US4545816A — Processes relating to the extraction of metals fr…

Claim 1

Independent Claim 155 words

A process for the extraction of ferrous, manganous and nonferrous metals from iron oxide and manganese oxide containing ores by reduction leaching comprising the steps of: contacting the pulverized ore with a stabilized acidic cuprous ion solution Cu + L in a suitable reactor at a temperature of up to about 90° C. while maintaining the pH between about 1.5 and 2.5 with acid to form a slurry, wherein L is a stabilizing ligand selected from the group consisting of CO, XRCN and Cl - , X being --H or --OH and R being aliphatic having from one to about four carbon atoms; separating said slurry into a solid tailings portion and a pregnant liquor, said pregnant liquor containing solubilized ferrous, manganous, cupric and other nonferrous metal ions; selectively extracting said solubilized metal ions; and regenerating said cuprous ion solution from said solubilized cupric ions and said ligand, L in the presence of a reductant.

Claim 2

Dependent Claim 155 words

A process for the extraction of ferrous, manganous and nonferrous metals from iron oxide and manganese oxide containing ores by reduction leaching comprising the steps of: contacting the pulverized ore with a stabilized acidic cuprous ion solution Cu + L in a suitable reactor at a temperature of up to about 90° C. while maintaining the pH between about 1.5 and 2.5 with acid to form a slurry, wherein L is a stabilizing ligand selected from the group consisting of CO, XRCN and Cl - , X being --H or --OH and R being aliphatic having from one to about four carbon atoms; separating said slurry into a solid tailings portion and a pregnant liquor, said pregnant liquor containing solubilized ferrous, manganous, cupric and other nonferrous metal ions; selectively extracting said solubilized metal ions; and regenerating said cuprous ion solution from said solubilized cupric ions and said ligand, L in the presence of a reductant.

Claim 3

Dependent Claim 48 words

A process, as set forth in claim 1, wherein said contacting step is conducted at low pressure ranging from about ambient to about 1.5 MPa and at a temperature of from about 20° to 90° C.; wherein said pH is about 2 and, wherein said acid is sulfuric.

Claim 4

Dependent Claim 28 words

A process, as set forth in claim 1, wherein said iron oxide ore comprises laterite and said manganese oxide ore comprises manganese sea nodules and terrestrial manganese ore.

Claim 5

Dependent Claim 37 words

A process, as set forth in claim 1, wherein said ferrous metal is iron, said manganous metal is manganese and said nonferrous metals comprise at least one member of the group consisting of nickel, cobalt and copper.

Claim 6

Dependent Claim 23 words

A process, as set forth in claim 4, wherein said iron and manganese metals are separated before said nickel, cobalt and copper metals.

Claim 7

Dependent Claim 25 words

A process, as set forth in claim 5, wherein said nickel and cobalt metals are separated before said step of regenerating said cuprous ion solution.

Claim 8

Dependent Claim 25 words

A process as set forth in claim 5, wherein said nickel and cobalt metals are separated after said step of regenerating said cuprous ion solution.

Claim 9

Dependent Claim 27 words

A process, as set forth in claim 4, wherein said iron, manganese, nickel and cobalt metals are separated after said step of regenerating said cuprous ion solution.

Claim 10

Dependent Claim 38 words

A process, as set forth in claim 1, wherein said tailings are essentially free of iron, manganese, nickel, cobalt and copper metals and are enriched in chromium and any precious metals other than silver contained in said ore.

Claim 11

Dependent Claim 91 words

A process, as set forth in claim 1, wherein L is CO and said step of regenerating includes the steps of: combining said solubilized cupric ions with CO and a quinolic compound selected from the group consisting of quinol, anthraquinols and naphthoquinols at a pressure of from about 0.1 to about 1.5 MPa and at a temperature of from about 20° to 90° C. to form an aqueous CuCO + lixiviant and the corresponding quinonic compound; separating said lixiviant from said quinonic compound; and regenerating said quinolic compound from said quinonic.

Claim 12

Dependent Claim 47 words

A process, as set forth in claim 10, wherein said step of regenerating said quinolic compound is conducted with hydrogen gas over a suitable catalyst at a pressure of from about 0.1 to about 1.2 MPa and a temperature of from about 20° to about 80° C.

Claim 13

Dependent Claim 89 words

A process, as set forth in claim 1, wherein L is XRCN and said step of regenerating includes the steps of: combining said solubilized cupric ions with XRCN and a quinolic compound selected from the group consisting of quinol, anthraquinols and naphthoquinols at a pressure of from about 0.1 to about 1.0 MPa and at a temperature of from about 20° to 90° C. to form a CuXRCN lixiviant and the corresponding quinonic compound; separating said lixiviant from said quinonic compound; and regenerating said quinolic compound from said quinonic.

Claim 14

Dependent Claim 14 words

A process, as set forth in claim 12, wherein L is CH 3 CN.

Claim 15

Dependent Claim 47 words

A process, as set forth in claim 13, wherein said step of regenerating said quinolic compound is conducted with hydrogen gas over a suitable catalyst at a pressure of from about 0.1 to about 1.2 MPa and a temperature of from about 20° to about 80° C.

Claim 16

Dependent Claim 110 words

A process, as set forth in claim 1, wherein said step of regenerating includes the steps of: dividing said cupric ion solution into first and second streams; combining said first stream with a quinolic compound selected from the group consisting of quinol and anthraquinols to form a three phase slurry consisting essentially of free copper metal, an aqueous acid phase and the corresponding quinonic compound; separating said quinonic compound from said copper metal and aqueous acid; and combining said second stream with said copper metal and aqueous acid and with said ligand L, where L is CO or XRCN, whereby the stabilized cuprous ion solution, Cu + L is formed.

Claim 17

Dependent Claim 43 words

A process, as set forth in claim 15, wherein L is CO and said second step of combining is conducted at a pressure of from about 0.1 to about 1.5 MPa and at a temperature of from about 20° to about 90° C.

Claim 18

Dependent Claim 43 words

A process, as set forth in claim 15, wherein L is XRCN and said second step of combining is conducted at a pressure of from about 0.1 to about 1.0 MPa and at a temperature of from about 20° to about 90° C.

Claim 19

Dependent Claim 14 words

A process, as set forth in claim 17, wherein L is CH 3 CN.

Claim 20

Dependent Claim 20 words

A process, as set forth in claim 15, including the additional step of regenerating said quinolic compound from said quinonic.

Claim 21

Dependent Claim 47 words

A process, as set forth in claim 19, wherein said step of regenerating said quinolic compound is conducted with hydrogen gas over a suitable catalyst at a pressure of from about 0.1 to about 1.2 MPa and a temperature of from about 20° to about 80° C.

Claim 22

Dependent Claim 60 words

A process, as set forth in claim 1, wherein said step of regenerating includes the steps of: reducing said solubilized cupric ions with hydrogen to form a slurry comprising copper metal, cupric ions and acid; and cooling and combining said slurry with said ligand L, where L is CO or XRCN, to form the stabilized ion solution Cu + L.

Claim 23

Dependent Claim 39 words

A process, as set forth in claim 21, wherein said step of reducing is conducted in an autoclave operating at a pressure of between about 1.5 and 5.0 and at a temperature of from about 200° to 280° C.

Claim 24

Dependent Claim 23 words

A process, as set forth in claim 22, wherein said slurry is cooled to at least about 140° C. and L is CO.

Claim 25

Dependent Claim 25 words

A process, as set forth in claim 22, wherein said slurry is cooled to at least about 90° C. and L is CH 3 CN.

Claim 26

Dependent Claim 60 words

A process, as set forth in claim 1, wherein said step of regenerating includes the steps of: reducing said solubilized cupric ions with CO to form a slurry comprising copper metal, cupric ions and acid; and cooling and combining said slurry with said ligand L, where L is CO or XRCN, to form the stabilized ion solution Cu + L.

Claim 27

Dependent Claim 40 words

A process, as set forth in claim 25, wherein said step of reducing is conducted in an autoclave operating at a pressure of between about 1.5 and 5.0 MPa and at a temperature of from about 150° to 260° C.

Claim 28

Dependent Claim 23 words

A process, as set forth in claim 26, wherein said slurry is cooled to at least about 140° C. and L is CO.

Claim 29

Dependent Claim 25 words

A process, as set forth in claim 26, wherein said slurry is cooled to at least about 90° C. and L is CH 3 CN.

Claim 30

Dependent Claim 62 words

A process, as set forth in claim 1, wherein said step of regenerating includes the steps of: reducing said solubilized cupric ions with syngas to form a slurry comprising copper metal, cupric ions, cuprous ions and acid; and cooling and combining said slurry with said ligand L, where L is CO or XRCN, to form the stabilized ion solution Cu + L.

Claim 31

Dependent Claim 40 words

A process, as set forth in claim 29, wherein said step of reducing is conducted in an autoclave operating at a pressure of between about 1.5 and 5.0 MPa and at a temperature of from about 150° to 280° C.

Claim 32

Dependent Claim 30 words

A process, as set forth in claim 1, including the additional step of: removing a portion of said cuprous ions from said cuprous ion solution after said step of regenerating.

Claim 33

Dependent Claim 48 words

A process, as set forth in claim 31, wherein said step of removing includes the steps of: drawing off a slipstream of said stabilized cuprous ion solution; allowing said slipstream to disproportionate, forming free copper metal and cupric ions; and separating said copper metal from said cupric ions.

Claim 34

Dependent Claim 20 words

A process, as set forth in claim 32, wherein said cupric ions are combined with said stabilized cuprous ion solution.

Claim 35

Dependent Claim 30 words

A process, as set forth in claim 1, including the additional step of: removing a portion of said copper ions from said copper ion solution before said step of regenerating.

Claim 36

Dependent Claim 62 words

A process, as set forth in claim 34, wherein said step of removing includes the steps of: combining said solubilized cupric ions with a quinolic compound selected from the group consisting of quinol and anthraquinols to form a three phase slurry consisting essentially of free copper metal, an aqueous acid phase and the corresponding quinonic compound; and separating said copper metal therefrom.

Claim 37

Dependent Claim 22 words

A process, as set forth in claim 1, including the additional step of: recycling said regenerated cuprous ion solution to said reactor.

Claim 38

Dependent Claim 131 words

A process for the extraction of ferrous, manganous and nonferrous metals from iron oxide and manganese oxide containing ores by reduction leaching comprising the steps of: contacting the pulverized ore with a stabilized acidic cuprous ion solution Cu + L at a temperature of up to about 90° C. while maintaining the pH between about 1.5 and 2.5 with acid to form a slurry, wherein L is a stabilizing ligand selected from the group consisting of CO, XRCN and Cl - , X being --H or --OH and R being aliphatic having from one to about four carbon atoms; separating said slurry into a solid tailings portion and a pregnant liquor, said pregnant liquor containing solubilized ferrous, manganous, cupric and other nonferrous metal ions; and selectively extracting said solubilized metal ions.

Claim 39

Dependent Claim 131 words

A process for the extraction of ferrous, manganous and nonferrous metals from iron oxide and manganese oxide containing ores by reduction leaching comprising the steps of: contacting the pulverized ore with a stabilized acidic cuprous ion solution Cu + L at a temperature of up to about 90° C. while maintaining the pH between about 1.5 and 2.5 with acid to form a slurry, wherein L is a stabilizing ligand selected from the group consisting of CO, XRCN and Cl - , X being --H or --OH and R being aliphatic having from one to about four carbon atoms; separating said slurry into a solid tailings portion and a pregnant liquor, said pregnant liquor containing solubilized ferrous, manganous, cupric and other nonferrous metal ions; and selectively extracting said solubilized metal ions.

Claim 40

Dependent Claim 48 words

A process, as set forth in claim 37, wherein said contacting step is conducted at low pressure ranging from about ambient to about 1.5 MPa and at a temperature of from about 20° to 90° C.; wherein said pH is about 2 and, wherein said acid is sulfuric.

Claim 41

Dependent Claim 28 words

A process, as set forth in claim 37, wherein said iron oxide ore comprises laterite and said manganese oxide ore comprises manganese sea nodules and terrestrial manganese ore.

Claim 42

Dependent Claim 37 words

A process, as set forth in claim 37, wherein said ferrous metal is iron, said manganous metal is manganese and said nonferrous metals comprise at least one member of the group consisting of nickel, cobalt and copper.

Claim 43

Dependent Claim 23 words

A process, as set forth in claim 40, wherein said iron and manganese metals are separated before said nickel, cobalt and copper metals.

Claim 44

Dependent Claim 38 words

A process, as set forth in claim 37, wherein said tailings are essentially free of iron, manganese, nickel, cobalt and copper metals and are enriched in chromium and any precious metals other than silver contained in said ore.

Claim 45

Dependent Claim 96 words

A process for the regeneration of stabilized cuprous ion solutions, usable as reductants, from acidic cupric ion solutions comprising the steps of: combining said solubilized cupric ions with CO as a stabilizing ligand and a quinolic compound selected from the group consisting of quinol, anthraquinols and naphthoquinols at a pressure of from about 0.1 to about 1.5 MPa and at a temperature of from about 20° to 90° C. to form an aqueous CuCO + lixiviant and the corresponding quinonic compound; separating said lixiviant from said quinonic compound; and regenerating said quinolic compound from said quinonic.

Claim 46

Dependent Claim 96 words

A process for the regeneration of stabilized cuprous ion solutions, usable as reductants, from acidic cupric ion solutions comprising the steps of: combining said solubilized cupric ions with CO as a stabilizing ligand and a quinolic compound selected from the group consisting of quinol, anthraquinols and naphthoquinols at a pressure of from about 0.1 to about 1.5 MPa and at a temperature of from about 20° to 90° C. to form an aqueous CuCO + lixiviant and the corresponding quinonic compound; separating said lixiviant from said quinonic compound; and regenerating said quinolic compound from said quinonic.

Claim 47

Dependent Claim 47 words

A process, as set forth in claim 43, wherein said step of regenerating said quinolic compound is conducted with hydrogen gas over a suitable catalyst at a pressure of from about 0.1 to about 1.2 MPa and a temperature of from about 20° to about 80° C.

Claim 48

Dependent Claim 116 words

A process for the regeneration of stabilized cuprous ion solutions, usable as reductants, from acidic cupric ion solutions comprising the steps of: dividing said cupric ion solution into first and second streams; combining said first stream with a quinolic compound selected from the group consisting of quinol and anthraquinols to form a three phase slurry consisting essentially of free copper metal, an aqueous acid phase and the corresponding quinonic compound; separating said quinonic compound from said copper metal and aqueous acid; and combining said second stream with said copper metal and aqueous acid and with a stabilizing ligand L, where L is CO or XRCN, whereby the stabilized cuprous ion solution, Cu + L is formed.

Claim 49

Dependent Claim 116 words

A process for the regeneration of stabilized cuprous ion solutions, usable as reductants, from acidic cupric ion solutions comprising the steps of: dividing said cupric ion solution into first and second streams; combining said first stream with a quinolic compound selected from the group consisting of quinol and anthraquinols to form a three phase slurry consisting essentially of free copper metal, an aqueous acid phase and the corresponding quinonic compound; separating said quinonic compound from said copper metal and aqueous acid; and combining said second stream with said copper metal and aqueous acid and with a stabilizing ligand L, where L is CO or XRCN, whereby the stabilized cuprous ion solution, Cu + L is formed.

Claim 50

Dependent Claim 43 words

A process, as set forth in claim 45, wherein L is CO and said second step of combining is conducted at a pressure of from about 0.1 to about 1.5 MPa and at a temperature of from about 20° to about 90° C.

Claim 51

Dependent Claim 44 words

A process, as set forth in claim 45, wherein L is XRCN and said second step of combining is conducted at a total pressure of from about 0.1 to about 1.0 MPa and at a temperature of from about 20° to about 90° C.

Claim 52

Dependent Claim 66 words

A process for the regeneration of stabilized cuprous ion solutions, usable as reductants, from acidic cupric ion solutions comprising the steps of: reducing said solubilized cupric ions with CO to form a slurry comprising copper metal, cupric ions and acid; and cooling and combining said slurry with a stabilizing ligand L, where L is CO or XRCN, to form the stabilized ion solution Cu + L.

Claim 53

Dependent Claim 66 words

A process for the regeneration of stabilized cuprous ion solutions, usable as reductants, from acidic cupric ion solutions comprising the steps of: reducing said solubilized cupric ions with CO to form a slurry comprising copper metal, cupric ions and acid; and cooling and combining said slurry with a stabilizing ligand L, where L is CO or XRCN, to form the stabilized ion solution Cu + L.

Claim 54

Dependent Claim 40 words

A process, as set forth in claim 48, wherein said step of reducing is conducted in an autoclave operating at a pressure of between about 1.5 and 5.0 MPa and at a temperature of from about 200° to 280° C.

Claim 55

Dependent Claim 31 words

A process, as set forth in claim 48, including the additional step of cooling said slurry to a temperature of at least about 140° C. prior to said step of combining.

Claim 56

Dependent Claim 93 words

A process for the regeneration of stabilized cuprous ion solutions, usable as reductants, from acidic cupric ion solutions comprising the steps of: reducing said solubilized cupric ions with syngas in an autoclave operating at a pressure of between about 1.5 and 5.0 MPa and at a temperature of from about 150° to 280° C. to form a slurry comprising copper metal, cupric ions, cuprous ions and acid; and cooling and combining said slurry with a stabilizing ligand L, where L is CO or XRCN, to form the stabilized ion solution Cu + L.

Claim 57

Dependent Claim 93 words

A process for the regeneration of stabilized cuprous ion solutions, usable as reductants, from acidic cupric ion solutions comprising the steps of: reducing said solubilized cupric ions with syngas in an autoclave operating at a pressure of between about 1.5 and 5.0 MPa and at a temperature of from about 150° to 280° C. to form a slurry comprising copper metal, cupric ions, cuprous ions and acid; and cooling and combining said slurry with a stabilizing ligand L, where L is CO or XRCN, to form the stabilized ion solution Cu + L.

Claim 58

Dependent Claim 183 words

A process for the extraction of ferrous, manganous and nonferrous metals from iron oxide and manganese oxide containing ores by reduction leaching comprising the steps of: contacting the pulverized ore with a stabilized acidic cuprous ion solution Cu + L at a temperature of up to about 90° C. while maintaining the pH between about 1.5 and 2.5 with acid to form a slurry, wherein L is a stabilizing ligand selected from the group consisting of CO, XRCN and Cl - , X being --H or --OH and R being aliphatic having from one to about four carbon atoms; separating said slurry into a solid tailings portion and a pregnant liquor, said pregnant liquor containing solubilized ferrous, manganous, cupric and other nonferrous metal ions; feeding said pregnant liquor to a second pulverized ore feed containing, at least partially, manganese oxide containing ore to form a second slurry; separating said second slurry into a solid tailings portion containing substantially unsolubilized iron oxide ore and a second pregnant liquor containing solubilized ferric, manganous, cupric and other nonferrous ions; and selectively extracting said solubilized metal ions.

Claim 59

Dependent Claim 183 words

A process for the extraction of ferrous, manganous and nonferrous metals from iron oxide and manganese oxide containing ores by reduction leaching comprising the steps of: contacting the pulverized ore with a stabilized acidic cuprous ion solution Cu + L at a temperature of up to about 90° C. while maintaining the pH between about 1.5 and 2.5 with acid to form a slurry, wherein L is a stabilizing ligand selected from the group consisting of CO, XRCN and Cl - , X being --H or --OH and R being aliphatic having from one to about four carbon atoms; separating said slurry into a solid tailings portion and a pregnant liquor, said pregnant liquor containing solubilized ferrous, manganous, cupric and other nonferrous metal ions; feeding said pregnant liquor to a second pulverized ore feed containing, at least partially, manganese oxide containing ore to form a second slurry; separating said second slurry into a solid tailings portion containing substantially unsolubilized iron oxide ore and a second pregnant liquor containing solubilized ferric, manganous, cupric and other nonferrous ions; and selectively extracting said solubilized metal ions.

Claim 60

Dependent Claim 28 words

A process, as set forth in claim 52, wherein said iron oxide ore comprises laterite and said manganese oxide ore comprises manganese sea nodules and terrestrial manganese ore.

Claim 61

Dependent Claim 37 words

A process, as set forth in claim 52, wherein said ferrous metal is iron, said manganous metal is manganese and said nonferrous metals comprise at least one member of the group consisting of nickel, cobalt and copper.

Claim 62

Dependent Claim 76 words

A process, as set forth in claim 52, wherein said contacting step is conducted at low pressure ranging from about ambient to about 1.5 MPa and at a temperature of from about 20° to 90° C.; wherein said feeding step is conducted at low pressure ranging from about ambient to about 0.3 MPa and at a temperature of from about 20° to 90° C.; wherein said pH is about 2 and, wherein said acid is sulfuric.

Claim 63

Dependent Claim 21 words

A process, as set forth in claim 52, including the additional step of: recycling said unsolubilized iron oxide to said reactor.

Claim 64

Dependent Claim 45 words

A process, as set forth in claim 52, including the additional steps of: separating said cupric ions from the other solubilized divalent metal ions; and regenerating said cuprous ion solution from said solubilized cupric ions and said ligand, L in the presence of a reductant.

Claim 65

Dependent Claim 93 words

A process for the selective extraction of manganous and nonferrous metals from iron oxide containing ores by reduction leaching comprising the steps of: contacting the pulverized ore with an acidic Fe 2+ solution in a suitable reaction at a temperature of up to about 90° C. while maintaining the pH between about 1.5 and 2.5 with acid to form a slurry; separating said slurry into a solid tailings portion and a pregnant liquor, said pregnant liquor containing solubilized ferric, manganous, cupric and other nonferrous metal ions; and selectively extracting said solubilized metal ions.

Claim 66

Dependent Claim 93 words

A process for the selective extraction of manganous and nonferrous metals from iron oxide containing ores by reduction leaching comprising the steps of: contacting the pulverized ore with an acidic Fe 2+ solution in a suitable reaction at a temperature of up to about 90° C. while maintaining the pH between about 1.5 and 2.5 with acid to form a slurry; separating said slurry into a solid tailings portion and a pregnant liquor, said pregnant liquor containing solubilized ferric, manganous, cupric and other nonferrous metal ions; and selectively extracting said solubilized metal ions.

Claim 67

Dependent Claim 48 words

A process, as set forth in claim 58, wherein said contacting step is conducted at low pressure ranging from about ambient to about 0.3 MPa and at a temperature of from about 20° to 90° C.; wherein said pH is about 2 and, wherein said acid is sulfuric.

Claim 68

Dependent Claim 120 words

A process, as set forth in claim 59, including the additional steps of: treating said solid tailings with a stabilized acidic cuprous ion solution Cu + L at a temperature of up to about 90° C. while maintaining the pH between about 1.5 and 2.5 with acid to form a slurry, wherein L is a stabilizing ligand selected from the group consisting of CO, XRCN and Cl - , X being --H or --OH and R being aliphatic having from one to about four carbon atoms; separating said slurry into a second solid tailings portion and a second pregnant liquor, said second pregnant liquor containing solubilized ferrous, cupric and other nonferrous metal ions; and selectively extracting said solubilized metal ions.

Claim 69

Dependent Claim 36 words

A process, as set forth in claim 60, wherein said treating step is conducted at low pressure ranging from about ambient to about 1.5 MPa and at a temperature of from about 20° to 90° C.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1988-10-07	1989-04-08	1989-10-08	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1992-10-07	1993-04-08	1993-10-08	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1996-10-07	1997-04-08	1997-10-08	$7700.00	Window Closed / Lapsed

Processes relating to the extraction of metals from laterites and ocean manganese nodules

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