Decontamination factors

Uranium Purification. Subsequent uranium cycles provide additional separation from residual plutonium and fission products, particularly zirconium— niobium and mthenium (30). This is accompHshed by repeating the extraction/stripping cycle. Decontamination factors greater than 10 at losses of less than 0.1 wt % are routinely attainable. However, mthenium can exist in several valence states simultaneously and can form several nitrosyl—nitrate complexes, some for which are extracted readily by TBP. Under certain conditions, the nitrates of zirconium and niobium form soluble compounds or hydrous coUoids that compHcate the Hquid—Hquid extraction. SiUca-gel adsorption or one of the similar Hquid—soHd techniques may also be used to further purify the product streams. 

Decontamination factor A logarithmic scale used to measure the collection efficiency of a particulate collection device. 

Decontamination index The logarithm to the base 10 of the decontamination factor. 

A radiochemical procedure is proposed for the determination of technetium activities from mixed fission products of uranium and thorium. The chief decontamination step is the extraction of TcO into a tetrapropylammonium hydroxide-bromoform mixture from 4.0 M NaOH solutions. Decontamination factors of 10 with chemical yields of 50-70% have been obtained. 

The extraction of TcO with methyl ethyl ketone, acetone, and pyridine results in a ruthenium decontamination factor of about 10 . Another effective separation method is based on the extraction of technetium as triphenylguanidinium pertechnetate from sulfuric acid by means of chlorex ()S-chloroethyl ether). Pertechnetate can be re-extracted with 3 N NH OH solution . 

For the rapid determination of Tc in a mixture of uranium fission products. Love and Greendale have used the method of amalgam polarography. It consists in a selective reduction of technetium at a dropping mercury electrode at a potential of —1.55 V vs. SCE in a medium of 1 M sodium citrate and 0.1 M NaOH. Under these conditions, technetium is reduced to an oxidation state which is soluble in mercury. The amalgam is removed from the solution of fission fragments and the amount of Tc determined in nitric acid solution of the amalgam by a y count. For Tc the measurement accuracy is within 1 %, and the decontamination factor from other fission products 10 . 

A decrease in the number of uranium and plutonium purification cycles from three to two, or even one, would be highly advantageous. First-cycle decontamination factors of uranium from neptunium and from the fission products ruthenium and zirconium must be significantly improved to realize such a decrease. 

Table 12.11 Decontamination Factors for Extraction (Mass in the Feed to Mass in Raffinate) and for the Stripping [(Mass in the Feed Minus Mass in the Raffinate)/Mass in the Organic Out] in DIAMEX Hot Test with Flow Sheet in Fig. 12.13...

Table 12.13 Decontamination Factors, DF, for the Extraction (Mass in the Feed/Mass in the Actinide Back-Extraction) in the SANEX 3 Hot Test Depicted in Fig. 12.21... 

The yield and rate of the tantalothermic reduction of plutonium carbide at 1975 K are given in Fig. 3. Producing actinide metals by metallothermic reduction of their carbides has some interesting advantages. The process is applicable in principle to all of the actinide metals, without exception, and at an acceptable purity level, even if quite impure starting material (waste) is used. High decontamination factors result from the selectivities achieved at the different steps of the process. Volatile oxides and metals are eliminated hy vaporization during the carboreduction. Lanthanides, Y, Ti, Zr, Hf, V, Nb, Ta, Mo, and W form stable carbides, whereas Rh, Os, Ir, Pt, and Pd remain as nonvolatile metals in the actinide carbides. Thus, these latter elements... 

Efficient refining of the more volatile actinide metals (Pu, Am, Cm, Bk, and Cf) is achieved by selective vaporization for those (Pu, Am, Cm) available in macro quantities. The metal is sublimed at the lowest possible temperature to avoid co-evaporation of the less volatile impurities and then deposited at the highest possible temperature to allow vaporization of the more volatile impurities. Deposition occurs below the melting point of the metal to avoid potential corrosion of the condenser by the liquid metal. Very good decontamination factors can be obtained for most metallic impurities. However, Ag, Ca, Be, Sn, Dy, and Ho are not separated from Am metal nor are Co, Fe, Cr, Ni, Si, Ge, Gd, Pr, Nd, Sc, Tb, and Lu from Cm and Pu metals. 

Sodium titanate has been found to be very effective in removing Sr from defense waste typified by a 6m NaNO - 0.6m NaOH solution also containing the sodium salts of aluminate, nitrite, phosphate, carbonate, sulfate, and chromate in the range of O.lU to 0.007 N and Sr in the analytical concentration range of O.OU to O.U ppm ( ). Sodium titanate columns have provided a Sr decontamination factor of greater than io3 for 2500 column volumes of the waste at flow rates of 2 to 6 column volumes per hour. The material has also been shown to remove residual actinide contamination from the same and similar waste streams ( ). 

The baseline process, including the pressure sintering step, was demonstrated with both simulated high level waste and under hot cell conditions using a waste solution prepared from typical spent light water reactor fuel. A batch contacting method using sodium titanate was also evaluated, but the overall decontamination factor was much lower than obtained in the column process. 

The Purex process, ie, plutonium uranium reduction extraction, employs an organic phase consisting of 30 wt % TBP dissolved in a kerosene-type diluent. Purification and separation of U and Pu is achieved because of the extractability of U02+2 and Pu(IV) nitrates by TBP and the relative inextractability of Pu(III) and most fission product nitrates. Plutonium nitrate and U02(N03)2 are extracted into the organic phase by the formation of compounds, eg, Pu(N03)4 -2TBP. The plutonium is reduced to Pu(III) by treatment with ferrous sulfamate, hydrazine, or hydroxylamine and is transferred to the aqueous phase U remains in the organic phase. Further purification is achieved by oxidation of Pu(III) to Pu(IV) and re-extraction with TBP. The plutonium is transferred to an aqueous product. Plutonium recovery from the Purex process is ca 99.9 wt % (128). Decontamination factors are 106 — 10s (97,126,129). A flow sheet of the Purex process is shown in Figure 7. 

There are certain unique features to the chemical separations used in radiochemistry compared to those in ordinary analytical chemistry that are worth noting. First of all, high yields are not necessarily needed, provided the yields of the separations can be measured. Emphasis is placed on radioactive purity, expressed as decontamination factors rather than chemical purity. Chemical purity is usually expressed as the ratio of the number of moles (molecules) of interest in the sample after separation to the number of all the moles (molecules) in the sample. Radioactive purity is usually expressed as the ratio of the activity of interest to that of all the activities in the sample. The decontamination factor is defined as the ratio of the radioactive purity after the separation to that prior to the separation. Decontamination factors of 105-107 are routinely achieved with higher values possible. In the event that the radionuclide(s) of interest are short-lived, then the time required for the separation is of paramount importance, as it does no good to have a very pure sample in which most of the desired activity has decayed during the separation. 

Table 10 Some Decontamination Factors Required of Fuel Reprocessing...

Required decontamination factors for process product streams Present BNFL processb PFR plantb... 

Table II Some Decontamination Factors in the Butex Process...

Despite the considerable body of knowledge now available on the extraction chemistry of ruthenium, it remains a problematic element for fuel reprocessors. A variety of means10 may be used to render the ruthenium less extractable. These include the addition of reagents such as oxalate or thiourea, the oxidation of Ru111 to inextractable RuIV or the addition of nitrogen dioxide to retain more Ru(NO) 3+ in the form of nitrito complexes of low DRu. However, such treatments may have undesirable effects on plant operation. It is possible to attain high decontamination factors for ruthenium over several process cycles, the penalty being that the ruthenium will appear in several waste streams, not just the HAW from the first decontamination cycle. 

Table 13 Typical Decontamination Factors Attained by the Purex Process285...

Cooling period Process cycles 30 days One Decontamination factors 250 days One 400 days Two ... 

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