This invention relates to a process that utilizes high-temperature oxidation with controlled stoichiometry in the concentration of vanadium from carbonaceous feedstock materials containing vanadium, such as residues, ashes and soots resulting from the combustion or gasification of petroleum vacuum residuum, petroleum coke, kerogen from oil shale, and bituminous sand, e.g., tar sand or oil sand, or extra heavy oil or other carbonaceous feedstocks that contain vanadium. A preferred embodiment uses a counter-rotating vortex reactor and a cyclonic, entrained-flow reactor to rapidly heat and oxidize feedstock at temperatures in the range of about 2100° F. to 2900° F., resulting in a vapor stream with entrained, solid materials comprising the concentrated vanadium species. The entrained, vanadium-rich product solids may be removed from the high-temperature vapor stream by a high-temperature filter assembly, with or without the aid of a high-temperature cyclone separator which removes a portion of the vanadium-rich solids upstream of the filter. The filtered vapor stream may be stored or then ducted to suitable unit operations for possible oxidation and heat recovery, followed by entailed pollution control prior to its final discharge to the atmosphere.