USRE33410E - Liquid-liquid extraction of germanium from aqueous solution using hydroxy-oximes - Google Patents
Liquid-liquid extraction of germanium from aqueous solution using hydroxy-oximes Download PDFInfo
- Publication number
- USRE33410E USRE33410E US07/485,902 US48590290A USRE33410E US RE33410 E USRE33410 E US RE33410E US 48590290 A US48590290 A US 48590290A US RE33410 E USRE33410 E US RE33410E
- Authority
- US
- United States
- Prior art keywords
- oxime
- hydroxy
- solution
- germanium
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 18
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 title claims description 11
- 238000000622 liquid--liquid extraction Methods 0.000 title claims description 3
- 238000000638 solvent extraction Methods 0.000 title claims description 3
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000012074 organic phase Substances 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- SLCANKHLTWZHRV-ICFOKQHNSA-N (7z)-5,8-diethyl-7-hydroxyiminododecan-6-ol Chemical compound CCCCC(CC)C(O)C(=N/O)\C(CC)CCCC SLCANKHLTWZHRV-ICFOKQHNSA-N 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 150000007513 acids Chemical class 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000011260 aqueous acid Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000010828 elution Methods 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910006113 GeCl4 Inorganic materials 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 229920002253 Tannate Polymers 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- Certain germanium containing Cu/Pb/Zn sulfide concentrates are processed by subjecting them to a selective roasting during which the germanium is oxidized at the same time as a part of the metals Zn, Fe and Cu. After lixiviation of the roast a sulfuric solution is obtained with a low germanium content. Impure Ge solutions are also obtained from residues of manufacture and from other by-products.
- Known methods for concentrating Ge from impure solutions consist in precipitating the Ge as tannate, sulfide or mixed hydroxides. The precipitates are subjected to treatments which end with the distillation of the GeCl 4 .
- the present invention describes a process for separating Ge by liquid-liquid extraction from various acid solution.
- Ge may be selectively extracted from acid solutions by means of a hydroxy-oxime and that the extraction capacity of such extractant increases with the acidity.
- the selectivity of the Ge extraction may thus be increased by choosing an appropriate acidity of the solution.
- the extractant is also very selective with regard to other metallic ions (only trivalent iron is partially extracted at the same time).
- Germanium is extracted from aqueous acid solutions containing metallic or non metallic impurities, by bringing said solution in contact, co-current or counter-currentwise, repeatedly or not, with an organic liquid containing a hydroxy-oxime.
- the aqueous solution may contain besides germanium also 10 to 500 g/liter of sulfuric acid or hydrochloric acid, or 10 to 100 g/liter of hydrofluoric acid, as well as other metallic or non-metallic ions at different concentrations.
- the organic liquid may consist of hydroxy-oxime, or of a solution of a hydroxy-oxime in an aliphatic solvent and/or an aromatic solvent, and possibly a higher alcohol.
- the organic liquid will preferelly contain at least 1% by volume of a hydroxy-oxime and up to 10% by volume of a higher alcohol.
- aliphatic products such as kerosene
- organic solvents for hydroxy-oxime are well suited as organic solvents for hydroxy-oxime.
- a higher alcohol which may advantageously be used is isodecanol.
- the invention also covers the re-extraction of the Ge from the organic solution by means of water or an acid or alkaline solution. Direct precipitation of the germanium in the organic solution is also possible.
- the precipitation may be obtained by adding a gaseous base such as NH 3 , or a solid base such as lime- or magnesia wash, or a liquid base such as a NaOH or a KOH solution.
- a gaseous base such as NH 3
- a solid base such as lime- or magnesia wash
- a liquid base such as a NaOH or a KOH solution.
- the organic solution may be used again for another extraction.
- the starting solutions contain Cu
- the latter may be re-extracted after the Ge, by means of an acid solution such as a sulfuric acid solution.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Process for extraction of germanium from aqueous acid solution by contacting with an organic liquid containing a hydroxy-oxime and recovering the extracted germanium from the organic phase.
Description
Certain germanium containing Cu/Pb/Zn sulfide concentrates are processed by subjecting them to a selective roasting during which the germanium is oxidized at the same time as a part of the metals Zn, Fe and Cu. After lixiviation of the roast a sulfuric solution is obtained with a low germanium content. Impure Ge solutions are also obtained from residues of manufacture and from other by-products.
Known methods for concentrating Ge from impure solutions consist in precipitating the Ge as tannate, sulfide or mixed hydroxides. The precipitates are subjected to treatments which end with the distillation of the GeCl4.
The present invention describes a process for separating Ge by liquid-liquid extraction from various acid solution.
It has now been found that Ge may be selectively extracted from acid solutions by means of a hydroxy-oxime and that the extraction capacity of such extractant increases with the acidity.
It is known that organic products containing a hydroxy-oxime can selectively extract copper at a very low acidity, while their extracting power for copper is strongly diminished when the acidity increases.
The selectivity of the Ge extraction, compared to that of the copper, may thus be increased by choosing an appropriate acidity of the solution.
The extractant is also very selective with regard to other metallic ions (only trivalent iron is partially extracted at the same time).
Germanium is extracted from aqueous acid solutions containing metallic or non metallic impurities, by bringing said solution in contact, co-current or counter-currentwise, repeatedly or not, with an organic liquid containing a hydroxy-oxime.
The aqueous solution may contain besides germanium also 10 to 500 g/liter of sulfuric acid or hydrochloric acid, or 10 to 100 g/liter of hydrofluoric acid, as well as other metallic or non-metallic ions at different concentrations.
The organic liquid may consist of hydroxy-oxime, or of a solution of a hydroxy-oxime in an aliphatic solvent and/or an aromatic solvent, and possibly a higher alcohol. The organic liquid will preferelly contain at least 1% by volume of a hydroxy-oxime and up to 10% by volume of a higher alcohol.
.[.It has been found that.]. 19-hydroxyhexatriaconta-9,28diene-18 oxime, .Iadd.an α-hydroxy-oxime, may be used. It has been found that 5,8-diethyl-hydroxydodecan-6-oxime, an α-hydroxy-oxime, .Iaddend.sold under the registered name of LIX-63 (made by "General Mills Inc." Tuscon, U.S.A.) is particularly well suited for the extraction of germanium.
It has been noted that aliphatic products, such as kerosene, are well suited as organic solvents for hydroxy-oxime.
A higher alcohol which may advantageously be used is isodecanol.
Examples given below show that the simultaneous extraction of Cu is low. However, copper may previously be eliminated, either by selective cementation in acid medium, or by previous selective extraction, or by any other known method entailing no loss of Ge.
The invention also covers the re-extraction of the Ge from the organic solution by means of water or an acid or alkaline solution. Direct precipitation of the germanium in the organic solution is also possible.
The precipitation may be obtained by adding a gaseous base such as NH3, or a solid base such as lime- or magnesia wash, or a liquid base such as a NaOH or a KOH solution.
After re-extraction of the germanium, the organic solution may be used again for another extraction.
When the starting solutions contain Cu, the latter may be re-extracted after the Ge, by means of an acid solution such as a sulfuric acid solution.
It is thus possible to control the separation selectivity of Ge and Cu by a suitable choice of the operating conditions for the extraction and for the reextraction.
______________________________________
Aqueous solution:
Ge 5 g/l
As 2.68 g/l
Zn 4.60 g/l
Ni 0.020 g/l
Cu 6.79 g/l
Fe.sup.III
3 g/l
Fe.sub.tot
59.82 g/l
Cl 0.130 g/l
H.sub.2 SO.sub.4
157 g/l
Extraction.
Organic solution: LIX 63 diluted at 50% with kerosene.
##STR1##
Number of extraction stages: 7
Raffinate obtained after extraction:
Ge 0.019 g/l
As 2.68 g/l
Zn 4.60 g/l
Ni 0.02 g/l
Cu 6.39 g/l
Fe.sup.III 1.5 g/l
Fe.sub.tot 58.3 g/l
Cl 0.130 g/l
H.sub.2 SO.sub.4 157 g/l
Yield of Ge extraction: 99.968%.
2-stage elution
1st stage:
Elution solution: NaOH 175 g/l
##STR2##
Number of elution stages: 6
Germanium-containing eluate:
Ge: 98 g/l
Cu: traces
Fe: 0.45 g/l
NaOH: 67 g/l
elution efficiency of Ge: 99%.
2nd stage:
Elution solution: H.sub.2 SO.sub.4 200 g/l
##STR3##
Number of elution stages: 2
Eluate obtained after elution:
Ge: traces
Cu: 16 g/l
______________________________________
______________________________________
Aqueous solution:
Ge 3.5 g/l
Cu 0.0008 g/l
Zn 2.5 g/l
Ni 0.008 g/l
As 0.79 g/l
Fe.sub.tot
45 g/l
Fe.sup.III
1.5 g/l
H.sub.2 SO.sub.4
460 g/l
Extraction
Organic solution: LIX-63 diluted at 30% with kerosene.
##STR4##
Number of extraction states: 7
Raffinate obtained after extraction:
Ge 0.007 g/l
Cu 0.0008 g/l
Zn 2.5 g/l
Ni 0.008 g/l
As 0.79 g/l
Fe.sup.III 0.5 g/l
Fe.sub.tot 44 g/l
H.sub.2 SO.sub.4 460 g/l
Yield of Ge extraction: 99.98%.
______________________________________
______________________________________
Aqueous solution:
Ge 5 g/l
Cu 0.0008 g/l
Zn 2.5 g/l
Ni 0.008 g/l
As 0.54 g/l
Fe.sub.tot
69 g/l
Fe.sup.III
1.3 g/l
H.sub.2 SO.sub.4
130 g/l
Extraction
Organic solution: LIX-63 100%
##STR5##
Number of extraction stages: 4
Raffinate obtained after extraction:
Ge 0.002 g/l
Cu 0.0008 g/l
Zn 2.47 g/l
Ni 0.008 g/l
As 0.48 g/l
Fe.sub.tot 67.3 g/l
Fe.sup.III traces
H.sub.2 SO.sub.4 130 g/l
Yield of Ge extraction: 99.99%.
______________________________________
Claims (17)
1. A process for liquid-liquid extraction of germanium from an aqueous solution, in which an organic liquid containing .[.hydroxy-oxime.]. .Iadd.α-hydroxy-oxime .Iaddend.is used as extractant comprising contacting an aqueous solution containing germanium and an acid selected from the group consisting of 10 to 500 grams per liter of hydrochloric acid, 10 to 500 grams per liter of sulfuric acid, and 10 to 100 grams per liter of hydrofluoric acid, with an organic liquid selected from the group consisting of non-diluted .[.hydroxy-oxime.]. .Iadd.α-hydroxy-oxime.Iaddend., a solution of .[.hydroxy-oxime.]. .Iadd.α-hydroxy-oxime .Iaddend.in an aliphatic solvent, a solution of .[.hydroxy-oxime.]. .Iadd.α-hydroxy-oxime .Iaddend.in an aromatic solvent, and a solution of .[.hydroxy-oxime.]. .Iadd.α-hydroxy-oxime .Iaddend.in a mixture of an aliphatic and an aromatic solvent, separating the organic liquid phase containing extracted germanium from the residual aqueous phase, and recovering the extracted germanium from the separated organic phase by contacting with an agent selected from the group consisting of water, acids, and bases.
2. A process as claimed in claim 1, in which the aqueous solution contains 10 to 500 g/l of an acid chosen in the class consisting of sulfuric acid and hydrochloric acid.
3. A process as claimed in claim 1, in which the aqueous solution contains 10 to 100 g/l hydrofluoric acid.
4. A process as claimed in claim 1, in which a non-diluted hydroxy-oxime is used as the organic liquid.
5. A process as claimed in claim 1, in which a solution of a hydroxy-oxime in an aliphatic solvent is used as the organic liquid.
6. A process as claimed in claim 1, in which a solution of a hydroxy-oxime in an aromatic solvent is used as the organic liquid.
7. A process as claimed in claim 5, in which a higher alcohol is added to the hydroxy-oxime solution.
8. A process as claimed in claim 5, in which the organic liquid contains at least 1% by volume of a hydroxy-oxime.
9. A process as claimed in claim 6, in which the organic liquid contains up to 10% by volume of a higher alcohol.
10. A process as claimed in claim 1, in which 19-hydroxyhexatriaconta-9,28 diene-18-oxime is used as hydroxy-oxime.
11. A process as claimed in claim 5, in which kerosene is used as the solvent.
12. A process as claimed in claim 7, in which isodecanol is used as the higher alcohol.
13. A process as claimed in claim 1, in which the separated organic phase is regenerated by contacting it with a base, and is used again for another extraction.
14. A process as claimed in claim 13, in which use is made as a base of an aqueous solution of a compound selected from the group consisting of NaOH, KOH, limewash, magnesiawash, and ammonia.
15. A process as claimed in claim 1, in which the aqueous solution contains copper.
16. A process as claimed in claim 15, in which the separated organic phase is regenerated first by contacting it with a base in order to separate the germanium, and afterwards with an acid solution in order to separate the copper, and is used again for another extraction. .Iadd.
17. A process as claimed in claim 1, in which 5,8-diethyl-7-hydroxydodecan-6-oxime is used as the α-hydroxy-oxime.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/485,902 USRE33410E (en) | 1973-05-14 | 1990-02-26 | Liquid-liquid extraction of germanium from aqueous solution using hydroxy-oximes |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU67596A LU67596A1 (en) | 1973-05-14 | 1973-05-14 | |
| BE67596 | 1973-05-14 | ||
| US07/485,902 USRE33410E (en) | 1973-05-14 | 1990-02-26 | Liquid-liquid extraction of germanium from aqueous solution using hydroxy-oximes |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US464387A Reissue US3883634A (en) | 1973-05-14 | 1974-04-26 | Liquid-liquid extraction of germanium from aqueous solution using hydroxy-oximes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE33410E true USRE33410E (en) | 1990-10-30 |
Family
ID=26640132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/485,902 Expired - Lifetime USRE33410E (en) | 1973-05-14 | 1990-02-26 | Liquid-liquid extraction of germanium from aqueous solution using hydroxy-oximes |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE33410E (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5277882A (en) * | 1989-04-28 | 1994-01-11 | Union Miniere S.A. | Process for recovering germanium |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3276863A (en) * | 1964-01-21 | 1966-10-04 | Gen Mills Inc | Separation of nickel and cobalt values using alpha-hydroxy oximes |
| US3284501A (en) * | 1965-07-02 | 1966-11-08 | Gen Mills Inc | alpha-hydroxy oximes |
| US3455680A (en) * | 1966-03-03 | 1969-07-15 | Canadian Patents Dev | Mixed extractant and process for separating copper from cobalt and nickel in acid medium |
| DE2125095A1 (en) * | 1970-05-21 | 1971-12-09 | Shell Internationale Research Maatschappij N.V., Den Haag (Niederlande) | Process for separating the metal components from an aqueous medium, hydroxyoximes and processes for their production |
| GB1322532A (en) * | 1970-05-21 | 1973-07-04 | Shell Int Research | Hydroxy-oximes and their use in the extraction of metal values |
| US3903236A (en) * | 1972-11-27 | 1975-09-02 | Deepsea Ventures Inc | Method for obtaining metal values by the halidation of a basic manganiferous ore with ferric chloride pre-treatment |
-
1990
- 1990-02-26 US US07/485,902 patent/USRE33410E/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3276863A (en) * | 1964-01-21 | 1966-10-04 | Gen Mills Inc | Separation of nickel and cobalt values using alpha-hydroxy oximes |
| US3284501A (en) * | 1965-07-02 | 1966-11-08 | Gen Mills Inc | alpha-hydroxy oximes |
| US3455680A (en) * | 1966-03-03 | 1969-07-15 | Canadian Patents Dev | Mixed extractant and process for separating copper from cobalt and nickel in acid medium |
| DE2125095A1 (en) * | 1970-05-21 | 1971-12-09 | Shell Internationale Research Maatschappij N.V., Den Haag (Niederlande) | Process for separating the metal components from an aqueous medium, hydroxyoximes and processes for their production |
| GB1322532A (en) * | 1970-05-21 | 1973-07-04 | Shell Int Research | Hydroxy-oximes and their use in the extraction of metal values |
| US3903236A (en) * | 1972-11-27 | 1975-09-02 | Deepsea Ventures Inc | Method for obtaining metal values by the halidation of a basic manganiferous ore with ferric chloride pre-treatment |
Non-Patent Citations (5)
| Title |
|---|
| Atwood, R. L. and Miller, J. D., Structure and Composition of Commercial Copper Chelate Extractants, preprint paper presented at The Annual Meeting of the American Institute of Mining, Metallurgical and Petoleum Engineers, San Francisco, Calif., on Feb. 20 24, 1972. * |
| Atwood, R. L. and Miller, J. D., Structure and Composition of Commercial Copper Chelate Extractants, preprint paper presented at The Annual Meeting of the American Institute of Mining, Metallurgical and Petoleum Engineers, San Francisco, Calif., on Feb. 20-24, 1972. |
| Habashi, Fathi, Extractive Metallurgy, vol. 2, Gordon and Breach, Science Publishers, Paris 1970, p. 339. * |
| Smithson, Jr. et al., Journal of Metals, Sep. 1966, pp. 1037 1046. * |
| Smithson, Jr. et al., Journal of Metals, Sep. 1966, pp. 1037-1046. |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5277882A (en) * | 1989-04-28 | 1994-01-11 | Union Miniere S.A. | Process for recovering germanium |
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|---|---|---|---|
| AS | Assignment |
Owner name: MHO, A DIVISION OF ACEC-UNION MINIERE S.A. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:METALLURGIE HOBOKEN-OVERPELT;REEL/FRAME:005405/0005 Effective date: 19900801 |