CN114990338B - Method for efficiently extracting tin from silver separating slag of copper anode slime - Google Patents
Method for efficiently extracting tin from silver separating slag of copper anode slime Download PDFInfo
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- CN114990338B CN114990338B CN202210493664.0A CN202210493664A CN114990338B CN 114990338 B CN114990338 B CN 114990338B CN 202210493664 A CN202210493664 A CN 202210493664A CN 114990338 B CN114990338 B CN 114990338B
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002893 slag Substances 0.000 title claims abstract description 77
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 25
- 239000010949 copper Substances 0.000 title claims abstract description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 24
- 239000004332 silver Substances 0.000 title claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002386 leaching Methods 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000012141 concentrate Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000004537 pulping Methods 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002817 coal dust Substances 0.000 claims 1
- 239000000571 coke Substances 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000003723 Smelting Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 238000001914 filtration Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940079864 sodium stannate Drugs 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 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
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
-
- 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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
-
- 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
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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Abstract
The invention belongs to the technical field of nonferrous metal smelting, and particularly relates to a method for efficiently extracting tin from silver separating slag of copper anode slime, which comprises the following steps: uniformly mixing silver-separating slag of copper anode slime, a carbon-containing material and an auxiliary agent, pressing the mixed material into blocks, roasting by adopting microwaves at the temperature of 350-950 ℃ for 1.5-4.5 hours; crushing and grinding the obtained roasting slag, adding the roasting slag into a sulfuric acid solution, stirring and pulping, adding an alkali-containing solution, heating to perform tin leaching, recycling other valuable elements from the obtained tin-leaching slag, adding a calcium-containing reagent into the tin-leaching solution to perform tin precipitation, recycling antimony from the obtained tin-precipitating solution, and washing the tin-precipitating slag to obtain tin concentrate. The beneficial effects of the invention are as follows: the method has the advantages of low treatment cost and stable tin recovery effect, and is more suitable for practical industrial production, and the recovery rate of tin from the silver separating slag of the copper anode slime to the tin concentrate is not lower than 90.0%.
Description
Technical Field
The invention belongs to the technical field of nonferrous metal smelting, and particularly relates to a method for efficiently extracting tin from silver separating slag of copper anode slime.
Background
Copper anode slime is an insoluble substance falling off at an anode in the copper smelting and electrorefining process, contains noble metals such as gold, silver, platinum, palladium and the like and scattered metals such as tellurium, selenium and the like, and is one of important sources of a plurality of metal resources. The copper anode slime treatment process usually comprises the steps of pretreatment, copper and arsenic removal, gold leaching, silver separation, refining and the like, wherein residues left after silver separation are called silver separation residues, contain trace gold and silver, also contain valuable metals such as tin, lead, antimony and the like, and still have quite large resource utilization value, and the tin contained in the residues has the highest extraction value due to high value and high grade.
In order to extract tin in silver separating slag of copper anode slime, various auxiliary agents such as silver separating slag and vulcanizing agent are mixed in the prior art, ball milling is carried out for 0.5-2 hours, then the mixture is put into a reaction furnace at 1200-1500 ℃ and smelted for 1-2 hours in an air-blown state, and lead-enriched tin smoke dust is obtained;
The silver separating slag is subjected to lead and silver removal under an acid chloride system, then concentrated sulfuric acid is heated for barium removal, then sodium stannate solution is obtained through alkali fusion, water immersion and the like, and sodium stannate product is obtained through evaporation crystallization after the sodium stannate solution is purified; or leaching silver-separating slag by adopting a mixed solution of hydrochloric acid and chloride, separating gold, silver and lead, and separating barium by using a carbonate conversion-hydrochloric acid leaching mode to obtain a tin enrichment. And firstly, carrying out reduction roasting on silver separating slag under the action of microwaves, and then realizing tin leaching through a wet process of oxidation acid leaching-alkali leaching.
The invention comprises the following steps:
in view of the above, the present invention provides a method for separating and recovering tin from silver-separated slag of copper anode slime, so as to solve any one of the above and other potential problems in the prior art.
In order to achieve the above purpose, the technical scheme of the invention is as follows: the method for efficiently extracting tin from the silver separating slag of the copper anode slime comprises the following steps in sequence:
S1) uniformly mixing silver-separating slag of copper anode slime, carbon-containing materials and auxiliary agents, and pressing the mixed materials into blocks.
S2) roasting the lump materials under microwaves for 1.5-4.5 h at the roasting temperature of 350-950 ℃ to obtain roasting slag.
S3) crushing and grinding roasting slag, adding the roasting slag into sulfuric acid solution, stirring and pulping, adding alkali containing solution, heating and leaching tin to obtain tin-leaching solution and tin-leaching slag, and conveying the tin-leaching slag to other valuable elements for recycling;
S4) adding a calcium-containing reagent into the tin immersion liquid to obtain a tin-precipitated liquid and tin-precipitated slag, delivering antimony to the tin-precipitated liquid for recovery, and washing the tin-precipitated slag to obtain tin concentrate.
Further, the carbon-containing material in the S1) is one or more of coal powder, charcoal powder, coke powder and graphite powder, the auxiliary agent is one or more of sodium sulfide, potassium sulfide, calcium sulfide and magnesium sulfide, and the silver-separating slag, the carbon-containing material and the auxiliary agent are mixed according to the mass ratio of 1:0.3-1.8:0.05-0.3.
Further, the sulfuric acid solution in the step S3) can be a waste acid solution, the adding amount is controlled by the pH of a slurrying end point, the pH of the slurrying end point is controlled to be 1-10, the alkali solution is a solution or waste liquid of sodium hydroxide and potassium hydroxide, the concentration of hydroxyl is 0.5-3.5 mol/L, the sulfuric acid solution is added according to the volume-mass ratio of the alkali solution to the roasting slag of 0.5-10, the tin leaching temperature is 40-90 ℃ and the time is 0.5-4 h.
Further, the calcium reagent in the S4) is one or a combination of more of calcium oxide, calcium hydroxide, calcium chloride and calcium sulfate, the amount of the calcium reagent is added according to the molar ratio of calcium to tin of 1.0-3.0, the tin precipitation temperature is 20-90 ℃, and the tin precipitation time is 0.5-4 h.
Compared with the prior art, the process has the beneficial effects and outstanding advantages that:
1) The auxiliary agent is added as the roasting auxiliary agent and the materials are pressed into blocks, so that the microwave roasting effect becomes stable, and when the silver slag component or the microwave roasting temperature fluctuates, the concentration of tin in the leaching solution is basically unchanged.
2) The method has the advantages that the method adopts the sulfuric acid solution to slurry and then adopts the alkaline solution to leach, so that the tin leaching is realized in one step, the flow is shortened, and the treatment cost is reduced.
3) Both the sulfuric acid solution and the alkali-containing solution can be waste liquid in production, so that the treatment cost can be reduced, and the discharge of the waste liquid can be reduced.
Drawings
Fig. 1 is a flow chart of a method for efficiently extracting tin from silver-separating slag of copper anode slime.
Detailed Description
The present invention will be described in further detail by way of examples, but the scope of the present invention is not limited to these examples.
As shown in fig. 1, the method for efficiently extracting tin from silver separating slag of copper anode slime comprises the following steps in sequence:
S1) uniformly mixing silver-separating slag of copper anode slime, a carbon-containing material and an auxiliary agent according to a set proportion, and pressing the mixed material into blocks to obtain blocks;
S2) placing the lump material obtained in the S1) under microwave for roasting to obtain roasting slag;
S3) crushing and grinding the roasting slag obtained in the step S2), adding the crushed and ground roasting slag into sulfuric acid solution, stirring and pulping, adding alkali containing solution, and then heating to leach tin to obtain tin-leaching solution and tin-leaching slag;
S4) adding a calcium-containing reagent into the tin immersion liquid obtained in the step S3) to carry out tin precipitation, so as to obtain a tin precipitation post-liquid and tin precipitation slag, sending antimony to the tin precipitation post-liquid for recovery, and washing the tin precipitation slag to obtain tin concentrate.
The mass ratio of the silver separating slag of the copper anode slime in the S1) to the carbon-containing material to the auxiliary agent is 1:0.3-1.8:0.05-0.3.
The carbon-containing material is one or more of coal powder, charcoal powder, coke powder and graphite powder;
the auxiliary agent is one or more of sodium sulfide, potassium sulfide, calcium sulfide and magnesium sulfide.
The roasting temperature in the step S2) is 350-950 ℃ and the roasting time is 1.5-4.5 h.
The specific process in the S3) is as follows:
S3.1) crushing the roasting slag, and grinding to obtain roasting slag powder;
s3.2) adding the roasting slag powder into sulfuric acid solution for pulping, wherein the pH of the pulping end point is controlled to be 1-10;
S3.3) adding the tin according to the volume-mass ratio of the alkali-containing solution to the roasting slag powder of 0.5-10, wherein the tin leaching temperature is 40-90 ℃ and the tin leaching time is 0.5-4 h, and obtaining tin-immersing liquid and tin-immersing slag.
The sulfuric acid solution is waste acid solution;
The alkali-containing solution is a solution of sodium hydroxide and potassium hydroxide or waste alkali solution, and the concentration of hydroxyl in the alkali-containing solution is 0.5-3.5 mol/L.
The technological parameters of tin precipitation in the S4) are as follows:
The amount of the calcium reagent is added according to the molar ratio of calcium to tin of 1.0-3.0, the tin precipitation temperature is 20-90 ℃, and the tin precipitation time is 0.5-4 h.
The calcium reagent is one or the combination of more of calcium oxide, calcium hydroxide, calcium chloride and calcium sulfate,
In the method, the yield of tin of the tin concentrate obtained after the silver separating slag treatment of the copper anode slime is not lower than 90.0%.
Example 1
Taking 100g of silver-separated slag, 105g of charcoal powder and 20g of sodium sulfide in practice, uniformly mixing, pressing into a block shape, and then roasting for 1.5h at 530 ℃ by microwaves to obtain roasting slag. Crushing and grinding roasting slag, adding vulcanized liquid, mixing, pulping, monitoring the pH of the slurry, stopping adding the vulcanized liquid when the pH is=3, adding 300mL of antimony precipitation waste liquid, uniformly stirring, heating to 75 ℃, stirring for 2.5 hours, filtering to obtain tin-immersed slag and tin-immersed liquid, conveying the tin-immersed slag to other valuable elements for recycling, adding calcium oxide into the tin-immersed liquid according to the molar ratio of calcium to tin of 1.4, heating to 90 ℃, stirring for 1 hour, filtering, conveying antimony from filtrate for recycling, and washing filter residues to obtain tin concentrate, wherein the yield of tin from silver-separated slag to tin concentrate is 90.6%.
Example 2
Taking 500g of silver-separated slag, 260g of charcoal powder and 110g of calcium sulfide, uniformly mixing, pressing into blocks, and then roasting for 2.5 hours at 600 ℃ by microwaves to obtain roasting slag. Crushing and grinding roasting slag, adding waste acid stock solution, mixing, pulping, monitoring the pH of the slurry, stopping adding the waste acid stock solution when the pH is=5, adding 2.0L of alkali solution with the concentration of sodium hydroxide of 1.2mol/L, stirring uniformly, heating to 80 ℃, stirring for 3.5 hours, filtering to obtain tin-immersed slag and tin-immersed solution, conveying the tin-immersed slag to other valuable elements for recycling, adding calcium chloride into the tin-immersed solution according to the molar ratio of calcium to tin of 1.4, heating to 75 ℃, stirring for 1.5 hours, filtering, conveying antimony from filtrate, recycling, washing filter residues to obtain tin concentrate, and obtaining the tin yield from silver-separated slag to tin concentrate of 91.0%.
Example 3
Taking 300g of silver-separated slag, 130g of charcoal powder and 63g of potassium sulfide, uniformly mixing, pressing into blocks, and then roasting for 3.0h at 700 ℃ by microwaves to obtain roasting slag. Crushing and grinding roasting slag, adding copper electrolysis waste liquid, mixing, pulping, monitoring the pH of the slurry, stopping adding the copper electrolysis waste liquid when the pH is 7, adding 1.2L of alkali liquid with the potassium hydroxide concentration of 1.5mol/L, stirring uniformly, heating to 80 ℃, stirring for 3.0h, filtering to obtain tin-immersed slag and tin-immersed liquid, feeding the tin-immersed slag with other valuable elements for recycling, adding calcium hydroxide into the tin-immersed liquid according to the molar ratio of calcium to tin of 2.0, heating to 65 ℃, stirring for 4h, filtering, feeding antimony into the filtrate for recycling, washing the filter residues to obtain tin concentrate, and obtaining the tin yield of 91.9% from silver-separated slag to tin concentrate.
Compared with the prior art, the method has the advantages of short flow, low treatment cost, stable tin recovery effect, simple operation and good industrial application prospect.
The foregoing is a further detailed description of the invention in connection with specific embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several simple deductions or substitutions can be made without departing from the spirit of the invention, and all such modifications are to be considered as falling within the scope of the invention.
Claims (4)
1. The method for efficiently extracting tin from the silver separating slag of the copper anode slime is characterized by comprising the following steps of:
S1) uniformly mixing silver-separating slag of copper anode slime, a carbon-containing material and an auxiliary agent according to a set proportion, and pressing the mixed material into blocks to obtain blocks;
The mass ratio of the silver separating slag of the copper anode slime to the carbon-containing material to the auxiliary agent is 1:0.3-1.8:0.05-0.3; the auxiliary agent is one or more of sodium sulfide, potassium sulfide, calcium sulfide and magnesium sulfide;
S2) placing the lump material obtained in the S1) under microwave for roasting to obtain roasting slag;
Roasting at 350-950 deg.c for 1.5-4.5 hr;
S3) crushing and grinding the roasting slag obtained in the step S2), adding the crushed and ground roasting slag into sulfuric acid solution, stirring and pulping, adding alkali containing solution, and then heating to leach tin to obtain tin-leaching solution and tin-leaching slag;
the specific process comprises the following steps: s3.1) crushing the roasting slag, and grinding to obtain roasting slag powder;
s3.2) adding the roasting slag powder into sulfuric acid solution for pulping, wherein the pH of the pulping end point is controlled to be 1-10;
s3.3) adding the tin according to the volume-mass ratio of the alkali-containing solution to the roasting slag powder of 0.5-10, wherein the tin leaching temperature is 40-90 ℃ and the tin leaching time is 0.5-4 h, so as to obtain tin-leaching solution and tin-leaching slag;
s4) adding a calcium-containing reagent into the tin immersion liquid obtained in the step S3) to perform tin precipitation, so as to obtain a tin precipitation post-liquid and tin precipitation slag, feeding antimony into the tin precipitation post-liquid for recovery, and washing the tin precipitation slag to obtain tin concentrate;
The technological parameters of tin precipitation are as follows: the amount of the calcium reagent is added according to the molar ratio of calcium to tin of 1.0-3.0, the tin precipitation temperature is 20-90 ℃, and the tin precipitation time is 0.5-4 h;
In the method, the yield of tin of the tin concentrate obtained after the silver separating slag treatment of the copper anode slime is not lower than 90.0%.
2. The method of claim 1, wherein the char-containing material is one or more of coal dust, charcoal dust, coke dust, and graphite dust.
3. The method of claim 1, wherein the sulfuric acid solution is a spent acid solution; the alkali-containing solution is a solution of sodium hydroxide and potassium hydroxide or waste alkali solution, and the concentration of hydroxyl in the alkali-containing solution is 0.5-3.5 mol/L.
4. The method of claim 1, wherein the calcium reagent is one or a combination of several of calcium oxide, calcium hydroxide, calcium chloride, and calcium sulfate.
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