Phosphorus Recovery by Liquid–Liquid Extraction

Abstract

It is acknowledged that phosphorus removal is more crucial in comparison with nitrogen removal for preventing algae glooming and eutrophication. Chemical and biological methods are common methods for the P removal. Excessive sludge production and difficulties of recovering phosphorus are concerns in terms of sustainable waste management. A liquid-liquid extraction (LLE) process is thus considered for the study aiming at recovering phosphorus from wastewater in a sustainable way. The results revealed that the best extractant is a mixture of kerosene and benzyl-di-methyl-amine (BDMA) at a volume ratio of 2:1. Under the study conditions, one part of extractant can react with four parts of wastewater to transfer >97% of P to the organic phase. In addition, in the stripping step, a 1:1 ratio of extract to recycled acid can result in 96% recovered P, implying an overall 93% phosphorus recovery efficiency can be achieved by the LLE process. Most importantly, the extractant can be recycled and reused at least 5 times if the residual P concentration should be less than 4 mg/L vs. the original P concentration of 21 mg/L. A complexion between amine groups in BDMA and phosphates and the positive charge of the micelles surface when the extractant (composed of kerosene and BDMA) mixed with P containing wastewater would contribute to the P recovery and this is a novel approach to recover P from wastewater.     

Extraction of 4‐Hydroxycinnamic Acid from Aqueous Solution by Emulsion Liquid Membranes

Abstract

This work reports a study of 4‐hydroxycinnamic acid extraction by emulsion liquid membranes. The effect of the presence of additives in the membrane phase on solute permeation was tested. The membrane with 2 wt.% of isodecanol, 2 wt.% of ECA4360J, and Shellsol T as diluent was selected to examine the permeation of 4‐hydroxycinnamic acid. The modeling of solute extraction was done by taking into account the mass transfer in the external phase and globule, and the reaction between the diffusing component and the stripping reagent. The agreement between the calculated results and the experimental data was found satisfactory.     

Liquid–Liquid Extraction of Butanol from Dilute Aqueous Solutions Using Soybean-Derived Biodiesel

Liquid–liquid extraction (LLE) of mixtures of butanol, 1,3-propanediol (PDO), and ethanol was performed using soybean-derived biodiesel as the extractant. The composition of the mixtures simulated the product of the anaerobic fermentation of biodiesel-derived crude glycerol, which has recently been reported for the first time by the authors. Using a biodiesel: with an aqueous phase volume ratio of 1:1, butanol recovery ranged from 45 to 51% at initial butanol concentrations of 150 and 225 mM, respectively. Less than 10% of the ethanol was extracted, and essentially no PDO was extracted. The partition coefficient for butanol in biodiesel was determined to be 0.91 ± 0.097. This partition coefficient is less than that of oleyl alcohol, which is considered the standard for LLE. However, butanol is suitable for blending with biodiesel, which would eliminate the need for separating the butanol after extraction. Additionally, biodiesel is much less costly than oleyl alcohol. If biodiesel-derived glycerol is used as the feedstock for butanol production, and biodiesel is used as the extractant to recover butanol from the fermentation broth, production of a biodiesel/butanol fuel blend could be a fully integrated process within a biodiesel facility. This process could ultimately help reduce the cost of butanol separation and ultimately help improve the overall economics of butanol fermentation using renewable feedstocks.     

Extraction Equilibrium of Aqueous Phenol–Long-Chain Alkylamine Solution System

Abstract

Distribution equilibrium of the aqueous phenol–Amberlite LA-2, a longchain secondary alkylamine solution system was studied with diluents such as n-hexane, cyclohexane, benzene, and carbon tetrachloride at 30°C. The physical partition coefficient of phenol between two phases and the equilibrium constant for dimerization of phenol in the organic phase were obtained for each diluent under the amine-free condition. The experimental results obtained with amine present were explained by a model in which an amine molecule is added by a few molecules of phenol in the organic phase. The equilibrium constants for these reactions were evaluated.     

Extraction of Uranium from “Abu-Tartur” Phosphate Aqueous Leachate Solution

Abstract

Uranium was effectively extracted from a synthetic aqueous monocalcium phosphate/phosphoric acid mixture (MCP/H₃PO₄) by tri-n-octylamine dissolved in different solvents and the presence of low concentrations of some counteranions (oxalate, citrate, chloroacetate) in the aqueous phase. The extraction efficiency was markedly enhanced by the salting out action of the concentration of calcium ions in the MCP/H₃PO₄ solution.     

Salt Effects on the Recovery of Phenol by Liquid‐Liquid Extraction with Cyanex 923

Abstract

In this work, the effect of salt addition on the recovery of phenol from a 46 g/L aqueous solution simulating a phenolic resin plant effluent by liquid‐liquid extraction at 298 K has been studied by using an organic phase containing 0.6 M Cyanex 923 extractant in ShellSol T. Addition of sodium sulfate, potassium nitrate, and sodium chloride to the aqueous phase was tested and sodium chloride was selected. Based on the obtained results, a study of phenol recovery process was undergone by taking advantage of the salting‐out effect. Equilibrium curves are presented for liquid‐liquid extraction with and without salt addition to the aqueous phase. An integrated process involving salting‐out and liquid‐liquid extraction was proposed. The stripping concentrates can be reused for phenolic resin production.     

Synergistic Extraction of Gallium from Sulfate Solution

A novel extractant mixture, di-2-ethylhexyl phosphate (DEHPA) plus HX, was proposed and tested for recovering gallium from sulfate solution. It was found that the extraction capacity of DEPHA for gallium from sulfate solution could be enhanced significantly due to the synergistic effect of acidic extractant HX. Gallium extraction is negligible below pH 0 and highly sensitive to pH of aqueous phase in the range from 0 to 1, and satisfactory extraction can be gained at pH>1. More than 96% Ga extraction was obtained using 15% DEHPA plus 2% HX. Although Fe (Ⅲ) was found to be extracted preferentially to Ga (Ⅲ), effective extraction of Ga (Ⅲ) was possible by reducing ferric to the ferrous state prior to extraction. A loaded organic phase containing 0.48g L-1 Ga could be produced from solution of 0.12g L-1 Ga at A/O ratio of 4 : 1 via three mixer-settler operation stages. Gallium was stripped quantitatively from the loaded organic phase with l,5mol L-1 of sulfuric acid.     

Recovery of Chloroform from Effluent with Solvent Extraction–Distillation Process

Abstract

A solvent extraction–distillation process for recovery of chloroform in aqueous effluent was developed. Sutfonated kerosene was used for extraction of chloroform. When the flow ratio of organic phase to aqueous phase is 0.1, the chloroform concentration in the aqueous effluent can be decreased from 10 g/L to about 100 mg/L by 3-stage countercurrent extraction. The distribution ratio of chloroform between sulfonated kerosene and water is about 50. Sodium sulfate in the aqueous effluent will enhance the distribution. A small amount of water was added to the distillation column for stripping chloroform in sulfonated kerosene. RPC was used as a commercial extractor. Scale-up from the data of the pilot test was based on the Karr correlation. Recovery of chloroform was over 90%, and residual kerosene in the aqueous effluent from the extraction was lower than 70 mg/L. It is expected that the technique can be used for the recovery of other organic solvents miscible with kerosene.     

Cloud Point-Dispersive Liquid–Liquid Microextraction for Extraction of Organic Acids from Biological Samples

A new method combining cloud point extraction (CPE) with dispersive liquid–liquid microextraction (DLLME) named “cloud point‐dispersive liquid–liquid microextraction (CP‐DLLME)” was presented in this work for the first time for the determination of organic acids as model compounds in biological samples using high performance liquid chromatography and UV detection (HPLC–UV). Water (disperser solvent) containing tert‐octylphenol ethoxylate (7.5EO) as extraction solvent, was rapidly injected into a warmed sample solution and cloudy state formed immediately. After that, phase separation was performed by centrifugation. The surfactant‐rich phase was diluted with acetonitrile and injected into a HPLC–UV apparatus. The influence of several important parameters on the extraction efficiencies was evaluated. Under optimized experimental conditions, the calibration graphs were linear in the range of 0.06–1,500 µg L^?1 for target analytes. Coefficient of determination (r²) ranged from 0.9985 to 0.9994. The limits of detection were in the range of 0.05–17.1 µg L^?1. The new method was successfully applied with satisfactory results for analysis of target analytes in spiked samples. The relative mean recoveries of the spiked samples ranged from 91.8 to 107.1 % with relative standard deviations in the range of 2.1 to 4.3 %.     

Homogeneous Liquid–Liquid Extraction of Rare Earths with the Betaine—Betainium Bis(trifluoromethylsulfonyl)imide Ionic Liquid System

Several fundamental extraction parameters such as the kinetics and loading were studied for a new type of metal solvent extraction system with ionic liquids. The binary mixture of the ionic liquid betainium bis(trifluoromethylsulfonyl)imide and water shows thermomorphic behavior with an upper critical solution temperature (UCST), which can be used to avoid the slower mass transfer due to the generally higher viscosity of ionic liquids. A less viscous homogeneous phase and mixing on a molecular scale are obtained when the mixture is heated up above 55 °C. The influence of the temperature, the heating and cooling times, were studied for the extraction of neodymium(III) with betaine. A plausible and equal extraction mechanism is proposed in bis(trifluoromethylsulfonyl)imide, nitrate, and chloride media. After stripping of the metals from the ionic liquid phase, a higher recovery of the ionic liquid was obtained by salting-out of the ionic liquid fraction lost by dissolution in the aqueous phase. The change of the upper critical solution temperature by the addition of HCl or betaine was investigated. In addition, the viscosity was measured below and above the UCST as a function of the temperature.     

Separation of the System NaCl-NaBr-Nal by “Solventing Out” from Aqueous Solution

Abstract

The precipitation of NaX (X = Cl, Br, I) from their saturated aqueous solution by three miscible organic solvents (MOS)-acetone, acetonitrile and isopropylamine-was studied for various MOS-aqueous solution volumes ratios. It was found that the fraction precipitated f is given by f = K log V/V_c where V is the volume ratio and K and V _c are constants. For the case of NaCl this plot was found to be a broken line composed of two straight lines intersecting at the point of “salting out.” A scheme is suggested to separate the three electrolytes using isopropylamine to precipitate NaCl and acetone to precipitate NaBr.     

Optimization‐Based Nonlinear Centralized Controller Tuning of Liquid‐Liquid Extraction Processes

Abstract

The control problem of an agitated contactor is considered in this work. A Scheibel extraction column is modeled using the non‐equilibrium backflow mixing cell model. Model dynamic analysis shows that this process is highly nonlinear, thus the control problem solution of such a system needs to tackle the process nonlinearity efficiently. The control problem of this process is solved by developing a multivariable nonlinear control system implemented in MATLAB?. In this control methodology, a new controller tuning method is adopted, in which the time‐domain control parameter‐tuning problem is solved as a constrained optimization problem. A MIMO (multi‐input multi‐output) PI controller structure is used in this strategy. The centralized controller uses a 2×2 transfer function and accounts for loops interaction. The controller parameters are tuned using an optimization‐based algorithm with constraints imposed on the process variables reference trajectories. Incremental tuning procedure is performed until the extractor output variables transient response satisfies a preset uncertainty which bounds around the reference trajectory. A decentralized model‐based IMC (internal model control) control strategy is compared with the newly developed centralized MIMO PI control one. Stability and robustness tests are applied to the two algorithms. The performance of the MIMO PI controller is found to be superior to that of the conventional IMC controller in terms of stability, robustness, loops interaction handling, and step‐change tracking characteristics.     

Liquid–Liquid Equilibrium in an Extraction System Based on Polyvinylpyrrolidone-3500 and Sodium Nitrate

Theoretical Foundations of Chemical Engineering - Liquid–liquid phase equilibrium for a new extraction system based on polyvinylpyrrolidone-3500 and sodium nitrate at 298.15, 313.15, and...     

Extraction of Caprolactam from Aqueous Ammonium Sulfate Solution in Pulsed Packed Column Using 250Y Mellapak Packings

1 INTRODUCTION Caprolactam is a major ingredient in the manufacture of nylon 6 fibers. In the process of caprolactam production, there is about 1% caprolactam in the aqueous ammonium sulfate solution after Beckmann rearrangement and neu-tralization. So far, the 1% caprolactam has been extracted by benzene in an ordinary sieve-plate column with 60% recovery in Zhejiang Juhua Group Company in China, while being extracted in a pulsed packed column with 95% recovery abroad[1—3]. Because …     

Recovery of Zinc by LIX 984N‐C from Electroplating Rinse Bath Solution

The development of a complete solvent extraction process at the laboratory scale for recovering zinc from the zinc electroplating first rinse bath solution (alkali solution) containing ～1.9 g/L zinc (ZEFRBS) by a solvent extraction route using LIX 984N‐C, which is a new SX reagent developed by Cognis, and dissolved in commercial kerosene was investigated. By using LIX 984N‐C, an electrolyte from ZEFRBS with ～12 g/L zinc content, which was addable to the alkali zinc electroplating bath, was generated by 10 vol.% LIX 984N‐C in commercial kerosene at the O/A ratio of 1/4 and equilibrium pH value of 8.00 ± 0.05 with a two‐stage countercurrent extraction, and stripping of the loaded organic by a strip solution with 150 g/L sulfuric acid and with the O/A ratio of 1.5 at a two‐stage countercurrent stripping process. A new complete flow sheet of 10 vol.% LIX 984N‐C process for the recovery of zinc from ZEFRBS has been demonstrated.     

Liquid–Liquid Extraction of Alkali Metal Cations by Calix[4]crowns with Pendant Groups

Abstract

The selective liquid–liquid extraction of alkali metal cations from the aqueous phase to the organic phase was carried out by using calix[4]crowns bearing two pendant groups with donor sites. It was found that calix[4]crown‐4 and calix[4]crown‐5 extractants with two pendant groups exhibit higher extraction efficiency than the parent compounds and possess obvious selectivity for Na⁺ and K⁺, respectively.     

Liquid–Liquid Extraction of Silver From Chloride Media by N,N′-Tetrasubstituted Dithiomalonamide Derivatives

N,N′-dimethyl-N,N′-diphenyldithiomalonamide (DMDPHDTMA) and N,N′-dimethyl-N,N′-dicyclohexyldithiomalonamide (DMDCHDTMA) were synthesized and tested as extractants for silver in chloride solutions. Even when relatively low concentrations are used, both compounds effectively extract Ag(I) from 2–5 M chloride concentrated aqueous phases. Ag(I) is successfully stripped by a stabilized sodium thiosulfate solution. Results obtained from sequential cycles of extraction-stripping suggest that both extractants exhibit a high Ag(I) loading capacity. The effects of the equilibration time, concentrations of extractant, chloride and hydrogen ions on Ag(I) extraction have been investigated. The chemical reactions involved on Ag(I) extraction are proposed. There is no selectivity of DMDPHDTMA or DMDCHDTMA for Ag(I) when Cu(II) and Fe(III) co-exist in the chloride aqueous solution.     

Liquid–Liquid Extraction of GSH Using DEHAP/Octanol Reverse Micelles

Abstract

In this study, di-(2-ethylhexyl) ammonium phosphate (DEHAP)/octanol reverse micellar extraction was investigated and demonstrated to be an effective method to separate GSH from yeast fermentation broth. The effect of several important factors i.e., pH, DEHAP concentration, and type & concentration of cations on both extraction and strip-extraction was investigated. The optimum operating conditions for both extraction and strip-extraction were obtained by two groups of orthogonal experiments. At the optimum operating conditions, the yield of GSH can reach 68%. In the lyophilized product, the purity of GSH was higher than 75%, all the proteins can be separated, and only a small portion of amino acids were left.     

Hollow-Fiber Membrane Extraction of Copper from Aqueous Nitrate Media by LIX® Reagents: Comparison of Extraction Efficiency and Fractional Resistances

Abstract

Extraction of copper from nitrate/nitric acid aqueous solutions was studied using a HF Membrane Module and four LIX reagents (LIX® 860N-I, LIX® 984N, LIX® 84-I, and LIX® 65N) containing different active compounds (ketoximes and/or salicylaldoximes). Kinetic experiments varying the flow rates of both phases, aqueous and organic, and the extractant concentration were carried out to compare the extraction rate and efficiency from nitrate-aqueous media. A mathematical model based on the “aqueous extraction mechanism” in which the chemical reaction takes place in an aqueous-reaction zone was applied to determine the individual resistances of the copper mass-transfer process. It was found that the fractional resistance due to chemical reaction in the aqueous reaction zone, which varied from 92.5% to 95.8% in the order LIX® 860N-I < LIX® 984N < LIX® 84-I < LIX® 65N, controlled the total rate of the hollow-fiber copper extraction from nitrate aqueous media.