Sulfurous acid leaching and reductive chlorination of high melting metal-containing ores

Claim 2

AN EXTRACTIVE METALLURGICAL PROCESS FOR RECOVERING IN CHLORIDE FORM A HIGH-MELTING, LOW-BOILING CHLORIDE FORMING METAL SELECTED FROM THE GROUP CONSISTING OF COLUMBIUM, TANTALUM, TITANIUM, VANADIUM, CHROMIUM, ZIRCONIUM, MOLYBDENUM AND TUNGSTEN FROM A CARBONATEBEARING ORE CONTAINING SUCH METAL THAT IS NONREFRACTORY TO REDUCTIVE CHLORINATION AND THAT ALSO CONTAINS A PREDOMINANT PROPORTION OF GANGUE MATERIALS OTHER THAN CARBONATES, COMPRISING DISSOLVING CARBONATES IN SAID ORE BY LEACHING THE SAME WITH AQUEOUS SULFUROUS ACID, AND CONTAINING SUCH LEACHING UNTIL THE PH OF THE REACTION MIXTURE REACHES A VALUE NOT GREATER THAN ABOUT 3, SEPARATING THE LEACHED SOLIDS FROM THE ATTENDANT LIQUOR AND DRYING THE LEACHED SOLIDS TO A MOISTURE CONTENT IN THE RANGE OF ABOUT 0 TO 0.4 PERCENT, FORMING A VAPOROUS CHLORIDE OF SAID METAL BY REDUCTIVE CHLORINATION OF SAID LEACHED AND DRIED SOLIDS WITH A VAPOR PHASE REDUCTIVE CHLORIATING AGENT SELECTED FROM THE GROUP CONSISTING OF PHOSGENE, CARBON TETRACHLORIDE, HEXACHLOROETHANE, OCTACHLOROPROPANE, SULFUR MONOCHLORIDE AND SULFUR DICHLORIDE, THAT FORMS A NONHYDROGENOUS REDUCING AGENT AT THE CONDITIONS OF THE REACTION, AT A TEMPERATURE IN THE RANGE OF ABOUT 240*C. TO 450*C. AND SUFFICIENT TO FORM SAID VAPOROUS METAL CHLORIDE BUT INSUFFICIENT TO CHLORINATE A SUBSTANTIAL PROPORTION OF THE GANGUE MATERIALS, REMOVING VAPOR PHASE MATERIAL FROM THE REACTION MIXTURE AND RECOVERING METAL CHLORIDE THEREFROM.

Claim 3

AN EXTRACTIVE METALLURGICAL PROCESS FOR RECOVERING IN CHLORIDE FORM A HIGH-MELTING, LOW-BOILING CHLORIDE FORMING METAL SELECTED FROM THE GROUP CONSISTING OF COLUMBIUM, TANTALUM, TITANIUM, VANADIUM, CHROMIUM, ZIRCONIUM, MOLYBDENUM AND TUNGSTEN FROM A CARBONATEBEARING ORE CONTAINING SUCH METAL THAT IS NONREFRACTORY TO REDUCTIVE CHLORINATION AND THAT ALSO CONTAINS A PREDOMINANT PROPORTION OF GANGUE MATERIALS OTHER THAN CARBONATES, COMPRISING LEACHING CARBONATES FROM SAID ORE BY INJECTING SULFUR DIOXIDE INTO AN AQUEOUS SLURRY OF THE ORE IN FINELY DIVIDED FORM, SAID SLURRY HAVING A WATER:SOLIDS RATIO IN THE RANGE OF ABOUT 2:1 TO 5:1, AND CONTINUING DIGESTION OF THE ORE UNTIL THE CARBONATE CONTENT THEREOF IS SUBSTANTIALLY REDUCED AND UNTIL THE PH OF TE SLURRY DIMISHES TO AT LEAST ABOUT 3, SEPARATING THE LEACHED SOLIDS FROM THE ATTENDANT LIQUOR, ACTIVATING THE LEACHED SOLIDS FOR REDUCTIVE CHLORINATION AND DRYING SAID SOLIDS TO A MOISTURE CONTENT IN THE RANGE OF ABOUT 0 TO 0.4 PERCENT BY INTIMATELY CONTACTING THE SAME IN FINELY DIVIDED FORM WITH OXYGEN AT AN ELEVATED TEMPERATURE IN THE RANGE OF ABOUT 200*C. TO 500*C. FOR AT LEAST ABOUT 20 MINUTES, AND FORMING A VAPOROUS CHLORIDE OF SAID METAL BY REDUCTIVE CHLORINATION OF SAID LEACHED AND DRIED SOLIDS WITH A VAPOR PHASE REDUCTIVE CHLORINATING AGENT THAT FORMS A NONHYDROGENOUS REDUCING AGENT AT THE CONDITIONS OF THE REACTION, SAID AGENT BEING SELECTED FROM THE GROUP CONSISTING OF PHOSGENE AND CARBON TETRACHLORIDE, IN A PROPORTION SUFFICIENT AS TO PROVIDE ABOUT 3 TO 20 TIMES THE STOICHIOMETRIC AMOUNT OF CHLORINE REQUIRED TO REACT WITH SAID METAL, AT A TEMPERATURE IN THE RANGE OF ABOUT 300*C. TO 400*C. AND SUFFICIENT TO FORM SAID VAPOROUS METAL CHLORIDE BUT INSUFFICIENT TO CHLORINATE A SUBSTANTIAL PROPORTION OF THE GANGUE MATERIALS, REMOVING VAPOR PHASE MATERIALS FROMTHE REACTION MIXTURE AND RECOVERING METAL CHLORIDE THEREFROM.

Claim 4

AN EXTRACTIVE METALLURGICAL PROCESS FOR RECOVERING IN CHLORIDE FORM A HIGH-MELTING, LOW-BOILING CHLORIDE FORMING METAL SELECTED FROM THE GROUP CONSISTING OF COLUMBIUM, TANTALUM, TITANIUM, VANADIUM, CHROMIUM, ZIRCONIUM, MOLYBDENUM AND TUNGSTEN FROM A CARBONATEBEARING ORE CONTAINING SUCH METAL THAT IS NONREFRACTORY TO REDUCTIVE CHLORINATION AND THAT ALSO CONTAINS A PREDOMINANT PROPORTION OF GANGUE MATERIALS OTHER THAN CARBONATES, COMPRISING LEACHING CARBONATES FROM SAID ORE BY INJECTING SULFUR DIOXIDE INTO AN AQUEOUS SLURRY OF THE ORE IN FINELY DIVIDED FORM, SAID SLURRY HAVING A WATER:SOLIDS RATIO IN THE RANGE OF ABOUT 2:1 TO 5:1, AND CONTINUING DIGESTION OF THE ORE UNTIL THE CARBONATE CONTENT THEREOF IS SUBSTANTIALLY REDUCED AND UNTIL THE PH OF TE SLURRY DIMISHES TO AT LEAST ABOUT 3, SEPARATING THE LEACHED SOLIDS FROM THE ATTENDANT LIQUOR, ACTIVATING THE LEACHED SOLIDS FOR REDUCTIVE CHLORINATION AND DRYING SAID SOLIDS TO A MOISTURE CONTENT IN THE RANGE OF ABOUT 0 TO 0.4 PERCENT BY INTIMATELY CONTACTING THE SAME IN FINELY DIVIDED FORM WITH OXYGEN AT AN ELEVATED TEMPERATURE IN THE RANGE OF ABOUT 200*C. TO 500*C. FOR AT LEAST ABOUT 20 MINUTES, AND FORMING A VAPOROUS CHLORIDE OF SAID METAL BY REDUCTIVE CHLORINATION OF SAID LEACHED AND DRIED SOLIDS WITH A VAPOR PHASE REDUCTIVE CHLORINATING AGENT THAT FORMS A NONHYDROGENOUS REDUCING AGENT AT THE CONDITIONS OF THE REACTION, SAID AGENT BEING SELECTED FROM THE GROUP CONSISTING OF PHOSGENE AND CARBON TETRACHLORIDE, IN A PROPORTION SUFFICIENT AS TO PROVIDE ABOUT 3 TO 20 TIMES THE STOICHIOMETRIC AMOUNT OF CHLORINE REQUIRED TO REACT WITH SAID METAL, AT A TEMPERATURE IN THE RANGE OF ABOUT 300*C. TO 400*C. AND SUFFICIENT TO FORM SAID VAPOROUS METAL CHLORIDE BUT INSUFFICIENT TO CHLORINATE A SUBSTANTIAL PROPORTION OF THE GANGUE MATERIALS, REMOVING VAPOR PHASE MATERIALS FROMTHE REACTION MIXTURE AND RECOVERING METAL CHLORIDE THEREFROM.