US3988224A
Expired / Lapsed
US
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Method of extraction of metallic elements from submarine nodules
Assignee: Commissariat à l'Énergie Atomique et Aux Énergies Alternatives
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Filing: 1975-12-16
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Granted: 1976-10-26
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Expires: 1995-12-16
Abstract
Abstract A hydrochloric acid leach solution is subjected to a first cycle of extraction by an organic solvent, solvent washing and stripping so that the stripping liquor contains iron, zinc, cadmium and gallium while the liquor constituted by the first raffinate at the outlet of the extraction unit mainly contains nickel, cobalt and copper. In a second extraction cycle, the stripping liquor contains copper while the second raffinate mainly contains cobalt and nickel. In a third extraction cycle, the stripping liquor contains cobalt while the third raffinate mainly contains nickel.
Inventors
- 👤 Jacques Barriere
- 👤 Michele Robaglia
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 18:22
CPC Classifications
C; C22; C22B; C22B47/00; C22B47/0018; C22B47/0045; C22B47/0054; C22B23/00; C22B23/04; C22B3/00; C22B3/20; C22B3/26; C22B3/28; C22B3/282; C22B3/38; C22B3/384; C22B3/3846; C22B3/42; C22B47/0081; Y; Y02; Y02P; Y02P10/00; Y02P10/20; Y10; Y10S; Y10S423/00; Y10S423/04
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
281 words
A method of extraction of metallic elements from manganiferous ores and more particularly from submarine nodules in which the ore is roasted in a controlled reducing atmosphere, cooled in an inert atmosphere, leached in a number of countercurrent stages by means of a mixture of ammonia and aerated ammonium carbonate in a concentration ratio such as to obtain a buffered pH value of the solution which is distilled by steam entrainment thereby causing precipitation of the carbonates, wherein the concentrate obtained is attacked by hydrochloric acid, the resultant hydrochloric acid leach solution is subjected to a first cycle of extraction by an organic solvent selected from tributylphosphate and a secondary amine diluted in an organic diluent comprising extraction, washing and stripping so that the stripping liquor contains iron, zinc, cadmium and gallium whilst the liquor constituted by the first raffinate at the outlet of the extraction unit mainly contains nickel, cobalt and copper, the hydrochloric liquor of the first raffinate is subjected to a second cycle of extraction by an organic solvent constituted by a tertiary amine hydrochlorate diluted in an organic diluent comprising extraction, washing and then stripping so that the stripping liquor contains copper while the liquor which constitutes the second raffinate at the outlet of the extraction unit mainly contains cobalt and nickel, the hydrochloric acid liquor of the second raffinate is reprocessed, concentrated and subjected to a third cycle of extraction by an organic solvent constituted by a tertiary amine hydrochlorate diluted in an organic diluent comprising extraction, washing and stripping so that the stripping liquor contains the cobalt whilst the liquor which constitutes the third raffinate at the outlet of the extraction unit mainly contains nickel.
Claim 2
Independent Claim
281 words
A method of extraction of metallic elements from manganiferous ores and more particularly from submarine nodules in which the ore is roasted in a controlled reducing atmosphere, cooled in an inert atmosphere, leached in a number of countercurrent stages by means of a mixture of ammonia and aerated ammonium carbonate in a concentration ratio such as to obtain a buffered pH value of the solution which is distilled by steam entrainment thereby causing precipitation of the carbonates, wherein the concentrate obtained is attacked by hydrochloric acid, the resultant hydrochloric acid leach solution is subjected to a first cycle of extraction by an organic solvent selected from tributylphosphate and a secondary amine diluted in an organic diluent comprising extraction, washing and stripping so that the stripping liquor contains iron, zinc, cadmium and gallium whilst the liquor constituted by the first raffinate at the outlet of the extraction unit mainly contains nickel, cobalt and copper, the hydrochloric liquor of the first raffinate is subjected to a second cycle of extraction by an organic solvent constituted by a tertiary amine hydrochlorate diluted in an organic diluent comprising extraction, washing and then stripping so that the stripping liquor contains copper while the liquor which constitutes the second raffinate at the outlet of the extraction unit mainly contains cobalt and nickel, the hydrochloric acid liquor of the second raffinate is reprocessed, concentrated and subjected to a third cycle of extraction by an organic solvent constituted by a tertiary amine hydrochlorate diluted in an organic diluent comprising extraction, washing and stripping so that the stripping liquor contains the cobalt whilst the liquor which constitutes the third raffinate at the outlet of the extraction unit mainly contains nickel.
Claim 3
Dependent Claim
34 words
A method according to claim 1 wherein, in the first extraction cycle, part of the aqueous stripping solution is used for washing the loaded solvent, the wash solution being then re-injected with the charge.
Claim 4
Dependent Claim
29 words
A method according to claim 1, wherein the zinc, gallium, cadmium and iron contained in the strip solution of the first cycle are precipitated in the state of carbonate.
Claim 5
Dependent Claim
30 words
A method according to claim 1 wherein, in the second extraction cycle, the wash solution is constituted by part of the aqueous stripping solution which is concentrated in copper chloride.
Claim 6
Dependent Claim
60 words
A method according to claim 1 wherein, after stripping of the copper, a small part of the solvent is diverted to a treatment circuit in which it is contacted with an aqueous solution which is capable of stripping the molybdenum, the vanadium, the sulphates and the chlorides and wherein the treated solvent is salified before being returned to the extraction.
Claim 7
Dependent Claim
62 words
A method according to claim 1, wherein the stripping liquor which is rich in copper and has previously been mixed with a heat-transporting fluid and with a sulphuric acid liquor is distilled after washing and wherein the distillate is solubilized, separated from the heat-transporting fluid which is recycled to the distillation whilst the copper sulphate which has formed is subjected to electrolysis.
Claim 8
Dependent Claim
24 words
A method according to claim 6, wherein the sulphuric acid liquor mixed with the heat-transporting fluid is obtained from the electrolysis of the copper.
Claim 9
Dependent Claim
43 words
A method according to claim 6, wherein there is performed during the electrolysis a purge which is treated so as to precipitate the copper and the cobalt to the state of carbonate, said copper and cobalt being recycled to the initial acid leach.
Claim 10
Dependent Claim
42 words
A method according to claim 1, wherein the raffinate of the second extraction is concentrated then sent to the third extraction cycle in which the wash solution is constituted by part of the aqueous stripping solution which is concentrated in copper chloride.
Claim 11
Dependent Claim
32 words
A method according to claim 1 wherein, at the stage of the third extraction cycle, the stripping liquor of the cobalt is washed, concentrated and pyrohydrolyzed in order to obtain cobalt oxide.
Claim 12
Dependent Claim
76 words
A method according to claim 1, wherein the raffinate from the extraction of the cobalt which contains nickel chloride and certain impurities is subjected to extraction by the nickel salt of di-(2-ethylhexyl) phosphoric acid diluted in an organic diluent in the presence of a heavy alcohol in order to separate the nickel and magnesium chlorides which are sent into a buffer store from which is carried out the electrolysis which produces the nickel and the chlorine.
Claim 13
Dependent Claim
47 words
A method according to claim 1, wherein the concentration of the magnesium chloride in the buffer is maintained constant by means of a purge from which the nickel is separated from the magnesium in order to salify the di-(2-ethylhexyl) phosphoric acid which is employed for the extraction.
Claim 14
Dependent Claim
25 words
A method according to claim 1, wherein the chlorine which is liberated during electrolysis is recombined with hydrogen in order to produce gaseous hydrochloric acid.
Claim 15
Dependent Claim
56 words
A method according to claim 1, wherein the gaseous hydrochloric acid which is liberated at the time of distillation of the copper chloride stripping liquor, at the time of pyrohydrolysis of cobalt chloride, at the time of recombination of the hydrogen and the chlorine of the nickel electrolysis is recycled to the initial hydrochloric acid leach.
Claim 16
Dependent Claim
47 words
A method according to claim 1, wherein the leach solution which is separated from the solid receives an addition of ammonium phosphate in an aerated medium in order to precipitate the magnesium, the calcium, the barium, the manganese, the iron and the traces of non-alkaline metallic cations.
Claim 17
Dependent Claim
25 words
A method according to claim 1, wherein gallium, molybdenum, vanadium and the anionic impurities are removed by treating the leach solution with an anionic resin.
Claim 18
Dependent Claim
50 words
A method according to claim 1 wherein, after leaching in a normal atmosphere, the solid phase is separated from the liquid phase which is aerated in order to recover the manganese carbonate whilst the solid phase is subjected to countercurrent leaching with the mixture of ammonia and aerated ammonium carbonate.
References Cited (Backward Citations)
US2937072A
Cited
US3085054A
Cited
US3151946A
Cited
US3446720A
Cited
US3950486A
Cited
US3734715A
Cited
US3880651A
Cited
US3751554A
Cited
US3887679A
Cited
US3950488A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1979-10-26 | 1980-04-26 | 1980-10-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-10-26 | 1984-04-26 | 1984-10-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-10-26 | 1988-04-26 | 1988-10-26 | $7700.00 | Window Closed / Lapsed |