Synthesis and evaluation of a camphorquinone-derived BTP for minor actinide separation from acidic high-level radioactive liquid waste

A camphorquinone-derived bis-triazinylpyridine, bis-2,6-(5,6,7,8-tetrahydro-5,9,9-trimethyl-5,8-methano-1,2,4-benzotriazin-3-yl)pyridine (CA-BTP), was synthesised and systematically evaluated for the selective separation of minor actinides (MA: <sup>241</sup>Am and <sup>154</sup>Eu) from acidic high-level radioactive liquid waste (HLW). The extractant was purified by gradient polarity chromatography, with structure confirmation <i>via</i> FT-IR, <sup>1</sup>H NMR, ESI-MS, and TG-DSC, affirming chemical purity and thermal robustness. Extraction studies revealed excellent solubility and stability in 1-octanol and isodecyl alcohol (IDA), with sharp phase separation and no third-phase formation. Radiotracer experiments using <sup>241</sup>Am and <sup>154</sup>Eu demonstrated high selectivity, achieving separation factors (SF<sub>Am/Eu</sub>) of 150-280 at 1 M HNO<sub>3</sub> using 0.1 M CA-BTP. Mechanistic investigations included acid uptake, nitrate ion dependence, temperature variation, and slope analysis, revealing a 3 : 1 ligand-to-metal stoichiometry and an exothermic extraction process (Δ<i>H</i> = -33.6 to -42.5 kJ mol<sup>-1</sup>). CA-BTP also showed efficient back-extraction under mild acidic conditions (0.01 M HNO<sub>3</sub>), without the need for synergists or complexing agents. These findings position CA-BTP as a robust, scalable, and selective extractant for advanced SANEX-type flowsheets aimed at minor actinide partitioning from chemically similar lanthanides.

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Publication Details

Journal
RSC Advances
Published
2025-01-01
DOI
https://doi.org/10.1039/d5ra05245a
Primary Topic
Radioactive element chemistry and processing
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article
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article

Synthesis and evaluation of a camphorquinone-derived BTP for minor actinide separation from acidic high-level radioactive liquid waste

Suneel Gattu, Kumari Anshul, S. Srinivasan, G. Srinivasa Rao et al.
RSC Advances
Radioactive element chemistry and processing
article

Synthesis and evaluation of a camphorquinone-derived BTP for minor actinide separation from acidic high-level radioactive liquid waste

Suneel Gattu, Kumari Anshul, S. Srinivasan, G. Srinivasa Rao, Selvakumar Jayaprakasam
article en

Abstract

A camphorquinone-derived bis-triazinylpyridine, bis-2,6-(5,6,7,8-tetrahydro-5,9,9-trimethyl-5,8-methano-1,2,4-benzotriazin-3-yl)pyridine (CA-BTP), was synthesised and systematically evaluated for the selective separation of minor actinides (MA: <sup>241</sup>Am and <sup>154</sup>Eu) from acidic high-level radioactive liquid waste (HLW). The extractant was purified by gradient polarity chromatography, with structure confirmation <i>via</i> FT-IR, <sup>1</sup>H NMR, ESI-MS, and TG-DSC, affirming chemical purity and thermal robustness. Extraction studies revealed excellent solubility and stability in 1-octanol and isodecyl alcohol (IDA), with sharp phase separation and no third-phase formation. Radiotracer experiments using <sup>241</sup>Am and <sup>154</sup>Eu demonstrated high selectivity, achieving separation factors (SF<sub>Am/Eu</sub>) of 150-280 at 1 M HNO<sub>3</sub> using 0.1 M CA-BTP. Mechanistic investigations included acid uptake, nitrate ion dependence, temperature variation, and slope analysis, revealing a 3 : 1 ligand-to-metal stoichiometry and an exothermic extraction process (Δ<i>H</i> = -33.6 to -42.5 kJ mol<sup>-1</sup>). CA-BTP also showed efficient back-extraction under mild acidic conditions (0.01 M HNO<sub>3</sub>), without the need for synergists or complexing agents. These findings position CA-BTP as a robust, scalable, and selective extractant for advanced SANEX-type flowsheets aimed at minor actinide partitioning from chemically similar lanthanides.

RSC AdvancesVol. 15(44)
Bhabha Atomic Research Centre (IN), Homi Bhabha National Institute (IN), Indira Gandhi Centre for Atomic Research (IN)
Openalex Percentile: Top 77%
Radioactive element chemistry and processing
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