An entrained flow process for chlorinating fine iron-containing titaniferous powder with chlorine gas and/or organochlorides in the presence of fine porous coal-based reductant powder for obtaining product chlorides of titanium and iron wherein said both of said powders are entrained in and flow downwardly through a chlorination reaction zone at a temperature of at least about 800 DEG C. is improved by: (a) supplying fine titaniferous and reductant powders to said reaction zone at a rate sufficient for establishing and maintaining titanium, iron and carbon reactants therein in substantial excess over those stoichiometric for the complete reaction of the chlorine present; (b) employing as at least the major portion of fresh reductant feed reactive char having surface area of at least about 10 m.2/g. and particle size of -140 mesh; (c) separating carbon and titaniferous solids from the effluent of said reaction zone; and (d) recycling at least a major portion of the resulting separated solids as about -140 mesh powder into said reaction zone.
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