Reid A. Peterson

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.

Development and Demonstration of Ultrafiltration Simulants

According to Bechtel National, Inc. (BNI) Test Specification 24590-PTF-TSP-RT-06-006, Rev 0, Simulant Development to Support the Development and Demonstration of Leaching and Ultrafiltration Pretreatment Processes,” simulants for boehmite, gibbsite, and filtration are to be developed that can be used in subsequent bench and integrated testing of the leaching/filtration processes for the waste treatment plant (WTP). These simulants will then be used to demonstrate the leaching process and to help refine processing conditions which may impact safety basis considerations (Smith 2006). This report documents the results of the filtration simulant development.

Process Development for Permanganate Addition During Oxidative Leaching of Hanford Tanks Sludges

Previous Bechtel National, Incorporated (BNI)-sponsored studies have targeted optimizing sodium permanganate for the selective oxidation of chromium from washed Hanford tank sludges (Rapko et al. 2004; Rapko et al. 2005). The recommendation from previous work was that contact with sodium permanganate in a minimally caustic solution, i.e., 0.1 to 0.25 M [OH-] initially, provided maximum Cr dissolution while minimizing concomitant Pu dissolution. At the request of BNI, further work on oxidative alkaline leaching was performed.

Development and Characterization of Boehmite Component Simulant

According to Bechtel National Inc.’s (BNI’s) Test Specification 24590-PTF-TSP-RT-06-006, Rev 0, “Simulant Development to Support the Development and Demonstration of Leaching and Ultrafiltration Pretreatment Processes,” simulants for boehmite, gibbsite, and filtration are to be developed that can be used in subsequent bench and integrated testing of the leaching/filtration processes. These simulants will then be used to demonstrate the leaching process and to help refine processing conditions that may impact safety basis considerations (Smith 2006). This report documents the results of the boehmite simulant development.

Modeling of Boehmite Leaching from Actual Hanford High‐Level Waste Samples

Abstract The Department of Energy plans to vitrify approximately 60,000 metric tons of high level waste sludge from underground storage tanks at the Hanford Nuclear Reservation. To reduce the volume of high level waste requiring treatment, a goal has been set to remove about 90 percent of the aluminum, which comprises nearly 70 percent of the sludge. Aluminum in the form of gibbsite and sodium aluminate can be easily dissolved by washing the waste stream with caustic, but boehmite, which comprises nearly half of the total aluminum, is more resistant to caustic dissolution, and requires higher treatment temperatures and hydroxide concentrations. In this work, the dissolution kinetics of aluminum species during caustic leaching of actual Hanford high level waste samples is examined. The experimental results are used to develop a shrinking platelet model that provides a basis for the prediction of dissolution dynamics from a known process temperature and hydroxide concentration. This model is further developed to include the effects of particle size polydispersity, which is found to strongly influence the rate of dissolution. Two identical parameters for this model are used to describe leaching data from two sets of leaching results. When compared to other common monodisperse shrinking particle models, this result suggests a more physically meaningful model.

Methods to avoid post-filtration precipitation in treatment of high-level waste

The Hanford Tank Waste Treatment and Immobilization Plant, currently under construction for treating high level waste at the Hanford Site, will rely on ultrafiltration to provide solids/liquid separation as a core part of the treatment process. A series of bench-scale simulant tests have been performed to evaluate the potential for post-filtration precipitation. These tests focused on identifying precipitation from a range of potential feed compositions and providing the data required to evaluate mitigation options. This data is also important to the Savannah River Site as they are also attempting to dissolve saltcake from their tanks. Inadvertent solids formation after saltcake dissolution, either within a staging tank or in transfer piping can have serious repercussions on the eventual retrieval and transfer of the waste. A series of tests were performed using a variety of simulant samples. These tests identified the expected extent of supersaturation that develops under normal operations and identified and characterized the solids phases that are expected to form when the filtrate solutions are stored. In addition, tests identified the potential to mitigate the formation of these solids through both dilution and the application of increased temperature.

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.

Development of a Chemistry-Based, Predictive Method for Determining the Amount of Non-Pertechnetate Technetium in the Hanford Tanks: FY 2012 Progress Report

This report describes investigations directed toward understanding the extent of the presence of highly alkaline soluble, non-pertechnetate technetium (n-Tc) in the Hanford Tank supernatants. The goals of this report are to: a) present a review of the available literature relevant to the speciation of technetium in the Hanford tank supernatants, b) attempt to establish a chemically logical correlation between available Hanford tank measurements and the presence of supernatant soluble n-Tc, c) use existing measurement data to estimate the amount of n-Tc in the Hanford tank supernatants, and d) report on any likely, process-friendly methods to eventually sequester soluble n-Tc from Hanford tank supernatants.

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.