Preparative-scale purification of petroleum vanadyl porphyrins by sulfuric acid loaded macroporous silica

Abstract

The practical potential of petroleum porphyrins still remains underestimated because of the absence of satisfactory simple and effective methods for their isolation in pure form. Our work aims to provide a solution for this problem via use of sulfuric acid loaded macroporous silica as an unprecedentedly effective adsorbent for deep petroporphyrin purification. Using chromatographic columns of reduced volume (4 cm3), a series of experiments on optimization of chromatographic conditions for silica-based sulfocationite were carried out. As a source of petroleum porphyrins, the primary concentrates of vanadyl porphyrins isolated on silica gel column from DMF extracts of heavy oil asphaltenes have been used. UV-vis and MALDI-TOF mass-spectrometric methods were employed for vanadyl porphyrin analysis and identification. We established that in a narrow range of water and acid content equal to [Formula: see text]25 and [Formula: see text]15 wt.%, respectively, silica-based sulfocationite becomes able to retain a bulk of polar petroleum components with exception of porphyrins, which thus leave the column first. A preparative-scale purification of vanadyl porphyrins by the sulfocationite-based method was performed for the first time and 18.5 mg of excellently pure product were obtained. Considering the extremely simple preparation and excellent purification performance of our novel sulfocationite, it could greatly facilitate access to high-purity petroleum porphyrins.