Quantitative and qualitative analysis of hemicellulose, cellulose and lignin bio-oils by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry

• Qualitative and quantitative analysis of bio-oils by GC × GC–ToFMS.
• Experimentally determined and statistically verified RRFs for 39 bio-oil compounds.
• Quantification results for thermal bio-oils from hemicellulose, cellulose and lignin.
• Quantification results for catalytic bio-oils from hemicellulose, cellulose and lignin.

Thermal and catalytic pyrolysis are efficient processes for the transformation of biomass to bio-oil, a liquid energy carrier and a general source of chemicals. The elucidation of the bio-oil's composition is essential for a rational design of both its production and utilization process. However, the complex composition of bio-oils hinders their complete qualitative and quantitative analysis, and conventional chromatographic techniques lack the necessary separation power. Two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC–ToFMS) is considered a suitable technique for bio-oil analysis due to its increased separation and resolution capacity. This work presents the tentative qualitative and quantitative analysis of bio-oils resulting from the thermal and catalytic pyrolysis of standard xylan, cellulose, lignin and their mixture by GC × GC–ToFMS. Emphasis is placed on the development of the quantitative method using phenol-d6 as internal standard. During the method development, a standard solution of 39 compounds was used for the determination of the respective Relative Response Factors (RRF) employing statistical methods, ANOVA and WLSLR, for verification of the data. The developed method was applied to the above mentioned bio-oils and their detailed analysis is presented. The different compounds produced and their diverse concentration allows for an elucidation of the pyrolysis mechanism and highlight the effect of the catalyst.