CN115261644A - Method for purifying germanium-containing material - Google Patents
Method for purifying germanium-containing material Download PDFInfo
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- CN115261644A CN115261644A CN202210984380.1A CN202210984380A CN115261644A CN 115261644 A CN115261644 A CN 115261644A CN 202210984380 A CN202210984380 A CN 202210984380A CN 115261644 A CN115261644 A CN 115261644A
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- germanium
- copper
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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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- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
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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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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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
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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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present disclosure provides a purification method of a germanium-containing material, which comprises the following steps: mixing a copper-zinc-germanium material and water; step two, heating the mixed material, and then adding concentrated sulfuric acid; step three, controlling the temperature of the solution, adding hydrogen peroxide, sampling and detecting the content of active metals, and performing filter pressing to obtain a filter cake which is germanium concentrate; step four, adding a ferric trichloride solution into the filtrate obtained in the step three, then adding liquid caustic soda to adjust the pH value, sampling the filtrate to detect the germanium content, performing filter pressing after the germanium content is qualified, wherein a filter cake is germanium concentrate, and the filtrate enters the step five; fifthly, extracting germanium from the filtrate, pumping the raffinate into a stirring tank, adding iron powder to precipitate copper, stirring, sampling, and performing filter pressing to obtain copper-precipitated liquid after the copper is qualified; and step six, pouring the copper-precipitated solution into a stirring tank, starting stirring and air draft, then adding liquid caustic soda or flake caustic soda, adjusting and stabilizing pH reaction, sampling, and performing filter pressing, wherein a filter cake is a zinc byproduct. The method provided by the disclosure is simple to operate, low in production cost and relatively thorough in germanium recovery.
Description
Technical Field
The invention relates to the technical field of wet metallurgy, in particular to a method for purifying a germanium-containing material.
Background
Germanium is a chemical element, the chemical symbol is Ge, has the dual properties of metal and nonmetal, is located in the IVA group in the fourth period in the periodic table of the chemical elements, is one of metals, and has very wide application. High purity germanium is a semiconductor material; the germanium single crystal doped with trace specific impurities can be used for manufacturing various transistors, rectifiers and other devices; germanium compounds are used in the manufacture of fluorescent panels and various high refractive index glasses. Germanium is a rare element in the earth crust, and most of coal, lead-zinc ores and iron ores contain trace germanium.
Germanium is present in the earth's crust in an amount of seven parts per million, which is less than the usual elements of oxygen, silicon, etc., but more than the elements of arsenic, uranium, mercury, iodine, silver, gold, etc. However, germanium is very dispersed and there is little if any relatively concentrated germanium mineral, and is therefore known as a "rare metal". The germanite is found to be thiogenitite (containing 5 to 7 percent of germanium), germanite (containing 10 percent of germanium) and pyrite-ferrogermanite (containing 7 percent of germanium). In addition, germanium is often mixed in a plurality of lead ores, copper ores, iron ores and silver ores, and even common coal generally contains about one hundred thousand of germanium, that is, about 10 grams of germanium is contained in one ton of coal on average. In ordinary earth, rock, and even spring water, it also contains trace amounts of germanium. Therefore, the purification of germanium is of great significance.
Disclosure of Invention
In view of the problems in the prior art, the present disclosure aims to provide a method for purifying a germanium-containing material.
In order to achieve the above object, the present disclosure provides a method for purifying a germanium-containing material, comprising the steps of: mixing a copper-zinc-germanium material and water; step two, heating the mixed material to 55-60 ℃, then adding concentrated sulfuric acid into the mixed material, and controlling the acidity of the solution to be 100-140g/L; step three, controlling the temperature of the solution to 50-60 ℃, then adding hydrogen peroxide, sampling and detecting the content of active metals, and performing filter pressing to obtain a filter cake which is germanium concentrate; step four, adding a ferric trichloride solution into the filtrate obtained in the step three, then adding liquid caustic soda to adjust the pH to be 4.5-4.8, sampling the filtrate to detect the germanium content, performing filter pressing after the filtrate is qualified, wherein a filter cake is germanium concentrate, and the filtrate enters the step five; fifthly, carrying out germanium extraction on the filtrate, pumping raffinate into a stirring tank, adding iron powder to precipitate copper, stirring, sampling, and carrying out filter pressing to obtain copper precipitation liquid after qualified; and step six, pouring the copper-precipitated solution into a stirring tank, starting stirring and air draft, then adding liquid caustic soda or flake caustic soda, adjusting and stabilizing the pH value to 8.5-9.0, reacting for 1-1.5h, sampling, and performing filter pressing, wherein a filter cake is a zinc byproduct.
In some embodiments, in step three, the amount of hydrogen peroxide added is: can completely convert the simple substance zinc into zinc oxide.
In some embodiments, in step four, the amount of ferric trichloride is 2-4 times the germanium content of the solution.
In some embodiments, in step four, the qualifying condition is: the pH is 4.5-4.8, and Ge is less than 800mg/L.
In some embodiments, in step five, the stirring time is 1-2h.
In some embodiments, in step five, acceptable conditions are less than 100ppm copper.
The beneficial effects of this disclosure are as follows:
the method for separating copper, zinc and germanium has the advantages of simple operation, low production cost and thorough germanium recovery, and is suitable for industrial production.
Detailed Description
The method of purifying a germanium-containing material according to the present disclosure is described in detail below.
The application discloses a method for purifying a germanium-containing material, which comprises the following steps: mixing a copper-zinc-germanium material and water; step two, heating the mixed material to 55-60 ℃, then adding concentrated sulfuric acid into the mixed material, and controlling the acidity of the solution to be 100-140g/L; step three, controlling the temperature of the solution to 50-60 ℃, then adding hydrogen peroxide, sampling and detecting the content of active metals, and performing filter pressing to obtain a filter cake which is germanium concentrate; step four, adding a ferric trichloride solution into the filtrate obtained in the step three, then adding liquid caustic soda to adjust the pH to be 4.5-4.8, sampling the filtrate to detect the germanium content, performing filter pressing after the filtrate is qualified, wherein a filter cake is germanium concentrate, and the filtrate enters the step five; step five, performing a germanium extraction process on the filtrate, pumping the raffinate into a stirring tank, adding iron powder to precipitate copper, stirring and sampling, and performing filter pressing to obtain a copper precipitation solution after the solution is qualified; and step six, pouring the copper-precipitated solution into a stirring tank, starting stirring and air draft, then adding liquid caustic soda or flake caustic soda, adjusting and stabilizing the pH value to 8.5-9.0, reacting for 1-1.5h, sampling, and performing filter pressing, wherein a filter cake is a zinc byproduct.
The method for separating copper, zinc and germanium is provided without carrying out pyrogenic treatment and directly carrying out wet process treatment.
In some embodiments, in step three, the amount of added hydrogen peroxide is: can completely convert the simple substance zinc into zinc oxide.
And in the third step, when adding hydrogen peroxide, avoiding the temperature of the solution in the leaching tank from being higher than 80 ℃, if the temperature reaches 80 ℃, stopping adding, cooling to 70 ℃, then continuing to add hydrogen peroxide, adding 800kg of hydrogen peroxide, sampling and detecting the solution, when the leaching rate of copper in the solution is more than 90% and the leaching solution of zinc is more than 90%, stopping adding hydrogen peroxide for reaction, sampling for active metal detection, performing pressure filtration when the solution is qualified to be detected, and if the solution is unqualified, continuing to add 30-60 kg of hydrogen peroxide, and sampling after the solution reacts for 2 hours until the active metal detection reaches the standard.
In some embodiments, in step four, the amount of ferric trichloride is 2-4 times the germanium content of the solution. The addition amount of ferric trichloride is too small to achieve the effect of coprecipitation with germanium, so that the germanium precipitation is incomplete.
In some embodiments, in step four, the qualifying condition is: the pH is 4.5-4.8, ge < 800ppm.
In some embodiments, in step five, the stirring time is 1-2h.
In some embodiments, in step five, an acceptable condition is less than 100ppm copper.
[ test ]
Example 1
Step one, mixing a copper-zinc material and water, wherein Ge:12.2%, cu:6.4%, zn:24.7%:
step two, heating the mixed material to 60 ℃, and then adding 2800kg of concentrated sulfuric acid into the mixed material at a speed of 100L/h;
step three, controlling the temperature of the solution to 60 ℃, then adding 1960kg of hydrogen peroxide at the speed of 100kg/h, sampling to detect the content of active metals, reacting with hydrochloric acid to generate hydrogen with the content not more than 5ppm, and performing filter pressing to obtain a filter cake which is germanium concentrate;
step four, adding 500kg of ferric trichloride solution into the filtrate obtained in the step three at the speed of 1000kg/h, then adding liquid caustic soda to adjust the pH value to be =4.8, sampling the filtrate to detect the germanium content, wherein the germanium content is 400ppm, performing filter pressing after the filtrate is qualified, wherein a filter cake is germanium concentrate, and enabling the filtrate to enter the step five;
step five, carrying out germanium extraction process on the filtrate, wherein the thickness of the filtrate is 25m 3 Pouring the raffinate into a stirring tank, adding 80kg of iron powder to precipitate copper, sampling and detecting after stirring until the copper is less than 100ppm, and performing filter pressing to obtain a copper precipitation solution after the copper precipitation solution is qualified;
step six, 25m 3 The copper-deposited solution is pumped into a stirring tank, stirring and air draft are started, then liquid caustic soda is added at the speed of 1000L/h, the pH is regulated and stabilized to be 9.0, reaction is carried out for 1.5h, sampling and filter pressing are carried out, and a filter cake is a zinc byproduct.
Three experiments were performed according to the above procedure, with the following experimental results:
the obtained germanium concentrate has the following grade 1 and copper and zinc contents:
| batches of | Water content% | Ge％ | Cu％ | Zn％ |
| 1 | 18.30％ | 6.02％ | 0.97％ | 1.72％ |
| 2 | 14.95％ | 5.15％ | 1.73％ | 0.88％ |
| 3 | 11.66％ | 6.81％ | 0.83％ | 0.96％ |
From the above table it can be seen that: the method of the invention controls the process conditions of each stage in the production process, so that the removal rate of copper and zinc reaches more than 95 percent, and the method can directly meet the downstream working procedures.
The above-disclosed features are not intended to limit the scope of practice of the present disclosure, and therefore, all equivalent variations that are described in the claims of the present disclosure are intended to be included within the scope of the claims of the present disclosure.
Claims (6)
1. A method of purifying a germanium-containing material, comprising the steps of:
mixing a copper-zinc-germanium material and water;
step two, heating the mixed material to 55-60 ℃, then adding concentrated sulfuric acid into the mixed material, and controlling the acidity of the solution to be 100-140g/L;
step three, controlling the temperature of the solution to 50-60 ℃, then adding hydrogen peroxide, sampling and detecting the content of active metals, and performing filter pressing to obtain a filter cake which is germanium concentrate;
step four, adding a ferric trichloride solution into the filtrate obtained in the step three, then adding liquid caustic soda to adjust the pH to be 4.5-4.8, sampling the filtrate to detect the germanium content, performing filter pressing after the filtrate is qualified, wherein a filter cake is germanium concentrate, and the filtrate enters the step five;
step five, performing a germanium extraction process on the filtrate, pumping the raffinate into a stirring tank, adding iron powder to precipitate copper, stirring and sampling, and performing filter pressing to obtain a copper precipitation solution after the solution is qualified;
and step six, pouring the copper-precipitated solution into a stirring tank, starting stirring and air draft, then adding liquid caustic soda or flake caustic soda, adjusting and stabilizing the pH value to 8.5-9.0, reacting for 1-1.5h, sampling, and performing filter pressing, wherein a filter cake is a zinc byproduct.
2. The method of claim 1, wherein the purification step of purifying the germanium-containing material,
in the third step, the amount of hydrogen peroxide added is as follows: can completely convert the simple substance zinc into zinc oxide.
3. The method of claim 1, wherein the purification step of purifying the germanium-containing material,
in the fourth step, the amount of the ferric trichloride is 2-4 times of the content of the germanium in the solution.
4. The method of purifying a germanium-containing material according to claim 1,
in step four, the qualified conditions are: the pH is 4.5-4.8, and Ge is less than 800mg/L.
5. The method of purifying a germanium-containing material according to claim 1,
in the fifth step, the stirring time is 1-2h.
6. The method of purifying a germanium-containing material according to claim 1,
in step five, an acceptable condition is that copper is less than 100ppm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210984380.1A CN115261644A (en) | 2022-08-16 | 2022-08-16 | Method for purifying germanium-containing material |
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| CN202210984380.1A CN115261644A (en) | 2022-08-16 | 2022-08-16 | Method for purifying germanium-containing material |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1238192A (en) * | 1984-12-21 | 1988-06-21 | Daniel W. Ashman | Method for the recovery of germanium |
| KR20030041841A (en) * | 2001-11-21 | 2003-05-27 | 쉬플리 캄파니, 엘.엘.씨. | A method for recovering catalytic metals |
| CN104818396A (en) * | 2015-05-19 | 2015-08-05 | 河北工程大学 | Technique for recovering germanium from electric furnace germanium slag |
| CN106834695A (en) * | 2017-01-14 | 2017-06-13 | 六盘水中联工贸实业有限公司 | A kind of method that germanium is extracted in the zinc replacement slag from smelting |
| CN112410584A (en) * | 2020-11-10 | 2021-02-26 | 广东先导稀材股份有限公司 | Method for recovering germanium from zinc leaching residues |
| CN112410570A (en) * | 2020-11-11 | 2021-02-26 | 广东先导稀材股份有限公司 | Method for recovering gallium and germanium from gallium and germanium material |
| CN112442606A (en) * | 2020-11-24 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for recovering germanium from germanium-containing copper-cobalt alloy |
-
2022
- 2022-08-16 CN CN202210984380.1A patent/CN115261644A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1238192A (en) * | 1984-12-21 | 1988-06-21 | Daniel W. Ashman | Method for the recovery of germanium |
| KR20030041841A (en) * | 2001-11-21 | 2003-05-27 | 쉬플리 캄파니, 엘.엘.씨. | A method for recovering catalytic metals |
| CN104818396A (en) * | 2015-05-19 | 2015-08-05 | 河北工程大学 | Technique for recovering germanium from electric furnace germanium slag |
| CN106834695A (en) * | 2017-01-14 | 2017-06-13 | 六盘水中联工贸实业有限公司 | A kind of method that germanium is extracted in the zinc replacement slag from smelting |
| CN112410584A (en) * | 2020-11-10 | 2021-02-26 | 广东先导稀材股份有限公司 | Method for recovering germanium from zinc leaching residues |
| CN112410570A (en) * | 2020-11-11 | 2021-02-26 | 广东先导稀材股份有限公司 | Method for recovering gallium and germanium from gallium and germanium material |
| CN112442606A (en) * | 2020-11-24 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for recovering germanium from germanium-containing copper-cobalt alloy |
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