Mitchell Greenhalgh

Radioactive Iodine and Krypton Control for Nuclear Fuel Reprocessing Facilities

The removal of volatile radionuclides generated during used nuclear fuel reprocessing in the US is almost certain to be necessary for the licensing of a reprocessing facility in the US. Various control technologies have been developed, tested, or used over the past 50 years for control of volatile radionuclide emissions from used fuel reprocessing plants. The US DOE has sponsored, since 2009, an Off-gas Sigma Team to perform research and development focused on the most pressing volatile radionuclide control and immobilization problems. In this paper, we focus on the control requirements and methodologies for 85Kr and 129I. Numerous candidate technologies have been studied and developed at laboratory and pilot-plant scales in an effort to meet the need for high iodine control efficiency and to advance alternatives to cryogenic separations for krypton control. Several of these show promising results. Iodine decontamination factors as high as 105, iodine loading capacities, and other adsorption parameters including adsorption rates have been demonstrated under some conditions for both silver zeolite (AgZ) and Ag-functionalized aerogel. Sorbents, including an engineered form of AgZ and selected metal organic framework materials (MOFs), have been successfully demonstrated to capture Kr and Xe without the need for separations at cryogenic temperatures.

Selective Extraction of Minor Actinides from Acidic Media Using Symmetric and Asymmetric Dithiophosphinic Acids

The minor actinides (Am and Cm) and other transplutonium elements represent significant, long-term hazards found in spent nuclear fuel. The selective extraction of the minor actinides from the lanthanides is an important part of advanced reprocessing of spent nuclear fuel. This separation would allow the minor actinides to be fabricated into a target and recycled to a reactor and the lanthanides to be disposed. Due to the similarities in the chemical properties of the trivalent actinides and lanthanides, this separation is difficult to accomplish. The introduction of soft donor groups, such as N or S, into similarly structured ligands increases the differentiation between An(III) and Ln(III) cation coordination. Partly because of limitations imposed by synthetic methodologies, previous studies of dithiophosphinic acid (DPAH) extractants has been restricted to a comparatively small number of symmetrical dialkyl and diaryl derivatives. Research efforts at the Idaho National Laboratory have resulted in the recent development of an innovative synthetic pathway yielding new regiospecific DPAH extractants. The synthesis improves DPAH designs that can address the issues concerning minor actinide separation efficiency and extractant stability. Several new symmetric and asymmetric DPAH extractants have been prepared. The use of these extractants for the separation of minor actinides from lanthanides will be discussed. In addition, the variation in the extent of Am(III) extraction by a related series of DPAH isomers will be presented.

Development of a hydrogen mordenite sorbent for the capture of krypton from used nuclear fuel reprocessing off-gas streams

A novel new sorbent for the separation of krypton from off-gas streams resulting from the reprocessing of used nuclear fuel has been developed and evaluated. A hydrogen mordenite powder was successfully incorporated into a macroporous polymer binder and formed into spherical beads. The engineered form sorbent retained the characteristic surface area and microporosity indicative of mordenite powder. The sorbent was evaluated for krypton adsorption capacities utilizing thermal swing operations achieving capacities of 100 mmol of krypton per kilogram of sorbent at a temperature of 191 K. A krypton adsorption isotherm was also obtained at 191 K with varying krypton feed gas concentrations. Adsorption/desorption cycling effects were also evaluated with results indicating that the sorbent experienced no decrease in krypton capacity throughout testing.

Superficial Velocity Effects on HZ-PAN and AgZ-PAN for Kr/Xe Capture

Nearly all previous testing of HZ-PAN and AgZ-PAN was conducted at the same flow rate in order to maintain consistency among tests. This testing was sufficient for sorbent capacity determinations, but did not ensure that sorbents were capable of functioning under a range of flow regimes. Tests were conducted on both HZ-PAN and AgZ-PAN at superficial velocities between 20 and 700 cm/min. For HZ-PAN, Kr capacity increased from 60 mmol/kg to 110 mmol/kg as superficial velocity increased from 21 to 679 cm/min. Results for AgZ-PAN were similar, with capacity ranging from 72 to 124 mmol/kg over the same range of superficial. These results are promising for scaling up to process flows, demonstrating flexibility to operate in a broad range of superficial velocities while maintaining sorbent capacity. While preparing for superficial velocity testing it was also discovered that AgZ-PAN Xe capacity, previously observed to diminish over time, could be recovered with increased desorption temperature. Further, a substantial Xe capacity increase was observed. Previous room temperature capacities in the range of 22-25 mmol Xe/kg AgZ-PAN were increased to over 60 mmol Xe/kg AgZ-PAN. While this finding has not yet been fully explored to optimize activation and desorption temperatures, it is encouraging.

Development and evaluation of a silver mordenite composite sorbent for the partitioning of xenon from krypton in gas compositions

ABSTRACT A new engineered form composite sorbent for the selective separation of xenon from krypton in simulant composition off-gas streams resulting from the reprocessing of used nuclear fuel has been developed and evaluated. A sodium mordenite powder was incorporated into a macroporous polymer binder, formed into spherical beads and successfully converted to a 9 wt.% silver form composite sorbent. The final engineered form sorbent retained the characteristic surface area indicative of sodium mordenite powder. The sorbent was evaluated for xenon adsorption potential with capacities measured as high as 30 millimoles of xenon per kilogram of sorbent achieved at ambient temperature and 460 millimoles of xenon per kilogram sorbent at 220 K. Xenon/krypton selectivity was calculated to be 22.4 with a 1020 µL/L xenon, 150 µL/L krypton in a balance of air feed gas at 220 K. Adsorption/desorption thermal cycling effects were evaluated with results indicating sorbent performance was not significantly impacted while undergoing numerous adsorption/desorption thermal cycles.

Adsorption Isotherms for Xenon and Krypton using INL HZ-PAN and AgZ-PAN Sorbents

The generation of adsorption isotherms compliments the scale-up of off-gas processes used to control the emission of encapsulated radioactive volatile fission and activation products released during Used Nuclear Fuel (UNF) reprocessing activities. A series of experiments were conducted to obtain capacity results for varying Kr and Xe gas concentrations using HZ-PAN and AgZ-PAN engineered form sorbents. Gas compositions for Kr ranged from 150-40,000 ppmv and 250-5020 ppmv for Xe in a helium balance. The experiments were all performed at 220 K at a flowrate of 50 sccm. Acquired capacities were then respectively fit to the Langmuir equation using the Langmuir linear regression method to obtain the equilibrium parameters Qmax and Keq. Generated experimental adsorption isotherms were then plotted with the Langmuir predicted isotherms to illustrate agreement between the two. The Langmuir parameters were provided for input into the OSPREY model to predict breakthrough of single component adsorption of Kr and Xe on HZ-PAN and AgZ-PAN sorbents at the experimental conditions tested. Kr and Xe capacities resulting from model breakthrough predictions were then compared to experimental capacities for model validation.

Development and design of a multi-column experimental setup for Kr/Xe separation

As a precursor to FY-15 Kr/Xe separation testing, design modifications to an existing experimental setup are warranted. The modifications would allow for multi-column testing to facilitate a Xe separation followed by a Kr separation using engineered form sorbents prepared using an INL patented process. A new cooling apparatus capable of achieving test temperatures to -40° C and able to house a newly designed Xe column was acquired. Modifications to the existing setup are being installed to allow for multi-column testing and gas constituent analyses using evacuated sample bombs. The new modifications will allow for independent temperature control for each column enabling a plethora of test conditions to be implemented. Sample analyses will be used to evaluate the Xe/Kr selectivity of the AgZ-PAN sorbent and determine the Kr purity of the effluent stream following Kr capture using the HZ-PAN sorbent.

FY-12 INL KR CAPTURE ACTIVITIES SUPPORTING THE OFF-GAS SIGMA TEAM

Tasks performed this year by INL Kr capture off-gas team members can be segregated into three separate task sub-sections which include: 1) The development and testing of a new engineered form sorbent, 2) An initial NDA gamma scan effort performed on the drum containing the Legacy Kr-85 sample materials, and 3) Collaborative research efforts with PNNL involving the testing of the Ni-DOBDC MOF and an initial attempt to make powdered chalcogel material into an engineered form using our binding process. This document describes the routes to success for the three task sub-sections.

Summary of FY-11 Krypton Capture Activities at the Idaho National Laboratory

This report contains a description of FY-11 Krypton capture activities utilizing physisorption techniques performed at the INL.

Temperature Profile Measurements in a Newly Constructed 30-Stage 5 cm Centrifugal Contactor pilot Plant

An annular centrifugal contactor pilot plant incorporating 30 stages of commercial 5 cm CINC V-02 units has been built and operated at INL during the past year. The pilot plant includes an automated process control and data acquisitioning system. The primary purpose of the pilot plant is to evaluate the performance of a large number of inter-connected centrifugal contactors and obtain temperature profile measurements within a 30-stage cascade. Additional solvent extraction flowsheet testing using stable surrogates is also being considered. Preliminary hydraulic testing was conducted with all 30 contactors interconnected for continuous counter-current flow. Hydraulic performance and system operational tests were conducted successfully but with higher single-stage rotor speeds found necessary to maintain steady interstage flow at flowrates of 1 L/min and higher. Initial temperature profile measurements were also completed in this configuration studying the performance during single aqueous and two-phase counter-current flow at ambient and elevated inlet solution temperatures. Temperature profile testing of two discreet sections of the cascade required additional feed and discharge connections. Lamp oil, a commercially available alkane mixture of C14 to C18 chains, and tap water adjusted to pH 2 were the solution feeds for all the testing described in this report. Numerous temperature profiles were completed using a newly constructed 30-stage centrifugal contactor pilot plant. The automated process control and data acquisition system worked very well throughout testing. Temperature data profiles for an array of total flowrates (FT) and contactor rpm values for both single-phase and two-phase systems have been collected with selected profiles and comparisons reported. Total flowrates (FT) ranged from 0.5-1.4 L/min with rotor speeds from 3500-4000 rpm. Solution inlet temperatures ranging from ambient up to 50° C were tested. Ambient temperature testing shows that a small amount of heat is added to the processed solution by the mechanical energy of the contactors. The temperature profiles match the ambient temperature of the laboratory but are nearly 10° C higher toward the middle of the cascade. Heated input solution testing provides temperature profiles with smaller temperature gradients and are more influenced by the temperature of the inlet solutions than the ambient laboratory temperature. The temperature effects of solution mixing, even at 4000 rpm, were insignificant in any of the studies conducted on lamp oil and water.