Revised Thermal Analysis of LANL Ion Exchange Column

Abstract

This document updates a previous calculation of the temperature distributions in a Los Alamos National Laboratory (LANL) ion exchange column.1 LANL operates two laboratory-scale anion exchange columns, in series, to extract Pu-238 from nitric acid solutions. The Defense Nuclear Facilities Safety Board has requested an updated analysis to calculate maximum temperatures for higher resin loading capacities obtained with a new formulation of the Reillex HPQ anion exchange resin. The increased resin loading capacity will not exceed 118 g plutonium per L of resin bed. Calculations were requested for normal operation of the resin bed at the minimum allowable solution feed rate of 30 mL/min and after an interruption of flow at the end of the feed stage, when one of the columns is fully loaded. The object of the analysis is to demonstrate that the decay heat from the Pu-238 will not cause resin bed temperatures to increase to a level where the resin significantly degrades. At low temperatures, resin bed temperatures increase primarily due to decay heat. At {approx}70 C a Low Temperature Exotherm (LTE) resulting from the reaction between 8-12 M HNO{sub 3} and the resin has been observed. The LTE has been attributed to an irreversible oxidation of pendant ethyl benzene groups at the termini of the resin polymer chains by nitric acid. The ethyl benzene groups are converted to benzoic acid moities. The resin can be treated to permanently remove the LTE by heating a resin suspension in 8M HNO{sub 3} for 30-45 minutes. No degradation of the resin performance is observed after the LTE removal treatment. In fact, heating the resin in boiling ({approx}115-120 C) 12 M HNO{sub 3} for 3 hr displays thermal stability analogous to resin that has been treated to remove the LTE. The analysis is based on a previous study of the SRS Frames Waste Recovery (FWR) column, performed in support of the Pu-238 production campaign for NASA's Cassini mission. In that study, temperature transients following an interruption of flow to the column were calculated. The transient calculations were terminated after the maximum resin bed temperature reached the Technical Standard of 60 C, which was set to prevent significant resin degradation. The LANL column differs from the FWR column in that it has a significantly smaller radius, 3.73 cm nominal versus approximately 28 cm. It follows that natural convection removes heat much more effectively from the LANL column, so that the column may reach thermal equilibrium. Consequently, the calculations for a flow interruption were extended until an approach to thermal equilibrium was observed. The LANL ion exchange process also uses a different resin than was used in the FWR column. The LANL column uses Reillex HPQ{trademark} resin, which is more resistant to attack by nitric acid than the Ionac 641{trademark} resin used in the FWR column. Heat generation from the resin oxidation reaction with nitric acid is neglected in this analysis since LANL will be treating the resin to remove the LTE prior to loading the resin in the columns. Calculations were performed using a finite difference computer code, which incorporates models for absorption and elution of plutonium and for forced and natural convection within the resin bed. Calculations for normal column operation during loading were performed using an initial temperature and a feed temperature equal to the ambient air temperature. The model for the normal flow calculations did not include natural convection within the resin bed. The no flow calculations were started with the temperature and concentration profiles at the end of the loading stage, when there would be a maximum amount of plutonium either adsorbed on the resin or in the feed solution in the column.