Sulfamate, ferrous plutonium reductant

HNA was incorporated into many nuclear fuel reprocessing plants in the early 1970s replacing the ferrous sulfamate and hydroxylamine sulfate for plutonium reduction because it possessed the proper Pu(IV) to Pu(III) reduction attributes and the gaseous reaction products N2, N2O, and water contributed to the minimization of the volume of solid wastes produced. The French PUREX process at the La Hague site safely uses a mixture of HNA and nitric acid for the reductive stripping phase of plutonium. The British also used HNA in the thermal oxide reprocessing plant (THORP) for over several years (Barney, 1998). 

Historically, ferrous sulfamate, Fe(NH2S02)2, was added to the HNO scmbbing solution in sufficient excess to ensure the destmction of nitrite ions and the resulting reduction of the Pu to the less extractable Pu . However, the sulfate ion is undesirable because sulfate complexes with the plutonium to compHcate the subsequent plutonium purification step, adds to corrosion problems, and as SO2 is an off-gas pollutant during any subsequent high temperature waste solidification operations. The associated ferric ion contributes significantly to the solidified waste volume. 

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. 

Tljie U-Pu separation is bas d on the much lower extractability of Pu3 ions by TBP than of Pu ions and the relative ease of oxidation and reduction of+plutonium in solutions. The original Pur x process utilized Fe2 to achieve the reduction of Pu1 to Pu. Since nitrite ions, whjch are generally present in nitric acid solutions, reoxidize Pu3 and thus affect the net reduction rate, a "holding reductant" is added to scavenge nitrite ions. Sulfamate ion, NH2S03 is an effective holding reductant and this led to the selection of ferrous sulfamate, Fe(NH2S03)2as the... 

In the Purex process, plutonium and uranium are coextracted into an organic phase and partitioned by reducing plutonium(IV) to the aqueous-favoring plutonium(III). This has been achieved chemically by use of a suitable reductant such as ferrous sulfamate ( 1) or uranium(IV). (2, 3, 4, 5) The use of ferrous sulfamate results in accelerated corrosion of the stainless steel, due to the presence of ferric ions and sulfuric acid, and in an increase in the volume of wastes. The use of natural uranium(IV) can cause dilution of the 235U in slightly enriched uranium, thus lowering the value of the recovered uranium. 

Ferrous sulfamate has been the reductant for plutonium during partitioning of uranium and plutonium in the Purex process at SRP since startup. In recent years, a desire to reduce waste volumes has led to studies of alternative reductants or combinations of FeSA with other reductants. The FeSA in the Pu strip solution produces Fe(OH) 3 and Na2S0i in neutralized waste these compounds account for a large percentage of the solid material in Purex low activity waste. In an effort to reduce these wastes, we investigated HAN as a substitute for part or all of the FeSA in the Purex first cycle. 

In the partition contactor, plutonium was converted to inextractable, trivalent Pu (N03)3 by a reductant solution of ferrous sulfamate containing aluminum nitrate to keep uranium in the hexone phase. Plutonium was thus separated from uranium and transferred back to the aqueous phase along with the aluminum nitrate. Impure plutonium nitrate was purified by additional cycles of solvent extraction, not shown. 

In the IB column remaining traces of plutonium are stripped from the solvent by a strippant IBX, stream 10, containing hydrazine as holding reductant. A decontamination factor of 200 for removal of plutonium from uranium is anticipated for the IB columns. The big advantage of this partitioning system is that it adds no nonvolatile materials such as ferrous sulfamate to the system. 

The second part of Table 10.22 gives equations for the concentration ratio of tetravalent to pentavalent neptunium calculated for the three reductants listed there. In the older Purex plants the ferrous sulfamate used to reduce plutonium to inextractable Pu reduced neptunium partly to inextractable Np(V) and partly to extractable Np(IV). The reductants now preferred, tetravalent uranium (possibly made electrolytically) or hydroxylamine, are sufficiently strong, in sufficient time, to make neptunium almost completely tetravalent, but the reactions are much slower than reduction of tetravalent plutonium, because of slow deoxidation of the NpOj radical. Kinetics of these reductions are also discussed in Sec. 7.5. 

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