Method for recovering germanium from germanium-containing smoke dust

Abstract

The invention discloses a method for recovering germanium from germanium-containing smoke dust, which comprises the steps of leaching, desilicication, germanium extraction and post-treatment, and specifically comprises the following steps: adding a sulfuric acid solution into the germanium-containing smoke dust, carrying out agitation leaching at the temperature of 50-90 DEG C, and carrying out solid-liquid separation to obtain a first-section leaching solution a and a first-section leaching residue b; adding a sulfuric acid solution, stirring and leaching at the temperature of 60-80 DEG C, carrying out solid-liquid separation to obtain a second-stage leaching solution c and second-stage leaching residues d, and adding gelatin or bovine gelatin into the first-stage leaching solution a for desilicication to obtain a germanium-containing solution e and a silicon-containing flocculent precipitate f; extracting the germanium-containing liquid e by adopting 10-30% of 7815, 3-10% of a synergistic extractant A and 60-87% of kerosene to obtain an organic phase g and a water phase h; the organic phase g is washed with a dilute sulfuric acid solution and then subjected to reverse extraction with a sodium hydroxide solution, a reverse extraction solution i and an organic phase j are obtained, a sulfuric acid solution is added into the reverse extraction solution i, hydrolysis is conducted, and germanium concentrate and mother liquor are obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of recycling and utilization, and further belongs to the technical field of germanium recycling and utilization, and specifically relates to a method for recovering germanium from germanium-containing smoke. Background Art

[0002] Germanium is a rare and precious metal and an important and scarce associated resource. Germanium has extensive and important applications in semiconductors, aerospace measurement and control, fiber optic communications, infrared optics, solar cells and other fields. China, the United States, Japan and other countries have listed it as a strategic reserve resource. With the development of high-tech industries, the demand for germanium is increasing, and the international market price is increasing year by year. There are no independent germanium metal deposits in nature. Germanium is mainly obtained from associated minerals or the recovery of secondary resources. Common germanium associated mineral sources include lead-zinc sulfide ores, lead-zinc oxide ores, coal mines and copper mines.

[0003] The conventional industrial production of germanium recovery adopts tannin precipitation method, and tannin germanium precipitate slag adopts pyrocalcination technology. The process of enriching germanium concentrate has the disadvantages of large germanium loss (about 5~8%), low germanium concentrate grade (about 19%Ge), high energy consumption, etc. With the fluctuation of tannic acid prices in recent years and the expansion of germanium production, whether the market supply and price of tannic acid can meet the production needs, the normal recovery of germanium is facing a test. Summary of the invention

[0004] The object of the present invention is to provide a method for recovering germanium from germanium-containing smoke.

[0005] The object of the present invention is achieved in that the method for recovering germanium from germanium-containing smoke comprises leaching, desiliconization, germanium extraction and post-treatment steps, specifically comprising: A. Leaching: 1) Add sulfuric acid solution to germanium-containing smoke, stir and leach at a temperature of 50-90°C, and separate the solid and liquid to obtain a leachate a and a leach residue b; 2) adding sulfuric acid solution to the first-stage leaching residue b, stirring and leaching at a temperature of 60-80°C, and separating the solid and liquid to obtain the second-stage leaching solution c and the second-stage leaching residue d, and returning to step 1 after acid is added to the second-stage leaching solution c); B. Desiliconization: gelatin or beef glue is added to a section of the leaching solution a for desiliconization to obtain a germanium-containing solution e and a silicon-containing flocculent precipitate f; the silicon-containing flocculent precipitate f is annealed to recover valuable metals; C. Germanium extraction: 1) The germanium-containing liquid e is extracted with 10-30% 7815 + 3-10% synergist A + 60-87% kerosene to obtain an organic phase g and an aqueous phase h; 2) washing the organic phase g with a dilute sulfuric acid solution and then stripping with a sodium hydroxide solution to obtain a stripping solution i and an organic phase j. The organic phase j is regenerated by adding sulfuric acid solution and can be recycled; D. Post-treatment: Add sulfuric acid solution to the stripping solution i for hydrolysis to obtain germanium concentrate and mother liquor.

[0006] The specific operations are as follows: (1) One-stage leaching: Mix the germanium-containing smoke and sulfuric acid solution in proportion, stir and leach at 50-90°C for 30-120 minutes to obtain a first-stage leaching solution and a first-stage leaching residue; (2) Second stage leaching: the first stage leaching residue is mixed with sulfuric acid solution in proportion, and leached under stirring at 60-80°C for 30-60 min to obtain a second stage leaching solution and second stage leaching residue. After the second stage leaching solution is supplemented with acid, it is returned to step (1) and step (1) is repeated; (3) Desiliconization of the first-stage leachate: gelatin or beef glue is added to the first-stage leachate for desiliconization to obtain a desiliconized germanium-containing liquid with a desiliconization rate of more than 96%; (4) Extraction: Use 7815 + co-extractant A + kerosene for extraction, and the germanium extraction rate reaches more than 98%; (5) Washing: Wash with dilute sulfuric acid; (6) Stripping: Stripping with sodium hydroxide, the germanium stripping rate is >97%; (7) Hydrolysis: The stripping solution is hydrolyzed with sulfuric acid to obtain germanium concentrate, the germanium content of the germanium concentrate is >45%.

[0007] The main components of the germanium-containing smoke are zinc, lead, iron, germanium, etc., and their contents in the smoke are respectively 30%-55% zinc, 10%-30% lead, 3%-15% iron, and 500-1000g / t germanium.

[0008] In the step (1), the concentration of sulfuric acid is 80 g / L-140 g / L, the liquid-to-solid ratio is 3:1-7:1 ml / g (the liquid-to-solid ratio is the volume mass ratio of liquid to smoke), the leaching time is 30-120 min, and the germanium leaching rate reaches more than 80%.

[0009] In step (2), the sulfuric acid concentration is 120-180 g / L, the liquid-to-solid ratio is 5:1-7:1 ml / g (the liquid-to-solid ratio is the volume mass ratio of liquid to smoke), the leaching time is 30-60 min, and the total germanium leaching rate reaches more than 90%.

[0010] The concentration of gelatin or bovine gelatin in step (3) is 0.5-1.0 g / L.

[0011] In the step (4), the content of 7815 is 10%-30%, the synergist A is P204, one or more of hydroxamic acid, YW100, TBP, etc., the content of the synergist is 3-10%, the kerosene is sulfonated aviation kerosene, the content is 60-87%, the extraction ratio is 3-5, and the extraction time is 2-5min.

[0012] The concentration of sulfuric acid in step (5) is 0.1-0.25M.

[0013] The concentration of sodium hydroxide in step (6) is 1-3M.

[0014] Beneficial effects of the present invention: (1) In the process of leaching germanium from germanium-containing smoke dust of the present invention, the germanium leaching rate is high, reaching more than 90%; (2) The present invention has high extraction rate, high stripping rate, high grade of germanium concentrate and low raw material consumption; (3) The process flow of the present invention is short and smooth. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a schematic diagram of the process flow of the present invention. DETAILED DESCRIPTION

[0016] The present invention is further described below in conjunction with the embodiments, but the present invention is not limited in any way. Any changes or substitutions made based on the teachings of the present invention belong to the protection scope of the present invention.

[0017] The method for recovering germanium from germanium-containing smoke of the present invention comprises leaching, desiliconization, germanium extraction and post-treatment steps, specifically comprising: A. Leaching: 1) Add sulfuric acid solution to germanium-containing smoke, stir and leach at a temperature of 50-90°C, and separate the solid and liquid to obtain a leachate a and a leach residue b; 2) adding sulfuric acid solution to the first-stage leaching residue b, stirring and leaching at a temperature of 60-80°C, and separating the solid and liquid to obtain the second-stage leaching solution c and the second-stage leaching residue d, and returning to step 1 after acid is added to the second-stage leaching solution c); B. Desiliconization: gelatin or beef glue is added to a section of the leaching solution a for desiliconization to obtain a germanium-containing solution e and a silicon-containing flocculent precipitate f; the silicon-containing flocculent precipitate f is annealed to recover valuable metals; C. Germanium extraction: 1) The germanium-containing liquid e is extracted with 10-30% 7815 + 3-10% synergist A + 60-87% kerosene to obtain an organic phase g and an aqueous phase h; 2) washing the organic phase g with a dilute sulfuric acid solution and then stripping with a sodium hydroxide solution to obtain a stripping solution i and an organic phase j. The organic phase j is regenerated by adding sulfuric acid solution and can be recycled; D. Post-treatment: Add sulfuric acid solution to the stripping solution i for hydrolysis to obtain germanium concentrate and mother liquor.

[0018] A The concentration of the sulfuric acid solution described in step 1) is 80-140 g / L.

[0019] The leaching time described in step A 1) is 30 to 120 minutes.

[0020] A. The concentration of the sulfuric acid solution described in step 2) is 120-180 g / L.

[0021] The leaching time described in step A 2) is 30 to 60 minutes.

[0022] The concentration of gelatin or bovine gelatin in step B is 0.5~1.0g / L.

[0023] C. The synergistic extractant A in step 1) is one or more of P204, hydroxamic acid, YW100 and TBP.

[0024] C. The kerosene described in step 1) is sulfonated aviation kerosene.

[0025] C. The concentration of the dilute sulfuric acid solution described in step 2) is 0.1-0.25M.

[0026] C. The concentration of the sodium hydroxide solution described in step 2) is 1-3M.

[0027] The present invention is further described below with specific implementation cases: Example 1 (1) One-stage leaching: 100 g of germanium-containing smoke was mixed with 120 g / L sulfuric acid at 60 °C and stirred for 60 min (liquid-to-solid ratio 6:1) to obtain a first-stage leaching solution and a first-stage leaching residue with a leaching rate of 82.31%; (2) Second stage leaching: The first stage leaching residue was leached with sulfuric acid having a concentration of 140 g / L at 70°C for 30 min with stirring (liquid-to-solid ratio of 6:1) to obtain second stage leaching residue and second stage leaching solution. The second stage leaching solution was supplemented with acid and returned to step (1) to repeat step (1). The total germanium leaching rate was 90.21%; (3) Desiliconization of the first-stage leachate: 1 g / L of gelatin was added to the first-stage leachate to obtain a desiliconized germanium-containing liquid with a silicon content of 45 mg / L and a desiliconization rate of 96.43%; (4) Extraction: 20% 7815 + 5% synergist A + 75% kerosene were used for extraction, with an O / A ratio of 3, an extraction time of 3 minutes, and a germanium extraction rate of 98.03%; (5) Washing: Wash with 0.25M dilute sulfuric acid; (6) Stripping: Stripping with 1M sodium hydroxide, compared with O / A is 1 / 3, the germanium stripping rate is 97.50%; (7) Hydrolysis: The stripping solution is hydrolyzed with sulfuric acid to obtain germanium concentrate, the germanium content of the germanium concentrate is 45.64%.

[0028] Example 2 (1) One-stage leaching: 100 g of germanium-containing smoke was mixed with 110 g / L sulfuric acid at 80 °C for 60 min (liquid-solid ratio 6:1) to obtain a first-stage leaching solution and a first-stage leaching residue with a leaching rate of 85.48%; (2) Second stage leaching: The first stage leaching residue was leached with sulfuric acid having a concentration of 160 g / L at 80°C for 60 min with stirring (liquid-to-solid ratio of 6:1) to obtain second stage leaching residue and second stage leaching solution. The second stage leaching solution was supplemented with acid and returned to step (1) to repeat step (1). The total germanium leaching rate was 90.05%; (3) Desiliconization of the first-stage leaching solution: 0.5 g / L of beef glue was added to the first-stage leaching solution to obtain a desiliconized germanium-containing solution with a silicon content of 68 mg / L and a desiliconization rate of 96.00%; (4) Extraction: 30% 7815 + 10% synergist A + 60% kerosene were used for extraction, with an O / A ratio of 3, an extraction time of 5 min, and a germanium extraction rate of 98.23%; (5) Washing: Wash with 0.25M dilute sulfuric acid; (6) Stripping: Stripping with 3M sodium hydroxide, compared with O / A is 1 / 3, the germanium stripping rate is 98.50%; (7) Hydrolysis: The stripping solution is hydrolyzed with sulfuric acid to obtain germanium concentrate, the germanium content of the germanium concentrate is 50.32%.

Claims

1. A method for recovering germanium from germanium-containing smoke, characterized in that: The method for recovering germanium from germanium-containing smoke comprises leaching, desiliconization, germanium extraction and post-treatment steps, specifically comprising: A. Leaching: 1) Add sulfuric acid solution to germanium-containing smoke, stir and leach at a temperature of 50-90°C, and separate the solid and liquid to obtain a leachate a and a leach residue b; 2) adding sulfuric acid solution to the first-stage leaching residue b, stirring and leaching at a temperature of 60-80°C, and separating the solid and liquid to obtain the second-stage leaching solution c and the second-stage leaching residue d, and returning to step 1 after acid is added to the second-stage leaching solution c); B. Desiliconization: gelatin or beef glue is added to a section of the leaching solution a for desiliconization to obtain a germanium-containing solution e and a silicon-containing flocculent precipitate f; the silicon-containing flocculent precipitate f is annealed to recover valuable metals; C. Germanium extraction: 1) The germanium-containing liquid e is extracted with 10-30% 7815 + 3-10% synergist A + 60-87% kerosene to obtain an organic phase g and an aqueous phase h; 2) washing the organic phase g with a dilute sulfuric acid solution and then stripping with a sodium hydroxide solution to obtain a stripping solution i and an organic phase j. The organic phase j is regenerated by adding sulfuric acid solution and can be recycled; D. Post-treatment: Add sulfuric acid solution to the stripping solution i for hydrolysis to obtain germanium concentrate and mother liquor.

2. The method for recovering germanium from germanium-containing smoke according to claim 1, characterized in that: A The concentration of the sulfuric acid solution described in step 1) is 80-140 g / L.

3. The method for recovering germanium from germanium-containing smoke according to claim 1, characterized in that: The leaching time described in step A 1) is 30 to 120 minutes.

4. The method for recovering germanium from germanium-containing smoke according to claim 1, characterized in that: A. The concentration of the sulfuric acid solution described in step 2) is 120-180 g / L.

5. The method for recovering germanium from germanium-containing smoke according to claim 1, characterized in that: The leaching time described in step A 2) is 30 to 60 minutes.

6. The method for recovering germanium from germanium-containing smoke according to claim 1, characterized in that: The concentration of gelatin or bovine gelatin in step B is 0.5~1.0g / L.

7. The method for recovering germanium from germanium-containing smoke according to claim 1, characterized in that: The synergistic extractant A in step 1) is one or more of P204, hydroxamic acid, YW100 and TBP.

8. The method for recovering germanium from germanium-containing smoke according to claim 1, characterized in that: The kerosene described in step C 1) is sulfonated aviation kerosene.

9. The method for recovering germanium from germanium-containing smoke according to claim 1, characterized in that: C. The concentration of the dilute sulfuric acid solution described in step 2) is 0.1-0.25M.

10. The method for recovering germanium from germanium-containing smoke according to claim 1, characterized in that: C. The concentration of the sodium hydroxide solution described in step 2) is 1-3M.

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