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

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

Received: 5 January 2013; in revised form: 1 February 2013 / Accepted: 26 February 2013 / Published: 11 March 2013
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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.
Keywords: bio-oil upgrading; model compound reactions; solid acid; reaction pathways; olefins; alcohols
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MDPI and ACS Style

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.

AMA Style

Zhang Z, Pittman CU, 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(3):1568-1589.

Chicago/Turabian Style

Zhang, Zhijun; Pittman, Charles U., Jr.; Sui, Shujuan; Sun, Jianping; Wang, Qingwen. 2013. "Catalytic Upgrading of Bio-Oil by Reacting with Olefins and Alcohols over Solid Acids: Reaction Paths via Model Compound Studies." Energies 6, no. 3: 1568-1589.

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