|Publication number||USRE33410 E|
|Application number||US 07/485,902|
|Publication date||Oct 30, 1990|
|Filing date||Feb 26, 1990|
|Priority date||May 14, 1973|
|Publication number||07485902, 485902, US RE33410 E, US RE33410E, US-E-RE33410, USRE33410 E, USRE33410E|
|Inventors||Achille De Schepper, Antoine Van Peteghem|
|Original Assignee||Acec-Union Miniere S.A., MHO Division|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (6), Non-Patent Citations (5), Referenced by (1), Classifications (9), Legal Events (1)|
|External Links: USPTO, USPTO Assignment, Espacenet|
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/lExtraction.Organic solution: LIX 63 diluted at 50% with kerosene. ##STR1##Number of extraction stages: 7Raffinate obtained after extraction:Ge 0.019 g/lAs 2.68 g/lZn 4.60 g/lNi 0.02 g/lCu 6.39 g/lFe.sup.III 1.5 g/lFe.sub.tot 58.3 g/lCl 0.130 g/lH.sub.2 SO.sub.4 157 g/lYield of Ge extraction: 99.968%.2-stage elution1st stage:Elution solution: NaOH 175 g/l ##STR2##Number of elution stages: 6Germanium-containing eluate: Ge: 98 g/l Cu: traces Fe: 0.45 g/l NaOH: 67 g/lelution efficiency of Ge: 99%.2nd stage:Elution solution: H.sub.2 SO.sub.4 200 g/l ##STR3##Number of elution stages: 2Eluate 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/lExtractionOrganic solution: LIX-63 diluted at 30% with kerosene. ##STR4##Number of extraction states: 7Raffinate obtained after extraction:Ge 0.007 g/lCu 0.0008 g/lZn 2.5 g/lNi 0.008 g/lAs 0.79 g/lFe.sup.III 0.5 g/lFe.sub.tot 44 g/lH.sub.2 SO.sub.4 460 g/lYield 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/lExtractionOrganic solution: LIX-63 100% ##STR5##Number of extraction stages: 4Raffinate obtained after extraction:Ge 0.002 g/lCu 0.0008 g/lZn 2.47 g/lNi 0.008 g/lAs 0.48 g/lFe.sub.tot 67.3 g/lFe.sup.III tracesH.sub.2 SO.sub.4 130 g/lYield of Ge extraction: 99.99%.______________________________________
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3276863 *||Jan 21, 1964||Oct 4, 1966||Gen Mills Inc||Separation of nickel and cobalt values using alpha-hydroxy oximes|
|US3284501 *||Jul 2, 1965||Nov 8, 1966||Gen Mills Inc||alpha-hydroxy oximes|
|US3455680 *||Mar 3, 1966||Jul 15, 1969||Canadian Patents Dev||Mixed extractant and process for separating copper from cobalt and nickel in acid medium|
|US3903236 *||Nov 27, 1972||Sep 2, 1975||Deepsea Ventures Inc||Method for obtaining metal values by the halidation of a basic manganiferous ore with ferric chloride pre-treatment|
|DE2125095A1 *||May 19, 1971||Dec 9, 1971||Title not available|
|GB1322532A *||Title not available|
|1||*||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.|
|2||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.|
|3||*||Habashi, Fathi, Extractive Metallurgy, vol. 2, Gordon and Breach, Science Publishers, Paris 1970, p. 339.|
|4||*||Smithson, Jr. et al., Journal of Metals, Sep. 1966, pp. 1037 1046.|
|5||Smithson, Jr. et al., Journal of Metals, Sep. 1966, pp. 1037-1046.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5277882 *||Apr 11, 1990||Jan 11, 1994||Union Miniere S.A.||Process for recovering germanium|
|U.S. Classification||423/89, 423/24|
|International Classification||C01G17/00, C22B3/30|
|Cooperative Classification||C01G17/003, C22B3/0017, Y02P10/234|
|European Classification||C01G17/00B, C22B3/00D2B2D|
|Aug 3, 1990||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