Application of N,N′‐Dimethyl‐N,N′‐Di(4‐Chlorophenyl)Tetradecyl Malonamide for the Selective Recovery of Iron(III) from Concentrated Chloride Solutions

Abstract

The feasibility of using two new diamides namely; N,N′‐dimethyl‐N,N′‐di(4‐chlorophenyl)malonamide (DMDPhClMA) and N,N′‐dimethyl‐N,N′‐di(4‐chlorophenyl)tetradecylmalonamide (DMDPhClTDMA), as agents for the selective extraction of iron(III) from chloride solution was investigated. A systematic investigation has been carried out on the detailed extraction properties of iron(III) with these extractants from chloride media. The extraction of iron(III) from an aqueous chloride solution in the presence of metal ions, such as Zn(II), Co(II), Mn(II) Cu(II), Pb(II), Ni(II) and Ag(I) was carried out using DMDPhClMA or DMDPhClTDMA in binary and multicomponent mixtures. The quantitative extraction of iron(III) with DMDPhClMA and DMDPhClTDMA in toluene is observed at 4 and 7 M HCl, respectively. The quantitative stripping of Fe(III), from the loaded organic phase was successfully achieved by simple contact with water.     

Extraction of Actinide(III,IV, V,VI) Ions and TcO4 − by N,N,N′,N′‐Tetraisobutyl‐3‐Oxa‐Glutaramide

Abstract

The extraction behavior of U(VI), Np(V), Pu(IV), Am(III), and TcO₄ ^? with N,N,N′,N′‐tetraisobutyl‐3‐oxa‐glutaramide (TiBOGA) were investigated. An organic phase of 0.2 mol/L TiBOGA in 40/60% (V/V) 1‐octanol/kerosene showed good extractability for actinides (III, IV, V VI) and TcO₄ ^? from aqueous solutions of HNO₃ (0.1 to 4 mol/L). At 25°C, the distribution ratio of the actinide ions (D _An) generally increased as the concentration of HNO₃ in the aqueous phase was increased from 0.1 to 4 mol/L, while the D _Tc at first increased, then decreased, with a maximum of 3.0 at 2 mol/L HNO₃. Based on the slope analysis of the dependence of D _M (M=An or Tc) on the concentrations of reagents, the formula of extracted complexes were assumed to be UO₂L₂(NO₃)₂, NpO₂L₂(NO₃), PuL(NO₃)₄, AmL₃(NO₃)₃, and HL₂(TcO₄) where L=TiBOGA. The enthalpy and entropy of the corresponding extraction reactions, Δ_r H and Δ_r S, were calculated from the dependence of D on temperature in the range of 15–55°C. For U(VI), Np(V), Am(III) and TcO₄ ^?, the extraction reactions are enthalpy driven and disfavored by entropy (Δ_r H<0 and Δ_r S<0). In contrast, the extraction reaction of Pu(IV) is entropy driven and disfavored by enthalpy (Δ_r H>0 and Δ_r S>0). A test run with 0.2 mol/L TiBOGA in 40/60% 1‐octanol/kerosene was performed to separate actinides and TcO₄ ^? from a simulated acidic high‐level liquid waste (HLLW), using tracer amounts of ²³⁸U(VI), ²³⁷Np(V), ²³⁹Pu(IV), ²⁴¹Am(III) and ⁹⁹TcO₄ ^?. The distribution ratios of U(VI), Np(V), Pu(IV), Am(III) and TcO₄ ^? were 12.4, 3.9, 87, >1000 and 1.5, respectively, confirming that TiBOGA is a promising extractant for the separation of all actinides and TcO₄ ^? from acidic HLLW. It is noteworthy that the extractability of TiBOGA for Np(V) from acidic HLLW (D _Np(V)=3.9) is much higher than that of many other extractants that have been studied for the separation of actinides from HLLW.     

Comparison of Hydrometallurgical Parameters of N,N‐Dialkylamides and of Tri‐n‐Butylphosphate

Straight‐chain N,N‐dihexyloctanamide (DHOA) and branched‐chain N,N‐di(2‐ethylhexyl)isobutyramide (D2EHIBA) have been identified as promising alternatives to tri‐n‐butylphosphate (TBP) for the reprocessing of spent uranium based fuels, and selective extraction of ²³³U from irradiated thorium fuels, respectively. The present work deals with the effects of different hydrodynamic parameters such as viscosity, density, and interfacial tension (IFT) on the phase‐separation time (PST) under uranium and thorium loading conditions. The IFT values have been determined under varying experimental conditions such as the aqueous nitric acid concentration, n‐dodecane purity, ligand concentration, and thorium/uranium loading conditions. These studies have suggested that the quality of n‐dodecane affects the IFT values of different solutions. The IFT values of D2EHIBA changed marginally (23.3 ± 0.9 mNm^?1) against THOREX feed solution for the wide range of D2EHIBA concentration (0.1–1.0 M). However, IFT, viscosity, and PST values increased with uranium loading of 1.1 M DHOA. These studies suggested that a lower phase‐disengagement rate with increased uranium loading was mainly due to the increased viscosity of the loaded 1.1 M DHOA solution.     

Synthesis of N,N′-Dimethyl-N,N′-Dioctyl-3-Oxadiglycolamide and its Extraction Properties for Lanthanides

Abstract

Tetraalkyl-3-oxadiglycolamides show good prospects in nuclear reprocessing because of their complete incinerability. In addition, their degradation products interfere much less in the separation process when compared with organophosphorus extractants. An asymmetric extractant, N,N′-dimethyl-N,N′-dioctyl-3-oxadiglycolamide, has been synthesized by a five-step process. The compound was applied to the extraction of selected lanthanides from nitric acid solutions using chloroform as diluent. Its extraction properties for lanthanides from nitrate media have been described. The distribution ratio of the selected metal ions has been studied as a function of aqueous HNO₃ concentrations, diglycolamide concentration and temperature.     

Highly Copper(II) Ion‐Selective Transport Through Liquid Membrane Containing N,N′‐bis(salicylidene)‐1,2‐phenyldiamine

Abstract

N,N′‐bis(salicylidene)‐1,2‐phenyldiamine was synthesized for examining their ability to extract and transport Cu²⁺ through a liquid membrane. By using hydrazine sulfate and potassium thiocyanate as reducing agent and acceptor respectively in the receiving phase at the optimum pH of 1.5, the amount of copper transported across the liquid membrane after 3.5 hours was 96%. The selectivity and efficiency of copper transport from aqueous solution containing various metal ions were investigated.     

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.     

N,N′-乙撑双硬脂酰胺的制备

<正> N,N’-乙撑双硬脂酰胺系合成树脂的润滑剂、离型脱模剂、粘度调整剂、色素分散剂。为粉状固形物,色白,熔点142～144℃,闪点285℃,比重(25℃)0.98。对酸、碱稳定,不溶于水,常温下不溶于大多数溶剂,但溶于热的氯代烃类和芳香类溶剂,溶液冷却后析出沉淀或胶体。原料:硬脂酸:一级品乙二胺:一级品反应方程式:     

N,N′-乙撑双硬脂酰胺的制备

研究了以硬脂酸和乙二胺为原料，分别以几种强酸为催化剂合成N，N′－乙撑双硬脂酯胺的生产工艺，着重讨论了几种催化剂的催化效果，实验结果表明，固体超强酸效果好，反应时间短，产率高。     

Metal complexes of an N,N′-diformylated 36-membered N8O4-oxaazamacrocycle

Dinuclear metal complexes of an N,N'-diformylated 36-membered N₈O₄-oxaazamacrocycle (L) have been synthesised and characterised. The structure of [Cd₂(L)(CH₃CN)₄](ClO₄)₄ has been determined.     

N,N′-二甲基-N,N′-二苯基秋兰姆二硫化物合成工艺研究

以N-甲基苯胺、二硫化碳、氢氧化钠、过氧化氢、浓硫酸合成N,N′-二甲基-N,N′-二苯基秋兰姆二硫化物(MPTD).考察了原料的物料配比、反应温度、反应时间对收率的影响.得出最优物料的物质的量比为n[N-甲基苯胺]:n[氢氧化钠]:n[二硫化碳]:n[过氧化氢]:n[浓硫酸]=1:1.15:1.60:0.66:0.5.最佳缩合温度20～25℃,氧化温度15～20℃;最佳缩合时间12～13 h;氧化时间4～6 h.     

An X-ray diffraction study of oriented lithium-N,N,N′,N′-tetramethyl-ethane-1,2-diamine intercalated graphite

The intercalation of N,N,N′,N′-tetramethyl-ethane-1,2-diamine (tmeda) into C₆Li derived from papyex, a partially oriented graphite foil, results in the co-presence of two ternary phases having out-of-plane (c-axis) identity periods of 11.5 and 9.1 Å. As we reported for the powdered sample prepared using a natural graphite source, these distances are associated with two tmeda orientations. The tmeda orientation had no significant effect on the in-plane lattice. The orientated texture of the sample gave in-plane (a-b plane) unit cell dimension, a = 4.3 Å, close to the √3a_o distance of the stage I C₆Li precursor unit cell and allowed changes in the in-plane packing to be detected by extending the reflux time of the reaction between C₆Li and tmeda or by using the stage II binary C₁₂Li as the precursor. An expansion of the in-plane lattice spacing to 4.6 Å occurred for part of the sample. The ideal stoichiometry of the unexpanded ternary compound based on the unit cell volume and having the maximum number of tmeda molecules within the P6/mmm unit cell was estimated to be C₆Li (tmeda)₁. However, a structure factor analysis indicated that tmeda occupancy within the unit cell is fractional.     

Dependence of water sorption-desorption characteristics of N,N′-methylene-bis-acrylamide and tetraethyleneglycol diacrylate-crosslinked polyacrylamides on crosslinking

Summary Hydrophilic monomers such as acrylamide (AA) when crosslinked with highly hydrophilic flexible tetraethyleneglycol diacrylate (TEGDA) and N,N-methylene-bis-acrylamide (NNMBA) of intermediate polarity and hydrophilicity provides highly water swellable hydrogels. These water-swellable but water insoluble macromolecules possess a number of physicochemical properties useful for applications in biomedical and other technological fields. This paper describes the swelling/deswelling characteristics and the ability for water retention of these polymers in different compositions. Water sorption in these crosslinked polyacrylamides is dependent on a number of variables of polymer synthesis.     

Influence of guests and protonation on the conformation of N,N′-dipyridyl-bis-aza-18-crown-6

Crystallisation of the sodium perchlorate adduct of N,N^′-dipyridyl-bis-aza-18-crown-6 from acidic aqueous conditions yielded [(H₃O)(N,N^′-dipyridyl-bis-aza-18-crown-6)][ClO₄] and [Na·N,N^′-dipyridyl-bis-aza-18-crown-6]₂ [(H⁺)₂N,N^′-dipyridyl-bis-aza-18-crown-6][ClO₄]₄·2H₂O. The conformations of crown ethers were significantly influenced by incorporation of an H₃O⁺ or sodium ion, or protonation of the amino nitrogen atoms resulting in three different structures for the macrocycle.     

N,N′-双聚氧乙烯醚氧化胺磷酸酯

简介了题示化合物的性能、合成、分析。     

N,N′-取代邻苯二胺的合成

通过2-取代苯并咪唑盐的还原开环反应制备了8个N,N′-不同取代的邻苯二胺,并经1HNMR、IR、MS及元素分析表征,其中5个未见文献报道。这是一条由邻苯二胺和羧酸经2-取代苯并咪唑制取该类化合物的简洁合成路线。     

A Study of the γ-Radiolysis of N,N-Didodecyl-N′,N′-Dioctyldiglycolamide Using UHPLC-ESI-MS Analysis

Solutions of N,N-didodecyl-N′,N′-dioctyldiglycolamide in n-dodecane were subjected to γ-irradiation in the presence and absence of both an aqueous nitric acid phase and air sparging. The solutions were analyzed using ultra-high-performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) to determine the rates of radiolytic decay of the extractant as well as to identify radiolysis products. The DGA concentration decreased exponentially with increasing dose, and the measured degradation rate constants were uninfluenced by the presence or absence of acidic aqueous phase, or by air sparging. The identified radiolysis products suggest that the bonds most vulnerable to radiolytic attack are those in the diglycolamide center of these molecules and not in the side chains.     

N,N,N′,N′-四苯基联苯胺的合成新方法

以联苯胺和二苯胺为原料，经两步反应合成了N，N，N′，N′－四苯基联苯胺（TPB)。与已报道的方法相比较，该方法具有产率高、操作简单、原料价格低廉等优点。     

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.     

Metal binding properties of poly[N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine methacrylate]

Summary When incorporated into a polymer hydrogel, the metal chelator, N,N,N,N-tetrakis(2-hydroxypropyl)ethylenediamine (THPED), retains its metal binding properties. The resultant poly(THPED methacrylate) homopolymer is a polybase with displacement binding constants for copper (II) and zinc(II) of-3.11 and-6.55, respectively, as compared to values for THPED of-3.83 and-7.44. The chelating capacity of the polymer for various divalent metal ions at pH 5.5 follows the order Cu>Cd>Co>Zn>Mn, while calcium and magnesium do not bind. Metal ion release curves indicate that after 30 hours, Cd(II), Co(II), Zn(II), and Mn(II) are released at a slow, steady rate, while Cu(II) is not released under experimental conditions.