Elimination Of Catalytic Hydrogen Generation In Defense Waste Processing Facility Slurries

Based on lab-scale simulations of Defense Waste Processing Facility (DWPF) slurry chemistry, the addition of sodium nitrite and sodium hydroxide to waste slurries at concentrations sufficient to take the aqueous phase into the alkaline region (pH > 7) with approximately 500 mg nitrite ion/kg slurry (assuming <25 wt% total solids, or equivalently 2,000 mg nitrite/kg total solids) is sufficient to effectively deactivate the noble metal catalysts at temperatures between room temperature and boiling. This is a potential strategy for eliminating catalytic hydrogen generation from the list of concerns for sludge carried over into the DWPF Slurry Mix Evaporator Condensate Tank (SMECT) or Recycle Collection Tank (RCT). These conclusions are drawn in large part from the various phases of the DWPF catalytic hydrogen generation program conducted between 2005 and 2009. The findings could apply to various situations, including a solids carry-over from either the Sludge Receipt and Adjustment Tank (SRAT) or Slurry Mix Evaporator (SME) into the SMECT with subsequent transfer to the RCT, as well as a spill of formic acid into the sump system and transfer into an RCT that already contains sludge solids. There are other potential mitigating factors for the SMECT and RCT, since these vessels are typically operated at temperatures close to the minimum temperatures that catalytic hydrogen has been observed to occur in either the SRAT or SME (pure slurry case), and these vessels are also likely to be considerably more dilute in both noble metals and formate ion (the two essential components to catalytic hydrogen generation) than the two primary process vessels. Rhodium certainly, and ruthenium likely, are present as metal-ligand complexes that are favored under certain concentrations of the surrounding species. Therefore, in the SMECT or RCT, where a small volume of SRAT or SME material would be significantly diluted, conditions would be less optimal for forming or sustaining the catalytic ligand species. Such conditions are likely to adversely impact the ability of the transferred mass to produce hydrogen at the same rate (per unit mass SRAT or SME slurry) as in the SRAT or SME vessels

Atomic spectroscopy with the shock tube

Spectroscopy of light atoms and ions and transition probability determinations using gas-driven shock tub

Development of student knowledge in competence-based pre-vocational education

The purpose of this study was to gain insight into the development of student knowledge in pre-vocational secondary education schools which differ in the manner and extent to which they have implemented characteristics of competence-based education. The implementation of these characteristics was examined using a teacher questionnaire and the development of knowledge was investigated using concept mapping. The results showed that students developed slightly more knowledge in learning situations with fewer characteristics of competence-based education. The organisational characteristics of the learning situations were further found to be distinctive for the development of knowledge

SCIX IMPACT ON DWPF CPC

A program was conducted to systematically evaluate potential impacts of the proposed Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) Chemical Processing Cell (CPC). The program involved a series of interrelated tasks. Past studies of the impact of crystalline silicotitanate (CST) and monosodium titanate (MST) on DWPF were reviewed. Paper studies and material balance calculations were used to establish reasonable bounding levels of CST and MST in sludge. Following the paper studies, Sludge Batch 10 (SB10) simulant was modified to have both bounding and intermediate levels of MST and ground CST. The SCIX flow sheet includes grinding of the CST which is larger than DWPF frit when not ground. Nominal ground CST was not yet available, therefore a similar CST ground previously in Savannah River National Laboratory (SRNL) was used. It was believed that this CST was over ground and that it would bound the impact of nominal CST on sludge slurry properties. Lab-scale simulations of the DWPF CPC were conducted using SB10 simulants with no, intermediate, and bounding levels of CST and MST. Tests included both the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles. Simulations were performed at high and low acid stoichiometry. A demonstration of the extended CPC flowsheet was made that included streams from the site interim salt processing operations. A simulation using irradiated CST and MST was also completed. An extensive set of rheological measurements was made to search for potential adverse consequences of CST and MST and slurry rheology in the CPC. The SCIX CPC impact program was conducted in parallel with a program to evaluate the impact of SCIX on the final DWPF glass waste form and on the DWPF melter throughput. The studies must be considered together when evaluating the full impact of SCIX on DWPF. Due to the fact that the alternant flowsheet for DWPF has not been selected, this study did not consider the impact of proposed future alternative DWPF CPC flowsheets. The impact of the SCIX streams on DWPF processing using the selected flowsheet need to be considered as part of the technical baseline studies for coupled processing with the selected flowsheet. In addition, the downstream impact of aluminum dissolution on waste containing CST and MST has not yet been evaluated. The current baseline would not subject CST to the aluminum dissolution process and technical concerns with performing the dissolution with CST have been expressed. Should this option become feasible, the downstream impact should be considered. The main area of concern for DWPF from aluminum dissolution is an impact on rheology. The SCIX project is planning for SRNL to complete MST, CST, and sludge rheology testing to evaluate any expected changes. The impact of ground CST transport and flush water on the DWPF CPC feed tank (and potential need for decanting) has not been defined or studied

DWPF SIMULANT CPC STUDIES FOR SB7B

Lab-scale DWPF simulations of Sludge Batch 7b (SB7b) processing were performed. Testing was performed at the Savannah River National Laboratory - Aiken County Technology Laboratory (SRNL-ACTL). The primary goal of the simulations was to define a likely operating window for acid stoichiometry for the DWPF Sludge Receipt and Adjustment Tank (SRAT). In addition, the testing established conditions for the SRNL Shielded Cells qualification simulation of SB7b-Tank 40 blend, supported validation of the current glass redox model, and validated the coupled process flowsheet at the nominal acid stoichiometry. An acid window of 105-140% by the Koopman minimum acid (KMA) equation (107-142% DWPF Hsu equation) worked for the sludge-only flowsheet. Nitrite was present in the SRAT product for the 105% KMA run at 366 mg/kg, while SME cycle hydrogen reached 94% of the DWPF Slurry Mix Evaporator (SME) cycle limit in the 140% KMA run. The window was determined for sludge with added caustic (0.28M additional base, or roughly 12,000 gallons 50% NaOH to 820,000 gallons waste slurry). A suitable processing window appears to be 107-130% DWPF acid equation for sludge-only processing allowing some conservatism for the mapping of lab-scale simulant data to full-scale real waste processing including potentially non-conservative noble metal and mercury concentrations. This window should be usable with or without the addition of up to 7,000 gallons of caustic to the batch. The window could potentially be wider if caustic is not added to SB7b. It is recommended that DWPF begin processing SB7b at 115% stoichiometry using the current DWPF equation. The factor could be increased if necessary, but changes should be made with caution and in small increments. DWPF should not concentrate past 48 wt.% total solids in the SME cycle if moderate hydrogen generation is occurring simultaneously. The coupled flowsheet simulation made more hydrogen in the SRAT and SME cycles than the sludge-only run with the same acid stoichiometric factor. The slow acid addition in MCU seemed to alter the reactions that consumed the small excess acid present such that hydrogen generation was promoted relative to sludge-only processing. The coupled test reached higher wt.% total solids, and this likely contributed to the SME cycle hydrogen limit being exceeded at 110% KMA. It is clear from the trends in the SME processing GC data, however, that the frit slurry formic acid contributed to driving the hydrogen generation rate above the SME cycle limit. Hydrogen generation rates after the second frit addition generally exceeded those after the first frit addition. SRAT formate loss increased with increasing acid stoichiometry (15% to 35%). A substantial nitrate gain which was observed to have occurred after acid addition (and nitrite destruction) was reversed to a net nitrate loss in runs with higher acid stoichiometry (nitrate in SRAT product less than sum of sludge nitrate and added nitric acid). Increased ammonium ion formation was also indicated in the runs with nitrate loss. Oxalate loss on the order 20% was indicated in three of the four acid stoichiometry runs and in the coupled flowsheet run. The minimum acid stoichiometry run had no indicated loss. The losses were of the same order as the official analytical uncertainty of the oxalate concentration measurement, but were not randomly distributed about zero loss, so some actual loss was likely occurring. Based on the entire set of SB7b test data, it is recommended that DWPF avoid concentrating additional sludge solids in single SRAT batches to limit the concentrations of noble metals to SB7a processing levels (on a grams noble metal per SRAT batch basis). It is also recommended that DWPF drop the formic acid addition that accompanies the process frit 418 additions, since SME cycle data showed considerable catalytic activity for hydrogen generation from this additional acid (about 5% increase in stoichiometry occurred from the frit formic acid). Frit 418 also does not appear to need formic acid addition to prevent gel formation in the frit slurry. Simulant processing was successful using 100 ppm of 747 antifoam added prior to nitric acid instead of 200 ppm. This is a potential area for DWPF to cut antifoam usage in any future test program. An additional 100 ppm was added before formic acid addition. Foaming during formic acid addition was not observed. No build-up of oily or waxy material was observed in the off-gas equipment. Lab-scale mercury stripping behavior was similar to SB6 and SB7a. More mercury was unaccounted for as the acid stoichiometry increased

CATALYTIC INTERACTIONS OF RHODIUM, RUTHENIUM, AND MERCURY DURING SIMULATED DWPF CPC PROCESSING WITH HYDROGEN GENERATION

Simulations of the Defense Waste Processing Facility (DWPF) Chemical Processing Cell (CPC) vessels were performed as part of the ongoing investigation into catalytic hydrogen generation. Rhodium, ruthenium, and mercury have been identified as the principal elemental factors affecting the peak hydrogen generation rate in the DWPF Sludge Receipt and Adjustment Tank (SRAT) for a given acid addition. The primary goal of this study is to identify any significant interactions between the three factors. Noble metal concentrations were similar to recent sludge batches. Rh ranged from 0.0026-0.013% and Ru ranged from 0.010-0.050% in the dried sludge solids, while initial Hg ranged from 0.5-2.5 wt%. An experimental matrix was developed to ensure that the existence of statistically significant two-way interactions could be determined without confounding of the main effects with the two-way interaction effects. The nominal matrix design consisted of twelve SRAT cycles. Testing included: a three factor (Rh, Ru, and Hg) study at two levels per factor (eight runs), two duplicate midpoint runs, and two additional replicate runs to assess reproducibility away from the midpoint. Midpoint testing can identify potential quadratic effects from the three factors. A single sludge simulant was used for all tests. Acid addition was kept effectively constant except to compensate for variations in the starting mercury concentration. Six Slurry Mix Evaporator (SME) cycles were performed to supplement the SME hydrogen generation database. Some of the preliminary findings from this study include: (1) Rh was linked to the maximum SRAT hydrogen generation rate in the first two hours after acid addition in preliminary statistical modeling. (2) Ru was linked conclusively to the maximum SRAT hydrogen generation rate in the last four hours of reflux in preliminary statistical modeling. (3) Increasing the ratio of Hg/Rh shifted the noble metal controlling the maximum SRAT hydrogen generation rate from Rh to Ru when Ru was at its fission yield ratio to Rh. (4) The inhibiting effect of Hg on hydrogen generation apparently does not require much mercury in terms of moles Hg/mole Rh (or Ru). Once the initial impact is realized, the benefit of additional Hg in reducing the hydrogen generation rate was minimal. Sludge Batch 3 and 4 simulant test data confirm this. (5) Low Hg runs do not necessarily bound high Hg runs for the maximum hydrogen generation rate over the full SRAT-SME cycle. Two of the four Rh-Ru combinations had a cross-over point where the hydrogen generation rate in high Hg run went from always lower to always higher than in the low Hg run. One cross-over was in the SRAT and one was in the SME. Maximum hydrogen generation rates in the high Hg runs could exceed the maximum hydrogen generation rates from the low Hg runs. (6) SME cycle hydrogen generation rates during the first decon canister dewatering period were similar to the rates at the end of the SRAT reflux period. (7) Corrosion of 400 series stainless steel shafts significantly impacted the hydrogen generation rate in two runs. (8) Preliminary data analysis indicates that several additional SRAT runs are needed to replace suspect data in the original set of twelve runs. A more detailed statistical evaluation is expected to occur once replacement run data from several additional SRAT runs has been obtained

NOBLE METAL CHEMISTRY AND HYDROGEN GENERATION DURING SIMULATED DWPF MELTER FEED PREPARATION

Simulations of the Defense Waste Processing Facility (DWPF) Chemical Processing Cell vessels were performed with the primary purpose of producing melter feeds for the beaded frit program plus obtaining samples of simulated slurries containing high concentrations of noble metals for off-site analytical studies for the hydrogen program. Eight pairs of 22-L simulations were performed of the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles. These sixteen simulations did not contain mercury. Six pairs were trimmed with a single noble metal (Ag, Pd, Rh, or Ru). One pair had all four noble metals, and one pair had no noble metals. One supporting 4-L simulation was completed with Ru and Hg. Several other 4-L supporting tests with mercury have not yet been performed. This report covers the calculations performed on SRNL analytical and process data related to the noble metals and hydrogen generation. It was originally envisioned as a supporting document for the off-site analytical studies. Significant new findings were made, and many previous hypotheses and findings were given additional support as summarized below. The timing of hydrogen generation events was reproduced very well within each of the eight pairs of runs, e.g. the onset of hydrogen, peak in hydrogen, etc. occurred at nearly identical times. Peak generation rates and total SRAT masses of CO{sub 2} and oxides of nitrogen were reproduced well. Comparable measures for hydrogen were reproduced with more variability, but still reasonably well. The extent of the reproducibility of the results validates the conclusions that were drawn from the data

Macro, industry and frailty effects in defaults: The 2008 credit crisis in perspective

Most TI discussion papers can be downloaded a