CN113249577B - Method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste - Google Patents
Method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste Download PDFInfo
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- CN113249577B CN113249577B CN202110447998.XA CN202110447998A CN113249577B CN 113249577 B CN113249577 B CN 113249577B CN 202110447998 A CN202110447998 A CN 202110447998A CN 113249577 B CN113249577 B CN 113249577B
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
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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 relates to a method for recovering tellurium and germanium from tellurium-germanium-chalcogenide glass waste, which comprises the following steps: 1) crushing and grinding: crushing and grinding tellurium-germanium-sulfur glass waste; 2) and (3) tellurium oxidation precipitation: pulping tellurium-germanium-sulfur glass waste with a NaOH solution, adding hydrogen peroxide to carry out potential control oxidation to precipitate tellurium, and obtaining tellurium concentrate and a germanium-containing leachate; 3) primary germanium precipitation: carrying out two-step germanium precipitation on the germanium-containing leachate, and adding sulfuric acid in the first step to obtain primary germanium concentrate; 4) secondary germanium precipitation: performing secondary germanium precipitation on the primary germanium precipitation solution, and adding a ferric trichloride solution to realize Fe 3+ /Ge 4+ Coprecipitating to obtain secondary germanium concentrate; 5) deep treatment: and discharging the secondary germanium-precipitated liquid into a sewage treatment workshop for advanced treatment. The process has the advantages of simple and safe technical process, large batch processing capacity, less environmental pollution, capability of completely separating valuable metals and the like.
Description
Technical Field
The invention relates to the field of resource recovery, in particular to a method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste.
Background
Chalcogenide glass is an important infrared lens material, has a large infrared transmission range, and can extend the long-edge transmission infrared cutoff wavelength from 12 micrometers to 20 micrometers. Chalcogenide glasses are commonly used commercially in infrared thermal imaging systems to collect infrared signals emitted at different temperatures. Furthermore, the transmission range of chalcogenide glass covers the third atmospheric transmission window, which means that it has great potential commercial application value in remote or chemical sensors and optical communication systems.
Defective products are generated in the process of processing and forming the tellurium-germanium-sulfur glass, and the defective products of the tellurium-germanium-sulfur glass have high tellurium content and germanium content and have high recovery value. At present, the main methods for extracting germanium from secondary resources are a chlorination distillation germanium method, a solvent extraction germanium method, an ion exchange germanium method, a germanium precipitation method, a hydrofluoric acid dissolved germanium extraction method, an oxidation tellurium precipitation germanium extraction method and a biochemical germanium extraction method. As for tellurium-germanium-sulfur glass, if a chlorination distillation method is directly adopted, hydrogen telluride which is a highly toxic gas is easily generated, and the intensity of the reaction is not easy to control.
Therefore, a new method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste is urgently needed.
Disclosure of Invention
The invention aims to provide a method for recovering tellurium and germanium from tellurium-germanium-chalcogenide glass waste, which has the advantages of simple process technical flow, low cost, high comprehensive recovery rate of germanium and tellurium, small environmental pollution and easy large-scale production and use.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste comprises the following steps:
s1, crushing and grinding: crushing and grinding tellurium-germanium-sulfur glass waste;
s2 tellurium oxidation and precipitation: pulping a tellurium-germanium-sulfur glass material and a NaOH solution according to a certain liquid-solid ratio, then adding hydrogen peroxide with the mass fraction of 50%, carrying out potential control oxidation to precipitate tellurium, carrying out heat preservation, stirring, and filtering to obtain tellurium concentrate and a germanium-containing leachate;
s3 primary germanium precipitation: regulating the pH of the germanium-containing leachate obtained in the step S2 with sulfuric acid, stirring and filtering to obtain primary germanium concentrate and primary germanium-precipitating solution;
s4 secondary germanium precipitation: adding 30% by mass of ferric trichloride solution into the primary germanium precipitation solution obtained in the step S3, stirring, adjusting the pH value of the solution, stirring, and filtering to obtain secondary germanium concentrate and secondary germanium precipitation solution;
and S5 deep processing: and discharging the liquid after secondary germanium precipitation into a sewage treatment workshop for advanced treatment.
As a further improvement of the invention, the mass fraction of tellurium in the tellurium-germanium-sulfur glass waste is 60-70%.
As a further improvement of the invention, the liquid-solid ratio of the NaOH solution for tellurium oxidation precipitation to the tellurium-germanium-sulfur glass waste is 4-7: 1, the concentration of the NaOH solution is 80-100 g/L.
As a further improvement of the invention, the potential of the potential-controlled tellurium oxide deposition is 100-200 mv.
As a further improvement of the method, the reaction temperature of the two germanium precipitation steps is controlled to be 70-85 ℃, and the reaction time is controlled to be 2-4 hours.
As a further improvement of the invention, the pH of the primary germanium precipitation is controlled to be 8-9.5.
As a further improvement of the invention, the pH of the secondary germanium precipitation is controlled to be 8-9.5.
As a further improvement of the invention, the addition amount of the 30% ferric trichloride solution is 13-18 times of the mass of the germanium contained in the solution after the primary germanium precipitation.
As a further improvement of the invention, the valuable metals in the tellurium-germanium-sulfur glass waste comprise tellurium and germanium.
The invention is directed to a method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste, compared with the prior art, firstly, after alkaline leaching, tellurium is precipitated by adopting potential control oxidation, so that the tellurium is oxidized from low valence to obtain a simple substance tellurium, and thus the tellurium and the germanium are effectively separated; secondly, the tellurium-germanium-sulfur glass waste is treated by adopting oxidation alkaline leaching, so that the problems that the reaction is violent in the acid leaching process in the traditional process, hydrogen telluride highly toxic gas is easy to generate, and the safety risk exists can be effectively avoided; thirdly, the direct yield of tellurium in the oxidation alkaline leaching process is high, and the loss of tellurium is effectively controlled. The process has the advantages of simple and safe technical process, large batch processing capacity, less environmental pollution, capability of completely separating valuable metals and the like.
Detailed Description
The invention provides a method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste, which comprises the following steps:
s1, crushing and grinding: crushing and grinding tellurium-germanium-sulfur glass waste;
s2 tellurium oxidation and precipitation: pulping a tellurium-germanium-sulfur glass material and a NaOH solution according to a certain liquid-solid ratio, then adding hydrogen peroxide with the mass fraction of 50%, carrying out potential control oxidation to precipitate tellurium, carrying out heat preservation, stirring, and filtering to obtain tellurium concentrate and a germanium-containing leachate;
s3 primary germanium precipitation: regulating the pH of the germanium-containing leachate obtained in the step S2 with sulfuric acid, stirring and filtering to obtain primary germanium concentrate and primary germanium-precipitating solution;
s4 secondary germanium precipitation: adding 30% ferric chloride solution into the primary germanium precipitation solution obtained in the step S3, stirring, adjusting the pH value of the solution, stirring, and filtering to obtain secondary germanium concentrate and secondary germanium precipitation solution;
and S5 deep processing: and discharging the secondary germanium-precipitated liquid into a sewage treatment workshop for advanced treatment.
The present invention will be described in detail with reference to the following embodiments.
Example 1.
Placing 80g of tellurium-germanium-sulfur glass waste crushed and ground to 200 meshes in a 1L beaker, adding 100g/L of sodium hydroxide solution according to the liquid-solid ratio of 5:1, adding 50% hydrogen peroxide after the materials are pulped to stabilize the potential of the solution to 200mv, heating to 75 ℃, and carrying out heat preservation reaction for 2h to obtain tellurium concentrate and germanium-containing leachate, wherein the leaching rate of Ge is more than 99%, and the direct yield of tellurium is more than 99%; regulating pH of the germanium-containing leachate to 8.5 with 98% sulfuric acid, stirring for 30min, and filtering to obtain primary germanium concentrate and primary germanium-precipitating solution; adding 30% ferric trichloride solution into the obtained primary germanium precipitation solution according to 13 times of the mass of germanium contained in the primary germanium precipitation solution, stirring, then adjusting the pH value of the solution to 9, stirring for 30min, filtering to obtain secondary germanium concentrate and secondary germanium precipitation solution, wherein the comprehensive recovery rate of Ge is more than 95%; and discharging the secondary germanium-precipitated liquid into a sewage treatment workshop for advanced treatment.
Example 2.
Placing 80g of tellurium-germanium-sulfur glass waste crushed and ground to 100 meshes in a 1L beaker, adding 90g/L of sodium hydroxide solution according to the liquid-solid ratio of 7:1, adding 50% hydrogen peroxide after the materials are pulped to stabilize the potential of the solution to 100mv, heating to 80 ℃, and carrying out heat preservation reaction for 3 hours to obtain tellurium concentrate and leachate, wherein the leaching rate of Ge is more than 99%, and the direct yield of tellurium is more than 99%; regulating pH of the germanium-containing leachate to 8 with 98% sulfuric acid, stirring for 30min, and filtering to obtain primary germanium concentrate and primary germanium-precipitating solution; adding 30% ferric trichloride solution into the obtained primary germanium precipitation solution according to 16 times of the mass of germanium contained in the primary germanium precipitation solution, stirring, then adjusting the pH of the solution to 9.5, stirring for 30min, filtering to obtain secondary germanium concentrate and secondary germanium precipitation solution, wherein the comprehensive recovery rate of Ge is more than 95%; and discharging the secondary germanium-precipitated liquid into a sewage treatment workshop for advanced treatment.
Example 3.
Placing 80g of tellurium-germanium-sulfur glass waste crushed and ground to 150 meshes in a 1L beaker, adding 80g/L of sodium hydroxide solution according to the liquid-solid ratio of 6:1, adding 50% hydrogen peroxide after the materials are pulped to stabilize the potential of the solution to 150mv, heating to 85 ℃, and carrying out heat preservation reaction for 4 hours to obtain tellurium concentrate and leachate, wherein the leaching rate of Ge is more than 99%, and the direct yield of tellurium is more than 99%; regulating pH of the germanium-containing leachate to 9 with 98% sulfuric acid, stirring for 30min, and filtering to obtain primary germanium concentrate and primary germanium-precipitating solution; adding 30% ferric trichloride solution into the obtained primary germanium precipitation solution according to 18 times of the mass of germanium contained in the primary germanium precipitation solution, stirring, then adjusting the pH value of the solution to 8.5, stirring for 30min, filtering to obtain secondary germanium concentrate and secondary germanium precipitation solution, wherein the comprehensive recovery rate of Ge is more than 95%; and discharging the secondary germanium-precipitated liquid into a sewage treatment workshop for advanced treatment.
The invention provides a method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste, which can efficiently and quickly treat the tellurium-germanium-sulfur glass waste, and valuable metals of tellurium and germanium in the waste are independently treated to realize full separation, so that the direct yield of tellurium is high, and the method has important significance for recovering tellurium-germanium-sulfur glass. Meanwhile, the method also reduces the production risk in the recycling process of the tellurium-germanium-sulfur glass waste.
The method has the advantages of simple and safe process, large batch processing capacity, less environmental pollution, capability of completely separating valuable metals and the like.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (5)
1. A method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste is characterized by comprising the following steps: the method comprises the following steps:
s1, crushing and grinding: crushing and grinding the tellurium-germanium-sulfur glass waste to 100-200 meshes;
s2 tellurium oxidation and precipitation: pulping a tellurium-germanium-sulfur glass material and a NaOH solution according to a certain liquid-solid ratio, then adding hydrogen peroxide with the mass fraction of 50%, carrying out potential control oxidation to precipitate tellurium, carrying out heat preservation, stirring, and filtering to obtain tellurium concentrate and a germanium-containing leachate;
s3 primary germanium precipitation: regulating the pH of the germanium-containing leachate obtained in the step S2 with sulfuric acid, stirring and filtering to obtain primary germanium concentrate and primary germanium-precipitating solution;
s4 secondary germanium precipitation: adding a ferric trichloride solution with the mass fraction of 30% into the primary germanium precipitation solution obtained in the step S3, stirring, adjusting the pH value of the solution, stirring, and filtering to obtain secondary germanium concentrate and a secondary germanium precipitation solution;
and S5 deep processing: discharging the secondary germanium-precipitated liquid into a sewage treatment workshop for advanced treatment;
the liquid-solid ratio of the NaOH solution for oxidizing and precipitating tellurium to the tellurium-germanium-sulfur glass waste is 5-7: 1, the concentration of NaOH solution is 80-100 g/L;
controlling the potential of the tellurium deposition by potential oxidation to be 100-200 mv;
the reaction temperature of the oxidation and tellurium precipitation is controlled to be 70-85 ℃, and the reaction time is controlled to be 2-4 h;
the adding amount of the 30% ferric trichloride solution is 13-18 times of the mass of germanium contained in the solution after primary germanium precipitation;
the valuable metals in the tellurium-germanium-sulfur glass waste comprise tellurium and germanium.
2. The method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste material as claimed in claim 1, wherein: the mass fraction of tellurium in the tellurium-germanium-sulfur glass waste is 60-70%.
3. The method of claim 1 for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste, wherein: the mass fraction of germanium in the tellurium-germanium-sulfur glass waste is 10-20%.
4. The method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste as claimed in claim 1, wherein: the pH value of the primary germanium precipitation is controlled to be 8-9.5.
5. The method for recovering tellurium and germanium from tellurium-germanium-sulfur glass waste material as claimed in claim 1, wherein: the pH value of the secondary germanium precipitation is controlled to be 8-9.5.
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| CN109385540A (en) * | 2018-10-18 | 2019-02-26 | 云南北方驰宏光电有限公司 | A kind of regeneration method of germanium in infrared chalcogenide glass waste material |
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