Analysis of oxidised heavy paraffininc products by high temperature comprehensive two-dimensional gas chromatography

•The separation of oxygenates in oxidised heavy paraffinic fractions by HT-GC × GC is reported for the first time.•HT-GC × GC column combinations for the separation of oxygenates in oxidised products were optimised.•The advantages of HT-GC × GC in monitoring oxidation reactions of heavy paraffinic fraction samples is Illustrated.•Selective relative quantification of oxygenate classes and obtaining the concentrations by carbon number.•Advantage of replacing separate titrimetric procedures by a single HT-GC × GC analysis is clearly Illustrated.

Heavy petroleum fractions are produced during crude and synthetic crude oil refining processes and they need to be upgraded to useable products to increase their market value. Usually these fractions are upgraded to fuel products by hydrocracking, hydroisomerization and hydrogenation processes. These fractions are also upgraded to other high value commercial products like lubricant oils and waxes by distillation, hydrogenation, and oxidation and/or blending. Oxidation of hydrogenated heavy paraffinic fractions produces high value products that contain a variety of oxygenates and the characterization of these heavy oxygenates is very important for the control of oxidation processes. Traditionally titrimetric procedures are used to monitor oxygenate formation, however, these titrimetric procedures are tedious and lack selectivity toward specific oxygenate classes in complex matrices. Comprehensive two-dimensional gas chromatography (GC × GC) is a way of increasing peak capacity for the comprehensive analysis of complex samples. Other groups have used HT-GC × GC to extend the carbon number range attainable by GC × GC and have optimised HT-GC × GC parameters for the separation of aromatics, nitrogen-containing compounds as well as sulphur-containing compounds in heavy petroleum fractions. HT-GC × GC column combinations for the separation of oxygenates in oxidised heavy paraffinic fractions are optimised in this study. The advantages of the HT-GC × GC method in the monitoring of the oxidation reactions of heavy paraffinic fraction samples are illustrated.