CN115612863B - Method for separating gallium from alkaline solution - Google Patents
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- CN115612863B CN115612863B CN202211050879.1A CN202211050879A CN115612863B CN 115612863 B CN115612863 B CN 115612863B CN 202211050879 A CN202211050879 A CN 202211050879A CN 115612863 B CN115612863 B CN 115612863B
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- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 72
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000012670 alkaline solution Substances 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 71
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000002893 slag Substances 0.000 claims abstract description 8
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- 239000008394 flocculating agent Substances 0.000 claims abstract 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000002244 precipitate Substances 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- -1 gallium ions Chemical class 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 239000012452 mother liquor Substances 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- 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
- 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
-
- 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 discloses a method for separating gallium from alkaline solution, which comprises the following steps: and (3) regulating the pH value of the alkaline solution containing gallium, sequentially adding a vulcanizing agent, a precipitator, a precipitation accelerator and a flocculating agent, and stirring and reacting to obtain the gallium-containing rare-earth slag. The invention can lead gallium ions in the solution to form precipitate substances (such as CuGaS2, cuGaS4 and the like) with very low solubility or/and enter the precipitate in a similar manner, thereby realizing the purpose of enriching scattered metals from the solution. The method provided by the invention has the advantages of simple steps, easy operation, low requirements on production conditions, low energy consumption, short process flow, reduced generation of byproducts, high production efficiency, less reactant waste, reduced process cost, and high gallium recovery rate and separation rate which are up to 96.4%.
Description
Technical Field
The invention belongs to the field of metal separation and gallium recovery, and particularly relates to a method for separating gallium from an alkaline solution.
Background
In recent years, with the development of demands for communication, electronic computers, aerospace development, energy, military, environmental sanitation and the like, the demand for scattered metals is increasing, and the smelting, recovery and comprehensive utilization of gallium are receiving a great deal of attention. At present, gallium is mainly from circulating mother liquor in the alumina production process, waste residues and smoke dust in the lead-zinc production, fly ash, vanadium titano-magnetite smelting slag and the like.
Patent publication No. CN102534214A discloses a method for recovering gallium from Bayer mother liquor by using chelate resin, which mainly comprises the step of carrying out adsorption separation on gallium by using the chelate resin. The patent with publication No. CN101333606A discloses a method for recovering gallium from waste liquid of purifying gallium, which is characterized in that gallic acid-containing solution and gallium-containing alkaline solution are adopted to neutralize each other, the pH value of the neutralization solution is controlled to enable gallium to form precipitate 6.5-7.0, and then alkali-soluble precipitation is used to enable gallium to be dissolved out, so that gallium separation is realized. In the patent with publication number CN103468977A, gallium is leached from complex germanium-gallium-containing smelting slag or ore by strong alkali, then pH is regulated by acid, and then gallium is precipitated by calcium chloride. Patent publication No. CN 109208032A discloses a method for electrowinning and recovering gallium from a gallium-containing alkaline solution, which can reduce the gallium content from 3g/L to 1g/L by adopting a cyclone electrowinning technology. The publication CN 109943709a uses an N964-Cyanex257-TBP extraction system to extract gallium from a solution.
At present, the gallium separation and enrichment are involved in the process of recycling gallium from circulating mother liquor in the production process of alumina, waste residues in the production of lead-zinc, smoke dust, fly ash and vanadium-titanium magnetite smelting slag, and a large number of wet smelting processes such as precipitation, displacement, extraction, back extraction, adsorption, analytical exchange and the like are required for the gallium enrichment from the substances. Often, a plurality of steps are needed to be carried out to separate and enrich gallium, and meanwhile, the method is difficult to separate and enrich gallium in the solution efficiently due to low gallium content and complex components in the solution in the smelting byproducts, and the efficiency of extracting gallium from the original solution is only about 60 percent.
Disclosure of Invention
The invention aims to solve the technical problems, overcome the defects and shortcomings in the background art, and provide a method for separating gallium from alkaline solution, so as to shorten the process flow, reduce the reagent consumption and the process cost, and realize the efficient and rapid separation of gallium in the alkaline solution.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for separating gallium from an alkaline solution, comprising the steps of:
(1) Adjusting the pH of the alkaline solution containing gallium to 6-11 to obtain a solution a;
(2) Adding a vulcanizing agent into the solution a, and stirring and mixing for reaction to obtain a solution b;
(3) Adding a precipitator and a precipitation accelerator into the solution b, stirring, mixing, reacting, and standing to obtain a mixed solution c;
(4) Adding flocculant into the mixed solution c, stirring and mixing, standing and then carrying out solid-liquid separation to obtain the gallium-containing rich dispersionAnd (5) metal slag. The mixed solution c contains gallium-containing precipitate such as CuGaS 2 、CuGaS 4 And the like.
Preferably, the regulator used for adjusting the pH of the alkaline solution containing gallium in the step (1) is any one or more of sodium hydroxide, sulfuric acid, carbon dioxide and hydrochloric acid. The pH is adjusted for better subsequent vulcanization and precipitation, so that CuGaS 2 、CuGaS 4 And so on.
Preferably, the vulcanizing agent in the step (2) is any one or a combination of more of sodium sulfide and thiourea; the adding ratio of the vulcanizing agent to the solution a is 1-8g/L; the reaction temperature is 45-90 ℃ and the reaction time is 2-8h.
Preferably, the precipitant in the step (3) is any one or more of copper sulfate, copper chloride and copper nitrate.
Preferably, the ratio of the precipitant to the solution b in the step (3) is 1-6g/L.
Preferably, the precipitation promoter in the step (3) is any one or more of sodium sulfite, sulfur dioxide or elemental sulfur, and the addition ratio of the precipitation promoter to the solution b is 0.8-2g/L.
Preferably, the temperature of the reaction in step (3) is 60-95℃and the time is 2-6 hours.
Preferably, the flocculant in the step (4) is any one or more of polyphosphoric ferric chloride, polyaluminum sulfate and polymeric ferric chloride.
Preferably, the mass ratio of the flocculant to the mixed liquor c in the step (4) is 0.01-0.1%; the stirring time is 2-6min, and the standing time is 10-20min.
Preferably, the stirring speed in the step (2) and the step (3) is 100r/min-400r/min.
The invention can make gallium ions in the solution form precipitate substances with very low solubility (such as CuGaS 2 、CuGaS 4 Etc.) or/and enter the sediment in a manner similar to the like, thereby achieving the purpose of enriching the scattered metals from the solution. Firstly, adding a vulcanizing agent into the solution to carry out vulcanization transformation on the solution to obtain a mixture containing a large amount of S 2- 、HS - 、S x+1 2- Iso-and micro-GaS x 2- And the like, while imparting some reducibility to the solution (making full use of the reducibility of thiourea, sodium sulfide, and the like); after the solution is vulcanized, copper ions are introduced into the solution, and meanwhile, a certain concentration of cuprous ions is formed in the system by means of a precipitation promoter; and then copper ions, cuprous ions and GaS in solution x 2- 、S 2- 、HS - 、S x+1 2- Waiting for reaction to form CuGaS 2 、CuGaS 4 Precipitation of CuS, cu2S, etc., simultaneously with CuGaS 2 、CuGaS 4 、CuS、Cu 2 In the S equivalent precipitation process, part of gallium in the solution enters copper sulfide precipitation in a similar manner, so that the precipitation of gallium in the solution is further enhanced, and the separation of gallium from the solution is realized.
Compared with the prior art, the invention has the beneficial effects that:
1. the method provided by the invention has the advantages of simple steps, easy operation, low requirements on production conditions, low energy consumption, short process flow, reduced generation of byproducts, high production efficiency, less reactant waste and reduced process cost.
2. The invention can make gallium ions in the solution form precipitate substances with very low solubility (such as CuGaS 2 、CuGaS 4 Etc.) or/and enter the sediment in a similar manner, thereby achieving the purpose of enriching the scattered metals from the solution, improving the recovery rate and the separation rate of gallium, and the separation rate is as high as 96.4 percent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a process flow for separating enriched gallium from an alkaline solution in accordance with the present invention.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
a method for separating and enriching gallium from alkaline solution comprises vacuum drying gallium-containing dispersed metal slag, detecting gallium in the slag, and calculating the separation rate and enrichment degree of gallium from the solution, wherein the process flow is shown in figure 1.
The specific operation is as follows:
the raw material is a solution obtained by carbon separation of circulating mother liquor in the production process of aluminum oxide, and the mother liquor contains 273mg/L gallium.
(1) Taking 2L of mother solution, introducing carbon dioxide into the solution, and regulating the pH value of the solution to 8;
(2) 3g of sodium sulfide is added into the solution, and the mixture is stirred at the speed of 200r/min and reacts for 6 hours at the temperature of 75 ℃;
(3) After the reaction is finished, adding 6g of copper sulfate and 1.8g of sodium sulfite into the solution, stirring at the speed of 300r/min, reacting at 80 ℃ for 6 hours, and standing for 16 hours;
(4) After the standing is finished, adding 0.05% of polyphosphoric ferric chloride by mass of the solution into the solution, stirring for 5min at 100r/min, standing for 15min, and filtering to obtain the gallium with the separation rate of 95.2%.
Example 2:
a method for separating and enriching gallium from alkaline solution comprises the following specific operations:
the raw material is circulating mother liquor in the production process of alumina, and the mother liquor contains 273mg/L gallium.
(1) Taking 2L of mother solution, adding sulfuric acid into the solution, and adjusting the pH value of the solution to 10;
(2) Adding 4g of sodium sulfide into the solution, stirring at a speed of 300r/min, and reacting at 85 ℃ for 8 hours;
(3) After the reaction is finished, 8g of copper chloride and 3g of sodium sulfite are added into the solution, stirred at the speed of 400r/min, reacted for 3 hours at the temperature of 90 ℃ and then kept stand for 10 hours;
(4) After the standing is finished, adding 0.05% of polyphosphoric ferric chloride by mass of the solution into the solution, stirring for 3min at 100r/min, standing for 20min, and filtering to obtain the gallium with the separation rate of 92.6%.
Example 3:
a method for separating and enriching gallium from alkaline solution comprises the following specific operations:
the raw material is alkaline system gallium electrodeposited liquid, and the concentration of gallium in the solution is 4.5g/L.
(1) Taking 2L of mother solution, introducing carbon dioxide into the solution, and regulating the pH value of the solution to 8;
(2) Adding 12g of sodium sulfide into the solution, stirring at a speed of 200r/min, and reacting at 45 ℃ for 8 hours;
(3) After the reaction is finished, adding 12g of copper sulfate and 3.5g of sodium sulfite into the solution, stirring at the speed of 300r/min, reacting at 90 ℃ for 6 hours, and standing for 22 hours;
(4) After the standing is finished, adding 0.1% of polyphosphoric ferric chloride by mass of the solution into the solution, stirring for 5min at 200r/min, standing for 15min, and filtering to obtain the gallium with the separation rate of 90.7%.
Example 4:
a method for separating and enriching gallium from alkaline solution comprises the following specific operations:
the raw material is alkaline system gallium electrodeposited liquid, and the concentration of gallium in the solution is 4.5g/L.
(1) Taking 2L of mother solution, introducing carbon dioxide into the solution, and regulating the pH value of the solution to 9;
(2) 16g of sodium sulfide is added into the solution, and the mixture is stirred at a speed of 200r/min and reacts for 8 hours at 85 ℃;
(3) After the reaction is finished, adding 12g of copper sulfate and 4g of sodium sulfite into the solution, stirring at the speed of 200r/min, reacting at 60 ℃ for 6 hours, and standing for 20 hours;
(4) After the standing is finished, adding 0.05% of polyphosphoric ferric chloride by mass of the solution into the solution, stirring for 5min at 200r/min, standing for 15min, and filtering to obtain the gallium with a separation rate of 96.4%.
Example 5:
a method for separating and enriching gallium from alkaline solution comprises the following specific operations:
the raw material is self-prepared gallium-containing alkaline solution (obtained by dissolving gallium oxide by sodium hydroxide), and the concentration of gallium is 147mg/L;
(1) Taking 2L of the mother solution, introducing carbon dioxide into the solution, and regulating the pH value of the solution to 8;
(2) 2g of sodium sulfide is added into the solution, and the mixture is stirred at the speed of 200r/min and reacts for 8 hours at the temperature of 70 ℃;
(3) After the reaction is finished, adding 2.4g of copper sulfate and 2g of sodium sulfite into the solution, stirring at the speed of 200r/min, reacting at 85 ℃ for 3 hours, and standing for 16 hours;
(4) After the standing is finished, adding 0.02% of polyphosphoric ferric chloride by mass of the solution into the solution, stirring for 5min at 200r/min, standing for 15min, and filtering to obtain the gallium with the separation rate of 95.1%.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall fall within the scope of the technical solution of the present invention.
Claims (5)
1. A method for separating gallium from an alkaline solution, comprising the steps of:
(1) Adjusting the pH of the alkaline solution containing gallium to 6-11 to obtain a solution a;
(2) Adding a vulcanizing agent into the solution a, and stirring and mixing for reaction to obtain a solution b;
(3) Adding a precipitator and a precipitation accelerator into the solution b, stirring, mixing, reacting, and standing to obtain a mixed solution c;
(4) Adding a flocculating agent into the mixed solution c, stirring and mixing, standing, and performing solid-liquid separation to obtain the gallium-containing dispersed metal slag;
the vulcanizing agent in the step (2) is any one or a combination of a plurality of sodium sulfide and thiourea; the adding ratio of the vulcanizing agent to the solution a is 1-8g/L; the reaction temperature is 45-90 ℃ and the reaction time is 2-8h;
the precipitant in the step (3) is any one or a combination of a plurality of copper sulfate, copper chloride and copper nitrate; the adding ratio of the precipitant to the solution b in the step (3) is 1-6g/L; the precipitation promoter in the step (3) is any one or a combination of a plurality of sodium sulfite, sulfur dioxide or elemental sulfur, and the addition ratio of the precipitation promoter to the solution b is 0.8-2g/L; the temperature of the reaction in the step (3) is 60-95 ℃ and the time is 2-6h.
2. The method of claim 1, wherein the adjusting agent used to adjust the pH of the alkaline solution containing gallium in step (1) is any one or more of sodium hydroxide, sulfuric acid, carbon dioxide, hydrochloric acid.
3. The method of claim 1, wherein the flocculant in step (4) is any one or a combination of more of polyphosphoric ferric chloride, polyaluminum sulfate, and polymeric ferric chloride.
4. The method according to claim 1, wherein the mass ratio of the flocculant to the mixed liquor c in the step (4) is 0.01-0.1%; the stirring time is 2-6min, and the standing time is 10-20min.
5. The method according to claim 1, wherein the stirring speed in the step (2) and the step (3) is 100r/min to 400r/min.
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| CN202211050879.1A CN115612863B (en) | 2022-08-30 | 2022-08-30 | Method for separating gallium from alkaline solution |
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| CN115612863B true CN115612863B (en) | 2024-01-16 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018012A (en) * | 2014-06-16 | 2014-09-03 | 中国神华能源股份有限公司 | Method of extracting gallium from aluminum chloride solution |
| CN104795456A (en) * | 2015-03-24 | 2015-07-22 | 湘潭大学 | Electro-deposition method for preparing three band gap Fe-doped with copper gallium sulfur solar cell materials |
| CN106024977A (en) * | 2016-06-15 | 2016-10-12 | 山东建筑大学 | Method for preparing copper gallium sulfide photoelectric thin film from copper sulfate |
| CN112430737A (en) * | 2020-10-29 | 2021-03-02 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for recovering gallium from extraction gallium precipitation slag |
| CN113512652A (en) * | 2021-06-29 | 2021-10-19 | 四川顺应动力电池材料有限公司 | Method for extracting gallium metal from coal-series solid waste |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018012A (en) * | 2014-06-16 | 2014-09-03 | 中国神华能源股份有限公司 | Method of extracting gallium from aluminum chloride solution |
| CN104795456A (en) * | 2015-03-24 | 2015-07-22 | 湘潭大学 | Electro-deposition method for preparing three band gap Fe-doped with copper gallium sulfur solar cell materials |
| CN106024977A (en) * | 2016-06-15 | 2016-10-12 | 山东建筑大学 | Method for preparing copper gallium sulfide photoelectric thin film from copper sulfate |
| CN112430737A (en) * | 2020-10-29 | 2021-03-02 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for recovering gallium from extraction gallium precipitation slag |
| CN113512652A (en) * | 2021-06-29 | 2021-10-19 | 四川顺应动力电池材料有限公司 | Method for extracting gallium metal from coal-series solid waste |
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