A process is disclosed for separation and recovery of vanadium, molybdenum, iron, tungsten, cobalt and nickel from alumina-based materials, mattes, ores, manufacturing by-products and waste. These elements are oxidized. The oxides are reacted with gaseous HCl to form volatile chloride-bearing compounds that subsequently sublimate. The volatile compounds are condensed in a downward-stepped thermal gradient that allows collection of moderate to high purity compounds of individual elements with exception of a nickel-cobalt co-condensate. Nickel is separated from cobalt by precipitation of nickel chloride from concentrated HCl pressurized with gaseous HCl.