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Title: Stability of the Caustic-Side Solvent Extraction (CSSX) Process Solvent: Effect of High Nitrite on Solvent Nitration

Abstract

The purpose of this investigation was to determine whether nitrated organic compounds could be formed during operation of the Caustic-Side Solvent Extraction (CSSX) process, and whether such compounds would present a safety concern. The CSSX process was developed to remove cesium from alkaline high-level salt waste stored at the US Department of Energy Savannah River Site (SRS). The solvent is composed of the cesium extractant calix[4]arene-bis-(4-tert-octylbenzo-crown-6) (BOBCalixC6), a fluorinated alcohol phase modifier, tri-n-octylamine (TOA), and an isoparaffinic diluent (Iospar{reg_sign}). During the CSSX process, the solvent is expected to be exposed to high concentrations of nitrate and nitrite dissolved in the alkaline waste feed. The solvent will also be exposed to dilute (50 mM) nitric acid solutions containing low concentrations of nitrite during scrubbing, followed by stripping with 1 mM nitric acid. The solvent is expected to last for one year of plant operation, and the temperatures the solvent may experience during the process could range from as low as 15 C to as high as 35 C. Excursions from standard process conditions could result in the solvent experiencing higher temperatures, as well as concentrations of nitrate, nitrite, and most importantly nitric acid, that exceed normal operating conditions. Accordingly, conditions maymore » exist where nitration reactions involving the solvent components, possibly leading to other chemical reactions stemming from nitration reactions, could occur. To model such nitration reactions, the solvent was exposed to the types of nitrate- and nitrite-containing solutions that might be expected to be encountered during the process (even under off-normal conditions), as a function of time, temperature, and concentration of nitrate, nitrite, and nitric acid. The experiments conducted as part of this report were designed to examine the more specific effect that high nitrite concentrations could have on forming nitrated organics. The present set of results supplement those obtained from earlier experiments conducted in FY 2001 in which nitration effects due to nitric acid alone and an average nitrite-containing alkaline simulant were examined.« less

Authors:
Publication Date:
Research Org.:
ORNL Oak Ridge National Laboratory (US)
Sponsoring Org.:
WORK FOR OTHERS (US)
OSTI Identifier:
814158
Report Number(s):
ORNL/TM-2002/115
TRN: US200317%%38
DOE Contract Number:
AC05-00OR22725
Resource Type:
Technical Report
Resource Relation:
Other Information: PBD: 26 Jun 2002
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; ALCOHOLS; CESIUM; CHEMICAL REACTIONS; NITRATES; NITRATION; NITRIC ACID; NITRITES; ORGANIC COMPOUNDS; SAFETY; SAVANNAH RIVER; SCRUBBING; SOLVENT EXTRACTION; SOLVENTS; STABILITY; WASTES

Citation Formats

Bonnesen, P.V. Stability of the Caustic-Side Solvent Extraction (CSSX) Process Solvent: Effect of High Nitrite on Solvent Nitration. United States: N. p., 2002. Web. doi:10.2172/814158.
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Bonnesen, P.V. Stability of the Caustic-Side Solvent Extraction (CSSX) Process Solvent: Effect of High Nitrite on Solvent Nitration. United States. doi:10.2172/814158.
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Bonnesen, P.V. Wed . "Stability of the Caustic-Side Solvent Extraction (CSSX) Process Solvent: Effect of High Nitrite on Solvent Nitration". United States. doi:10.2172/814158. https://www.osti.gov/servlets/purl/814158.
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@article{osti_814158,
title = {Stability of the Caustic-Side Solvent Extraction (CSSX) Process Solvent: Effect of High Nitrite on Solvent Nitration},
author = {Bonnesen, P.V.},
abstractNote = {The purpose of this investigation was to determine whether nitrated organic compounds could be formed during operation of the Caustic-Side Solvent Extraction (CSSX) process, and whether such compounds would present a safety concern. The CSSX process was developed to remove cesium from alkaline high-level salt waste stored at the US Department of Energy Savannah River Site (SRS). The solvent is composed of the cesium extractant calix[4]arene-bis-(4-tert-octylbenzo-crown-6) (BOBCalixC6), a fluorinated alcohol phase modifier, tri-n-octylamine (TOA), and an isoparaffinic diluent (Iospar{reg_sign}). During the CSSX process, the solvent is expected to be exposed to high concentrations of nitrate and nitrite dissolved in the alkaline waste feed. The solvent will also be exposed to dilute (50 mM) nitric acid solutions containing low concentrations of nitrite during scrubbing, followed by stripping with 1 mM nitric acid. The solvent is expected to last for one year of plant operation, and the temperatures the solvent may experience during the process could range from as low as 15 C to as high as 35 C. Excursions from standard process conditions could result in the solvent experiencing higher temperatures, as well as concentrations of nitrate, nitrite, and most importantly nitric acid, that exceed normal operating conditions. Accordingly, conditions may exist where nitration reactions involving the solvent components, possibly leading to other chemical reactions stemming from nitration reactions, could occur. To model such nitration reactions, the solvent was exposed to the types of nitrate- and nitrite-containing solutions that might be expected to be encountered during the process (even under off-normal conditions), as a function of time, temperature, and concentration of nitrate, nitrite, and nitric acid. The experiments conducted as part of this report were designed to examine the more specific effect that high nitrite concentrations could have on forming nitrated organics. The present set of results supplement those obtained from earlier experiments conducted in FY 2001 in which nitration effects due to nitric acid alone and an average nitrite-containing alkaline simulant were examined.},
doi = {10.2172/814158},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Jun 26 00:00:00 EDT 2002},
month = {Wed Jun 26 00:00:00 EDT 2002}
}
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DOI:  10.2172/814158
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