Results for “Headspace Sampling” — Page 5

DOE OSTI2020

Thermal Stability of a Eutectic Mixture of Bis(2,2-dinitropropyl) Acetal and Formal: Part C. Kinetic Compensation Effect

Here, the aging behavior of a eutectic mixture of bis(2,2-dinitropropyl) acetal and formal [called NP here] has been studied in various atmospheres [dry (air or nitrogen) versus wet] at temperatures 70 °C and below. The properties of aged samples were analyzed using Fourier transform infrared (FTIR) spectroscopy, Karl Fischer (KF) titration, liquid chromatography/mass spectrometry (LC/MS), and thermogravimetric analysis (TGA) over a period of three years. The results indicate that at aging temperatures up to 55 °C, the initial rates of water production from nitrous acid (HONO) formation and decomposition into the water, NO, and NO 2 follows a 1st order rate law and the rate constants follow an Arrhenius law as a function of temperature. The activation energies and pre-factors for water and volatiles production yield a single linear kinetic compensation plot, suggesting a common degradation pathway between NP and the various combinations of its constituents. Within a narrow temperature range, around 55 °C, a trace amount of water in NP stabilizes its properties by preventing HONO elimination. When the aging temperature is substantially higher than 55 °C, the nature of the degradation mechanism changes. It is suspected that the degradation products of NO x , water, and HNO 3 serve as catalysts to auto-catalyze (kinetics beyond the 1st order) and further degrade NP. The effect of headspace volume on this auto-catalytic process will be discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Uranium Oxide Elutriation at Higher Flow Rates and Longer Times

This work supports the recovery of high-assay low-enriched uranium (i.e., U enriched in 235 U to >5% and <20%) from used nuclear fuel. One step includes elutriating triuranium octoxide (U 3 O 8 ) from a fluidized bed of alumina (Al 2 O 3 ) that fills the main reaction chamber. The experiments outlined in this report assessed the effects of the time and flow rate on the elutriation of U 3 O 8 powder from the reaction vessel. Testing at Oak Ridge National Laboratory (ORNL) was performed in a one-fourth scale experimental apparatus based on a pilot-scale system, which is the Material Recovery Pilot Plant (MRPP) at Idaho National Laboratory (INL). The experimental system comprises a supply of pressurized nitrogen (N 2 ), a gas heater, the reaction vessel, a knock-out pot, and a water trap where elutriated particles are collected for sampling. An Al 2 O 3 fluidized bed is contained within the reaction vessel. A bed of Al 2 O 3 with a nominal size of 180 µm and U 3 O 8 with a nominal size of 7 µm was fluidized at 2 different flow rates so the U 3 O 8 physically separated from the bed. The apparatus was simple and had no valves or sharp bends downstream from the reactor. The flow exited the reactor through a side port at the top. The flow passed through a knock-out vessel before the flow was passed through a bubbler to capture the U 3 O 8 . Seven tests were completed with U 3 O 8 using an elutriating gas of N 2 heated to 200°C. Tests were performed with bed loadings that comprise 25.0 g of U 3 O 8 , or 3.6 wt% of the bed mass. Except for one test performed at 12 SLPM, the gas flow rate through the bed for the other experiments was set at 10 SLPM as measured by the mass flow meter. Linear velocities through the bed were calculated as 28 and 34 cm/s, or 0.9 and 1.1 ft·s -1 . The duration of the tests ranged from 20 to 180 min, and one test had a flow cycled between 0 and 5 SLPM every 5 min for 40 min. The testing successfully demonstrated elutriation of U 3 O 8 from the fluidized bed as up to a 100% of the U 3 O 8 was transferred out of the bed. The removal of U 3 O 8 had a logarithmic dependence on flow rate. The design changes made the apparatus easier to clean, and the mass balances were better than those used in previous studies. Some elutriated Al 2 O 3 collected in the tubing that connected the reactor to the knock-out pot, but the amount of Al 2 O 3 was minimal for 10 SLPM. The flow at 12 SLPM showed considerable transport of Al 2 O 3 bed material into the reaction-vessel headspace and the transfer line to the knock-out pot.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗