Degradation of the mixed organic solvents of tributyl phosphate and n-dodecane by heterogeneous Fenton-like oxidation using nanoscale zero-valent iron as the catalyst

Abstract

The treatment and disposal of spent radioactive organic solvents, i.e., tributyl phosphate (TBP) and diluent (such as kerosene, n-dodecane, etc.), produced in the reprocessing of spent fuel in the closed cycle are crucial for the sustainable development of the nuclear industry. In this study, the synthesized nanoscale zero-valent iron (nZVI) was used as the heterogeneous Fenton-like catalyst to promote the generation of hydroxyl radicals (•OH) by reacting with H2O2 to degrade the mixed organic solvents of TBP and n-dodecane. nZVI was characterized by scanning electron microscopy (SEM), nitrogen adsorption/desorption isotherms, and X-ray photoelectron spectroscopy (XPS) to investigate the micro-morphology, nano-particle size, and surface valence state. The change of Fe2+/Fe3+ concentration ratio during the reaction was measured to clarify the performance of nZVI. The effects of temperature, catalyst dosage, H2O2 dosage, and acidifier concentration on the degradation of TBP and n-dodecane were studied, and the results were complemented by the COD of the aqueous solution and the volume reduction rate of the organic phase. The mixed organic solvents of TBP and n-dodecane containing Co2+ were used to simulate the spent radioactive organic solvents and to study the distribution of nuclides after the reaction. The results showed that most of the radioactivity was in the residual solution, and the condensate contained almost no radioactivity. The degradation of TBP and n-dodecane was carried out separately, which showed that n-dodecane was more difficult to degrade. Density functional theory (DFT) calculations were applied to determine the adsorption energy of organic solvents and nZVI. According to the Fourier transform infrared spectra (FTIR) and their corresponding DFT calculations, liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) of the sample after the reaction, the possible intermediates were analyzed, and the degradation mechanism was speculated.