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Title: Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating

Abstract

We consider catalytic hydroprocessing of pyrolysis oils from biomass which produces hydrocarbons for liquid fuel production. This process requires removal of oxygen and cracking of the heavier molecular weight bio-oil constituents into smaller fragments at high temperatures and pressures under hydrogen. Here, we present in this paper the characterization of a group of five distillate fractions from each of two types of hydroprocessed oils from oak pyrolysis oil: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. The LOC oil was generated using a sulfided hydrotreating system consisting of RuS/C and xMoS/Al 2O 3 while the MOC was produced using non-sulfided catalysts, Ru/C and Pd/C. Elemental analysis and 13C NMR (nuclear magnetic resonance) results suggest that the distillate fractions from both oils become more aromatic/unsaturated as they become heavier. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. Paraffin, iso-paraffin, olefin, naphthene, aromatic (PIONA) analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. Sulfur analysis showed the comparative concentration of sulfur in the different fractionsmore » as well as the surprising similarity in content in some sulfided and non-sulfided fractions. Our results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.« less

Authors:
ORCiD logo [1];  [1];  [2];  [2];  [1];  [1];  [1];  [1];  [1];  [2];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
OSTI Identifier:
1355772
Alternate Identifier(s):
OSTI ID: 1358685; OSTI ID: 1397651
Report Number(s):
NREL/JA-5100-68239
Journal ID: ISSN 0016-2361; PII: S0016236117303277
Grant/Contract Number:
AC05-76RL01830; AC36-08GO28308; AC36-08-GO28308
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Fuel
Additional Journal Information:
Journal Volume: 202; Journal Issue: C; Journal ID: ISSN 0016-2361
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; fast pyrolysis; catalytic upgrading; PIONA; simulated distillation; oxygen content; biofuels; sulfur; sulfided and non-sulfided catalysts; distillate fractions; hydrotreating; pyrolysis; upgrading; hydroprocessing; distillation

Citation Formats

Olarte, Mariefel V., Padmaperuma, Asanga B., Ferrell, III, Jack R., Christensen, Earl D., Hallen, Richard T., Lucke, Richard B., Burton, Sarah D., Lemmon, Teresa L., Swita, Marie S., Fioroni, Gina, Elliott, Douglas C., and Drennan, Corinne. Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating. United States: N. p., 2017. Web. doi:10.1016/j.fuel.2017.03.051.
Olarte, Mariefel V., Padmaperuma, Asanga B., Ferrell, III, Jack R., Christensen, Earl D., Hallen, Richard T., Lucke, Richard B., Burton, Sarah D., Lemmon, Teresa L., Swita, Marie S., Fioroni, Gina, Elliott, Douglas C., & Drennan, Corinne. Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating. United States. doi:10.1016/j.fuel.2017.03.051.
Olarte, Mariefel V., Padmaperuma, Asanga B., Ferrell, III, Jack R., Christensen, Earl D., Hallen, Richard T., Lucke, Richard B., Burton, Sarah D., Lemmon, Teresa L., Swita, Marie S., Fioroni, Gina, Elliott, Douglas C., and Drennan, Corinne. Thu . "Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating". United States. doi:10.1016/j.fuel.2017.03.051. https://www.osti.gov/servlets/purl/1355772.
@article{osti_1355772,
title = {Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating},
author = {Olarte, Mariefel V. and Padmaperuma, Asanga B. and Ferrell, III, Jack R. and Christensen, Earl D. and Hallen, Richard T. and Lucke, Richard B. and Burton, Sarah D. and Lemmon, Teresa L. and Swita, Marie S. and Fioroni, Gina and Elliott, Douglas C. and Drennan, Corinne},
abstractNote = {We consider catalytic hydroprocessing of pyrolysis oils from biomass which produces hydrocarbons for liquid fuel production. This process requires removal of oxygen and cracking of the heavier molecular weight bio-oil constituents into smaller fragments at high temperatures and pressures under hydrogen. Here, we present in this paper the characterization of a group of five distillate fractions from each of two types of hydroprocessed oils from oak pyrolysis oil: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. The LOC oil was generated using a sulfided hydrotreating system consisting of RuS/C and xMoS/Al2O3 while the MOC was produced using non-sulfided catalysts, Ru/C and Pd/C. Elemental analysis and 13C NMR (nuclear magnetic resonance) results suggest that the distillate fractions from both oils become more aromatic/unsaturated as they become heavier. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. Paraffin, iso-paraffin, olefin, naphthene, aromatic (PIONA) analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. Sulfur analysis showed the comparative concentration of sulfur in the different fractions as well as the surprising similarity in content in some sulfided and non-sulfided fractions. Our results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.},
doi = {10.1016/j.fuel.2017.03.051},
journal = {Fuel},
number = C,
volume = 202,
place = {United States},
year = {Thu Apr 06 00:00:00 EDT 2017},
month = {Thu Apr 06 00:00:00 EDT 2017}
}

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  • Catalytic hydroprocessing of pyrolysis oils from biomass produces hydrocarbons that can be considered for liquid fuel production. This process requires removal of oxygen and cracking of the heavier molecular weight bio-oil constituents into smaller fragments at high temperatures and pressures under hydrogen. A comprehensive understanding of product oils is useful to optimize cost versus degree of deoxygenation. Additionally, a better understanding of the chemical composition of the distillate fractions can open up other uses of upgraded oils for potentially higher-value chemical streams. We present in this paper the characterization data for five well-defined distillate fractions of two hydroprocessed oils withmore » different oxygen levels: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. Elemental analysis and 13C NMR results suggest that the distillate fractions become more aromatic/unsaturated as they become heavier. Our results also show that the use of sulfided catalysts directly affects the S content of the lightest distillate fraction. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. PIONA analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. These results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.« less
  • Catalytic hydroprocessing of pyrolysis oils from biomass produces hydrocarbons that can be considered for liquid fuel production. This process requires removal of oxygen and cracking of the heavier molecular weight bio-oil constituents into smaller fragments at high temperatures and pressures under hydrogen. We present in this paper the characterization of a group of five distillate fractions from each of two types of hydroprocessed oils from oak pyrolysis oil: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. The LOC oil was generated using a sulfided hydrotreating system consistingmore » of RuS/C and xMoS/Al2O3 while the MOC was produced using non-sulfided catalysts, Ru/C and Pd/C. Elemental analysis and 13C NMR (nuclear magnetic resonance) results suggest that the distillate fractions from both oils become more aromatic/unsaturated as they become heavier. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. Paraffin, iso-paraffin, olefin, naphthene, aromatic (PIONA) analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. Sulfur analysis showed the comparative concentration of sulfur in the different fractions as well as the surprising similarity in content in some sulfided and non-sulfided fractions. These results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.« less
  • 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 andmore » 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.« less