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Title: Effect of Oxalate on the Recycle of Neptunium Filtrate Solution by Anion Exchange

Abstract

A series of laboratory column runs has been performed that demonstrates the recovery of neptunium (Np) containing up to 0.05 M oxalate. Np losses were generally less than one percent to the raffinate for feed solutions that contained 2 to 10 g Np/L. Up to 16 percent Np losses were observed with lower Np feed concentrations, but those losses were attributed to the shortened residence times rather than the higher oxalate to Np ratios. Losses in the plant are expected to be significantly less due to the lower cross-section flowrate possible with existing plant pumps. Elimination of the permanganate treatment of filtrates appears to be reasonable since the amount of Np in those filtrates does not appear to be practical to recover. Combination of untreated filtrates with other actinide rich solutions is not advisable as precipitation problems are likely. If untreated filtrates are kept segregated from other actinide rich streams, the recovery of the remaining Np is probably still possible, but could be limited due to the excessively high oxalate to Np ratio. The persistence of hydrazine/hydrazoic acid in filtrate solutions dictates that the nitrite treatment be retained to eliminate those species from the filtrates prior to transfer to themore » canyon. Elimination of the permanganate treatment of precipitator flushes and recovery by anion exchange does not appear to be limited by the oxalate effect on anion exchange. Np from solutions with higher oxalate to Np molar ratios than expected in precipitator flushes was recovered with low to modest losses. Solubility problems appear to be unlikely when the moles of oxalate involved are less than the total number of moles of Np due to complexation effects. The presence of significant concentrations of iron (Fe) in the solutions will further decrease the probability of Np oxalate precipitation due the formation of Fe oxalate complexes. Np oxalate solubility data in 8 M HNO{sub 3} with from one to six times as much oxalate as Np have been obtained. These data supplement literature data in the high HNO{sub 3} low oxalate region, but provide additional data for solutions with relatively large amounts of Np present. Enhanced solubility of Np oxalate over that reported in the literature was observed.« less

Authors:
Publication Date:
Research Org.:
SRS
Sponsoring Org.:
USDOE
OSTI Identifier:
890156
Report Number(s):
WSRC-TR-2004-00554
TRN: US0604648
DOE Contract Number:
DE-AC09-96SR18500
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; NEPTUNIUM; OXALATES; CATALYTIC EFFECTS; PRECIPITATION; SOLUBILITY; RADIOACTIVE WASTE PROCESSING; ION EXCHANGE

Citation Formats

Kyser, E. Effect of Oxalate on the Recycle of Neptunium Filtrate Solution by Anion Exchange. United States: N. p., 2004. Web. doi:10.2172/890156.
Kyser, E. Effect of Oxalate on the Recycle of Neptunium Filtrate Solution by Anion Exchange. United States. doi:10.2172/890156.
Kyser, E. Thu . "Effect of Oxalate on the Recycle of Neptunium Filtrate Solution by Anion Exchange". United States. doi:10.2172/890156. https://www.osti.gov/servlets/purl/890156.
@article{osti_890156,
title = {Effect of Oxalate on the Recycle of Neptunium Filtrate Solution by Anion Exchange},
author = {Kyser, E},
abstractNote = {A series of laboratory column runs has been performed that demonstrates the recovery of neptunium (Np) containing up to 0.05 M oxalate. Np losses were generally less than one percent to the raffinate for feed solutions that contained 2 to 10 g Np/L. Up to 16 percent Np losses were observed with lower Np feed concentrations, but those losses were attributed to the shortened residence times rather than the higher oxalate to Np ratios. Losses in the plant are expected to be significantly less due to the lower cross-section flowrate possible with existing plant pumps. Elimination of the permanganate treatment of filtrates appears to be reasonable since the amount of Np in those filtrates does not appear to be practical to recover. Combination of untreated filtrates with other actinide rich solutions is not advisable as precipitation problems are likely. If untreated filtrates are kept segregated from other actinide rich streams, the recovery of the remaining Np is probably still possible, but could be limited due to the excessively high oxalate to Np ratio. The persistence of hydrazine/hydrazoic acid in filtrate solutions dictates that the nitrite treatment be retained to eliminate those species from the filtrates prior to transfer to the canyon. Elimination of the permanganate treatment of precipitator flushes and recovery by anion exchange does not appear to be limited by the oxalate effect on anion exchange. Np from solutions with higher oxalate to Np molar ratios than expected in precipitator flushes was recovered with low to modest losses. Solubility problems appear to be unlikely when the moles of oxalate involved are less than the total number of moles of Np due to complexation effects. The presence of significant concentrations of iron (Fe) in the solutions will further decrease the probability of Np oxalate precipitation due the formation of Fe oxalate complexes. Np oxalate solubility data in 8 M HNO{sub 3} with from one to six times as much oxalate as Np have been obtained. These data supplement literature data in the high HNO{sub 3} low oxalate region, but provide additional data for solutions with relatively large amounts of Np present. Enhanced solubility of Np oxalate over that reported in the literature was observed.},
doi = {10.2172/890156},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu Nov 18 00:00:00 EST 2004},
month = {Thu Nov 18 00:00:00 EST 2004}
}

Technical Report:

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  • Resulte of a laboratory investigation undertaken to adapt the Pu anion exchange process to the direct recovery of the Pu lost to the Task I oxalate filtrate are reported. It was found that the Button Line Task I Filtrate can be recovered by HNO/sub 3/ anion exchange process, thus isolating the Button Line from any solvent extraction process. (J.R.D.)
  • The effect of ferrous sulfamate (FS) oxidation and variation in nitric acid concentration on the removal of {sup 238}Pu contamination from Np by the HB-Line anion exchange flowsheet has been tested. Significant rejection of {sup 238}Pu was observed by washing with a reductive wash solution containing 6.0 to 6.8 M nitric acid (HNO{sub 3}) with as little as 30% of the Fe{sup 2+} from the FS remaining in its reduced form. To achieve the desired 30% removal of {sup 238}Pu from the process, conditions should be controlled to maintain the Fe{sup 2+}/Fe{sup 3+} ratio in the reductive wash to bemore » greater than 60%/40% (or 1.5). Since Fe{sup 2+} oxidation is strongly affected by temperature and nitric acid concentration, these parameters (as well as time after FS addition) need to be controlled to ensure predictable results. A shortened-height column was utilized in these tests to match changes in the plant equipment. Lab experiments scaled to plant batch sizes of 2000 g Np were observed with modest losses for ''up-flow'' washing. The following are recommended conditions for removing {sup 238}Pu from Np solutions by anion exchange in HB-Line: (1) Feed conditions: ''Up-flow'' 6.4-8.0 M HNO{sub 3}, 0.02 M hydrazine (N{sub 2}H{sub 4}), 0.05 M excess FS. (2) Reductive Wash conditions: ''Up-flow'' 6 Bed volumes (BV) of 6.4 M HNO{sub 3}, 0.05 M FS (minimum 0.03M Fe{sup 2+} during wash cycle), 0.05 M hydrazine, less than 1.8 mL/min/cm{sup 2} flowrate. (3) Decontamination Wash conditions: ''Up-flow'' 1-2 BV of 6.4-8.0 M HNO{sub 3}, no FS, no hydrazine, less than 1.8 mL/min/cm{sup 2} flowrate. (4) Elution conditions: ''Down-flow'' 0.17 M HNO{sub 3}, 0.05 M hydrazine, no FS.« less
  • Full text of publication follows: Anion exchange was investigated as a means to recover and purify neptunium (Np) from solutions containing significant plutonium (Pu), sodium (Na), and manganese (Mn) impurities and a high nitrate concentration. The solution being evaluated resulted from lean filtrate and precipitator clean-out solutions which were generated during Np processing at the Savannah River Site. Prior to anion exchange, valence adjustment of the Np using ferrous sulfamate (i.e., Fe{sub 2}(SO{sub 3}NH{sub 2}){sub 2} or FS) was evaluated. For testing, a simulated filtrate solution was made with {approx}1.5 g Np/L and slightly elevated levels of impurities. Two anionmore » exchange column runs were performed. In both runs, Np was loaded onto Reillex HPQ resin in high nitric acid (HNO{sub 3}) solution, typical for Np processing. The resin wash step differed in the two runs, but the elution step was the same. In the first column run, 12 column bed volumes (BV) of reductive or partition wash with 6.4 M nitric acid / 0.05 M FS were used. In the second run, six BV of 5 M HNO{sub 3} / 0.05 M FS were used as the reductive wash. Reported results will include Pu rejection, Np losses and decontamination factors for Na and Mn. (authors)« less
  • A new anion flowsheet for use in HB-Line was tested in the lab with Reillex{trademark} HPQ for removal of Pu{sup 238} contamination from Np. Significant rejection of Pu{sup 238} was observed by washing with 6 to 12 bed volumes (BV) of reductive wash containing reduced nitric acid concentration along with both ferrous sulfamate (FS) and hydrazine. A shortened-height column was utilized in these tests to match changes in the plant equipment. Lab experiments scaled to plant batch sizes of 1500 to 2200 g Np were observed with modest losses for up-flow washing. Down-flow washing was observed to have high losses.more » The following are recommended conditions for removing Pu{sup 238} from Np solutions by anion exchange in HB-Line: (1) Feed conditions: Up-flow 6.4-8 M HNO{sub 3}, 0.02 M hydrazine, 0.05 M excess FS, less than 5 days storage of solution after FS addition. (2) Reductive Wash conditions: Up-flow 6-12 BV of 6.4 M HNO{sub 3}, 0.05 M FS, 0.05 M hydrazine. 1.8 mL/min/cm{sup 2} flowrate. (3) Decontamination Wash conditions: Up-flow 1-2 BV of 6.4-8 M HNO{sub 3}, no FS, no hydrazine. (4) Elution conditions: Down-flow 0.17 M HNO{sub 3}, 0.05 M hydrazine, no FS.« less