Method for separating nickel from cobalt in aqueous solution

Claim 2

A PROCESS FOR THE SEPARATION OF INDIVIDUAL METAL VALUES FROM AN AQUEOUS SOLUTION COMPRISING A MIXTURE OF DISSOLVED METAL VALUES, AS THE HALIDES, THE SOLUTION COMPRISING AS THE PRIMARY METAL VALUE, MANGANESE, AND AS SECONDARY METAL VALUES, COBALT AND NICKEL, THE PROCESS COMPRISING: (1) EXTRACTING COBALT HALIDE FROM THE AQUEOUS SOLUTION WITH AN ORGANIC AMINE SOLUTION, THE AMINE BEING SELECTED FROM THE GROUP CONSISTING OF SECONDARY AMINES, TERTIARY AMINES AND QUATERNARY AMINES, SO AS TO FORM AN ORGANIC AMINE SOLUTION EXTRACT CONTAINING COBALT TETRAHALIDE COMPLEX AND SOME MANGANESE, AND AN AQUEOUS FIRST RAFFINATE, SUBSTANTIALLY DEPLETED IN COBALT HALIDE; (2) SEPARATING THE COBALT AND MANGANESE VALUES FROM THE ORGANIC AMINE EXTRACT INTO INDIVIDUAL AQUEOUS SOLUTIONS BY SELECTIVELY STRIPPING THE MANGANESE VALUE FROM THE EXTRACT WITH FROM ABOUT 1 TO ABOUT 12N HCL AQUEOUS SOLUTION TO FORM AN AQUEOUS SOLUTION OF MANGANESE HALIDE AND AN ORGANIC SOLUTION SUBSTANTIALLY DEPLETED IN MANGANESE VALUE AND THEN STRIPPING THE COBALT VALUE FROM THE ORGANIC SOLUTION USING AN AQUEOUS SOLUTION HAVING A PH OF NOT GREATER THAN ABOUT 5, TO FORM AN AQUEOUS SOLUTION OF COBALT HALIDE; (3) EXTRACTING THE NICKEL FROM THE FIRST RAFFINATE WITH A LIQUID ION EXCHANGE AGENT TO FORM AN AQUEOUS SECOND RAFFINATE CONTAINING MANGANESE HALIDE AND SUBSTANTIALLY DEPLETED IN NICKEL VALUE AND AN ORGANIC EXTRACT CONTAINING THE NICKEL VALUE; AND (4(STRIPPING THE NICKEL VALUE FROM THE ORGANIC EXTRACT WITH AN ACIDIC AQUEOUS SOLUTION.

Claim 3

The process of claim 1 wherein the aqueous solution of step 1 has a concentration of halide ions of at least about 2N.

Claim 4

The process of claim 1, wherein the pH of the first raffinate is adjusted to within the range of about 3 to about 6 prior to extracting the nickel and wherein the liquid ion exchange agent is selected from the group consisting of Alpha -hydroxy oximes and hydrocarbon-substituted 8-hydroxyquinolines.

Claim 5

The process of claim 1, wherein the halides comprise chlorides.

Claim 6

A process for the separation of individual metal values from an aqueous solution comprising a mixture of dissolved metal values, as the halides, the solution comprising as the primary value, manganese, and, as secondary metal values cobalt and nickel, the process comprising: (1) extracting cobalt halide from the aqueous solution with an organic amine solution, the amine being selected from the group consisting of secondary amines, tertiary amines and quaternary amines, so as to form an organic amine solution extract containing a cobalt tetrahalide complex and some manganese, and an aqueous first raffinate substantially depleted in cobalt halide; (2) separating the cobalt and manganese values from the organic amine extract by simultaneously stripping the cobalt and manganese together from the amine utilizing a water solution, so as to form an aqueous strip solution containing manganese halide and cobalt halide, and separating the cobalt and manganese metal values from the aqueous strip solution by selectively extracting one of the cobalt or manganese values therefrom, using an organic extract selective for one of the metal values, and then stripping the extracted metal value into a separate acidic aqueous solution, thereby forming two separate aqueous solutions of the individual cobalt and manganese values; (3) extracting the nickel from the first raffinate with a liquid ion exchange agent to form an aqueousj second raffinate containing manganese halide and substantially depleted in nickel value and an organic extract containing the nickel value; and (4) stripping the nickel value from the organic extract with an acidic aqueous solution.

Claim 7

A process for the separation of individual metal values from an aqueous solution comprising a mixture of dissolved metal values, as the halides, the solution comprising as the primary value, manganese, and, as secondary metal values cobalt and nickel, the process comprising: (1) extracting cobalt halide from the aqueous solution with an organic amine solution, the amine being selected from the group consisting of secondary amines, tertiary amines and quaternary amines, so as to form an organic amine solution extract containing a cobalt tetrahalide complex and some manganese, and an aqueous first raffinate substantially depleted in cobalt halide; (2) separating the cobalt and manganese values from the organic amine extract by simultaneously stripping the cobalt and manganese together from the amine utilizing a water solution, so as to form an aqueous strip solution containing manganese halide and cobalt halide, and separating the cobalt and manganese metal values from the aqueous strip solution by selectively extracting one of the cobalt or manganese values therefrom, using an organic extract selective for one of the metal values, and then stripping the extracted metal value into a separate acidic aqueous solution, thereby forming two separate aqueous solutions of the individual cobalt and manganese values; (3) extracting the nickel from the first raffinate with a liquid ion exchange agent to form an aqueousj second raffinate containing manganese halide and substantially depleted in nickel value and an organic extract containing the nickel value; and (4) stripping the nickel value from the organic extract with an acidic aqueous solution.

Claim 8

The process of claim 5 wherein the cobalt and manganese are separated from the aqueous solution by (a) adjusting the pH to a value in the range of from about 3.5 to about 6; (b) selectively extracting the cobalt from the aqueous solution with a liquid ion exchange agent selected from the group consisting of Alpha -hydroxy oximes and hydrocarbon-substituted 8-hydroxyquinolines to form an aqueous raffinate substantially depleted in cobalt and an organic extract containing cobalt and substantially free from manganese; and (c) stripping the cobalt from the extract with an aqueous solution containing a hydrogen ion concentration of at least 6 Normal and a halide ion concentration of at least 6 Normal.

Claim 9

The process of claim 5 wherein the cobalt and manganese are separated from the aqueous solution by (a) adjusting the pH of the aqueous solution to a value of not greater than about 3.5, (b) extracting manganese from the aqueous solution with an organic solution of a phosphoric acid diester to form an organic extract containing the manganese and a cobalt-containing manganese raffinate substantially free from manganese and (c) stripping the manganese from the organic extract using an acidic aqueous solution.

Claim 10

The process of claim 5, wherein the halides comprise chlorides.

Claim 11

The process of claim 5, wherein the pH of the first raffinate is adjusted to within the range of about 3 to about 6 prior to extracting the nickel and wherein the liquid ion exchange agent is selected from the group consisting of Alpha -hydroxy oximes and hydrocarbon-substituted 8-hydroxyquinolines.

Claim 12

A process for the separation of nickel and cobalt values found in ocean floor nodule ore, the ore comprising, as major components, the oxide of manganese and iron and, as secondary components, compounds of copper, cobalt and nickel, the process comprising the steps of: (a) reacting the nodule ore with a halide-forming agent under reducing conditions to form a mixture comprising water-soluble halides of divalent manganese, trivalent iron, copper, nickel and cobalt; (b) separating the iron from the remaining salts and forming an aqueous solution of the water-soluble metal halides; c) adjusting the pH of the aqueous solution to a value of not greater than about 2.5; (d) contacting the aqueous solution with a liquid ion exchange extracting medium immiscible with water, the medium comprising an extracting agent designed and adapted to extract copper selectively from the solution, until the aqueous solution is substantially depleted in copper, thus forming an organic extract containing the copper value and a first aqueous raffinate solution substantially depleted in copper; (e) extracting cobalt halide from the first raffinate with an organic amine solution, the amine being selected from the group consisting of secondary amines, tertiary amines and quaternary amines, so as to form an organic amine solution extract containing a cobalt tetrahalide complex and some manganese, and an aqueous second raffinate, substantially depleted in cobalt halide; (f) separating the cobalt and manganese values from the organic amine extract into individual aqueous solutions by selectivey stripping the manganese value from the extract with from about 1 to about 12 N HCl aqueous solution to form an aqueous solution of manganese halide and an organic solution substantially depleted in manganese value, and then stripping the cobalt value from the organic solution using an aqueous solution having a pH of not greater than about 5, to form an aqueous solution of cobalt halide; (g) extracting the nickel from the second raffinate with a liquid ion exchange agent to form an aqueous third raffinate containing manganese halide and substantially depleted in nickel value and an organic extract containing the nickel value; and (h) stripping the nickel values from the organic extract with an acidic aqueous solution.

Claim 13

A process for the separation of nickel and cobalt values found in ocean floor nodule ore, the ore comprising, as major components, the oxide of manganese and iron and, as secondary components, compounds of copper, cobalt and nickel, the process comprising the steps of: (a) reacting the nodule ore with a halide-forming agent under reducing conditions to form a mixture comprising water-soluble halides of divalent manganese, trivalent iron, copper, nickel and cobalt; (b) separating the iron from the remaining salts and forming an aqueous solution of the water-soluble metal halides; c) adjusting the pH of the aqueous solution to a value of not greater than about 2.5; (d) contacting the aqueous solution with a liquid ion exchange extracting medium immiscible with water, the medium comprising an extracting agent designed and adapted to extract copper selectively from the solution, until the aqueous solution is substantially depleted in copper, thus forming an organic extract containing the copper value and a first aqueous raffinate solution substantially depleted in copper; (e) extracting cobalt halide from the first raffinate with an organic amine solution, the amine being selected from the group consisting of secondary amines, tertiary amines and quaternary amines, so as to form an organic amine solution extract containing a cobalt tetrahalide complex and some manganese, and an aqueous second raffinate, substantially depleted in cobalt halide; (f) separating the cobalt and manganese values from the organic amine extract into individual aqueous solutions by selectivey stripping the manganese value from the extract with from about 1 to about 12 N HCl aqueous solution to form an aqueous solution of manganese halide and an organic solution substantially depleted in manganese value, and then stripping the cobalt value from the organic solution using an aqueous solution having a pH of not greater than about 5, to form an aqueous solution of cobalt halide; (g) extracting the nickel from the second raffinate with a liquid ion exchange agent to form an aqueous third raffinate containing manganese halide and substantially depleted in nickel value and an organic extract containing the nickel value; and (h) stripping the nickel values from the organic extract with an acidic aqueous solution.

Claim 14

A process for the separation of nickel and cobalt values found in ocean floor nodule ore, the ore comprising as major components the oxides of manganese and of iron and as secondary components, compounds of copper, cobalt and nickel, the process comprising the steps of: (a) reacting the nodules with a halide forming agent under reducing conditions to form a mixture comprising water soluble halides of divalent manganese, trivalent iron, copper, nickel and cobalt; (b) separating the iron from the remaining salts and forming an aqueous solution of the water-soluble metal halides; (c) adjusting the pH of the aqueous solution to a value of not greater than about 2.5; (d) contacting the aqueous solution with a liquid ioN exchange extracting medium immiscible with water, the medium comprising an extracting agent designed and adapted to extract copper selectively from the solution, until the aqueous solution is substantially depleted in copper, thus forming an organic extract containing the copper value and a first aqueous raffinate solution substantially depleted in copper; (e) extracting cobalt halide from the first raffinate with an organic amine solution, the amine being selected from the group consisting of secondary amines, tertiary amines and quaternary amines, so as to form an organic amine solution extract containing a cobalt tetrahalide complex and some manganese, and an aqueous second raffinate, substantially depleted in cobalt halide; (f) separating the cobalt and manganese values from the organic amine extract by simultaneously stripping the cobalt and manganese together from the amine, utilizing a water solution, so as to form an aqueous strip solution containing manganese halide and cobalt halide, and separating the cobalt and manganese metal values from the aqueous strip solution by selectively extracting one of the cobalt or manganese values therefrom, using an organic extract selective for one of the metal values, and then stripping the extracted metal values into a separate acidic aqueous solution, thereby forming two separate aqueous solutions of the individual cobalt and manganese values; (g) extracting the nickel from the second raffinate with a liquid ion exchange agent to form an aqueous third raffinate containing manganese halide and substantially depleted in nickel halide and an organic extract containing the nickel values; and (h) stripping the nickel value from the organic extract with an acidic aqueous solution.

Claim 15

A process for the separation of nickel and cobalt values found in ocean floor nodule ore, the ore comprising as major components the oxides of manganese and of iron and as secondary components, compounds of copper, cobalt and nickel, the process comprising the steps of: (a) reacting the nodules with a halide forming agent under reducing conditions to form a mixture comprising water soluble halides of divalent manganese, trivalent iron, copper, nickel and cobalt; (b) separating the iron from the remaining salts and forming an aqueous solution of the water-soluble metal halides; (c) adjusting the pH of the aqueous solution to a value of not greater than about 2.5; (d) contacting the aqueous solution with a liquid ioN exchange extracting medium immiscible with water, the medium comprising an extracting agent designed and adapted to extract copper selectively from the solution, until the aqueous solution is substantially depleted in copper, thus forming an organic extract containing the copper value and a first aqueous raffinate solution substantially depleted in copper; (e) extracting cobalt halide from the first raffinate with an organic amine solution, the amine being selected from the group consisting of secondary amines, tertiary amines and quaternary amines, so as to form an organic amine solution extract containing a cobalt tetrahalide complex and some manganese, and an aqueous second raffinate, substantially depleted in cobalt halide; (f) separating the cobalt and manganese values from the organic amine extract by simultaneously stripping the cobalt and manganese together from the amine, utilizing a water solution, so as to form an aqueous strip solution containing manganese halide and cobalt halide, and separating the cobalt and manganese metal values from the aqueous strip solution by selectively extracting one of the cobalt or manganese values therefrom, using an organic extract selective for one of the metal values, and then stripping the extracted metal values into a separate acidic aqueous solution, thereby forming two separate aqueous solutions of the individual cobalt and manganese values; (g) extracting the nickel from the second raffinate with a liquid ion exchange agent to form an aqueous third raffinate containing manganese halide and substantially depleted in nickel halide and an organic extract containing the nickel values; and (h) stripping the nickel value from the organic extract with an acidic aqueous solution.