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.     

Synergistic Extraction of Lanthanides(III) by Mixtures of N‐p‐Methoxybenzoyl‐N‐phenylhydroxylamine and 1,10‐Phenanthroline

Abstract

We conducted a study on the equilibrium extraction behavior of the trivalent lanthanide ions (M³⁺), La, Pr, Eu, Ho, and Yb, from tartrate aqueous solutions into chloroform solutions containing N‐p‐methoxybenzoyl‐N‐phenylhydroxylamine (Methoxy‐BPHA, HL) and 1,10‐phenanthroline (phen). The synergistic species extracted was found to be {ML₂(phen) (HL)}⁺(1/2)Tar^2?, where Tar^2? is tartrate ion. The extraction constants were calculated. The extraction separation behavior and extractability of lanthanides are discussed in comparison with the self‐adducted chelate, ML₃(HL)₂, which was extracted in the absence of phen, and synergistic extraction by mixtures of other extractants such as 2‐thenoyltrifluoroacetone, and neutral donors.     

Solid‐Liquid Extraction of Taxane Compounds from Yew Needle

Abstract

Solid‐liquid extraction of the taxane compounds in yew needles is carried out with methanol. The concentration of each component in the raffinate is estimated from the observed concentration in the extract and material balance equations with a solvent‐permeation model that solvent permeates the solid. The obtained distribution coefficient is found to be independent of the particle size. It suggests a possibility that the extract is in equilibrium with the liquid solution in the raffinate. Based on the experimental results, the effect of operating conditions on separation performance of countercurrent‐multistage extraction is studied by using the ideal stage calculation.     

Cobalt‐catalyzed amination of 1,3‐cyclohexanediol and 2,4‐pentanediol in supercritical ammonia

The onestep procedure of amination of bifunctional secondary alcohols to diamines has been investigated in a continuous fixedbed reactor. Application of supercritical NH₃ as a solvent and reactant suppressed catalyst deactivation and improved selectivities to amino alcohol intermediates, whereas selectivities to diamines remained poor (8–10%). The main reason for the low diamine selectivity of 1,3dihydroxy compounds is water elimination leading to undesired monofunctional products via ,unsaturated alcohol, ketone or amine intermediates. This side reaction does not occur with 1,4dihydroxy compounds which afford high aminol and diamine selectivities under similar conditions. Amination of secondary diols with ammonia was found to be faster, but less selective than that of the corresponding primary 1,3propanediol.     

Solvent Extraction of Au(I) from Auro‐Cyanide Solution with Cetyltrimethylammonium Bromide/Tri‐n‐Butyl Phosphate System using Column‐Shaped Extraction Equipment

Abstract

Solvent extraction of Au(I) from alkaline cyanide solution containing several milligram per liter of gold was investigated with column‐shaped extraction equipment using tri‐n‐butylphosphate (TBP) as extractant with addition of quaternary ammonium salt, cetyltrimethylammonium bromide (CTAB), directly into the aurous aqueous phase in advance. The influences of the volume of TBP and the NaCl concentration in the aurous aqueous phase on Au(I) extraction were investigated. The experimental results for treating 50 L of synthetic auro‐cyanide solution containing 10 mg/L Au(I) and for treating real auro‐cyanide leaching liquor by CTAB/TBP system were reported. The results obtained establish that the column‐shaped extraction equipment was suitable for extracting Au(I) from low content auro‐cyanide solution at high aqueous/organic phase ratio, and that more than 97% of gold(I) could be extracted while the Au(I) concentration in the raffinate was less than 0.3 mg/L. In addition, the stripping of Au(I) from the loaded organic phase and the recycle of the organic phase were also discussed.     

Extraction of Ternary Beta‐Diketonates of Uranyl Ion Using Some Substituted Monoamides

Abstract

The extraction behavior of uranyl ion from dilute nitric acid medium employing 1‐phenyl‐3‐methyl‐4‐benzoyl‐5‐pyrazolone (HPMBP)/2‐thenoyl‐ trifluoroacetone (HTTA) in toluene and their mixture with several structurally modified monoamides viz. di‐2‐ethylhexyl acetamide (D2EHAA), di‐2‐ethylhexyl propanamide (D2EHPrA), di‐2‐ethylhexyl isobutyramide (D2EHiBA), and di‐2‐ethylhexyl pivalamide (D2EHPvA) was investigated. The species of the type UO₂(A)₂ and UO₂(A)₂·B were extracted for the binary and ternary extraction systems respectively where A = PMBP/TTA and B = D2EHAA, D2EHPrA, D2EHiBA, or D2EHPvA. The extraction constants (log K _ex) for the binary species UO₂(A)₂ were determined to be ?2.32 ± 0.03 for HTTA and 0.21 ± 0.02 for HPMBP, which was an inverse function of their pK _a value. The overall extraction constants (log K) for the ternary species UO₂(A)₂·B were determined as 4.70, 4.22, 4.00, 3.61, 2.65, 2.39, 2.32, and 1.76 for UO₂(PMBP)₂·D2EHAA, UO₂(PMBP)₂·D2EHPrA, UO₂(PMBP)₂·D2EHiBA, UO₂(PMBP)₂·D2EHPvA, UO₂(TTA)₂·D2EHAA, UO₂ (TTA)₂·D2EHPrA, UO₂(TTA)₂·D2EHiBA, and UO₂(TTA)₂·D2EHPvA, respectively. A linear correlation was observed between the basicity of the amide and the corresponding adduct's formation constants.     

Synergistic Extraction of Lanthanides(III) with N‐p‐Methoxybenzoyl‐N‐Phenylhydroxylamine and Neutral Nitrogen Donors

Abstract

We investigated the extraction equilibrium behavior of a series of trivalent lanthanide ions, (M³⁺), La, Pr, Eu, Ho, and Yb, from tartrate aqueous solutions using a chloroform solution containing N‐p‐methoxybenzoyl‐N‐phenylhydroxylamine (Methoxy‐BPHA or HL) combined with an adductant, 1,10‐phenanthroline (phen) or 2,2′‐bipyridyl (bipy). The synergistic species extracted were found to be {ML₂(phen)(HL)}⁺(1/2)Tar^2? and {ML₂(bipy)(HL)₂}⁺(1/2)Tar^2?, where Tar^2? is the tartrate ion. The stoichiometry, the extraction constants, and the separation factors of these systems were determined. We discuss the extractability and the separation factors in comparison with self‐adduct chelates, ML₃(HL)_2,(o), which were formed in the absence of phen or bipy.     

A Striking Effect of Ionic‐Liquid Anions in the Extraction of Sr2+ and Cs+ by Dicyclohexano‐18‐Crown‐6

Abstract

The nature of the ionic‐liquid (IL) anion has been found to have a remarkable effect on the solvent extraction of Sr²⁺ and Cs⁺ by dicyclohexano‐18‐crown‐6 dissolved in ionic liquids. In particular, the extraction efficiency increases with the hydrophobicity of the IL anion as reflected by the solubility in water of ILs having a common cation. Since a cation‐exchange mechanism is operating in these systems, the influence of the IL anion is in large part attributable to an expected Le Chatelier effect in which a greater aqueous concentration of IL cation, obtained when using an IL anion of lower hydrophobicity, opposes cation exchange. This dependence is opposite to that found for IL cations, indicating a significant advantage of using ILs with hydrophobic anions for cation extraction. Furthermore, the extraction selectivity for Sr²⁺ over Na⁺, K⁺, and Cs⁺ can be significantly improved through the use of hydrophobic anions for the ILs containing 1‐ethyl‐3‐methylimidazolium or 1‐butyl‐3‐methylimidazolium cations.     

Effect of Anions on the Extraction of Lanthanides (III) by N,N′‐Dimethyl‐N,N′‐Diphenyl‐3‐Oxapentanediamide

Abstract

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y by N,N′‐dimethyl‐N,N′‐diphenyl‐3‐oxapentanediamide (DMDPhOPDA) in 1,2‐dichloroethane from aqueous media containing ClO₄ ^?, PF₆ ^?, (CF₃SO₂)₂N^? anions or by DMDPhOPDA in 1,2‐dichloroethane in the presence of 1‐butyl‐3‐methylimidazolium bis[(trifluoremethyl)sulfonyl]imide ([C₄mim][Tf₂N]) and 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([C₄mim][PF₆]) from HNO₃ solutions has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. The addition of HPF₆ and (CF₃SO₂)₂NH or their salts to the aqueous HNO₃ or HCl solutions leads to an enchancement of lanthanides (III) extraction by DMDPhOPDA. A considerable synergistic effect was observed in the presence of ionic liquids (IL) in the organic phase containing DMDPhOPDA. This effect is connected with the hydrophobic nature of the IL anion. The distribution of ILs between the equilibrium organic and aqueous phases can govern the extractability of lanthanides (III) in DMDPhOPDA‐IL systems.     

Solvent Extraction of Heavy Lanthanides(III) with 5,7‐Dibromo‐8‐hydroxyquinoline from Aqueous Perchlorate Solution

Abstract

The extraction of Tb(III), Dy(III), Ho(III), Er(III), Tm(III), and Yb(III) with 5,7‐dibromo‐8‐hydroxyquinoline (Hdbq or HA) in chloroform from aqueous perchlorate solutions was investigated. The formation of the LnA₃ species (where Ln = Tb, Dy, Ho, Er, Tm, and Yb) in the organic phase was supported by the data. The parameters of the extraction processes were determined, and the separation factors between two adjacent lanthanides(III) were calculated.     

Optimization of Microwave‐Assisted Extraction of Flavonoid from Radix Astragali using Response Surface Methodology

Abstract

Response surface methodology (RSM) was applied to predict optimum conditions for microwave‐assisted extraction (MAE) of flavonoid from Radix Astragali. A central composite design was used to monitor the effect of temperature, extraction time, solvent‐to‐material ratio, and the ethanol concentration on yield of total flavanoid (TFA). Optimum extraction conditions were predicted as 108.2°C, 26.7 min, 23.1 ml/g solvent‐to‐material ratio and 86.2% ethanol. The maximum yield 1.234±0.031 mg/g was close to the yield of Soxhlet and higher than that of ultrasound assisted extraction and heat reflux extraction. MAE was an effective alternative to conventional extraction methods.     

Experimental Verification of Caustic‐Side Solvent Extraction for Removal of Cesium from Tank Waste

Abstract

A caustic‐side solvent extraction (CSSX) process was developed to remove Cs from Savannah River Site (SRS) high‐level waste. The CSSX process was verified in a series of flowsheet tests at Argonne National Laboratory (ANL) in a minicontactor (2‐cm centrifugal contactor) using simulant. The CSSX solvent, which was developed at Oak Ridge National Laboratory (ORNL), consists of a calixarene‐crown ether as the extractant, an alkyl aryl polyether as the modifier, trioctylamine as the suppressant, and Isopar®L as the diluent. For Cs removal from the SRS tank waste, the key process goals are that: (1) Cs is removed from the waste with a decontamination factor greater than 40,000 and (2) the recovered Cs is concentrated by a factor of 15 in dilute nitric acid. In the flowsheet verification tests, the objectives were to: (1) prove that these process goals could be met; (2) demonstrate that they could be maintained over a period of several days as the CSSX solvent is recycled; and (3) verify that the process goals could still be met after the solvent composition was adjusted. The change in composition eliminated the possibility that the calixarene‐crown ether could precipitate from the solvent. The process goals were met for each of the verification tests. The results of these tests, which are summarized here, show that the CSSX process is a very effective way to remove Cs from caustic‐side waste.     

Extraction Behavior of Nickel(II) using some of the BTBP‐Class Ligands

Abstract

Recently the BTBP‐family of solvating ligands have been studied for their ability to separate trivalent actinides from lanthanides. Five of the BTBPs were evaluated for their ability to extract nickel(II) from aqueous nitrate media into cyclohexanone. It was shown by both solvent extraction and X‐ray diffraction experiments that the BTBPs are capable of forming both 1:1 and 1:2 complexes with nickel(II). When the BTBP concentration is low the nickel distribution ratio is governed by the formation of the nickel/BTBP complex while at higher BTBP concentrations the partitioning of the nickel complex between the two phases dictates the nickel distribution ratio.     

Extraction of Palladium(II) from Nitric Acid Solutions with 1‐Benzoyl‐3‐[6‐(3‐benzoyl‐thioureido)‐hexyl]‐thiourea

The extraction of palladium (II) from HNO₃ solutions with 1‐Benzoyl‐3‐[6‐(3‐benzoyl‐thioureido)‐hexyl]‐thiourea (Ia) and several monodentate thiourea derivatives in 1,2‐dichloroethane has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant in the organic phase on the Pd(II) extraction is considered. The stoichiometry of the extracted complexes has been determined. The increasing number of thioamide groups in the molecule of Ia increases its extraction efficiency towards Pd(II). The potentialities of a polymeric resin impregnated with compound Ia for selective extraction of Pd(II) from nitric acid solutions are demonstrated.     

Extraction Properties of 6,6′‐Bis‐(5,6‐dipentyl‐[1,2,4]triazin‐3‐yl)‐[2,2′]bipyridinyl (C5‐BTBP)

Abstract

The extraction of americium(III) and europium(III) into a variety of organic diluents by 6,6′‐bis‐(5,6,‐dipentyl‐[1,2,4]triazin‐3‐yl)‐[2,2′]bipyridinyl (C5‐BTBP) has been investigated. In addition to determining the stoichiometry for the extraction, the dependence of extraction on contact time and temperature was also studied. The resistance of the ligand to gamma irradiation and the possibility to recycle the organic phase after stripping were tested to determine how the molecule would perform in a radiochemical process. Different organic diluents gave different extraction results, ranging from no extraction to distribution ratios of over 1000 for americium(III). In 1,1,2,2‐tetrachloroethane, the extraction and separation of americium from europium and the extraction kinetics were good; a separation factor above 60 was obtained at equilibrium, ～5 min contact time. The extraction capabilities are adequate for C5‐BTBP to be used in a process for separating trivalent actinides from lanthanides. However, C5‐BTBP is susceptible to radiolysis (americium extraction decreases ～80% after a dose of 17 kGy) and may not be the best choice in the processing of spent nuclear fuel. Nonetheless it is a useful starting point for further development of this type of molecule. It could also prove useful for analytical scale separations for which radiolytic instability is less important.     

The Influence of Alkyl Chain Length and Steric Effect on Extraction of Zinc(II) Complexes with 1‐Alkyl‐2‐Methylimidazoles

Abstract

The extraction of Zn(II) complexes with six 1‐alkyl‐2‐methylimidazoles (alkyl is from C₅H₁₁ up to C₁₂H₂₅) from nitric solution was studied as a function of pH of the aqueous phase. As the organic solvents toluene, p‐xylene and 1,2,3,4‐tetrahydronaphthalene were used. The stability constants of the complexes in the aqueous phase as well as partition constants of the extractable species were determined. It was demonstrated that both the stability constants (β_c) and the partition constants (P_c) of the complexes increased with increasing alkyl chain length. Pseudo‐tetrahedral complexes were found to dominate at the second and third complexation steps, thus increasing the stability constants and facilitating extraction of the Zn(II) complexes with 1‐alkyl‐2‐methylimidazoles.     

Extraction of Actinides with Different 6,6′‐Bis(5,6‐Dialkyl‐[1,2,4]‐Triazin‐3‐yl)‐[2,2′]‐Bipyridines (BTBPs)

Abstract

The extraction of Am(III), Th(IV), Np(V), and U(VI) from nitric acid by 6,6′‐bis(5,6‐dialkyl‐[1,2,4]‐triazin‐3‐yl)‐[2,2′]‐bipyridines (C2‐, C4‐, C5‐, and CyMe₄‐BTBP) was studied. Since only americium and neptunium extraction was dependent on the BTBP concentration, computational chemistry was used to explain this behavior. It has been shown that the coordination of the metal played an important role in forming an extractable complex into the organic phase, thus making it possible to extract pentavalent and trivalent elements from tetravalent and hexavalent elements. This is very important, especially because it shows other possible utilizations of a group of molecules meant to separate the actinides from the lanthanides. In addition, the level of extraction at very low or no BTBP concentration was explained by coordination chemistry.     

Extraction of Zirconium and Hafnium in Polyethylene Glycol‐Based Aqueous Biphasic System

Abstract

The behavior of zirconium and hafnium in PEG 2000‐Na₂SO₄‐HCl aqueous biphasic system has been investigated. The dependences of HCl concentration (0.185–0.55 M), extraction temperature (298–318 K), and extraction time (5–120 min) on distribution ratios have been determined. Extraction of this metals in PEG 2000‐Na₂SO₄‐H₂SO₄ and PEG 2000‐Na₃Cit‐HCl systems has been also studied. The sulfate and citrate complexes of Zr and Hf prefer salt‐rich phase in contrast to chloride complexes which pass into PEG rich phase in about 50% (w/w) to the greatest degree in room temperature and at short extraction time. The increase of distribution ratios (D*_Zr=3.75, D*_Hf=4.31) was observed after addition of water soluble organic ligand ‐ tiron (4,5‐dihydroxy‐m benzenedisulfonic acid disodium salt). The results obtained in studied conditions are not very useful for the separation of zirconium and hafnium.     

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.