Precipitation methods uranium separation

The discovery of nuclear fission in 1938 proved the next driver in the development of coordination chemistry. Uranium-235 and plutonium-239 both undergo fission with slow neutrons, and can support neutron chain reactions, making them suitable for weaponization in the context of the Manhattan project. This rapidly drove the development of large-scale separation chemistry, as methods were developed to separate and purify these elements. While the first recovery processes employed precipitation methods (e.g., the bismuth phosphate cycle for plutonium isolation). 

The sucessful experiments for the retention of plutonium onto alumina from TTN0 -HF solution gave enough confidence to recomend the proposed method to separate traces of plutonium from waste solutions in the presence of macroamounts of uranium (VI). Of course, only macroamounts of thorium, uranium (IV) and rare earths are serious interfering ions, since they precipitate with HF. The behavior expected for neptunium in the same system should be similar to plutonium, thorium and rare earths. The retention of neptunium from HNO - HF solutions is in progress. The sorption yield for Pu was around 95%. The sorption mechanism is not well established. Figure 3 shows the proposed flowsheet for recovery of Pu traces from reprocessing waste solutions. 

The various processes available for fuel reprocessing are aqueous solvent extraction, precipitation, ion exchange, fractional distillation, pyrometal-lurgy, and fluoride volatility. Most of the commercial development experience has come from the solvent-extraction method for separation of uranium, plutonium, and fission products. 

In the following paragraphs, the separation of uranium by precipitation, solvent extraction, and Ion exchange are described In some detail. Reference Is made also to other methods of separation chromatography, electrodeposition, volatilization and pyrometallurgy. 

A number of the prooeradiometric determination of wanlum. The method of separation in these procedures, however, is applicable to radiochemical analysis and is, therefore, included. A number of papers and reports describe, in detail, procedures for the determination of uranium. These should be noted. The work of Rodden and Warf has frequently been mentioned in this paper. In addition to procedures for the precipitation, solvent extraction, volatilization, and electrodeposltlon of uranium, these authors have presented a number of selected procedures for the solution of ores and minerals and the separation and determination of uranium. Procedures for the analytical determination in naturally occurring materials have also been described by Hodden and Tregonning,- Grimaldi, May, Fletcher, and Tltcomb, 2Z. Sohoeller and Powell,and in the "Handbook of Chemical Determination of Uranium in Minerals and Ores." 2 The recent publication by Hoore on extraction with amines contains a collection of procedures., many of which have to do with the separation of uranium. 

Initially, the only means of obtaining elements higher than uranium was by a-particle bombardment of uranium in the cyclotron, and it was by this means that the first, exceedingly minute amounts of neptunium and plutonium were obtained. The separation of these elements from other products and from uranium was difficult methods were devised involving co-precipitation of the minute amounts of their salts on a larger amount of a precipitate with a similar crystal structure (the carrier ). The properties were studied, using quantities of the order of 10 g in volumes of... 

The wastes from uranium and plutonium processing of the reactor fuel usually contain the neptunium. Precipitation, solvent extraction, ion exchange, and volatihty procedures (see Diffusion separation methods) can be used to isolate and purify the neptunium. 

Crystallisation was one of the earliest methods used for separation of radioactive microcomponents from a mass of inert material. Uranium X, a thorium isotope, is readily concentrated in good yield in the mother liquors of crystallisation of uranyl nitrate (11), (33), (108). A similar method has been used to separate sulphur-35 [produced by the (n, p) reaction on chlorine-35] from pile irradiated sodium ot potassium chloride (54), (133). Advantage is taken of the low solubility of the target materials in concentrated ice-cold hydrochloric acid, when the sulphur-35 as sulphate remains in the mother-liquors. Subsequent purification of the sulphur-35 from small amounts of phosphorus-32 produced by the (n, a) reaction on the chlorine is, of course, required. Other examples are the precipitation of barium chloride containing barium-1 from concentrated hydrochloric acid solution, leaving the daughter product, carrier-free caesium-131, in solution (21) and a similar separation of calcium-45 from added barium carrier has been used (60). 

Radioactivity of uranium can be measured by alpha counters. The metal is digested in nitric acid. Alpha activity is measured by a counting instrument, such as an alpha scintillation counter or gas-flow proportional counter. Uranium may be separated from the other radioactive substances by radiochemical methods. The metal or its compound(s) is first dissolved. Uranium is coprecipitated with ferric hydroxide. Precipitate is dissolved in an acid and the solution passed through an anion exchange column. Uranium is eluted with dilute hydrochloric acid. The solution is evaporated to near dryness. Uranium is converted to its nitrate and alpha activity is counted. Alternatively, uranium is separated and electrodeposited onto a stainless steel disk and alpha particles counted by alpha pulse height analysis using a silicon surface barrier detector, a semiconductor particle-type detector. 

A general method for the separation of vanadium from arsenic, molybdenum, phosphorus, chromium, uranium, tungsten, and silicon, consists in precipitating these metals as their respective lead salts and digesting the precipitate with potassium carbonate, whereupon all the lead salts are decomposed with the exception of the lead vanadate.5... 

Protactinium (of mass number 231) is found in nature iu all uranium ores, since it is a long-lived member of the uranium series. It occurs in such ores to the extent of about part per million parts of uranium. An efficient method for the separation of protactinium is by a carrier technique using zirconium phosphate which, when precipitated from strongly acid solutions, coprecipitates protactinium nearly quantitatively. Then the protactinium is separated from the carrier by fractional crystallization of zirconium oxychloride. 

Quantitative methods of obtaining protactinium start from the carbonate precipitate from the treatment of the acid extract of certain uranium ores. After this carbonate precipitate is dissolved, the protactinium remains 111 the silica gel residue, from the solution of which it is obtained on a manganese dioxide carrier. An alternate method effects final separation... 

The uranium and thorium ore concentrates received by fuel fabrication plants still contain a variety of impurities, some of which may be quite effective neutron absorbers. Such impurities must be almost completely removed if they are not seriously to impair reactor performance. The thermal neutron capture cross sections of the more important contaminants, along with some typical maximum concentrations acceptable for fuel fabrication, are given in Table 9. The removal of these unwanted elements may be effected either by precipitation and fractional crystallization methods, or by solvent extraction. The former methods have been historically important but have now been superseded by solvent extraction with TBP. The thorium or uranium salts so produced are then of sufficient purity to be accepted for fuel preparation or uranium enrichment. Solvent extraction by TBP also forms the basis of the Purex process for separating uranium and plutonium, and the Thorex process for separating uranium and thorium, in irradiated fuels. These processes and the principles of solvent extraction are described in more detail in Section 65.2.4, but the chemistry of U022+ and Th4+ extraction by TBP is considered here. 

To illustrate three common radiochemical separation techniques - precipitation, solvent extraction, and cation exchange - in parts 7A, 7B, and 1C. These methods separate thorium from its uranium parent. Radionuclide recovery is measured by comparing count rates to the original sample, not by carrier yield determination. 

The ion exchange column separates not only uranium from thorium but a number of other elements. What advantage(s) do you see in the ion exchange procedure relative to the precipitation or the extraction procedure If you were designing a separation scheme, which of the method would you use Why ... 

Drinking water Concentrated by co-precipitation separation clean-up by ion-exchange Gross a-counting (total uranium) 1 pCi/L 92.6% Krieger and Whittaker 1980 (EPA Method 908.0)... 

The radiochemical method quantifies gross a activity utilizing either a gas flow proportional counter or a scintillation detection system following chemical separation. In the EPA radiochemical method, the uranium is co-precipitated with ferric hydroxide, purified through anion exchange chromatography, and converted to a nitrate salt. The residue is transferred to a stainless steel planchet, dried, flamed, and counted for a particle activity (Krieger and Whittaker 1980). 

The EPA developed two methods for the radiochemical analysis of uranium in soils, vegetation, ores, and biota, using the equipment described above. The first is a fusion method in which the sample is ashed, the silica volatilized, the sample fused with potassium fluoride and pyrosulphate, a tracer is added, and the uranium extracted with triisooctylamine, purified on an anion exchange column, coprecipitated with lanthanum, filtered, and prepared in a planchet. Individual uranium isotopes are separately quantified by high resolution alpha spectroscopy and the sample concentration calculated using the yield. The second is a nonfusion method in which the sample is ashed, the siUca volatilized, a tracer added, and the uranium extracted with triisooctylamine, stripped with nitric acid, co-precipitated with lanthanum, transferred to a planchet, and analyzed in the same way by high resolution a-spectroscopy (EPA 1984). 

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