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.     

Semi-Empirical Modeling of Gas–Liquid Mass Transfer in Gas–Liquid–Liquid Systems in Stirred Tanks

Two semi-empirical models of gas–liquid mass transfer in gas–liquid–liquid systems are presented, one for the case where the dispersed liquid phase has a positive spreading coefficient S > 0, the other for S < 0. The models are based on mathematical expressions inspired by assumed mass transfer mechanisms, which are different depending on the oil spreading characteristics. Model simulations compare well with experimental data (up to oil phase holdup ? ～ 0.1), managing to simulate the shape of the experimental curves of oxygen mass transfer enhancement factor E vs. ? for the air–water–heptane (S > 0) and air–water–dodecane (S < 0) systems, better than other models available in the literature.     

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.     

Sequential Reaction-Separation in a Microchannel Reactor for Liquid–Liquid Phase Transfer Catalysis

A microchannel reactor with guideline structure was investigated to carry out sequential reaction- separation. The catalytic reaction between benzyl chloride and sodium sulfide was demonstrated. Under parallel multiphase flow conditions, the catalytic reaction proceeded with phase separation could be ensured. The phase separation performance was enhanced by performing surface modification.     

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.     

Open-Source CFD Simulations of Liquid–Liquid Flow in the Annular Centrifugal Contactor

Simulation of the fluid dynamics of solvent extraction in centrifugal contactors requires advanced models to account for complex physical phenomena including turbulent free-surface flow and liquid-liquid dispersion physics. The use of an open-source computational fluid dynamics (CFD) framework allows for implementation of advanced models not feasible in commercial CFD applications. The open-source CFD package OpenFOAM has been used to simulate turbulent, multiphase flow in the annular centrifugal contactor, including simulations of the mixing zone (annular region), and of the coupled operation of the mixing and separation (rotor interior) zones. These simulations are based on the Volume of Fluid (VOF) methodology along with Large Eddy Simulation (LES) for turbulence. The results from these simulations compare favorably with previous simulations using a commercial CFD tool and with available experimental data. They also give insight into the requirements for more advanced multiphase models needed to accurately capture flows in these devices.     

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.     

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Liquid–Liquid Mixing Studies in Annular Centrifugal Contactors Comparing Stationary Mixing Vane Options

Comparative studies of multiphase operation of an annular centrifugal contactor show the impact of housing stationary mixing vane configuration. A number of experimental results for several different mixing vane options are reported for operation of a 12.5 cm engineering-scale contactor unit. Fewer straight vanes give greater mixing-zone hold-up compared to curved vanes. Quantitative comparison of droplet size distribution also showed a significant decrease in mean diameter for four straight vanes versus eight curved vanes. This set of measurements gives a compelling case for careful consideration of mixing vane geometry when evaluating hydraulic operation and extraction process efficiency of annular centrifugal contactors.     

Rapid Removal of Nitrobenzene in a Three-Phase Ozone Loaded System with Gas–Liquid–Liquid

This study explores the removal rate of nitrobenzene (NB) using a new gas–liquid–liquid (G–L–L) three-phase ozone-loaded system consisting of a gaseous ozone, an aqueous solvent phase, and a fluorinated solvent phase (perfluorodecalin, or FDC). The removal rate of NB was quantified in relation to six factors including (1) initial pH, (2) initial NB dosage, (3) gaseous ozone dosage, (4) free radical scavenger, (5) FDC pre-aerated gaseous ozone, and (6) reuse of FDC. NB removal rate is positively affected by the first three of these factors. Compared with the conventional gas–liquid (water) (G–L) two-phase ozonation system, the free radical scavenger (tertiary butyl alcohol) has much less influence on the removal rate of NB in the G–L–L system. The FDC-loaded ozone acts as an ozone reservoir and serves as the main reactive phase in the G–L–L three-phase system. The reuse of FDC has little influence on the removal rate of NB. These experimental results suggest that the oxidation efficiency of ozonation in the G–L–L three-phase system is better than that in the conventional G–L two-phase system.     

Liquid–Liquid Equilibria of Ternary Systemscis-1,2-Dimethylcyclohexane + Toluene + Sulfolane

Liquid–Liquid Equilibrium (LLE) data for three Ternary Systems comprising cis-1,2-dimethylcyclohexane + toluene + sulfolane were measured at 298.15, 313.15 and 328.15 K under atmospheric pressure. The phase diagrams for the ternary systems were presented. The reliability of the experiment data was tested using the Othmer–Tobias correlation. The LLE data were then correlated with the universal functional activity coefficient for liquid–liquid systems (UNIF-LL) and non-random two liquid using dataset 2 (NRTL/2) activity coefficient models to obtain the binary interaction parameters as programmed by the Aspen Plus simulation. The results showed that the experimental data were satisfactorily represented by both the UNIF-LL and the NRTL/2 models as revealed from the very small values of the root mean square error and the absolute deviation in composition.     

Liquid backmixing and circulation in rectangular downcomer

1 INTRODUCTIONDowncomers,employed in tray columns,are widely used nowadays in industrialseparation processes.They function as channels for the liquid phase to fall fluentlyfrom one tray onto its neighbouring places for the held-up bubble to separate fromthe liquid phase.It is well known that liquid flow patterns and mixing characteristicsin downcomers are closely related to the initial liquid distribution on the tray,andhence to tray efficiency.For a long period of time,little attention has been paid to     

Longkou Liquid Chemicals Dock Put into Operation

Norwegian'Long-nose Bear'cargo ship laden with 40000 tons of liquid causticsoda sailed smoothly apart from the 50000 Tonnage-class Longkou BingangLiquid Chemicals Dock.Shandong province,eastern China for Australia.It was     

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 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 mixing using micro-fluidised beds

This study experimentally investigates the application of a solid–liquid micro-fluidised bed as a micro-mixing device. The experiments were performed in a borosilicate capillary tube with an internal diameter of 1.2 mm (i.e. near the upper-limit dimension of a micro-fluidic system) using borosilicate particles with a mean diameter of 98 μm. Refractive index matching technique using sodium iodide solution was employed to achieve a transparent fluidised bed. Mixing performance of the micro-fluidised bed in terms of mixing time was investigated using a dye dilution technique. Experiments were carried out in the creeping flow regime at Reynolds numbers ranging between 0.27 and 0.72. It was demonstrated that the micro-fluidised bed mixing time sharply decreases as the Reynolds number increases. That is because at relatively high Reynolds numbers, the particle oscillation is stronger creating larger disturbances in the flow. The energy dissipation rate in micro fluidised bed was estimated to be four orders of magnitude less than other passive micro mixers which operate in the turbulent regime. It was also demonstrated that the ratio of mixing time and the energy dissipation rate for fluidised bed micro-mixer was comparable to K-M, Tangential IMTEK, and interdigital micro-mixers. However, the fluidised bed micro-mixer was found to operate at much lower Reynolds numbers compared to other passive mixers, with a mixing time of the order of few seconds.     

Liquid–Liquid Equilibrium for Systems Containing Epoxidized Oils,Formic Acid,and Water: Experimental and Modeling

Epoxidized oils are eco-friendly plasticizers, which are industrially produced through the epoxidation reaction in a formic acid-hydrogen peroxide autocatalyzed system. The fundamental knowledge to describe the phase equilibrium of systems after epoxidation reaction is lacking, which is crucial for the design of the purification facilities. This work reported experimental data for the liquid–liquid equilibrium of three systems, i.e., epoxidized fatty acid methyl esters + formic acid + water, epoxidized fatty acid 2-ethylhexyl esters + formic acid + water, and epoxidized soybean oil + formic acid + water, in the temperature range (303.15–348.15) K under atmospheric pressure. The results indicated that the liquid–liquid equilibrium constant of formic acid in the systems followed the order of epoxidized fatty acid 2-ethylhexyl esters > epoxidized fatty acid methyl esters > epoxidized soybean oil. Moreover, the obtained experimental data were correlated using nonrandom two liquid (NRTL) and universal quasi chemical (UNIQUAC) models. The maximum root mean square deviation (RMSD) values as low as 0.0052 and 0.0263 were estimated using the NRTL and UNIQUAC model, respectively. The NRTL model is more suitable than the UNIQUAC model to describe the liquid–liquid equilibrium behavior of these ternary systems.     

Solid–Liquid and Solid–Liquid–Liquid Equilibria in the KI+H2O+i-C3H7OH Ternary System within 10–120°C

The solubility of components, phase equilibria, and critical phenomena in the ternary potassium iodide (KI) +water (H₂O) +isopropyl alcohol (i-C₃H₇OH) system were studied in the range of 10–120°C by the visual polythermal method. Potassium iodide was found to have a salting-out effect at temperatures above 97.0°C, and homogeneous water–isopropanol solutions were delaminated. The formation temperature of the critical tie line of the monotectic state (97.0°C) and the compositions of the solutions corresponding to the critical liquid–liquid solubility points at 104.2, 110.1, 115.6, and 120.1°C were determined. The distribution coefficients of isopropyl alcohol between the organic and aqueous phases in the monotectic state at 100.0, 110.0, and 120.0°C were calculated. The salting-out effect of potassium iodide relative to isopropyl alcohol from aqueous solution is small (the distribution coefficient K_d of isopropanol is 1.8 at 100.0°C) and slightly increases with temperature (K_d is 3.4 at 120.0°C).     

Measuring and Modeling Liquid–Liquid Equilibria for a Soybean Oil, Oleic Acid, Ethanol, and Water System

Vegetable oils can be deacidified by liquid–liquid extraction based on differences in polarity between triglycerides and fatty acids and differences in solubility. Information on the equilibrium between the phases of such systems is important for designing separation processes. The present paper reports experimental data for the extraction of fatty acid from soybean oil by (ethanol + water) as a mixed-solvent for system of soybean oil + oleic acid + ethanol + water at 30 °C at different water contents. The liquid–liquid equilibrium data of the systems were used to obtain interaction parameters in the universal quasi-chemical theory (UNIQUAC) activity coefficient model. These parameters can be used to predict equilibrium data of ternary and quaternary systems. The deviations between experimental and calculated compositions in both phases for each system using this model were calculated. The distribution coefficients and the selectivity factors of solvents for extraction of fatty acid from oil at 30 °C were calculated. Increasing of the water content as the co-solvent decreased the distribution coefficients and increased the selectivity factors of mixed-solvents, therefore considering the economical and practical aspects the optimum water content may be used for extracting oleic acid from soybean oil. We concluded that (ethanol + water) as a mixed-solvent can be used for extracting fatty acids from edible oils in a normal temperature.     

Liquid – Liquid Extraction and Pertraction of Eu(III) from Nitric Acid Medium Using Several Substituted Diglycolamide Extractants

Solvent extraction and supported liquid membrane (SLM) transport properties of Eu(III) from nitric acid feed conditions were investigated using several substituted diglycolamide (DGA) extractants such as N,N,N′N′-tetra-n-octyl diglycolamide (TODGA), N,N,N′N′-tetra(2-ethylhexyl) diglycolamide (T2EHDGA), N,N,N′N′-tetra-n-hexyl diglycolamide (THDGA), N,N,N′N′-tetra-n-pentyl diglycolamide (TPDGA), and N,N,N′N′-tetra-n-decyl diglycolamide (TDDGA). Effects of feed acidity and phase modifier composition on Eu(III) extraction were investigated using the DGAs and the nature of extracted species were ascertained by slope analysis method. The Eu(III) distribution ratio (D_Eu) values were found to decrease in the presence of iso-decanol. In general, the D_Eu values decreased with increased alkyl chain length of the DGA. The extracted species contained only 2 extractant molecules when TPDGA and TDDGA were used while for TODGA about four extractant molecules were found to be present in the extracted species.

The supported liquid membrane transport of Eu(III) was studied under varying experimental conditions using the five DGA extractants. Transport studies using 0.1 M DGA as the extractant suggested the trend as TDDGA > TODGA > T2EHDGA ～ THDGA which significantly changed to TPDGA > THDGA > TODGA > TDDGA > T2EHDGA in the presence of 30% iso-decanol as the phase modifier. The permeability coefficient (P) values were also determined with membranes of varying pore sizes.