二(2,4,4-三甲基戊基)膦酸萃取分离稀土元素(Ⅲ)的研究

本文研究了二(2,4,4-三甲基戊基)磷酸(Cyanex 272)的煤油溶液在不同介质(HCI,HNO_3)中对三价混合稀土的萃取分离性能.观测了平衡水相酸度对萃取平衡的影响,由酸度曲线求出相邻元素的平均分离系数,并考察了酸度对反萃取平衡的影响.比较了HCI和HNO_3介质中,Cyanex 272对混合稀土(Ⅲ)的萃取性能.     

二(2,4,4-三甲基戊基)膦酸从盐酸介质中萃取分离钪(Ⅲ)和铁(Ⅲ)

本文研究了二(2,4,4-三甲基戊基)膦酸(HBTMPP)的正辛烷溶液对Sc(Ⅲ),Fe(Ⅱ)的萃取平衡影响,研究了酸度对Sc(Ⅲ)、Fe(Ⅲ)分配比影响,探讨了Sc(Ⅲ)和Fe(Ⅲ)的分离可能性。用斜率法确定了萃合物组成和萃取反应机理,并研究了萃合物的IR、NMR谱,求得了萃取反应的平衡常数和热力学函数。     

二（2,4,4—三甲基戊基）膦酸萃取分离稀土元素（Ⅲ）的研究

本文研究了二（２，４，４－三甲戊基）膦酸的煤油溶液在不同介质中对三价混合稀土的萃取分离性能，观测了平衡水相酸度对萃取平衡的影响，由酸度曲线求出相邻元素的平均分离系数，并考察了酸度对反萃取平衡的影响，比较了ＨＣｌ和ＨＮＯ３介质中，Ｃｙａｎｅｘ２７２混合稀土（Ⅲ）的萃取性能。     

二—（2,4,4—三甲基戊基）膦酸浸渍树脂分离Tb^3＋,Dy^3＋,Ho^3＋,Er^3＋的研究

研究了大孔风状树脂ＸＡＤ－Ｒ,ＸＡＤ－７,ＸＡＤ－１１８０对二－（２,４,４－三甲基戊基）膦酸浸渍树脂的吸附及制备方法,并对Ｃｙａｎｅｘ５７１浸渍树脂分离稀土的性能进行了研究,发现在盐酸介质中Ｃｙａｎｅｘ５７１／ＸＡＤ－７具有最强的萃取能力,树脂中的萃取剂含量在０．３５－０．４５ｇ．ｇ＾－１时,其萃取性能最好,将上述浸渍树装入色层柱对稀土元素进行了分离,且降低负载量和流速分离效果量好。     

以双(2,4,4-三甲基戊基)膦酸为流动载体的乳状液膜分离汞与常见离子的研究

用双(2,4,4-三甲基戊基)膦酸-Span 80-甲苯乳状液膜体系研究了汞的迁移行为,确定了用此种乳状液膜迁移分离汞的适宜条件,汞在5min内可迁移96％以上。在同样条件下,一些常见过渡金属离于如Co~(2+)、Ni~(2+)、Cu~(2+)、Cd~(2+)等通过此乳状液膜的迁移率很低,因此汞可与这些元素得到很好的分离。     

二(2,4,4-三甲基戊基)单硫代膦酸-上胺205-正庚烷乳状液膜萃取分离钪(Ⅲ)、铁(Ⅲ)和镥(Ⅲ)

本文研究了外水相ｐＨ值、流动载体浓度、表面活性剂浓度、内相解析酸浓度、水乳比、油内比等因素对二（２，４，４－三甲基戊基）单硫代膦酸（Ｃｙａｎｅｘ３０２）－上胺２０５－正庚烷乳状液 膜迁移Ｓｃ（Ⅲ）的影响。在一定条件下，Ｓｃ（Ⅲ）可以快速而完全地迁移，有可能实现Ｓｃ（Ⅲ）与Ｆｅ（Ⅲ）、Ｌｕ（Ⅲ）的分离。     

二(2,4,4-三甲基戊基)膦酸-上胺205-正庚烷乳状液膜分离钪(Ⅲ)、铁(Ⅲ)和镥(Ⅲ)

本文研究了二（2，4，4-三甲基戊基）膦酸（Cyanex272）-上胺205-正庚烷乳状液膜分离Sc（Ⅲ）、Fe（Ⅲ）和Lu（Ⅲ）。考察了外相酸度、表面活性剂浓度、流动载体浓度及内相盐酸浓度对Sc（Ⅲ）迁移的影响。并探讨了该液膜体系分离Sc（Ⅲ）、Fe（Ⅲ）和Lu（Ⅲ）的可能性，结果表明，该体系对于稀土矿中Sc（Ⅲ）的分离与分析有良好的应用前景。     

二(2,4,4-三甲基戊基)膦酸在中空纤维膜器中萃取镱、铒及传质研究

中空纤维膜萃取技术是将液液萃取过程与膜过程相结合的新型分离技术．二（２,４,４三甲基戊基）膦酸（ＨＢＴＭＰＰ,ＨＬ）萃取稀土及其它高价金属离子时所需水相酸度低,反萃容易,加之空间位阻等因素,很可能成为优于２乙基己基膦酸单２乙基己基酯（ＨＥＨ／...     

二（2,4,4—三甲基戊基）膦酸萃取Er（Ⅲ）的动力学

用新型恒界面池法首次研究了二（２，４，４－三甲基戊基）膦酸在盐酸介质中萃取Ｅｒ（Ⅲ）的动力学，测定了流体线性流速、有机相浓度、水相浓度和酸度、温度及界面面积等因素对萃取速率的影响，提出其速率方程，求出萃取反应的活化能，并对萃取反应机理进行了探讨．     

二（2,4,4—三甲基戊基）膦酸从盐酸介质中萃取钍（Ⅳ）的机理

研究了二（２，４，４－三甲基戊基）膦酸的正辛烷溶液从盐酸介质中萃取钍的机理。在未控制离子强度下，萃取平衡反应为：Ｔｈ＾４＋＋Ｃｌ＾－＋３（ＨＡ）２（ｏ）→ＴｈＣｌＡ３（ＨＡ）３（ｏ）＋３Ｈ＾＋。在控制离子强度为１．０ｍｏｌ／Ｌ时，萃取反应为Ｔｈ＾４＋＋２Ｃｌ＾－＋３（ＨＡ）２（Ｏ）→ＴｈＣｌ２Ａ２．（ＨＡ）４（Ｐ）＋２Ｈ＾＋。用饮和法确定的萃合物组成为ＴｈＣｌＡ３．计算了萃取反应的平衡常数及热力学     

Cyanex272-P507浸渍树脂协同萃取色层分离铥镱镥的研究

以Cyanex272-P507浸渍树脂采用萃取色层法对铥镱镥富集物进行了吸附和淋洗分离研究,考察了淋洗剂浓度、稀土负载量、淋洗液流速等因素对分离铥镱镥富集物的影响。结果表明,在充填的树脂粒度为0.3~0.6 mm的色层柱中,以0.2 ml.cm-2.min-1进料流速时能得到较大的吸附率;在稀土负载量为树脂重量的0.6%,淋洗液流速为1.0 ml.cm-2.min-1,温度为30℃,装柱树脂高度为400 mm(高径比为25∶1)的条件下,用1.0,1.5,2.0 mol.L-1盐酸梯度淋洗Tm,Yb,Lu,可实现铥镱镥富集物三者的完全分离。     

二-(2-乙基己基)磷酸与仲壬基苯氧基取代乙酸混合体系对稀土元素的萃取

考察了二-(2-乙基己基)磷酸(D2EHPA,H2A2)和仲壬基苯氧基取代乙酸(CA100,H2B2)混合体系在HCl介质中对15种镧系元素(除钷)及钇的萃取性能,计算了稀土元素间的分离系数,并比较了混合萃取体系与D2EHPA单独萃取体系对稀土元素的分离能力.研究了D2EHPA-CA100混合体系对镧的协同萃取机理,用斜率法和恒摩尔法探讨了萃取反应方程式,考察了酸度、萃取剂浓度及温度对萃取性能的影响.结果表明:D2EHPA-CA100混合体系对镧系元素的协同效应随原子序数的增加而减弱.在适当的萃取剂配比下,此混合体系对某些稀土元素的分离能力优于D2EHPA,可用于这些稀土元素的分离.D2EHPA-CA100混合体系协同萃取镧的萃合物组成为LaH5A6B2,反应为吸热反应.     

On the interaction of metal extractant reagents. Investigation of the aggregation ofdi(2,4,4-trimethylpentyl)phosphinic acid anddi(n-octyl)phosphinic acid in toluene by vapour-pressure osmometry

Summary The aggregation equilibria ofdi(2,4,4-trimethylpentyl)phosphinic acid (HDTMPP) anddi(n-octyl)phosphinic acid (HDOP) dissolved in toluene have been investigated by vapour-pressure osmometry (VPO) at different temperatures. The experimental data have been treated both graphically and numerically, and the average aggregation numberñ as well as the aggregation constant have been determined. The results suggest that dimers are formed and that the dimerization constant decreases with temperature. Finally, the enthalpies for the aggregation ofdi(2,4,4-trimethylpentyl)phosphinic acid anddi(n-octyl)phosphinic acid in toluene have been estimated using thevan't Hoff equation.

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Über die Wechselwirkung metallextrahierender Reagentien. Untersuchung der Aggregation vondi-(2,2,4-Trimethylpentyl)-phosphinsäure unddi-(n-Octyl)-phosphinsäure in Toluol mittels Dampfdruckosmometrie

Zusammenfassung Die Aggregationsgleichgewichte von in Toluol gelösterdi-(2,4,4-Trimethylphentyl)-phosphinsäure (HDTMPP) unddi-(n-Octyl)-phosphinsäure (HDOP) wurden mittels Dampfdruckosmometrie (VPO) bei verschiedenen Temperaturen untersucht. Die experimentellen Daten wurden sowohl graphisch als auch numerisch ausgewertet; es wurden sowohl die mittlere Aggregationszahlñ als auch die Aggregationskonstante bestimmt. Die Resultate lassen vermuten, daß Dimere gebildet werden und die Dimerisationskonstante mit der Temperatur abnimmt. Mit Hilfe dervan't Hoffschen Gleichung wurden die Enthalpien der Aggregation vondi-(2,4,4-Trimethylpentyl)-phosphinsäure unddi-(n-Octyl)-phosphinsäure in Toluol abgeschätzt.

     

阻燃剂2-羧乙基苯基次磷酸的合成方法改进

以三氯化磷、苯、三氯化铝、氯化钠、丙烯酸为原料合成了阻燃剂2-羧乙基苯基次磷酸,收率69.2%。考察了原料摩尔比、加料顺序、反应温度、反应时间、置换剂等对反应结果的影响。     

Extraction of cobalt (II) and nickel (II) by a solvent impregnated resin containing bis(2,4,4-trimethylpentyl)monothiophosphinic acid

In the present work, studies have been conducted on the equilibrium distribution of cobalt (II) and nickel (II) between aqueous hydrochloric solution and macromolecular resin impregnated with bis(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex302, HL). Effects of extraction time, pH values, metal ion concentration, and temperature were investigated. Analysis of the results shows that the extraction of the two metal ions can be explained assuming the formation of metal complexes in the resin phase with a general composition ML ₂. An extraction reaction is proposed and the equilibrium constants of the complexes were determined. The Freundlich isotherm and thermodynamic quantities, i.e., ΔG, ΔH and ΔS were also obtained. Both of the extraction reactions of cobalt (II) and nickel (II) are endothermic ones. The efficiency of the resin in the separation of cobalt (II) and nickel (II) is provided according to the separation factors. Under the experimental conditions employed, pH₅₀ values for cobalt (II) and nickel (II) are 3.76, 5.01, respectively. The logarithmic value of separation factor was calculated as 2.50.     

二（2-乙基己基）二硫代磷酸溶剂萃取铊的热动力学

在Tl₂SO₄＋Na₂SO₄＋二（2-乙基己基）二硫代磷酸＋n-C₈H₁₈＋水体系中， 测定了0.1－2.0 mol•kg^－1离子强度范围内Tl^＋ 的平衡摩尔浓度。水相中电解质Na₂SO₄ 控制溶液离子强度， 有机相中萃取剂取278.15 K至303.15 K范围内的恒定摩尔浓度。通过外推法和多项式近似得到了不同温度下的标准萃取常数K⁰，计算了萃取过程的热动力学量。     

Solvent-Impregnated Resins Based on the Mixture of (2-Diphenylphosphoryl)-4-ethylphenoxy)methyl) diphenylphosphine Oxide and Ionic Liquid for Nd(III) Recovery from Nitric Acid Media

Novel solvent-impregnated resins (SIRs) were prepared by treatment of styrene–divinylbenzene copolymer (LPS-500) with mixtures of the promising polydentante extractant (2-diphenylphosphoryl)-4-ethylphenoxy)methyl)diphenylphosphine oxide (L) and an ionic liquid [C₄mim]⁺[Tf₂N]⁻for the extraction chromatography recovery of Nd(III) from nitric acid solutions. It was shown that introduction of the ionic liquid into the SIR composition results in considerable enhancement of the Nd(III) recovery efficiency compared with resin impregnated only by L in slightly acidic media. The influence of the L: ionic liquid molar ratio in the SIRs composition, their percentages, concentration of metal and HNO₃ in the eluent, and acid type on the value of synergistic effect and adsorption efficiency of Nd(III) recovery was studied. The SIR containing 40% of mixture of L and [C₄mim]⁺[Tf₂N]⁻ with molar ratio 2:1 turned out to be the most efficient. The selectivity of Nd(III) separation from light and heavy rare-earth elements was studied and the optimal conditions of Nd(III) adsorption recovery and stripping by this SIR were chosen. It was found that in recovery efficiency of Nd(III) developed SIR exceeded the SIR containing Cyanex 923 (a mixture of monodentate trialkylphosphine oxides) and [C₄mim]⁺[Tf₂N]⁻.