Bio-oil hydrodeoxygenation: Adsorption of phenolic compounds on sulfided (Co)Mo catalysts

• Published in: Journal of catalysis Vol. 297; pp. 176 - 186
• Main Authors: Popov, Andrey, Kondratieva, Elena, Mariey, Laurence, Goupil, Jean Michel, El Fallah, Jaafar, Gilson, Jean-Pierre, Travert, Arnaud, Maugé, Françoise
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier Inc 01.01.2013; Elsevier; Elsevier BV
• Subjects: active sites; adsorption; Adsorption mode; aluminum oxide; biofuels; Biosynthesis; Catalysis; catalysts; Chemical Sciences; Chemistry; cobalt; Deactivation; Exact sciences and technology; General and physical chemistry; Guaiacol; HDO; infrared spectroscopy; IR spectroscopy; molybdenum; Oxidation; Phenol; poisoning; pyrolysis; Spectrum analysis; Sulfide catalyst; Surface physical chemistry; temperature; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; HDO; Phenol; Guaiacol; Adsorption mode; Deactivation; Sulfide catalyst; IR spectroscopy; Ternary compound; Molybdenum Sulfides; Cobalt Sulfides; Alcohol; Supported catalyst; Infrared spectrometry; Heterogeneous catalysis; Oil; Adsorption; Phenols; Benzenic compound; Alumina; Catalyst; guaiacol; phenol; adsorption mode; deactivation
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2012.10.005

The interaction of aromatic compounds representative of oxygenated functions of pyrolysis bio-oils (phenol, ethylphenols, and guaiacol) with sulfided (Co)Mo/Al2O3 catalyst was studied. In hydrodeoxygenation conditions, phenate-type species anchored on alumina hinder the accessibility of the sulfide edge sites and are responsible for the catalyst deactivation. [Display omitted] ► Phenol, ethylphenols, and guaiacol were adsorbed on sulfided (Co)Mo/Al2O3. ► All these phenolic compounds anchor on the alumina support as phenate-type species. ► Only the most basic molecules interact with the sulfide phase. ► Phenates anchored on alumina hinder the accessibility of the sulfide edge sites. ► Phenate on the support is responsible for the deactivation in HDO reaction. This paper reports the interaction of aromatic compounds (as phenol, ethylphenols, and guaiacol) representative of oxygenated functions of pyrolysis bio-oils, with sulfided (Co)Mo/Al2O3 catalyst in order to determine the origin of catalyst deactivation in hydrodeoxygenation (HDO) reaction. Infrared spectroscopy shows that all the studied phenolic compounds anchor on the alumina support as phenate-type species, whereas only the most basic ones (2(4)-ethylphenol and guaiacol) interact also with the sulfide phase. At 623K (typical temperature of the HDO reactions), only phenate species on the support are formed that is confirmed by study of the catalyst tested in HDO reaction. Phenate-type species anchored on alumina hinder the accessibility of the sulfide edge sites. This shows that the nature of the oxygenated compound (basicity and nature of the substituent) as well as the surface properties of the catalyst support are crucial in the mode and extent of HDO active sites poisoning.