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Title: RECALIBRATION OF H CANYON ONLINE SPECTROPHOTOMETER AT EXTENDED URANIUM CONCENTRATION

Abstract

The H Canyon online spectrophotometers are calibrated for measurement of the uranium and nitric acid concentrations of several tanks in the 2nd Uranium Cycle.[1] The spectrometers, flow cells, and prediction models are currently optimized for a process in which uranium concentrations are expected to range from 0-15 g/L and nitric acid concentrations from 0.05-6 M. However, an upcoming processing campaign will involve 'Super Kukla' material, which has a lower than usual enrichment of fissionable uranium. Total uranium concentrations will be higher, spanning approximately 0-30 g/L U, with no change in the nitric acid concentrations. The new processing conditions require the installation of new flow cells with shorter path lengths. As the process solutions have a higher uranium concentration, the shorter path length is required to decrease the absorptivity to values closer to the optimal range for the instrument. Also, new uranium and nitric acid prediction models are required to span the extended uranium concentration range. The models will be developed for the 17.5 and 15.4 tanks, for which nitric acid concentrations will not exceed 1 M. The restricted acid range compared to the original models is anticipated to reduce the measurement uncertainty for both uranium and nitric acid. The onlinemore » spectrophotometers in H Canyon Second Uranium Cycle were modified to allow measurement of uranium and nitric acid for the Super Kukla processing campaign. The expected uranium concentrations, which are higher than those that have been recently processed, required new flow cells with one-third the optical path length of the existing cells. Also, new uranium and nitric acid calibrations were made. The estimated reading uncertainties (2{sigma}) for Tanks 15.4 and 17.5 are {approx}5% for uranium and {approx}25% for nitric acid.« less

Authors:
Publication Date:
Research Org.:
SRS
Sponsoring Org.:
USDOE
OSTI Identifier:
940391
Report Number(s):
SRNL-STI-2008-00411
TRN: US0807177
DOE Contract Number:
DE-AC09-08SR22470
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; PROCESS SOLUTIONS; SPECTROPHOTOMETERS; URANIUM; CALIBRATION; ON-LINE MEASUREMENT SYSTEMS; CONCENTRATION RATIO; SAMPLE HOLDERS; DESIGN

Citation Formats

Lascola, R. RECALIBRATION OF H CANYON ONLINE SPECTROPHOTOMETER AT EXTENDED URANIUM CONCENTRATION. United States: N. p., 2008. Web. doi:10.2172/940391.
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Lascola, R. RECALIBRATION OF H CANYON ONLINE SPECTROPHOTOMETER AT EXTENDED URANIUM CONCENTRATION. United States. doi:10.2172/940391.
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Lascola, R. Wed . "RECALIBRATION OF H CANYON ONLINE SPECTROPHOTOMETER AT EXTENDED URANIUM CONCENTRATION". United States. doi:10.2172/940391. https://www.osti.gov/servlets/purl/940391.
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@article{osti_940391,
title = {RECALIBRATION OF H CANYON ONLINE SPECTROPHOTOMETER AT EXTENDED URANIUM CONCENTRATION},
author = {Lascola, R},
abstractNote = {The H Canyon online spectrophotometers are calibrated for measurement of the uranium and nitric acid concentrations of several tanks in the 2nd Uranium Cycle.[1] The spectrometers, flow cells, and prediction models are currently optimized for a process in which uranium concentrations are expected to range from 0-15 g/L and nitric acid concentrations from 0.05-6 M. However, an upcoming processing campaign will involve 'Super Kukla' material, which has a lower than usual enrichment of fissionable uranium. Total uranium concentrations will be higher, spanning approximately 0-30 g/L U, with no change in the nitric acid concentrations. The new processing conditions require the installation of new flow cells with shorter path lengths. As the process solutions have a higher uranium concentration, the shorter path length is required to decrease the absorptivity to values closer to the optimal range for the instrument. Also, new uranium and nitric acid prediction models are required to span the extended uranium concentration range. The models will be developed for the 17.5 and 15.4 tanks, for which nitric acid concentrations will not exceed 1 M. The restricted acid range compared to the original models is anticipated to reduce the measurement uncertainty for both uranium and nitric acid. The online spectrophotometers in H Canyon Second Uranium Cycle were modified to allow measurement of uranium and nitric acid for the Super Kukla processing campaign. The expected uranium concentrations, which are higher than those that have been recently processed, required new flow cells with one-third the optical path length of the existing cells. Also, new uranium and nitric acid calibrations were made. The estimated reading uncertainties (2{sigma}) for Tanks 15.4 and 17.5 are {approx}5% for uranium and {approx}25% for nitric acid.},
doi = {10.2172/940391},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Oct 29 00:00:00 EDT 2008},
month = {Wed Oct 29 00:00:00 EDT 2008}
}
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DOI:  10.2172/940391
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  • Savannah River Technology Center (SRTC) evaluated the feasibility of using the H Canyon on-line diode array spectrophotometer to measure uranium concentrations in Tank 16.7. On-line measurements will allow an increase in highly enriched uranium (HEU) production by removing delays associated with off-line measurements. The instrument must be able to measure uranium at concentrations below 1.0 g/L with an uncertainty no greater than 0.3 g/L. SRTC determined that the system has a limit of quantitation of 0.15 g/L. At concentrations of 0.5 and 1.0 g/L, the spectrometer uncertainty is 0.10 g/L. No design changes, such as an increase in flow cellmore » path length, are required to obtain this performance. Expected levels of iron in Tank 16.7 solutions will not interfere with the measurement. The CHEMCHEK method should not be used for confirmatory analysis, as it contributes excessively to the overall uncertainty of the measurement. SRTC expects that the spectrophotometer will meet the measurement requirements for Tank 16.7.« less

  • ;
    An SRNL H-Canyon Test Bed performance evaluation project was completed jointly by SRNL and LANL on a prototype monochromatic energy dispersive x-ray fluorescence instrument, the hiRX. A series of uncertainty propagations were generated based upon plutonium and uranium measurements performed using the alpha-prototype hiRX instrument. Data reduction and uncertainty modeling provided in this report were performed by the SRNL authors. Observations and lessons learned from this evaluation were also used to predict the expected uncertainties that should be achievable at multiple plutonium and uranium concentration levels provided instrument hardware and software upgrades being recommended by LANL and SRNL are performed.

  • This report describes the on-line instrumentation developed by the Analytical Development Section of Savannah River Technology Center in support of Highly Enriched Uranium Blend Down processing in H Canyon.

  • Solution conductivity data from the 1CU conductivity meter in H-Canyon shows that uranium concentration in the 0 to 30 gram per liter (g/L) range has no statistically significant effect on the calibration of free nitric acid measurement. Based on these results, no additional actions are needed on the 1CU Conductivity Meter prior to or during the processing of uranium solutions in the 0 to 30 g/L range. A model based only on free nitric acid concentration is shown to be appropriate for explaining the data. Data uncertainties for the free acid measurement of uranium-bearing solutions are 8.5% or less atmore » 95% confidence. The analytical uncertainty for calibrating solutions is an order of magnitude smaller only when uranium is not present, allowing use of a more accurate analytical procedure. Literature work shows that at a free nitric acid level of 0.33 M, uranium concentration of 30 g/L and 25 C, solution conductivity is 96.4% of that of a uranium-free solution. The level of uncertainties in the literature data and its fitting equation do not justify calibration changes based on this small depression in solution conductivity. This work supports preparation of H-Canyon processing of Super Kukla fuel; however, the results will be applicable to the processing of any similar concentration uranium and nitric acid solution. Super Kukla fuel processing will increase the uranium concentration above the nominal zero to 10 g/L level, though not above 30 g/L. This work examined free nitric acid levels ranging from 0.18 to 0.52 molar. Temperature ranged from 27.9 to 28.3 C during conductivity testing. The data indicates that sequential order of measurement is not a significant factor. The conductivity meter was thus flushed effectively between measurements as desired.« less

  • ;
    Prior to the dissolution of Pu-containing materials in HB-Line, highly enriched uranium (HEU) solutions stored in Tanks 11.1 and 12.2 of H-Canyon must be transferred to provide storage space. The proposed plan is to centrifuge the solutions to remove solids which may present downstream criticality concerns or cause operational problems with the 1st Cycle solvent extraction due to the formation of stable emulsions. An evaluation of the efficiency of the H-Canyon centrifuge concluded that a sufficient amount (> 90%) of the solids in the Tank 11.1 and 12.2 solutions will be removed to prevent any problems. We based this conclusionmore » on the particle size distribution of the solids isolated from samples of the solutions and the calculation of particle settling times in the centrifuge. The particle size distributions were calculated from images generated by scanning electron microscopy (SEM). The mean particle diameters for the distributions were 1-3 {micro}m. A significant fraction (30-50%) of the particles had diameters which were < 1 {micro}m; however, the mass of these solids is insignificant (< 1% of the total solids mass) when compared to particles with larger diameters. It is also probable that the number of submicron particles was overestimated by the software used to generate the particle distribution due to the morphology of the filter paper used to isolate the solids. The settling times calculated for the H-Canyon centrifuge showed that particles with diameters less than 1 to 0.5 {micro}m will not have sufficient time to settle. For this reason, we recommend the use of a gelatin strike to coagulate the submicron particles and facilitate their removal from the solution; although we have no experimental basis to estimate the level of improvement. Incomplete removal of particles with diameters < 1 {micro}m should not cause problems during purification of the HEU in the 1st Cycle solvent extraction. Particles with diameters > 1 {micro}m account for > 99% of the solid mass and will be efficiently removed by the centrifuge; therefore, the formation of emulsions during solvent extraction operations is not an issue. Under the current processing plan, the solutions from Tanks 11.1 and 12.2 will be transferred to the enriched uranium storage (EUS) tank following centrifugation. The solution from Tanks 11.1 and 12.2 may remain in the EUS tank for an extended time prior to purification. The effects of extended storage on the solution were not evaluated as part of this study.« less