Non-Dispersive Solvent Extraction of Neodymium using N,N,N’,N’-Tetraoctyl Diglycolamide (TODGA)

Hollow fiber contactor was used to study non-dispersive extraction (NDSX) of Nd³⁺ ions from aqueous solutions. N,N,N′,N′-tetraoctyl diglycolamide (TODGA) diluted with n-dodecane was used as the organic phase with di-n-hexyl octanamide (DHOA) as the phase modifier. The role of cations (H⁺/Na⁺) on the transport of Nd³⁺ ions has been investigated for this system. It was observed that H⁺ ion has a significant role to play in the Nd³⁺/TODGA complexation reaction. A mathematical model has also been developed to simulate the NDSX process in a hollow fiber contactor. A comparison has also been made between extraction profiles from the NDSX process and the hollow fiber supported liquid membrane (HFSLM) process. It was observed that NDSX gave comparatively faster rates of extraction in the presence of H⁺ ions but slower in the absence of H⁺ ions.     

Evaluation of the Hydrophilic Complexant N,N,N’,N’-tetraethyldiglycolamide (TEDGA) and its Methyl-substituted Analogues in the Selective Am(III) Separation

ABSTRACT

N,N,N’,N’-tetraethyldiglycolamide (TEDGA) is used in the French EXAm (extraction of americium) process to separate Am(III) from Cm(III) and Ln(III). In this study, the complexation behavior of TEDGA towards actinides(III) and lanthanides(III) was compared to its methyl-substituted derivatives Me-TEDGA and Me₂-TEDGA under experimental conditions applying to the EXAm process. Using the EXAm solvent, 0.6 mol/L N,N’-dimethyl-N,N’-dioctyl-hexylethoxymalonamide (DMDOHEMA) and 0.45 mol/L bis(2-ethylhexyl)-phosphoric acid (HDEHP), An(III) and Ln(III) distribution ratios increase in the order TEDGA < Me-TEDGA < Me₂-TEDGA. This is explained by differences in the strength of complexation in the aqueous phase: Conditional stability constants for the formation of [Cm(DGA)_x]³⁺ complexes decrease in the order TEDGA > Me-TEDGA > Me₂-TEDGA, as shown by time-resolved laser fluorescence spectroscopy (TRLFS). TRLFS measurements verified the exclusive existence of [Cm(DGA)₃]³⁺ complexes in the aqueous phase. Both the homoleptic [Cm(DMDOHEMA)_n]³⁺ and the heteroleptic [Cm(DGA)_x(DMDOHEMA)_y]³⁺ complexes were detected in the organic phase, as postulated in the literature.^[14]     

N,N,N’,N’-四丁基-3-氧戊二酰胺萃取铁(Ⅲ)的研究

在两种稀释剂体系中研究了N,N,N’,N’-四丁基-3-氧戊二酰胺(TBOPDA)从盐酸介质中萃取铁离子的性能和反应机理。考察了水相盐酸浓度、萃取剂浓度及温度对其萃取性能的影响。实验结果表明分配比随盐酸浓度的增加而增加;随萃取剂浓度的增加而增大;萃取过程为放热过程,升高温度不利于萃取。     

Insight into nitric acid extraction and aggregation of N,N, N’, N’-Tetraoctyl diglycolamide (TODGA) in organic solutions by molecular dynamics simulation

The molecular dynamics (MD) simulation of TODGA in n-dodecane shows formation of nanostructures of TODGA aggregates with nitric acid and water. These aggregates are dispersed in dodecane phase or form well defined reverse micelles grown sufficient in size depending on the acid concentration. With increasing nitric acid concentration, aggregation number of TODGA in reverse micelles also increases which, however, is independent of TODGA concentration. Aggregation number rises from 2 to 8 in presence of 0–3.5 M nitric acid in corresponding aqueous phase. The formation of the aggregates explains remarkable acid co-extraction from aqueous phase to organic dodecane phase by TODGA.     

Synthesis and Thermal Decomposition Studies of Silicon (IV) Compounds with N,N’-Bis(Salicylidene)Ethylenediimine

The silicon (IV) compounds possessing SiN₄O₂ (6), SiN₂O₂C₂ (7, 8), SiN₂O₂CCl (9) and SiN₄O₄ (10) coordinating frameworks have been synthesized in high yield by the reaction of the O,N,N,O- donor salen-type ligand N,N’-bis(salicylidene)ethylenediimine L with different silanes i.e. diethoxydiisocyanatosilane-(C₂H₅O)₂Si(NCO)₂ 1, dichlorodiphenylsilane-Ph₂SiCl₂ 2, dichloromethyl- phenylsilane-MePhSiCl₂ 3, trichlorophenylsilane-PhSiCl₃ 4 and silicon tetrachloride-SiCl₄ 5. The compounds 6–10 have been characterized by elemental analysis, IR, ¹H, ¹³C and ²⁹Si NMR and mass spectrometry. The decomposition reactivity of these compounds has been studied using a Thermal Gravimetric Analyzer (TGA) at a heating rate of 10°C/minute in an inert atmosphere.     

N,N’-双(4-甲基苄基)脲的简易合成及晶体结构

以对甲基苄胺和苄胺为原料,四氯化碳为溶剂,在光照条件下回流,分别合成了对应的N,N’-二取代脲的产物1,3-双(4-甲基苄基)脲和1,3-双苄基脲,它们的结构经过了核磁共振氢谱、质谱、红外和元素分析的表征,其中1,3-双(4-甲基苄基)脲还获得了晶体结构的进一步证实。     

Extraction behavior of strontium from nitric acid medium with N,N’-dimethyl-N,N’-dioctyldiglcolamide

Strontium-90 (⁹⁰Sr), one of the most significant fission products carried into high-level waste (HLW), should preferably be separated from HLW. In this investigation, the extraction of Sr²⁺ was carried out using N,N’-dimethyl-N,N’-dioctyldiglcolamide (DMDODGA) in 40/60 (V/V)% 1-octanol/kerosene or ionic liquid (IL) [C₆mim][Tf₂N]. The composition of the extracted complex between DMDODGA and HNO₃ depends on the aqueous HNO₃ concentration. The distribution ratio of Sr²⁺ (D_Sr) is influenced by the initial concentration of HNO₃ and strontium in the aqueous phase, the concentration of DMDODGA, and temperature. The stoichiometry of Sr²⁺ and DMDODGA in the extracted complex is 1:3. D_Sr in the IL is two orders of magnitude higher than that in 40/60 (V/V)% 1-octanol/kerosene at lower acidity.     

N,N′-乙撑双(硬脂酰胺)

分了C:7H。。一e一NH一CH:CH:一NH一C一Ci:Ha。 C:.H,eN,O: 分子量593 l英文名IN,N‘一Ethylene bis(s-tearanl记e) l国外商品名1 Chemetronwa、一100(Chemetron);Armowax EBS(Armak)书H佣ehst WaxC(Hoechst);AerawaxC(Glyeo),Kemam溉w 20(枷mko);Lubro/EA(ICI)。 l性状】白色至淡黄色粉末或粒状物。熔点130一145℃,闪点约285℃,比重0.98。不溶于水,常温下不溶于乙醇、丙酮等大多数溶剂,可溶于混合二甲苯、菇烯、丁醇、甲基溶纤素及大多数氯代烃类。游离脂肪酸含量低于4%,水份低于。.5%。 【制法】乙撑双硬脂酞胺的制备是…     

Extraction of Uranium(VI) and Thorium(IV) from Nitric Acid Solution by N,N,N′,N′ – Tetraoctylglutaricamide

Synthesis and characterization of N,N,N′,N′-tetraoctylglutaricamide (TOGA) was carried out and used for extraction of U(VI) and Th(IV) from nitric acid solutions. The processes of extraction were determined by the slope analysis and by analyzing a function that allows the simultaneous treatment of all the experimental points obtained in different conditions. The different factors affecting the extraction distribution ratio(D) of U(VI) and Th(IV) (extraction concentration, concentrations of nitric acid, salting-out agent NaNO₃ concentration, equilibration time, temperature, and types of diluents) were investigated. The results obtained indicated that the extraction species of U(VI) and Th(IV) are mainly extracted as UO₂(NO₃)₂·1.0TOGA and Th(NO₃)₄·1.5TOGA. The apparent equilibrium constant of U(VI) and Th(IV) extraction determined are 3.35 ± 0.03 L³/mol³ and 1.87 ± 0.01 L⁵/mol⁵ at 298 ± 1 K. Thermodynamic parameters such as the free energy(ΔG), enthalpy(ΔH), and entropy(ΔS) changes associated with the extraction processes could be evaluated. Back-extraction of U(VI) and Th(IV) from organic phases was also studied.     

N,N,N′,N′-四丁基丁二酰胺萃取Ce(Ⅲ)的研究

合成了新型萃取剂N,N,N′,N′-四丁基丁二酰胺(TBSA),研究了其萃取Ce(Ⅲ)的性能,详细考察了硝酸浓度、萃取剂浓度、硝酸锂浓度以及温度等对萃取分配比的影响,得出了TBSA以甲苯为稀释剂时萃取反应的表观平衡常数为(0.29±0.16)L6/mol6及298K时的热力学焓变为-17.90kJ/mol,并用红外光谱表征了配合物Ce(NO3)3.3TBSA的结构。     

N,N,N',N'-四(3-氨基丙基)乙二胺合成和表征

利用乙二胺和丙烯腈的亲核加成反应合成了一种新型有机多腈N,N,N’,N’-四（2-氰基乙基）乙二胺。在Raney Ni存在下对N,N,N’N’-四（2-氰基乙基）乙二胺进行催化加氢,得到N,N,N’N’-四（3-氨基丙基）乙二胺。并用红外、核磁、质谱等对N,N,N’N’-四（3-氨基丙基）乙二胺进行了表征,结果表明所合成的化合物即为标题化合物。     

Electrospin of polysulfone in N,N’-dimethyl acetamide solutions

Nanofibers of polysulfone (PSU) were prepared by electro-spinning from 10∼20 wt.% PSU solutions in N,N’-dimethyl acetamide (DMAc) mixed with 0.0∼0.1 wt.% LiCl. With increasing PSU concentration, the morphology of fibers electrospun were bead, mixture of bead-fiber and fiber, and smooth fibers when PSU concentration was 10, 12–15, and 18–20 wt.%, respectively. The bead sizes decreased and fiber diameters increased as PSU concentration was increased. The fiber diameter decreased with increases of the LiCl concentration and the distance from spinneret to collection plate. The fiber diameter also decreased with decreasing solution feeding rate. The fiber diameter distribution electrospun from 20 wt.% PSU solutions was much broader than those electrospun from 18 wt.% PSU solution. For 18 wt.% PSU solution, the average fiber diameter (AFD) decreased when the applied voltage V was increased from 7 to 12 kV. However, for 20 wt.% PSU solutions, the AFD increased when V was increased from 7 to 12 kV. The different morphology of fibers electrospun from 18 and 20 wt.% PSU solutions was attributed to the much higher viscosity of 20 wt.% PSU solution than 18 wt.% PSU solution.     

Synthesis and Properties of Novel Soluble and Thermally Stable Optically Active Poly(amide-imide)s from N,N’-(4,4’-Oxydiphthaloyl)-bis-L-phenylalanine Diacid Chloride and Aromatic Diamines

Summary In this research work, 4,4-oxydiphthalic anhydride (1) was reacted with L-phenylalanine (2) in acetic acid and the resulting imide-acid 3 was obtained in high yield. This imide-acid 3 was converted to diacid chloride 4 by reaction with thionyl chloride. The polycondensation reaction of diacid chloride 4 with several aromatic diamines such as 4,4-sulfonyldianiline (5a), 4,4-diaminodiphenyl methane (5b), 4,4-diaminodiphenylether (5c), p-phenylenediamine (5d), m-phenylenediamine (5e), and 4,4-diaminobiphenyl (5f) was performed by two conventional methods: low temperature solution polycondensation and short period reflux conditions. Several new thermally stable optically active poly(amide-imide)s with inherent viscosity ranging from 0.34–0.62 dL/g were obtained with high yield. All of the above polymers were fully characterized by ¹H-NMR, FT-IR, elemental analyses and specific rotation techniques. Some structural characterizations and physical properties of this new optically active poly (amide-imide)s are reported.     

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.     

二步法合成N,N,N′,N′-四(β-羟乙基)己二酰胺

标题化合物("552")是一种新型的粉末涂料固化剂,具有高效、节能、环保的特性.用己二酸二甲酯和二乙醇胺的氨解反应,二步法合成"552",产率86%.具体的条件为:1)n(己二酸二甲酯)∶n(二乙醇胺)=1∶1.1,在甲醇钠和氢氧化钾的催化下,100 ℃反应3 h;2)继续加入二乙醇胺(与己二酸二甲酯的物质的量比为0.95)和甲醇钠,70 ℃反应3 h;总的物质的量比n(己二酸二甲酯)∶n(二乙醇胺)=1∶2.05.探索该反应的过程,分离提纯出中间体并进行 1HNMR 表征,为提高"552"的产率提供理论依据.     

N,N’-二(2-羟丙基)哌嗪的合成及其在烟气脱硫工艺中的应用

利用无水哌嗪和环氧丙烷合成了N,N’-二(2-羟丙基)哌嗪(HPP),利用红外光谱对其进行了表征,利用滴定法计算出HPP的共轭酸的pKa1和pKa2值,通过热重分析仪研究了HPP的半盐溶液与SO2的反应行为和SO42-在湿法烟气脱硫中对HPP挥发损失的影响。结果表明,HPP的合成反应是按照反应物的化学计量比进行的,且工艺过程简单,得到的产物纯度较高。HPP的共轭酸的pKa1和pKa2分别为3.8和8.2。SO42-能够有效的抑制HPP的挥发,可以作为烟气脱硫工艺中HPP半盐溶液的阴离子。     

甲基丙烯酸(N,N-二甲基氨基)乙酯

甲基丙烯酸(N,N—二甲基氨基)乙酯(简称DMA)是具有聚合性乙烯基及叔氨基的反应性单体。一、DMA的物性 DMA的结构式如下所示,其一般物     

间(N,N-二甲胺基)苯甲酸的合成

间(N,N-二甲胺基)苯甲酸是重要的生化试剂间羧基二甲胺基碘乙烷季铵盐的前体化合物,目前国内尚无商品出售。文献中报道的合成路线有两条。一是,将间氨基苯甲酸在碱性条件下(如氢氧化钠或碳酸钠)与过量硫酸二甲酯反应,生成间(N,N-二甲胺基)苯甲酸甲酯,与氨水在140℃的封管中水解,再用酸中和。二是,将间氨基苯甲酸与甲醛在10%