DOE OSTI2019
The reprocessing of used nuclear fuel would release volatile radionuclides into the off-gas streams of a processing plant, including ³H, ¹⁴C, ⁸⁵Kr, and ¹²⁹I. One potential simplification to the management of the off-gas streams could be achieved through an efficient tritium pretreatment (TPT) step in which the UO₂ fuel is oxidized by either air or NO₂ before dissolution. The oxidation of the UO₂ fuel matrix will result in the release of tritium from the fuel. Upfront release of tritium from the fuel in a pretreatment step with subsequent tritium abatement can minimize or eliminate the distribution of tritium throughout a plant. This can decrease or eliminate the need for tritium capture on multiple off-gas streams and prevent distribution to the aqueous inventory. The use of NO₂ as the oxidant in an advanced tritium pretreatment (ATPT) allows for the oxidation to be performed at lower temperatures and may also result in the quantitative release of iodine from the fuel. The ATPT off-gas will contain up to 75 vol% NO₂ gas. Spencer et al. identified the most promising iodine sorbent as silver nitrate-impregnated alumina (AgA) and the most promising tritium sorbents as 3Å molecular sieve (3Å MS) and silica gel for radionuclide capture from ATPT off-gas streams. An initial series of tests were conducted in fiscal years 2017–2018 with the intent of demonstrating the recovery of iodine and tritium using these sorbents from a recirculating gas stream that simulated the NO₂ recycle loop envisioned for the ATPT system. These initial tests showed low tritium recoveries and significant variations in the iodine recovery on the AgA. Ultimately it was concluded, following disassembly of the system, that corrosion within the system was partially the cause of the poor recovery of both species. All components of that system were disposed of at the end of the analysis. One of the conclusions drawn from the initial tests pointed to the reconsideration of the materials of construction. Based on that recommendation a new test bed for the advanced TPT off-gas system, that addresses the issues identified in the fiscal years 2017 and 2018 scoping tests, was designed and constructed. The test bed used high nickel alloys wherever possible to address the previously observed corrosion issues, a redesigned surge tank to permit ease of purging, an improved feed injection system and a more modular system design that allowed testing of incremental increases in system complexity to allow the isolation of any element that results in changes to recovery of target species. Accompanying that design, a multifaceted test plan was completed. The overarching goals of this test series were two-fold. The first goal was to demonstrate the ability to recover both the iodine and tritium that would be released during TPT in a manner that the releases from the fuel can be quantified. The second goal was to demonstrate that the combined recovery system could operate in any of the three proposed TPT modes (once-through air or O₂, recirculating air or O₂, or recirculating NO x ). A total of 22 tests were completed. Ten tests examined tritium behavior under varying operating parameters, 8 tests examined iodine behavior under varying operating parameters, and 4 tests examined both tritium and iodine behavior. Silica gel was used for the tritium sorbent, and AgA or Ag-mordenite (AgZ) was used as the iodine sorbent. The following conclusions were drawn: Full recovery is achieved for both sorbates when no sorbent is in place indicating no accumulation within the test system. In even the simplest of the configurations (i.e., no sorbents in the columns), iodine is more difficult to transport and recover from the system than tritium. Analysis of the AgA iodine sorbent beds from the integrated tritium and iodine tests indicate quantitative iodine recovery can be achieved (within anticipated experimental errors). This system may provide a means for the quantification of the iodine released by the ATPT process within the experimental uncertainties. This would support 0.33 to 1.00 kg demonstrations of the ATPT process with actual used nuclear fuel. Iodine penetrated further into AgZ than into AgA when operated in gas recirculation mode. Tritium adsorbs to and cannot be fully recovered from the 10-cm column of silica gel at regeneration temperatures up to 140 °C.; Tritium adsorbs to and cannot be recovered from the 10-cm column of AgA at desorption temperatures up to 200 °C. Co-adsorbed tritium was recovered to a greater extent from AgZ than from AgA, but recovery was not complete. No visible corrosion was observed in the test system.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗