H2C2O4对TODGA萃取Nd3+的影响

以N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)为代表的酰胺荚醚类萃取剂可以有效萃取高放废液中的An(Ⅲ)和Ln(Ⅲ),为防止Zr⁴⁺、Pd²⁺等裂片元素萃入有机相,通常需要加入H₂C₂O₄作为水相络合剂,目前,H₂C₂O₄对TODGA萃取Ln(Ⅲ)的影响尚未报道。本工作研究了HNO₃、H₂C₂O₄浓度对TODGA或TODGA+TBP体系萃取Nd³⁺的影响,同时测定了有机相中的H₂C₂O₄浓度,并用紫外-可见吸收光谱分析了有机相中的H₂C₂O₄与有机相中Nd³⁺的配位情况。研究结果表明：HNO₃浓度在1.0~3.0 mol/L的范围内,Nd³⁺的分配比D(Nd³⁺)随HNO₃浓度的增加而增加;H₂C₂O₄浓度在0.1~0.5 mol/L的范围内,D(Nd³⁺)随H₂C₂O₄浓度的增加而增加。HNO₃浓度在1.0~3.0 mol/L的范围内,萃入有机相中H₂C₂O₄浓度随HNO₃浓度的增加而减小,且存在于有机相中的H₂C₂O₄并未与有机相Nd³⁺配位。     

用于锕系元素提取分离的萃取剂——TiAP

对磷酸三异戊酯(TiAP)和磷酸三丁酯(TBP)萃取体系的物理性质、萃取能力、耐辐照等方面进行了比较,结果表明,TiAP作为萃取剂在物理性质、萃取Pu(Ⅳ)和Np(Ⅳ)的能力以及辐照稳定性能等方面明显好于TBP。提出TiAP是一种很好的并有可能用于锕系元素提取分离的萃取剂。     

硫酸铀酰体系中混合萃取剂的研究

试验考察了以7301,TBP,P204和醋酸丁脂 煤油组成的混合萃取体系对硫酸铀酰的萃取情况,同时分别考察了7301,TBP,P204和醋酸丁脂各组分对铀纯化效果的影响。通过小型试验、台架试验和扩大试验,筛选出混合萃取体系的最佳组成,同时确定了以黄饼为原料制备核电级U3O8的工艺流程和工艺参数。试验结果表明:醋酸丁脂虽有助于两相的分离,但溶解损失过大,不宜用作相改良剂;阳离子萃取剂P204可萃取一定量的阳离子杂质,不宜加入;中性分子萃取剂TBP与三脂肪胺一同使用时,其相改良剂的作用优于传统的高碳醇,需要加入;阴离子萃取剂7301可以萃取硫酸铀酰溶液中呈阴离子状态的UO2(SO4)32-。最终确定新混合萃取体系为7301 TBP的煤油溶液。     

DHDECMP-TBP/煤油萃取 HNO_3-稀土过程中防止形成第二有机相的研究

研究了ＤＨＤＥＣＭＰ－ＴＢＰ／煤油萃取ＨＮＯ３后形成和防止形成第二有机相的各影响因素。以Ｇｄ代表稀土，探讨了ＤＨＤＥＣＭＰ－ＴＢＰ／煤油萃取稀土时ＤＨＤＥＣＭＰ浓度、ＴＢＰ浓度、水相ＨＮＯ３浓度和温度对有机相萃取负载量的影响。结果表明：０．６０ｍｏｌ／ＬＤＨＤＥＣＭＰ－１．４０ｍｏｌ／ＬＴＢＰ／煤油能有效避免第二有机相的形成，又能满足工艺负载量的要求。     

TBP对N,N-二丁基辛酰胺萃取铀的影响

研究了Ｎ,Ｎ－二丁基辛酰胺从硝酸介质中萃取铀的机理,考察了水相酸度,盐析剂ＬｉＮＯ３浓度以及萃取剂浓度对萃取分配比的影响。结合红外光谱分析了萃合物结构。ＴＢＰ对ＤＢＯＡ萃取铀的影响比较复杂,在低ＴＢＰ浓度下,两种萃取剂具有协同效应,但随着ＴＢＰ浓度的增大出现反协同效应。     

Extraction of Some Elements by Mixture of DIDPA-TBP and Its Application to Actinoid Partitioning Process

Effect of TBP on the extraction of Pu(IV), Zr(IV), Nb(V), Nd(III) and Am (III) was studied with diisodecylphosphoric acid(DIDPA) as an extractant. Hydrolyzable elements contained in the high-level liquid waste of fuel reprocessing,i.e. Pu(IV), Zr(IV) and Nb(V), could be extracted with mixtures of DIDPA and TBP of different compositions. Addition of TBP to DIDPA causes an increase and a decrease of respectively distribution rate and ratio of Zr(IV). These elements extracted were completely stripped with the aid of oxalic acid. An effect of TBP on separation of transplutonides (III) from lanthanoids(III) in the DIDPA and DTPA extraction system was also studied.

Based on the results, a process flow sheet utilizing the extractant of DIDPA and TBP mixture was contrived for partitioning actinoids in the high-level liquid waste.     

Separation of Actinide Elements by Solvent Extraction Using Centrifugal Contactors in the NEXT Process

Using the advanced aqueous reprocessing system named NEXT process, actinides recovery was attempted by both a simplified solvent extraction process using TBP as an extractant for U, Pu and Np co-recovery and the SETFICS process for Am and Cm recovery from the raffinate. In U, Pu and Np co-recovery experiments a single cycle flow sheet was used under high nitric acid concentration in the feed solution or scrubbing solution. High nitric acid concentration in the feed solution aided Np oxidation not only in the feed solution, but also at the extraction section. This oxidation reaction accomplished Np extraction by TBP with U and Pu. Most of Np could be recovered into the product solution. In the SETFICS process, a TRUEX solvent of 0.2 mol/dm³ CMPO and 1.4 mol/dm³ TBP in n-dodecane was employed instead of 0.2 mol/dm³ CMPO and 1.0 mol/dm³ TBP in n-dodecane in order to increase the loading of metals. Instead of sodium nitrate, hydroxylamine nitrate was applied to this experimental flow sheet in accordance with a “salt-free” concept. The counter current experiment succeeded with the Am and Cm product. On the high-loading flow sheet, compared with the previous flow sheet, the flow of the aqueous effluents and spent solvent were expected to decrease by about one half. Two solvent extraction experiments for actinides recovery demonstrated the utility of the flow sheet of these processes in the NEXT process.     

甲醛肟在Purex流程铀钚分离中的应用

为了进一步优化Purex流程,研究了甲醛肟（FO）的硝酸水溶液对30%TBP/煤油中Pu(Ⅳ)的还原反萃取行为,考察了FO浓度、两相接触时间、两相相比、反萃液硝酸浓度、NO₃^-浓度、有机相U浓度和温度对Pu(Ⅳ)的还原反萃的影响。结果表明：延长两相接触时间能显著提高Pu(Ⅳ)的反萃率,增加甲醛肟的浓度、降低反萃液酸度、降低NO₃^-浓度、增加有机相U浓度和升高温度也对Pu(Ⅳ)的反萃率有一定的提高。采用16级逆流反萃取实验（还原反萃段12级,补充萃取段4级）,模拟Purex流程1B槽U/Pu分离工艺,在相比（1BF∶1BX∶1BS）为4∶1∶1的条件下,U和Pu 的回收率均大于99.99%;铀中去钚的分离因子SF(Pu/U)＝1.0×10⁴;钚中去铀的分离因子SF(U/Pu)＝8.3×10⁴。FO作为新型络合 还原反萃取剂,可有效实现铀钚分离。     

Extraction of Thorium and Uranium from Chloride Solutions by Tri-n-Butyl Phosphate and Tri-n-Octyl Phosphine Oxide

The extraction of thorium and uranium chlorides by TBP and TOPO was studied. The composition of complexes extracted from the chloride solutions of low acid concentration was established by partition study to be UO₂Cl₂ (TOPO)₂, UO₂Cl₄ (TOPO)₂, UO₂Cl₄ (TOPO)₂ and UCl₄ (TBP)₂. Composition of the thorium complex in the TBP phase free from hydrochloric acid was revealed by infrared study to be ThCl₄ (TBP)4. The extraction behavior of thorium chloride by TBP was different from that of U (N) and Pu(N) chloride, and the composition of the complex was presumed to be HThCl₅(TBP)₄ in the extraction from concentrated chloride solution containing hydrochloric acid.     

Extraction properties of diisoamyl methylphosphinite

The properties of one of the new, efficient extractants for uranium, diisoamyl methylphosphinate (DAMP), are described. It was shown that uranyl nitrate is extracted from nitric acid solutions by this extractant with considerably higher distribution coefficients than tributyl phosphate (TBP). The extraction of uranyl nitrate and HNO³ with DAMP solutions in hydrogenated kerosene was studied. It was shown that uranyl nitrate is extracted in the form of the complex [UO₂(NO₃)₂ (DAMP)₂], whose stability constant equals 2540±200, and HNO₃ is extracted in the form of the compound HNO₃ DAMP, whose stability constant is 0.30±0.03.     

Solvent Extraction of Pentavalent Neptunium with n-Octyl(phenyl)-N,N-Diisobutyl- carbamoylmethylphosphine Oxide

Solvent extraction of Np(V) from HNO₃ solution was experimentally studied with n-octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) as an extractant mixed with TBP and n-dodecane. In the low HNO₃ concentration, the Np(V) is weakly extractable, but effectively extracted in the high HNO₃ concentration (>4M) due to the disproportionation of Np(V) to Np(IV)and Np(VI). The distribution ratio of Np was increased by use of H₂O₂as a reductant of Np(V). More than 95% of Np was extracted with 0.8 M H₂O² in 2.2 M HNO₃ solution. It was shown that most of the Np extracted is in tetravalent state as expected from redox mechanism. The Np(IV) extracted in the organic phase was effectively stripped to the aqueous phase with H₂C₂O₄.     

γ辐照30%三烷基氧化膦-煤油体系萃取乳化的研究

研究了γ辐射三烷基氧化膦（TRPO）的乳化性能，实验表明，萃取水相酸度的增加，有利于去乳化作用。γ辐射对305TRPO－煤油－硝酸体系的乳化作用有显著影响，不同厂家生产的TRPO具有不同的乳化性能。γ辐照的磷酸三丁酯(TBR)－煤油－硝酸体系较TRPO－煤油－HNO3体系分相和去乳化速度较快。但当用5％Na2CO3溶液洗涤上述两个体系时，TBP－煤油体系有机相去乳化速度较慢，其平衡水相有乳化现象，而TRPO－煤油体系虽分相慢，但分相后有机相的去乳化速度较快，其平衡水相无乳化现象。     

HNO3-H2C2O4体系中Np和Pu的分离研究

研究了30％TBP-煤油在不同的硝酸-草酸混合溶液中对Np,Pu各价态的萃取分配,在HNO     

Me-TODGA与TODGA萃取锶性能对比

以N,N,N′,N′-四辛基-2-甲基-3-氧戊二酰胺(Me-TODGA)或N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)为萃取剂、磷酸三丁酯(TBP)为相改良剂、煤油为稀释剂,对比研究了水相酸度、萃取剂浓度、锶浓度、温度对Me-TODGA-TBP体系和TODGA-TBP体系萃取Sr²⁺的影响,并采用斜率法确定了萃合物的组成。结果表明,2种酰胺荚醚萃取Sr²⁺的分配比(D_Sr)随HNO₃浓度(c(HNO₃)=0.1～2.7 mol/L)、萃取剂浓度(c(萃取剂)=0.05～0.3 mol/L)的增加而增大,随Sr²⁺浓度的升高略有下降,随温度的升高而下降。2种萃取剂的萃合物组成分别为Sr(NO₃)2•3Me-TODGA和Sr(NO₃)2•2TODGA。萃取反应的ΔH分别为-69.46 kJ/mol和-51.39 kJ/mol,ΔS分别为-190.5 J/(mol•K)和-128.4 J/(mol•K),ΔG分别为-12.68 kJ/mol和-13.12 kJ/mol。相比之下,Me-TODGA萃取Sr²⁺的分配比不到TODGA的1/5。     

Coextraction of uranium(VI) from nitric acid solutions by N,N-diethyldecanamide and TBP

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Calculation of Distribution Ratios of Rare Earth Elements in Multistage Counter Current Extraction with HDEHP

Extraction of rare earth elements with di (2-ethylhexyl) phosphoric acid (HDEHP) - tributyl-phosphate (TBP)-n-paraffin system was studied as functions of concentrations of the quantity of H⁺ released into aqueous phase. The ratio of rare earth elements extracted into organic phase was found to depend on the initial composition of the aqueous solution. The ratios determined for various concentrations of rare earth elements and acid were shown as a linear function of the concentrations of acid in aqueous phase and that of rare earth elements in organic phase after extraction. The acid concentration in aqueous phase after extraction can be estimated from any initial concentrations of acid and rare earth elements in aqueous solution by this equation. Also a graphic process of experimental results could give approximate values of distribution ratio for various initial concentrations of rare earth elements and nitric acid. For calculation of the distribution ratio of each stage in multi-stage counter current extraction, a computation code was programmed on the basis of the graphical process. The calculated values agreed well with those obtained experimentally in multistage extraction.     

Separation of Am(III) from Eu(III) by extraction based on in situ extractant formation of dithiocarbamate derivatives

A new solvent-extraction technique based on in situ formation of dithiocarbamate derivatives in order to separate Am(III) from Eu(III) was carried out. In this technique, the extractant is formed during the extraction course by the reaction between the organic materials, which are needed to synthesize the extractant. The synthesis of extractant in in situ extractant-formation method was carried out as follows. Di-substituted amine, such as dioctylamine (DOA), dibenzylamine (DBzA) and so on, and carbon disulfide (CS₂) were mixed in organic solvents, such as nitrobenzene, to produce dioctylammonium dioctyldithiocarbamate (DOA⁺·DODTC⁻), dibenzylammonium dibenzyldithiocarbamate (DBzA⁺·DODTC⁻), or so on. These organic solutions are also the organic phase in the solvent extraction, whereas the aqueous phase is 1.00 mol/dm³ (H, Na)NO₃ solution. The elements of Am(III) and Eu(III) were extracted into organic phase from different hydrogen ion concentrations of aqueous phase. The SF of Am(III)/Eu(III) is 3.2 × 10⁴ at pH_eq = 6.25 in DOA–CS₂/nitrobenzene system. This separation technique of Am(III) from Eu(III) by extraction based on in situ extractant formation has the following advantages. (a) It is unnecessary to take the chemical stability of extractant into account for storage purpose, and (b) Am(III) can be completely separated from Eu(III) by a single extraction procedure.     

亚硝酸分配比测定及其初步模拟计算

Purex流程的计算机模拟研究有助于流程的优化和改进。HNO2不可避免地存在于Purex流程中,影响许多重要核素的萃取,因此需要建立HNO2的分配比模型,以完善Purex流程计算机模拟程序。采用酸碱滴定法和重氮偶联法同时测定了平衡水相和有机相中HNO3和HNO2的浓度,进而获得分配比数据。在研究范围内,水相HNO2浓度对HNO2和HNO3的分配比影响不明显。水相HNO3浓度升高,HNO2的分配比下降,而HNO3的分配比先升高后下降。有机相中TBP浓度升高,HNO2和HNO3的分配比均增加。初步建立了HNO2分配比与水相酸度和自由TBP的关联式,计算结果与实验值比较吻合。     

Thorex流程钍铀分离工艺单元计算机模拟研究

在Th(NO₃)₄-UO₂(NO₃)₂-HNO₃-H₂O/30%TBP-正十二烷分配比模型的基础上,使用串级萃取理论编写了Thorex流程钍铀分离工艺单元(1B)的计算机模拟程序,该程序可对钍、铀、硝酸的萃取行为进行模拟计算。通过文献数据对该程序的可靠性进行了验证,结果表明,该程序的计算值与文献值符合良好。在此基础上利用该模拟程序对钍铀分离单元的工艺参数进行了计算分析,结果表明：工艺运行状况受工艺参数的综合影响,其中反萃液(1BX)硝酸浓度是影响因素之一,铀产品(1BU)中钍含量随酸度的增大而增大,而钍产品(1BT)中铀含量则随酸度的增大而降低,酸度过大或过小均不能实现二者的良好分离;1BX流比对分离效果的影响与酸度相反,随着1BX流比的增大,1BU中钍含量显著降低,而1BT中铀含量增大;补萃剂(1BS)流比对分离效果的影响与1BX流比的影响趋势相反,因此在工艺寻优中可利用本程序选择分离效果最好的条件组合。此外,还可利用本程序进行其他工艺要求的钍铀分离工艺参数寻优计算等。     

Fundamental Study on Separation of Uranium from Other Metals by Solvent Extraction with Tributylphosphate or Tributylphosphine Oxide in Molten Naphthalene

The extraction behaviors of U and other metals has been studied as functions of the concentration of nitric acid or hydrochloric acid in aqueous media and as functions of the amount of naphthalene as diluents, when tributylphosphine oxide (TBPO) or tributylphosphate (TBP) was used as a extractant. Uranium could be quickly extracted over 95% from 25 cm³ of the 1 mol·dm^?3 nitric acid solution with 150 mg of TBPO and 350 mg of naphthalene at 80°C. On the other hand, about 80% of U could be extracted under better conditions, when 25 cm³ of 4 mol·dm^?3 nitric acid solution and 1cm³ of TBP and 3 g of naphthalene were used. In either case, the extraction phases could be easily separated as a solid by cooling to room temparature. Uranium could be separated from alkaline earth metals, transition metals and rare earth metals, and U was efficiently concentrated by extraction with molten naphthalene, compared with usual solvent extraction which used toluene, etc.