大块液膜技术处理含六价铬废水

以磷酸三丁酯(TBP)为载体,煤油为稀释剂,NaOH为反萃剂,采用大块液膜技术处理含95~100mg/LCr(VI)的模拟废水。考察了液膜相用量、载体体积分数及反萃剂浓度对大块液膜过程中Cr(VI)传质过程的影响。结果表明,大块液膜技术对废水中Cr(VI)的去除效果较好。Cr(VI)迁移速率随TBP体积分数的提高而加快。当反萃剂NaOH浓度大于0.5mol/L时,反萃剂浓度对Cr(VI)传质过程的影响较小。处理后废水中Cr(VI)含量降至0.5mg/L以下,达到国家排放标准。     

梯形波脉冲筛板萃取柱传质性能

本文以UO_2(NO_3)_2—30％TBP(KO)为实验体系,进行了梯形波脉冲筛板柱传质性能的研究。实验中测量了两组分的两相稳态浓度剖面共13组,以扩散模型为基础,求得了梯形波脉冲柱的“真实”传质单元高度HTU_(ox),分散单元高度HDU及表观传质单元高度HTU_(oxp)。通过对实验结果进行分析,选择出了适于本实验体系的较好的操作条件。     

锝的TBP萃取化学行为研究

报道了在硝酸体系中用３０％ＴＢＰ－正十二烷萃取Ｔｃ（Ⅶ）的实验结果。详细研究了硝酸、硝酸铀酰、硝酸铀（Ⅳ）、硝酸铵、亚硝酸钠、硝酸锆、硝酸钚、硝酸铈，亚硝酰钌、硝酸羟胺、硝酸肼浓度及温度、相比等因素对Ｔｃ（Ⅶ）萃取化学行为的影响。实验结果表明，在不含铀的硝酸体系中，硝酸、硝酸铵、硝酸钚、硝酸锆、硝酸铈、亚硝酸酰钌浓度及萃取温度对Ｔｃ（Ⅶ）的分配比影响很大，而亚硝酸钠、硝酸肼及硝酸羟胺浓度对Ｔｃ（Ⅶ）的分配比影响较小；在含铀的硝酸体系中，硝酸浓度对Ｔｃ（Ⅶ）的分配比有影响，而萃取温度、硝酸钚、锆的影响较小。Ｔｃ（Ⅶ）在含或不含铀的硝酸体系中，与ＴＢＰ分别形成ＵＯ２ＮＯ３·ＴｃＯ４·２ＴＢＰ和ＨＴｃＯ４·３ＴＢＰ萃合物。     

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。     

在UO_2(NO_3)_2-TBP-CCI_4有机相中光化还原制备铀(Ⅳ)的研究

本文的目的是研究在TBP有机相中光化还原铀(Ⅵ)以制备铀(Ⅳ)。选用了高压汞灯作为激发光源,CCl_4为TBP的稀释剂。研究了反应温度、原始水相溶液组成等因素对铀(Ⅳ)产额和亚硝酸生成量的影响。推荐了制备铀(Ⅳ)的适宜条件。     

磷酸三丁酯和磷酸二丁酯与Pu(Ⅳ)配合物的密度泛函研究

采用B3LYP密度泛函方法,Pu(Ⅳ)和其他原子分别采用相对论有效原子实势(RECP)和6-311g(d,p)全电子基组,研究了Pu(NO3)4TBP2和Pu(NO3)2DBP2的几何结构、热力学参数及紫外可见光谱。几何结构计算结果表明,由于配体空间位阻的影响,Pu与DBP的键长更短,自然布居分析(NPA)结果也表明,Pu与DBP之间的电荷转移更多,因此二者之间相互作用更强。热力学分析显示,Pu(NO3)4TBP2与HDBP发生配体交换的反应自由能为-178.9kJ/mol,说明DBP与Pu之间的相互作用更强。Pu(NO3)4TBP2的紫外吸收光谱主要来源于硝酸根到Pu的f轨道的跃迁,TBP贡献不大;而Pu(NO3)2DBP2的跃迁同时来源于硝酸根和DBP到Pu的f轨道的配体-金属电荷转移跃迁(LMCT)。     

石油馏分三种蒸馏曲线数学模型的研究

石油馏分三种蒸馏曲线换算的经验计算图表,依然是炼油工业设计、生产和科研中广泛使用的计算方法。但文献中有关石油馏分三种蒸馏曲线相关模型形式复杂、相对误差大,只能单向换算。本文研究了石油馏分的恩氏蒸馏曲线分别与实沸点蒸馏曲线、平衡汽化蒸馏曲线各段温差关系图之后,提出一个形式简单、误差相对小、能双向换算的新数学模型。结果表明:其计算结果与该曲线给出的数值吻合好,计算准确度高,明显优于前人的模型。     

富集渣中铪的TBP萃取分离研究

以铪钛富集渣为原料,经硝酸溶解后采用TBP进行铪的萃取分离试验,主要考察铪钛质量浓度、有机相初始酸度、萃取时间、水相初始酸度、相比等对铪钛分离的影响,同时进行了不同浓度硝酸洗涤试验,以萃取和洗涤得到数据为基础进行了分馏萃取理论级数的计算。结果表明,最优萃取条件为:铪钛总质量浓度2.8g/L、有机相初始酸度3.1mol/L、萃取时间6min、水相初始酸度6.5mol/L、相比1∶1,铪、钛萃取率分别为84.8%和5.1%,铪、钛分配比分别为5.6和0.054,萃取分离系数β_(Hf/Ti)=104。选用10mol/L硝酸洗涤TBP载铪有机相,得到洗涤β_(Hf/Ti)=105,基本与β_(Hf/Ti)保持一致,经计算分馏萃取分离铪钛需要萃取级数3级,洗涤级数4级。     

Recovery of oxalate from scrubbing solution containing rare earths and iron produced during uranium recovery from phosphoric acid

A solution containing oxalate complexes of rare earths, yttrium and iron (III) is obtained during the processing of wet process phosphoric acid for uranium recovery by solvent extraction. A process is described to recover oxalic acid from such a solution. The process is based on the conversion of iron (III) oxalate into calcium oxalate by calcium chloride followed by the metathesis of calcium oxalate with sulphuric acid to produce calcium sulphate and free oxalic acid. Data is presented to illustrate the influence of various parameters such as pH, temperature, digestion time and amount of calcium chloride on effective conversion of calcium oxalate. Under optimized conditions of pH 1, digestion time 2 h, twice the stoichiometric ratio of calcium chloride at ambient temperature (30±1°C) the recovery of calcium oxalate was found to be >94%. An overall schematic material balance flow -sheet for treating the oxalate solution of rare earths, yttrium and iron (III) to oxalic acid recovery has been presented. An improvement in the second cycle of patented process flow-sheet based on 1.5 M D2EHPA + 0.2 M TBP incorporating oxalic acid scrubbing / recycle for uranium recovery from phosphoric acid has been tested and found to be simple in terms of operations and capable of meeting product specifications..     

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.