Comprehensive two-dimensional liquid chromatography with inductively coupled plasma mass spectrometry detection for the characterization of sulfur, vanadium and nickel compounds in petroleum products

Abstract

The petroleum industry is increasingly concerned with the conversion of vacuum residues as a consequence of decreased conventional crude oil availability. The compositional analysis of heavy oil products has become a key step in conversion processes, but the complexity of these oil matrices tends to increase with their boiling point. In this study, comprehensive two-dimensional liquid chromatography (LCxLC) coupled to inductively coupled mass spectrometry (ICP-MS/MS) is considered with a view to meet new requirements and to bring additional information regarding the species present in these matrices. In search for a high degree of orthogonality, two separation techniques involving two different retention mechanisms were evaluated: Size Exclusion Chromatography (SEC) and Reverse Phase Liquid Chromatography (RPLC). In SEC, the analytes are separated according to their molecular weight while according to their hydrophobicity in RPLC. The separation power of both individual separation techniques was first evaluated. Off-line and on-line LCxLC were compared on the basis of an optimization approach. It is shown that off-line SECxRPLC can provide, for the same analysis time of 150 min, a higher peak capacity (2600 vs 1700) than on-line RPLCxSEC while a similar dilution factor (close to 30) but also requires far fewer fractions to be analyzed (12 vs 400). Asphaltenes which constitute the heaviest fraction of crude oils (obtained from petroleum industry) were analyzed by the developed off-line SECxRPLC method. The resulting 2D-contour plots show that co-elutions could be removed leading, for the first time, to new information on high molecular weight species containing sulfur and vanadium.