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

Zhijun Zhang, Charles U. Pittman, Shujuan Sui, Jianping Sun and Qingwen Wang
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Zhijun Zhang: MOE Key Laboratory of Bio-based Material Science and Technology, Northeast Forestry University, Harbin 150040, China
Charles U. Pittman: Department of Chemistry, Mississippi State University, Mississippi State, MS 39762, USA
Shujuan Sui: MOE Key Laboratory of Bio-based Material Science and Technology, Northeast Forestry University, Harbin 150040, China
Jianping Sun: MOE Key Laboratory of Bio-based Material Science and Technology, Northeast Forestry University, Harbin 150040, China
Qingwen Wang: MOE Key Laboratory of Bio-based Material Science and Technology, Northeast Forestry University, Harbin 150040, China

Energies, 2013, vol. 6, issue 3, 1-22

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 Cs 2.5 H 0.5 PW 12 O 40 supported on K10 clay (Cs 2.5 /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. Cs 2.5 /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 (search for similar items in EconPapers)
JEL-codes: Q Q0 Q4 Q40 Q41 Q42 Q43 Q47 Q48 Q49 (search for similar items in EconPapers)
Date: 2013
References: View complete reference list from CitEc
Citations: View citations in EconPapers (3)

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