Mechanism of selective methanol oxidation over vanadium oxide-titanium oxide catalysts: a FT-IT and flow reactor study

Journal Article · Thu Sep 24 00:00:00 EDT 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100304a026· OSTI ID:5527910

Busca, G; Elmi, A S; Forzatti, P

The mechanism of the selective oxidation of methanol on two V-Ti oxide catalyst samples, prepared by impregnation and coprecipitation techniques, respectively is investigated. The interaction of methanol and its oxidation products (i.e., formaldehyde, dimethoxymethane, formic acid, and methyl formate) is studied by FR-IR spectroscopy and compares with the results of flow reactor measurements performed at different temperatures, contact times, and methanol/oxygen molar feed ratios. The data are interpreted on the basis of a reaction mechanism which involved the following steps: (i) condensation of methanol with surface VOH groups; (ii) H abstraction from methoxy groups leading to coordinated formaldehyde; (iii) formation of dioxymethylene species by interaction of adsorbed formaldehyde with nucelophilic sites; (iv) reaction of dioxymethylene species with methanol to give dimethoxymethane; (v) successive oxidation of dioxymethylene groups to formate ions; (vi) reaction of these ions either with methanol to produce methyl formate or with water to give formic acid; (vii) decomposition of formate species to produce carbon monoxide; (viii) parallel oxidation of methanol to carbon dioxide. The behaviors of the surface species are compared with those monitored on other systems and the catalyst requirements for the title reaction are discussed.

• Research Organization: Universita Fiera del Mare, Genova, Italy
• OSTI ID: 5527910
• Journal Information: J. Phys. Chem.; (United States), Vol. 91:201
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
10 SYNTHETIC FUELS
METHANOL
OXIDATION
TITANIUM OXIDES
CATALYTIC EFFECTS
VANADIUM OXIDES
ABSORPTION SPECTROSCOPY
CARBOXYLIC ACID SALTS
CATALYSIS
CATALYSTS
CHEMICAL REACTORS
EXPERIMENTAL DATA
FORMIC ACID
FOURIER TRANSFORM SPECTROMETERS
INFRARED SPECTRA
ALCOHOLS
CARBOXYLIC ACIDS
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
HYDROXY COMPOUNDS
INFORMATION
MEASURING INSTRUMENTS
MONOCARBOXYLIC ACIDS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
SPECTRA
SPECTROMETERS
SPECTROSCOPY
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
VANADIUM COMPOUNDS
400201* - Chemical & Physicochemical Properties
090210 - Alcohol Fuels- Properties- (1976-1989)