CN111500869A - Copper smelting byproduct co-processing technology - Google Patents
Copper smelting byproduct co-processing technology Download PDFInfo
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- CN111500869A CN111500869A CN202010327548.2A CN202010327548A CN111500869A CN 111500869 A CN111500869 A CN 111500869A CN 202010327548 A CN202010327548 A CN 202010327548A CN 111500869 A CN111500869 A CN 111500869A
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- concentration
- flue gas
- leaching
- copper
- copper smelting
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- 239000010949 copper Substances 0.000 title claims abstract description 68
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000003723 Smelting Methods 0.000 title claims abstract description 41
- 239000006227 byproduct Substances 0.000 title claims abstract description 23
- 238000005516 engineering process Methods 0.000 title description 6
- 238000002386 leaching Methods 0.000 claims abstract description 93
- 239000002253 acid Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000002699 waste material Substances 0.000 claims abstract description 59
- 239000003546 flue gas Substances 0.000 claims abstract description 54
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000779 smoke Substances 0.000 claims abstract description 38
- 230000008569 process Effects 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 239000000428 dust Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 150000002739 metals Chemical class 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000011550 stock solution Substances 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- 230000002195 synergetic effect Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- 239000007788 liquid Substances 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 43
- 238000006477 desulfuration reaction Methods 0.000 claims description 36
- 230000023556 desulfurization Effects 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 25
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000000746 purification Methods 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 13
- 229910052797 bismuth Inorganic materials 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 239000011686 zinc sulphate Substances 0.000 claims description 5
- 230000003009 desulfurizing effect Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- 238000011278 co-treatment Methods 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 46
- 229910052785 arsenic Inorganic materials 0.000 abstract description 37
- 229910052725 zinc Inorganic materials 0.000 abstract description 25
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002920 hazardous waste Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 7
- 235000011941 Tilia x europaea Nutrition 0.000 description 7
- 239000004571 lime Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000008267 milk Substances 0.000 description 6
- 210000004080 milk Anatomy 0.000 description 6
- 235000013336 milk Nutrition 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- GSYZQGSEKUWOHL-UHFFFAOYSA-N arsenic calcium Chemical compound [Ca].[As] GSYZQGSEKUWOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 1
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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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
- C22B7/02—Working-up flue dust
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0093—Treating solutions by chemical methods by gases, e.g. hydrogen or hydrogen sulfide
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/007—Wet processes by acid 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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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a synergistic treatment process for copper smelting byproducts, which is characterized in that the copper smelting byproducts are low-concentration SO2Flue gas, smoke dust, waste acid and high-concentration SO2The flue gas is treated cooperatively by treating low-concentration SO2Flue gas is carried out in three stagesDesulfurizing, heating and oxidizing leaching twice, volatilizing in high temperature system, recovering valuable metal and high concentration SO2Heating flue gas, reducing, precipitating, dearsenizing, vulcanizing, precipitating copper, evaporating, concentrating, crystallizing and the like to carry out synergistic treatment on the copper smelting by-products; the process of the invention can reduce the concentration of SO2SO in flue gas2Most of the arsenic is removed, the using amount of a desulfurizer is small, the cost is saved, the leaching rate of metals such As arsenic, copper, zinc and the like is high, the arsenic leached from the smoke dust and the waste acid stock solution is easy to be reduced and separated out, and the arsenic is used As2O3The method has the advantages of high recovery rate of copper and zinc, consumption of a large amount of waste acid stock solution, no hazardous waste residue, comprehensive treatment of tail gas and good environmental protection effect.
Description
Technical Field
The invention relates to the field of environmental protection and treatment, in particular to a copper smelting byproduct synergistic treatment process.
Background
In copper smelting enterprises, the generated byproducts are basically treated in a single treatment mode.
Low concentration of SO2The waste water can be discharged only after reaching the standard after being desulfurized, the existing desulfurization method is basically desulfurization technologies such as lime milk, sodium hydroxide, a hydrogen peroxide method, regenerated ammonia adsorption and the like, and new environmental problems exist in the desulfurization processes of the lime milk and the sodium hydroxide, such as solid waste gypsum residue, sodium-salt-containing waste water and the like in the desulfurization process; the production cost is high by using hydrogen peroxide for desulfurization and regenerated ammonia adsorption, and the sewage produced by the method can be recycled or used as other production water only after entering a sewage treatment system.
Most of the existing methods for treating copper smelting dust are wet methods, the main technological processes are leaching, dearsenifying, replacement, zinc precipitation and other procedures, and most of the methods are to mix the dust with industrial sulfuric acid and use MnO in the leaching process2Or potassium permanganate and the like are used as oxidants, a large amount of arsenic enters the leachate, then lime milk is used for adjusting the pH value, arsenic is removed by + 2-valent iron, iron powder or zinc powder is used for replacing and precipitating copper, and then the lime milk is used for adjusting the pH value to precipitate zinc, manganese and the like. The method brings different metal ions which need to be removed in the following process, thereby complicating the process flow, generating dangerous wastes such as arsenic iron slag, gypsum slag and the like, and treating the dangerous wastesThe method has the advantages that the treatment is required to be standardized, the cost is high, the environmental protection management risk exists, a large amount of valuable metals enter the generated lime mud, the recovery rate is low, iron salt, lime milk, industrial sulfuric acid and the like are required to be added, the operation cost is increased, and the wastewater produced by the method can be recycled or used as other production water after being treated in a sewage treatment system.
At present, Na is basically used in waste acid generated in the purification process of a flue gas acid-making system2Arsenic sulfide slag, arsenic calcium slag and the like generated in the process belong to hazardous wastes, so that the process has great environmental protection risk, the hazardous wastes need to be treated in a standardized way, the cost is high, and in the production process, iron powder or zinc powder and Na are added2S, lime milk and the like, increase the production cost, and the treated sewage can be recycled or used as other production water after entering a sewage treatment system for treatment.
In order to solve the defects existing in the single treatment process of the intermediate byproducts, the technical problem to be solved by technical personnel in the field is to develop a treatment process with high efficiency, energy conservation, environmental protection and low cost.
Disclosure of Invention
In view of the above, the present invention provides a copper smelting byproduct co-processing process, which can process low concentration SO2The waste acid stock solution of the flue gas, smelting smoke dust and a flue gas acid making system is subjected to synergistic treatment, so that part of arsenic in arsenic-containing materials can be efficiently separated in the copper smelting process, the production of production wastewater and other dangerous wastes is reduced as much as possible, the purpose of treating wastes with wastes is achieved, and the process flow is simplified.
In order to achieve the purpose, the invention adopts the following technical scheme:
a co-processing technique of copper smelting by-products, which is to subject the copper smelting by-products to low concentration SO2Flue gas, smoke dust, waste acid and high-concentration SO2The flue gas cooperative treatment comprises the following steps:
(1) the copper smelting smoke dust is used as a smelting tail gas desulfurizer after size mixing, and low-concentration SO is treated2Desulfurizing the flue gas to obtain a productSulfur waste residue A and desulfurized liquid A;
(2) mixing smoke dust and waste acid, adding the desulfurized liquid A, and then carrying out first-stage heating oxidation leaching to obtain a leaching solution B and leaching residues B;
(3) mixing waste acid and leaching residue B, adding desulfurized waste residue A and an oxidant, and carrying out two-stage heating oxidation leaching to obtain leaching residue C and leaching solution C;
(4) putting the leaching residue C into a high-temperature system for volatilization, recovering valuable metals, and returning volatilized flue gas to the step (1) for desulfurization;
(5) mixing the leaching solution B with the leaching solution C, and introducing high-concentration SO2Flue gas, SO2Heating, reducing, precipitating and dearsenizing to obtain As2O3And post-dearsenification liquor D;
(6) introducing H into the arsenic-removed liquid D2S, carrying out vulcanization copper precipitation to obtain decoppered slag and decoppered liquid E, and purifying the generated tail gas by using a NaOH solution and then discharging;
(7) evaporating, concentrating and crystallizing the decoppered liquid E to obtain ZnSO4And (4) returning the concentrated solution F to the step (3) for secondary heating oxidation leaching, and discharging tail gas generated in the evaporation concentration process after acid mist removal and purification by using a NaOH solution.
Further, the preparation method of the smelting tail gas desulfurizer in the step (1) comprises the following steps of mixing the smoke dust and water according to a ratio of 1: and (3) mixing and slurrying the solid-liquid ratio of (3) to (6). .
Further, the above is for low concentration SO2The desulfurization method for desulfurizing the flue gas comprises the following steps: for containing SO2The concentration is 400mg/Nm3～10000mg/Nm3Low concentration of SO2The flue gas is subjected to three-stage desulfurization, and NaOH is used as emergency desulfurization to ensure that SO of the discharged flue gas is2The concentration is less than 200mg/Nm3。
Adopt above-mentioned further beneficial effect to lie in: the invention limits the solid-liquid ratio to be 1: (3-6), the concentration of a desulfurizing agent can be ensured, and the generated desulfurized liquid can be completely recycled in the subsequent two-stage leaching process on the premise that the desulfurization process can achieve a good desulfurization effect; the adoption of three-stage desulfurization can improve the desulfurization efficiency of the low-concentration SO2 flue gas.
Further, the heating temperature of the first-stage heating oxidation leaching in the step (2) is 70-90 ℃; the heating temperature of the second-stage heating oxidation leaching in the step (3) is 70-90 ℃;
the solid-liquid ratio of the total amount of the smoke dust to the waste acid and the desulfurized liquid A in the step (2) is 1: 3-5, and the total mass of the leaching residue B and the desulfurized waste residue A in the step (3) to the solid-liquid ratio of the waste acid is 1: 3-5;
furthermore, the waste acid is waste acid stock solution generated in the flue gas purification process; the acid concentration of the waste acid stock solution is 4-11%.
Adopt above-mentioned further beneficial effect to lie in: the heating temperature limited by the invention is easy to control, and the leaching rate of metals such as copper, zinc, arsenic and the like is high in the temperature range. The solid-to-liquid ratio concentration range defined by the invention can ensure that the concentration of copper, zinc, arsenic and other metals in the leaching solution can be improved as much as possible while the sufficient leaching rate of copper, zinc, arsenic and other metals is ensured in the leaching process, and the direct recovery rate of the subsequent metals of arsenic, copper, zinc and the like is improved. The waste acid stock solution adopted by the invention is beneficial to the recovery of arsenic in the waste acid, reduces the treatment capacity of the traditional method for the waste acid, reduces the generation of hazardous wastes containing arsenic, such as arsenic sulfide slag, arsenic calcium slag and the like, and reduces the amount of wastewater entering a sewage treatment system.
Further, the oxidant in the step (3) is air or hydrogen peroxide.
Adopt above-mentioned further beneficial effect to lie in: air or hydrogen peroxide is used as an oxidant, so that compared with potassium permanganate, manganese dioxide and other oxidants, the introduction of potassium salt, manganese ions and other metal ions is reduced, and the removal and open circuit of other impurity ions in the subsequent process are reduced.
Further, the temperature of the high-temperature system in the step (4) is 1250-1400 ℃; the valuable metals are metals such as lead, bismuth, tin and the like, and the valuable metals are recovered in a smoke form.
Adopt above-mentioned further beneficial effect to lie in: in the temperature range limited by the invention, valuable metals such as lead, bismuth, tin and the like can be comprehensively recovered, and the valuable metals in the smoke dust are completely utilized, so that the utilization value of the smoke dust is improved.
Further, the high concentration SO in the step (5) is2The flue gas is SO generated in the smelting process2The purified flue gas with the concentration of 8-20 percent.
Adopt above-mentioned further beneficial effect to lie in: the invention adopts the purified SO generated in the smelting process2The flue gas has stable source and no other cost, and is not brought by other impurity ions, thereby being convenient for recovering arsenic.
Further, H is introduced into the arsenic-removed solution D in the step (6)2And S, carrying out copper sulfide deposition.
Adopt above-mentioned further beneficial effect to lie in: by means of H2S sulfurizing to deposit copper can reduce the introduction of other metal ions compared with the replacement of iron powder or zinc powder.
Compared with the prior art, the invention has the beneficial effects that: the process of the invention can reduce the concentration of SO2SO in flue gas2Most of the arsenic is removed, in the subsequent NaOH desulfurization process, the usage amount of the desulfurizer is small, the cost is saved, the leaching rate of arsenic, copper, zinc and other metals is high, the arsenic leached from the smoke dust and the waste acid stock solution is easy to be reduced and separated out, and the arsenic is used As2O3The method has the advantages of high recovery rate of copper and zinc, consumption of a large amount of waste acid stock solution, no hazardous waste residues, comprehensive treatment of all tail gases and good environmental protection effect.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Detecting copper smeltingThe smoke dust comprises 3.5 percent of Cu, 15.83 percent of Pb, 12.92 percent of Zn, 15.15 percent of As, 1.07 percent of Fe, 5.02 percent of Bi, 3.06 percent of Sn, 185.4g/t of Ag, 10800 mg/L percent of As, and H2SO4：42.5g/L。
The copper smelting by-product co-processing technology comprises the following steps:
(1) mixing smoke dust and water according to the proportion of 1:4, mixing and slurrying the solid-liquid ratio to obtain the smelting tail gas desulfurizer for the SO-containing2The concentration is 3650mg/Nm3Low concentration of SO2The flue gas is subjected to three-stage desulfurization, and NaOH is used as emergency desulfurization to ensure that SO of the discharged flue gas is2The concentration is less than 200mg/Nm3Low concentration of SO2Introducing flue gas for 60min to obtain desulfurized waste residue A and desulfurized liquid A;
(2) mixing smoke dust and waste acid, adding the mixture into a desulfurized liquid A, wherein the solid-liquid ratio of the smoke dust to the total amount of the waste acid to the desulfurized liquid A is 1:4, then adding air at 90 ℃, and carrying out primary heating oxidation leaching for 2 hours to obtain a leaching solution B and leaching residue B, wherein the waste acid is a waste acid stock solution generated in the flue gas purification process, and the acid concentration is 42.5 g/L;
(3) mixing the total mass of the leaching residue B and the desulphurization residue A with waste acid according to a solid-liquid ratio of 1:4, introducing air, and carrying out two-stage heating oxidation leaching at 90 ℃ for 2h to obtain leaching residue C and leaching solution C, wherein the waste acid is waste acid stock solution generated in the flue gas purification process, and the acid concentration is 42.5 g/L;
(4) putting the leaching residue C into a 1300 ℃ high-temperature system for volatilization, recovering valuable metals such as lead, bismuth, tin and the like in a smoke form, and returning volatilized smoke to the step (1) for desulfurization;
(5) mixing the leaching solution B with the leaching solution C, and introducing high-concentration SO2Flue gas, SO2Heating to 55 deg.C to obtain As2O3And post-dearsenification liquor D; high concentration of SO2The flue gas is purified SO generated in the smelting process2Smoke with a detection concentration of 16.5%;
(6) introducing H into the arsenic-removed liquid D2S, carrying out copper sulfide deposition to obtain decoppered slag and decoppered liquid E, and purifying the generated tail gas by using NaOH solutionAnd (5) discharging.
(7) Evaporating, concentrating and crystallizing the decoppered liquid E to obtain ZnSO4And (4) returning the concentrated solution F to the step (3) for secondary heating oxidation leaching, and discharging tail gas generated in the evaporation concentration process after acid mist removal and purification by using a NaOH solution.
In example 1, tested: in the step (1), before the NaOH emergency desulfurization, the desulfurization tail gas SO2The concentration is 88mg/Nm3The desulfurization efficiency was 97.59%.
In the step (2), the obtained first-stage leaching residue B comprises 0.96% of Cu, 2.13% of Zn, 3.67% of As, 23.98% of Pb, 5.89% of Sns and 6.09% of Bis, and the obtained leaching solution B comprises 6.56 g/L% of Cu, 29.6 g/L% of Zn and 46.3 g/L of As.
In the step (3), the obtained second-stage leaching residue C comprises 0.16% of Cu, 0.306% of Zn, 1.98% of As, 29.06% of Pb, 6.01% of Sn6 and 9.26% of Bi9, and the obtained leaching solution C comprises 0.524 g/L of Cu, 2.43 g/L of Zn and 20.7 g/L of As.
And (4) volatilizing the leached residues leached out in the second stage at high temperature, crushing the volatilized residues, merging the crushed residues into smoke dust, and leaching in the first stage.
In the step (5), the obtained As component of the filter residue is 73.9 percent, the filtrate components are Cu 3.86 g/L, Zn 17.03 g/L and As 4.09 g/L.
In the step (6), the obtained filter residue has a Cu content of 58.22%, and the obtained filtrate has Cu content of 0.27 g/L, Zn content of 16.62 g/L and As content of 3.98 g/L.
In the step (7), the Zn content of the filter residue is 38.72%, the filtrate components are 0.63 g/L for Cu, 14.63 g/L for Zn and 12.56 g/L for As.
First-stage leaching rate in example 1: cu: 88.7%, Zn: 90.3%, As: 86.2 percent. The total leaching rate of the two-stage leaching is as follows: cu: 92.5%, Zn: 97.12%, As: 92.4 percent. Metal direct yield: cu: 90.6%, Zn: 93.5%, As: 91.1 percent, comprehensively recovering valuable metals such as lead, tin, bismuth and the like; the generated waste gas is effectively treated, and no production wastewater and hazardous waste are generated.
EXAMPLE 2
Detecting copper smelting smokeThe components of Cu 4.2%, Pb 16.55%, Zn 13.9%, As 12.15%, Fe 0.99%, Bi 4.87%, Sn 3.44%, Ag 225.3 g/t.waste acid stock solution contains As 9900 mg/L%, H2SO4：50.3g/L。
The copper smelting by-product co-processing technology comprises the following steps:
(1) mixing smoke dust and water according to the proportion of 1: 6, mixing and slurrying the solid-liquid ratio to obtain the smelting tail gas desulfurizer, and detecting SO2The concentration is 7639mg/Nm3Low concentration of SO2The flue gas is subjected to three-stage desulfurization, and NaOH is used as emergency desulfurization to ensure that SO of the discharged flue gas is2The concentration is less than 200mg/Nm3Low concentration of SO2Introducing flue gas for 60min to obtain desulfurized waste residue A and desulfurized liquid A;
(2) mixing smoke dust and waste acid, adding the mixture into a desulfurized liquid A, wherein the solid-liquid ratio of the smoke dust to the total amount of the waste acid to the desulfurized liquid A is 1:5, then gradually adding hydrogen peroxide at 70 ℃, and carrying out first-stage heating oxidation leaching for 1.5h to obtain a leaching solution B and leaching residue B, wherein the waste acid is a waste acid stock solution generated in the flue gas purification process and has an acid concentration of 50.3 g/L;
(3) mixing the total mass of the leaching residue B and the desulphurization residue A with waste acid according to a solid-liquid ratio of 1:3, gradually adding hydrogen peroxide, and carrying out two-stage heating oxidation leaching at 70 ℃ for 1.5h to obtain leaching residue C and leaching solution C, wherein the waste acid is waste acid stock solution generated in the flue gas purification process, and the acid concentration is 50.3 g/L;
(4) putting the leaching residue C into a high-temperature system at 1400 ℃ for volatilization, recovering valuable metals such as lead, bismuth, tin and the like in a smoke form, and returning volatilized smoke to the step (1) for desulfurization;
(5) mixing the leaching solution B with the leaching solution C, and introducing high-concentration SO2Flue gas, SO2Heating the precipitate to 60 ℃ for dearsenification by reduction to obtain As2O3And post-dearsenification liquor D; high concentration of SO2The flue gas is purified SO generated in the smelting process2Smoke with detection concentration of 12.3%;
(6) introducing H into the arsenic-removed liquid D2S, carrying out copper sulfide deposition to obtain decoppered slag and decoppered liquid E, and utilizing generated tail gasAnd purifying the NaOH solution and then discharging.
(7) Evaporating, concentrating and crystallizing the decoppered liquid E to obtain ZnSO4And (4) returning the concentrated solution F to the step (3) for secondary heating oxidation leaching, and discharging tail gas generated in the evaporation concentration process after acid mist removal and purification by using a NaOH solution.
In example 2 tested: in the step (1), before the NaOH emergency desulfurization, the desulfurization tail gas SO2The concentration was 163mg/Nm3The desulfurization efficiency was 97.87%.
In the step (2), the obtained first-stage leaching residue B comprises 1.12% of Cu, 2.27% of Zn, 3.39% of As, 26.66% of Pb, 6.23% of Sn6 and 7.11% of Bi7, and the obtained leaching solution B comprises 7.03 g/L% of Cu, 25.88 g/L% of Zn and 42.03 g/L of As.
In the step (3), the obtained second-stage leaching residue C comprises 0.156% of Cu, 0.268% of Zn, 2.02% of As, 33.07% of Pb, 6.78% of Sn6 and 8.63%, and the obtained leaching solution C comprises 0.495 g/L% of Cu, 2.18 g/L of Zn and 21.7 g/L of As.
And (4) volatilizing the leached residues leached out in the second stage at high temperature, crushing the volatilized residues, merging the crushed residues into smoke dust, and leaching in the first stage.
In the step (5), the obtained As component of the filter residue is 72.7 percent, the filtrate components are Cu 4.12 g/L, Zn 15.68 g/L and As 3.97 g/L.
In the step (6), the obtained filter residue has a Cu content of 54.37%, and the obtained filtrate has Cu content of 0.33 g/L, Zn content of 17.16 g/L and As content of 4.21 g/L.
In the step (7), the Zn content of the filter residue is 40.54 percent, the filtrate components are 0.81 g/L percent of Cu, 14.3 g/L percent of Zn and 11.63 g/L percent of As.
First stage leaching rate in example 2: cu: 85.5%, Zn: 92.3%, As: 83.6 percent. The total leaching rate of the two-stage leaching is as follows: cu: 94.8%, Zn: 97.49%, As: 90.91 percent. Metal direct yield: cu: 91.2%, Zn: 92.7%, As: 90 percent, comprehensively recovering valuable metals such as lead, tin, bismuth and the like; the generated waste gas is effectively treated, and no production wastewater and hazardous waste are generated.
Example 3
The detected copper smelting dust comprises 2.98 percent of Cu, 16.35 percent of Pb, 14.22 percent of Zn, 14.71 percent of As, 1.43 percent of Fe, 4.96 percent of Bi, 3.17 percent of Sn, 207.6g/t of Ag, 11900 mg/L percent of As, H and waste acid stock solution2SO4：46.3g/L。
The copper smelting by-product co-processing technology comprises the following steps:
(1) mixing smoke dust and water according to the proportion of 1:3, mixing and slurrying the solid-liquid ratio to obtain the smelting tail gas desulfurizer, and detecting SO2The concentration is 1280mg/Nm3Low concentration of SO2The flue gas is subjected to three-stage desulfurization, and NaOH is used as emergency desulfurization to ensure that SO of the discharged flue gas is2The concentration is less than 200mg/Nm3Low concentration of SO2Introducing flue gas for 60min to obtain desulfurized waste residue A and desulfurized liquid A;
(2) mixing smoke dust and waste acid, adding the mixture into a desulfurized liquid A, wherein the solid-liquid ratio of the smoke dust to the total amount of the waste acid and the desulfurized liquid A is 1:3, then gradually adding hydrogen peroxide at 75 ℃, introducing air, and carrying out first-stage heating oxidation leaching for 3 hours to obtain a leaching solution B and leaching residue B, wherein the waste acid is a waste acid stock solution generated in the flue gas purification process and has an acid concentration of 46.3 g/L;
(3) mixing the total mass of the leaching residue B and the desulphurization residue A with waste acid according to a solid-liquid ratio of 1:5, gradually adding hydrogen peroxide, introducing air, and carrying out two-stage heating oxidation leaching at 80 ℃ for 1h to obtain leaching residue C and leaching solution C, wherein the waste acid is waste acid stock solution generated in the flue gas purification process, and the acid concentration is 46.3 g/L;
(4) putting the leaching residue C into a 1250 ℃ high-temperature system for volatilization, recovering valuable metals such as lead, bismuth, tin and the like in a smoke form, and returning volatilized smoke to the step (1) for desulfurization;
(5) mixing the leaching solution B with the leaching solution C, and introducing high-concentration SO2Flue gas, SO2Heating the precipitate to 60 ℃ for dearsenification by reduction to obtain As2O3And post-dearsenification liquor D; high concentration of SO2The flue gas is purified SO generated in the smelting process2Smoke with detection concentration of 10.9%;
(6) introducing H into the arsenic-removed liquid D2S, carrying out copper sulfide deposition,and obtaining the decoppered slag and the decoppered liquid E, and purifying the generated tail gas by using NaOH solution and then discharging.
(7) Evaporating, concentrating and crystallizing the decoppered liquid E to obtain ZnSO4And (4) concentrating the solution, and returning the concentrated solution F to the step (3) for secondary heating oxidation leaching. Tail gas generated in the evaporation concentration process is subjected to acid mist removal purification by NaOH solution and then is discharged.
In example 3 tested: in the step (1), before the NaOH emergency desulfurization, the desulfurization tail gas SO2The concentration was 14mg/Nm3The desulfurization efficiency was 98.91%.
In the step (2), the obtained first-stage leaching residue B comprises 1.03 percent of Cu, 2.31 percent of Zn, 4.11 percent of As, 28.37 percent of Pb, 6 percent of Sn and 7.11 percent of Bi7, and the obtained leaching solution B comprises 9.88 g/L percent of Cu, 36.2 g/L percent of Zn and 70.1 g/L percent of As.
In the step (3), the obtained second-stage leaching residue C comprises 0.174% of Cu, 0.211% of Zn, 2.53% of As, 36.02% of Pb, 6.21% of Sn6 and 8.23% of Bi8.32 g/L% of Cu, 2.18 g/L% of Zn and 18.75 g/L% of As.
And (4) volatilizing the leached residues leached out in the second stage at high temperature, crushing the volatilized residues, merging the crushed residues into smoke dust, and leaching in the first stage.
In the step (5), the obtained As component of the filter residue is 71.86 percent, the filtrate components are Cu 6.33 g/L, Zn 19.46 g/L and As 4.26 g/L.
In the step (6), the obtained filter residue has a Cu content of 56.91%, and the obtained filtrate has Cu content of 0.4 g/L, Zn content of 21.02 g/L and As content of 4.32 g/L.
In the step (7), the Zn content of the filter residue is 39.27%, the components of the filtrate are 0.92 g/L of Cu, 12.63 g/L of Zn and 12.17 g/L of As.
First stage leaching rate in example 3: cu: 84.7%, Zn: 91.69%, As: 82.42 percent. The total leaching rate of the two-stage leaching is as follows: cu: 93.66%, Zn: 96.9%, As: 90.22 percent. Metal direct yield: cu: 90.71%, Zn: 91.89%, As: 89.98 percent, and comprehensively recovering valuable metals such as lead, tin, bismuth and the like; the generated waste gas is effectively treated, and no production wastewater and hazardous waste are generated.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. A co-processing technique of copper smelting by-products, which is to subject the copper smelting by-products to low concentration SO2Flue gas, smoke dust, waste acid and high-concentration SO2The flue gas coprocessing method is characterized by comprising the following steps:
(1) adopts a smelting tail gas desulfurizer to treat low-concentration SO2Desulfurizing the flue gas to obtain desulfurized waste residue A and desulfurized liquid A;
(2) mixing smoke dust and waste acid, adding the desulfurized liquid A, and then carrying out primary heating oxidation leaching for 1.5-3 hours to obtain a leaching solution B and leaching residues B;
(3) mixing waste acid, leaching residue B and desulfurization waste residue A, adding an oxidant, and carrying out two-stage heating oxidation leaching for 1-2.5 hours to obtain leaching residue C and leaching solution C;
(4) putting the leaching residue C into a high-temperature system for volatilization, recovering valuable metals, and returning volatilized flue gas to the step (1) for desulfurization;
(5) mixing the leaching solution B with the leaching solution C, and introducing high-concentration SO2Flue gas, SO2Heating, reducing, precipitating and dearsenizing to obtain As2O3And post-dearsenification liquor D;
(6) introducing H into the arsenic-removed liquid D2S, carrying out vulcanization copper precipitation to obtain decoppered slag and decoppered liquid E, and purifying the generated tail gas by using a NaOH solution and then discharging;
(7) evaporating, concentrating and crystallizing the decoppered liquid E to obtain ZnSO4And (4) returning the concentrated solution F to the step (3) for secondary heating oxidation leaching, and discharging tail gas generated in the evaporation concentration process after acid mist removal and purification by using a NaOH solution.
2. The copper smelting byproduct synergistic treatment process according to claim 1, wherein the preparation method of the smelting tail gas desulfurizer in the step (1) is that the ratio of smoke dust and water is 1: (3-6) mixing and slurrying to obtain the slurry.
3. The process of claim 2, wherein the co-treatment of the low-concentration SO is performed2The desulfurization method for desulfurizing the flue gas comprises the following steps: for containing SO2The concentration is 400mg/Nm3～10000mg/Nm3Low concentration of SO2The flue gas is subjected to three-level desulfurization, and NaOH is used as an emergency desulfurizer to ensure that SO in the discharged flue gas2The concentration is less than 200mg/Nm3。
4. The copper smelting byproduct coprocessing process according to claim 1, wherein the heating temperature of the primary heating oxidation leaching in the step (2) is 70-90 ℃; and (4) heating the second-stage heating oxidation leaching in the step (3) at a temperature of 70-90 ℃.
5. The copper smelting byproduct co-processing process according to claim 4, wherein the waste acid is a waste acid stock solution generated in a flue gas purification process.
6. The copper smelting byproduct co-processing process according to claim 5, wherein the acid concentration of the waste acid stock solution is 4-11%.
7. The copper smelting byproduct coprocessing process of claim 4, wherein the oxidant is air or hydrogen peroxide.
8. The copper smelting byproduct coprocessing process according to claim 1, wherein the temperature of the high temperature system in the step (4) is 1250-1400 ℃; the valuable metals are metals such as lead, bismuth, tin and the like, and the valuable metals are recovered in a smoke form.
9. The process of claim 1, wherein the high SO concentration in step (5) is determined by co-processing the copper smelting by-product2The flue gas is SO generated in the smelting process2The purified flue gas with the concentration of 8-20 percent.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113088708A (en) * | 2021-03-30 | 2021-07-09 | 中南大学 | Method for recycling polymetallic through resource synergistic treatment of copper smelting white smoke and dirty acid |
| CN114015893A (en) * | 2021-11-09 | 2022-02-08 | 江苏科技大学 | Method for recovering copper from refining slag of copper smelting anode furnace |
| US11293076B2 (en) * | 2019-04-16 | 2022-04-05 | Kunming University Of Science And Technology | Method for preparing iron ore concentrates by recycling copper slag tailings |
| CN114892007A (en) * | 2022-05-18 | 2022-08-12 | 云南锡业股份有限公司铜业分公司 | Method for recovering valuable metals from selenium steaming slag of complex copper anode slime |
| CN115677302A (en) * | 2022-09-06 | 2023-02-03 | 昆明理工大学 | Method for preparing roadbed water stabilization layer by utilizing copper slag in cooperation with various solid wastes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326178A (en) * | 2017-05-22 | 2017-11-07 | 昆明理工大学 | A kind of method that tail gas recycle is utilized during Zinc Hydrometallurgy Residue reducing leaching |
| CN107502748A (en) * | 2017-09-11 | 2017-12-22 | 中南大学 | A kind of method of Bellamya aeruginosa pressurization Strengthen education |
| WO2018217083A8 (en) * | 2017-05-22 | 2019-01-31 | Elemetal Holding B.V. | Process for metal recovery by ammonia leaching and solvent extraction with gas desorption and absorption |
| CN110331300A (en) * | 2019-06-28 | 2019-10-15 | 东营方圆有色金属有限公司 | A kind of method of Copper making industry waste acid and the comprehensive extraction arsenic of flue dust |
-
2020
- 2020-04-23 CN CN202010327548.2A patent/CN111500869B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326178A (en) * | 2017-05-22 | 2017-11-07 | 昆明理工大学 | A kind of method that tail gas recycle is utilized during Zinc Hydrometallurgy Residue reducing leaching |
| WO2018217083A8 (en) * | 2017-05-22 | 2019-01-31 | Elemetal Holding B.V. | Process for metal recovery by ammonia leaching and solvent extraction with gas desorption and absorption |
| CN107502748A (en) * | 2017-09-11 | 2017-12-22 | 中南大学 | A kind of method of Bellamya aeruginosa pressurization Strengthen education |
| CN110331300A (en) * | 2019-06-28 | 2019-10-15 | 东营方圆有色金属有限公司 | A kind of method of Copper making industry waste acid and the comprehensive extraction arsenic of flue dust |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11293076B2 (en) * | 2019-04-16 | 2022-04-05 | Kunming University Of Science And Technology | Method for preparing iron ore concentrates by recycling copper slag tailings |
| CN113088708A (en) * | 2021-03-30 | 2021-07-09 | 中南大学 | Method for recycling polymetallic through resource synergistic treatment of copper smelting white smoke and dirty acid |
| CN114015893A (en) * | 2021-11-09 | 2022-02-08 | 江苏科技大学 | Method for recovering copper from refining slag of copper smelting anode furnace |
| CN114892007A (en) * | 2022-05-18 | 2022-08-12 | 云南锡业股份有限公司铜业分公司 | Method for recovering valuable metals from selenium steaming slag of complex copper anode slime |
| CN115677302A (en) * | 2022-09-06 | 2023-02-03 | 昆明理工大学 | Method for preparing roadbed water stabilization layer by utilizing copper slag in cooperation with various solid wastes |
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