A DUAL, SEQUENTIAL MECHANISM FOR THE OXIDATION OF PETROLEUM ASPHALTS

ABSTRACT Examination of kinetic data for asphalt oxidative age hardening and the chemistry of the oxidation reactions has led to the proposal of a sequential, dual mechanism for asphalt oxidation. The dual mechanism rationalizes conflicts between results of earlier mechanistic investigations and provides a fundamental explanation for the hyperbolic-like, property-versus-time plots characteristic of asphalt oxidative aging. The oxidation kinetics are in harmony with and provide further confirmation of the microstructural model of asphalt. It is proposed that the rapid oxidation rate at the onset of asphalt oxidation results from reaction of oxygen with a limited amount of highly reactive hydrocarbon components. Final oxidation products of this initial reaction are sulfoxides and most likely aromatized rings. During this initial reaction, a much slower oxidation of benzytic carbons is initiated with both ketones and sulfoxides being formed. The ratio of ketones to sulfoxides formed and the rate of oxidative...

[1]  J. C. Petersen,et al.  Molecular interactions of asphalt. Infrared study of the hydrogen-bonding basicity of asphalt , 1974 .

[2]  J. C. Petersen,et al.  Direct evidence of ketones in oxidized asphalts , 1974 .

[3]  J. C. Petersen,et al.  THE EFFECT OF MATTALOPORHYRINS ON ASPHALT OXIDATION. II. THE EFFECT OF VANADYL CHELATES FOUND IN PETROLEUM , 1984 .

[4]  E. Sheu,et al.  Development of Solid Properties and Thermochemistry of Asphalt Binders in the 25−65 °C Temperature Range , 1996 .

[5]  C. Bamford,et al.  Comprehensive Chemical Kinetics , 1976 .

[6]  Meng Liu,et al.  The kinetics of carbonyl formation in asphalt , 1996 .

[7]  G. King,et al.  OXYCYCLICS: UNDERSTANDING CATALYZED OXIDATION MECHANISMS IN BITUMEN AND OTHER PETROLEUM PRODUCTS , 1993 .

[8]  Theodore Mill,et al.  Homolytic decompositions of hydroperoxides. III. Radical-induced decompositions of primary and secondary hydroperoxides , 1968 .

[9]  D. Riley,et al.  Selective autoxidation of electron-rich substrates under elevated oxygen pressures , 1988 .

[10]  J. C. Petersen,et al.  Adaptation of inverse gas-liquid chromatography to asphalt oxidation studies , 1966 .

[11]  J. C. Petersen,et al.  Quantitative determination of carboxylic acids and their salts and anhydrides in asphalts by selective chemical reactions and differential infrared spectrometry , 1981 .

[12]  J. C. Petersen,et al.  Identification of dicarboxylic anhydrides in oxidized asphalts , 1975 .

[13]  A. Bridgewater,et al.  Mechanism of antioxidant action: reactions of alkyl and aryl sulphides with hydroperoxides , 1978 .

[14]  P. Jerabek,et al.  Am Chem Soc Div Fuel Chem Prepr , 1977 .

[15]  K. G. Martin.  Influence of stabilisers on bitumen durability , 1966 .

[16]  C. Walling.  Free Radicals In Solution , 1957 .

[17]  George W. Mushrush,et al.  Reaction of Organosulfur Compounds with Naturally Occurring Peroxides in Jet Fuel , 1996 .

[18]  K. Hargrave,et al.  Oxidation of organic sulphides. I. Interaction of cyclohexyl methyl sulphide with hydroperoxides in alcohols , 1954, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[19]  George W. Mushrush,et al.  FUEL INSTABILITY 1: ORGANO-SULFUR HYDROPEROXIDE REACTIONS , 1992 .