CN115505762A - Indium extraction method of indium-containing multi-metal smelting slag - Google Patents
Indium extraction method of indium-containing multi-metal smelting slag Download PDFInfo
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- CN115505762A CN115505762A CN202211170367.9A CN202211170367A CN115505762A CN 115505762 A CN115505762 A CN 115505762A CN 202211170367 A CN202211170367 A CN 202211170367A CN 115505762 A CN115505762 A CN 115505762A
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 130
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000002893 slag Substances 0.000 title claims abstract description 88
- 238000000605 extraction Methods 0.000 title claims abstract description 65
- 238000003723 Smelting Methods 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 238000005406 washing Methods 0.000 claims abstract description 83
- 238000002386 leaching Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 24
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003500 flue dust Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000000428 dust Substances 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 239000000779 smoke Substances 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 56
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 46
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 238000000746 purification Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 28
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 14
- 239000011775 sodium fluoride Substances 0.000 claims description 13
- 235000013024 sodium fluoride Nutrition 0.000 claims description 13
- 238000004064 recycling Methods 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000000873 masking effect Effects 0.000 claims description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 150000004673 fluoride salts Chemical class 0.000 claims description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- 239000010881 fly ash Substances 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052718 tin Inorganic materials 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 11
- 229910052785 arsenic Inorganic materials 0.000 abstract description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 239000010949 copper Substances 0.000 abstract description 6
- 239000002244 precipitate Substances 0.000 abstract description 6
- 150000001450 anions Chemical class 0.000 abstract description 5
- 159000000000 sodium salts Chemical class 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 235000011164 potassium chloride Nutrition 0.000 abstract 1
- 239000001103 potassium chloride Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 16
- 239000003350 kerosene Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- AJAXZLXLXZWIIE-UHFFFAOYSA-N indium;hydrochloride Chemical compound Cl.[In] AJAXZLXLXZWIIE-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000010453 quartz Substances 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
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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
-
- 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
- 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
-
- 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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- 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 relates to an indium extraction method of indium-containing multi-metal smelting slag, which comprises the steps of firstly carrying out oxygen-enriched side-blown smelting treatment on the indium-containing multi-metal smelting slag, collecting indium-containing smoke dust at the rear end of an arsenic-collecting filter membrane to obtain low-arsenic indium-containing multi-metal flue dust, adding fluorine-containing combined salt serving as a selective leaching promoter after acid washing, breaking the wrapping of silicon on indium, improving the leaching rate of indium, and simultaneously stably combining fluorine with silicon and aluminum, and removing the generated precipitate with sodium salt and sylvite; tin and fluorine exist in the form of complex anion and are not extracted, reducing agent is added to enable impurities containing arsenic, iron and copper elements to form precipitate to be removed, organic acid is added to mask other impurity metal ions in the solution to be extracted, and therefore the extraction process of indium is carried out smoothly and efficiently. The indium recovery rate by the method reaches more than 95 percent.
Description
Technical Field
The invention belongs to the technical field of rare metal metallurgy, and particularly relates to an indium extraction method of indium-containing multi-metal smelting slag.
Background
Indium is a rare metal, and the extraction process of indium mainly adopts an extraction-electrolysis method, which is also the mainstream process technology for indium production in the world nowadays. The principle process flow is as follows: indium-containing raw material → enrichment → chemical dissolution → purification → extraction → back extraction → zinc (aluminum) displacement → sponge indium → electrolytic refining → refined indium. The purification and extraction process is a core process and directly determines the product quality.
The existing indium-containing smelting waste almost coexists with multi-metal elements and contains toxic and harmful elements such as arsenic, fluorine, chlorine and the like, and in the pyrogenic process enrichment process, arsenic, fluorine, chlorine, part of volatile metals such as lead, zinc, bismuth, germanium, gallium, tin and the like and indium are enriched in smoke dust.
The existing indium extraction method is mainly carried out by using an organic phosphorus extractant, such as P204 or P507, and mainly extracts cations. Trivalent iron element is preferentially extracted by P204, so trivalent iron needs to be reduced before extraction, a small amount of impurity elements such as tin and the like are extracted into an organic phase together with indium during extraction, and in addition, if the fluorine content in the solution is too high, due to the complexing performance of fluorine, indium, tin and the like form complex anions and exist in the solution, so that the extraction efficiency is influenced.
Chinese patent application CN112646985A discloses a method for enriching and purifying metal indium in ITO film etching waste liquid, which comprises the steps of firstly filtering the ITO film etching waste liquid, then adding strong base to adjust the pH value of the solution, then adopting a P204-EDTA sulfonated kerosene extraction system to extract to obtain an indium-loaded organic phase, and finally adopting hydrochloric acid to perform back extraction to obtain an indium hydrochloric acid solution. By adjusting the acidity and the phase ratio of extraction and back extraction, the concentration of indium in the water phase is greatly improved, and finally the separation of indium from other metal ions such as tin, molybdenum and aluminum is realized, so that the subsequent electrolytic refining is guaranteed, and the recovery rate of indium can reach more than 90%. However, the recovery rate of indium is low due to the influence of impurities such as tin and aluminum.
Chinese patent application CN111778395A discloses a method for maintaining high-efficiency extraction of indium, which mixes an organic phase subjected to back extraction in an indium extraction process with a separating agent to obtain a diluent, an extracting agent, a first water phase and a precipitate which are distributed in a layered manner from top to bottom. And then recovering the diluent, the extracting agent and the fluxing agent, mixing and re-fusing to obtain a new organic phase, and returning to the indium extraction process for use. In the process, on one hand, the impurities in the poor organic phase are generated and precipitated and separated out, thereby solving the problem of organic phase poisoning and ensuring the purity of the organic phase. On the other hand, after the diluent and the extracting agent are added into the separator, the diluent and the extracting agent are thoroughly separated into two layers, and the proportion of the diluent and the extracting agent can be intuitively and accurately judged so as to adjust the proportion of the diluent and the extracting agent in time and ensure the high-efficiency indium extraction. Because indium and impurities are simultaneously extracted and enriched, the separation by back extraction is not complete.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an indium extraction method of indium-containing multi-metal smelting slag, which solves the problems that the indium content in the indium-containing multi-metal smelting slag is low and is difficult to economically recover, and the impurity purification efficiency and the indium extraction rate are low in the indium extraction process of the indium-containing multi-metal smelting slag.
In order to solve the technical problems, the technical scheme of the invention is as follows:
an indium extraction method of indium-containing multi-metal smelting slag comprises the following steps:
s1, oxygen-enriched side-blown smelting is carried out on indium-containing polymetallic smelting slag, indium-containing smoke dust is collected at the rear end of an arsenic-collecting filter membrane, and low-arsenic indium-containing polymetallic flue dust is obtained;
s2, mixing the low-arsenic indium-containing polymetallic flue ash with water, adjusting the pH value to 4.5-5.3, and carrying out solid-liquid separation to obtain primary washing slag and primary washing liquid;
s3, adjusting the pH value of the primary washing slag to 0.3-0.8, adding fluorine-containing combined salt, stirring, and after the reaction end point is reached, carrying out solid-liquid separation to obtain primary leaching slag and primary leaching liquid;
s4, adding a reducing agent into the primary leaching solution, standing and settling, and performing solid-liquid separation to obtain primary purification slag and primary purification liquid;
s5, adjusting the pH value of the primary purification liquid to 0.2-0.3, and extracting indium to obtain an extract phase and a raffinate phase;
s6, carrying out back extraction on the extract phase to obtain a back extraction solution and an organic phase;
s7, replacing indium in the strip liquor by zinc powder to obtain sponge indium.
The indium content in the indium-containing multi-metal smelting slag is low, and the indium is difficult to be economically recovered, and in addition, the impurity purification efficiency in the indium extracting process of the indium-containing multi-metal smelting slag is not high, so that the extraction rate of the indium is low. In the invention, valuable metal elements in the indium-containing polymetallic smelting slag are preliminarily enriched, arsenic trioxide is separated by an arsenic-collecting filter membrane to obtain low-arsenic indium-containing polymetallic flue dust, and impurities containing zinc elements are removed by washing with an acidic solution; by adding fluorine-containing combined salt as a selective leaching promoter, the wrapping of silicon on indium is broken, the leaching rate of indium is improved, and meanwhile, fluorine can be stably combined with silicon and aluminum and can generate precipitates with sodium salt and potassium salt to be removed; the remaining small amount of fluorine forms SnF with Sn 6 2- Complex anions are not extracted, the influence of tin on the subsequent extraction of indium is eliminated, and impurities containing arsenic, iron and copper elements are generated and precipitated by adding a reducing agent and are removed; in addition, organic acid is added as a masking agent in the extraction process, so that the distribution coefficient of indium in the extraction process is improved, and the recovery rate of indium is improved.
Optionally, the subsequent treatment of the primary leaching residue obtained in step S3 includes the following steps:
(1) Mixing the primary leaching residue with water, and performing solid-liquid separation to obtain secondary washing residue and secondary washing liquid;
(2) And mixing the secondary washing slag with an alkaline solution, and performing solid-liquid separation to obtain an alkaline solution and alkaline washing slag.
Further, in the step (1), the secondary washing liquid is recovered and used for adjusting the pH value in the steps S2, S3 and S5.
Further, in the step (2), the alkaline solution is one or two of a sodium hydroxide solution and a potassium hydroxide solution; recycling the alkaline washing liquid, and preparing fluorine-containing combined salt for the step S3; and returning the alkali washing slag to the oxygen-enriched side-blown smelting furnace to smelt and recover metals such as lead, silver and the like.
The equation of the reaction in step (2) is:
Na 2 SiF 6 +4NaOH＝6NaF+SiO 2 +2H 2 O
K 2 SiF 6 +4KOH＝6KF+SiO 2 +2H 2 O
further, in S1, the indium-containing multi-metal smelting slag comprises the following main components in percentage by mass: 0.01 to 0.05 percent of indium, 1 to 3 percent of zinc oxide, 0.1 to 0.5 percent of copper, 20 to 30 percent of iron, 1 to 3 percent of aluminum, 3 to 7 percent of arsenic, 0.1 to 0.5 percent of tin, 30 to 35 percent of silicon dioxide and 0.5 to 2 percent of fluorine.
Further, in S1, mixing the indium-containing multi-metal smelting slag with quartz stone, pyrite and carbon according to a mass ratio of 1: (0.02-0.05): (0.01-0.05): (0.08-0.15), adding the mixture into an oxygen-enriched side-blown smelting furnace for metallurgical reaction, and collecting indium-containing smoke dust at the rear end of the arsenic-collecting filter membrane to obtain low-arsenic indium-containing multi-metal flue dust.
Further, the low-arsenic indium-containing multi-metal flue dust comprises the following main components in percentage by mass: 0.1 to 0.5 percent of indium, 20 to 40 percent of zinc oxide, 0.1 to 0.5 percent of copper, 2 to 8 percent of iron, 0.5 to 2 percent of aluminum, 0.1 to 0.5 percent of arsenic, 1 to 5 percent of tin, 10 to 20 percent of silicon dioxide and 1 to 8 percent of fluorine.
Further, pH is adjusted by using an acidic solution in S2, S3 and S5, wherein the acidic solution is one or more of a sulfuric acid solution, a hydrochloric acid solution and a nitric acid solution; preferably a sulfuric acid solution.
Further, in the step S2, the mass ratio of the low-arsenic indium-containing polymetallic flue dust to water is 1:3-1:6.
further, in step S2, the primary washing liquid is recycled to produce zinc carbonate.
Further, in step S3, the fluorine-containing combined salt is a mixture of a fluoride salt and a sulfate salt, the fluoride salt is one or two of sodium fluoride and potassium fluoride, the sulfate salt is one or two of sodium sulfate and potassium sulfate, and the mass ratio of the fluoride salt to the sulfate salt is 1:3-1:5, the addition amount of the fluorine-containing combined salt is 10-20% of the mass of the primary washing slag.
In the step S3, fluorine-containing combined salt is used as a selective leaching promoter, so that the wrapping of silicon on indium is broken, the leaching rate of indium is improved, and meanwhile, fluorine can be stably combined with silicon and aluminum and can be removed together with sodium salt and potassium salt to generate precipitates; the remaining small amount of fluorine forms SnF with Sn 6 2- Complex anion, excluding the influence of tin on the subsequent extraction of indium, and the reaction equation is as follows:
SiO 2 +6F - +6H + +Na 2 SO 4 ＝Na 2 SiF 6 ↓+H 2 SO 4 +2H 2 O
SiO 2 +6F - +6H + +K 2 SO 4 ＝K 2 SiF 6 ↓+H 2 SO 4 +2H 2 O
SiO 2 +6NaF+2H 2 SO 4 ＝Na 2 SiF 6 ↓+2Na 2 SO 4 +2H 2 O
SiO 2 +6KF+2H 2 SO 4 ＝K 2 SiF 6 ↓+2K 2 SO 4 +2H 2 O
Al 3+ +3F - ＝AlF 3 ↓
Sn 4+ +6F - ＝SnF 6 2-
further, the reaction temperature in step S3 is 70 ℃ to 90 ℃, preferably 80 ℃.
Alternatively, in step S3, the end point of the reaction is determined by one of the following methods:
the method comprises the following steps: stirring until the pH value is stabilized at 0-1 as a reaction end point;
the second method comprises the following steps: stirring until the aluminum and silicon contents in the leachate are lower than 1g/L, and taking the reaction as a reaction end point;
the first method is preferred to determine the reaction end point, and the pH value of the reaction end point is preferably 0.3-0.6.
Further, the primary leachate comprises the following main components: 1-1.2g/L of indium, 8-10g/L of zinc, 0.5-0.8g/L of aluminum, 4-5g/L of tin, 0.1-0.2g/L of copper, 5-8g/L of iron, 0.5-1g/L of arsenic, 0.3-0.8g/L of silicon and 1-3g/L of fluorine.
Further, in step S4, the reducing agent is iron powder, the theoretical addition amount of the reducing agent is calculated according to the sum of the contents of arsenic, iron and copper in the primary leachate, the addition amount of the reducing agent is 0.8-1.5 times of the theoretical addition amount, and the standing and settling time is 24 hours.
Further, in step S4, the primary purified slag is returned to the oxygen-enriched side-blown smelting furnace for smelting.
Further, in step S5, an organic acid is added to the primary purification solution as a masking agent, the organic acid is one or more of tartaric acid, citric acid and EDTA, and the addition amount of the organic acid is 1-5% of the mass of the primary purification solution.
Further, in step S5, one or two of P204 and P507 are mixed with 260# kerosene to be used as an extracting agent.
Further, in step S6, hydrochloric acid is used as a stripping agent.
Further, the extraction process adopts 5-stage countercurrent extraction, 2-stage clarification, 2-stage washing, 3-stage back extraction, 2-stage regeneration and 2-stage washing.
Further, in step S7, the strip liquor is reduced with zinc powder to obtain sponge indium.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, fluorine-containing combined salt is added as a selective leaching promoter, so that the wrapping of silicon on indium is broken, the leaching rate of indium is improved, and meanwhile, fluorine can be stably combined with silicon and aluminum and can generate precipitates with sodium salt and potassium salt to be removed; tin is present as a complex anion with fluorine and is not extracted; the influence of other impurity elements on the extraction of indium is eliminated by adding organic acid as a masking agent, and the recovery rate of indium can reach more than 95%.
(2) The waste liquid and the waste residue can be recycled, which is not only beneficial to environmental protection, but also realizes the recycling and comprehensive utilization of resources.
Drawings
FIG. 1 is a process flow diagram of the method for extracting indium from an indium-containing polymetallic slag according to the invention.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The contents of the main components of the indium-containing polymetallic slag and the low-arsenic indium-containing polymetallic flue dust in the following examples are shown in Table 1.
TABLE 1 content of main constituents of indium-containing polymetallic smelting slag and low-arsenic indium-containing polymetallic flue dust
Example 1
The embodiment provides an indium extraction method of indium-containing multi-metal smelting slag, which comprises the following steps:
s1, smelting the indium-containing multi-metal smelting slag by an RE type oxygen-enriched side-blown converter, and collecting indium-containing smoke dust at the rear end of an arsenic-collecting filter membrane to obtain low-arsenic indium-containing multi-metal flue dust.
S2, mixing the low-arsenic indium-containing multi-metal flue dust and water according to a mass ratio of 1:4, uniformly mixing; and adding a sulfuric acid solution into the mixture slurry to adjust the pH value to 5.3, keeping the pH value constant for 30 minutes, and filtering and separating to obtain primary washing slag and primary washing liquid.
And S3, mixing the primary washing slag with a sulfuric acid solution, adjusting the pH value to be 0.5, adding a sodium fluoride and sodium sulfate combined salt according to 10% of the mass of the primary washing slag, wherein the mass ratio of the sodium fluoride to the sodium sulfate in the combined salt is 1:3,80 deg.C, stirring uniformly at constant temperature until the pH value of the mixed liquor is stabilized to 0.5, filtering and separating to obtain primary leaching residue and primary leaching liquid.
And S4, adding iron powder with the theoretical addition amount of 0.95 time into the primary leaching solution for reduction and purification, settling for 24 hours, and filtering and separating to obtain primary purification slag and primary purification liquid.
And S5, adding 0.5wt% of citric acid serving as a masking agent into the primary purifying liquid, wherein the addition amount of the 0.5wt% of citric acid is 2 per mill of the mass of the primary purifying liquid, adding a sulfuric acid solution to adjust the pH value to be 0.3, taking supernate, and extracting indium by using an extracting agent prepared from P204 and 260# kerosene according to the mass ratio of 1.
And S6, circulating the extraction phase for 10 times after back extraction.
And S7, replacing indium in the strip liquor by zinc powder to obtain sponge indium.
The extraction process has no emulsification phenomenon, the three-stage extraction rate of indium is more than 99.5 percent, and the indium recovery rate of the whole process is more than 95 percent.
The subsequent treatment of the primary leached slag comprises the following steps:
washing the primary leached slag with water to obtain secondary washed slag and secondary washing liquid; and (5) recycling the secondary washing liquid, and preparing a sulfuric acid solution for regulating the pH value in the steps S2, S3 and S5.
Mixing the secondary washing slag with a sodium hydroxide solution, and performing solid-liquid separation to obtain an alkaline washing liquid and alkaline washing slag; and (4) recycling the alkaline washing liquid, preparing sodium fluoride for step S3, and returning alkaline washing slag to the oxygen-enriched side-blown smelting furnace for smelting.
Comparative example 1
Example 1 was repeated, with the only difference that in step S3 no sodium fluoride and sodium sulphate combination salt was added, the specific steps were as follows:
s1, smelting the indium-containing multi-metal smelting slag by an RE type oxygen-enriched side-blown converter, and collecting indium-containing smoke dust at the rear end of an arsenic-collecting filter membrane to obtain low-arsenic indium-containing multi-metal flue dust.
S2, mixing the low-arsenic indium-containing multi-metal flue ash and water according to a mass ratio of 1:4, uniformly mixing; and adding a sulfuric acid solution into the mixture slurry to adjust the pH value to 5.3, keeping the pH value constant for 30 minutes, and filtering and separating to obtain primary washing slag and primary washing liquid.
And S3, mixing the primary leaching residue with a sulfuric acid solution, adjusting the pH value to 0.5, uniformly stirring at a constant temperature of 80 ℃ until the pH value of the mixed solution is stable, and filtering and separating to obtain the primary leaching residue and the primary leaching solution.
And S4, adding iron powder with the theoretical addition amount of 0.95 time into the primary leaching solution for reduction and purification, settling for 24 hours, and filtering and separating to obtain primary purification slag and primary purification liquid.
And S5, adding 0.5wt% of citric acid serving as a masking agent into the primary purifying liquid, wherein the addition amount of the 0.5wt% of citric acid is 2 per mill of the mass of the primary purifying liquid, adding a sulfuric acid solution to adjust the pH value to be 0.3, taking supernate, and extracting indium by using an extracting agent prepared from P204 and 260# kerosene according to the mass ratio of 1.
And S6, circulating the extraction phase for 10 times after back extraction.
And S7, replacing indium with the stripping solution through zinc powder to obtain sponge indium.
The subsequent treatment of the primary leaching residue comprises the following steps:
washing the primary leached slag with water to obtain secondary washed slag and secondary washing liquid; and (5) recycling the secondary washing liquid, and preparing a sulfuric acid solution for regulating the pH value in the steps S2, S3 and S5.
And (2) mixing the secondary washing slag with a sodium hydroxide solution, carrying out solid-liquid separation to obtain alkaline washing liquid and alkaline washing slag, and returning the alkaline washing slag to the oxygen-enriched side-blown smelting furnace for smelting.
By comparison with example 1, in step S3, no sodium fluoride and sodium sulfate salt is added, and the subsequent extraction and emulsification phenomena in the indium extraction step are severe, the tertiary extraction rate of indium is less than 90%, and the recovery rate of indium in the whole process is less than 80%.
Comparative example 2
Example 1 was repeated with the only difference that in step S5 no 0.5% citric acid was added as masking agent, the specific steps are as follows:
s1, smelting the indium-containing multi-metal smelting slag by an RE type oxygen-enriched side-blown converter, and collecting indium-containing smoke dust at the rear end of an arsenic-collecting filter membrane to obtain low-arsenic indium-containing multi-metal flue dust.
S2, mixing the low-arsenic indium-containing multi-metal flue ash and water according to a mass ratio of 1:4, uniformly mixing; and adding a sulfuric acid solution into the mixture slurry to adjust the pH value to 5.3, keeping the pH value constant for 30 minutes, and filtering and separating to obtain primary washing slag and primary washing liquid.
And S3, mixing the primary washing slag with a sulfuric acid solution, adjusting the pH value to be 0.5, adding sodium fluoride and sodium sulfate combined salt according to 10% of the mass of the primary washing slag, wherein the mass ratio of the sodium fluoride to the sodium sulfate in the combined salt is 1:3,80 deg.C, stirring uniformly at constant temperature until the pH value of the mixed liquor is stabilized to 0.5, filtering and separating to obtain primary leaching residue and primary leaching liquid.
And S4, adding iron powder with the theoretical addition amount of 0.95 time into the primary leaching solution for reduction and purification, settling for 24 hours, and filtering and separating to obtain primary purification slag and primary purification liquid.
And S5, adding a sulfuric acid solution into the primary purification solution to adjust the pH value to 0.3, taking supernate, and extracting indium by using an extracting agent prepared from P204 and 260# kerosene according to the mass ratio of 1.
And S6, circulating the extraction phase for 10 times after back extraction.
And S7, replacing indium with the stripping solution through zinc powder to obtain sponge indium.
The subsequent treatment of the primary leaching residue comprises the following steps:
washing the primary leached slag with water to obtain secondary washed slag and secondary washing liquid; and (5) recycling the secondary washing liquid, and preparing a sulfuric acid solution for regulating the pH value in the steps S2, S3 and S5.
Mixing the secondary washing slag with a sodium hydroxide solution, and performing solid-liquid separation to obtain an alkaline washing liquid and alkaline washing slag; and (4) recycling the alkaline washing liquid, preparing sodium fluoride for step S3, and returning alkaline washing slag to the oxygen-enriched side-blown smelting furnace for smelting.
By comparison with example 1, 0.5% citric acid is not added as a masking agent in step S5, a slight emulsification phenomenon occurs in the extraction process, the three-stage extraction rate of indium is less than 95%, the indium recovery rate in the whole process is less than 93%, and the indium recovery rate is reduced.
Example 2
The embodiment provides an indium extraction method of indium-containing multi-metal smelting slag, which comprises the following steps:
s1, smelting the indium-containing multi-metal smelting slag by an RE type oxygen-enriched side-blown converter, and collecting indium-containing smoke dust at the rear end of an arsenic-collecting filter membrane to obtain low-arsenic indium-containing multi-metal flue dust.
S2, mixing the low-arsenic indium-containing multi-metal flue dust and water according to a mass ratio of 1:6, uniformly mixing; and adding a sulfuric acid solution into the mixture slurry to adjust the pH value to 5.0, keeping the pH value constant for 30 minutes, and filtering and separating to obtain primary washing slag and primary washing liquid.
And S3, mixing the primary washing slag with a sulfuric acid solution, adjusting the pH value to be 0.5, adding a potassium fluoride and potassium sulfate combined salt according to 15% of the mass of the primary washing slag, wherein the mass ratio of potassium fluoride to potassium sulfate in the combined salt is 1:4, when the aluminum content in the leachate is lower than 1g/L and the silicon content is lower than 0.5g/L, filtering and separating to obtain primary leaching slag and primary leachate.
And S4, adding iron powder with the theoretical addition amount of 1.0 time into the primary leaching solution for reduction and purification, settling for 24 hours, and filtering and separating to obtain primary purification slag and primary purification liquid.
And S5, adding 0.5wt% of citric acid serving as a masking agent into the primary purifying liquid, wherein the addition amount of the 0.5wt% of citric acid is 1 per mill of the mass of the primary purifying liquid, adding a sulfuric acid solution to adjust the pH value to be 0.3, taking supernate, and extracting indium by using an extracting agent prepared from P204 and No. 260 kerosene according to the mass ratio of 1.
And S6, circulating the extraction phase for 10 times after back extraction.
And S7, replacing indium with the stripping solution through zinc powder to obtain sponge indium.
The extraction has no emulsification phenomenon, the three-stage extraction rate of indium is more than 99.0 percent, and the recovery rate of indium in the whole process is more than 95 percent.
The subsequent treatment of the primary leaching residue comprises the following steps:
washing the primary leached slag with water to obtain secondary washed slag and secondary washing liquid; and (4) recycling the secondary washing liquid, and preparing a sulfuric acid solution for adjusting the pH value in the steps S2, S3 and S5.
Mixing the secondary washing slag with a potassium hydroxide solution, and performing solid-liquid separation to obtain an alkaline washing liquid and alkaline washing slag; and (4) recycling the alkaline washing liquid, preparing potassium fluoride for step S3, and returning alkaline washing slag to the oxygen-enriched side-blown smelting furnace for smelting.
Example 3
The embodiment provides an indium extraction method of indium-containing multi-metal smelting slag, which comprises the following steps:
s1, smelting the indium-containing multi-metal smelting slag by an RE type oxygen-enriched side-blown converter, and collecting indium-containing smoke dust at the rear end of an arsenic-collecting filter membrane to obtain low-arsenic indium-containing multi-metal flue dust.
S2, mixing the low-arsenic indium-containing multi-metal flue ash and water according to a mass ratio of 1:3, uniformly mixing; and adding a sulfuric acid solution into the mixture slurry to adjust the pH value to 4.5, keeping the pH value constant for 30 minutes, and filtering and separating to obtain primary washing slag and primary washing liquid.
And S3, mixing the primary washing slag with a sulfuric acid solution, adjusting the pH value to be 0.5, adding a sodium fluoride and sodium sulfate combined salt according to 20% of the mass of the primary washing slag, wherein the mass ratio of the sodium fluoride to the sodium sulfate in the combined salt is 1:5,80 deg.C, stirring uniformly at constant temperature until the pH value of the mixed liquor is stabilized to 0.5, filtering and separating to obtain primary leaching residue and primary leaching liquid.
And S4, adding iron powder with the theoretical addition amount of 0.95 time into the primary leaching solution for reduction and purification, settling for 24 hours, and filtering and separating to obtain primary purification slag and primary purification liquid.
And S5, adding 0.5wt% of tartaric acid serving as a masking agent into the primary purifying liquid, wherein the adding amount of the 0.5wt% of tartaric acid is 5 per mill of the mass of the primary purifying liquid, adding a sulfuric acid solution to adjust the pH value to be 0.3, taking supernate, and extracting indium by using an extracting agent prepared from P204 and 260# kerosene according to the mass ratio of 1.
And S6, circulating the extraction phase for 10 times after back extraction.
And S7, replacing indium with the stripping solution through zinc powder to obtain sponge indium.
The extraction has no emulsification phenomenon, the three-stage extraction rate of indium is more than 99 percent, and the recovery rate of indium in the whole process is more than 97 percent.
The subsequent treatment of the primary leaching residue comprises the following steps:
washing the primary leached slag with water to obtain secondary washed slag and secondary washing liquid; and (5) recycling the secondary washing liquid, and preparing a sulfuric acid solution for regulating the pH value in the steps S2, S3 and S5.
Mixing the secondary washing slag with a sodium hydroxide solution, and performing solid-liquid separation to obtain an alkaline washing liquid and alkaline washing slag; and (4) recycling the alkaline washing liquid, preparing sodium fluoride for step S3, and returning alkaline washing slag to the oxygen-enriched side-blown smelting furnace for smelting.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.
Claims (10)
1. The indium extraction method of the indium-containing multi-metal smelting slag is characterized by comprising the following steps of:
s1, oxygen-enriched side-blown smelting is carried out on indium-containing polymetallic smelting slag, indium-containing smoke dust is collected at the rear end of an arsenic-collecting filter membrane, and low-arsenic indium-containing polymetallic flue dust is obtained;
s2, mixing the low-arsenic indium-containing polymetallic flue ash with water, adjusting the pH value to 4.5-5.3, and carrying out solid-liquid separation to obtain primary washing slag and primary washing liquid;
s3, adjusting the pH value of the primary leaching residue to 0.3-0.8, adding fluorine-containing combined salt, stirring, and after the reaction end point is reached, carrying out solid-liquid separation to obtain primary leaching residue and primary leaching liquid;
s4, adding a reducing agent into the primary leaching solution, standing and settling, and performing solid-liquid separation to obtain primary purification slag and primary purification liquid;
s5, adjusting the pH value of the primary purification liquid to 0.2-0.3, and extracting indium to obtain an extract phase and a raffinate phase;
s6, carrying out back extraction on the extract phase to obtain a back extraction solution and an organic phase;
s7, replacing indium with the stripping solution through zinc powder to obtain sponge indium.
2. The method according to claim 1, wherein in step S5, an organic acid is added as a masking agent to the primary cleaning solution; preferably, the organic acid is one or more of tartaric acid, citric acid and EDTA; the addition amount of the organic acid is preferably 1-5 per mill of the mass of the primary purification liquid.
3. The method according to claim 1, characterized in that the post-treatment of the primary leaching residue in S3 comprises the following steps:
(1) Mixing the primary leaching residue with water, and performing solid-liquid separation to obtain secondary washing residue and secondary washing liquid;
(2) And mixing the secondary washing slag with an alkaline solution, and performing solid-liquid separation to obtain an alkaline solution and alkaline washing slag.
4. The method according to claim 3, wherein the secondary washing liquid is recycled for adjusting the pH value in steps S2, S3 and S5; the alkaline solution is one or two of sodium hydroxide solution and potassium hydroxide solution; and (4) recycling the alkaline washing liquid, wherein the alkaline washing slag is returned to the oxygen-enriched side-blown smelting furnace for smelting in the step S3.
5. The method according to any one of claims 1 to 4, wherein the mass ratio of the low-arsenic indium-containing multi-metal flue dust and water in S2 is 1:3-1:6.
6. the method according to any one of claims 1 to 4, wherein the pH of S2, S3 and S5 is adjusted by using an acidic solution, and the acidic solution is one or more of a sulfuric acid solution, a hydrochloric acid solution and a nitric acid solution.
7. The method according to any one of claims 1 to 4, wherein in S3, the fluorine-containing combined salt is a mixture of a fluoride salt and a sulfate salt, the fluoride salt is one or two of sodium fluoride and potassium fluoride, the sulfate salt is one or two of sodium sulfate and potassium sulfate, and the mass ratio of the fluoride salt to the sulfate salt is 1:3-1:5, the addition amount of the fluorine-containing combined salt is 10-20% of the mass of the primary washing slag.
8. The method according to any one of claims 1 to 4, wherein in S3, the reaction temperature is 70 ℃ to 90 ℃.
9. The method according to any one of claims 1 to 4, wherein in S3, the end point of the reaction is determined by one of the following methods:
the method comprises the following steps: stirring until the pH value is stabilized at 0-1 as a reaction end point;
the second method comprises the following steps: stirring until the aluminum and silicon contents in the leachate are lower than 1g/L, and taking the reaction as the end point.
10. The method according to any one of claims 1 to 4, wherein in S4, the reducing agent is iron powder, and the amount of the reducing agent added is 0.8 to 1.5 times the theoretical amount of addition.
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