CN108300877A - The method of gallium germanium indium in extraction and recovery zinc replacement slag leachate - Google Patents
The method of gallium germanium indium in extraction and recovery zinc replacement slag leachate Download PDFInfo
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- CN108300877A CN108300877A CN201711469342.8A CN201711469342A CN108300877A CN 108300877 A CN108300877 A CN 108300877A CN 201711469342 A CN201711469342 A CN 201711469342A CN 108300877 A CN108300877 A CN 108300877A
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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
- C22B3/20—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
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
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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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- 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 invention relates to a kind of methods of gallium germanium indium in extraction and recovery zinc replacement slag leachate, the described method comprises the following steps：(1) it neutralizes, restore：Neutralizer to pH value is added in zinc replacement slag leachate and reaches 1.5 1.8, reducing agent is then added and is reacted, the content of ferric ion (Fe3+) is less than 1g/L in solution after control reaction；(2) it extracts：Use the solution obtained by extractant, synergic reagent and diluent hybrid extraction step (1)；(3) sulfuric acid is used to be stripped gallium；(4) hydrochloric acid is used to be stripped indium；(5) fluoride aqueous solution is used to be stripped germanium；(6) acidification regeneration：Acidification regeneration treatment is carried out to the organic phase of step (5) extraction gained using sulfuric acid, the organic phase return to step (2) after regeneration is for extracting.The method of gallium germanium indium has the advantages that recovery of extraction is high, simple for process, at low cost in extraction and recovery zinc replacement slag leachate of the present invention.
Description
Technical field
The present invention relates to technical field of wet metallurgy, more particularly to gallium germanium in a kind of extraction and recovery zinc replacement slag leachate
The method of indium.
Background technology
Zinc concentrate passes through oxygen leaching, and zinc and associated metal therein enter in leachate, adds zinc dust precipitation, make
Associated valuable metals precipitation enrichment, forms the zinc replacement slag with high added value.Zinc replacement slag generally be rich in valuable metal gallium,
Germanium, indium, zinc, iron etc., also contain free silica.Zinc replacement slag needs further acidleach to extract valuable metal, especially
Gallium germanium indium therein is extracted, the solution of zinc replacement slag gained after acidleach, filtering is zinc replacement slag leachate.
Currently, the method for comprehensively recovering valuable metal in zinc abstraction technique is mainly at pyrogenic attack technique and wet method
Science and engineering skill.Valuable element in zinc replacement slag is volatized into cigarette ash by pyrogenic attack technique through high temperature, then is soaked cigarette ash with acid
Go out, which has the drawbacks such as energy consumption is big, discharge gas is seriously polluted.Wet processing process mostly uses molten to being rich in valuable metal
The method of liquid fractional extraction will carry out neutralization separation after often walking a kind of valuable metal of extraction, and the technological operation is cumbersome, metal damage
Mistake rate is high, and extraction system is more, greatly increases production cost.
Invention content
Based on this, the object of the present invention is to provide a kind of method of gallium germanium indium in extraction and recovery zinc replacement slag leachate,
It has the advantages that recovery of extraction is high, simple for process, at low cost.
The present invention takes technical solution as follows：
The method of gallium germanium indium, includes the following steps in a kind of extraction and recovery zinc replacement slag leachate：
(1) it neutralizes, restore：Neutralizer to pH value is added in zinc replacement slag leachate and reaches 1.5-1.8, is then added also
Former agent is reacted, ferric ion (Fe in solution after control reaction3+) content be less than 1g/L；
(2) it extracts：Use the solution obtained by extractant, synergic reagent and diluent hybrid extraction step (1)；
(3) it is stripped gallium：Use the organic phase of sulfuric acid extraction step (2) extraction gained；
(4) it is stripped indium：Use the organic phase of hydrochloric acid extraction step (3) extraction gained；
(5) it is stripped germanium：Use the organic phase of fluoride aqueous solution extraction step (4) extraction gained；
(6) acidification regeneration：Acidification regeneration treatment is carried out to the organic phase of step (5) extraction gained using sulfuric acid, after regeneration
Organic phase return to step (2) for extracting.
In the step of the method for the invention (1), first the zinc replacement slag leachate containing high concentrated acid is neutralized,
Make the control of its pH value in optimum range, is conducive to improve the effect subsequently extracted, reducing agent is added after neutralisation treatment by Fe3+Also
Originally it was Fe2+, avoid Fe3+It is entered in the extract liquor of step (2) with together with gallium germanium indium, to effectively improve the choosing to gallium germanium indium
Extraction yield is selected, the extraction yield of gallium in step (2), germanium, indium is made to reach 97% or more.Step (3) to (5) select different reagents according to
Ordered pair gallium, indium, germanium carry out substep back extraction, ensure often step back extraction in only single-element be transferred in strip liquor, effectively realize gallium,
The separation of three kinds of indium, germanium elements makes the back extraction ratio of gallium in step (3) reach 95% or more, and the back extraction ratio of indium reaches in step (4)
95%, the back extraction ratio of germanium reaches 99% or more in step (5).
Method of the present invention is using first neutralizing, restore, then coextraction gallium germanium indium, last substep back extraction gallium, indium, germanium
Process route, in being completed to leachate in an extracting system gallium germanium indium coextraction recycling and to extraction organic phase in
The substep back extraction separation of gallium germanium indium, extraction yield is high, and simple for process, and investment cost is low, and production cost is low.
Further, the zinc replacement slag leachate is the sulfuric acid leaching solution of zinc replacement slag.
Further, the neutralizer is any one or more mixing in zinc oxide, basic zinc carbonate, lime stone,
The reducing agent is any one or more mixing in reduced iron powder, sodium sulfite, sulfur dioxide.
Further, the extractant is phosphoric acid kind of extractants, the dosage volume of the extractant, synergic reagent and diluent
Than for 1-3:0.2-2:68-89.8.
Further, the extractant is di-(2-ethylhexyl)phosphoric acid ester (P204 extractants), 2- ethylhexyl phosphonic acids
Any one in single 2-ethyl hexyl ester (P507 extractants) or two kinds of mixing, the synergic reagent are C6-C9 alkyl hydroximic acids
In any one or more mixing (such as YW100 synergic reagents, 7815 synergic reagents, H106 synergic reagents, G315 synergic reagents, G8315 association
Extract agent etc.), the diluent is any one or two kinds in sulfonated kerosene (260# solvent naphthas), rosin (200# solvent naphthas)
Mixing.
Further, step (2) is specially：It is 1-3 according to the volume ratio of organic phase and water phase:1, extractant, association are extracted
Agent, diluent are mixed with the solution obtained by step (1), carry out 1-8 stage countercurrent extractions.
Further, step (3) is specially：It is 3-6 according to the volume ratio of organic phase and water phase:1, step (2) are extracted
The organic phase of gained is mixed with sulfuric acid, carries out 1-4 stage countercurrent extractions, a concentration of 1-3mol/L of sulfuric acid used.
Further, step (4) is specially：It is 3-6 according to the volume ratio of organic phase and water phase:1, step (3) are extracted
The organic phase and mixed in hydrochloric acid of gained carry out 1-4 stage countercurrent extractions, a concentration of 1-6mol/L of hydrochloric acid used.
Further, step (5) is specially：It is 3-6 according to the volume ratio of organic phase and water phase:1, step (4) are extracted
The organic phase of gained is mixed with fluoride aqueous solution, carries out 1-4 stage countercurrent extractions, and fluoride aqueous solution used is sodium fluoride, hydrogen
The aqueous solution of any one in fluoric acid, ammonium fluoride, potassium fluoride, a concentration of 1-6mol/L.
Further, in step (6), a concentration of 2mol/L of sulfuric acid used carries out 1-6 grades of acidification regeneration treatments.
Specific implementation mode
Embodiment one
Extraction and recovery gallium germanium indium is carried out to the sulfuric acid leaching solution of zinc replacement slag, gallium (Ga) contains in the zinc replacement slag leachate
Amount is 350mg/L, and germanium (Ge) content is 455mg/L, and indium (In) content is 57mg/L, and iron (Fe) content is 5.5g/L, zinc (Zn)
Content is 56g/L, sulfuric acid (H2SO4) content be 15g/L, be as follows：
(1) it neutralizes, restore：Zinc replacement slag leachate is added in stirred tank, stirring is opened, adds zinc oxide to pH value
Reach 1.6, reduced iron powder is then added and carries out reaction 1 hour, detects after reaction Fe in solution3+Content be 0.8g/L, will
Solution filtering is spare.
(2) it extracts：It is 20 according to dosage volume ratio:0.2:79.8, P207 extractants, YW100 synergic reagents and 260# is molten
Agent oil is mixed and made into mixed extractant, is then 1 according to organic phase and water phase volume ratio:1, by manufactured mixed extractant and step
Suddenly the solution obtained by (1) is added in mixed settler extractor and mixes, and carries out 4 stage countercurrent extractions.The organic phase of extraction gained is extraction
Liquid is taken, the water phase for extracting gained is raffinate, and wherein Ga contents are 8mg/L, and Ge contents are 2mg/L, and In contents are 0.2mg/L,
Fe contents are 4.7g/L, Fe3+It can not detect, Zn contents are 51g/L.
(3) it is stripped gallium：It is 4 according to the volume ratio of organic phase and water phase:1, by step (2) extraction gained organic phase with it is dense
The sulfuric acid that degree is 3mol/L, which is added in mixed settler extractor, to be mixed, and 4 stage countercurrent extractions are carried out.The water phase of extraction gained is extraction
Liquid, wherein Ga contents are 1342mg/L, and the organic phase for extracting gained is raffinate.
(4) it is stripped indium：It is 4 according to organic phase and water phase volume ratio:1, by the organic phase and concentration of step (3) extraction gained
To be mixed in the hydrochloric acid addition mixed settler extractor of 6mol/L, 4 stage countercurrent extractions are carried out.The water phase of extraction gained is extraction
Liquid, wherein In contents are 227mg/L, and Fe contents are 2980mg/L, and the organic phase for extracting gained is raffinate.
(5) it is stripped germanium：It is 4 according to organic phase and water phase volume ratio:1, by step (4) extract gained organic phase with it is a concentration of
The ammonium fluoride aqueous solution of 3mol/L is added in mixed settler extractor and mixes, and carries out 4 stage countercurrent extractions.Extraction gained water phase be
Extract liquor, wherein Ge contents are 1810mg/L, and the organic phase for extracting gained is raffinate.
(6) acidification regeneration：4 grades of acid are carried out to the organic phase of step (5) extraction gained using the sulfuric acid of a concentration of 2mol/L
Change regeneration treatment, the organic phase return to step (2) after regeneration is for extracting.
By the above method, Ga extraction yields reach 97.7%, Ge extraction yields and reach 99.5%, In extraction yields in step (2)
Reach 99.6%；Ga back extraction ratios reach 95.3% in step (3), and In back extraction ratios reach 99.91% in step (4), in step (5)
Ge back extraction ratios reach 99.88%, realize the coextraction from zinc replacement slag leachate and recycle gallium germanium indium；In addition, Zn extraction yields reach
To 5.2%, Fe3+Extraction yield reaches 100%.
Embodiment two
Extraction and recovery gallium germanium indium is carried out to the sulfuric acid leaching solution of zinc replacement slag, gallium (Ga) contains in the zinc replacement slag leachate
Amount is 550mg/L, and germanium (Ge) content is 450mg/L, and indium (In) content is 60mg/L, and iron (Fe) content is 10.5g/L, zinc (Zn)
Content is 58g/L, sulfuric acid (H2SO4) content be 30g/L, be as follows：
(1) it neutralizes, restore：Zinc replacement slag leachate is added in stirred tank, stirring is opened, adds zinc oxide to pH value
Reach 1.5, sodium sulfite is then added and carries out reaction 1 hour, detects after reaction Fe in solution3+Content be 1.0g/L, will
Solution filtering is spare.
(2) it extracts：It is 18 according to dosage volume ratio:1:81, by P207 extractants, YW100 synergic reagents and 260# solvent naphthas
It is mixed and made into mixed extractant, is then 1 according to organic phase and water phase volume ratio:1, by manufactured mixed extractant and step
(1) solution obtained by, which is added in mixed settler extractor, to be mixed, and 4 stage countercurrent extractions are carried out.The organic phase of extraction gained is extraction
Liquid, the water phase for extracting gained are raffinate, and wherein Ga contents are 10mg/L, and Ge contents are 1.5mg/L, and In contents are 0.2mg/L,
Fe contents are 9.5g/L, Fe3+It can not detect, Zn contents are 54g/L.
(3) it is stripped gallium：It is 4 according to the volume ratio of organic phase and water phase:1, by step (2) extraction gained organic phase with it is dense
The sulfuric acid that degree is 3mol/L, which is added in mixed settler extractor, to be mixed, and 4 stage countercurrent extractions are carried out.The water phase of extraction gained is extraction
Liquid, wherein Ga contents are 2101mg/L, and the organic phase for extracting gained is raffinate.
(4) it is stripped indium：It is 4 according to organic phase and water phase volume ratio:1, by the organic phase and concentration of step (3) extraction gained
To be mixed in the hydrochloric acid addition mixed settler extractor of 6mol/L, 4 stage countercurrent extractions are carried out.The water phase of extraction gained is extraction
Liquid, wherein In contents are 239mg/L, and Fe contents are 2980mg/L, and the organic phase for extracting gained is raffinate.
(5) it is stripped germanium：It is 4 according to organic phase and water phase volume ratio:1, by step (4) extract gained organic phase with it is a concentration of
The ammonium fluoride aqueous solution of 3mol/L is added in mixed settler extractor and mixes, and carries out 4 stage countercurrent extractions.Extraction gained water phase be
Extract liquor, wherein Ge contents are 1790mg/L, and the organic phase for extracting gained is raffinate.
(6) acidification regeneration：4 grades of acid are carried out to the organic phase of step (5) extraction gained using the sulfuric acid of a concentration of 2mol/L
Change regeneration treatment, the organic phase return to step (2) after regeneration is for extracting.
By the above method, Ga extraction yields reach 98.2%, Ge extraction yields and reach 99.6%, In extraction yields in step (2)
Reach 99.6%；Ga back extraction ratios reach 97.27% in step (3), and In back extraction ratios reach 99.91% in step (4), step (5)
Middle Ge back extraction ratios reach 99.78%, realize the coextraction from zinc replacement slag leachate and recycle gallium germanium indium；In addition, Zn extraction yields
Reach 7.9%, Fe3+Extraction yield reaches 100%.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.
Claims (10)
1. a kind of method of gallium germanium indium in extraction and recovery zinc replacement slag leachate, it is characterised in that：Include the following steps：
(1) it neutralizes, restore：Neutralizer to pH value is added in zinc replacement slag leachate and reaches 1.5-1.8, reducing agent is then added
It is reacted, the content of ferric ion is less than 1g/L in solution after control reaction；
(2) it extracts：Use the solution obtained by extractant, synergic reagent and diluent hybrid extraction step (1)；
(3) it is stripped gallium：Use the organic phase of sulfuric acid extraction step (2) extraction gained；
(4) it is stripped indium：Use the organic phase of hydrochloric acid extraction step (3) extraction gained；
(5) it is stripped germanium：Use the organic phase of fluoride aqueous solution extraction step (4) extraction gained；
(6) acidification regeneration：Acidification regeneration treatment is carried out to the organic phase of step (5) extraction gained using sulfuric acid, having after regeneration
Machine phase return to step (2) is for extracting.
2. the method for gallium germanium indium in extraction and recovery zinc replacement slag leachate according to claim 1, it is characterised in that：It is described
Zinc replacement slag leachate is the sulfuric acid leaching solution of zinc replacement slag.
3. the method for gallium germanium indium in extraction and recovery zinc replacement slag leachate according to claim 2, it is characterised in that：It is described
Neutralizer is zinc oxide, basic zinc carbonate, any one or more mixing in lime stone, the reducing agent be reduced iron powder,
Any one or more mixing in sodium sulfite, sulfur dioxide.
4. the method for gallium germanium indium in extraction and recovery zinc replacement slag leachate according to claim 3, it is characterised in that：It is described
Extractant is phosphoric acid kind of extractants, and the dosage volume ratio of the extractant, synergic reagent and diluent is 1-3:0.2-2:68-
89.8。
5. the method for gallium germanium indium in extraction and recovery zinc replacement slag leachate according to claim 4, it is characterised in that：It is described
Extractant is that di-(2-ethylhexyl)phosphoric acid ester, any one or two kinds in di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester are mixed
It closes, the synergic reagent is any one or more mixing in C6-C9 alkyl hydroximic acids, and the diluent is sulfonated kerosene, pine
Any one in perfume or two kinds of mixing.
6. according to the method for gallium germanium indium in claim 1-5 any one of them extraction and recovery zinc replacement slag leachates, feature
It is：Step (2) is specially：It is 1-3 according to the volume ratio of organic phase and water phase:1, by extractant, synergic reagent, diluent and step
Suddenly the solution mixing obtained by (1), carries out 1-8 stage countercurrent extractions.
7. the method for gallium germanium indium in extraction and recovery zinc replacement slag leachate according to claim 6, it is characterised in that：Step
(3) it is specially：It is 3-6 according to the volume ratio of organic phase and water phase:1, the organic phase of step (2) extraction gained and sulfuric acid is mixed
It closes, carries out 1-4 stage countercurrent extractions, a concentration of 1-3mol/L of sulfuric acid used.
8. the method for gallium germanium indium in extraction and recovery zinc replacement slag leachate according to claim 6, it is characterised in that：Step
(4) it is specially：It is 3-6 according to the volume ratio of organic phase and water phase:1, the organic phase of step (3) extraction gained and hydrochloric acid is mixed
It closes, carries out 1-4 stage countercurrent extractions, a concentration of 1-6mol/L of hydrochloric acid used.
9. the method for gallium germanium indium in extraction and recovery zinc replacement slag leachate according to claim 6, it is characterised in that：Step
(5) it is specially：It is 3-6 according to the volume ratio of organic phase and water phase:1, by the organic phase and fluoride water of step (4) extraction gained
Solution mixes, and carries out 1-4 stage countercurrent extractions, and fluoride aqueous solution used is to appoint in sodium fluoride, hydrofluoric acid, ammonium fluoride, potassium fluoride
It anticipates a kind of aqueous solution, a concentration of 1-6mol/L.
10. the method for gallium germanium indium in extraction and recovery zinc replacement slag leachate according to claim 6, it is characterised in that：Step
Suddenly in (6), a concentration of 2mol/L of sulfuric acid used carries out 1-6 grades of acidification regeneration treatments.
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| 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 |
| CN110306070A (en) * | 2019-07-31 | 2019-10-08 | 河海大学常州校区 | A kind of extracting process of indium |
| CN110791648A (en) * | 2019-11-07 | 2020-02-14 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for extracting and recovering germanium from sulfuric acid leaching solution |
| CN111254295A (en) * | 2020-01-20 | 2020-06-09 | 广东省稀有金属研究所 | Method for extracting and separating gallium from sulfuric acid leaching solution of zinc replacement slag and application thereof |
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| CN117965914A (en) * | 2024-03-28 | 2024-05-03 | 赣南科技学院 | Method for extracting and separating gallium and germanium from zinc replacement slag sulfuric acid leaching solution |
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| CN110306070A (en) * | 2019-07-31 | 2019-10-08 | 河海大学常州校区 | A kind of extracting process of indium |
| CN110791648A (en) * | 2019-11-07 | 2020-02-14 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for extracting and recovering germanium from sulfuric acid leaching solution |
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| CN114921665A (en) * | 2022-06-01 | 2022-08-19 | 朝阳金美镓业有限公司 | Method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by extraction method |
| CN114921665B (en) * | 2022-06-01 | 2023-08-22 | 朝阳金美镓业有限公司 | Method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by extraction method |
| CN116272877A (en) * | 2022-09-08 | 2023-06-23 | 中国科学院城市环境研究所 | Carbon adsorption material and preparation method and application thereof |
| CN117947268A (en) * | 2024-03-22 | 2024-04-30 | 矿冶科技集团有限公司 | Method for extracting and recovering gallium from zinc leaching solution |
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