Rick W. Shimskey

Filtration and Leach Testing for REDOX Sludge and S-Saltcake Actual Waste Sample Composites

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan.( ) The test program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Under test plan TP-RPP-WTP-467, eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. Under this test plan, a waste-testing program was implemented that included: • Homogenizing the archive samples by group as defined in the test plan • Characterizing the homogenized sample groups • Performing parametric leaching testing on each group for compounds of interest • Performing bench-top filtration/leaching tests in the hot cell for each group to simulate filtration and leaching activities if they occurred in the UFP2 vessel of the WTP Pretreatment Facility. This report focuses on filtration/leaching tests performed on two of the eight waste composite samples and follow-on parametric tests to support aluminum leaching results from those tests.

Filtration Understanding: FY10 Testing Results and Filtration Model Update

This document completes the requirements of Milestone 2-4, Final Report of FY10 Testing, discussed in the scope of work outlined in the EM31 task plan WP-2.3.6-2010-1. The focus of task WP 2.3.6 is to improve the U.S. Department of Energy’s (DOE’s) understanding of filtration operations for high-level waste (HLW) to improve filtration and cleaning efficiencies, thereby increasing process throughput and reducing the Na demand (through acid neutralization). Developing the cleaning/backpulsing requirements will produce much more efficient operations for both the Hanford Tank Waste Treatment and Immobilization Plant (WTP) and the Savannah River Site (SRS), thereby significantly increasing throughput by limiting cleaning cycles. The scope of this work is to develop the understanding of filter fouling to allow developing this cleaning/backpulsing strategy.

A Brief Review of Filtration Studies for Waste Treatment at the Hanford Site

This document completes the requirements of Milestone 1-2, PNNL Draft Literature Review, discussed in the scope of work outlined in the EM-31 Support Project task plan WP-2.3.6-2010-1. The focus of task WP 2.3.6 is to improve the U.S. Department of Energy’s (DOE’s) understanding of filtration operations for high-level waste (HLW) to enhance filtration and cleaning efficiencies, thereby increasing process throughput and reducing the sodium demand (through acid neutralization). Developing the processes for fulfilling the cleaning/backpulsing requirements will result in more efficient operations for both the Hanford Tank Waste Treatment and Immobilization Plant (WTP) and the Savannah River Site (SRS), thereby increasing throughput by limiting cleaning cycles. The purpose of this document is to summarize Pacific Northwest National Laboratory’s (PNNL’s) literature review of historical filtration testing at the laboratory and of testing found in peer-reviewed journals. Eventually, the contents of this document will be merged with a literature review by SRS to produce a summary report for DOE of the results of previous filtration testing at the laboratories and the types of testing that still need to be completed to address the questions about improved filtration performance at WTP and SRS. To this end, this report presents 1) a review of the current state of crossflow filtration knowledge available in the peer-reviewed literature, 2) a detailed review of PNNL-related filtration studies specific to the Hanford site, and 3) an overview of current waste filtration models developed by PNNL and suggested avenues for future model development.

Filtration and Leach Testing for PUREX Cladding Sludge and REDOX Cladding Sludge Actual Waste Sample Composites

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan (Barnes and Voke 2006). The test program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Hanford Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Under test plan TP RPP WTP 467 (Fiskum et al. 2007), eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. Under this test plan, a waste testing program was implemented that included: • Homogenizing the archive samples by group as defined in the test plan. • Characterizing the homogenized sample groups. • Performing parametric leaching testing on each group for compounds of interest. • Performing bench-top filtration/leaching tests in the hot cell for each group to simulate filtration and leaching activities if they occurred in the UFP2 vessel of the WTP Pretreatment Facility. This report focuses on a filtration/leaching test performed using two of the eight waste composite samples. The sample groups examined in this report were the plutonium-uranium extraction (PUREX) cladding waste sludge (Group 3, or CWP) and reduction-oxidation (REDOX) cladding waste sludge (Group 4, or CWR). Both the Group 3 and 4 waste composites were anticipated to be high in gibbsite, thus requiring caustic leaching. WTP RPT 167 (Snow et al. 2008) describes the homogenization, characterization, and parametric leaching activities before benchtop filtration/leaching testing of these two waste groups. Characterization and initial parametric data in that report were used to plan a single filtration/leaching test using a blend of both wastes. The test focused on filtration testing of the waste and caustic leaching for aluminum, in the form of gibbsite, and its impact on filtration. The initial sample was diluted with a liquid simulant to simulate the receiving concentration of retrieved tank waste into the UFP2 vessel (< 10 wt% undissolved solids). Filtration testing was performed on the dilute waste sample and dewatered to a higher solids concentration. Filtration testing was then performed on the concentrated slurry. Afterwards, the slurry was caustic leached to remove aluminum present in the undissolved solid present in the waste. The leach was planned to simulate leaching conditions in the UFP2 vessel. During the leach, slurry supernate samples were collected to measure the dissolution rate of aluminum in the waste. After the slurry cooled down from the elevated leach temperature, the leach liquor was dewatered from the solids. The remaining slurry was rinsed and dewatered with caustic solutions to remove a majority of the dissolved aluminum from the leached slurry. The concentration of sodium hydroxide in the rinse solutions was high enough to maintain the solubility of the aluminum in the dewatered rinse solutions after dilution of the slurry supernate. Filtration tests were performed on the final slurry to compare to filtration performance before and after caustic leaching.

Radiolytic microscale power generation based on single chamber fuel cell operation

Proof-of-principle test results are presented for a nuclear-to-electric power generation technique utilizing closed-cycle fuel cell operation. The approach being developed is to first use the decay energy of a radioisotope to generate H2 and O2 from water, and then to utilize these species in a fuel cell to generate electricity. The principle of operation allows the device to regenerate its own reactants and operate continuously as a closed system for as long as the primary source of power, namely the radioisotope, is active. With micro engineering and fabrication techniques available today, a miniaturized integrated package of 1 cm3 in size and producing power in the 10 mW range appears feasible in a mature design. Smaller devices producing less power would also be possible. For this project, a unique fuel cell capable of utilizing mixed reactants at room temperature has been developed. The efficiency of this early fuel cell design falls in the range between 10 and 20%. Measured power output from a radioisotope fueled test cell approached 0.45 mW for several hours with a radiation leakage rate estimated at 490 mrem yr−1.

Characterization, Leaching, and Filtrations Testing of Ferrocyanide Tank sludge (Group 8) Actual Waste Composite

This is the final report in a series of eight reports defining characterization, leach, and filtration testing of a wide variety of Hanford tank waste sludges. The information generated from this series is intended to supplement the Waste Treatment and Immobilization Plant (WTP) project understanding of actual waste behaviors associated with tank waste sludge processing through the pretreatment portion of the WTP. The work described in this report presents information on a high-iron waste form, specifically the ferrocyanide tank waste sludge. Iron hydroxide has been shown to pose technical challenges during filtration processing; the ferrocyanide tank waste sludge represented a good source of the high-iron matrix to test the filtration processing.

Optimization of Hydride Rim Formation in Unirradiated Zr 4 Cladding

The purpose of this work is to build on the results reported in the M2 milestone M2FT 13PN0805051, document number FCRD-USED-2013-000151 (Hanson, 2013). In that work, it was demonstrated that unirradiated samples of zircaloy-4 cladding could be pre-hydrided at temperatures below 400°C in pure hydrogen gas and that the growth of hydrides on the surface could be controlled by changing the surface condition of the samples and form a desired hydride rim on the outside diameter of the cladding. The work performed at Pacific Northwest National Laboratory since the issuing of the M2 milestone has focused its efforts to optimize the formation of a hydride rim on available zircaloy-4 cladding samples by controlling temperature variation and gas flow control during pre-hydriding treatments. Surface conditioning of the outside surface was also examined as a variable. The results of test indicate that much of the variability in the hydride thickness is due to temperature variation occurring in the furnaces as well as how hydrogen gas flows across the sample surface. Efforts to examine other alloys, gas concentrations, and different surface conditioning plan to be pursed in the next FY as more cladding samples become available

Evaluation of Gas Retention in Waste Simulants: Tall Column Experiments

Gas generation in Hanford’s underground waste storage tanks can lead to gas accumulation within the layer of settled solids (sludge) at the tank bottom. The gas, which typically has hydrogen as the major component together with other flammable species, is formed principally by radiation-driven chemical reactions. Accumulation of these gases within the sludge in a waste tank is undesirable and limits the amount of tank volume for waste storage. Further, accumulation of large amounts of gas in the sludge may potentially result in an unacceptable release of the accumulated gas if the sludge-layer density is reduced to less than that of the overlying sludge or that of the supernatant liquid. Rapid release of large amounts of flammable gases could endanger personnel and equipment near the tank. For this reason, a thorough understanding of the circumstances that can lead to a potentially problematic gas accumulation in sludge layers is needed. To respond to this need, the Deep Sludge Gas Release Event Program (DSGREP) was commissioned to examine gas release behavior in sludges.

Fuel-in-air FY07 summary report

Results of the testing program to determine fractional release rates and particle size distributions from failed commercial spent fuel related to the operations in the surface facility at Yucca Mountain are presented.