Analysis of Oxygenated Compounds in Hydrotreated Biomass Fast Pyrolysis Oil Distillate Fractions
Three hydrotreated bio-oils with different oxygen contents (8.2, 4.9, and 0.4 w/w) were distilled to produce Light, Naphtha, Jet, Diesel, and Gasoil boiling range fractions that were characterized for oxygen containing species by a variety of analytical methods. The bio-oils were originally generated from lignocellulosic biomass in an entrained-flow fast pyrolysis reactor. Analyses included elemental composition, carbon type distribution by {sup 13}C NMR, acid number, GC-MS, volatile organic acids by LC, and carbonyl compounds by DNPH derivatization and LC. Acid number titrations employed an improved titrant-electrode combination with faster response that allowed detection of multiple endpoints in many samples and for acid values attributable to carboxylic acids and to phenols to be distinguished. Results of these analyses showed that the highest oxygen content bio-oil fractions contained oxygen as carboxylic acids, carbonyls, aryl ethers, phenols, and alcohols. Carboxylic acids and carbonyl compounds detected in this sample were concentrated in the Light, Naphtha, and Jet fractions (<260 C boiling point). Carboxylic acid content of all of the high oxygen content fractions was likely too high for these materials to be considered as fuel blendstocks although potential for blending with crude oil or refinery intermediate streams may exist for the Diesel and Gasoil fractions. The 4.9 % oxygen sample contained almost exclusively phenolic compounds found to be present throughout the boiling range of this sample, but imparting measurable acidity primarily in the Light, Naphtha and Jet fractions. Additional study is required to understand what levels of the weakly acidic phenols could be tolerated in a refinery feedstock. The Diesel and Gasoil fractions from this upgraded oil had low acidity but still contained 3 to 4 wt% oxygen present as phenols that could not be specifically identified. These materials appear to have excellent potential as refinery feedstocks and some potential for blending into finished fuels. Fractions from the lowest oxygen content oil exhibited some phenolic acidity, but generally contained very low levels of oxygen functional groups. These materials would likely be suitable as refinery feedstocks and potentially as fuel blend components. PIONA analysis of the Light and Naphtha fractions shows benzene content of 0.5 and 0.4 vol%, and predicted (RON + MON)/2 of 63 and 70, respectively.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1035429
- Report Number(s):
- PNNL-SA-80425; ENFUEM; BM0101010; TRN: US201204%%599
- Journal Information:
- Energy and Fuels, Vol. 25, Issue 11; ISSN 0887-0624
- Country of Publication:
- United States
- Language:
- English
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