CN115261626A - Method for recovering gallium from gallium-zinc-containing material under normal pressure - Google Patents

Method for recovering gallium from gallium-zinc-containing material under normal pressure Download PDF

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Publication number
CN115261626A
CN115261626A CN202210913816.8A CN202210913816A CN115261626A CN 115261626 A CN115261626 A CN 115261626A CN 202210913816 A CN202210913816 A CN 202210913816A CN 115261626 A CN115261626 A CN 115261626A
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China
Prior art keywords
gallium
zinc
filtrate
containing material
mixing
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CN202210913816.8A
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Chinese (zh)
Inventor
栾飞
彭永延
陈应红
罗桂添
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First Rare Materials Co Ltd
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First Rare Materials Co Ltd
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Priority to CN202210913816.8A priority Critical patent/CN115261626A/en
Publication of CN115261626A publication Critical patent/CN115261626A/en
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Classifications

    • 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
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • 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
    • C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
    • 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
    • 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
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
    • 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 invention provides a method for recovering gallium metal from gallium-zinc-containing materials under normal pressure, which comprises the following steps: firstly, slurrying a gallium-zinc-containing material with water to form a slurried material; adjusting the internal alkalinity of the slurry, heating, carrying out heat preservation stirring reaction, and then carrying out solid-liquid separation; step three, adding sulfuric acid or hydrochloric acid solution into the filtrate generated in the step two, controlling the pH value, and carrying out solid-liquid separation; step four, adding a sulfuric acid or hydrochloric acid solution into the filtrate obtained in the step two, controlling the pH value, and carrying out solid-liquid separation; step five, adding sodium hydroxide into tap water to prepare washing liquid, heating the washing liquid, mixing and washing the filter cake obtained in the step three with the washing liquid, and filtering; mixing the washed filter cake with water, adjusting alkalinity, heating and stirring for reaction, and performing solid-liquid separation; and step seven, transferring the filtrate into electrolysis equipment for electrolysis. The method has simple process flow and uses less chemical reagents.

Description

Method for recovering gallium from gallium-zinc-containing material under normal pressure
Technical Field
The invention relates to the field of hydrometallurgy recovery, in particular to a method for recovering metal gallium from gallium and zinc containing materials under normal pressure.
Background
With the development scale of industries such as LED, integrated circuit, laser and solar battery, etc. becoming ever larger, the demand of the society for gallium metal is increasing day by day. The storage amount of primary gallium ore in natural resources is small, and how to effectively recycle gallium from gallium-containing slag generated by smelting zinc and aluminum in aluminum and zinc ore is a focus of attention of people. Most of the existing methods for extracting gallium from gallium-containing zinc materials adopt acid liquor leaching, then impurity removal and extraction are carried out, and then metal gallium is further recovered.
Disclosure of Invention
In view of the problems in the prior art, the present disclosure is directed to a method for recovering gallium metal from gallium-zinc-containing materials at normal pressure.
In order to achieve the above object, the present disclosure provides a method for recovering gallium metal from gallium-zinc-containing material under normal pressure, which comprises the following steps: mixing a gallium and zinc-containing material and water according to the mass ratio of 1: 4-1: 5 to prepare slurry, and forming slurry; adding sodium hydroxide into the slurried material to adjust the alkalinity of the system to be 100-120 g/L, heating, carrying out heat preservation stirring reaction, and then carrying out solid-liquid separation to obtain a No. 1 filtrate and a No. 1 filter cake; step three, adding sulfuric acid or hydrochloric acid solution into the filtrate 1# generated in the step two, controlling the pH value to be 12-12.5, and performing solid-liquid separation to obtain filtrate 2# and filter cake 2 #; step four, adding sulfuric acid or hydrochloric acid solution into the No. 2 filtrate, controlling the pH to be 8-9, and obtaining No. 3 filtrate and No. 3 filter cake through solid-liquid separation; adding sodium hydroxide into tap water, adjusting the pH value to 8-9 to prepare washing liquid, heating the temperature of the washing liquid to 40-50 ℃, mixing and washing the No. 3 filter cake and the washing liquid according to the mixing mass ratio of 1: 4-1: 5, and filtering; mixing the washed 3# filter cake with water according to the mass ratio of 1: 4-1: 5, then adding sodium hydroxide to adjust the alkalinity to 100-160 g/L, heating and stirring for reaction, and carrying out solid-liquid separation to obtain 4# filtrate; and step seven, transferring the filtrate No. 4 to an electrolysis device for electrolysis.
In some embodiments, in step two, the added sodium hydroxide is selected from at least one of a solid or a liquid.
In some embodiments, in the second step, the temperature is raised to 80-90 ℃, and the reaction is carried out for 1-4 hours under the condition of heat preservation and stirring.
In some embodiments, in step five, wash is for 2 to 4 hours.
In some embodiments, in the sixth step, the temperature is raised to 30-70 ℃, and the stirring reaction time is 2-4 h.
In some embodiments, in step seven, the 4# filtrate temperature is controlled to be 30-60 ℃.
In some embodiments, in step seven, the current density of the electrolysis apparatus is controlled to be 700 to 1000A/m2。
The beneficial effects of this disclosure are as follows:
the method has the advantages of simple process flow, less used chemical reagents, higher zinc content of the zinc hydroxide byproduct generated in the recovery process, and convenience for smelting and recovering zinc.
Detailed Description
The process for recovering gallium metal from a gallium and zinc containing material at atmospheric pressure according to the present disclosure is described in detail below.
The application discloses a method for recovering metal gallium from gallium-zinc-containing materials under normal pressure, which comprises the following steps: mixing a gallium-zinc-containing material and water according to a mass ratio of 1: 4-1: 5 to prepare slurry, and forming slurry; adding sodium hydroxide into the slurried material to adjust the alkalinity of the system to be 100-120 g/L, heating, carrying out heat preservation stirring reaction, and then carrying out solid-liquid separation to obtain a No. 1 filtrate and a No. 1 filter cake; step three, adding sulfuric acid or hydrochloric acid solution into the No. 1 filtrate generated in the step two, controlling the pH value to be 12-12.5, and performing solid-liquid separation to obtain No. 2 filtrate and No. 2 filter cake; step four, adding sulfuric acid or hydrochloric acid solution into the No. 2 filtrate, controlling the pH to be 8-9, and obtaining No. 3 filtrate and No. 3 filter cake through solid-liquid separation; adding sodium hydroxide into tap water, adjusting the pH value to 8-9 to prepare washing liquid, heating the temperature of the washing liquid to 40-50 ℃, mixing and washing the No. 3 filter cake and the washing liquid according to the mixing mass ratio of 1: 4-1: 5, and filtering; mixing the washed 3# filter cake with water according to the mass ratio of 1: 4-1: 5, then adding sodium hydroxide to adjust the alkalinity to 100-160 g/L, heating and stirring for reaction, and carrying out solid-liquid separation to obtain 4# filtrate; and step seven, transferring the filtrate No. 4 to an electrolysis device for electrolysis.
According to the method, alkaline liquor leaching is carried out on the gallium-zinc-containing material, so that amphoteric compounds of gallium and zinc in the material are precipitated and dissolved in the solution, precipitates of other non-amphoteric compounds (such as hydroxides of iron, copper and the like) are continuously left in slag, separation of gallium and zinc from other substances is realized, then the separation of gallium and zinc is realized by adjusting the pH of the solution step by utilizing the difference of the precipitation pH of gallium hydroxide and zinc hydroxide, and finally metal gallium is produced through electrolysis.
In some embodiments, in step two, the added sodium hydroxide is selected from at least one of a solid or a liquid.
In some embodiments, in the second step, the temperature is raised to 80-90 ℃, and the reaction is carried out for 1-4 hours under the condition of heat preservation and stirring.
In the third step, after adjusting the pH, zinc ions in the filtrate No. 1 precipitate in the form of zinc hydroxide, and gallium ions in the leachate continue to remain in solution.
In step three, the 2# filter cake is a zinc hydroxide byproduct.
In step three, the reaction equation involved is: zn2++2OH-＝Zn(OH)2。
In step four, the gallium ions in the filtrate # 2 after pH adjustment will precipitate as gallium hydroxide, and other impurity ions will remain in solution.
In step four, the # 3 filter cake is gallium hydroxide.
In step four, the reaction equation involved is: ga3++3OH-＝Ga(OH)3。
In some embodiments, in step five, wash is for 2 to 4 hours.
In step five, the sulfate or chlorate in the 3# filter cake after washing and filtering is washed clean.
In some embodiments, in the sixth step, the temperature is raised to 30-70 ℃, and the stirring reaction time is 2-4 h.
In some embodiments, in step seven, the filtrate temperature of # 4 is controlled to be 30-60 ℃.
In some embodiments, in step seven, the current density of the electrolysis apparatus is controlled to be 700 to 1000A/m2。
[ test ]
Example 1
Mixing a gallium and zinc-containing material and water according to the mass ratio of 1:5 to prepare slurry, and forming slurry;
the gallium-zinc-containing material used had the following composition:
element(s) Ga Zn Cu Al Moisture content
Content/%) 5.6 11.5 0.8 4.3 45
Adding sodium hydroxide into the slurry to adjust the alkalinity of the system to be 100g/L, heating to 85 ℃, keeping the temperature, stirring and reacting for 3 hours, and then carrying out solid-liquid separation to obtain a No. 1 filtrate and a No. 1 filter cake;
the content of main impurities in the filtrate No. 1 is as follows:
element(s) Ga Zn Cu Al
Content/ppm 8445 11200 85 3249
Step three, adding sulfuric acid into the filtrate 1# generated in the step two, controlling the pH value to be 12, and performing solid-liquid separation to obtain filtrate 2# and a filter cake 2 #;
the Ga and Zn contents of the No. 2 filtrate are as follows:
element(s) Ga Zn
Content/ppm 7872 13
The precipitation rate of zinc in the third step: 99 percent; the loss of gallium was 7%.
Step four, adding a sulfuric acid solution into the filtrate No. 2, controlling the pH to be 8.5, and performing solid-liquid separation to obtain a filtrate No. 3 and a filter cake No. 3;
the contents of Ga and Zn in the filtrate No. 3 are as follows
Element(s) Ga Zn
Content/ppm 142 7
The precipitation rate of gallium in step 4 was 98%.
Step five, adding sodium hydroxide into tap water, adjusting the pH value to 8.5 to prepare washing liquid, heating the temperature of the washing liquid to 45 ℃, mixing and washing the No. 3 filter cake and the washing liquid according to the mixing mass ratio of 1:5 for 2 hours, and filtering;
step six, mixing the washed 3# filter cake with water according to the mass ratio of 1:4, then adding sodium hydroxide to adjust the alkalinity to 120g/L, heating to 65 ℃, stirring for reaction for 3 hours, and carrying out solid-liquid separation to obtain 4# filtrate;
step seven, transferring the 4# filtrate into electrolytic equipment, controlling the temperature of the 4# filtrate to be 40 ℃ and the current density to be 1000A/m2And electrolyzing to obtain the metal gallium.
The main impurity content of gallium metal is as follows:
element(s) Fe Cu Pb In Sn Bi
Content/ppm ＜1 ＜3 ＜3 ＜1 ＜3 ＜3
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 (7)

1. A method for recovering metal gallium from gallium-zinc-containing materials under normal pressure comprises the following steps:
mixing a gallium-zinc-containing material and water according to a mass ratio of 1: 4-1: 5 to prepare slurry, and forming slurry;
adding sodium hydroxide into the slurried material to adjust the alkalinity of the system to be 100-120 g/L, heating, carrying out heat preservation stirring reaction, and then carrying out solid-liquid separation to obtain a No. 1 filtrate and a No. 1 filter cake;
step three, adding sulfuric acid or hydrochloric acid solution into the No. 1 filtrate generated in the step two, controlling the pH value to be 12-12.5, and performing solid-liquid separation to obtain No. 2 filtrate and No. 2 filter cake;
step four, adding sulfuric acid or hydrochloric acid solution into the No. 2 filtrate, controlling the pH to be 8-9, and obtaining No. 3 filtrate and No. 3 filter cake through solid-liquid separation;
step five, adding sodium hydroxide into tap water, adjusting the pH value to 8-9 to prepare washing liquid, heating the temperature of the washing liquid to 40-50 ℃, mixing the No. 3 filter cake and the washing liquid according to the mixing mass ratio of 1: 4-1: 5, mixing, washing and filtering;
step six, mixing the washed 3# filter cake and water according to the mass ratio of 1:4 to 1:5, mixing, adding sodium hydroxide to adjust the alkalinity to be 100-160 g/L, heating and stirring for reaction, and carrying out solid-liquid separation to obtain No. 4 filtrate;
and step seven, transferring the filtrate No. 4 to an electrolysis device for electrolysis.
2. The method for recovering metallic gallium from gallium and zinc-containing material under atmospheric pressure according to claim 1,
in the second step, the added sodium hydroxide is selected from at least one of solid or liquid.
3. The method for recovering metallic gallium from gallium and zinc-containing material under atmospheric pressure according to claim 1,
in the second step, the temperature is raised to 80-90 ℃, and the reaction is carried out for 1-4 h under the condition of heat preservation and stirring.
4. The method for recovering metallic gallium from gallium and zinc-containing material under atmospheric pressure according to claim 1,
and in the fifth step, washing for 2-4 h.
5. The method for recovering metallic gallium from gallium and zinc-containing material under atmospheric pressure according to claim 1,
in the sixth step, the temperature is raised to 30-70 ℃, and the stirring reaction time is 2-4 h.
6. The method for recovering metallic gallium from gallium and zinc-containing material under atmospheric pressure according to claim 1,
in the seventh step, the temperature of the 4# filtrate is controlled to be 30-60 ℃.
7. The method for recovering metallic gallium from gallium and zinc-containing material under atmospheric pressure according to claim 1,
in the seventh step, the current density of the electrolysis device is controlled to be 700-1000A/m2。
CN202210913816.8A 2022-07-29 2022-07-29 Method for recovering gallium from gallium-zinc-containing material under normal pressure Pending CN115261626A (en)

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CN202210913816.8A CN115261626A (en) 2022-07-29 2022-07-29 Method for recovering gallium from gallium-zinc-containing material under normal pressure

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012193396A (en) * 2011-03-15 2012-10-11 Mitsui Mining & Smelting Co Ltd Method for producing metallic gallium
JP2014214358A (en) * 2013-04-26 2014-11-17 アサヒプリテック株式会社 Method of separating gallium from zinc
CN104745841A (en) * 2015-04-10 2015-07-01 平顶山博迈特科技有限公司 Method for extracting metal gallium from coal ash
WO2017078315A1 (en) * 2015-11-03 2017-05-11 (주)코리아테크노브레인 Method for recovering valuable metals from valuable metal-containing target waste
CN108467942A (en) * 2018-02-13 2018-08-31 武汉科技大学 A method of Selectively leaching zinc, lead, gallium and germanium from zinc replacement slag
CN109576510A (en) * 2019-01-02 2019-04-05 建水正业矿冶有限公司 The method of gallium is recycled from zinc replacement slag

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012193396A (en) * 2011-03-15 2012-10-11 Mitsui Mining & Smelting Co Ltd Method for producing metallic gallium
JP2014214358A (en) * 2013-04-26 2014-11-17 アサヒプリテック株式会社 Method of separating gallium from zinc
CN104745841A (en) * 2015-04-10 2015-07-01 平顶山博迈特科技有限公司 Method for extracting metal gallium from coal ash
WO2017078315A1 (en) * 2015-11-03 2017-05-11 (주)코리아테크노브레인 Method for recovering valuable metals from valuable metal-containing target waste
CN108467942A (en) * 2018-02-13 2018-08-31 武汉科技大学 A method of Selectively leaching zinc, lead, gallium and germanium from zinc replacement slag
CN109576510A (en) * 2019-01-02 2019-04-05 建水正业矿冶有限公司 The method of gallium is recycled from zinc replacement slag

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