CN112708764A - Method for comprehensively recovering germanium dioxide and copper from copper-germanium alloy material - Google Patents
Method for comprehensively recovering germanium dioxide and copper from copper-germanium alloy material Download PDFInfo
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Abstract
The invention discloses a method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material, which comprises the steps of adding a recovered copper material according to the germanium content of copper, adjusting the copper content to a proper proportion of copper and germanium, then casting an anode plate, taking pure copper or stainless steel as a cathode plate, electrodepositing in a sulfuric acid system (by adopting a diaphragm), obtaining pure copper by electrodeposition of copper in the alloy, enriching germanium in the form of anode mud, washing the anode mud by dilute sulfuric acid to remove copper, adding hydrochloric acid for distillation, washing hydrolyzed germanium dioxide by deionized water, and drying to obtain pure germanium dioxide. The method has simple process, produces copper products by electrolyzing copper in one step and using cathode copper, has high enrichment multiple of anode mud germanium, high recovery rate, friendly operation environment and low recovery cost, and is a clean comprehensive recovery process of copper-germanium alloy.
Description
Technical Field
The invention belongs to the field of waste metal recovery, and particularly discloses a method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material.
Background
Germanium metal has health promotion effect on human body. The germanium metal can convert light energy into electric energy, generate electricity by utilizing temperature difference, continuously generate electric energy at the temperature of over 32 ℃, and the electric energy is emitted in a far infrared mode, so that the health care effect is realized after a human body receives the far infrared rays. However, germanium metal is very brittle and easy to break, and the germanium metal is made into particles to be inlaid on other metals such as titanium metal in the past, so that the germanium metal has a certain health care function after being worn by a human body, but is easy to fall off and inconvenient to use. The germanium alloy can effectively solve the problem, the gold germanium alloy, the silver germanium alloy, the copper germanium alloy and the like are mainly used at present, and because gold, silver and germanium metals are expensive, the gold germanium alloy and the silver germanium alloy are less in consumption, the copper germanium alloy can reduce the alloy cost to the maximum extent, and the copper germanium alloy can be used in large quantities. The products and applications of the copper-germanium alloy are more and more as follows:
1. the copper-germanium alloy can act through a small amount of energy (body temperature), can adjust the ion balance of the body, enables the abnormal state of the nerve circuit of the body to be recovered to be normal, and has the effects of preventing and improving the uncomfortable feeling of the body, massaging the hot spring and the like.
2. The copper-germanium alloy also has the function of adjusting the abnormal potential of a human body, and can improve the body temperature, thereby promoting blood circulation and relieving fatigue.
3. The ornament made of the copper-germanium alloy has the effects of resisting fatigue, preventing radiation, relieving cervical vertebra and muscle ache, stabilizing blood pressure, accelerating metabolism, regulating asthma, dizziness, insomnia and the like.
4. The cup made of the copper-germanium alloy can change domestic drinking water and natural water into active water, and helps improve immunity of human body.
The dosage of the traditional Chinese medicine is large in developed countries such as Europe and America, Japan and the like, the traditional Chinese medicine is mainly used in daily necessities such as ornaments, water cups, bathtubs, waistbands, pillows and the like, the dosage is about 300-500 tons every year, and the dosage is increased by more than 30% every year. The current annual dosage of China is about 20-30 tons. With the continuous improvement of the living standard of people in China, the health care consciousness of people is continuously enhanced, and the future dosage of the copper-germanium alloy will be larger and larger.
Germanium is most commonly used in semiconductors to fabricate transistors. Germanium has good semiconductor properties such as electron mobility and hole mobility, can convert light energy into electric energy, can generate electricity by using temperature difference and the like. Germanium produced in modern industry mainly comes from the by-products of copper, lead and zinc smelting. Germanium is used in the form of germanium alloy, and copper-germanium alloy is one of the most common.
For the waste materials and recovery raw materials produced in the production and manufacture of copper-germanium alloy, the wet oxidation leaching is reported at present, copper powder with a small amount of germanium is produced by replacing copper with iron powder, and the leaching residue is distilled and recovered, the process is only simple, the germanium content in the copper powder is up to 0.4 percent, and the displaced liquid needs to be disposed. Therefore, the research on the high-efficiency recovery of copper and germanium by a simple process has economic and environmental protection significance.
Disclosure of Invention
Based on the method, the invention provides a method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material.
The technical scheme of the invention is as follows:
1. a method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material comprises the following steps:
1) blending: blending the waste copper-germanium alloy and the waste copper to ensure that the blended mixed metal comprises the following components in percentage by mass: the copper content is more than or equal to 95 percent, and the germanium and other elements are less than or equal to 5 percent;
2) casting: melting the mixed metal at 1150-1250 ℃, introducing the melt into an anode die, cooling to obtain an anode plate, and taking pure copper or a stainless steel plate to manufacture a cathode plate;
3) electrolysis: placing the manufactured anode plate and the manufactured cathode plate in a mixed electrolyte system of copper sulfate, dilute sulfuric acid and sodium chloride for electrolysis to generate anode mud and cathode mud, and recovering the cathode mud to be pure copper;
4) chlorination distillation: co-distilling the anode mud obtained in the previous step and hydrochloric acid to generate germanium tetrachloride and residual liquid,
5) hydrolysis: hydrolyzing germanium tetrachloride, washing and filtering to obtain germanium hydroxide precipitate;
6) drying and oxidizing: and drying the germanium hydroxide precipitate obtained in the previous step at the temperature of 130-140 ℃ for 12h, and recovering to obtain pure germanium dioxide.
Further, in the above method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material, the step 3 of electrolysis comprises: and the anode plate is wrapped by a cloth bag to form a diaphragm.
Further, in the above method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material, the step 3 of electrolysis comprises: in the mixed electrolyte system, the electrolyte comprises the following components: CuSO470-100g/L of NaCl and 40-60g/L of NaCl; the pH is controlled to be 2.5-4.5.
Further, in the above method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material, the step 3 of electrolysis comprises: the parameters of the electrolysis are as follows: the voltage of the cell is 1.8-2.8V, the current density is 180 plus 300A/square meter, the pole distance is 20-30mm, the temperature is 30-50 ℃, and the electrolyte circulates.
Further, in the above method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material, the step 3 of electrolysis comprises: the standard of the electrolysis step is that cathode copper Cu is 99.0 percent, anode mud accounts for 4 to 8 percent of the total amount of the anode mud, germanium is enriched to 30 to 50 percent, and the enrichment multiple is 10 times.
Further, in the above method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material, the chlorination distillation step of step 4 is: the distillation conditions are that the anode mud and 8mol/L hydrochloric acid are distilled for 10 hours at the liquid-solid ratio of 5:1 and the temperature of 115 ℃, and the distillation residual liquid germanium is less than 0.1 g/L.
Further, in the step 5 of hydrolysis, the proportion of hydrolysis is H according to the mass ratio2O:GeCl46.5: 1; rate of addition of water<45mL/min。
Further, the method for comprehensively recovering germanium dioxide and copper from the copper-germanium alloy material specifically comprises the following steps: the method comprises the following steps:
1) blending: blending the waste copper-germanium alloy and the waste copper to ensure that the blended mixed metal comprises the following components in percentage by mass: the copper content is more than or equal to 95 percent, and the germanium and other elements are less than or equal to 5 percent;
2) casting: melting the mixed metal at 1150-1250 ℃, introducing the melt into an anode die, cooling to obtain an anode plate, and taking pure copper or a stainless steel plate to manufacture a cathode plate;
3) electrolysis: placing the manufactured anode plate and the manufactured cathode plate in a mixed electrolyte system of copper sulfate, dilute sulfuric acid and sodium chloride for electrolysis, wrapping the anode plate with a cloth bag to form a diaphragm, generating anode mud and cathode mud, and recovering the cathode mud to be pure copper; in the mixed electrolyte system, the electrolyte comprises the following components: CuSO 470-100 g/L and NaCl 40-60 g/L; controlling the pH value to be 2.5-4.5; the parameters of the electrolysis are as follows: the voltage of the cell is 1.8-2.8V, the current density is 180-; the standard of the electrolysis step is that cathode copper Cu is 99.0 percent, anode mud accounts for 4 to 8 percent of the total amount of the anode mud, germanium is enriched to 30 to 50 percent, and the enrichment multiple is 10 times;
4) chlorination distillation: co-distilling the anode mud obtained in the previous step and hydrochloric acid to generate germanium tetrachloride and residual liquid; the distillation conditions are that the anode mud and 8mol/L hydrochloric acid are distilled for 10 hours at the liquid-solid ratio of 5:1 and the temperature of 115 ℃, and the distillation residual liquid germanium is less than 0.1 g/L;
5) hydrolysis: hydrolyzing germanium tetrachloride, washing and filtering to obtain germanium hydroxide precipitate; the hydrolysis ratio is H2O to GeCl4 to 6.5 to 1; the rate of addition of water was <45 mL/min.
6) Drying and oxidizing: and drying the germanium hydroxide precipitate obtained in the previous step at the temperature of 130-140 ℃ for 12h, and recovering to obtain pure germanium dioxide.
The chemical formula of the hydrolysis drying oxidation is
GeCl4+4H2O＝Ge(OH)4+4HCl
Ge(OH)4＝GeO2+2H2O。
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material, which is characterized in that copper is electrolyzed in one step and produced by cathode copper to obtain a copper product, the enrichment multiple of anode mud germanium is high, the recovery rate is high, the operation environment is friendly, the recovery cost is low, the method is a clean copper-germanium alloy comprehensive recovery process, and meanwhile, the method has the characteristics of short flow, environmental protection, economy and strong operability, and is suitable for industrial application.
Drawings
FIG. 1 is a schematic flow chart of a method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
A method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material comprises the following steps:
1) blending: blending the waste copper-germanium alloy and the waste copper to ensure that the blended mixed metal comprises the following components in percentage by mass: copper content 95%, germanium and other elements equal to 5%;
2) casting: melting the mixed metal at 1150 ℃, introducing the melt into an anode die, cooling to obtain an anode plate, and taking pure copper or a stainless steel plate to manufacture a cathode plate;
3) electrolysis: placing the manufactured anode plate and the manufactured cathode plate in a mixed electrolyte system of copper sulfate, dilute sulfuric acid and sodium chloride for electrolysis, wrapping the anode plate with a cloth bag to form a diaphragm, generating anode mud and cathode mud, and recovering the cathode mud to be pure copper; in the mixed electrolyte system, the electrolyte comprises the following components: CuSO470g/L and 40g/L NaCl; controlling the pH value to be 2.5; the parameters of the electrolysis are as follows: the voltage of the cell is 1.8V, the current density is 180A/square meter, the polar distance is 20mm, the temperature is 30 ℃, and the electrolyte circulates; the standard of the electrolysis step is that the cathode copper Cu accounts for 99.2 percent, the anode mud accounts for 4 percent of the total amount of the anode mud, the germanium is enriched to 30 percent, and the enrichment multiple is 10 times;
4) chlorination distillation: co-distilling the anode mud obtained in the previous step and hydrochloric acid to generate germanium tetrachloride and residual liquid; the distillation conditions are that the anode mud and 8mol/L hydrochloric acid are distilled for 10 hours at the liquid-solid ratio of 5:1 and the temperature of 115 ℃, and the distillation residual liquid germanium is less than 0.1 g/L;
5) hydrolysis: hydrolyzing germanium tetrachloride, washing and filtering to obtain germanium hydroxide precipitate; the hydrolysis ratio is H2O to GeCl4 to 6.5 to 1; the rate of addition of water was <45 mL/min.
6) Drying and oxidizing: and drying the germanium hydroxide precipitate obtained in the previous step at 130 ℃ for 12h, and recovering to obtain pure germanium dioxide.
Example 2
A method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material is characterized by comprising the following steps:
1) blending: blending the waste copper-germanium alloy and the waste copper to ensure that the blended mixed metal comprises the following components in percentage by mass: copper content equal to 97%, germanium and other elements equal to 3%;
2) casting: melting the mixed metal at 1200 ℃, introducing the melt into an anode die, cooling to obtain an anode plate, and taking pure copper or a stainless steel plate to manufacture a cathode plate;
3) electrolysis: placing the manufactured anode plate and the manufactured cathode plate in a mixed electrolyte system of copper sulfate, dilute sulfuric acid and sodium chloride for electrolysis, wrapping the anode plate with a cloth bag to form a diaphragm, generating anode mud and cathode mud, and recovering the cathode mud to be pure copper; in the mixed electrolyte system, the electrolyte comprises the following components: CuSO485g/L and 50g/L NaCl; controlling the pH value to be 3.5; the parameters of the electrolysis are as follows: the voltage of the cell is 2.3V, the current density is 250A/square meter, the polar distance is 25mm, the temperature is 40 ℃, and the electrolyte circulates; the standard of the electrolysis step is that the cathode copper Cu is 99.5 percent, the anode mud accounts for 6 percent of the total amount of the anode mud, the germanium is enriched to 40 percent, and the enrichment multiple is 10 times;
4) chlorination distillation: co-distilling the anode mud obtained in the previous step and hydrochloric acid to generate germanium tetrachloride and residual liquid; the distillation conditions are that the anode mud and 8mol/L hydrochloric acid are distilled for 10 hours at the liquid-solid ratio of 5:1 and the temperature of 115 ℃, and the distillation residual liquid germanium is less than 0.1 g/L;
5) hydrolysis: hydrolyzing germanium tetrachloride, washing and filtering to obtain germanium hydroxide precipitate; the hydrolysis ratio is H2O to GeCl4 to 6.5 to 1; the rate of addition of water was <45 mL/min.
6) Drying and oxidizing: drying the germanium hydroxide precipitate obtained in the previous step at the temperature of 1135 ℃ for 12h, and recovering to obtain pure germanium dioxide.
Example 3
A method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material is characterized by comprising the following steps:
1) blending: blending the waste copper-germanium alloy and the waste copper to ensure that the blended mixed metal comprises the following components in percentage by mass: copper content equal to 96%, germanium and other elements equal to 4%;
2) casting: melting the mixed metal at 1250 ℃, introducing the melt into an anode die, cooling to obtain an anode plate, and taking pure copper or a stainless steel plate to manufacture a cathode plate;
3) electrolysis: placing the manufactured anode plate and the manufactured cathode plate in a mixed electrolyte system of copper sulfate, dilute sulfuric acid and sodium chloride for electrolysis, wrapping the anode plate with a cloth bag to form a diaphragm, generating anode mud and cathode mud, and recovering the cathode mud to be pure copper; in the mixed electrolyte system, the electrolyte comprises the following components: CuSO4100g/L and 60g/L NaCl; controlling the pH value to be 4.5; the parameters of the electrolysis are as follows: the voltage of the cell is 2.8V, the current density is 300A/square meter, the polar distance is 30mm, the temperature is 50 ℃, and the electrolyte circulates; the standard of the electrolysis step is that cathode copper Cu is 99.3%, anode mud accounts for 8% of the total amount of the anode mud, germanium is enriched to 50%, and the enrichment multiple is 10 times;
4) chlorination distillation: co-distilling the anode mud obtained in the previous step and hydrochloric acid to generate germanium tetrachloride and residual liquid; the distillation conditions are that the anode mud and 8mol/L hydrochloric acid are distilled for 10 hours at the liquid-solid ratio of 5:1 and the temperature of 115 ℃, and the distillation residual liquid germanium is less than 0.1 g/L;
5) hydrolysis: hydrolyzing germanium tetrachloride, washing and filtering to obtain germanium hydroxide precipitate; the hydrolysis ratio is H2O to GeCl4 to 6.5 to 1; the rate of addition of water was <45 mL/min.
6) Drying and oxidizing: and drying the germanium hydroxide precipitate obtained in the previous step at 140 ℃ for 12h, and recovering to obtain pure germanium dioxide.
Test example
The recovery and purity of the recovered germanium dioxide and copper were compared in the processes of examples 1, 2, 3 and the data are shown in table 1.
Table 1 comparative testing
| Example 1 | Example 2 | Example 3 | |
| Purity of germanium dioxide% | 98.9 | 99.5 | 99.3 |
| The recovery rate of germanium dioxide | 98.6 | 97.8 | 98.3 |
| Purity of copper% | 99.2 | 99.5 | 99.3 |
| Copper recovery rate% | 98.7 | 98.4 | 98.1 |
According to the data in the table 1, the process has high recovery rate and high purity of the recovered metal, and is worthy of great popularization.
The foregoing is only a preferred embodiment of the present invention. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material is characterized by comprising the following steps:
1) blending: blending the waste copper-germanium alloy and the waste copper to ensure that the blended mixed metal comprises the following components in percentage by mass: the copper content is more than or equal to 95 percent, and the germanium and other elements are less than or equal to 5 percent;
2) casting: melting the mixed metal at 1150-1250 ℃, introducing the melt into an anode die, cooling to obtain an anode plate, and taking pure copper or a stainless steel plate to manufacture a cathode plate;
3) electrolysis: placing the manufactured anode plate and the manufactured cathode plate in a mixed electrolyte system of copper sulfate, dilute sulfuric acid and sodium chloride for electrolysis to generate anode mud and cathode mud, and recovering the cathode mud to be pure copper;
4) chlorination distillation: co-distilling the anode mud obtained in the previous step and hydrochloric acid to generate germanium tetrachloride and residual liquid,
5) hydrolysis: hydrolyzing germanium tetrachloride, washing and filtering to obtain germanium hydroxide precipitate;
6) drying and oxidizing: and drying the germanium hydroxide precipitate obtained in the previous step at the temperature of 130-140 ℃ for 12h, and recovering to obtain pure germanium dioxide.
2. The method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material according to claim 1, wherein in the step 3 electrolysis step: and the anode plate is wrapped by a cloth bag to form a diaphragm.
3. The method for comprehensively recovering the copper-germanium alloy material according to claim 1, wherein in the step 3 electrolysis step: in the mixed electrolyte system, the electrolyte comprises the following components: CuSO 470-100 g/L and NaCl 40-60 g/L; the pH is controlled to be 2.5-4.5.
4. The method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material according to claim 1, wherein in the step 3 electrolysis step: the parameters of the electrolysis are as follows: the voltage of the cell is 1.8-2.8V, the current density is 180 plus 300A/square meter, the pole distance is 20-30mm, the temperature is 30-50 ℃, and the electrolyte circulates.
5. The method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material according to claim 1, wherein in the step 3 electrolysis step: the standard of the electrolysis step is that cathode copper Cu is 99.0 percent, anode mud accounts for 4 to 8 percent of the total amount of the anode mud, germanium is enriched to 30 to 50 percent, and the enrichment multiple is 10 times.
6. The method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material according to claim 1, wherein in the step 4, the chlorination distillation step: the distillation conditions are that the anode mud and 8mol/L hydrochloric acid are distilled for 10 hours at the liquid-solid ratio of 5:1 and the temperature of 115 ℃, and the distillation residual liquid germanium is less than 0.1 g/L.
7. The method for comprehensively recovering germanium dioxide and copper from copper-germanium alloy material according to claim 1, wherein in the hydrolysis step of the step 5, the hydrolysis proportion is H according to the mass ratio2O GeCl4 ═ 6.5: 1; rate of addition of water<45mL/min。
8. The method for comprehensively recovering germanium dioxide and copper from a copper-germanium alloy material as claimed in claim 1, characterized by comprising the following steps:
1) blending: blending the waste copper-germanium alloy and the waste copper to ensure that the blended mixed metal comprises the following components in percentage by mass: the copper content is more than or equal to 95 percent, and the germanium and other elements are less than or equal to 5 percent;
2) casting: melting the mixed metal at 1150-1250 ℃, introducing the melt into an anode die, cooling to obtain an anode plate, and taking pure copper or a stainless steel plate to manufacture a cathode plate;
3) electrolysis: placing the manufactured anode plate and the manufactured cathode plate in a mixed electrolyte system of copper sulfate, dilute sulfuric acid and sodium chloride for electrolysis, wrapping the anode plate with a cloth bag to form a diaphragm, generating anode mud and cathode mud, and recovering the cathode mud to be pure copper; in the mixed electrolyte system, the electrolyte comprises the following components: CuSO 470-100 g/L and NaCl 40-60 g/L; controlling the pH value to be 2.5-4.5; the parameters of the electrolysis are as follows: the voltage of the cell is 1.8-2.8V, the current density is 180-; the standard of the electrolysis step is that cathode copper Cu is 99.0 percent, anode mud accounts for 4 to 8 percent of the total amount of the anode mud, germanium is enriched to 30 to 50 percent, and the enrichment multiple is 10 times;
4) chlorination distillation: co-distilling the anode mud obtained in the previous step and hydrochloric acid to generate germanium tetrachloride and residual liquid; the distillation conditions are that the anode mud and 8mol/L hydrochloric acid are distilled for 10 hours at the liquid-solid ratio of 5:1 and the temperature of 115 ℃, and the distillation residual liquid germanium is less than 0.1 g/L;
5) hydrolysis: hydrolyzing germanium tetrachloride, washing and filtering to obtain germanium hydroxide precipitate; the hydrolysis ratio is H2O to GeCl4 to 6.5 to 1; the rate of addition of water was <45 mL/min.
6) Drying and oxidizing: and drying the germanium hydroxide precipitate obtained in the previous step at the temperature of 130-140 ℃ for 12h, and recovering to obtain pure germanium dioxide.
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| CN113337723A (en) * | 2021-06-10 | 2021-09-03 | 广东先导稀材股份有限公司 | Method for separating and extracting silver, palladium, copper and germanium from silver separating slag |
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