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

Author

Listed:
  • Zhijun Zhang

    (MOE Key Laboratory of Bio-based Material Science and Technology, Northeast Forestry University, Harbin 150040, China
    Department of Chemistry, Mississippi State University, Mississippi State, MS 39762, USA)

  • 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)

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.

Suggested Citation

  • Zhijun Zhang & Charles U. Pittman & Shujuan Sui & Jianping Sun & Qingwen Wang, 2013. "Catalytic Upgrading of Bio-Oil by Reacting with Olefins and Alcohols over Solid Acids: Reaction Paths via Model Compound Studies," Energies, MDPI, vol. 6(3), pages 1-22, March.
    • Handle: RePEc:gam:jeners:v:6:y:2013:i:3:p:1568-1589:d:24126
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    Citations

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    Cited by:

    1. Stella Bezergianni & Athanasios Dimitriadis & Gian-Claudio Faussone & Dimitrios Karonis, 2017. "Alternative Diesel from Waste Plastics," Energies, MDPI, vol. 10(11), pages 1-12, October.
    2. Zhijun Zhang & Shujuan Sui & Fengqiang Wang & Qingwen Wang & Charles U. Pittman, 2013. "Catalytic Conversion of Bio-Oil to Oxygen-Containing Fuels by Acid-Catalyzed Reaction with Olefins and Alcohols over Silica Sulfuric Acid," Energies, MDPI, vol. 6(9), pages 1-20, September.
    3. Shanmugam Palanisamy & Börje Sten Gevert & Pranav Sankaran & Kannan Kandasamy, 2019. "Produce Low Aromatic Contents with Enhanced Cold Properties of Hydrotreated Renewable Diesel Using Pt/Alumina-Beta-Zeolite: Reaction Path Studied via Monoaromatic Model Compound," Energies, MDPI, vol. 12(15), pages 1-15, July.

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