Uranium complexes enrichment

A comprehensive review of uranium determinations in sea water was given by Rogers and Adams. Ocean water contains uranium at a broadly uniform concentration (0.001-0.004 ppm). The average uranium concentration in stream water is less than 1 ppb U. Groundwater shows remarkable variability of concentration as a result of, for example, the presence of enriched mineralization, the time of contact of the water with the source rocks and the concentration of ligands that either form soluble uranium complexes or insoluble uranium compounds. 

Uranium ores are leached with dilute sulfuric acid or an alkaline carbonate [3812-32-6] solution. Hexavalent uranium forms anionic complexes, such as uranyl sulfate [56959-61-6], U02(S0 3, which are more selectively adsorbed by strong base anion exchangers than are other anions in the leach Hquors. Sulfate complexes are eluted with an acidified NaCl or ammonium nitrate [6484-52-2], NH NO, solution. Carbonate complexes are eluted with a neutral brine solution. Uranium is precipitated from the eluent and shipped to other locations for enrichment. Columnar recovery systems were popular in South Africa and Canada. Continuous resin-in-pulp (RIP) systems gained popularity in the United States since they eliminated a difficult and cosdy ore particle/leach hquor separation step. 

In TBP extraction, the yeUowcake is dissolved ia nitric acid and extracted with tributyl phosphate ia a kerosene or hexane diluent. The uranyl ion forms the mixed complex U02(N02)2(TBP)2 which is extracted iato the diluent. The purified uranium is then back-extracted iato nitric acid or water, and concentrated. The uranyl nitrate solution is evaporated to uranyl nitrate hexahydrate [13520-83-7], U02(N02)2 6H20. The uranyl nitrate hexahydrate is dehydrated and denitrated duting a pyrolysis step to form uranium trioxide [1344-58-7], UO, as shown ia equation 10. The pyrolysis is most often carried out ia either a batch reactor (Fig. 2) or a fluidized-bed denitrator (Fig. 3). The UO is reduced with hydrogen to uranium dioxide [1344-57-6], UO2 (eq. 11), and converted to uranium tetrafluoride [10049-14-6], UF, with HF at elevated temperatures (eq. 12). The UF can be either reduced to uranium metal or fluotinated to uranium hexafluoride [7783-81-5], UF, for isotope enrichment. The chemistry and operating conditions of the TBP refining process, and conversion to UO, UO2, and ultimately UF have been discussed ia detail (40). 

Uranium hexafluoride [7783-81-5], UF, is an extremely corrosive, colorless, crystalline soHd, which sublimes with ease at room temperature and atmospheric pressure. The complex can be obtained by multiple routes, ie, fluorination of UF [10049-14-6] with F2, oxidation of UF with O2, or fluorination of UO [1344-58-7] by F2. The hexafluoride is monomeric in nature having an octahedral geometry. UF is soluble in H2O, CCl and other chlorinated hydrocarbons, is insoluble in CS2, and decomposes in alcohols and ethers. The importance of UF in isotopic enrichment and the subsequent apphcations of uranium metal cannot be overstated. The U.S. government has approximately 500,000 t of UF stockpiled for enrichment or quick conversion into nuclear weapons had the need arisen (57). With the change in pohtical tides and the downsizing of the nation s nuclear arsenal, debates over releasing the stockpiles for use in the production of fuel for civiUan nuclear reactors continue. 

This removal may also include diffusion of soluble U(VI) from seawater into the sediment via pore water. Uranium-organic matter complexes are also prevalent in the marine environment. Organically bound uranium was found to make up to 20% of the dissolved U concentration in the open ocean." ° Uranium may also be enriched in estuarine colloids and in suspended organic matter within the surface ocean. " Scott" and Maeda and Windom" have suggested the possibility that humic acids can efficiently scavenge uranium in low salinity regions of some estuaries. Finally, sedimentary organic matter can also efficiently complex or adsorb uranium and other radionuclides. 

Although not part of soil, lichens, by virtue of their solubilising action on rocks, contribute to the elemental enrichment of soil. Several studies have identified lichen acids as complexing agents for the iron and aluminium of rocks (95, 96). An examination of the various structures indicates that the basic structure responsible for the chelation is the carboxylic acid group with an orthophenolic group. Grodzinskii (97) has found lichens to be intense accumulators of elements in the uranium-radium, actinouranium and thorium orders. 

The stoichiometry of the complexes between HDBP and U(VI) changes with the acidity, that is, at high nitric acidity, the presence of [U02(N03)2(HDBP)TBP] and [U02(N03)2(HDBP)2], and at low nitric acidity, the forms [U02(N03)(DBP)(HDBP)J, [U02(DBP)2(HDBP)J (where x = 1 or 2) dominate. The presence of such complexes can explain the difficulties in U(VI) recovery (114, 115, 120). Otherwise, various authors have indicated the presence of insoluble compounds for enriched uranium solutions (121-124). Recently, Powell identified the solid forms with various spectroscopic methods at lower acid concentrations, the well-characterized polymer U02(DBP)2 precipitates as a yellow powder, whereas a sticky solid or gels are formed at high acidity. The global formula is U02(N03)(H(DBP)2)(HDBP)2 (106). 

Bukharin, Oleg, Russia s Gaseous Centrifuge Technology and Uranium Enrichment Complex, Program on Science and Global Security, Woodrow Wilson School of Public and International Affairs, Princeton University, January 2004. 

Uranium is a heavy metal that forms compounds and complexes of different varieties and solubilities. The chemical action of all isotopes and isotopic mixtures of uranium is identical, regardless of the specific activity (i.e., enrichment), because chemical action depends only on chemical properties. Thus, the chemical toxicity of a given amount or weight of natural, depleted, and enriched uranium is identical. 

Seawater Uranium enriched by chelation with APDC in the presence of Fe", complexation with APDC followed by adsorption on activated carbon X-ray fluorescence (total uranium) 0.56-0.64 pg/L No data Nagj et al. 1986... 

In the reduction stripping process uranium(IV) in the raw wet process acid is oxidized to uranium(Vl) by treatment with sodium chlorate, hydrogen peroxide or air at 60 to 70°C, the uranium(VI) formed being extracted with trioctylphosphine oxide/di-(2-ethylhexyl)phosphate in kerosene and the resulting solution finally reductively stripped repeatedly with aqueous iron(II) solutions. This results in an enrichment by a factor of 40. After oxidation of the stripped solution with sodium chlorate or ambient oxygen and renewed extraction of the uranium(VI) formed with trioctylphosphine oxide/di-(2-ethylhexyl)phosphate, the phosphoric acid is removed from the organic phase by washing. The uranium(Vl) is then stripped with ammonium carbonate and precipitated as the ammonium diuranyl-tricarbonato-complex. This is filtered off, washed and calcined. 

Kazakhstan has a nuclear scientific-industrial complex which was set up as a part of a nuclear infrastructure of the former USSR. More than 50% of the uranium resources of the former Soviet Union are in Kazakhstan, with seven uranium mines. Two UO2 plants produced up to 35% of the total uranium in the USSR in 1990. There are extensive facilities for producing UO2 pellets for VVER fuel elements from Russian enriched uranium. Kazakhstan has several research reactors and one operating nuclear power plant, the BN-350 fast reactor, which started operation in 1973 with a design life of 20 years. Work on its lifetime extension has the intention of bringing it into compliance with current safety standards. 1995 and 1996 were devoted to this work. In October 1996. experimental investigation on accident-proofdecay heat removal by natural circulation was carried out. The reactor BN-350 was restarted in February 4, 1997 at a power level of 420 MW(th). 

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