Fluoride processing of oil hydrocarbon cracking catalyst with REE concentrate extraction

It is proposed to use a spent cracking catalyst of petroleum hydrocarbons containing 1 wt.% of rare earth element (REE) oxides as an alternative REE feed source. The study covers the process of removing silicon in the form of ammonium hexafluorosilicate (NH4)2SiF6 by sintering an oil cracking catalyst sample with NH4F and subsequent (NH4)2SiF6 sublimation to produce an aluminum-containing concentrate of rare earth elements. The orthogonal central compositional planning of the experiment was used to study the effect of three factors: sublimation temperature (350 to 400 °С), duration (40 to 80 min), and weight of the catalyst fluorinated sintered mass (5 to 10 g) on the (NH4)2SiF6 sublimation completeness. Results obtained in the experiment were used to build a second-order model, which correlate with experimental data. The dynamics of (NH4)2SiF6 sublimation removal was determined for sublimation durations of τ = 10, 20, 40 and 80 min at processing temperatures of 350, 375 and 400 °C. The (NH4)2SiF6 removal degree values calculated based on the second-order model for τ = 44, 48, 52, 56, 60, 64, 68, 72, and 76 min fit well the experimental curves. Spectra of fluorinated catalyst samples before and after sublimation were studied using X-ray phase analysis and IR spectroscopy. The data of IR spectroscopy and X-ray phase analysis are in good agreement and show that (NH4)2SiF6, (NH4)3AlF6 and unreacted NH4F are present in the catalyst with NH4F sintered mass, and only aluminum compounds are detected – NH4AlF4 and AlF3 after sublimation. These data indicate the completeness of the sublimation removal of silicon from the catalyst and NH4F sintered mass with NH4AlF4 and AlF3 aluminum compounds only observed after sublimation. REE concentration is 15 % due to silicon removal.

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