CN115261645A - Method for purifying gallium-containing material - Google Patents
Method for purifying gallium-containing material Download PDFInfo
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- CN115261645A CN115261645A CN202210888047.0A CN202210888047A CN115261645A CN 115261645 A CN115261645 A CN 115261645A CN 202210888047 A CN202210888047 A CN 202210888047A CN 115261645 A CN115261645 A CN 115261645A
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- gallium
- caustic soda
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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
- C22B58/00—Obtaining gallium or indium
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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
- C22B3/44—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
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Abstract
The present disclosure provides a method for purifying a gallium-containing material, comprising the steps of: step one, adding water into a ground gallium-silicon material, stirring, and then adjusting the pH value with sulfuric acid; step two, stirring, heating, leaching, carrying out heat preservation reaction, sampling and detecting the contents of Ga and Si in the solution, comparing the contents of Ga and Si in the input materials according to the detection result, and calculating the leaching rate of Ga metal and whether Si is leached or not; step three, after the reaction is completed, cooling, filtering, sampling filter residues, analyzing the contents of Ga and Si, and determining the comprehensive recovery rate of Ga metal; and step four, adding liquid caustic soda or caustic soda flakes into the filtrate, controlling the adding speed, controlling the temperature, adjusting the pH value, keeping the pH value in the range for 2 hours, cooling, performing filter pressing, wherein the filter cake is a gallium product, sampling the filter cake to analyze Ga, and detecting the content of Ga to facilitate the purification treatment of the next procedure. The method disclosed by the invention can effectively separate impurity silicon to obtain crude gallium hydroxide, reduce the subsequent treatment difficulty of recovered finished product gallium metal and improve the product quality.
Description
Technical Field
The invention relates to the technical field of wet metallurgy, in particular to a method for purifying gallium-containing materials.
Background
Gallium is a chemical element, the chemical symbol is Ga, is located in the fourth period group III a in the periodic table of chemical elements, has a very wide application, and can be applied to various fields such as metallurgy, optical glass, vacuum tubes, semiconductors, and the like. In nature, gallium often coexists with minerals of aluminum, zinc, and germanium as trace elements. The earth crust abundance of gallium is 15 multiplied by 10-6The earth crust content is 1 to 2 orders of magnitude higher than that of other dispersed elements, and the bauxite and the sphalerite also haveContains a small amount of gallium.
At present, no independent gallium deposit is found in China. In addition, the currently known gallium-rich deposit has a general enrichment factor of about 4 to 5, and only in sphalerite and germanite of a few deposits, the enrichment factor can be as high as about 330, which is not comparable to the mineralization of other dispersed elements, so that it is necessary to explore a method for purifying gallium.
Disclosure of Invention
In view of the problems in the prior art, the present disclosure aims to provide a method for purifying gallium-containing materials.
In order to achieve the above object, the present disclosure provides a method for purifying a gallium-containing material, comprising the steps of: step one, adding water into the ground gallium-silicon material, stirring, and adjusting the pH value to be =0.3-0.5 by using sulfuric acid after uniformly stirring; step two, after the pH is adjusted, stirring, heating and leaching, carrying out heat preservation reaction on the gallium-silicon material, sampling and detecting the contents of Ga and Si in the solution, comparing the contents of Ga and Si in the input material according to the detection result, and calculating whether the leaching rate of Ga metal is more than 90% and whether Si is leached; step three, after the reaction is completed, cooling, filtering, sampling filter residue to analyze the contents of Ga and Si, determining the comprehensive recovery rate of Ga metal, and providing a basis for the secondary recovery of a Si-containing byproduct in the next step; and step four, adding liquid caustic soda or flake caustic soda into the filtrate, controlling the adding speed in the adding process, controlling the temperature to be 70-80 ℃, adjusting the pH to be 5.5-6.5, keeping the pH value in the range for 2h, cooling to 60-65 ℃, and then performing filter pressing, wherein the filter cake is a gallium product, the filter cake is sampled to analyze Ga, the detection of the Ga content is convenient for the purification treatment of the next procedure, and the detection of the Ga content in the filtrate provides a basis for the next sewage treatment.
In some embodiments, in step two, the heating temperature is 70-80 ℃.
In some embodiments, in step two, the incubation time is between 3 and 4 hours.
In some embodiments, in step three, the temperature is reduced to 60-65 ℃.
In some embodiments, in step four, the rate of addition of caustic soda is controlled to be 15 to 20L/min if caustic soda is added and 4 to 6kg/min if caustic soda is added.
The beneficial effects of this disclosure are as follows:
the method disclosed by the invention can effectively separate impurity silicon to obtain crude gallium hydroxide, reduce the subsequent treatment difficulty of recovered finished product gallium metal, and improve the product quality.
Detailed Description
The process for purifying a gallium-containing material according to the present disclosure is described in detail below.
The application discloses a method for purifying a gallium-containing material, which comprises the following steps: step one, adding water into the ground gallium-silicon material, stirring, and adjusting the pH value to be =0.3-0.5 by using sulfuric acid after uniformly stirring; step two, after the pH value is adjusted, stirring, heating and leaching, carrying out heat preservation reaction on the gallium-silicon material, sampling and detecting the contents of Ga and Si in the solution, comparing the contents of Ga and Si in the input material according to the detection result, and calculating whether the leaching rate of Ga metal is more than 90% and whether Si is leached; step three, after the reaction is completed, cooling, filtering, sampling filter residue to analyze the contents of Ga and Si, determining the comprehensive recovery rate of Ga metal, and providing a basis for the secondary recovery of a Si-containing byproduct in the next step; and step four, adding liquid caustic soda or flake caustic soda into the filtrate, controlling the adding speed in the adding process, controlling the temperature to be 70-80 ℃, adjusting the pH to be 5.5-6.5, keeping the pH value in the range for 2h, cooling to 60-65 ℃, and then performing filter pressing, wherein the filter cake is a gallium product, the filter cake is sampled to analyze Ga, the detection of the Ga content is convenient for the purification treatment of the next procedure, and the detection of the Ga content in the filtrate provides a basis for the next sewage treatment.
In some embodiments, in step two, the heating temperature is 70-80 ℃. The temperature of 70-80 ℃ is a proper reaction temperature, the leaching is incomplete when the temperature is too low, the evaporation is too fast when the temperature is too high, the solid-liquid ratio is unbalanced, and the energy waste is caused.
In some embodiments, in step two, the incubation time is 3-4h.
In some embodiments, in step three, the temperature is reduced to 60-65 ℃.
In step three, the conditions after the reaction is completed are as follows: the leaching rate of Ga metal is more than 90 percent.
In some embodiments, in step four, the rate of addition of caustic soda is controlled to be 15 to 20L/min if caustic soda is added and 4 to 6kg/min if caustic soda is added. The reaction process is acid-base neutralization reaction, and the solution can react violently in the stirring tank due to the excessively high adding speed, so that the temperature rises sharply, the solution is splashed or overflows, and personnel injury can be caused; too slow of an addition rate may cause waste of labor cost and waste of electric energy.
[ test ]
Example 1
The crude gallium hydroxide is obtained by industrially treating one of the following grades, wherein Ga:0.75%, si:22.4 percent, extracting gallium from the silicon-gallium material and separating silicon from gallium.
Step one, adding water 25m into milled 4000kg of gallium-silicon material3Stirring, and after stirring uniformly, adjusting the pH value to be =0.4 by using sulfuric acid;
step two, after the pH is adjusted, stirring and heating to 75 ℃ for leaching, keeping the temperature of the gallium-silicon material for reaction for 3 hours, sampling and detecting the contents of Ga and Si in the solution: amount of Ga metal in charged materials: 4000 × 96% (moisture 4%) 0.75% =28.8kg, content of gallium in the assay detection solution: 1.20g/L solution volume 23m3=27.6kg, extraction rate: 27.6/28.8=95.83%, si:25ppm, no leaching, and judging complete reaction according to a detection result;
step three, cooling to 60 ℃, filtering, sampling filter residues, analyzing the contents of Ga and Si, and determining the comprehensive recovery rate of Ga metal: 5500kg of slag charge is produced, and the slag charge is sampled and analyzed: h2O:63.16%, si:24.9%, ga:470ppm and 0.96kg of Ga content, thereby meeting the requirement of recovery rate;
and step four, slowly adding 32% of industrial-grade liquid caustic soda into the reaction tank, stopping adding the liquid caustic soda until the pH of the solution is =5.5-6.5, controlling the temperature to be 75 ℃, keeping the pH value in the range for 2 hours, controlling Ga to be less than or equal to 10ppm, cooling to 60 ℃, performing pressure filtration, wherein a filter cake is a gallium product, sampling the filter cake to analyze Ga, detecting the Ga content to facilitate purification treatment of the next procedure, and detecting the Ga content in filtrate to provide a basis for sewage treatment of the next procedure.
Three batches of product processing were performed according to this procedure.
Obtaining a gallium product test result:
from the above table it can be seen that: the method of the invention effectively separates gallium and silicon by controlling the process conditions of each stage in the production process, the removal rate of silicon reaches more than 99.8 percent, and the method can directly meet the downstream gallium electrolysis process.
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 (5)
1. A method for purifying a gallium-containing material, comprising the steps of:
step one, adding water into a ground gallium-silicon material, stirring, and adjusting the pH to be =0.3-0.5 by using sulfuric acid after uniformly stirring;
step two, after the pH is adjusted, stirring, heating and leaching, carrying out heat preservation reaction on the gallium-silicon material, sampling and detecting the contents of Ga and Si in the solution, comparing the contents of Ga and Si in the input material according to the detection result, and calculating whether the leaching rate of Ga metal is more than 90% and whether Si is leached;
step three, after the reaction is completed, cooling, filtering, sampling filter residues, analyzing the contents of Ga and Si, determining the comprehensive recovery rate of Ga metal, and providing a basis for secondary recovery of a Si-containing byproduct in the next step;
and step four, adding liquid caustic soda or flake caustic soda into the filtrate, controlling the adding speed in the adding process, controlling the temperature to be 70-80 ℃, adjusting the pH to be 5.5-6.5, keeping the pH value in the range for 2h, cooling to 60-65 ℃, and then performing filter pressing, wherein the filter cake is a gallium product, the filter cake is sampled to analyze Ga, the detection of the Ga content is convenient for the purification treatment of the next procedure, and the detection of the Ga content in the filtrate provides a basis for the next sewage treatment.
2. The method of purifying a gallium-containing material according to claim 1,
in the second step, the heating temperature is 70-80 ℃.
3. The method of purifying a gallium-containing material according to claim 1,
in the second step, the reaction time is kept for 3-4h.
4. The method of claim 1, wherein the purification step further comprises,
in the third step, the temperature is reduced to 60-65 ℃.
5. The method of purifying a gallium-containing material according to claim 1,
in the fourth step, if liquid caustic soda is added, the adding speed of the liquid caustic soda is controlled to be 15-20L/min, and if flake caustic soda is added, the adding speed of the flake caustic soda is controlled to be 4-6kg/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210888047.0A CN115261645A (en) | 2022-07-25 | 2022-07-25 | Method for purifying gallium-containing material |
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| CN202210888047.0A CN115261645A (en) | 2022-07-25 | 2022-07-25 | Method for purifying gallium-containing material |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186279A (en) * | 2007-12-24 | 2008-05-28 | 黄昌海 | Reclamation of sodium sulfide from NaGaO2 solution |
| CN101255502A (en) * | 2008-04-02 | 2008-09-03 | 河南豫光金铅股份有限公司 | Process for comprehensive recovery of indium, cadmium, thallium and zinc from lead system smoke |
| CN102618719A (en) * | 2012-04-17 | 2012-08-01 | 长沙有色冶金设计研究院有限公司 | Method for directly leaching zinc and recovering gallium, germanium and indium from zinc sulfide concentrate |
| CN102925682A (en) * | 2012-11-19 | 2013-02-13 | 河北工程大学 | Method for extracting gallium-combined aluminium hydroxide from gallium-containing porcelain clay |
| US20140065037A1 (en) * | 2010-11-26 | 2014-03-06 | Molycorp Minerals Canada Ulc | Treatment of indium gallium alloys and recovery of indium and gallium |
| CN108004409A (en) * | 2017-12-15 | 2018-05-08 | 清远先导材料有限公司 | The separation and recovery method of gallium in a kind of GaAs sludge |
| 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 |
-
2022
- 2022-07-25 CN CN202210888047.0A patent/CN115261645A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186279A (en) * | 2007-12-24 | 2008-05-28 | 黄昌海 | Reclamation of sodium sulfide from NaGaO2 solution |
| CN101255502A (en) * | 2008-04-02 | 2008-09-03 | 河南豫光金铅股份有限公司 | Process for comprehensive recovery of indium, cadmium, thallium and zinc from lead system smoke |
| US20140065037A1 (en) * | 2010-11-26 | 2014-03-06 | Molycorp Minerals Canada Ulc | Treatment of indium gallium alloys and recovery of indium and gallium |
| CN102618719A (en) * | 2012-04-17 | 2012-08-01 | 长沙有色冶金设计研究院有限公司 | Method for directly leaching zinc and recovering gallium, germanium and indium from zinc sulfide concentrate |
| CN102925682A (en) * | 2012-11-19 | 2013-02-13 | 河北工程大学 | Method for extracting gallium-combined aluminium hydroxide from gallium-containing porcelain clay |
| CN108004409A (en) * | 2017-12-15 | 2018-05-08 | 清远先导材料有限公司 | The separation and recovery method of gallium in a kind of GaAs sludge |
| 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 |
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