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.     

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.     

Fundamental Chemistry of Cesium Extraction from Acidic Media by HCCD in FS‐13

Abstract

We previously published a model for cesium extraction from acidic media by the protonated form of the hexachlorinated derivative of the chloro‐protected cobalt bis(dicarbollide), HCCD, dissolved in trifluoromethylphenyl sulfone, FS‐13. The model indicated that Cs extraction proceeds through a series of ion‐paired and/or dissociated extraction equilibria. Additional Cs distribution ratio data has been obtained and the model refined and simplified. It is demonstrated that the equilibrium exclusively involving the exchange of proton for cesium by formation of ion‐paired CsCCD models the Cs distribution data very well, particularly for the concentrations of HCCD greater than ～0.0005 M (0.5 mM). Finally, activity corrections for the aqueous phase to the Cs distribution data results in good agreement to the theoretical value of ?1 for slope (log‐log) analysis of the data over a wide range of HNO₃ and HCCD concentrations.     

Modelling of the Extraction and Back‐Extraction Equilibria of Zinc from Spent Pickling Solutions

Abstract

This work reports the study of the chemical equilibria of the extraction and back‐extraction of zinc from spent pickling solutions. Tributyl phosphate was used as a selective extractant and service water as a back extraction agent. Feed solutions had an average composition of 6.4 M Cl^?, 1.2 M Zn⁺², 1.7 M Fe⁺² and traces of other heavy metals i.e., Pb, Ni, Cu, Mn. Under the experimental conditions the ion ZnCl₄ ^2? was the predominant zinc species in feed. A careful experimental design was performed obtaining the equilibria mathematical models and parameters, K_EX=0.137 (mol/L)^?4, and K_BEX=1.46 [?].     

Modification and Evaluation of Non‐Polar Sorbents for Solid‐Phase Extraction

Abstract

Modification of packings for solid‐phase extraction through high‐frequency low‐temperature plasma treatment is a new method to obtain a wide variety of sorbents. This method is still in the process of investigation and application. In this study, several commercial sorbents have been modified in high‐frequency low‐temperature plasma with the mixed hydrogen/benzene system. The solvation parameter model is used to characterize the sorption properties of commercially available and plasma treated sorbents for solid‐phase extraction. Chromatographic test mixtures from the literature were used to probe hydrophobicity, free silanol interactions and shape selectivity of the sorbents. The physical and retention properties of the plasma treated sorbents indicate their suitability to be used in solid‐phase extraction. Some suggestions concerning the possible practical application of the newly obtained sorbents have been made.     

Application of Synchrotron Radiation for Studying Detonation and Shock‐Wave Processes

A new method of remote investigation of detonation and shockwave processes with the use of synchrotron radiation is proposed. The facility used for the first experiments with measurement of density and smallangle xray scattering in detonation of condensed explosives is described. The high time and spatial resolution of the techniques proposed allows one to determine the character and mechanism of destruction of the condensed phase and the growth dynamics of new structures, including crystalline ones, in detonation flows. The capabilities of the new technique are described.     

Ultra‐selective epoxidation of styrene on pure Cu{111} and the effects of Cs promotion

Styrene undergoes efficient epoxidation to styrene epoxide on the Cu{111} surface. At the optimum condition (Θ_o = 0.03 ML) ∼20% of the styrene is converted to the epoxide with almost 100% selectivity. Comparison with Ag{111} shows that the epoxidation activity and selectivity of Cu greatly exceed those of Ag. Incipient oxidation of the Cu{111} surface does not suppress the adsorption of styrene, but the oxidised metal is catalytically inert. Submonolayer amounts of Cs enhance styrene uptake and increase conversion to the epoxide without adversely affecting epoxidation selectivity. This effect is due to inhibition of Cu oxidation by Cs. Our findings are discussed in the light of current understanding of Ag‐catalysed alkene epoxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of the Steric Hindrance,Ligand Hydrophobicity,and DN of solvents on Structure and Extraction of Cu(II) Complexes of 1‐Alkyl‐2‐Ethylimidazoles

Abstract

Formation of Cu(II) complexes of 1‐alkyl‐2‐ethylimidazoles (where alkyl=propyl, butyl, pentyl, hexyl, and octyl) has been studied by using the liquid‐liquid partition method, at 25°C and a fixed ionic strength of the aqueous phase (I=0.5; (HL)NO₃, KNO₃). The complexes were extracted with 2‐pentanone, 2‐butanol, isoamyl alcohol, 2‐ethyl‐1‐hexanol, dichloromethane, trichloromethane, and toluene. The length of the 1‐alkyl group and the nature of solvent have been shown to influence the extraction process. Extraction curves (log D_M vs. pH) are displaced towards lower pH's with increasing chain length of the 1‐alkyl substituent and donor number of the solvents. Stability constants of the complexes in aqueous solution were determined as well as their partition ratios between the aqueous and organic phase. The stability of the Cu(II) complexes increased with increasing 1‐alkyl chain length. The stability constants are comparable with β_n ones for the Cu(II) complexes of 1‐alkyl‐2‐methylimidazoles, but smaller than those of the Cu(II)–1‐alkylimidazole counterparts. The P_c‐partition ratios of the 1‐alkyl‐2‐ethylimidazole complexes with Cu(II) are high, and increased with increasing 1‐alkyl chain length and the donor number of the solvents. Both the strong steric effect of the ethyl substituent at position 2 and the bulkiness of the 1‐alkyl‐2‐ethylimidazole molecules as well as the strong electron‐donating properties of the solvent molecules have an effect on the change of the coordination number of Cu(II) from 6 to 4. The 4‐coordinate Cu(II) complexes (distorted tetrahedron) are more readily extractable by organic solvent than are the 6‐coordinate ones and for this reason their partition constants, P_c, are high. This finding offers the possibility of extraction of the Cu(II) ions from a mixture cations.     

Effect of Alkyl Chain Length on the Extraction of Copper(II) Complexes with 1‐Alkyl‐2‐Methylimidazoles

Abstract

By using the liquid‐liquid partition method, the formation of Cu(II) complexes with 1‐alkyl‐2‐methylimidazoles (where alkyl=isobutyl, pentyl, isopentyl, hexyl, octyl, decyl, and dodecyl) has been studied at 25°C and at fixed ionic strength of the aqueous phase (I=0.5; (HL)NO₃, KNO₃). The complexes were extracted with 2‐ethyl‐1‐hexanol, dichloromethane, trichloromethane and, in one system only, toluene. Stability constants of the complexes in aqueous solution as well as partition constants of the extractable species were determined. It has been shown that the stability constants are invariable and do not depend on the 1‐alkyl chain length. The constants were smaller than those of the previously studied Cu(II) – 1‐alkylimidazole complexes owing to the steric effect of the methyl group at position 2. The partition constants of the complexes incereased with increasing alkyl chain length. Branched 1‐alkyl substituents (isobutyl, isopentyl) suppressed both stability constants and the partition constants of the complexes.     

Influence of pH and Diluent on the Ion‐Pair Solvent Extraction of Aromatic Carboxylic Acids Using Quaternary Ammonium Salts

Abstract

The influence of pH and diluent on the ion‐pair solvent extraction of benzene polycarboxylic acids have been investigated for the separation of the coal oxidation products, which are formed by the treatment with alkaline solutions at high temperatures. Although the extent of the solvent extraction of benzoic acid (1BE) with a quaternary ammonium reagent (tri‐n‐octylmethylammonium chloride) into chloroform and benzene did not change at a very acidic and alkaline solutions, those of 1,2‐benzenedicarboxylic acid (12BE) and trimellitic acid (124BE) somewhat decreased at very low pH and very high pH. The magnitudes of the equilibrium constants (K_ex) of 1BE using a different diluent decreased in the order benzene>carbontetrachloride>1,2‐dichloroethane>cyclohexane>hexane>chloroform>1‐octanol and those of 12BE decreased in the order benzene>cyclohexane>carbontetrachloride>hexane>1,2‐dichloroethane>chloroform. The inspection of the correlation between the values of K_ex and several parameters of the diluent implies that the magnitude of K_ex can be described by using the dielectric constant and the solubility parameter of diluent.     

Influence of Extractant Aggregation on the Extraction of Trivalent f‐Element Cations by a Tetraalkyldiglycolamide

Abstract

The influence of nitric acid extraction on the aggregation state of 0.10 M N,N,N′,N′‐tetra‐n‐octyl‐3‐oxapentane‐1,5‐diamide (TODGA) in n‐octane or n‐heptane was studied by small‐angle neutron scattering (SANS) and vapor pressure osmometry (VPO). When the equilibrium concentration of nitric acid in the aqueous phase is less than 0.7 M, TODGA exists as a mixture of monomers and dimers. As the aqueous phase acidity is increased, the extractant molecules form higher aggregates containing up to an average of seven molecules of TODGA. The formation of the larger TODGA aggregates takes place over the same range of aqueous acidities where the extraction of trivalent f‐element cations displays a hyperstoichiometric sixth power nitric acid dependence. This suggests that acid‐driven aggregation of TODGA is responsible for the unusual acid and extractant dependencies observed for the extraction of trivalent metal nitrates with this ligand.     

Purification of Glucose Oxidase and β‐Galactosidase by Partitioning in a PEG‐Salt Aqueous Two‐Phase System in the Presence of PEG‐Derivatives

Abstract

Purification of glucose oxidase from Aspergillus niger and that of β‐galactosidase from Kluyveromyces lactis have been attempted using poly(ethylene glycol) (PEG)‐sodium sulfate aqueous two phase system (ATPS) in the presence of PEG‐derivatives, i.e. PEG‐Coomassie brilliant blue G‐250 and PEG‐benzoate, PEG‐palmitate and PEG‐TMA, respectively. The enzymes showed poor partitioning towards the PEG phase in comparison with other proteins in ATPS containing no ligands. Selective partitioning of other proteins was observed towards the PEG phase in the presence of PEG‐benzoate and PEG‐palmitate enriching β‐galactosidase in the salt phase whereas in the case of glucose oxidase, PEG‐Coomassie brilliant blue G‐250 derivative worked as a better affinity ligand for other proteins. A 19‐fold purification was obtained with the PEG dye derivative after 5 stage cross extractions with 80% recovery of glucose oxidase and an enrichment factor upto ～7 for β‐galactosidase with the PEG‐TMA derivative. The interaction of PEG‐benzoate and PEG‐TMA ligands with the active site of β‐galactosidase has been evaluated by molecular modeling. The effect of the molecular weight of glucose oxidase on its partitioning was confirmed as the molecular simulation shows strong affinity interaction of PEG‐glucoside with the enzyme.     

Microgels for the Intensification of Liquid-Liquid Extraction Processes – Feasibility and Advantages

Microgels are cross-linked polymers with a high application potential in liquid-liquid systems due to their surface activity and switchable stabilization properties. A process concept utilizing microgels in extraction processes is presented. The microgels are located at the drop surface and prevent coalescence, enabling monodisperse operation. At the column top, the stabilization is switched off by temperature shift. The switchable stabilization and the absence of additional mass transfer resistance are crucial requirements for the concept and tested experimentally. The results provide the basis for the model-based evaluation of the process performance, revealing a broader operating window, capacity increase at equal height equivalent of theoretical stage (HETS) for high loads, and reduced HETS for small loads.     

Aqueous Two‐Phase Partitioning of Glucose Isomerase from Actinoplanes missouriensis in the Presence of PEG‐Derivatives and its Immobilization on Chitosan Beads

Abstract

Purification of glucose isomerase by its partitioning in a PEG‐salt aqueous two‐phase system (ATPS) in the presence of PEG derivatives has been studied. Selective partitioning of the proteins was observed towards the PEG phase containing PEG‐benzoate and PEG‐palmitate, enriching glucose isomerase in the salt phase. Cross‐current extraction in 4 stages in the presence of PEG‐palmitate gave an enrichment factor of ～5 for the enzyme. After initial purification with ATPS, glucose isomerase was immobilized on cross‐linked chitosan beads. The immobilized enzyme was stable over a wider pH range (5.2–9.0) and showed an optimum pH of 6.5     

The Solvent Extraction of Boron with Synthesized Aliphatic 1,3‐Diols: Stripping and Extraction Behavior of Boron by 2,2,5‐Trimethyl‐1,3‐hexanediol

Abstract

A variety of aliphatic 1,3‐diols (4a–c, 5a–c, 6a–c) was synthesized from β‐hydroxy carbonyl compounds (1–3) for potential use in the solvent extraction of boron. Primary‐secondary and primary‐tertiary alcohol structures of 1,3‐diols substituted with isopropyl, isobutyl, and isopentyl groups have been demonstrated to be very efficient for the solvent extraction of boric acid from aqueous solutions. The extraction ability of 2,2,5‐trimethyl‐1,3‐hexanediol (5b) was investigated as a function of 5b concentration, solution pH, solvent properties, and stripping conditions. Extraction efficiency increased with increasing concentration of 5b, and the best extraction of boron (96.8%) was found to be at an equilibrium pH of 2 with 0.5 M of 5b. Chloroform, toluene, chlorobenzene, 2‐octanol, and n‐amyl alcohol were found to be suitable solvents for the solvent extraction of boron. The boron complex can be recovered from the organic phase by treatment with an aqueous solution of sodium hydroxide. The highest ratio (96.7%) of boron was recovered by 0.1 M of sodium hydroxide solution.     

Effect of a Gas‐Phase Reaction on the Combustion Performance of a Sandwich Layered System

This paper considers a sandwich layered combustion model (an oxidizer and a fuel) that takes into account condensed and gasphase chemical reactions and transverse heat and mass transfer. Under particular simplifications, algebraic expressions are obtained for the burning rates of the components and the temperature and concentration of gaseous reagents on the burning surface. Calculated dependences of the burning rate on the sandwich size agree with experiments.     

State‐of‐the‐Art Adsorption and Membrane Separation Processes for Hydrogen Production in the Chemical and Petrochemical Industries

Abstract

This review on the use of adsorption and membrane technologies in H₂ production is directed toward the chemical and petrochemical industries. The growing requirements for H₂ in chemical manufacturing, petroleum refining, and the newly emerging clean energy concepts will place greater demands on sourcing, production capacity and supplies of H₂. Currently, about 41 MM tons/yr of H₂ is produced worldwide, with 80% of it being produced from natural gas by steam reforming, partial oxidation and autothermal reforming. H₂ is used commercially to produce CO, syngas, ammonia, methanol, and higher alcohols, urea and hydrochloric acid. It is also used in Fischer Tropsch reactions, as a reducing agent (metallurgy), and to upgrade petroleum products and oils (hydrogenation).

It has been estimated that the reforming of natural gas to produce H₂ consumes about 31,800 Btu/lb of H₂ produced at 331 psig based on 35.5 MM tons/yr production. It is further estimated that 450 trillion Btu/yr could be saved with a 20% improvement in just the H₂ separation and purification train after the H₂ reformer. Clearly, with the judicious and further use of adsorption or membrane technology, which are both classified as low energy separation processes, energy savings could be readily achieved in a reasonable time frame.

To assist in this endeavor of fostering the development of new adsorption and membrane technologies suitable for H₂, CO and syngas production, the current industrial practice is summarized in terms of the key reforming and shift reactions and reactor conditions, along with the four most widely used separation techniques, i.e., absorption, adsorption, membrane, and cryogenic, to expose the typical conditions and unit processes involved in the reforming of methane. Since all of the reactions are reversible, the H₂ or CO productivity in each one of them is limited by equilibrium, which certainly provides for process improvement. Hence, the goal of this review is to foster the development of adsorption and membrane technologies that will economically augment in the near term and completely revamp in the far term a typical H₂, CO or syngas production plant that produces these gases from natural gas and hydrocarbon feedstocks.

A review of the emerging literature concepts on evolving adsorption and membrane separations applicable to H₂ production is provided, with an emphasis placed on where the state‐of‐the‐art is and where it needs to go. Recommendations for future research and development needs in adsorbent and membrane materials are discussed, and detailed performance requirements are provided. An emphasis is also placed on flow sheet design modification with adsorption or membrane units being added to existing plants for near term impact, and on new designs with complete flow sheet modification for new adsorption or membrane reactor/separators replacing current reactor and separator units in an existing plant for a longer term sustainable impact.     

Trans‐Lanthanide Extraction Studies in the TALSPEAK System: Investigating the Effect of Acidity and Temperature

A recent review of the TALSPEAK (Trivalent Actinide ‐ Lanthanide Separation by Phosphorous reagent Extraction from Aqueous Komplexes) process summarized previous research characterizing the performance of this system. Attempts were made in that report to develop correlations between the previous separations data and the thermodynamic data that describes the interactions among the components of the separation system. However, the diversity of observations and the breadth of conditions employed in the many studies from the literature make comparisons between the TALSPEAK system performance and existing thermodynamic data challenging. To better test the adequacy of the available thermodynamic database for modeling this system, an internally consistent set of observations of lanthanide extraction under TALSPEAK conditions is offered in this report. The extraction of the lanthanides from La through Lu (excluding Pm) plus Y, and that of Am³⁺ from buffered lactic acid solutions containing diethylenetriamine‐N,N,N′,N″,N″‐pentaacetic acid (DTPA) into organic solutions of bis‐(2‐ethylhexyl)phosphoric acid (HDEHP) solutions in 1,4‐diisopropylbenzene has been investigated as a function of temperature, pH, and ionic strength. Extraction of both lanthanides and Am³⁺ decreases with increasing pH and with temperature. At the same time, separation factors remain approximately constant. Calculations based on an internally consistent thermodynamic data set confirm the prior conclusion that the existing thermodynamic data do not predict the observed decline in partitioning with increased pH, though the data do support the constancy of the separation factors. The relationship between the basic thermodynamic data, calculated speciation, and the performance of the separation system is discussed.