title: Sulfonic acid resin-catalyzed addition of phenols, carboxylic acids, and water to olefins: Model reactions for catalytic upgrading of bio-oil.
abstract: Acid-catalyzed 1-octene reactions with phenol and mixtures of phenol with water, acetic acid and 1-butanol were studied as partial bio-oil upgrading models. Bio-oil from fast biomass pyrolysis has poor fuel properties due to the presence of substantial amounts of water, carboxylic acid, phenolic derivatives and other hydroxyl-containing compounds. Additions across olefins offer a route to simultaneously lower water content and acidity while increasing hydrophobicity, stability and heating value. Amberlyst15, Dowex50WX2 and Dowex50WX4 effectively catalyzed phenol O- and C-alkylation from 65 to 120 degrees C, giving high O-alkylation selectivities in the presence of water, acetic acid and 1-butanol. Octanols and dioctyl ethers were formed from water and octyl acetates and phenol acetates from acetic acid. Phenol alkylation slowed in the presence of water. Dowex50WX2 and Dowex50WX4 were more stable in the presence of water than Amberlyst15 and were successfully recycled. Adding 1-butanol to phenol/water/1-octene, gave emulsion-like mixtures which improved phenol conversion and olefin hydration.
authors.affiliation: Key Laboratory of Bio-based Material Science and Technology (Northeast Forestry University), Ministry of Education, Harbin 150040, PR China.
authors.forename: Zhi-Jun
authors.initials: ZJ
authors.lastname: Zhang
authors.forename: Qing-Wen
authors.initials: QW
authors.lastname: Wang
authors.forename: Xu-Lai
authors.initials: XL
authors.lastname: Yang
authors.forename: Sabornie
authors.initials: S
authors.lastname: Chatterjee
authors.forename: Charles U
authors.initials: CU
authors.lastname: Pittman
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000478:Alkylation; D056804:Biofuels; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D007700:Kinetics; D010636:Phenols / Q000737:chemistry*; D013451:Sulfonic Acids / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D000475:Alkenes; D056804:Biofuels; D002264:Carboxylic Acids; D010636:Phenols; D013451:Sulfonic Acids; D014867:Water