CN110791648B - Method for extracting and recovering germanium from sulfuric acid leaching solution - Google Patents
Method for extracting and recovering germanium from sulfuric acid leaching solution Download PDFInfo
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- 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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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- 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
- C22B41/00—Obtaining germanium
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Abstract
The invention discloses a method for extracting and recovering germanium from sulfuric acid leaching solution, which comprises the following steps: (1) and (3) extraction: mixing an extracting agent, a co-extracting agent and a diluent with the germanium-containing sulfuric acid leaching solution; (2) washing with water: mixing the organic phase obtained in the step (1) with pure water; (3) back extraction: extracting the organic phase obtained by mixing in the step (2) by using an amino compound aqueous solution as a stripping agent; (4) regeneration: and (3) carrying out regeneration treatment on the organic phase obtained by extraction in the step (3) by using pure water, and returning the regenerated organic phase to the step (1) for extraction. The method can complete extraction and recovery of germanium in the leaching solution in one extraction system, and has the advantages of high extraction rate, simple process, low investment cost, low production cost, no fluorine in germanium products and low loss of the co-extractant.
Description
Technical Field
The invention relates to the field of rare and dispersed germanium metal recovery, in particular to a method for extracting and recovering germanium from sulfuric acid leaching solution.
Background
Hydroxamic acid is a chelating extractant, is difficult to back extract, is not used for extracting germanium independently, and needs to be added with a synergistic extractant. The addition of the synergistic extractant not only enhances the synergistic extraction effect, but also enables the back extraction to be easier, the best combination of the synergistic extractant mainly comprises P204, naphthenic acid, fatty acid and the like, and the synergistic extractant is generally most widely applied to P204.
The synergistic system formed by P204 and hydroxamic acid can realize the extraction of germanium in a sulfuric acid system, wherein the synergistic agents capable of realizing the synergistic effect mainly comprise YW100, 7815, H106, HGS98, G315, G8315 and the like. The above belong to hydroxamic acid products, wherein YW100 is C7-9 alkyl hydroxamic acid, generally in the form of light yellow hard grease or yellow viscous liquid, and is a very weak organic acid; 7815 is a hydroxamic acid synthesized by Beijing institute of chemical and metallurgical technology in nuclear industry, and has good extraction operation for germanium; h106 is a tertiary alkyl hydroxamic acid, and is a gallium-germanium extracting agent synthesized by the institute of Changsha mining and metallurgy; g315 is a hydroxamic acid synthesized by Beijing institute of mining and metallurgy, and G8315 is subsequently researched on the basis of the hydroxamic acid.
At present, the process is applied to production, and the enrichment and separation of germanium are realized by mainly adopting 2-3M ammonium fluoride for back extraction. After the P204 is taken as a main body and the germanium is extracted by a synergistic extraction system, the back extraction of the germanium is very difficult, reported back extraction reagents comprise ammonium sulfate, hydrofluoric acid, sodium hydroxide, ammonium fluoride, perchloric acid, hypochlorous acid and the like, wherein the back extraction efficiency taking the ammonium sulfate as the system is low, the back extraction reagents are less used in production, the back extraction effect taking the hydrofluoric acid and the ammonium fluoride as main bodies is better, but fluorine contained in the germanium enrichment solution has a larger influence on the product quality, in addition, the corrosion is more serious, a certain influence is caused on the use, and the perchloric acid and the hypochlorous acid are less in application report.
Disclosure of Invention
The invention aims to solve the defects and shortcomings of the prior art and provides a method for extracting and recovering germanium from sulfuric acid leaching solution, which has the advantages of high extraction recovery rate, simple process, no fluorine in germanium products and low loss of a synergist.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for extracting and recovering germanium from sulfuric acid leaching solution comprises the following steps:
(1) and (3) extraction: mixing an extracting agent, a co-extracting agent and a diluent with the germanium-containing sulfuric acid leaching solution;
(2) washing with water: mixing the organic phase obtained in the step (1) with pure water;
(3) back extraction: extracting the organic phase obtained by mixing in the step (2) by using an amino compound aqueous solution as a stripping agent;
(4) regeneration: and (3) carrying out regeneration treatment on the organic phase obtained by extraction in the step (3) by using pure water, and returning the regenerated organic phase to the step (1) for extraction.
Further, if the sulfuric acid leaching solution contains Fe3+Then a reducing agent needs to be added for reduction before the extraction step.
Further, the sulfuric acid leaching solution is a germanium-containing solution obtained by leaching zinc smelting slag with sulfuric acid.
Further, the volume ratio of the dosage of the extractant, the synergist and the diluent in the step (1) is 1-3:0.2-2: 68-89.8.
Further, the extractant in the step (1) is a P204 extractant, namely di (2-ethylhexyl) phosphate.
Further, the synergist in step (1) is any one or more mixtures of hydroxamic acids (such as YW100 synergist, 7815 synergist, H106 synergist, G315 synergist, G8315 synergist, etc.), and the diluent is at least one of sulfonated kerosene (260# solvent oil) and rosin water (200# solvent oil).
Further, the step (1) is specifically as follows: mixing an extracting agent, a co-extracting agent and a diluting agent with the germanium-containing sulfuric acid leaching solution according to the volume ratio of the organic phase to the water phase of 1-3:1, and carrying out 1-8-stage countercurrent extraction.
Further, the step (2) is specifically as follows: mixing the organic phase obtained by extraction in the step (1) with pure water according to the volume ratio of the organic phase to the aqueous solution of 3-8:1, carrying out 1-4-stage countercurrent extraction, and returning the washing liquid to the step (1) in a countercurrent manner.
Further, the step (3) is specifically: mixing the organic phase obtained in the step (2) with an amino compound aqueous solution according to the volume ratio of the organic phase to the aqueous phase of 3-6:1, and performing 1-4-stage countercurrent extraction; the amino compound aqueous solution is an aqueous solution of ammonium oxalate, ammonium citrate or ammonium tartrate, and the concentration of the aqueous solution is 10-200 g/L.
Further, the pure water used for the regeneration treatment in the step (4) is grade 1-6 pure water. Washing the regenerated organic phase with water can reduce the loss of the synergist.
The method adopts the processes of extraction, water washing, back extraction of germanium from amino compounds and regeneration of pure water, can finish extraction and recovery of germanium in the leachate in one extraction system, and has the advantages of high extraction rate, simple process, low investment cost, low production cost, no fluorine in germanium products and low loss of co-extractant. The method can extract the germanium in the leaching solution with the sulfuric acid concentration of 10-120g/L, and the germanium extraction rate reaches more than 97%.
Detailed Description
All materials, reagents and equipment selected for use in the present invention are well known in the art, but do not limit the practice of the invention, and other reagents and equipment well known in the art may be suitable for use in the practice of the following embodiments of the invention.
Example 1
Extracting sulfuric acid leaching solution to recover germanium, wherein the solution mainly contains Ge: 455mg/L, Zn: 56g/L, H2SO 4: 25g/L, Cu: 24g/L, Cd: 780mg/L, and the specific steps are as follows:
(1) and (3) extraction: mixing a P204 extractant, a YW100 synergist and No. 260 solvent oil according to the volume ratio of 15:2:83 to prepare a mixed extractant, then mixing the prepared mixed extractant and a sulfuric acid leaching solution containing germanium in an extraction tank for clarification according to the volume ratio of an organic phase to a water phase of 1:1, and carrying out 4-stage countercurrent extraction. The organic phase obtained by extraction is extraction liquid, the aqueous phase obtained by extraction is raffinate, and the raffinate contains Ge: 2mg/L, Zn: 55mg/L, H2SO 4: 24g/L, Cu: 22.7g/L, Cd: 782 mg/L.
(2) Washing with water: and (3) according to the volume ratio of the organic phase to the water phase of 3:1, adding pure water and the organic phase obtained in the step (1) into a mixing and clarifying extraction tank for mixing, performing 4-stage countercurrent extraction washing, and returning the washing liquid to the step (1) in a countercurrent manner.
(3) Back extraction: and (3) according to the volume ratio of the organic phase to the water phase of 4:1, adding ammonium oxalate and the organic phase obtained in the step (2) into a mixed clarification extraction tank for mixing, performing 4-stage countercurrent extraction washing, and finally, obtaining a back extraction solution containing Ge: 1810 mg/L. Wherein the preparation of the ammonium oxalate is completed at 30-60 ℃, and the preparation concentration is 30 g/L.
(4) Regeneration: and (3) adding 6-grade pure water and the organic phase obtained in the step (3) into a mixing and clarifying extraction tank according to the volume ratio of the organic phase to the water phase of 8:1, mixing, performing 4-grade countercurrent extraction and regeneration, and recycling the organic phase.
By adopting the method of the embodiment, the final germanium back extraction rate is 99.88%.
Example 2
Extracting sulfuric acid leaching solution to recover germanium, wherein the solution mainly contains Ge: 450mg/L, Zn: 58g/L, H2SO 4: 30g/L, Cu: 29g/L, Cd: 1820mg/L, and the specific steps are as follows:
(1) and (3) extraction: mixing a P204 extractant, a YW100 synergist and No. 260 solvent oil according to the volume ratio of 15:2:83 to prepare a mixed extractant, then mixing the prepared mixed extractant and a sulfuric acid leaching solution containing germanium in an extraction tank for clarification according to the volume ratio of an organic phase to a water phase of 1:1, and carrying out 4-stage countercurrent extraction. The organic phase obtained by extraction is extraction liquid, the aqueous phase obtained by extraction is raffinate, and the ratio of the raffinate Ge: 1.5mg/L, Zn: 54mg/L, H2SO 4: 28g/L, Cu: 27.7g/L, Cd: 1782 mg/L.
(2) Washing with water: and (3) according to the volume ratio of the organic phase to the water phase of 8:1, adding pure water and the organic phase obtained in the step (1) into a mixing and clarifying extraction tank for mixing, performing 4-stage countercurrent extraction washing, and returning the washing liquid to the step (1) in a countercurrent manner.
(3) Back extraction: and (3) according to the volume ratio of the organic phase to the water phase of 4:1, adding ammonium citrate and the organic phase obtained in the step (2) into a mixed clarification extraction tank for mixing, performing 4-stage countercurrent extraction washing, and finally, obtaining a back extraction solution containing Ge: 1790 mg/L. Wherein the preparation concentration of the citric acid is 100 g/L.
(4) Regeneration: and (3) adding 3-grade pure water and the organic phase obtained in the step (3) into a mixing and clarifying extraction tank according to the volume ratio of the organic phase to the water phase of 8:1, mixing, performing 4-grade countercurrent extraction regeneration, and recycling the organic phase.
By adopting the method of the embodiment, the final germanium back extraction rate is 99.78%.
The present invention is not limited to the above-described embodiments, and various modifications and variations of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.
Claims (7)
1. A method for extracting and recovering germanium from sulfuric acid leaching solution is characterized by comprising the following steps:
1) and (3) extraction: mixing an extracting agent, a co-extracting agent and a diluent with a germanium-containing sulfuric acid leaching solution, wherein the using volume ratio of the extracting agent to the co-extracting agent to the diluent is 1-3:0.2-2:68-89.8, the extracting agent is a P204 extracting agent, the co-extracting agent is a YW100 co-extracting agent, and the diluent is No. 260 solvent oil;
2) washing with water: mixing pure water with the organic phase in the step 1), performing 1-4-stage countercurrent extraction, and returning the washing liquid to the step 1) in a countercurrent manner;
3) back extraction: extracting the organic phase obtained by mixing in the step 2) by using an amino compound aqueous solution as a stripping agent, wherein the amino compound aqueous solution is an ammonium oxalate or ammonium citrate aqueous solution;
4) regeneration: and (3) carrying out regeneration treatment on the organic phase obtained by extraction in the step 3) by using pure water, and returning the regenerated organic phase to the step 1) for extraction.
2. The process of claim 1, wherein if the leach solution contains Fe, the process further comprises recovering germanium from the leach solution3+Then a reducing agent needs to be added for reduction before the extraction step.
3. The method of claim 1, wherein the sulphuric acid leach solution is a germanium solution obtained by leaching zinc smelting slag with sulphuric acid.
4. The method for extracting and recovering germanium from a sulfuric acid leach solution according to claim 1, wherein the step 1) is specifically as follows: mixing an extracting agent, a co-extracting agent and a diluting agent with the germanium-containing sulfuric acid leaching solution according to the volume ratio of the organic phase to the water phase of 1-3:1, and carrying out 1-8-stage countercurrent extraction.
5. The method for extracting and recovering germanium from a sulfuric acid leach solution according to claim 1, wherein the step 2) is specifically as follows: mixing the organic phase obtained by the extraction in the step 1) with pure water according to the volume ratio of the organic phase to the aqueous solution of 3-8: 1.
6. The method for extracting and recovering germanium from a sulfuric acid leach solution according to claim 1, wherein the step 3) is specifically: mixing the organic phase obtained in the step 2) with an amino compound aqueous solution according to the volume ratio of the organic phase to the aqueous phase of 3-6:1, and performing 1-4-stage countercurrent extraction; the concentration of the amino compound aqueous solution is 10-200 g/L.
7. The method for extracting and recovering germanium from sulfuric acid leach solution according to claim 1, wherein the pure water used in the regeneration treatment in step 4) is grade 1-6 pure water.
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| CN112695212B (en) * | 2020-12-10 | 2023-05-05 | 衢州华友钴新材料有限公司 | Ternary synergistic extraction method for separating germanium from high-iron high-arsenic sulfate solution |
| CN115109950B (en) * | 2022-06-13 | 2023-10-20 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for producing germanium concentrate by back extraction from hydroxamic acid loaded organic phase |
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| CN103388086B (en) * | 2012-05-09 | 2014-12-10 | 深圳市格林美高新技术股份有限公司 | Method for extracting germanium from germanium-containing abandoned element |
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