Insight of unresolved complex mixtures of saturated hydrocarbons in heavy oil via GC×GC-TOFMS analysis

The saturated hydrocarbon fraction of a heavily biodegraded crude oil from Liaohe oilfield was analyzed by using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS). The "humps", which was termed as unresolved complex mixtures (UCMs) in conventional gas chromatographic analysis, was separated for identification of the individual compound. Main compounds of UCMs were identified according to the combined information of characteristics of GC×GC chromatogram and time-of-flight mass spectra. It’s found that UCMs are mainly composed of great number of ring compounds with extremely low concentration. The ring compounds are separated according to their boiling point diversity in the first dimension column, then to their polarity or ring number variety in the second dimension column. In the sample there are two groups of UCMs, i.e., the first group compounds with boiling point lower that of C24 and the second group compounds with boiling point higher than that of C24. The first group of UCMs mainly consists of monocyclic, bicyclic and tricyclic ring compounds. The first group of UCMs is mainly composed of saturated hydrocarbons, in which the percentage of ring compounds with signal-to-noise ratio above 100 is about 75% of the total quantity of saturated hydrocarbon, while its mass is over 80% of the total saturated hydrocarbon. The second group of UCMs is mainly composed of tetracyclic and pentacyclic ring compounds, in which the percentage of UCM compounds with signal-to-noise ratio over 100 is about 17% of the total quantity of saturated hydrocarbon, and its mass is about 0.5% of the total saturated hydrocarbon. The results of this study are helpful for heavy oil developing and genesis mechanism understanding.