Separation, cesium

Moyer, B.A., Bazelaire, E., Bonnesen, P.V. et al. 2005. Next generation extractants for cesium separation from high-level waste From fundamental concepts to site implementation. FY 2005 Annual Report, Environmental Management Science Program, Project 73803. 

USE OF MACROCYCLES IN NUCLEAR-WASTE CLEANUP A REAL-WORLD APPLICATION OF A CALIXCROWN IN CESIUM SEPARATION TECHNOLOGY... 

Cesium Separation. Cesium will be removed from the waste super-nate by sorption on a phenol-sulfonic ion exchange resin such as Duolite (Diamond Shamrock Chemical Co.) ARC 359, as shown in Figure 3. This flowsheet is a modification of one currently being used by ARHCO at Hanford (3), Cesium will be absorbed on the two columns in tandem until breakthrough from the first column exceeds a predetermined level, after which the column will be washed with water (not shown in the diagram) and eluted with a mixture of ammonium carbonate and ammonium hydroxide. Breakthrough will be detected by a gamma ray monitor on the line between the two columns. 

Many types of separation systems other than solvent extraction have been found to exhibit high cesium selectivity. Such systems represent a point of comparison by which the effectiveness of solvent extraction systems may be measured. Table 1 lists some representative examples. These systems include inorganic ion exchangers, precipitation methods, and ion-exchange resins. For a variety of reasons, these materials have considerable potential for, and application in, cesium separations and may for specific tasks be the method of choice in the nuclear industry. The reader may consult the sampling of references cited in Table 1 for further information. 

Mohapatra, F. K., Lakshmi, D. S., Bhattacharyya, A., and Manchanda, V. K. 2009. Evaluation of polymer inclusion membranes containing crown ethers for selective cesium separation from nuclear waste solution. Journal of Hazardous Materials 169 472-479. 

The properties of hydrated titanium dioxide as an ion-exchange (qv) medium have been widely studied (51—55). Separations include those of alkaH and alkaline-earth metals, zinc, copper, cobalt, cesium, strontium, and barium. The use of hydrated titanium dioxide to separate uranium from seawater and also for the treatment of radioactive wastes from nuclear-reactor installations has been proposed (56). 

Bromine can function as a solvent. One of the very few metal bromides that has significant solubiUty in bromine is cesium bromide, 19.3 g/100 g of solution, thus providing a method of separating cesium bromide from the other alkah bromides (12). Aluminum bromide also is reported to have significant solubiUty in bromine but the pubUshed solubiUty values are not in good agreement (13). Bromine serves as the solvent in some brominations of organic compounds, such as 1,2-diphenylethane (14). 

Decomposition with Bases. Alkaline decomposition of poUucite can be carried out by roasting poUucite with either a calcium carbonate—calcium chloride mix at 800—900°C or a sodium carbonate—sodium chloride mix at 600—800°C foUowed by a water leach of the roasted mass, to give an impure cesium chloride solution that is separated from the gangue by filtration (22). The solution can then be converted to cesium alum [7784-17-OJ, CS2SO4 Al2(S0 2 24H20. Extraction of cesium from the poUucite is almost complete. Solvent extraction of cesium carbonate from the cesium chloride solution using a phenol in kerosene has also been developed (23). 

Hydrochloric acid digestion takes place at elevated temperatures and produces a solution of the mixed chlorides of cesium, aluminum, and other alkah metals separated from the sUiceous residue by filtration. The impure cesium chloride can be purified as cesium chloride double salts such as cesium antimony chloride [14590-08-0] 4CsCl SbCl, cesium iodine chloride [15605 2-2], CS2CI2I, or cesium hexachlorocerate [19153 4-7] Cs2[CeClg] (26). Such salts are recrystaUized and the purified double salts decomposed to cesium chloride by hydrolysis, or precipitated with hydrogen sulfide. Alternatively, solvent extraction of cesium chloride direct from the hydrochloric acid leach Hquor can be used. 

Toyopearl HW-75 resin, with pores larger than 1000 A, have been used in place of ultracentrifugation steps for the purification of plasmid DNA. Ultracentrifugation is a time-consuming process and requires expensive chemicals, such as cesium chloride. Toyopearl HW-75 resin provides superior separation performance for plasmid DNA and also provides high yields (54). 

Interaction between niobium oxide and fluorides, chlorides or carbonates of alkali metals in an ammonium hydrofluoride melt, yielded monooxyfluoroniobates with different compositions, MxNbOF3+x, where they were subsequently investigated [123-127]. According to DTA patterns of the Nb205 - 6NFL HF2 - 2MF system, (Fig. 18) a rich variety of endothermic effects result from the formation of ammonium monooxyfluoroniobate, its thermal decomposition and its interaction with alkali metal fluorides. The number of effects decreases and separation of ammonium ceases at lower temperatures and when going from lithium to cesium in the sequence of alkali metal fluorides. 

The volatile metal is separated by distillation and condensed. Mercury is the only metallic element that is liquid at room temperature (gallium and cesium are liquids on warm days). It has a long liquid range, from its melting point of — 39°C to its boiling point of 357°C, and so it is well suited for its use in thermometers, silent electrical switches, and high-vacuum pumps. 

In the technique developed by Willard Libby in Chicago in the late 1940s, the proportion of carbon-14 in a sample is determined by monitoring the (1 radiation from C02 obtained by burning the sample. This procedure is illustrated in Example 17.4. In the modern version of the technique, which requires only a few milligrams of sample, the carbon atoms are converted into C ions by bombardment of the sample with cesium atoms. The C ions are then accelerated with electric fields, and the carbon isotopes are separated and counted with a mass spectrometer (Fig. 17.19). 

Final alcohol precipitation not only allows for removal of the phenol and any remaining non-covalently bound hydrocarbon but also concentrates the DNA. Ribonuclease treatment removes any contaminating RNA. Additional purification by cesium chloride centrifugation (35) is also often performed. This is particularly suited to small quantities of DNA. Hydroxyapatite chromatography is also effective in separating RNA, proteins, and DNA (36.37). 

Except for sensor applications, the intercalation of alkali metal ions in metal hexacyanoferrates was used for adsorption and separation of cesium ions from different aqueous solutions with Prussian blue [43,44] and cupric hexacyanoferrate [45,46],... 

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