US3923615A
Expired / Lapsed
US
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Winning of metal values from ore utilizing recycled acid leaching agent
Assignee: Deepsea Ventures Inc
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Filing: 1973-07-16
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Granted: 1975-12-02
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Expires: 1993-07-16
Abstract
Abstract This invention provides a process for selectively removing desirable metal values from an ocean floor nodule ore wherein the ore is initially leached with an aqueous solution of a mineral acid to preferentially form water-soluble salts of nickel and copper, which are dissolved in the leach solution, followed by releaching the solid leached ore under reducing conditions using a reducing reagent capable of reducing tetravalent manganese to divalent manganese and of forming water-soluble salts of cobalt and divalent manganese which are in turn dissolved into the leach solution resulting preferably in a single aqueous pregnant leach solution comprising the dissolved salts of copper, cobalt, nickel and divalent manganese. Preferably, the above four named metal values are individually separated into individual aqueous solutions which preferably are in turn reduced to the elemental metals by electrolysis procedures. The advantage of this process lies in the fact that it can utilize waste products from this and other industrial procedures. The reducing reagents, which can be used, include ferrous salts obtained from pickling procedures, and the mineral acid leach solution can be recycled as spent electrolyte from the electrolysis procedures especially that for the formation of elemental manganese.
Inventors
- 👤 William S Kane
- 👤 Paul H Cardwell
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 01:04
CPC Classifications
C; C25; C25C; C25C1/00; C25C1/06; C25C1/10; C22; C22B; C22B47/00; C22B47/0018; C22B47/0045; C22B47/0054; C22B47/0063; Y; Y02; Y02P; Y02P10/00; Y02P10/20; Y10; Y10S; Y10S423/00; Y10S423/04
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
168 words
A PROCESS FOR SELECTIVELY REMOVING METAL VALUES FROM AN OCEAN FLOOR NODULE ORE, THE ORE COMPRISING A PRIMARY PROPORTION OF MANGANESE AND IRON AND SECONDARY PROPORTIONS OF NICKEL, COPPER AND COBALT, THE PROCESS COMPRISING THE STEPS OF (A) LEACHING THE ORE WITH AN AQUEOUS SOLUTION OF A MINERAL ACID WHICH IS CAPABLE OF REACTING WITH THE ORE TO PREFERENTIALLY FORM WATER-SOLUBLE SALTS OF NICKEL AND COPPER, TO OBTAIN AN INITIAL AQUEOUS LEACH SOLUTION COMPRISING DISSOLVED IRON, COPPER AND NICKEL SALTS DERIVED FROM THE RESPECTIVE METAL VALUES PRESENT IN THE ORE AND A SOLID LEACHED ORE, AND (B) RELEACHING THE SOLID LEACHED ORE UNDER REDUCING CONDITIONS, WITH AN AQUEOUS SOLUTION OF A REDUCING REAGENT WHICH IS CAPABLE OF REDUCING TETRAVALENT MANGANESE TO DIVALENT MANGANESE, AND OF FORMING WATER-SOLUBLE SALTS OF COBALT AND DIVALENT MANGANESE, SO AS TO FORM A FINAL AQUEOUS LEACH SOLUTION COMPRISING DISSOLVED MANGANESE AND COBALT SALTS, WHEREBY THE COPPER, COBALT, NICKEL AND MANGANESE VALUES IN THE ORE ARE REMOVED THEREFROM IN THE FORM OF DISSOLVED SALTS.
Claim 2
Dependent Claim
168 words
A PROCESS FOR SELECTIVELY REMOVING METAL VALUES FROM AN OCEAN FLOOR NODULE ORE, THE ORE COMPRISING A PRIMARY PROPORTION OF MANGANESE AND IRON AND SECONDARY PROPORTIONS OF NICKEL, COPPER AND COBALT, THE PROCESS COMPRISING THE STEPS OF (A) LEACHING THE ORE WITH AN AQUEOUS SOLUTION OF A MINERAL ACID WHICH IS CAPABLE OF REACTING WITH THE ORE TO PREFERENTIALLY FORM WATER-SOLUBLE SALTS OF NICKEL AND COPPER, TO OBTAIN AN INITIAL AQUEOUS LEACH SOLUTION COMPRISING DISSOLVED IRON, COPPER AND NICKEL SALTS DERIVED FROM THE RESPECTIVE METAL VALUES PRESENT IN THE ORE AND A SOLID LEACHED ORE, AND (B) RELEACHING THE SOLID LEACHED ORE UNDER REDUCING CONDITIONS, WITH AN AQUEOUS SOLUTION OF A REDUCING REAGENT WHICH IS CAPABLE OF REDUCING TETRAVALENT MANGANESE TO DIVALENT MANGANESE, AND OF FORMING WATER-SOLUBLE SALTS OF COBALT AND DIVALENT MANGANESE, SO AS TO FORM A FINAL AQUEOUS LEACH SOLUTION COMPRISING DISSOLVED MANGANESE AND COBALT SALTS, WHEREBY THE COPPER, COBALT, NICKEL AND MANGANESE VALUES IN THE ORE ARE REMOVED THEREFROM IN THE FORM OF DISSOLVED SALTS.
Claim 3
Dependent Claim
31 words
The process of claim 1, wherein the final aqueous leach solution is a combined aqueous pregnant leach solution which comprises the dissolved salts of copper, cobalt, nickel, iron and divalent manganese.
Claim 4
Dependent Claim
51 words
The process of claim 2, comprising in addition, separating the solid ore residue from the initial leach solution prior to releaching the leached ore and admixing the initial and final leach solutions to form a combined aqueous pregnant leach solution comprising the dissolved salts of copper, nickel, cobalt, iron and manganese.
Claim 5
Dependent Claim
25 words
The process of claim 1, wherein the mineral acid is selected from the group consisting of sulfuric acid and aqueous solutions of a hydrogen halide.
Claim 6
Dependent Claim
12 words
The process of claim 4, wherein the mineral acid is sulfuric acid.
Claim 7
Dependent Claim
16 words
The process of claim 4, wherein the mineral acid is an aqueous solution of hydrogen chloride.
Claim 8
Dependent Claim
25 words
The process of claim 1, wherein the reducing reagent is selected from the group consisting of sulfur dioxide, ferrous sulfate, ferrous halides and hydrogen halides.
Claim 9
Dependent Claim
12 words
The process of claim 7, wherein the reducing agent is ferrous sulfate.
Claim 10
Dependent Claim
12 words
The process of claim 7, wherein the reducing agent is ferrous chloride.
Claim 11
Dependent Claim
17 words
The process of claim 7, wherein the reducing agent is sulfur dioxide and additional iron is dissolved.
Claim 12
Dependent Claim
17 words
The process of claim 7, wherein the reducing agent is hydrogen chloride and additional iron is dissolved.
Claim 13
Dependent Claim
28 words
The process of claim 1, wherein the reducing agent is an aqueous solution of ferrous sulfate or ferrous chloride, which is the effluent from an acid pickling plant.
Claim 14
Dependent Claim
155 words
A process for selectively removing metal values from an ocean floor nodule ore, the ore comprising a primary proportion of manganese, and iron and secondary proportions of nickel, copper and cobalt, the process comprising the steps of (a) leaching the ore with an aqueous solution of a mineral acid which is capable of reacting with the ore to preferentially form water-soluble salts of nickel and copper, to obtain an initial aqueous leach solution comprising dissolved iron, copper and nickel salts derived from the respective metal values present in the ore, in admixture with the solid leached ore, and (b) releaching, the solid leached ore in admixture with the initial aqueous leach solution under reducing conditions, whereby tetravalent manganese can be reduced to divalent manganese and water-soluble salts of cobalt and divalent manganese can be formed, to form a combined aqueous pregnant leach solution which comprises the dissolved salts of copper, cobalt, nickel, iron and manganese.
Claim 15
Dependent Claim
155 words
A process for selectively removing metal values from an ocean floor nodule ore, the ore comprising a primary proportion of manganese, and iron and secondary proportions of nickel, copper and cobalt, the process comprising the steps of (a) leaching the ore with an aqueous solution of a mineral acid which is capable of reacting with the ore to preferentially form water-soluble salts of nickel and copper, to obtain an initial aqueous leach solution comprising dissolved iron, copper and nickel salts derived from the respective metal values present in the ore, in admixture with the solid leached ore, and (b) releaching, the solid leached ore in admixture with the initial aqueous leach solution under reducing conditions, whereby tetravalent manganese can be reduced to divalent manganese and water-soluble salts of cobalt and divalent manganese can be formed, to form a combined aqueous pregnant leach solution which comprises the dissolved salts of copper, cobalt, nickel, iron and manganese.
Claim 16
Dependent Claim
32 words
The process of claim 13, comprising, in addition, separating the iron, copper, cobalt and nickel values from the combined aqueous leach solution to form a single aqueous solution comprising dissolved manganese salt.
Claim 17
Dependent Claim
64 words
The process of claim 14, wherein the single aqueous solution is suitable for use as an electrolyte for the cathodic electroplating of manganese metal, and comprising, in addition, subjecting the single solution to electrolysis to cathodically electroplate elemental manganese metal and to form the acid corresponding to the manganese salt, and recycling the acid for use as the mineral acid for leaching the ore.
Claim 18
Dependent Claim
30 words
The process of claim 15, wherein the manganese salt is manganous sulfate or a manganous halide and the corresponding mineral acid is sulfuric acid or an aqueous hydrogen halide, respectively.
Claim 19
Dependent Claim
34 words
The process of claim 13, comprising, in addition, adding to the solid ore-initial leach solution mixture, a reducing agent selected from the group consisting of ferrous sulfate, sulfur dioxide, ferrous halides and hydrogen halides.
Claim 20
Dependent Claim
41 words
The process of claim 13, wherein a metal value is selectively extracted from the combined pregnant leach solution by contacting the solution with a liquid ion exchange agent so as to form a solution comprising the substantially pure dissolved metal value.
Claim 21
Dependent Claim
212 words
The process for obtaining desirable metals from ocean floor nodule ore, 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 (a) leaching the ore with an aqueous solution of a mineral acid which is capable of reacting with the ore to preferentially form water-soluble salts of nickel and copper to obtain an initial aqueous leach solution comprising dissolved iron, copper and nickel salts derived from the respective metal values present in the ore and a solid leached ore, (b) releaching the solid leached ore, under reducing conditions, with an aqueous solution of a reducing agent which is capable of reducing tetravalent manganese to divalent manganese and forming the water-soluble salts of cobalt and divalent manganese, so as to form the water-soluble salts of cobalt and divalent manganese, (c) forming a combined aqueous pregnant leach solution which comprises the dissolved salts of iron, copper, cobalt, nickel and manganese, (d) separating the dissolved iron, nickel, cobalt and copper values from the aqueous solution so as to form a single aqueous solution comprising a soluble manganese salt which is suitable for use as a feed solution to an electrolytic cell to form the elemental manganese metal.
Claim 22
Dependent Claim
212 words
The process for obtaining desirable metals from ocean floor nodule ore, 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 (a) leaching the ore with an aqueous solution of a mineral acid which is capable of reacting with the ore to preferentially form water-soluble salts of nickel and copper to obtain an initial aqueous leach solution comprising dissolved iron, copper and nickel salts derived from the respective metal values present in the ore and a solid leached ore, (b) releaching the solid leached ore, under reducing conditions, with an aqueous solution of a reducing agent which is capable of reducing tetravalent manganese to divalent manganese and forming the water-soluble salts of cobalt and divalent manganese, so as to form the water-soluble salts of cobalt and divalent manganese, (c) forming a combined aqueous pregnant leach solution which comprises the dissolved salts of iron, copper, cobalt, nickel and manganese, (d) separating the dissolved iron, nickel, cobalt and copper values from the aqueous solution so as to form a single aqueous solution comprising a soluble manganese salt which is suitable for use as a feed solution to an electrolytic cell to form the elemental manganese metal.
Claim 23
Dependent Claim
36 words
The process of claim 19, comprising in addition, oxygenating the combined aqueous pregnant leach solution so as to precipitate insoluble iron oxide therefrom whereby the aqueous pregnant leach solution is rendered free of undesirable dissolved iron.
Claim 24
Dependent Claim
39 words
The process of claim 20, wherein the copper, nickel and cobalt values are sequentially selectively extracted from the combined pregnant leach solution so as to form independent streams comprising the salts of each of copper, cobalt and nickel, respectively.
Claim 25
Dependent Claim
87 words
The process of claim 21, wherein the reducing agent is sulfur dioxide or ferrous sulfate, the leaching acid is sulphuric acid and comprising in addition, obtaining a solution comprising manganese sulfate sufficiently free from metal values more noble than manganese as to be satisfactory for use as an electrolyte feed to an electrolysis cell; feeding the solution of manganese sulfate to an electrolysis cell so as to cathodically electroplate elemental manganese metal and form sulphuric acid; and recycling the sulphuric acid thus formed to leach the ore.
Claim 26
Dependent Claim
107 words
The process of claim 21, wherein the reducing agent is selected from the group consisting of ferrous halides and hydrogen halides and wherein the leaching acid is a hydrogen halide aqueous solution and comprising, in addition, obtaining a solution comprising a manganese halide substantially free from metal values more noble than manganese as to be satisfactory for use as an electrolyte feed to an electrolysis cell; feeding the manganese halide solution to an electrolysis cell so as to cathodically electroplate elemental manganese metal and to form an aqueous solution of the corresponding hydrogen halide; and recycling the aqueous solution of the hydrogen halide to leach the ore.
Claim 27
Dependent Claim
22 words
The process of claim 19, wherein the reducing releaching is carried out at a temperature of from about 50 to about 100*C.
Claim 28
Dependent Claim
22 words
The procedure of claim 19, wherein the acid leaching is carried out at a temperature of from about 40* to about 80*C.
Claim 29
Dependent Claim
28 words
The procedure of claim 19, wherein the reducing agent is hydrochloric acid and the releaching is carried out at a temperature of from about 95* to about 110*C.
Claim 30
Dependent Claim
203 words
A process for selectively removing metal values from an ocean floor nodule ore, the ore comprising a primary proportion of manganese and iron and secondary proportion of nickel, copper and cobalt, the process comprising the steps of (a) leaching the ore with an aqueous solution of a mineral acid which is capable of reacting with the ore to preferentially form water-soluble salts of nickel and copper, to obtain an initial leach solution comprising dissolved iron, copper and nickel salts derived from respective metal values present in the ore and a solid leached ore; (b) separating the initial aqueous leach solution from the solid leached ore; (c) releaching the solid leached ore under reducing conditions with an aqueous solution of a reducing agent which is capable of reducing tetravalent manganese to divalent manganese and forming water-soluble salts of cobalt and divalent manganese, so as to form a final aqueous leach solution comprising dissolved manganese and cobalt salts, whereby the copper, cobalt, nickel and manganese values are removed in the form of dissolved salts; and (d) admixing the initial leach solution and the final leach solution to obtain a combined aqueous pregnant leach solution comprising the dissolved salts of iron, copper, cobalt, nickel and manganese.
Claim 31
Dependent Claim
203 words
A process for selectively removing metal values from an ocean floor nodule ore, the ore comprising a primary proportion of manganese and iron and secondary proportion of nickel, copper and cobalt, the process comprising the steps of (a) leaching the ore with an aqueous solution of a mineral acid which is capable of reacting with the ore to preferentially form water-soluble salts of nickel and copper, to obtain an initial leach solution comprising dissolved iron, copper and nickel salts derived from respective metal values present in the ore and a solid leached ore; (b) separating the initial aqueous leach solution from the solid leached ore; (c) releaching the solid leached ore under reducing conditions with an aqueous solution of a reducing agent which is capable of reducing tetravalent manganese to divalent manganese and forming water-soluble salts of cobalt and divalent manganese, so as to form a final aqueous leach solution comprising dissolved manganese and cobalt salts, whereby the copper, cobalt, nickel and manganese values are removed in the form of dissolved salts; and (d) admixing the initial leach solution and the final leach solution to obtain a combined aqueous pregnant leach solution comprising the dissolved salts of iron, copper, cobalt, nickel and manganese.
Claim 32
Dependent Claim
37 words
The process of claim 1, wherein the reducing reagent is ferrous sulfate or ferrous chloride, which is the effluent from an acid pickling plant, and wherein the final aqueous leach solution also comprises a dissolved ferrous compound.
Claim 33
Dependent Claim
45 words
The process of claim 28, comprising in addition, removing any dissolved ferrous compound from the final aqueous leach solution by maintaining the pH of the solution at least at about 2 and oxygenating the solution so as to precipitate iron as an insoluble iron oxide.
References Cited (Backward Citations)
US2430346A
Cited
US3723095A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-12-01 | 1979-06-02 | 1979-12-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-12-01 | 1983-06-02 | 1983-12-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-12-01 | 1987-06-02 | 1987-12-02 | $7700.00 | Window Closed / Lapsed |