CN105567986A - Method for recycling gallium and germanium from zinc powder replacement gallium and germanium residues through resin - Google Patents
Method for recycling gallium and germanium from zinc powder replacement gallium and germanium residues through resin Download PDFInfo
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- CN105567986A CN105567986A CN201511014055.9A CN201511014055A CN105567986A CN 105567986 A CN105567986 A CN 105567986A CN 201511014055 A CN201511014055 A CN 201511014055A CN 105567986 A CN105567986 A CN 105567986A
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- Prior art keywords
- germanium
- gallium
- alkali
- reaction
- leaching
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 118
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 107
- 239000011347 resin Substances 0.000 title claims abstract description 37
- 229920005989 resin Polymers 0.000 title claims abstract description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004064 recycling Methods 0.000 title abstract 2
- 239000003513 alkali Substances 0.000 claims abstract description 67
- 238000002386 leaching Methods 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000012141 concentrate Substances 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 12
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 12
- 239000001648 tannin Substances 0.000 claims abstract description 11
- 235000018553 tannin Nutrition 0.000 claims abstract description 11
- 229920001864 tannin Polymers 0.000 claims abstract description 11
- 239000002699 waste material Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims description 29
- 238000001556 precipitation Methods 0.000 claims description 20
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 17
- 238000007654 immersion Methods 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 9
- 238000005554 pickling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 3
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 2
- 239000002956 ash Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 5
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 230000035484 reaction time Effects 0.000 description 7
- 239000012670 alkaline solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003500 flue dust Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- RNKMOGIPOMVCHO-SJMVAQJGSA-N 1,3,6-trigalloyl glucose Chemical compound C([C@@H]1[C@H]([C@@H]([C@@H](O)[C@H](OC(=O)C=2C=C(O)C(O)=C(O)C=2)O1)OC(=O)C=1C=C(O)C(O)=C(O)C=1)O)OC(=O)C1=CC(O)=C(O)C(O)=C1 RNKMOGIPOMVCHO-SJMVAQJGSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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
- C22B7/04—Working-up slag
-
- 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
-
- 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
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recycling gallium and germanium from zinc powder replacement gallium and germanium residues through resin. The method comprises the following steps that A, zinc electrolytic waste liquid, water and the gallium and germanium residues are subjected to acid leaching; B, copper of primary acid leaching liquid obtained in the step A is replaced through iron powder, and a solution after replacement is obtained; C, germanium of the solution after replacement sinks through tannin, and germanium concentrates are obtained after filtering; D, gallium and germanium of primary alkali leaching liquid obtained after primary alkali leaching of acid leaching residues obtained in the step A are adsorbed by the resin, desorbing sulfuric acid is added, a desorbed solution containing gallium and germanium is obtained, the PH value is controlled by sodium hydroxide added into the desorbed solution, and after a reaction is conducted and gallium sinks, gallium concentrates and gallium-sunk liquid are obtained by filtering; and E, the PH value of the gallium-sunk liquid obtained in the step D is adjusted, magnesium sulfate is added, germanium sinks after a reaction, and germanium concentrates are obtained by filtering. The acid leaching rate of gallium and germanium is decreased by adjusting the acid leaching conditions, the alkali leaching rate of gallium and germanium is increased, gallium and germanium are adsorbed in alkali leaching liquid by the resin, a sulfuric acid solution is desorbed and neutralized with alkali, the gallium concentrates and a germanium alkali solution are obtained, and the germanium alkali solution subsides through the magnesium sulfate.
Description
Technical field
The present invention relates to a kind of method that resin reclaims gallium germanium from zinc dust precipitation gallium germanium slag, belong to dissipated metal field of metallurgy.
Background technology
Gallium is a kind of dissipated metal, and the concentration in the earth's crust is very low, and distribution is very extensive, and occurring in nature is often scattered in the ore such as bauxite, zink sulphide with trace.Present most primary gallium is in the world all reclaim in the bayer liquor in production aluminium process.The production of germanium is generally that the flue dust produced from enriched germanium flue dust or the germanic coal of zinc abstraction generation utilizes sulfuric acid leaching, and tannin precipitation reclaims.Have simultaneously containing gallium germanium in some zinc ore concentrates, utilize zinc dust precipitation to generate gallium germanium replacement slag, present common process utilizes sulfuric acid leaching or pressure leaching, and the germanium of leach liquor germanium utilizes tannin to precipitate and reclaims, and gallium is then difficult to reclaim.The patent No. is that a kind of " method of high efficiente callback germanium " of CN201410839448.2 adopts acidleach to soak with alkali the technique combined, and synthetical recovery gallium germanium, but the problem of the grade that there is the germanium in germanic acid magnesium lower (5-10%), follow-up distillation cost is higher.The acidleach leaching yield of gallium germanium is reduced by adjustment acidleach condition by the present invention, improve gallium germanium alkali leaching leaching yield, with resin absorption gallium germanium in alkali immersion liquid, sulphuric acid soln is resolved, neutralize with alkali again, obtain gallium concentrate and germanium alkaline solution, germanium alkaline solution by magnesium sulfate precipitation, obtains the germanium concentrate of germanic more than 20% again.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides a kind of resin from zinc dust precipitation gallium germanium slag, reclaim the method for gallium germanium.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
Resin reclaims a method for gallium germanium from zinc dust precipitation gallium germanium slag, comprises the steps:
After A, acidleach of sizing mixing with zinc electrolytic waste liquid, water and gallium germanium slag, obtain acid leaching residue and a pickling liquor;
B, the pickling liquor iron replacement copper that steps A is produced, iron powder add-on is 1.2-1.5 times of copper amount, temperature of reaction 50-70 DEG C, and reaction 1-2h, obtains displaced liquid and copper ashes;
C, the displaced liquid tannin sinking germanium that step B is produced, tannin consumption is 25-30 times of germanium amount, temperature of reaction 50-70 DEG C, and reaction 10-60 minute, filters and obtain germanium concentrate;
D, by the leaching of the alkali of the acid leaching residue in steps A, alkali immersion liquid resin absorption gallium germanium after an alkali leaching, resin absorption alkali immersion liquid amount is 20-100 times of resin volume, add the parsing sulfuric acid that concentration is 0.05-2mol/l, obtain containing gallium germanium desorbed solution, in desorbed solution, add the sodium hydroxide of concentration 10-25%, after controlling the heavy gallium of reaction in pH value 3.5-5.0, filter and obtain liquid after gallium concentrate and heavy gallium;
After the heavy gallium that E, set-up procedure D obtain, the pH value of liquid is between 7.0-11.0, adds magnesium sulfate, and the heavy germanium of reaction, filters to obtain germanium concentrate.
Further, an alkaline residue after an alkali leaching carries out the leaching of secondary alkali, and secondary alkali soaks the secondary alkali immersion liquid obtained and soaks dosing as an alkali, and secondary alkali soaks the secondary alkali leaching slag obtained and enters in plumbous treatment system.
Resin according to claim 2 reclaims the method for gallium germanium from zinc dust precipitation gallium germanium slag, it is characterized in that, the leaching of secondary alkali is carried out with sodium hydroxide solution, its alkali leaching condition is, liquid-solid ratio: 5-10:1, temperature of reaction: 60-95 DEG C, reaction 1-4h, terminal sodium hydrate content: 20-100g/l.
In step D, carry out an alkali leaching with sodium hydroxide solution, its alkali leaching condition is, liquid-solid ratio: 5-10:1, temperature of reaction: 60-95 DEG C, reaction 1-4h, terminal sodium hydrate content: 20-100g/l.
In steps A, zinc electrolytic waste liquid, water and gallium germanium slag are sized mixing acidleach, control temperature of reaction 70-95 DEG C, and reaction 2-4 hour, terminal PH are 2.0-3.5.
Further, the above-mentioned germanium concentrate be obtained by reacting enters in chlorinated distillation system.
In step e, after adding magnesium sulfate to heavy gallium, in liquid, react 30-60 minute.
Compared with prior art, the invention has the advantages that:
Resin provided by the invention reclaims the method for gallium germanium from zinc dust precipitation gallium germanium slag, first zinc electrolytic waste liquid is utilized by gallium germanium slag gallium from zinc dust precipitation to add water leaching, copper, zinc and part germanium are leached, and reclaim copper, germanium wherein respectively, zinc returns zinc and produces system; Gallium and remainder germanium with twice alkali leaching, leach, by alkali immersion liquid by resin dedicated (X900#) adsorption column by acid leaching residue again, gallium germanium is resolved again with dilute sulphuric acid, obtain the gallium germanium desorbed solution that impurity is low, the desorbed solution heavy gallium of alkali displacement, after heavy gallium, liquid magnesium sulfate sinks germanium.
The acidleach leaching yield of gallium germanium is reduced by adjustment acidleach condition by the present invention, improve gallium germanium alkali leaching leaching yield, with resin absorption gallium germanium in alkali immersion liquid, sulphuric acid soln is resolved, neutralize with alkali again, obtain gallium concentrate and germanium alkaline solution, germanium alkaline solution by magnesium sulfate precipitation, obtains the germanium concentrate of germanic more than 20% again.
High by its rate of recovery of the inventive method, the direct yield of gallium, germanium reaches more than 90%, because adopting resin absorption gallium germanium and other component separating, gallium, germanium precipitation is of high grade, reach 20-30%, simultaneously due to because of gallium germanium of high grade, successive refinements gallium germanium technique is simple, facility investment reduces, and greatly reduces production cost.
Accompanying drawing explanation
Fig. 1 is theory structure schematic diagram of the present invention.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
A kind of resin by reference to the accompanying drawings reclaims the method for gallium germanium from zinc dust precipitation gallium germanium slag, comprises following technique:
After A, acidleach of sizing mixing with zinc electrolytic waste liquid, water and gallium germanium slag, obtain acid leaching residue and a pickling liquor, operational condition: ratio=(1-4) of electrolysis waste solution and water: 1
1. liquid-solid ratio: 5-8:1
2. temperature of reaction: 70-95 DEG C
3. the reaction times: 2-4h
4. terminal pH value: 2.0-3.5
B, a pickling liquor iron replacement copper, operational condition
1. iron powder add-on: the 1.2-1.5 of copper amount doubly
2. temperature of reaction: 50-70 DEG C
3. the reaction times: 1-2h
C, displaced liquid tannin sinking germanium, operational condition
1. tannin consumption: the 25-30 of germanium amount doubly
2. temperature of reaction: 50-70 DEG C
3. the reaction times: 10-60 minute
D, by the leaching of the alkali of the acid leaching residue in steps A, heavy gallium, operational condition
1. liquid-solid ratio: 5-8:1
2. temperature of reaction: 60-95 DEG C
3. the reaction times: 1-3h
4. terminal sodium hydrate content: 10-40g/l
An alkaline residue after an alkali leaching carries out the leaching of secondary alkali, operational condition
1. liquid-solid ratio: 5-10:1
2. temperature of reaction: 60-95 DEG C
3. the reaction times: 1-4h
4. terminal sodium hydrate content: 20-100g/l
Secondary alkali soaks the secondary alkali immersion liquid obtained and soaks dosing as an alkali, and secondary alkali soaks the secondary alkali leaching slag obtained and enters in plumbous treatment system;
Resin (X900#) adsorbs an alkali immersion liquid gallium germanium, operational condition
1. resin absorption reduction of feed volume: the 20-100 of resin volume doubly
2. sulfuric acid concentration is resolved: 0.05-2mol/l
3. naoh concentration: 10-25%
4. absorption, desorbed solution rate of flow of fluid: 2-5 times resin volume/h
Obtain after operation containing gallium germanium desorbed solution, in desorbed solution, adding sodium hydroxide, control pH value 3.5-5.0, after reaction times 30-60 minute heavy gallium, filter and obtain liquid after gallium concentrate and heavy gallium;
After E, heavy gallium, liquid adds the heavy germanium of magnesium sulfate reaction, operational condition
1. pH value is at 7.0-11.0
2. germanium is sunk with 10-25 times of magnesium sulfate of germanium amount, the reaction times: 30-60 minute
The germanium concentrate produced by present method is entered in chlorinated distillation system.
With reference to above-mentioned concrete technology, implement three embodiments as follows:
Raw material: gallium germanium slag ingredient is in table 1
Table 1 gallium germanium slag ingredient table (%)
Concrete operations condition:
Acidleach adopts electrolysis waste solution to add water dosing, it is 30-50g/l that secondary alkali soaks naoh concentration used, and institute responds and all carries out in 50 cubes of mechanic whirl-nett reaction grooves, pressure filter press filtration, other conditions are all pressed described in process explanation, and each operation solution and slag specimen the results are shown in following each table:
A, acidleach, 5 cubes, 10 tons of gallium germanium slag zinc electrolytic waste liquid 35 cubic nonlinearity water is sized mixing, and controls temperature of reaction 70-95 DEG C, and reaction 2-4 hour, terminal PH are 2.0-3.5.Filtrate component is in table 2.
Table 2 pickling liquor component list (g/l)
B, a pickling liquor iron replacement copper, iron powder add-on is 1.25 times of copper amount, temperature of reaction: 50-70 DEG C,
Reaction 1-2h.
C, displaced liquid tannin sinking germanium, tannin consumption: 24 times of germanium amount, temperature of reaction: 50-70 DEG C, reaction 10-60 minute, tannin sinking germanium slag is germanic to be respectively: implementation column 1:3.24%, implementation column 2:2.98%; Implementation column 3:3.64%.
D, an alkali leaching, liquid-solid ratio: 5-8:1, temperature of reaction: 60-95 DEG C, reaction 1-3h, terminal sodium hydrate content: 20-40g/l.An alkali bath constituents is in table 3:
Table 3 alkali bath constituents table (g/l)
Secondary alkali soaks, liquid-solid ratio: 5-10:1, temperature of reaction: 60-95 DEG C, reaction 1-4h, terminal sodium hydrate content: 20-100g/l.Secondary alkali leaching composition is in table 4:
Table 4 two alkali bath constituents tables (g/l)
Resin (X900#) adsorbs an alkali immersion liquid gallium germanium, 4 cubes of resin absorption feed liquids, resolve sulfuric acid concentration: 0.5mol/l, consumption 9 cubes, regeneration concentration of lye: 1.0mol/lNaOH, consumption 6 cubes, absorption, resolve and recovering liquid flow velocity: 10 cubic meters/hour, alkali immersion liquid resin absorption gallium germanium after a concrete operations alkali leaching, resin absorption alkali immersion liquid amount is 20-100 times of resin volume, add the parsing sulfuric acid that concentration is 0.05-2mol/l, obtain containing gallium germanium desorbed solution, the sodium hydroxide of concentration 10-25% is added in desorbed solution, after controlling the heavy gallium of reaction in pH value 3.5-5.0, filtration obtains liquid after gallium concentrate and heavy gallium.Desorbed solution composition is in table 5:
Table 5 desorbed solution component list (g/l)
After the heavy gallium that E, set-up procedure D obtain, the pH value of liquid is between 7.0-11.0, adds magnesium sulfate, and the heavy germanium of reaction, filters to obtain germanium concentrate.After heavy gallium germanium, liquid and gallium, germanium concentrate composition are in table 7:
Table 6 sinks liquid and gallium, germanium concentrate component list (g/l) after gallium germanium
Above-mentioned just preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention.Therefore, every content not departing from technical solution of the present invention, according to the technology of the present invention essence to any simple modification made for any of the above embodiments, equivalent variations and modification, all should drop in the scope of technical solution of the present invention protection.
Claims (7)
1. from zinc dust precipitation gallium germanium slag, reclaim a method for gallium germanium with resin, it is characterized in that, comprise the steps:
After A, acidleach of sizing mixing with zinc electrolytic waste liquid, water and gallium germanium slag, obtain acid leaching residue and a pickling liquor;
B, the pickling liquor iron replacement copper that steps A is produced, iron powder add-on is 1.2-1.5 times of copper amount, temperature of reaction 50-70 DEG C, and reaction 1-2h, obtains displaced liquid and copper ashes;
C, the displaced liquid tannin sinking germanium that step B is produced, tannin consumption is 25-30 times of germanium amount, temperature of reaction 50-70 DEG C, and reaction 10-60 minute, filters and obtain germanium concentrate;
D, by the leaching of the alkali of the acid leaching residue in steps A, alkali immersion liquid resin absorption gallium germanium after an alkali leaching, resin absorption alkali immersion liquid amount is 20-100 times of resin volume, add the parsing sulfuric acid that concentration is 0.05-2mol/l, obtain containing gallium germanium desorbed solution, in desorbed solution, add the sodium hydroxide of concentration 10-25%, after controlling the heavy gallium of reaction in pH value 3.5-5.0, filter and obtain liquid after gallium concentrate and heavy gallium;
After the heavy gallium that E, set-up procedure D obtain, the pH value of liquid is between 7.0-11.0, adds magnesium sulfate, and the heavy germanium of reaction, filters to obtain germanium concentrate.
2. resin according to claim 1 reclaims the method for gallium germanium from zinc dust precipitation gallium germanium slag, it is characterized in that, an alkaline residue after an alkali leaching carries out the leaching of secondary alkali, secondary alkali soaks the secondary alkali immersion liquid obtained and soaks dosing as an alkali, and secondary alkali soaks the secondary alkali leaching slag obtained and enters in plumbous treatment system.
3. resin according to claim 2 reclaims the method for gallium germanium from zinc dust precipitation gallium germanium slag, it is characterized in that, the leaching of secondary alkali is carried out with sodium hydroxide solution, its alkali leaching condition is, liquid-solid ratio: 5-10:1, temperature of reaction: 60-95 DEG C, reaction 1-4h, terminal sodium hydrate content: 20-100g/l.
4. resin according to claim 1 reclaims the method for gallium germanium from zinc dust precipitation gallium germanium slag, it is characterized in that, in step D, an alkali leaching is carried out with sodium hydroxide solution, its alkali leaching condition is, liquid-solid ratio: 5-10:1, temperature of reaction: 60-95 DEG C, reaction 1-4h, terminal sodium hydrate content: 20-100g/l.
5. resin according to claim 1 reclaims the method for gallium germanium from zinc dust precipitation gallium germanium slag, it is characterized in that, in steps A, zinc electrolytic waste liquid, water and gallium germanium slag are sized mixing acidleach, control temperature of reaction 70-95 DEG C, and reaction 2-4 hour, terminal PH are 2.0-3.5.
6. resin according to claim 1 reclaims the method for gallium germanium from zinc dust precipitation gallium germanium slag, and it is characterized in that, the germanium concentrate be obtained by reacting enters in chlorinated distillation system.
7. resin according to claim 1 reclaims the method for gallium germanium from zinc dust precipitation gallium germanium slag, it is characterized in that, in step e, reacts 30-60 minute after adding magnesium sulfate to heavy gallium in liquid.
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| CN201511014055.9A CN105567986B (en) | 2015-12-31 | 2015-12-31 | A kind of method for reclaiming gallium germanium from zinc dust precipitation gallium germanium slag with resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112410570A (en) * | 2020-11-11 | 2021-02-26 | 广东先导稀材股份有限公司 | Method for recovering gallium germanium from gallium germanium material |
| CN112626341A (en) * | 2020-12-11 | 2021-04-09 | 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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| CN112410570A (en) * | 2020-11-11 | 2021-02-26 | 广东先导稀材股份有限公司 | Method for recovering gallium germanium from gallium germanium material |
| CN112410570B (en) * | 2020-11-11 | 2022-06-17 | 广东先导稀材股份有限公司 | Method for recovering gallium germanium from gallium germanium material |
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| CN116397102A (en) * | 2023-04-04 | 2023-07-07 | 云南罗平锌电股份有限公司 | A method for harmlessly recovering copper and germanium from high iron and high copper solution |
| CN116397102B (en) * | 2023-04-04 | 2025-09-02 | 云南罗平锌电股份有限公司 | A method for harmlessly recovering copper and germanium from high-iron and high-copper solution |
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