CN112662899A - Method for selectively extracting and separating germanium from high-arsenic high-silicon sulfate solution by using Lix-63-based multi-element synergistic extraction system - Google Patents
Method for selectively extracting and separating germanium from high-arsenic high-silicon sulfate solution by using Lix-63-based multi-element synergistic extraction system Download PDFInfo
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Abstract
The invention discloses a method for selectively extracting and separating germanium from a high-arsenic high-silicon sulfate solution by using a multi-element synergistic extraction system mainly comprising Lix-63. The extraction organic phase adopted by the invention is a multi-element synergistic extraction system mainly comprising a hydroximic extractant Lix-63, wherein the multi-element synergistic extraction system consists of the hydroximic extractant Lix-63, an extraction additive a, an extraction additive b and a diluent, the hydroximic extractant Lix-63, the extraction additive a and the extraction additive b are respectively P507 and P229, the diluent is an organic solvent immiscible with water, and the volume ratio of the hydroximic extractant, the extraction additive a, the extraction additive b and the diluent is 10-30:1-10:1-10: 50-88. The extraction organic phase adopted by the invention has strong extraction capability and good germanium extraction selectivity in the high-arsenic high-silicon sulfate solution, reduces the generation of a third phase, reduces the acidity of the original feed liquid required by extracting germanium, simultaneously reduces the alkali consumption required by organic back extraction, effectively prolongs the service life of the extractant, and plays an active role in comprehensively recycling germanium.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and relates to a method for selectively extracting and separating germanium, in particular to a method for selectively extracting and separating germanium from a high-arsenic high-silicon sulfate solution by using a multi-element synergistic extraction system mainly comprising Lix-63.
Background
Germanium is an important semiconductor material, is one of the most important metals in modern information industry, and is widely applied to the fields of optical fibers, electronics, solar cells and the like. However, germanium, a rare metal element, is usually associated with minerals such as lead-zinc ore and coal in nature, and is rarely independently formed into ores, so that germanium element is found later. The copper-cobalt alloy from Africa is leached, extracted, separated and purified to obtain sulfate acid solution containing a large amount of cobalt, iron, germanium, copper, arsenic, silicon and other elements. Since the solution contains more impurity metals and the solution contains silicon to form orthosilicic acid, it is necessary to research the selective separation of germanium from a large amount of accompanying elements in the separation process of germanium.
At present, the most common recovery methods of germanium in hydrometallurgy mainly comprise a tannin precipitation method, a solvent separation method and the like, wherein the tannin precipitation method has the problems that the tannin addition amount is large, the recovery cannot be realized, the cost is high, impurity metals are easy to form coprecipitation, the taste of the produced germanium concentrate is difficult to reach more than 30%, and the like, so the solvent separation method is the main method for recovering germanium at present.
The solvent separation method has the advantages of strong selectivity, good separation and enrichment effects, large processing capacity, low reagent consumption and the like, and is suitable for extracting germanium. The hydroximic extractant Lix-63 has good germanium selectivity in a high-concentration extractant and feed liquid acidity, but the back extraction needs higher alkali concentration, so that the service life of the extractant is easily reduced, in a high-arsenic and high-silicon sulfate solution, the separation difficulty of germanium and arsenic is higher, and the silicon content is high, so that an organic phase is easily induced to generate a third phase.
Disclosure of Invention
Aiming at the defects existing in the prior art of recovering germanium from the high-arsenic high-silicon sulfate solution, the invention provides a method for selectively extracting and separating germanium from the high-arsenic high-silicon sulfate solution by using a multi-element synergistic extraction system mainly comprising Lix-63, so as to realize the high-efficiency separation of germanium from arsenic, silicon and other impurity ions.
Therefore, the invention adopts the following technical scheme: a method for selectively extracting and separating germanium from a high-arsenic high-silicon sulfate solution by using a multi-element synergistic extraction system mainly comprising Lix-63, wherein an extraction organic phase is a multi-element synergistic extraction system mainly comprising a hydroximic extractant Lix-63, the multi-element synergistic extraction system comprises the hydroximic extractant, an extraction additive a, an extraction additive b and a diluent, the hydroximic extractant is Lix-63, the extraction additive a and the extraction additive b are respectively P507 and P229, the diluent is an organic solvent immiscible with water, and the volume ratio of the hydroximic extractant, the extraction additive a, the extraction additive b and the diluent is 10-30:1-10:1-10:50-88, preferably 15-25: 3-5: 1-5: 70-80, most preferably 22.5:5:2.5:70 or 15:4:1: 80.
Furthermore, in the high-arsenic high-silicon sulfate solution, the concentration of germanium is 0.5-1g/L, the concentration of arsenic is 4-5g/L, the concentration of silicon is 0.5-1g/L, and the high-arsenic high-silicon sulfate solution simultaneously contains copper, cobalt and iron impurity ions.
Further, the method for selectively extracting and separating germanium from the high-arsenic high-silicon sulfate solution by using a multi-element synergistic extraction system mainly comprising Lix-63 comprises the following steps:
1) adding sulfuric acid into the germanium-containing high-arsenic high-silicon sulfate solution to homogenize and adjust the concentration of aqueous phase sulfuric acid, and then fully mixing and contacting the aqueous phase sulfuric acid with the extraction organic phase to obtain a loaded organic phase rich in most germanium in the pre-extraction solution (namely the loaded organic phase of the chelated germanium) and an aqueous phase containing a small amount of germanium and impurity ions of arsenic, silicon, copper, cobalt and iron;
2) washing and purifying the loaded organic phase by using clear water, and washing off the carried organic phase;
3) and performing back extraction on the purified loaded organic phase by using an alkali solution to obtain a pure germanium-containing back extraction solution, wherein the germanium concentration can reach 40-55 g/L.
Further, the concentration of the aqueous phase sulfuric acid before extraction is 0.5-2 mol/L.
Further, the extraction temperature is 30-50 ℃, the volume ratio of the organic phase to the aqueous phase is 1-4:1, and the extraction stages are 3-5 stages.
Furthermore, the volume ratio of the washing organic phase to the water phase is 1:6-10, and the washing grade is 1-2.
Further, the alkali solution is ammonia water or sodium hydroxide solution. Preferably, the alkali solution is 4-6mol/L sodium hydroxide solution.
Further, the back extraction temperature is 30-50 ℃, the volume ratio of the back extraction organic phase to the water phase is 6-10:1, and the number of back extraction stages is 3-5.
Further, the organic phase obtained by back extraction is recycled.
Further, the diluent is sulfonated kerosene.
The invention has the following beneficial effects:
1. the invention adopts the extraction process of extracting, washing and sodium hydroxide back extracting germanium, can selectively extract and separate germanium from the high-arsenic high-silicon sulfate solution, the separation coefficient of germanium and arsenic, silicon and other impurity metal ions can reach more than 35, and the direct yield of the germanium in the whole process is more than 95%.
2. The extraction liquid is a sulfate system, silicon in the system is easy to form ortho-silicic acid to form a third phase in extraction, and P507 and P229 are used as extraction additives, so that the ortho-silicic acid solution can be effectively dispersed, the interfacial tension of two phases is reduced, emulsification is reduced, and the phase separation of the two phases is promoted.
3. Compared with the simple Lix-63 extraction, the multi-element synergistic extraction system for extracting germanium is easy to perform back extraction, reduces the acidity of the original feed liquid required by extracting germanium, reduces the alkali consumption required by organic back extraction, prolongs the service life of an extractant, and plays a positive role in comprehensively recycling germanium.
Drawings
FIG. 1 is a flow chart of an extraction process in an example of the invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the examples described are only for the aid of understanding the present invention and should not be construed as specifically limiting the present invention.
Example 1
At the extraction temperature of 30 ℃, in a feed liquid (namely a high-arsenic high-silicon sulfate solution) with sulfuric acid concentration of 1.6mol/L, a multi-element synergistic extraction system taking Lix-63 as a main part is used for extracting germanium from the organic high-arsenic high-silicon sulfate solution, the volume ratio of an extracting agent Lix-63, an extraction additive a, an extraction additive b and a diluent in the synergistic extraction system taking Lix-63 as a main part is 15:4:1:80, 3-stage countercurrent extraction is carried out under the condition that the volume ratio of an extraction organic phase to a water phase is 3:1, the extraction rate of germanium after extraction balance is more than 95%, and the extraction separation coefficient of each impurity metal is shown in the table I; then carrying out 1-stage countercurrent washing, purifying and washing on the loaded organic phase by pure water to remove impurity metals, and obtaining a purified germanium-containing loaded organic phase; and then carrying out three-stage back extraction on the purified organic phase loaded with the organic germanium by using 4mol/L sodium hydroxide solution, wherein the volume ratio of the back extraction organic phase to the back extraction aqueous phase is 10:1, the concentration of the back extraction liquid germanium after the three-stage back extraction by using the sodium hydroxide is 43.84g/L, and the germanium back extraction rate is more than 97%. The separation coefficient of germanium from arsenic and silicon and other impurity metal ions is shown in table one.
Table-feed liquid impurity metal extraction separation coefficient table
| Element ratio | Ge/As | Ge/Si | Ge/Co | Ge/Cu | Ge/Fe |
| Coefficient of separation beta | 767.07 | 147.55 | 623.02 | 70.53 | 251.83 |
Example 2
At the extraction temperature of 50 ℃, in feed liquid (namely high-arsenic high-silicon sulfate solution) with sulfuric acid concentration of 1.6mol/L, a multi-element synergistic extraction system mainly comprising Lix-63 is used for extracting germanium from organic relatively high-arsenic high-silicon sulfate solution for extraction and separation, the volume ratio of an extracting agent Lix-63, an extraction additive a, an extraction additive b and a diluent in the Lix-63 synergistic extraction system is 22.5:5:2.5:70, 3-stage countercurrent extraction is carried out under the condition that the volume ratio of an extraction organic phase to a water phase is 4:1, and the extraction rate of the germanium after extraction balance is more than 98%; then carrying out 1-stage countercurrent washing, purifying and washing on the loaded organic phase by pure water to remove impurity metals, and obtaining a purified germanium-containing loaded organic phase; and then carrying out three-stage back extraction on the purified organic phase loaded with the organic germanium by using 6mol/L sodium hydroxide solution, wherein the volume ratio of the back extraction organic phase to the back extraction aqueous phase is 10:1, the concentration of the germanium in the back extraction solution after the sodium hydroxide is subjected to three-stage back extraction is 54.9g/L, and the back extraction rate of the germanium is more than 99%. The separation coefficient of germanium from arsenic, silicon and other impurity metal ions is shown in the second table.
Table two material liquid impurity metal extraction separation coefficient table
| Element ratio | Ge/As | Ge/Si | Ge/Co | Ge/Cu | Ge/Fe |
| Coefficient of separation beta | 4703.06 | 554.08 | 821.31 | 70.89 | 432.93 |
Claims (10)
1. A method for selectively extracting and separating germanium from a high-arsenic high-silicon sulfate solution by using a multi-element synergistic extraction system mainly comprising Lix-63 is characterized in that an extraction organic phase is a multi-element synergistic extraction system mainly comprising a hydroximic extractant Lix-63, the multi-element synergistic extraction system comprises a hydroximic extractant, an extraction additive a, an extraction additive b and a diluent, wherein the hydroximic extractant is Lix-63, the extraction additive a and the extraction additive b are respectively P507 and P229, the diluent is an organic solvent immiscible with water, and the volume ratio of the hydroximic extractant, the extraction additive a, the extraction additive b and the diluent is 10-30:1-10:1-10: 50-88.
2. The method of claim 1, wherein the high-arsenic high-silicon sulfate solution contains 0.5-1g/L Ge, 4-5g/L As, and 0.5-1g/L Si, as well as Cu, Co, and Fe as impurity ions.
3. The method for selectively extracting and separating germanium from the high-arsenic high-silicon sulfate solution by using the Lix-63-based multi-element synergistic extraction system as claimed in claim 1 or 2, which is characterized by comprising the following steps:
1) adding sulfuric acid into the germanium-containing high-arsenic high-silicon sulfate solution to homogenize and adjust the concentration of aqueous phase sulfuric acid, and then fully mixing and contacting with the extraction organic phase to obtain a loaded organic phase rich in most germanium of extraction front liquid and an aqueous phase containing a small amount of germanium and impurity ions of arsenic, silicon, copper, cobalt and iron;
2) washing and purifying the loaded organic phase by using clear water, and washing off the carried organic phase;
3) and performing back extraction on the purified loaded organic phase by using an alkali solution to obtain a pure germanium-containing back extraction solution.
4. The method for selectively extracting and separating germanium from the high-arsenic high-silicon sulfate solution by using the Lix-63-based multi-element synergistic extraction system as claimed in claim 3, wherein the concentration of sulfuric acid in the aqueous phase before extraction is 0.5-2 mol/L.
5. The method for selectively extracting and separating germanium from the high-arsenic high-silicon sulfate solution by using the Lix-63-based multi-element synergistic extraction system as claimed in claim 3, wherein the extraction temperature is 30-50 ℃, the volume ratio of the organic phase to the aqueous phase is 1-4:1, and the extraction stages are 3-5 stages.
6. The method for selectively extracting and separating germanium from the high-arsenic high-silicon sulfate solution by using the Lix-63-based multi-element synergistic extraction system as claimed in claim 3, wherein the volume ratio of the washing organic phase to the water phase is 1:6-10, and the washing number is 1-2.
7. The method of claim 3, wherein the alkali solution is ammonia or sodium hydroxide solution.
8. The method for selectively extracting and separating germanium from the high-arsenic high-silicon sulfate solution by using the Lix-63-based multi-element synergistic extraction system as the claim 3, wherein the back extraction temperature is 30-50 ℃, the volume ratio of the back extraction organic phase to the water phase is 6-10:1, and the number of the back extraction stages is 3-5.
9. The method for selectively extracting and separating germanium from the high-arsenic high-silicon sulfate solution by using the Lix-63-based multi-element synergistic extraction system as claimed in claim 3, wherein the organic phase obtained by back extraction is recycled.
10. The method of claim 1 wherein the diluent is sulfonated kerosene.
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| CN112695212A (en) * | 2020-12-10 | 2021-04-23 | 衢州华友钴新材料有限公司 | Method for separating germanium from high-iron high-arsenic sulfate solution through ternary co-extraction |
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