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Energies 2013, 6(3), 1568-1589; https://doi.org/10.3390/en6031568

Catalytic Upgrading of Bio-Oil by Reacting with Olefins and Alcohols over Solid Acids: Reaction Paths via Model Compound Studies

1
MOE Key Laboratory of Bio-based Material Science and Technology, Northeast Forestry University, Harbin 150040, China
2
Department of Chemistry, Mississippi State University, Mississippi State, MS 39762, USA
*
Author to whom correspondence should be addressed.
Received: 5 January 2013 / Revised: 1 February 2013 / Accepted: 26 February 2013 / Published: 11 March 2013
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Abstract

Catalytic refining of bio-oil by reacting with olefin/alcohol over solid acids can convert bio-oil to oxygen-containing fuels. Reactivities of groups of compounds typically present in bio-oil with 1-octene (or 1-butanol) were studied at 120 °C/3 h over Dowex50WX2, Amberlyst15, Amberlyst36, silica sulfuric acid (SSA) and Cs2.5H0.5PW12O40 supported on K10 clay (Cs2.5/K10, 30 wt. %). These compounds include phenol, water, acetic acid, acetaldehyde, hydroxyacetone, d-glucose and 2-hydroxymethylfuran. Mechanisms for the overall conversions were proposed. Other olefins (1,7-octadiene, cyclohexene, and 2,4,4-trimethylpentene) and alcohols (iso-butanol) with different activities were also investigated. All the olefins and alcohols used were effective but produced varying product selectivities. A complex model bio-oil, synthesized by mixing all the above-stated model compounds, was refined under similar conditions to test the catalyst’s activity. SSA shows the highest hydrothermal stability. Cs2.5/K10 lost most of its activity. A global reaction pathway is outlined. Simultaneous and competing esterification, etherfication, acetal formation, hydration, isomerization and other equilibria were involved. Synergistic interactions among reactants and products were determined. Acid-catalyzed olefin hydration removed water and drove the esterification and acetal formation equilibria toward ester and acetal products. View Full-Text
Keywords: bio-oil upgrading; model compound reactions; solid acid; reaction pathways; olefins; alcohols bio-oil upgrading; model compound reactions; solid acid; reaction pathways; olefins; alcohols
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Zhang, Z.; Pittman, C.U., Jr.; Sui, S.; Sun, J.; Wang, Q. Catalytic Upgrading of Bio-Oil by Reacting with Olefins and Alcohols over Solid Acids: Reaction Paths via Model Compound Studies. Energies 2013, 6, 1568-1589.

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