CN112375915A - Method for removing harmful elements arsenic and antimony in high-content bismuth-silver smelting slag - Google Patents
Method for removing harmful elements arsenic and antimony in high-content bismuth-silver smelting slag Download PDFInfo
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 88
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 81
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002893 slag Substances 0.000 title claims abstract description 62
- 238000003723 Smelting Methods 0.000 title claims abstract description 43
- CCXYPVYRAOXCHB-UHFFFAOYSA-N bismuth silver Chemical compound [Ag].[Bi] CCXYPVYRAOXCHB-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000002386 leaching Methods 0.000 claims abstract description 113
- 229910052709 silver Inorganic materials 0.000 claims abstract description 32
- 239000004332 silver Substances 0.000 claims abstract description 32
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 89
- 238000005406 washing Methods 0.000 claims description 82
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- 239000007787 solid Substances 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000004317 sodium nitrate Substances 0.000 claims description 43
- 235000010344 sodium nitrate Nutrition 0.000 claims description 43
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 33
- 238000000926 separation method Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 18
- 239000000292 calcium oxide Substances 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 18
- 238000011010 flushing procedure Methods 0.000 claims description 16
- 238000003801 milling Methods 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 238000005086 pumping Methods 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 claims description 9
- 229940103357 calcium arsenate Drugs 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000000498 cooling water Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052797 bismuth Inorganic materials 0.000 abstract description 33
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 154
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 14
- 239000011575 calcium Substances 0.000 description 14
- 229910052791 calcium Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000001698 pyrogenic effect Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910000070 arsenic hydride Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910017251 AsO4 Inorganic materials 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/044—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- 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
- C22B30/06—Obtaining bismuth
-
- 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
- C22B7/006—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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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of comprehensive recovery of non-ferrous metal smelting, and discloses a method for removing harmful elements arsenic and antimony in high-content bismuth-silver smelting slag3The treatment medium is alkaline medium, the corrosion of equipment is small, the production environment is friendly, the main components in the leaching residue are still bismuth and silver, but the grades are all improved in different degrees.
Description
Technical Field
The invention belongs to the technical field of comprehensive recovery of non-ferrous metal smelting, relates to a method for removing harmful elements, and particularly relates to a method for removing harmful elements arsenic and antimony in high-content bismuth silver smelting slag.
Background
Lead-bismuth alloy containing lead of about 60%, bismuth of 20% and silver of 3-5% is produced in the copper smelting production, and is usually smelted into a lead anode by adopting an anode furnace, and is electrolyzed in a silicofluoric acid-lead silicofluoride medium to obtain cathode lead of about 99.5% and high-content bismuth-silver smelting slag.
The high-content bismuth silver smelting slag generally comprises 50-60% of bismuth (Bi), 8-15% of silver (Ag), 3-8% of lead (Pb), 2-4% of arsenic (As), 8-14% of antimony (Sb) and a small amount of copper (Cu), and is a dangerous solid waste with high content of valuable metals, high additional harmful elements such As arsenic and antimony.
Along with the increasing scarcity of non-ferrous metal rich ores, more and more attention is paid to the comprehensive recovery of various valuable metal elements from secondary resources like high-content bismuth silver smelting slag and the like. However, because of containing a lot of dangerous elements of arsenic and antimony, great difficulty is brought to the recovery work, and the prior art does not have a safe and mature recovery process, so that serious safety accidents are easy to occur in a certain link.
At present, the material with high bismuth content is mainly recycled by the following three ways.
1. Carrying out pyrogenic process treatment: for materials with low content of dangerous elements such as arsenic, antimony and the like, carrying out pyrometallurgy, adding sulfur to remove copper, removing arsenic, adding antimony, adding zinc to remove silver, removing lead by chlorination, carrying out zinc-alkaline refining, and recycling bismuth ingots; the pyrogenic process treatment process has high requirements on the arsenic and antimony contents in the slag, and generally requires that the antimony content is not higher than 5%.
2. And (3) wet treatment of nitric acid: ball-milling bismuth-containing materials, leaching with a high-concentration nitric acid solution, adding sulfuric acid into leachate for lead precipitation reaction, adding saturated salt solution into filtrate after filtering lead sulfate slag for silver precipitation, adjusting the pH value of the solution after silver precipitation to 3-4 by using a sodium carbonate solution to obtain basic bismuth nitrate white precipitate, and reducing the filtered bismuth slag by adopting a pyrogenic process to obtain metal bismuth; complexing the silver slag with ammonia water to obtain a silver ammonia solution, and reducing with hydrazine hydrate to obtain silver powder; in the production process of nitric acid treatment, the production of highly toxic chemical gas AsH3 is difficult to ensure, and high personal safety hidden danger exists.
3. Chloride salt method: by utilizing the characteristic that the material is easy to oxidize, firstly, the impurities such as arsenic, antimony, bismuth and the like in the material are converted into corresponding oxides through natural stacking oxidation or baking oxidation, and then the corresponding oxides are leached in an acid solution containing chloridion (Cl-) such as H2SO4+ NaCl or HCl + NaCl system. By controlling the Cl & lt- & gt concentration in the solution, the leaching rate of metals such as antimony, lead, copper, bismuth and the like is improved under the condition of preventing Ag from dissolving, the metals such as antimony, bismuth, copper and the like in the leaching solution are recovered by adopting a step-by-step hydrolysis process, and the leaching residue is subjected to oxidation, ammonia leaching, hydrazine or formaldehyde reduction to recover silver; the chloride method treatment has the defects of quick corrosion of equipment, poor production environment, harsh hydrolysis operation conditions and the like, and is difficult to popularize and apply in a large range.
Disclosure of Invention
The invention aims to provide a method for removing harmful elements arsenic and antimony in high-content bismuth silver smelting slag, which comprises the following steps:
performing ball milling in the step (1), performing ore flushing and wet ball milling on the high-bismuth-content silver smelting slag according to the ratio of solution (L) to slag (kg) = (3-4) to 1 by using a washing liquid, wherein the milling time is 30min, and the milling granularity reaches-60 meshes when 100%; pumping the supernatant after standing back to the elevated tank by a clean liquid pump to be used as grinding flushing water, and taking the underflow A as the raw material leached in the step (2);
pumping the bottom flow A obtained in the step (1) into a closed leaching tank by using an ore pulp pump, adding a regeneration solution G, controlling the solid-to-solid ratio of a leaching solution to be solution amount (L): slag amount (= 6-8): 1, adding a proper amount of a reaction reagent (the reaction reagent is prepared by adding reagent-grade solid sodium hydroxide to the solution concentration of 150-170G/L, stirring uniformly and then adding reagent-grade solid sodium nitrate to the solution concentration of 30-40G/L); heating and maintaining the reaction temperature to be more than 95 ℃, stirring for reaction for 180-240 minutes, and filtering to obtain alkaline leaching solution B and leaching residue C;
washing the leaching residue in the step (3), pulping the leaching residue C obtained in the step (2) at normal temperature by using water, carrying out two-stage countercurrent washing, wherein the solid-to-solid ratio of a washing solution is water amount (L): the amount of the leaching residue (kg) = (1.5-2): 1, and carrying out liquid-solid separation to obtain washing residue D and a washing solution E;
antimony and arsenic removal is carried out on the leachate obtained in the step (4), the leachate B obtained in the step (2) is pumped into an indirect heating reaction kettle, the temperature is increased to 80 +/-10 ℃, sodium nitrate is added to enable the initial concentration of the sodium nitrate to be 3-5g/L, the reaction is carried out for 30-40 min, and NaSbO2 in the solution is oxidized; after the oxidation reaction is finished, introducing cooling water, cooling the solution to 25 +/-5 ℃ to precipitate antimony in the solution by amorphous NaH2SbO4, and carrying out liquid-solid separation to obtain antimony-removed liquid F;
and (5) removing arsenic from the antimony-removed liquid and recycling, adding calcium oxide into the antimony-removed liquid F obtained in the step (4) in a reaction tank, wherein the addition amount is 3-3.5 g/L of CaO in the solution, the stirring temperature is 50 +/-10 ℃, the reaction time is 60min, and the arsenic is precipitated in the form of calcium arsenate.
Further, the reaction reagents in the step (2) are sodium hydroxide and sodium nitrate, wherein the initial concentration of the sodium hydroxide is 150-170g/L, and the initial concentration of the sodium nitrate is 30-40 g/L.
Further, the washing solution E obtained in the step (3) is introduced into the step (1) as a washing solution.
And (3) further, performing liquid-solid separation after arsenic precipitation in the step (5) to obtain a regenerated solution G, and reusing the regenerated solution G for alkaline leaching of the high-content bismuth silver smelting slag in the step (2).
High content of harmful elements in bismuth-silver smelting slagArsenic and antimony both exist mainly in trivalent oxide form, and a small amount exists in elementary substance form and Cu3As intermetallic compound exists in the form of As, wherein arsenic is in NaOH-NaNO3In alkaline oxidation system with Na3AsO4Dissolving the product form of (A) into the leaching solution; in the control of NaNO3Antimony can be soluble product of antimonite (NaSbO) under the condition of using amount of oxidation system2) The form is selectively dissolved out, thereby realizing the removal of the harmful elements of arsenic and antimony and the reaction product (Bi) of bismuth2O3) Silver and silver are insoluble in the solution, so that effective separation of the main metal and the harmful elements is realized; when the leaching solution containing arsenic and antimony is treated and reused, antimonite (NaSbO) is mainly used2) By NaNO3Oxidation to antimonate (Na)3SbO4) Antimonate is converted to the amorphous dihydrogen antimonate (NaH) with very low solubility at low temperature2SbO4) And separating out to release sodium hydroxide alkali reagent, reducing the concentration of metal ions in the solution, and regenerating the leaching reagent to a certain degree.
And (3) the washing slag C obtained in the step (2) is a qualified intermediate product for removing harmful elements such as arsenic, antimony and the like, the pyrometallurgical reduction smelting and anode ingot casting are adopted, electrolytic bismuth meeting the national standard quality is produced by an electrolytic process, and the anode mud is used for recovering the noble metal silver.
Unshaped NaH in step (4)2SbO4The precipitate can be reused as a remover for harmful impurities such as arsenic, antimony, bismuth and the like in the copper electrolyte of copper smelting and producing enterprises.
In the step (5), the calcium arsenate precipitate obtained by liquid-solid separation can be provided for qualified production enterprises of simple substance arsenic, and can also be entrusted to a hazardous waste treatment plant for landfill treatment.
The main reaction equation of the invention is as follows:
ball milling and leaching:
leaching to remove arsenic and antimony and regenerating:
compared with the prior art, the invention has the following beneficial effects: (1) the invention effectively reserves valuable elements of bismuth and silver in the high-content bismuth-silver smelting slag, and harmful elements of arsenic and antimony are recovered in a byproduct form, thereby realizing the aim of changing waste into benefit; (2) the production process of the invention does not produce dangerous toxic gas AsH3The treatment medium is an alkaline medium, so that the equipment corrosion is small, and the production environment is friendly; (3) leaching slag with the weight of about 70 percent of the original slag is produced through alkaline oxidation leaching, the main components in the slag are still bismuth and silver, but the grades of the slag are improved in different degrees, wherein the bismuth is improved by about 20 percent and about 76 percent, and the silver is improved by about 5 percent and about 18 percent; after the leached slag is washed in a counter-current way, the content of harmful elements such as arsenic, antimony and the like is very low, and the leaching slag does not cause harm to the recovery of bismuth and silver. The washing slag is reduced and smelted by a pyrogenic process and cast into ingots by an anode, electrolytic bismuth meeting the national standard quality can be produced by an electrolytic process, and bismuth anode mud is used for recovering noble metal silver; (4) the alkali reagent in the leaching solution can be regenerated, the closed-circuit operation and the cyclic utilization of the liquid can be realized, and no wastewater is discharged.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
A method for removing harmful elements arsenic and antimony in high-content bismuth silver smelting slag comprises the following steps:
performing ball milling, namely performing ore flushing and wet ball milling on the high-content bismuth-silver smelting slag according to the ratio of solution (L) to slag (kg) =4:1 by using a washing liquid, wherein the milling time is 30min, and the milling granularity reaches-60 meshes when 100%; pumping the supernatant after standing back to the elevated tank by a clean liquid pump to be used as grinding flushing water, and taking the underflow A as the raw material leached in the step (2);
leaching in the step (2), pumping the bottom flow A in the step (1) into a closed leaching tank by using an ore pulp pump, adding a regeneration solution G, controlling the solid-to-solid ratio of a leaching solution to be the solution amount (L), adding reagent-grade solid sodium hydroxide, stirring uniformly, and then adding reagent-grade solid sodium nitrate; heating and maintaining the reaction temperature to be more than 95 ℃, stirring for reaction for 180 minutes, and filtering to obtain alkaline leaching solution B and leaching residues C; in the step (2), the reaction reagents are sodium hydroxide and sodium nitrate, wherein the initial concentration of the sodium hydroxide is 160g/L, and the initial concentration of the sodium nitrate is 30 g/L;
washing the leaching residue in the step (3), namely performing normal-temperature slurrying two-stage countercurrent washing on the leaching residue C obtained in the step (2) by using water, wherein the solid-to-solid ratio of a washing solution is water amount (L): the amount of the leaching residue (kg) =2:1, and performing liquid-solid separation to obtain washing residue D and a washing solution E; the washing liquid E obtained in the step (3) enters the step (1) to be used as washing liquid;
antimony and arsenic removal is carried out on the leaching solution obtained in the step (4), the leaching solution B obtained in the step (2) is pumped into an indirect heating reaction kettle, the temperature is heated to 80 ℃, sodium nitrate is added to enable the initial concentration of the sodium nitrate to be 3.5g/L, the reaction is carried out for 30min, and NaSbO in the solution is obtained2Oxidizing; after the oxidation reaction is finished, cooling water is introduced, the temperature of the solution is reduced to 20 ℃, and the antimony in the solution is in an amorphous NaH form2SbO4Precipitating, and carrying out liquid-solid separation to obtain antimony-removed liquid F;
removing arsenic from the antimony-removed liquid obtained in the step (5) and recycling, adding calcium oxide into the antimony-removed liquid F obtained in the step (4) in a reaction tank, wherein the adding amount is 3.5g/L of CaO concentration in the solution, stirring at 50 ℃, reacting for 60min, and precipitating arsenic in the form of calcium arsenate; and (5) performing liquid-solid separation after arsenic precipitation to obtain a regenerated solution G, and reusing the regenerated solution G for alkaline leaching of the high-content bismuth silver smelting slag in the step (2).
Through analysis, the arsenic concentration in the leaching solution (containing the slurry washing liquid) is 3.02g/L, and the antimony concentration is 12.86 g/L; the yield of the leached residue is 72.4 percent, the bismuth content is 77.91 percent, the silver content is 18.68 percent, the arsenic content is 0.41 percent, and the antimony content is 0.84 percent; after leaching solution (containing pulp washing solution) is subjected to antimony and calcium precipitation, the concentrations of residual calcium and antimony in the solution are 83.68mg/L and 65.38mg/L respectively; the removal rate of antimony and arsenic in the whole process is 94.16 percent and 96.29 percent, and the total yield of bismuth and silver is 99.85 percent and 99.93 percent.
Example 2
A method for removing harmful elements arsenic and antimony in high-content bismuth silver smelting slag comprises the following steps:
performing ball milling, namely performing ore flushing and wet ball milling on the high-content bismuth-silver smelting slag according to the ratio of solution (L) to slag (kg) =3:1 by using a washing solution, wherein the milling time is 30min, and the milling granularity reaches-60 meshes when 100%; pumping the supernatant after standing back to the elevated tank by a clean liquid pump to be used as grinding flushing water, and taking the underflow A as the raw material leached in the step (2);
leaching in the step (2), pumping the bottom flow A in the step (1) into a closed leaching tank by using an ore pulp pump, adding a regeneration solution G, controlling the solid-to-solid ratio of a leaching solution to be the solution amount (L), adding reagent-grade solid sodium hydroxide, stirring uniformly, and then adding reagent-grade solid sodium nitrate; heating and maintaining the reaction temperature to be more than 95 ℃, stirring for reaction for 150 minutes, and filtering to obtain alkaline leaching solution B and leaching residue C; in the step (2), the reaction reagents are sodium hydroxide and sodium nitrate, wherein the initial concentration of the sodium hydroxide is 160g/L, and the initial concentration of the sodium nitrate is 40 g/L;
washing the leaching residue in the step (3), namely performing normal-temperature slurrying two-stage countercurrent washing on the leaching residue C obtained in the step (2) by using water, wherein the solid-to-solid ratio of a washing solution is water amount (L): the amount of the leaching residue (kg) =2:1, and performing liquid-solid separation to obtain washing residue D and a washing solution E; the washing liquid E obtained in the step (3) enters the step (1) to be used as washing liquid;
antimony and arsenic removal is carried out on the leaching solution obtained in the step (4), the leaching solution B obtained in the step (2) is pumped into an indirect heating reaction kettle, the temperature is heated to 80 ℃, sodium nitrate is added to enable the initial concentration of the sodium nitrate to be 4g/L, the reaction is carried out for 30min, and NaSbO in the solution is obtained2Oxidizing; after the oxidation reaction is finished, cooling water is introduced, the temperature of the solution is reduced to 20 ℃, and the antimony in the solution is in an amorphous NaH form2SbO4Precipitating, and carrying out liquid-solid separation to obtain antimony-removed liquid F;
removing arsenic from the antimony-removed liquid obtained in the step (5) and recycling, adding calcium oxide into the antimony-removed liquid F obtained in the step (4) in a reaction tank, wherein the adding amount is 3.5g/L of CaO concentration in the solution, stirring at 50 ℃, reacting for 60min, and precipitating arsenic in the form of calcium arsenate; and (5) performing liquid-solid separation after arsenic precipitation to obtain a regenerated solution G, and reusing the regenerated solution G for alkaline leaching of the high-content bismuth silver smelting slag in the step (2).
Through analysis, the arsenic concentration in the leaching solution (containing the slurry washing liquid) is 3.24g/L, and the antimony concentration is 13.15 g/L; the yield of the leached residue is 71.7 percent, the bismuth content is 77.98 percent, the silver content is 18.74 percent, the arsenic content is 0.40 percent, and the antimony content is 0.81 percent; after leaching solution (containing pulp washing solution) is subjected to antimony and calcium precipitation, the concentrations of residual calcium and antimony in the solution are respectively 91.75mg/L and 59.42 mg/L; the removal rate of antimony and arsenic in the whole process is 94.36 percent and 96.98 percent, and the total yield of bismuth and silver is 99.87 percent and 99.95 percent.
Example 3
A method for removing harmful elements arsenic and antimony in high-content bismuth silver smelting slag comprises the following steps:
performing ball milling, namely performing ore flushing and wet ball milling on the high-content bismuth-silver smelting slag according to the ratio of solution (L) to slag (kg) =4:1 by using a washing liquid, wherein the milling time is 30min, and the milling granularity reaches-60 meshes when 100%; pumping the supernatant after standing back to the elevated tank by a clean liquid pump to be used as grinding flushing water, and taking the underflow A as the raw material leached in the step (2);
leaching in the step (2), pumping the bottom flow A in the step (1) into a closed leaching tank by using an ore pulp pump, adding a regeneration solution G, controlling the solid-to-solid ratio of a leaching solution to be the solution amount (L), adding reagent-grade solid sodium hydroxide, stirring uniformly, and then adding reagent-grade solid sodium nitrate; heating and maintaining the reaction temperature to be more than 95 ℃, stirring for reaction for 150 minutes, and filtering to obtain alkaline leaching solution B and leaching residue C; in the step (2), the reaction reagents are sodium hydroxide and sodium nitrate, wherein the initial concentration of the sodium hydroxide is 180g/L, and the initial concentration of the sodium nitrate is 40 g/L;
washing the leaching residue in the step (3), namely performing normal-temperature slurrying two-stage countercurrent washing on the leaching residue C obtained in the step (2) by using water, wherein the solid-to-solid ratio of a washing solution is water amount (L): the amount of the leaching residue (kg) =2:1, and performing liquid-solid separation to obtain washing residue D and a washing solution E; the washing liquid E obtained in the step (3) enters the step (1) to be used as washing liquid;
antimony and arsenic removal is carried out on the leaching solution obtained in the step (4), the leaching solution B obtained in the step (2) is pumped into an indirect heating reaction kettle, the temperature is heated to 80 ℃, sodium nitrate is added to enable the initial concentration of the sodium nitrate to be 5g/L, and the reaction is carried out30min, adding NaSbO in the solution2Oxidizing; after the oxidation reaction is finished, cooling water is introduced, the temperature of the solution is reduced to 25 ℃, and the antimony in the solution is in an amorphous NaH form2SbO4Precipitating, and carrying out liquid-solid separation to obtain antimony-removed liquid F;
adding calcium oxide into the antimony-removed liquid F obtained in the step (4) in a reaction tank, wherein the adding amount is 4g/L of CaO concentration in the solution, the stirring temperature is 50 ℃, the reaction time is 60min, and arsenic is precipitated in the form of calcium arsenate; and (5) performing liquid-solid separation after arsenic precipitation to obtain a regenerated solution G, and reusing the regenerated solution G for alkaline leaching of the high-content bismuth silver smelting slag in the step (2).
Through analysis, the arsenic concentration in the leaching solution (containing the slurry washing liquid) is 3.18g/L, and the antimony concentration is 12.95 g/L; the yield of the leached slag is 70.55 percent, the bismuth content is 78.36 percent, the silver content is 18.92 percent, the arsenic content is 0.34 percent, and the antimony content is 0.76 percent; after leaching solution (containing pulp washing solution) is subjected to antimony and calcium precipitation, the concentrations of residual calcium and antimony in the solution are respectively 83.37mg/L and 54.86 mg/L; the removal rate of antimony and arsenic in the whole process is 96.25 percent and 97.32 percent, and the total yield of bismuth and silver is 99.36 percent and 99.96 percent.
Example 4
A method for removing harmful elements arsenic and antimony in high-content bismuth silver smelting slag comprises the following steps:
performing ball milling, namely performing ore flushing and wet ball milling on the high-content bismuth-silver smelting slag according to the ratio of solution (L) to slag (kg) =3:1 by using a washing solution, wherein the milling time is 30min, and the milling granularity reaches-60 meshes when 100%; pumping the supernatant after standing back to the elevated tank by a clean liquid pump to be used as grinding flushing water, and taking the underflow A as the raw material leached in the step (2);
leaching in the step (2), pumping the bottom flow A in the step (1) into a closed leaching tank by using an ore pulp pump, adding a regeneration solution G, controlling the solid-to-solid ratio of a leaching solution to be the solution amount (L), adding reagent-grade solid sodium hydroxide, stirring uniformly, and then adding reagent-grade solid sodium nitrate; heating and maintaining the reaction temperature to be more than 95 ℃, stirring for reaction for 240 minutes, and filtering to obtain alkaline leaching solution B and leaching residues C; in the step (2), the reaction reagents are sodium hydroxide and sodium nitrate, wherein the initial concentration of the sodium hydroxide is 160g/L, and the initial concentration of the sodium nitrate is 35 g/L;
washing the leaching residue in the step (3), namely performing normal-temperature slurrying two-stage countercurrent washing on the leaching residue C obtained in the step (2) by using water, wherein the solid-to-solid ratio of a washing solution is water amount (L): the amount of the leaching residue (kg) =2:1, and performing liquid-solid separation to obtain washing residue D and a washing solution E; the washing liquid E obtained in the step (3) enters the step (1) to be used as washing liquid;
antimony and arsenic removal is carried out on the leaching solution obtained in the step (4), the leaching solution B obtained in the step (2) is pumped into an indirect heating reaction kettle, the temperature is heated to 80 ℃, sodium nitrate is added to enable the initial concentration of the sodium nitrate to be 5g/L, the reaction is carried out for 40min, and NaSbO in the solution is obtained2Oxidizing; after the oxidation reaction is finished, cooling water is introduced, the temperature of the solution is reduced to 20 ℃, and the antimony in the solution is in an amorphous NaH form2SbO4Precipitating, and carrying out liquid-solid separation to obtain antimony-removed liquid F;
adding calcium oxide into the antimony-removed liquid F obtained in the step (4) in a reaction tank, wherein the adding amount is 4g/L of CaO concentration in the solution, the stirring temperature is 50 ℃, the reaction time is 60min, and arsenic is precipitated in the form of calcium arsenate; and (5) performing liquid-solid separation after arsenic precipitation to obtain a regenerated solution G, and reusing the regenerated solution G for alkaline leaching of the high-content bismuth silver smelting slag in the step (2).
Through analysis, the arsenic concentration in the leaching solution (containing the slurry washing liquid) is 2.96g/L, and the antimony concentration is 10.72 g/L; the yield of the leached residue is 75.84 percent, the bismuth content is 75.68 percent, the silver content is 16.46 percent, the arsenic content is 0.31 percent, and the antimony content is 0.97 percent; after leaching solution (containing pulp washing solution) is subjected to antimony and calcium precipitation, the concentrations of residual calcium and antimony in the solution are 79.63mg/L and 42.65mg/L respectively; the removal rate of antimony and arsenic in the whole process is 89.38 percent and 98.18 percent, and the total yield of bismuth and silver is 99.61 percent and 99.95 percent.
Example 5
A method for removing harmful elements arsenic and antimony in high-content bismuth silver smelting slag comprises the following steps:
performing ball milling, namely performing ore flushing and wet ball milling on the high-content bismuth-silver smelting slag according to the ratio of solution (L) to slag (kg) =3:1 by using a washing solution, wherein the milling time is 30min, and the milling granularity reaches-60 meshes when 100%; pumping the supernatant after standing back to the elevated tank by a clean liquid pump to be used as grinding flushing water, and taking the underflow A as the raw material leached in the step (2);
leaching in the step (2), pumping the bottom flow A in the step (1) into a closed leaching tank by using an ore pulp pump, adding a regeneration solution G, controlling the solid-to-solid ratio of a leaching solution to be the solution amount (L), adding reagent-grade solid sodium hydroxide, stirring uniformly, and then adding reagent-grade solid sodium nitrate; heating and maintaining the reaction temperature to be more than 95 ℃, stirring for reaction for 240 minutes, and filtering to obtain alkaline leaching solution B and leaching residues C; in the step (2), the reaction reagents are sodium hydroxide and sodium nitrate, wherein the initial concentration of the sodium hydroxide is 160g/L, and the initial concentration of the sodium nitrate is 40 g/L;
washing the leaching residue in the step (3), namely performing normal-temperature slurrying two-stage countercurrent washing on the leaching residue C obtained in the step (2) by using water, wherein the solid-to-solid ratio of a washing solution is water amount (L): the amount of the leaching residue (kg) =2:1, and performing liquid-solid separation to obtain washing residue D and a washing solution E; the washing liquid E obtained in the step (3) enters the step (1) to be used as washing liquid;
antimony and arsenic removal is carried out on the leaching solution obtained in the step (4), the leaching solution B obtained in the step (2) is pumped into an indirect heating reaction kettle, the temperature is heated to 80 ℃, sodium nitrate is added to enable the initial concentration of the sodium nitrate to be 5g/L, the reaction is carried out for 40min, and NaSbO in the solution is obtained2Oxidizing; after the oxidation reaction is finished, cooling water is introduced, the temperature of the solution is reduced to 30 ℃, and the antimony in the solution is in an amorphous NaH form2SbO4Precipitating, and carrying out liquid-solid separation to obtain antimony-removed liquid F;
adding calcium oxide into the antimony-removed liquid F obtained in the step (4) in a reaction tank, wherein the adding amount is 4g/L of CaO concentration in the solution, the stirring temperature is 50 ℃, the reaction time is 60min, and arsenic is precipitated in the form of calcium arsenate; and (5) performing liquid-solid separation after arsenic precipitation to obtain a regenerated solution G, and reusing the regenerated solution G for alkaline leaching of the high-content bismuth silver smelting slag in the step (2).
Through analysis, the arsenic concentration in the leaching solution (containing the slurry washing liquid) is 2.98g/L, and the antimony concentration is 11.56 g/L; the yield of the leached residue is 72.45 percent, the bismuth content is 77.52 percent, the silver content is 18.14 percent, the arsenic content is 0.30 percent, and the antimony content is 0.68 percent; after leaching solution (containing pulp washing solution) is subjected to antimony and calcium precipitation, the concentrations of residual calcium and antimony in the solution are 85.28mg/L and 52.48mg/L respectively; the removal rate of antimony and arsenic in the whole process is 96.88 percent and 98.48 percent, and the total yield of bismuth and silver is 99.63 percent and 99.95 percent.
Example 6
A method for removing harmful elements arsenic and antimony in high-content bismuth silver smelting slag comprises the following steps:
performing ball milling, namely performing ore flushing and wet ball milling on the high-content bismuth-silver smelting slag according to the ratio of solution (L) to slag (kg) =4:1 by using a washing liquid, wherein the milling time is 30min, and the milling granularity reaches-60 meshes when 100%; pumping the supernatant after standing back to the elevated tank by a clean liquid pump to be used as grinding flushing water, and taking the underflow A as the raw material leached in the step (2);
leaching in the step (2), pumping the bottom flow A in the step (1) into a closed leaching tank by using an ore pulp pump, adding a regeneration solution G, controlling the solid-to-solid ratio of a leaching solution to be the solution amount (L), adding reagent-grade solid sodium hydroxide, stirring uniformly, and then adding reagent-grade solid sodium nitrate; heating and maintaining the reaction temperature to be more than 95 ℃, stirring for reaction for 210 minutes, and filtering to obtain alkaline leaching solution B and leaching residue C; in the step (2), the reaction reagents are sodium hydroxide and sodium nitrate, wherein the initial concentration of the sodium hydroxide is 170g/L, and the initial concentration of the sodium nitrate is 30 g/L;
washing the leaching residue in the step (3), namely performing normal-temperature slurrying two-stage countercurrent washing on the leaching residue C obtained in the step (2) by using water, wherein the solid-to-solid ratio of a washing solution is water amount (L): the amount of the leaching residue (kg) =2:1, and performing liquid-solid separation to obtain washing residue D and a washing solution E; the washing liquid E obtained in the step (3) enters the step (1) to be used as washing liquid;
antimony and arsenic removal is carried out on the leaching solution obtained in the step (4), the leaching solution B obtained in the step (2) is pumped into an indirect heating reaction kettle, the temperature is heated to 80 ℃, sodium nitrate is added to enable the initial concentration of the sodium nitrate to be 4g/L, the reaction is carried out for 40min, and NaSbO in the solution is obtained2Oxidizing; after the oxidation reaction is finished, cooling water is introduced, the temperature of the solution is reduced to 20 ℃, and the antimony in the solution is in an amorphous NaH form2SbO4Precipitating, and carrying out liquid-solid separation to obtain antimony-removed liquid F;
adding calcium oxide into the antimony-removed liquid F obtained in the step (4) in a reaction tank, wherein the adding amount is 4g/L of CaO concentration in the solution, the stirring temperature is 50 ℃, the reaction time is 60min, and arsenic is precipitated in the form of calcium arsenate; and (5) performing liquid-solid separation after arsenic precipitation to obtain a regenerated solution G, and reusing the regenerated solution G for alkaline leaching of the high-content bismuth silver smelting slag in the step (2).
Through analysis, the arsenic concentration in the leaching solution (containing the slurry washing liquid) is 2.99g/L, and the antimony concentration is 12.36 g/L; the yield of the leaching residue is 71.54 percent, the bismuth content is 78.18 percent, the silver content is 18.73 percent, the arsenic content is 0.39 percent, and the antimony content is 0.83 percent; after leaching solution (containing pulp washing solution) is subjected to antimony and calcium precipitation, the concentrations of residual calcium and antimony in the solution are 81.34mg/L and 55.26mg/L respectively; the removal rate of antimony and arsenic in the whole process is 95.41 percent and 96.84 percent, and the total yield of bismuth and silver is 99.58 percent and 99.96 percent.
Example 1: grinding the high-content bismuth silver smelting slag to 100-60 meshes, adding sodium hydroxide to the concentration of 160/L and adding sodium nitrate to the concentration of 30/L under the conditions that a liquid-solid ratio solution (L) is used for slag (= 6: 1); heating and maintaining the reaction temperature to be higher than 95 ℃, stirring and reacting for 180 minutes, carrying out liquid-solid separation, carrying out slurry washing on the leached residues according to the liquid-solid ratio of solution (L) to residues (= kg) =2:1, combining the slurry washing solutions, and testing and analyzing; heating the mixed solution to 80 ℃, adding sodium nitrate until the concentration of the sodium nitrate is 3.5g/L, and reacting for 30 min; after the oxidation reaction is finished, reducing the temperature of the solution to 20 ℃, standing for 60min, and carrying out solid-liquid separation to obtain antimony slag and a liquid after antimony removal; adding calcium oxide into the antimony-removed solution until the CaO concentration is 3.5g/L, and reacting at 50 ℃ for 60 min. Through analysis, the arsenic concentration in the leaching solution (containing the slurry washing liquid) is 3.02g/L, and the antimony concentration is 12.86 g/L; the yield of the leached residue is 72.4 percent, the bismuth content is 77.91 percent, the silver content is 18.68 percent, the arsenic content is 0.41 percent, and the antimony content is 0.84 percent; after leaching solution (containing pulp washing solution) is subjected to antimony and calcium precipitation, the concentrations of residual calcium and antimony in the solution are 83.68mg/L and 65.38mg/L respectively; the removal rate of antimony and arsenic in the whole process is 94.16 percent and 96.29 percent, and the total yield of bismuth and silver is 99.85 percent and 99.93 percent.
Claims (5)
1. A method for removing harmful elements arsenic and antimony in high-content bismuth silver smelting slag is characterized by comprising the following steps:
performing ball milling in the step (1), performing ore flushing and wet ball milling on the high-bismuth-content silver smelting slag according to the ratio of solution (L) to slag (kg) = (3-4) to 1 by using a washing liquid, wherein the milling time is 30min, and the milling granularity reaches-60 meshes when 100%; pumping the supernatant after standing back to the elevated tank by a clean liquid pump to be used as grinding flushing water, and taking the underflow A as the raw material leached in the step (2);
leaching in the step (2), pumping the bottom flow A in the step (1) into a closed leaching tank by using an ore pulp pump, adding a regeneration solution G, controlling the solid-to-solid ratio of a leaching solution to be solution amount (L): slag amount (kg) = (6-8): 1, and adding a proper amount of reaction reagent; heating and maintaining the reaction temperature to be more than 95 ℃, stirring for reaction for 180-240 minutes, and filtering to obtain alkaline leaching solution B and leaching residue C;
washing the leaching residue in the step (3), pulping the leaching residue C obtained in the step (2) at normal temperature by using water, carrying out two-stage countercurrent washing, wherein the solid-to-solid ratio of a washing solution is water amount (L): the amount of the leaching residue (kg) = (1.5-2): 1, and carrying out liquid-solid separation to obtain washing residue D and a washing solution E;
antimony and arsenic removal is carried out on the leachate obtained in the step (4), the leachate B obtained in the step (2) is pumped into an indirect heating reaction kettle, the temperature is increased to 80 +/-10 ℃, sodium nitrate is added to enable the initial concentration of the sodium nitrate to be 3-5g/L, the reaction is carried out for 30-40 min, and NaSbO2 in the solution is oxidized; after the oxidation reaction is finished, introducing cooling water, cooling the solution to 25 +/-5 ℃ to precipitate antimony in the solution by amorphous NaH2SbO4, and carrying out liquid-solid separation to obtain antimony-removed liquid F;
and (5) removing arsenic from the antimony-removed liquid and recycling, adding calcium oxide into the antimony-removed liquid F obtained in the step (4) in a reaction tank, wherein the addition amount is 3-3.5 g/L of CaO in the solution, the stirring temperature is 50 +/-10 ℃, the reaction time is 60min, and the arsenic is precipitated in the form of calcium arsenate.
2. The method for removing harmful elements arsenic and antimony in the high-content bismuth silver smelting slag according to claim 1, which is characterized in that: the reaction reagents in the step (2) are sodium hydroxide and sodium nitrate, wherein the initial concentration of the sodium hydroxide is 150-170g/L, and the initial concentration of the sodium nitrate is 30-40 g/L.
3. The method for removing harmful elements arsenic and antimony in the high-content bismuth silver smelting slag according to claim 1, which is characterized in that: and (3) feeding the washing liquid E obtained in the step (3) into the step (1) as a washing liquid.
4. The method for removing harmful elements arsenic and antimony in the high-content bismuth silver smelting slag according to claim 1, which is characterized in that: and (3) performing liquid-solid separation after arsenic precipitation in the step (5) to obtain a regenerated solution G, and reusing the regenerated solution G for alkaline leaching of the high-content bismuth silver smelting slag in the step (2).
5. The method for removing harmful elements arsenic and antimony in high-content bismuth silver smelting slag according to claim 1, wherein the reaction reagent in the step (2) is prepared by adding reagent-grade solid sodium hydroxide to a solution concentration of 150-170g/L, stirring uniformly, and then adding reagent-grade solid sodium nitrate to a solution concentration of 30-40 g/L.
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