Supercritical fluid extraction and fractionation (SFEF) has been used to separate a variety of petroleum residua and other heavy oils into narrow-cut fractions with total yields up to 75-90%. Any insoluble material, or end-cut, corresponds to the asphaltene fraction in the parent oil. The narrow-cut fractions were analyzed comprehensively and separated into the solubility classes of saturate, aromatic, resin, and asphaltene fractions. The boiling points were measured up to 700 degreesC and correlations were established with the key factors such as density and molecular weight. This allows extrapolation of boiling points of residue fractions up to 1000 degreesC. Unlike bulk property measurements, the narrow-cut characterization data show increasing concentrations of key contaminants as the fractions become heavier. The solubility parameter for each narrow-cut fraction was measured using high-pressure fluid phase equilibrium with propane. The corresponding values for the end-cuts were obtained by the conventional precipitation method. The distribution and reactivity of sulfur species were determined by XPS in the bitumen pitch fractions and the corresponding residua produced during thermocracking and hydrocracking. The average structures for the narrow-cuts were constructed from molecular weight and elemental analyses together with FTIR, H-1-NMR and C-13-NMR data. The results were used to develop a generalized feedstock characteristic index, K-R. This index shows good correlation with feedstock hydrocarbon constituents and can be used to assess feedstock reactivity and processability. Downstream refiners can use the narrow-cut data and K-R values for process optimization by either cutting deeper into residua bottoms to increase yield or by selecting the most appropriate process units for the various residue fractions. This information can also be used by upstream operators to determine the economic feasibility of utilizing the end-cut onsite. (C) 2004 Elsevier Ltd. All rights reserved.