DM100 AND DM1200 MELTER TESTING WITH HIGH WASTE LOADING GLASS FORMULATIONS FOR HANFORD HIGH-ALUMINUM HLW STREAMS

This Test Plan describes work to support the development and testing of high waste loading glass formulations that achieve high glass melting rates for Hanford high aluminum high level waste (HLW). In particular, the present testing is designed to evaluate the effect of using low activity waste (LAW) waste streams as a source of sodium in place ofchemical additives, sugar or cellulose as a reductant, boehmite as an aluminum source, and further enhancements to waste processing rate while meeting all processing and product quality requirements. The work will include preparation and characterization of crucible melts in support of subsequent DuraMelter 100 (DM 100) tests designed to examine the effects of enhanced glass formulations, glass processing temperature, incorporation of the LAW waste stream as a sodium source, type of organic reductant, and feed solids content on waste processing rate and product quality. Also included is a confirmatory test on the HLW Pilot Melter (DM1200) with a composition selected from those tested on the DM100. This work builds on previous work performed at the Vitreous State Laboratory (VSL) for Department of Energy's (DOE's) Office of River Protection (ORP) to increase waste loading and processing rates for high-iron HLW waste streams as well as previous tests conducted for ORP on the same waste composition. This Test Plan is prepared in response to an ORP-supplied statement of work. It is currently estimated that the number of HLW canisters to be produced in the Hanford Tank Waste Treatment and Immobilization Plant (WTP) is about 12,500. This estimate is based upon the inventory ofthe tank wastes, the anticipated performance of the sludge treatment processes, and current understanding of the capability of the borosilicate glass waste form. The WTP HLW melter design, unlike earlier DOE melter designs, incorporates an active glass bubbler system. The bubblers create active glass pool convection and thereby improve heat transfer and glass melting rate. The WTP HLW melter has a glass surface area of 3.75 m{sup 2} and depth of {approx}1.1 m. The two melters in the HLW facility together are designed to produce up to 7.5 MT of glass per day at 100% availability. Further increases in HLW waste processing rates can potentially be achieved by increasing the melter operating temperature above 1150 C and by increasing the waste loading in the glass product Increasing the waste loading also has the added benefit of decreasing the number of canisters for storage. The current estimates and glass formulation efforts have been conservative in terms of achievable waste loadings. These formulations have been specified to ensure that the glasses are homogenous, contain essentially no crystalline phases, are processable in joule-heated, ceramic-lined melters and meet WTP contract requirements. The WTP's overall mission will require the immobilization oftank waste compositions that are dominated by mixtures of aluminum (Al), chromium (Cr), bismuth (Bi), iron (Fe), phosphorous (P), zirconium (Zr), and sulfur (S) compounds as waste-limiting components. Glass compositions for these waste mixtures have been developed based upon previous experience and current glass property models. Recently, DOE has initiated a testing program to develop and characterize HLW glasses with higher waste loadings. Results of this work have demonstrated the feasibility of increases in waste-loading from about 25 wt% to 33-50 wt% (based on oxide loading) in the glass depending on the waste stream. It is expected that these higher waste loading glasses will reduce the HLW canister production requirement by about 25% or more

FINAL REPORT DETERMINATION OF THE PROCESSING RATE OF RPP WTP HLW SIMULANTS USING A DURAMELTER J 1000 VITRIFICATION SYSTEM VSL-00R2590-2 REV 0 8/21/00

This report provides data, analysis, and conclusions from a series of tests that were conducted at the Vitreous State Laboratory of The Catholic University of America (VSL) to determine the melter processing rates that are achievable with RPP-WTP HLW simulants. The principal findings were presented earlier in a summary report (VSL-00R2S90-l) but the present report provides additional details. One of the most critical pieces of information in determining the required size of the RPP-WTP HLW melter is the specific glass production rate in terms of the mass of glass that can be produced per unit area of melt surface per unit time. The specific glass production rate together with the waste loading (essentially, the ratio of waste-in to glass-out, which is determined from glass formulation activities) determines the melt area that is needed to achieve a given waste processing rate with due allowance for system availability. As a consequence of the limited amount of relevant information, there exists, for good reasons, a significant disparity between design-base specific glass production rates for the RPP-WTP LAW and HLW conceptual designs (1.0 MT/m{sup 2}/d and 0.4 MT/m{sup 2}/d, respectively); furthermore, small-scale melter tests with HLW simulants that were conducted during Part A indicated typical processing rates with bubbling of around 2.0 MT/m{sup 2}/d. This range translates into more than a factor of five variation in the resultant surface area of the HLW melter, which is clearly not without significant consequence. It is clear that an undersized melter is undesirable in that it will not be able to support the required waste processing rates. It is less obvious that there are potential disadvantages associated with an oversized melter, over and above the increased capital costs. A melt surface that is consistently underutilized will have poor cold cap coverage, which will result in increased volatilization from the melt (which is generally undesirable) and increased plenum temperatures due to increased thermal radiation from the melt surface (which mayor may not be desirable but the flexibility to choose may be lost). Increased volatilization is an issue both in terms of the increased challenge to the off-gas system as well as for the ability to effectively close the recycle loops for volatile species that must be immobilized in the glass product, most notably technetium and cesium. For these reasons, improved information is needed on the specific glass production rates of RPP-WTP HLW streams in DuraMelterJ systems over a range of operating conditions. Unlike the RPP-WTP LAW program, for which a pilot melter system to provide large-scale throughout information is already in operation, there is no comparable HLW activity; the results of the present study are therefore especially important. This information will reduce project risk by reducing the uncertainty associated with the amount of conservatism that mayor may not be associated with the baseline RPP-WTP HLW melter sizing decision. After the submission of the first Test Plan for this work, the RPP-WTP requested revisions to include tests to determine the processing rates that are achievable without bubbling, which was driven by the potential advantages of omitting bubblers from the HLW melter design in terms of reduced maintenance. A further objective of this effort became the determination of whether the basis of design processing rate could be achieved without bubbling. Ideally, processing rate tests would be conducted on a full-scale RPP-WTP melter system with actual HLW materials, but that is clearly unrealistic during Part B1. As a practical compromise the processing rate determinations were made with HL W simulants on a DuraMelter J system at as close to full scale as possible and the DM 1000 system at VSL was selected for that purpose. That system has a melt surface area of 1.2 m{sup 2}, which corresponds to about one-third scale based on the specific glass processing rate of 0.4 MT/m{sup 2}/d assumed in the RPP-WTP HLW conceptual design, but would correspond to larger than full scale if the typical Part A test results of about 2.0 MT/m{sup 2}/d were realized. The DM 1000 system was used with the existing off-gas treatment system in order to expedite the collection of this information; while that system is somewhat different from the RPP-WTP conceptual design, that should have no effect on the processing rate measurements. Subsequent tasks supported the later modification of that off-gas system to obtain large-scale system performance information on the baseline off-gas design and those modifications are now complete. Work planned for Part B2 includes similar pilot-scale testing with the prototypical off-gas system. Three HLW simulant compositions were used in the present tests: the tank AZ-101 waste (the first B2 HLW feed to the RPP-WTP), the 106-C/AY-102 blend (the largest B2 HLW tank), and the HLW composition processed at West Valley

INTEGRATED DM 1200 MELTER TESTING OF HLW C-106/AY-102 COMPOSITION USING BUBBLERS VSL-03R3800-1 REV 0 9/15/03

This report documents melter and off-gas performance results obtained on the DM1200 HLW Pilot Melter during processing of simulated HLW C-106/AY-102 feed. The principal objectives of the DM1200 melter testing were to determine the achievable glass production rates for simulated HLW C-106/AY-102 feed; determine the effect of bubbling rate on production rate; characterize melter off-gas emissions; characterize the performance of the prototypical off-gas system components as well as their integrated performance; characterize the feed, glass product, and off-gas effluents; and to perform pre- and post test inspections of system components

FINAL REPORT START-UP AND COMMISSIONING TESTS ON THE DURAMELTER 1200 HLW PILOT MELTER SYSTEM USING AZ-101 HLW SIMULANTS VSL-01R0100-2 REV 0 1/20/03

This document provides the final report on data and results obtained from commissioning tests performed on the one-third scale DuraMelter{trademark} 1200 (DM 1200) HLW Pilot Melter system that has been installed at VSL with an integrated prototypical off-gas treatment system. That system has replaced the DM1000 system that was used for HLW throughput testing during Part BI [1]. Both melters have similar melt surface areas (1.2 m{sup 2}) but the DM1200 is prototypical of the present RPP-WTP HLW melter design whereas the DM1000 was not. These tests were performed under a corresponding RPP-WTP Test Specification and associated Test Plan. This report is a followup to the previously issued Preliminary Data Summary Report. The DM1200 system will be used for testing and confirmation of basic design, operability, flow sheet, and process control assumptions as well as for support of waste form qualification and permitting. This will include data on processing rates, off-gas treatment system performance, recycle stream compositions, as well as process operability and reliability. Consequently, this system is a key component of the overall HLW vitrification development strategy. The results presented in this report are from the initial series of short-duration tests that were conducted to support the start-up and commissioning of this system prior to conducting the main body of development tests that have been planned for this system. These tests were directed primarily at system 'debugging,' operator training, and procedure refinement. The AZ-101 waste simulant and glass composition that was used for previous testing was selected for these tests

Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy

Our knowledge of actinide chemical bonds lags far behind our understanding of the bonding regimes of any other series of elements. This is a major issue given the technological as well as fundamental importance of f-block elements. Some key chemical differences between actinides and lanthanides—and between different actinides—can be ascribed to minor differences in covalency, that is, the degree to which electrons are shared between the f-block element and coordinated ligands. Yet there are almost no direct measures of such covalency for actinides. Here we report the first pulsed electron paramagnetic resonance spectra of actinide compounds. We apply the hyperfine sublevel correlation technique to quantify the electron-spin density at ligand nuclei (via the weak hyperfine interactions) in molecular thorium(III) and uranium(III) species and therefore the extent of covalency. Such information will be important in developing our understanding of the chemical bonding, and therefore the reactivity, of actinides

FINAL REPORT MELTER TESTS WITH AZ-101 HLW SIMULANT USING A DURAMELTER 100 VITRIFICATION SYSTEM VSL-01R10N0-1 REV 1 2/25/02

This report provides data, analyses, and conclusions from a series of tests that were conducted at the Vitreous State Laboratory of The Catholic of America (VSL) to determine the processing rates that are achievable with AZ-101 HLW simulants and corresponding melter feeds on a DuraMelter 100 (DM100) vitrification system. One of the most critical pieces of information in determining the required size of the RPP-WTP HLW melter is the specific glass production rate in terms of the mass of glass that can be produced per unit area of melt surface per unit time. The specific glass production rate together with the waste loading (essentially, the ratio of waste-in to glass-out, which is determined from glass formulation activities) determines the melt area that is needed to achieve a given waste processing rate with due allowance for system availability. Tests conducted during Part B1 (VSL-00R2590-2) on the DM1000 vitrification system installed at the Vitreous State Laboratory of The Catholic University of America showed that, without the use of bubblers, glass production rates with AZ-101 and C-106/AY-102 simulants were significantly lower than the Project design basis rate of 0.4 MT/m{sup 2}/d. Conversely, three-fold increases over the design basis rate were demonstrated with the use of bubblers. Furthermore, an un-bubbled control test using a replica of the melter feed used in cold commissioning tests at West Valley reproduced the rates that were observed with that feed on the WVDP production melter. More recent tests conducted on the DM1200 system, which more closely represents the present RPP-WTP design, are in general agreement with these earlier results. Screening tests conducted on the DM10 system have provided good indications of the larger-scale processing rates with bubblers (for both HL W and LAW feeds) but significantly overestimated the DM1000 un-bubbled rate observed for C-106/AY-102 melter feeds. This behavior is believed to be a consequence of the role of heat transfer in rate attainment and the much greater role of wall effects in heat transfer when the melt pool is not agitated. The DM100 melter used for the present tests has a surface area of 0.108 m{sup 2}, which is approximately 5 times larger than that of the DM10 (0.021 m{sup 2}) and approximately 11 times smaller than that of the DM1000 (1.2 m{sup 2}) (the DM1000 has since been replaced by a pilot-scale prototypical HLW melter, designated the DM1200, which has the same surface area as the DM1000). Testing on smaller melters is the most economical method for obtaining data over a wide range of operating conditions (particularly at extremes) and for guiding the more expensive tests that are performed at pilot-scale. Thus, one objective of these tests was to determine whether the DM100 melters are sufficiently large to reproduce the un-bubbled melt rates observed at the DM1000 scale, or to determine the extent of any off-set. DM100-scale tests can then be used to screen feed chemistry variations that may serve to increase the un-bubbled production rates prior to confirmation at pilot scale. Finally, extensive characterization data obtained on simulated HLW melter feeds formed from various glass forming additives indicated that there may be advantages in terms of feed rheology and stability to the replacement of some of the hydroxides by carbonates. A further objective of the present tests was therefore to identify any deleterious processing effects of such a change before adopting the carbonate feed as the baseline. Data from the WVDP melter using acidified (nitrated) feeds, and without bubbling, showed productions rates that are higher than those observed with the alkaline RPP feeds at the VSL. Therefore, the effect of feed acidification on production rate also was investigated. This work was performed under Test Specification, 'TSP-W375-00-00019, Rev 0, 'HLW-DM10 and DM100 Melter Tests' dated November 13, 2000 and the corresponding Test Plan. It should be noted, however, that the RPP-WTP Project directed a series of changes to the Test Plan as the results from previous tests were reported. As a result, the test matrix that was executed differs from that in the Test Plan

HIGH ALUMINUM HLW (HIGH LEVEL WASTE ) GLASSES FOR HANFORDS WTP (WASTE TREATMENT PROJECT)

This paper presents the results of glass formulation development and melter testing to identify high waste loading glasses to treat high-Al high level waste (HLW) at Hanford. Previous glass formulations developed for this HLW had high waste loadings but their processing rates were lower that desired. The present work was aimed at improving the glass processing rate while maintaining high waste loadings. Glass formulations were designed, prepared at crucible-scale and characterized to determine their properties relevant to processing and product quality. Glass formulations that met these requirements were screened for melt rates using small-scale tests. The small-scale melt rate screening included vertical gradient furnace (VGF) and direct feed consumption (DFC) melter tests. Based on the results of these tests, modified glass formulations were developed and selected for larger scale melter tests to determine their processing rate. Melter tests were conducted on the DuraMelter 100 (DMIOO) with a melt surface area of 0.11 m{sup 2} and the DuraMelter 1200 (DMI200) HLW Pilot Melter with a melt surface area of 1.2 m{sup 2}. The newly developed glass formulations had waste loadings as high as 50 wt%, with corresponding Al{sub 2}O{sub 3} concentration in the glass of 26.63 wt%. The new glass formulations showed glass production rates as high as 1900 kg/(m{sup 2}.day) under nominal melter operating conditions. The demonstrated glass production rates are much higher than the current requirement of 800 kg/(m{sup 2}.day) and anticipated future enhanced Hanford Tank Waste Treatment and Immobilization Plant (WTP) requirement of 1000 kg/(m{sup 2}.day)

FINAL REPORT TESTS ON THE DURAMELTER 1200 HLW PILOT MELTER SYSTEM USING AZ-101 HLW SIMULANTS VSL-02R0100-2 REV 1 2/17/03

This document provides the final report on data and results obtained from a series of nine tests performed on the one-third scale DuraMelter{trademark} 1200 (DM1200) HLW Pilot Melter system that has been installed at VSL with an integrated prototypical off-gas treatment system. That system has replaced the DM1000 system that was used for HLW throughput testing during Part B1 [1]. Both melters have similar melt surface areas (1.2 m{sup 2}) but the DM1200 is prototypical of the present RPP-WTP HLW melter design whereas the DM1000 was not. These tests were performed under a corresponding RPP-WTP Test Specification and associated Test Plans. The nine tests reported here were preceded by an initial series of short-duration tests conducted to support the start-up and commissioning of this system. This report is a followup to the previously issued Preliminary Data Summary Reports. The DM1200 system was deployed for testing and confirmation of basic design, operability, flow sheet, and process control assumptions as well as for support of waste form qualification and permitting. These tests include data on processing rates, off-gas treatment system performance, recycle stream compositions, as well as process operability and reliability. Consequently, this system is a key component of the overall HLW vitrification development strategy. The primary objective of the present series of tests was to determine the effects of a variety of parameters on the glass production rate in comparison to the RPP-WTP HL W design basis of 400 kg/m{sup 2}/d. Previous testing on the DMIOOO system [1] concluded that achievement of that rate with simulants of projected WTP melter feeds (AZ-101 and C-106/AY-102) was unlikely without the use of bubblers. As part of those tests, the same feed that was used during the cold-commissioning of the West Valley Demonstration Project (WVDP) HLW vitrification system was run on the DM1000 system. The DM1000 tests reproduced the rates that were obtained at the larger WVDP facility, lending confidence to the tests results [1]. Since the inclusion or exclusion of a bubbler has significant design implications, the Project commissioned further tests to address this issue. In an effort to identify factors that might increase the glass production rate for projected WTP melter feeds, a subsequent series of tests was performed on the DM100 system. Several tests variables led to glass production rate increases to values significantly above the 400 kg/m2/d requirement. However, while small-scale melter tests are useful for screening relative effects, they tend to overestimate absolute glass production rates, particularly for un-bubbled tests. Consequently, when scale-up effects were taken into account, it was not clear that any of the variables investigated would conclusively meet the 400 kg/m{sup 2}/d requirement without bubbling. The present series of tests was therefore performed on the DM1200 one-third scale HLW pilot melter system to provide the required basis for a final decision on whether bubblers would be included in the HLW melter. The present tests employed the same AZ-101 waste simulant and glass composition that was used for previous testing for consistency and comparability with the results from the earlier tests

FINAL REPORT INTEGRATED DM1200 MELTER TESTING USING AZ 102 AND C 106/AY-102 HLW SIMULANTS: HLW SIMULANT VERIFICATION VSL-05R5800-1 REV 0 6/27/05

The principal objectives of the DM1200 melter tests were to determine the effects of feed rheology, feed solid content, and bubbler configuration on glass production rate and off-gas system performance while processing the HLW AZ-101 and C-106/AY-102 feed compositions; characterize melter off-gas emissions; characterize the performance of the prototypical off-gas system components, as well as their integrated performance; characterize the feed, glass product, and off-gas effluents; and perform pre- and post test inspections of system components. The specific objectives (including test success criteria) of this testing, along with how each objective was met, are outlined in a table. The data provided in this Final Report address the impacts of HLW melter feed rheology on melter throughput and validation of the simulated HLW melter feeds. The primary purpose of this testing is to further validate/verify the HLW melter simulants that have been used for previous melter testing and to support their continued use in developing melter and off-gas related processing information for the Project. The primary simulant property in question is rheology. Simulants and melter feeds used in all previous melter tests were produced by direct addition of chemicals; these feed tend to be less viscous than rheological the upper-bound feeds made from actual wastes. Data provided here compare melter processing for the melter feed used in all previous DM100 and DM1200 tests (nominal melter feed) with feed adjusted by the feed vendor (NOAH Technologies) to be more viscous, thereby simulating more closely the upperbounding feed produced from actual waste. This report provides results of tests that are described in the Test Plan for this work. The Test Plan is responsive to one of several test objectives covered in the WTP Test Specification for this work; consequently, only part of the scope described in the Test Specification was addressed in this particular Test Plan. For the purpose of comparison, the tests reported here were performed with AZ-102 and C-106/AY-102 HLW simulants and glass compositions that are essentially the same as those used for recent DM1200 tests. One exception was the use of an alternate, higher-waste-loading C-106/AY-102 glass composition that was used in previous DM100 tests to further evaluate the performance of the optimized bubbler configuration