Gas Chromatographic Analysis of Solvent Used in Reactor Fuel Reprocessing and Fission Product Recovery.

Campbell, M.H.

doi:10.1021/ac60234a022

Cited by 6 publications

(1 citation statement)

References 15 publications

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“…In the PUREX process, where TBP exposed to acidic conditions (nitric acidaqueous phase) and gamma radiation (U, Th, and fission products), undergoes hydrolytic and radiolytic reactions resulting into formation of some undesired components mainly dibutyl phosphate (DBP) and to a lesser extent monobutyl phosphate (MBP). Numerous analytical methods like GC-FID [16][17][18][19], titrimetry [20], complex-gravimetry [21], ion pair chromatography [22][23][24], colorimetry [25,26], IR, UV-VIS, NMR spectroscopy [7,22], and AAS [27] exist to determine TBP at higher concentration level. High speed isotachophoresis [28] was successfully used to analyze degradation mixture of TBP.…”

Section: Introductionmentioning

confidence: 99%

Thermal Decomposition of Nitrated Tri-n-Butyl Phosphate in a Flow Reactor

Patil

Gaikar

Kumar

et al. 2012

ISRN Chemical Engineering

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Tri-n-butyl phosphate (TBP) is a universal nuclear extractant, commercially used in the PUREX process for the last 60 years. However, it is prone to nitration and thermal degradation, and as a consequence a red-oil event may be initiated under several operating conditions resulting in severe pressurization of vessel/cell if venting is inadequate. In this work, an attempt was made to understand the reaction pathway of thermal decomposition of nitrated TBP in a flow reactor at atmospheric pressure. Many reaction products were identified and quantified by instrumental methods like HPLC-RI and GC-TCD. The experimental data was analysed with a power law model and the apparent rate constants were estimated. The activation energy for thermal decomposition of nitrated TBP, assuming an Arrhenius type of temperature dependency, was estimated to be 47.39 ± 0.25 kJ·mol −1 . The effect of both varying temperature and concentration of nitric acid on conversion of TBP into degradation products and products distribution was experimentally studied. Based on the experimental observations, a reaction mechanism framework for thermal decomposition of nitrated TBP is proposed.

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