Reduction of metal oxides in an electrolytic cell

Abstract

A method of reducing a titanium oxide in a solid state in an electrolytic cell which includes an anode, a cathode formed at least in part from the titanium oxide, and a molten electrolyte which includes cations of a metal that is capable of chemically reducing the cathode titanium oxide, which method includes operating the cell at a potential that is above a potential at which cations of the metal that is capable of chemically reducing the cathode titanium oxide deposit as the metal on the cathode, whereby the metal chemically reduces the cathode titanium oxide, and which method is characterised by refreshing the electrolyte and/or changing the cell potential in later stages of the operation of the cell as required having regard to the reactions occurring in the cell and the concentration of oxygen in the titanium oxide in the cell in order to produce high purity titanium.

1 - 9 . (canceled) 
     
     
         10 . A method of reducing a titanium oxide in a solid state in an electrolytic cell which includes an anode, a cathode formed at least in-part from the titanium oxide, and a molten electrolyte which includes cations of a metal that is capable of chemically reducing the cathode titanium oxide, said method includes:
 operating the cell at a potential that is above a potential at which cations of the metal that is capable of chemically reducing the cathode titanium oxide deposit as the metal on the cathode, whereby the metal chemically reduces the cathode titanium oxide; and   operating the cell at constant current and refreshing the electrolyte in later stages of the operation of the cell as required having regard to reactions occurring in the cell and a concentration of oxygen in the titanium oxide in the cell in order to produce high purity titanium (αTi).   
     
     
         11 . The method defined in  claim 10 , wherein the metal deposited on the cathode is soluble in the electrolyte and can dissolve in the electrolyte and thereby migrate to the vicinity of the cathode titanium oxide. 
     
     
         12 . The method defined in  claim 10 , wherein the electrolyte is a CaCl 2 -based electrolyte that includes CaO as one of a plurality of constituents of the electrolyte. 
     
     
         13 . The method defined in  claim 12 , wherein the cell potential is above a decomposition potential of CaO, at which potential Ca metal can deposit on the cathode. 
     
     
         14 . The method defined in  claim 12 , wherein the cell potential is below the decomposition potential of CaCl 2 . 
     
     
         15 . The method defined in  claim 12 , wherein a graphite anode is employed, and said cell is operated at a temperature in the range of 600-1100° C., with the cell potential being between 1.3 and 3.5V. 
     
     
         16 . The method defined in  claim 12 , wherein the CaCl 2 -based electrolyte is a commercially available source of CaCl 2  that partially decomposes on heating and produces CaO or otherwise includes CaO. 
     
     
         17 . The method defined in  claim 12 , wherein the CaCl 2 -based electrolyte includes CaCl 2  and CaO that are added separately or pre-mixed to form the electrolyte. 
     
     
         18 . The method defined in  claim 10 , wherein the anode is graphite or an inert anode. 
     
     
         19 . A method of reducing titanium oxide in a solid state in an electrolytic cell in order to produce high purity titanium (αTi), the electrolytic cell including an anode, a cathode formed at least in-part from the titanium oxide, and a molten electrolyte which includes cations of a metal that is capable of chemically reducing the cathode titanium oxide, the method comprising:
 operating the cell at a potential that is above a potential at which cations of the metal that is capable of chemically reducing the cathode titanium oxide deposit as the metal on the cathode, whereby the metal chemically reduces the cathode titanium oxide; 
 operating the cell at a constant current; and 
 refreshing the electrolyte in the cell based on a concentration of oxygen present in the titanium oxide at different stages of the titanium oxide reduction. 
 
     
     
         20 . The method defined in  claim 19 , wherein the metal deposited on the cathode is soluble in the electrolyte and can dissolve in the electrolyte and thereby migrate to the vicinity of the cathode titanium oxide. 
     
     
         21 . The method defined in  claim 19 , wherein the electrolyte is a CaCl 2 -based electrolyte that includes CaO as one of a plurality of constituents of the electrolyte. 
     
     
         22 . The method defined in  claim 21 , wherein the cell potential is above a decomposition potential of CaO, at which potential Ca metal can deposit on the cathode. 
     
     
         23 . The method defined in  claim 21 , wherein the cell potential is below the decomposition potential of CaCl 2 . 
     
     
         24 . The method defined in  claim 21 , wherein a graphite anode is employed, and said cell is operated at a temperature in the range of 600-1100° C., with the cell potential being between 1.3 and 3.5V. 
     
     
         25 . The method defined in  claim 21 , wherein the CaCl 2 -based electrolyte is a commercially available source of CaCl 2  that partially decomposes on heating and produces CaO or otherwise includes CaO. 
     
     
         26 . The method defined in  claim 21 , wherein the CaCl 2 -based electrolyte includes CaCl 2  and CaO that are added separately or pre-mixed to form the electrolyte. 
     
     
         27 . The method defined in  claim 19 , wherein the anode is graphite or an inert anode. 
     
     
         28 . A method of operating an electrolytic cell in order to produce high purity titanium (αTi) by reducing titanium oxide in a solid state in the electrolytic cell, the electrolytic cell including an anode, a cathode formed at least in-part from the titanium oxide, and a molten electrolyte which includes cations of a metal that is capable of chemically reducing the cathode titanium oxide, the method comprising:
 operating the operating the cell at a potential that is above a potential at which cations of the metal that is capable of chemically reducing the cathode titanium oxide deposit as the metal on the cathode, whereby the metal chemically reduces the cathode titanium oxide; 
 operating the cell at a constant current; and 
 refreshing the electrolyte and/or changing the electrolyte composition in the electrolytic cell in order to remove oxygen from partially reduced titanium oxide at later stages of the reduction process. 
 
     
     
         29 . The method defined in  claim 28 , wherein the high purity titanium is obtained without processing the titanium oxide outside of the electrolytic cell.