In this study, compositions of bio-oil and bio-oil with composite additives before and after accelerated aging treatment were analyzed by two-dimensional gas chromatography with time flight mass spectrometry detector (GC × GC-TOFMS) in order to evaluate the effect of the composite additives on the characteristics of bio-oil. The effects of composite additives on bio-oil components and the changes of the components of the bio-oil with or without accelerated aging treatment were compared. A structured distribution of compounds of classification groups was observed in the two-dimensional space. At a signal-to-noise ratio of 1000, more than 3000 peaks were detected by GC × GC-TOFMS, and more than 340 peaks (relative content > 0.02%) were identified after further analysis. After accelerated aging, the content of various compounds in bio-oil decreased. The content of the classification group and the total content of compounds in the bio-oil with composite additives changed less than that of the crude bio-oil. Before aging, the most abundant substance in bio-oil was 2(5H)-furanone. After aging, the largest content in crude bio-oil is 2(5H)-furanone, and the most abundant substance in the bio-oil with composite additives is Hydroxyacetone. Regardless of whether composite additives are added or not, the component with the highest content before and after aging of bio-oil is ketones. In crude bio-oil, the substance with the most reduced content was phenols, whose content was reduced by 0.51 wt%. The contents of alcohols, esters, furanones, furans and sugars in the bio-oil with composite additives were increased after aging. The maximum increase in content was furanones, whose content was increased by 0.15 wt%. Analysis of bio-oil components showed that high added value compounds existed in bio-oil such as 2(5H)-furanone, Hydroxyacetone and (S)-(+)-2′,3′-Dideoxyribonolactone. The research can provide detailed information on bio-oil composition.
