It is possible to retrieve a large fraction of soluble waste from the Hanford single-shell waste tanks (SSTs) by dissolving it with water. This retrieval method will be demonstrated in Tanks U-107 and S-112 in the next few years. If saltcake dissolution proves practical and effective, many of the saltcake SSTs may be retrieved by this method. Many of the SSTs retain flammable gas that will be released into the tank headspace as the waste dissolves. This report describes the physical processes that control dissolution and gas release. Calculation results are shown and describe how the headspace hydrogen concentration evolves during dissolution. The observed spontaneous and induced gas releases from SSTs are summarized, and the dissolution of the crust layer in SY-101 is discussed as a recent example of full-scale dissolution of saltcake containing a large volume of retained gas. The report concludes that the dissolution rate is self-limiting and that gas release rates are relatively low.

It is possible to retrieve a large fraction of soluble waste from the Hanford single-shell waste tanks (SST) by dissolving it with water. This retrieval method will be demonstrated in U-107 and S-112 in the next few years. If saltcake dissolution proves practical and effective, many of the saltcake SSTs may be retrieved by this method. Many of the SSTs retain a large volume of flammable gas that will be released into the tank headspace as the waste dissolves. This report describes the physical processes that control dissolution and gas release. Calculation results are shown describing the headspace hydrogen concentration transient during dissolution. The observed spontaneous and induced gas releases from SSTs is summarized and the dissolution of the crust layer in SY-101 is discussed as a recent example of full-scale dissolution of saltcake containing a very large volume of retained gas. The report concludes that the dissolution rate is self limiting and gas release rates are relatively low.

The high-level radioactive wastes in many single-shell tanks (SSTs) at the Hanford Site are to be retrieved by a modified sluicing method that uses water jets to dissolve the water-soluble waste and mobilize the water-insoluble waste. Retrieval operations will liberate any waste gases trapped in the wetted solid waste matrix, and these gases will be released into the tank headspaces. Because the trapped gases include the flammable species hydrogen, methane, and ammonia, a concern exists that a flammable mixture could be formed in the tank headspaces. This report combines conservative retained gas inventory estimates and tank data with anticipated waste retrieval rates to estimate the potential headspace flammability of selected SSTs during modified sluicing waste retrieval operations. Considered here are nine of the 12 tanks from the 241-S tank farm (241-S-107, 241-S-111, and 241-S 112 are not considered) and Tank 241-U-107. This report is intended to support the specification of process controls that ensure flammable conditions do not develop in the tank headspaces. Consequently, the physical scenarios considered, the models developed to estimate retained gas releases and the tank headspace compositions under these scenarios, and the model input data are intended to conservatively assess the potential to reach headspace flammability. The analyses are intended to address worst-case conditions and establish reasonable upper bounds on the achievable flammability of the tank headspaces. Flammable retained gas inventories, for example, are based on the 95th percentile developed by Barker and Hedengren (2003), giving 95% confidence that actual inventories are smaller than those used in the calculations. Gas releases and headspace flammability were evaluated for three general scenarios: a very aggressive dissolution and erosion of saltcake waste by water jets impinging on the waste surface, the drainage of interstitial liquids from saltcake during a shutdown of the retrieval process, and the dissolution of saltcake by unsaturated liquids during a shutdown of the retrieval process. The simple model of waste retrieval using the modified sluicing approach indicated that the flammable gas headspace concentrations can rapidly approach the action level of 25% of the lower flammability limit (LFL) when the tank is passively ventilated. While it is not necessary to use the portable exhauster to maintain the headspace hydrogen concentration below this action level, retrieval rates would probably be limited by the slow removal of flammable gases by passive ventilation. It was determined that using a portable exhauster anywhere in the assumed operating range of 270 to 475 cfm would prevent the headspaces from reaching the 25% of LFL action level even if the water jets are very effective at eroding the saltcake. Specific guidelines are developed to ensure that, in the event of a catastrophic loss of the retrieval pump and portable exhauster, headspace flammability will not reach the LFL. This report is Revision 1 of PNNL-14271. This revision expands the analysis of interstitial liquid drainage-induced gas releases to address a general retrieval scenario (the previous version of this report assumed a center-out retrieval approach and conditions). Tank waste conditions (waste volumes, interstitial liquid levels, temperatures, retained gas void fractions, etc.) have also been updated from the previous version.

This document describes the process controls for the tank 241-U-107 (U-107) saltcake dissolution proof-of-concept operations. Saltcake dissolution is defined as a method by which water-soluble salts will be retrieved from the Hanford Site radioactive waste tanks utilizing dissolution as the mobilizing mechanism. The proof-of-concept operations will monitor the retrieval process and transfer at least 100 kgal of fluid from tank U-107 to the double-shell tank (DST) system during the performance period. Tank U-107 has been identified as posing the highest long-term risk to the Columbia River of all single shell tanks (SSTs). This is because of the high content of mobile, long-lived radionuclides mostly in the saltcake waste in the tank. To meet current contractual and consent decree commitments, tank U-107 is being prepared for interim stabilization in August 2001. It is currently scheduled for saltcake retrieval in 2023, near the end of the SST retrieval campaign because of a lack of infrastructure in U-Farm. The proof-of-concept test will install a system to dissolve and retrieve a portion of the saltcake as part of, and operating in parallel with, the standard interim stabilization system to be installed on tank U-107. This proof-of-concept should provide key information on spray nozzle selection and effective spray patterns, leak detection, monitoring, and mitigation (LDMM) and in-tank saltcake solubility data that will help in the design of a full-tank retrieval demonstration system.

Results of column dissolution experiments designed to evaluate the physical and chemical processes inherent to saltcake dissolution are presented along with model chemical equilibrium calculations. Two different compositions representing saltcakes in Hanford tanks were characterized, and porosities and permeabilities for a third composition based upon the saltcake waste in Tank 41H at the Savannah River Site (SRS) were also evaluated. Whereas the surrogates are all chemically similar, the presence of high phosphate loadings for the Hanford (HNF) simulants was noted as significantly affecting draining. The permeability was higher for the SRS saltcake, and the sodium nitrate loading in this saltcake was roughly 80% by weight compared to less than 60% by weight for the HNF compositions. Average values of the permeability and porosity were reduced for the surrogates based on Hanford Tanks S-112 and S-101. Here a secondary layer formed above the saltcake bed and was found to contain a large amount of gibbsite, Al(OH)3. Experiments with 3 molal (m) NaOH as a diluent, compared to water, did not result in additional layer formation that has been attributed to a change in local pH thereby altering the solid liquid equilibrium. Chemical analysis of the two HNF saltcakes indicated solids re-precipitation as a function of diluent added. The events were signified by large decreases in the nitrate and carbonate anion concentrations and were confined to low % dilution by weight values. Solids re-precipitation is noted as arising from the mixing of the dissolved saltcake stream with pockets of saturated interstitial liquor.