Richard C. Daniel

Characterization and Leach Testing for PUREX Cladding Waste Sludge (Group 3) and REDOX Cladding Waste Sludge (Group 4) 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.(a) The testing 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. Eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. The actual wastetesting program included homogenizing the samples by group, characterizing the solids and aqueous phases, and performing parametric leaching tests. Two of the eight defined groups—plutonium-uranium extraction (PUREX) cladding waste sludge (Group 3, or CWP) and reduction-oxidation (REDOX) cladding waste sludge (Group 4, or CWR)—are the subjects of this report. Both the Group 3 and 4 waste composites were anticipated to be high in gibbsite, requiring caustic leaching. Characterization of the composite Group 3 and Group 4 waste samples confirmed them to be high in gibbsite. The focus of the Group 3 and 4 testing was on determining the behavior of gibbsite during caustic leaching. The waste-type definition, archived sample conditions, homogenization activities, characterization (physical, chemical, radioisotope, and crystal habit), and caustic leaching behavior as functions of time, temperature, and hydroxide concentration are discussed in this report. Testing was conducted according to TP-RPP-WTP-467.

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.

Review of the Scientific Understanding of Radioactive Waste at the U.S. DOE Hanford Site

This Critical Review reviews the origin and chemical and rheological complexity of radioactive waste at the U.S. Department of Energy Hanford Site. The waste, stored in underground tanks, was generated via three distinct processes over decades of plutonium extraction operations. Although close records were kept of original waste disposition, tank-to-tank transfers and conditions that impede equilibrium complicate our understanding of the chemistry, phase composition, and rheology of the waste. Tank waste slurries comprise particles and aggregates from nano to micro scales, with varying densities, morphologies, heterogeneous compositions, and complicated responses to flow regimes and process conditions. Further, remnant or changing radiation fields may affect the stability and rheology of the waste. These conditions pose challenges for transport through conduits or pipes to treatment plants for vitrification. Additionally, recalcitrant boehmite degrades glass quality and the high aluminum content must be reduced prior to vitrification for the manufacture of waste glass of acceptable durability. However, caustic leaching indicates that boehmite dissolves much more slowly than predicted given surface normalized rates. Existing empirical models based on ex situ experiments and observations generally only describe material balances and have not effectively predicted process performance. Recent advances in the areas of in situ microscopy, aberration-corrected transmission electron microscopy, theoretical modeling across scales, and experimental methods for probing the physics and chemistry at mineral-fluid and mineral-mineral interfaces are being implemented to build robustly predictive physics-based models.

PEP Run Report for Integrated Test A, Caustic Leaching in UFP-VSL-T01A, Oxidative Leaching in UFP-VSL-T02A

Pacific Northwest National Laboratory (PNNL) was tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed and constructed and operated as part of a plan to respond to issue M12, “Undemonstrated Leaching Processes.”(a) The PEP, located in the Process Engineering Laboratory-West (PDLW) located in Richland, Washington, is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP replicates the WTP leaching processes using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing.

Shear Strength Measurement Benchmarking Tests for K Basin Sludge Simulants

Equipment development and demonstration testing for sludge retrieval is being conducted by the K Basin Sludge Treatment Project (STP) at the MASF (Maintenance and Storage Facility) using sludge simulants. In testing performed at the Pacific Northwest National Laboratory (under contract with the CH2M Hill Plateau Remediation Company), the performance of the Geovane instrument was successfully benchmarked against the M5 Haake rheometer using a series of simulants with shear strengths (τ) ranging from about 700 to 22,000 Pa (shaft corrected). Operating steps for obtaining consistent shear strength measurements with the Geovane instrument during the benchmark testing were refined and documented.

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.