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Title: Bicarbonate Elution of Uranium from Amidoxime-Based Polymer Adsorbents for Sequestering Uranium from Seawater

Abstract

Uranium adsorbed on amidoxime-based polyethylene fibers in simulated seawater can be quantitatively eluted using 3 M KHCO 3 at 40°C. Thermodynamic calculations are in agreement with the experimental observation that at high bicarbonate concentrations (3 M) uranyl ions bound to amidoxime molecules are converted to uranyl tris-carbonato complex in the aqueous solution. The elution process is basically the reverse reaction of the uranium adsorption process which occurs at a very low bicarbonate concentration (~10 -3 M) in seawater. The bicarbonate elution is followed by a NaOH treatment to remove natural organic matter adsorbed on the polymer adsorbent, in real seawater experiments. Furthermore, by using the sequential bicarbonate and NaOH elution, the adsorbent is reusable after rinsing with deionized water and the recycled adsorbent shows no loss of uranium loading capacity based on real seawater experiments.

Authors:
 [1];  [1];  [2];  [2];  [3];  [3];  [4];  [4];  [4]
  1. Univ. of Idaho, Moscow, ID (United States). Dept. of Chemistry
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Marine Sciences Lab.
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1362216
Alternate Identifier(s):
OSTI ID: 1400853
Grant/Contract Number:
AC05-00OR22725; 00042246
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry Select
Additional Journal Information:
Journal Volume: 2; Journal Issue: 13; Journal ID: ISSN 2365-6549
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; uranium; polyethyethylene; amidoxime; bicarbonate; seawater

Citation Formats

Pan, Horng-Bin, Wai, Chien M., Kuo, Li-Jung, Gill, Gary, Tian, Guoxin, Rao, Linfeng, Das, Sadananda, Mayes, Richard T., and Janke, Christopher J.. Bicarbonate Elution of Uranium from Amidoxime-Based Polymer Adsorbents for Sequestering Uranium from Seawater. United States: N. p., 2017. Web. doi:10.1002/slct.201700177.
Pan, Horng-Bin, Wai, Chien M., Kuo, Li-Jung, Gill, Gary, Tian, Guoxin, Rao, Linfeng, Das, Sadananda, Mayes, Richard T., & Janke, Christopher J.. Bicarbonate Elution of Uranium from Amidoxime-Based Polymer Adsorbents for Sequestering Uranium from Seawater. United States. doi:10.1002/slct.201700177.
Pan, Horng-Bin, Wai, Chien M., Kuo, Li-Jung, Gill, Gary, Tian, Guoxin, Rao, Linfeng, Das, Sadananda, Mayes, Richard T., and Janke, Christopher J.. Tue . "Bicarbonate Elution of Uranium from Amidoxime-Based Polymer Adsorbents for Sequestering Uranium from Seawater". United States. doi:10.1002/slct.201700177. https://www.osti.gov/servlets/purl/1362216.
@article{osti_1362216,
title = {Bicarbonate Elution of Uranium from Amidoxime-Based Polymer Adsorbents for Sequestering Uranium from Seawater},
author = {Pan, Horng-Bin and Wai, Chien M. and Kuo, Li-Jung and Gill, Gary and Tian, Guoxin and Rao, Linfeng and Das, Sadananda and Mayes, Richard T. and Janke, Christopher J.},
abstractNote = {Uranium adsorbed on amidoxime-based polyethylene fibers in simulated seawater can be quantitatively eluted using 3 M KHCO3 at 40°C. Thermodynamic calculations are in agreement with the experimental observation that at high bicarbonate concentrations (3 M) uranyl ions bound to amidoxime molecules are converted to uranyl tris-carbonato complex in the aqueous solution. The elution process is basically the reverse reaction of the uranium adsorption process which occurs at a very low bicarbonate concentration (~10-3 M) in seawater. The bicarbonate elution is followed by a NaOH treatment to remove natural organic matter adsorbed on the polymer adsorbent, in real seawater experiments. Furthermore, by using the sequential bicarbonate and NaOH elution, the adsorbent is reusable after rinsing with deionized water and the recycled adsorbent shows no loss of uranium loading capacity based on real seawater experiments.},
doi = {10.1002/slct.201700177},
journal = {Chemistry Select},
number = 13,
volume = 2,
place = {United States},
year = {Tue May 02 00:00:00 EDT 2017},
month = {Tue May 02 00:00:00 EDT 2017}
}

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  • Uranium adsorbed on amidoxime-based polyethylene fibers in simulated seawater can be quantitatively eluted using 3 M KHCO3 at 40°C. Thermodynamic calculations are in agreement with the experimental observation that at high bicarbonate concentrations (3 M) uranyl ions bound to amidoxime molecules are converted to uranyl tris-carbonato complex in the aqueous solution. The elution process is basically the reverse reaction of the uranium adsorption process which occurs at a very low bicarbonate concentration (~10-3 M) in seawater. In real seawater experiments, the bicarbonate elution is followed by a NaOH treatment to remove natural organic matter adsorbed on the polymer adsorbent. Usingmore » the sequential bicarbonate and NaOH elution, the adsorbent is reusable after rinsing with deionized water and the recycled adsorbent shows no loss of uranium loading capacity based on real seawater experiments.« less
  • Cited by 1
  • High-surface-area amidoxime and carboxylic acid grafted polymer adsorbents developed at Oak Ridge National Laboratory were tested for sequestering uranium in a flowing seawater flume system at the PNNL-Marine Sciences Laboratory. FTIR spectra indicate that a KOH conditioning process is necessary to remove the proton from the carboxylic acid and make the sorbent effective for sequestering uranium from seawater. The alkaline conditioning process also converts the amidoxime groups to carboxylate groups in the adsorbent. Both Na 2CO 3-H 2O 2 and hydrochloric acid elution methods can remove ~95% of the uranium sequestered by the adsorbent after 42 days of exposure inmore » real seawater. The Na 2CO 3-H 2O 2 elution method is more selective for uranium than conventional acid elution. Iron and vanadium are the two major transition metals competing with uranium for adsorption to the amidoxime-based adsorbents in real seawater.« less
  • High-surface-area amidoxime and carboxylic acid grafted polymer adsorbents developed at Oak Ridge National Laboratory were tested for sequestering uranium in a flowing seawater flume system at the PNNL-Marine Sciences Laboratory. FTIR spectra indicate that a KOH conditioning process is necessary to remove the proton from the carboxylic acid and make the sorbent effective for sequestering uranium from seawater. The alkaline conditioning process also converts the amidoxime groups to carboxylate groups in the adsorbent. Both Na 2CO 3 H 2O 2 and hydrochloric acid elution methods can remove ~95% of the uranium sequestered by the adsorbent after 42 days of exposuremore » in real seawater. The Na 2CO 3 H 2O 2 elution method is more selective for uranium than conventional acid elution. Iron and vanadium are the two major transition metals competing with uranium for adsorption to the amidoxime-based adsorbents in real seawater. Tiron (4,5-Dihydroxy-1,3-benzenedisulfonic acid disodium salt, 1 M) can remove iron from the adsorbent very effectively at pH around 7. The coordination between vanadium (V) and amidoxime is also discussed based on our 51V NMR data.« less
  • Conditioning of polymer fiber adsorbents grafted with amidoxime and carboxylic acid groups is necessary to make the materials hydrophilic for sequestering uranium from seawater. Spectroscopic techniques were employed to study the effectiveness of the traditional KOH conditioning method (2.5% KOH at 80 oC) on recently developed high-surface-area amidoxime-based polymer fiber adsorbents developed at Oak Ridge National Laboratory. FTIR spectra reveal that the KOH conditioning process removes the proton from the carboxylic acids and also converts the amidoxime groups to carboxylate groups in the adsorbent. With prolonged KOH treatment (>1 hr) at 80 oC, physical damage to the adsorbent material occursmore » which can lead to a significant reduction in the adsorbent’s uranium adsorption capability in real seawater during extended exposure times (>21 days). The physical damage to the adsorbent can be minimized by lowering KOH conditioning temperature. For the high-surface-area amidoxime-based adsorbents, 20 min of conditioning in 2.5% KOH at 80 oC or 1 hr of conditioning in 2.5% KOH at 60 oC appears sufficient to achieve de-protonation of the carboxylic acid with minimal harmful effects to the adsorbent material. The use of NaOH instead of KOH can also reduce the cost of the base treatment process required for conditioning the amidoxime-based sorbents with minimal loss of adsorption capacity (≤ 7%).« less