Reduction method for separating metal values from ocean floor nodule ore

Claim 2

A PROCESS FOR SEPARATING METAL VALUES FROM OCEAN FLOOR NODULE ORES, THE ORE COMPRISING AS PRIMARY COMPONENTS THE OXIDES OF MANGANESE AND IRON AND AS SECONDARY COMPONENTS COMPOUNDS OF COPPER, COBALT AND NICKEL, THE PROCESS COMPRISING THE STEPS OF:

Claim 3

REACTING THE NODULE ORE, IN THE PRESENCE OF OXYGEN, WITH A SULFUR DIOXIDE ACIDIC REDUCING AGENT TO FORM AS REACTION PRODUCTS THE WATER-SOLUBLE SULFATES OF DIVALENT MANGANESE, NICKEL, COBALT AND COPPER (2) CONTACTING THE METAL VALUES WITH SUFFICIENT OXYGEN TO CONVERT SUBSTANTIALLY ALL OF THE IRON PRESENT TO INSOLUBLE IRON OXIDE, (3) LEACHING THE REACTED ORE WITH AN AQUEOUS LEACH LIQUID TO FORM AN AQUEOUS PREGNANT LEACH SOLUTION COMPRISING THE WATERSOLUBLE SALTS OF DIVALENT MANGANESE, COPPER, NICKEL AND COBALT, (4) SEPARATING THE SOLUTION FROM ANY INSOLUBLE RESIDUE OF THE ORE,

Claim 4

REACTING THE NODULE ORE, IN THE PRESENCE OF OXYGEN, WITH A SULFUR DIOXIDE ACIDIC REDUCING AGENT TO FORM AS REACTION PRODUCTS THE WATER-SOLUBLE SULFATES OF DIVALENT MANGANESE, NICKEL, COBALT AND COPPER (2) CONTACTING THE METAL VALUES WITH SUFFICIENT OXYGEN TO CONVERT SUBSTANTIALLY ALL OF THE IRON PRESENT TO INSOLUBLE IRON OXIDE, (3) LEACHING THE REACTED ORE WITH AN AQUEOUS LEACH LIQUID TO FORM AN AQUEOUS PREGNANT LEACH SOLUTION COMPRISING THE WATERSOLUBLE SALTS OF DIVALENT MANGANESE, COPPER, NICKEL AND COBALT, (4) SEPARATING THE SOLUTION FROM ANY INSOLUBLE RESIDUE OF THE ORE,

Claim 5

Contacting the product with sufficient oxygen to convert all of the iron compounds to insoluble iron oxide;

Claim 6

Contacting the product with sufficient oxygen to convert all of the iron compounds to insoluble iron oxide;

Claim 7

The process of claim 1 wherein the liquid ion exchange process comprises contacting the aqueous pregnant leach solution with a liquid ion exchange medium selective for the metal, separating the medium from the aqueous solution and stripping the metal value from the medium with an aqueous stripping solution.

Claim 8

The process of claim 2 wherein the medium comprises a metal extractant selected from the group consisting of alpha-hydroxyoximes and 8-hydroxyquinolines.

Claim 9

leaching the reacted ore with water to form an aqueous leach solution comprising the water-soluble salts of divalent manganese, copper, nickel and cobalt;

Claim 10

leaching the reacted ore with water to form an aqueous leach solution comprising the water-soluble salts of divalent manganese, copper, nickel and cobalt;

Claim 11

separating the solution from any insoluble residue of the ore;

Claim 12

separating the solution from any insoluble residue of the ore;

Claim 13

The process of claim 3 wherein the metal extractant is dissolved in a water-immiscible organic liquid solvent.

Claim 14

The process of claim 1 wherein the nodule ore is reacted with the sulfur dioxide and in excess of oxygen in an aqueous medium to form directly an aqueous pregnant leach solution of the water-soluble salts of divalent manganese, copper, nickel and cobalt.

Claim 15

Separating out an individual metal value by treating the aqueous solution in a liquid ion exchange process to form a solution of the individual metal in the form of a water-soluble salt;

Claim 16

Separating out an individual metal value by treating the aqueous solution in a liquid ion exchange process to form a solution of the individual metal in the form of a water-soluble salt;

Claim 17

reducing the metal value to the elemental metal by cathodically electroplating from the solution of the water-soluble salt.

Claim 18

reducing the metal value to the elemental metal by cathodically electroplating from the solution of the water-soluble salt.

Claim 19

The process of claim 5 wherein the nodule ore is comminuted and the ore particles are slurried in an aqueous medium prior to reaction with the sulfur dioxide in the presence of oxygen.

Claim 20

The process of claim 1 wherein oxygen is present in excess when the ore is reacted with sulfur dioxide.

Claim 21

The process of claim 1 wherein the nodule ore is reacted with sulfur dioxide in an anhydrous environment.

Claim 22

The process of claim 1 wherein the ore and the sulfur dioxide are both at substantially ambient temperatures when they are reacted.

Claim 23

The process of claim 1 wherein the aqueous leach liquid is at substantially ambient temperature when it contacts the reacted ore.

Claim 24

The process of claim 1 wherein the leach liquid has a pH of not greater than about 3.

Claim 25

A process for separating metal values from ocean floor nodule ore, the ore comprising as primary components the oxides of manganese and of iron and as secondary components compounds of copper, cobalt and nickel, the process comprising the steps of: (1) comminuting the nodule ore; (2) reacting the nodule ore with sulfur dioxide in the presence of excess oxygen; (3) forming a pregnant leach solution comprising a solution in water of manganese sulfate, nickel sulfate, cobalt sulfate and copper sulfate and separating the pregnant leach solution from the insoluble solids; (4) separating individual metal values from the pregnant leach solution by subjecting said leach liquid to a liquid ion exchange medium and stripping individual metal values therefrom to form separate aqueous solutions of soluble copper salt, nickel salt, cobalt salt, and manganese salt; (6) reducing the copper to copper metal by cathodically electroplating the aqueous solution of copper (7) reducing the nickel salt and cobalt salt to elemental cobalt and nickel by cathodically electroplating respectively, and (8) reducing the manganese sulfate to manganese metal by cathodically electroplating the aqueous solution of manganese sulfate.

Claim 26

A process for separating metal values from ocean floor nodule ore, the ore comprising as primary components the oxides of manganese and of iron and as secondary components compounds of copper, cobalt and nickel, the process comprising the steps of: (1) comminuting the nodule ore; (2) reacting the nodule ore with sulfur dioxide in the presence of excess oxygen; (3) forming a pregnant leach solution comprising a solution in water of manganese sulfate, nickel sulfate, cobalt sulfate and copper sulfate and separating the pregnant leach solution from the insoluble solids; (4) separating individual metal values from the pregnant leach solution by subjecting said leach liquid to a liquid ion exchange medium and stripping individual metal values therefrom to form separate aqueous solutions of soluble copper salt, nickel salt, cobalt salt, and manganese salt; (6) reducing the copper to copper metal by cathodically electroplating the aqueous solution of copper (7) reducing the nickel salt and cobalt salt to elemental cobalt and nickel by cathodically electroplating respectively, and (8) reducing the manganese sulfate to manganese metal by cathodically electroplating the aqueous solution of manganese sulfate.

Claim 27

The process of claim 12 wherein the liquid ion exchange agent is selected from the group consisting of 8-hydroxyquinolines and alphahydroxyoximes.

Claim 28

A process for separating metal values from ocean floor nodule ores, the ore comprising as primary components the oxides of manganese and iron and as secondary components compounds of copper, cobalt and nickel, the process comprising the steps of:

Claim 29

A process for separating metal values from ocean floor nodule ores, the ore comprising as primary components the oxides of manganese and iron and as secondary components compounds of copper, cobalt and nickel, the process comprising the steps of: