Method for separating metal constituents from ocean floor nodules

Claim 2

A process for the recovery of pure metal halides from ocean floor nodule ore, the ore comprising, as major components, the oxides of manganese and iron and as secondary components, compounds of copper, cobalt and nickel, the weight ratio of manganese-to-nickel-plus cobalt being at least about 9, the process comprising the steps of (1) reacting the nodule ore with a halide salt-forming reagent, selected from the group consisting of hydrogen halides and combinations of an elemental halogen with a selective reducing reagent, to form a mixture comprising the corresponding water-soluble halide salts of divalent manganese, trivalent iron, copper, nickel and cobalt, the reducing reagent being selected from the group consisting of carbon, hydrocarbons and carbon monoxide; (2) converting the ferric halide to water-insoluble ferric oxide; (3) dissolving the remaining metal halide salts in water to form an iron-free pregnant aqueous solution of the water-soluble halides, containing concentration of manganese and concentration of nickel, cobalt plus copper proportional to the concentrations in the nodule ore and separating the solution from the insoluble ferric oxide; and (4) contacting the pregnant aqueous solution with a water-immiscible organic extracting solution comprising an extraction agent selective for copper and selected from the group consisting of alpha-hydroxyoximes and hydrocarbon-substituted-8-hydroxy quinolines, the aqueous solution having a pH not greater than about 2.5.

Claim 3

The process of claim 1 wherein the halides of manganese, copper, nickel, cobalt and iron are formed as solids and wherein the halides are reacted with water at a temperature of at least about 200° C. to form a solid mixture of the halides of manganese, copper, nickel, and cobalt and iron oxide, the solid mixture is then leached with water to form a solution of the halides of manganese, copper, nickel and cobalt, the insoluble residue comprising iron oxide is separated therefrom.

Claim 4

The process of claim 1 wherein the nodule ore is reacted with a hydrogen halide generated in situ by the mixing of the nodule ore with a metal halide selected from the group consisting of alkali metal and alkaline earth metal halides of groups 1 and 2 of the periodic table with a strong mineral acid.

Claim 5

The process of claim 1 wherein the salt-forming reagent is a hydrogen halide and the hydrogen halide is reacted with the ocean floor nodule ore at a temperature of at least about 110° C.

Claim 6

The process of claim 4 wherein the hydrogen halide is reacted with the nodule ore at a temperature in the range of from about 1:0 to about 600° C.

Claim 7

The process of claim 4, wherein the hydrogen halide is reacted at a temperature of at least about 500° C.

Claim 8

A process in accordance with claim 1 wherein the ore is reacted at a temperature of at least about 500° C with a mixture comprising a halogen and a selective reducing agent selected from the group consisting of carbon, hydrocarbons and carbon monoxide.

Claim 9

The process of claim 7 comprising, in addition, prior to converting the ferric halide to ferric oxide, vaporizing the metal halides formed and then condensing and collecting.

Claim 10

The process of claim 7 wherein ferric oxide is formed by reacting the metal halides with water at a temperature of at least about 200° C. to selectively convert ferric halide to ferric oxide.

Claim 11

The process of claim 7 wherein the halide is hydrogen chloride.

Claim 12

The process of claim 7 wherein the vaporized metal halides are fractionated so as to separate the various halides present.

Claim 13

The process of claim 7 wherein the nodule ore is reacted with a mixture of chlorine, hydrogen chloride and a carbonaceous material.

Claim 14

The process of claim 7 wherein the nodule ore is reacted with chlorine and carbon monoxide.

Claim 15

The process of claim 7 wherein the nodule ore is reacted with chlorine and a hydrocarbon.

Claim 16

The process of claim 7 wherein the nodule ore is reacted with a mixture of chlorine and hydrogen chloride and carbon monoxide.

Claim 17

A process for the recovery of pure metal halide from ocean floor nodule ore, the ore comprising, as major components, the oxides of manganese and iron and as secondary components, compounds of copper, cobalt and nickel, the weight ratio of manganese to nickel-plus-cobalt being at least about 9 the process comprising the steps of (1) reacting the nodule ore with a halide salt-forming reagent selected from the group consisting of hydrogen halides and combinations of an elemental halogen with a selective reducing reagent, to form a mixture comprising the corresponding water-soluble salts of divalent manganese, trivalent iron, copper, nickel and cobalt, the reducing reagent being selected from the group consisting of carbon, hydrocarbons and carbon monoxide; (2) dissolving the metal halide salts in water to form a pregnant aqueous solution of the water-soluble metal halide salts, containing concentrations of manganese and concentrations of nickel, cobalt and copper proportional to their concentrations in the nodule ore; (3) extracting the ferric halide from the pregnant solution with an extracting agent selected from the group consisting or organic solutions of organic phosphate esters and amines to form a substantially iron-free aqueous raffinate; and (4) contacting the iron-free aqueous raffinate with water-immiscible organic extracting solution comprising an extraction agent selective for copper and selected from the group consisting of alpha-hydroxy oximes and hydrocarbon-substituted-8-hydroxy quinolines, the aqueous solution having a pH not greater than about 2.5.

Claim 18

A process for the recovery of pure metal halide from ocean floor nodule ore, the ore comprising, as major components, the oxides of manganese and iron and as secondary components, compounds of copper, cobalt and nickel, the weight ratio of manganese to nickel-plus-cobalt being at least about 9 the process comprising the steps of (1) reacting the nodule ore with a halide salt-forming reagent selected from the group consisting of hydrogen halides and combinations of an elemental halogen with a selective reducing reagent, to form a mixture comprising the corresponding water-soluble salts of divalent manganese, trivalent iron, copper, nickel and cobalt, the reducing reagent being selected from the group consisting of carbon, hydrocarbons and carbon monoxide; (2) dissolving the metal halide salts in water to form a pregnant aqueous solution of the water-soluble metal halide salts, containing concentrations of manganese and concentrations of nickel, cobalt and copper proportional to their concentrations in the nodule ore; (3) extracting the ferric halide from the pregnant solution with an extracting agent selected from the group consisting or organic solutions of organic phosphate esters and amines to form a substantially iron-free aqueous raffinate; and (4) contacting the iron-free aqueous raffinate with water-immiscible organic extracting solution comprising an extraction agent selective for copper and selected from the group consisting of alpha-hydroxy oximes and hydrocarbon-substituted-8-hydroxy quinolines, the aqueous solution having a pH not greater than about 2.5.

Claim 19

A process for the refining and obtaining of metal values from ocean floor nodule ore, the nodules comprising primarily manganese oxide and iron oxide and secondary amounts of compounds of copper, nickel and cobalt, the weight ratio of manganese-to-nickel-plus-cobalt being at least about 9, the process comprising: (1) reacting the nodule ore with a hydrogen halide at a temperature in the range of at least about 600° C so as to form manganous halide, ferric halide, copper halide, nickel halide and cobalt halide; (2) evaporating the halides thus formed; (3) condensing and collecting the halides so evaporated and converting the ferric halide to ferric oxide; (4) forming a pregnant aqueous solution of the condensed halides of manganese copper, nickel and cobalt substantially free from dissolved iron, and containing concentrations of manganese, nickel, cobalt and copper proportional to their concentrations in the nodule ore; and (5) contacting the pregnant aqueous solution with a water-immiscible organic extracting solution comprising an extraction agent selective for copper and selected from the group consisting of alpha-hydroxy oximes and hydrocarbon-substituted-8-hydroxy quinolines, the aqueous solution having a pH not greater than about 2.5.

Claim 20

A process for the refining and obtaining of metal values from ocean floor nodule ore, the nodules comprising primarily manganese oxide and iron oxide and secondary amounts of compounds of copper, nickel and cobalt, the weight ratio of manganese-to-nickel-plus-cobalt being at least about 9, the process comprising: (1) reacting the nodule ore with a hydrogen halide at a temperature in the range of at least about 600° C so as to form manganous halide, ferric halide, copper halide, nickel halide and cobalt halide; (2) evaporating the halides thus formed; (3) condensing and collecting the halides so evaporated and converting the ferric halide to ferric oxide; (4) forming a pregnant aqueous solution of the condensed halides of manganese copper, nickel and cobalt substantially free from dissolved iron, and containing concentrations of manganese, nickel, cobalt and copper proportional to their concentrations in the nodule ore; and (5) contacting the pregnant aqueous solution with a water-immiscible organic extracting solution comprising an extraction agent selective for copper and selected from the group consisting of alpha-hydroxy oximes and hydrocarbon-substituted-8-hydroxy quinolines, the aqueous solution having a pH not greater than about 2.5.

Claim 21

The process of claim 17 wherein the hydrogen halide is hydrogen chloride.

Claim 22

The process of claim 17 wherein the reaction occurs at a temperature of from about 600° to about 1000° C.

Claim 23

The process in accordance with claim 17 wherein the vaporized metal halides are condensed and collected as a mixture, and wherein the mixed halides are contacted with water to form ferric oxide so that insoluble ferric oxide is separated from the water soluble metal halides by leaching with an aqueous solution.

Claim 24

The process of claim 17 wherein the nodule ore is contacted with a mixture of a hydrogen halide and an elemental halogen vapor.

Claim 25

The process of claim 21 wherein the metal halides are evaporated at successively higher temperatures and the vapor removed from the product at each temperature is separately condensed, thus separating the halides having a higher vapor pressure from those having a lower vapor pressure.

Claim 26

The process of claim 21 wherein the metal halide vapors from the nodule ore are fractionally condensed to separate the vapors of metal halides having higher vapor pressures from those having lower vapor pressures. pg,67

Claim 27

A process for the refining and obtaining of metal values from ocean floor nodule ore, the nodules comprising primarily manganese oxide and iron oxide and secondary amounts of compounds of copper, nickel and cobalt, the weight ratio of manganese-to-nickel-plus-cobalt being at least about 9, the process comprising: (1) reacting the nodule ore with a hydrogen halide at a temperature in the range of at least about 600° C so as to form manganous halide, ferric halide, copper halide, nickel halide and cobalt halide; (2) evaporating the halides thus formed; (c) converting the ferric halide to ferric oxide and condensing and collecting the remaining vaporized halides; (4) forming a pregnant aqueous solution of the condensed halides of manganese, nickel, cobalt and copper substantially free from dissolved iron, and containing concentrations of manganese, nickel, cobalt and copper proportional to their concentrations in the nodule ore; and (5) contacting the pregnant aqueous solution with a water-immiscible organic extracting solution comprising an extraction agent selective for copper and selected from the group consisting of alpha-hydroxy oximes and hydrocarbon-substituted-8-hydroxy quinolines, the aqueous solution having a pH not greater than about 2.5.

Claim 28

A process for the refining and obtaining of metal values from ocean floor nodule ore, the nodules comprising primarily manganese oxide and iron oxide and secondary amounts of compounds of copper, nickel and cobalt, the weight ratio of manganese-to-nickel-plus-cobalt being at least about 9, the process comprising: (1) reacting the nodule ore with a hydrogen halide at a temperature in the range of at least about 600° C so as to form manganous halide, ferric halide, copper halide, nickel halide and cobalt halide; (2) evaporating the halides thus formed; (c) converting the ferric halide to ferric oxide and condensing and collecting the remaining vaporized halides; (4) forming a pregnant aqueous solution of the condensed halides of manganese, nickel, cobalt and copper substantially free from dissolved iron, and containing concentrations of manganese, nickel, cobalt and copper proportional to their concentrations in the nodule ore; and (5) contacting the pregnant aqueous solution with a water-immiscible organic extracting solution comprising an extraction agent selective for copper and selected from the group consisting of alpha-hydroxy oximes and hydrocarbon-substituted-8-hydroxy quinolines, the aqueous solution having a pH not greater than about 2.5.