metal ions was observed when leaving the system for longer times which agrees with our model. The membrane was investigated for degradation and shown to be stable after contact with up to 7 M nitric acid for over 2000 minutes. Finally, we examined the possibility of partitioning americium from curium using a SLM impregnated by TBP. Separation of americium from curium was observed although not to a degree that was expected based on the Ce(IV) transport. Incomplete oxidation of Am(III) to Am(V) and reduction of Am(VI) on the membrane surface are possible causes for this observed discrepancy. Our model was, however, able to accurately predict Cm(III) transport through the membrane.