CN109536730B - Method for extracting lead-bismuth alloy from copper anode slime smelting waste residues - Google Patents

Method for extracting lead-bismuth alloy from copper anode slime smelting waste residues Download PDF

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CN109536730B
CN109536730B CN201811280169.1A CN201811280169A CN109536730B CN 109536730 B CN109536730 B CN 109536730B CN 201811280169 A CN201811280169 A CN 201811280169A CN 109536730 B CN109536730 B CN 109536730B
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lead
bismuth alloy
silver
melt
copper anode
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CN109536730A (en
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杜彦君
钟清慎
张燕
王立
俞宏山
罗明儒
李生民
田飞
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Jinchuan Group Copper Gui Co ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/04Working-up slag
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • C22B11/02Obtaining noble metals by dry processes
    • C22B11/021Recovery of noble metals from waste materials
    • C22B11/023Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/02Obtaining lead by dry processes
    • C22B13/025Recovery from waste materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/06Obtaining bismuth
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes
    • C22B7/002Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes
    • C22B7/004Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
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  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention belongs to the technical field of metallurgy, and relates to a method for extracting a lead-bismuth alloy from copper anode slime smelting waste residues. The method comprises the following steps: mixing copper anode mud smelting waste residues and a flux, adding the mixture into a Kaldo furnace for reduction smelting, slagging off after the reduction smelting to obtain a crude lead bismuth alloy, transferring the crude lead bismuth alloy melt to an intermediate frequency furnace, and then sequentially carrying out liquation to remove copper, sulfur and nickel, and zinc and silver to obtain a refined lead bismuth alloy; the flux comprises coke, limestone and sodium carbonate, and the addition amount of each component of the flux is calculated by the mass percentage of the copper anode slime smelting waste residue: 5-6% of coke, 15-19% of limestone and 2-4% of sodium carbonate. The refined lead bismuth alloy obtained by the invention has higher lead grade and less impurities, can directly carry out lead electrolytic separation to recover lead and bismuth, and returns the silver-zinc shell to the furnace to recover gold and silver, thereby realizing the high-efficiency separation and recovery of lead, bismuth and gold and silver in the copper anode slime smelting waste residue.

Description

Method for extracting lead-bismuth alloy from copper anode slime smelting waste residues
Technical Field
The invention belongs to the technical field of metallurgy, and relates to a method for extracting a lead-bismuth alloy from copper anode slime smelting waste residues.
Background
The main treatment process of the copper anode slime combines a wet process and a pyrogenic process, the copper anode slime-pressure leaching of copper, tellurium-pyrogenic smelting, blowing-silver electrolysis-silver anode slime recovery of gold, the smelting waste slag generated in the pyrogenic smelting process contains low gold and silver, contains high lead and bismuth, generally contains 0.1-0.3% of Ags, 5-20g/t of Au, 25-30% of Pb and 4-6%, the smelting waste slag of the part of the copper anode slime has large amount and low Ag content, and cannot return to a copper anode slime pyrometallurgical system to recover precious metals, and the part of lead and bismuth enters a copper smelting system to further enrich gold and silver to the copper anode slime to cause dispersion loss of gold and silver, and the part of lead and bismuth enters the copper smelting waste slag to cause loss of lead and bismuth. The method for treating the copper anode slime smelting waste residue has the advantages of incapability of recycling lead and bismuth, long treatment process and high cost.
Disclosure of Invention
The invention aims to provide a method for extracting lead-bismuth alloy from copper anode slime smelting waste residues aiming at the problems in the prior art.
The specific technical scheme of the invention is as follows:
a method for extracting lead-bismuth alloy from copper anode slime smelting waste residues comprises the following steps: mixing copper anode mud smelting waste residues and a flux, adding the mixture into a Kaldo furnace for reduction smelting, slagging off after the reduction smelting to obtain a crude lead bismuth alloy, transferring the crude lead bismuth alloy melt to an intermediate frequency furnace, and then sequentially carrying out liquation to remove copper, sulfur and nickel, and zinc and silver to obtain a refined lead bismuth alloy; the flux comprises coke, limestone and sodium carbonate, and the addition amount of each component of the flux is calculated by the mass percentage of the copper anode slime smelting waste residue: 5-6% of coke, 15-19% of limestone and 2-4% of sodium carbonate;
further, after the medium frequency furnace is transferred, the temperature of the melt is maintained at 700-;
further, when the copper is removed by liquation, the melt temperature is 600 ℃, 1-2% of broken coke and 0.05-1% of waste slag from copper anode mud smelting are added according to the mass percentage for reaction for 1-2 hours;
further, the melt temperature is 350-;
furthermore, when adding zinc and separating silver, the melt temperature is 530 ℃ and 560 ℃, zinc particles are added according to 2-4% of the silver content of the melt for removing silver, the silver removing time is 4-6h, and then the temperature is reduced to 400 ℃ for slag fishing.
The invention has the following beneficial effects: reducing and smelting the copper anode slime smelting waste residue, reducing lead, bismuth, copper and nickel into simple substances, forming a crude lead bismuth alloy with low gold and silver content with a small amount of gold and silver, slagging limestone and the original silicon in the smelting waste residue into a reduction tail material, and transferring the crude lead bismuth alloy melt into an intermediate frequency furnace through a tundish; keeping the temperature of the crude lead bismuth alloy melt in an intermediate frequency furnace at 700-800 ℃ for 0.5h, then, keeping the temperature to 600 ℃, adding broken coke and quartz, wherein the copper has low solubility in lead water and high affinity with arsenic and antimony at low temperature, can form compounds, solid solutions and eutectic crystals, has high melting point and low density, and floats after being mixed into solid slag; then adding sulfur, elemental sulfur and nickel to form light nickel matte which is not melted in lead, and removing scum; and finally, adding zinc to extract silver, wherein the affinity of gold and silver and zinc is high, so that zinc gold and zinc silver compounds which have high melting points and low density and are insoluble in lead water are combined, the zinc gold and zinc silver compounds float on the surface in a silver-zinc shell form to be separated from lead, the obtained refined lead-bismuth alloy has high lead-containing grade and few impurities, lead and bismuth can be directly recovered by lead electrolytic separation, the silver-zinc shell is returned to a furnace to recover gold and silver, and the high-efficiency separation and recovery of lead bismuth and gold and silver in the copper anode slime smelting waste residue are realized.
Detailed Description
The method is adopted to extract the lead-bismuth alloy from the copper anode slime smelting waste slag, and the copper anode slime smelting waste slag contains 0.3% of Ag0.3%, 15g/t of Au, 28% of Pb, 5% of Bi, 2.6% of Ni and 2.8% of Cu.
Example 1
Mixing 4t of copper anode slime smelting waste residue, 0.2t of coke, 0.6t of limestone and 0.08t of sodium carbonate, adding the mixture into a Kaldo furnace for reduction smelting, skimming after the reduction smelting to obtain 1.81t of crude lead bismuth alloy melt, transferring the crude lead bismuth alloy melt into an intermediate frequency furnace through a tundish, keeping the melt temperature at 700 ℃ in the intermediate frequency furnace for 0.5h, then reducing the melt temperature to 600 ℃, adding 0.018t of broken coke and 0.009t of quartz for liquation to remove copper for 1h, and skimming the slag after forming copper dross slag; cooling the melt to 350 ℃, adding 0.065t of sulfur to remove nickel for 2h, and fishing slag; and (3) raising the temperature of the melt to 530 ℃, adding 0.22kg of zinc particles to remove silver for 4 hours, reducing the temperature of the melt to 400 ℃, and fishing slag to obtain the refined lead bismuth alloy.
The refined lead bismuth alloy contains Cu 0.021%, Ni 0.013%, Ag 0.008%, Pb 85.1% and Bi 12.8%.
Example 2
Mixing 4t of copper anode slime smelting waste residue, 0.22t of coke, 0.68t of limestone and 0.12t of sodium carbonate, adding the mixture into a Kaldo furnace for reduction smelting, removing slag after reduction smelting to obtain 1.76t of crude lead bismuth alloy, transferring the crude lead bismuth alloy melt into an intermediate frequency furnace through a tundish, keeping the melt temperature at 750 ℃ in the intermediate frequency furnace for 0.5h, then reducing the melt temperature to 600 ℃, adding 0.026t of crushed coke and 0.014t of quartz for liquation to remove copper for 1.5h, forming copper scum, and removing slag; cooling the melt to 380 ℃, adding 0.073t of sulfur to remove nickel for 2.5h, and fishing slag; and (3) raising the temperature of the melt to 545 ℃, adding 0.36kg of zinc particles to remove silver for 5 hours, reducing the temperature of the melt to 400 ℃, and fishing slag to obtain the refined lead bismuth alloy.
The refined lead bismuth alloy comprises 0.020% of Cu, 0.011% of Ni, 0.007% of Ag, 85.3% of Pb and 12.9% of Bi.
Example 3
Mixing 4t of copper anode slime smelting waste residue, 0.24t of coke, 0.76t of limestone and 0.16t of sodium carbonate, adding the mixture into a Kaldo furnace for reduction smelting, removing slag after reduction smelting to obtain 1.75t of crude lead bismuth alloy, transferring the crude lead bismuth alloy melt into an intermediate frequency furnace through a tundish, keeping the melt temperature of 800 ℃ in the intermediate frequency furnace for 0.5h, then reducing the melt temperature to 600 ℃, adding 0.035t of broken coke and 0.017t of quartz for liquation to remove copper for 2h, and removing slag after forming copper dross slag; cooling the melt to 400 ℃, adding 0.087t of sulfur to remove nickel for 3h, and fishing out slag; and raising the temperature of the melt to 560 ℃, adding 0.44kg of zinc particles to remove silver for 6 hours, reducing the temperature of the melt to 400 ℃, and fishing slag to obtain the refined lead bismuth alloy.
The refined lead bismuth alloy comprises 0.019% of Cu, 0.010% of Ni, 0.006% of Ag, 85.8% of Pb and 13.1% of Bi.

Claims (1)

1. A method for extracting lead-bismuth alloy from copper anode slime smelting waste residues is characterized by comprising the following steps: mixing copper anode mud smelting waste residues and a flux, adding the mixture into a Kaldo furnace for reduction smelting, slagging off after the reduction smelting to obtain a crude lead bismuth alloy, transferring the crude lead bismuth alloy melt to an intermediate frequency furnace through a tundish, and then sequentially carrying out liquation to remove copper, sulfur and nickel, and zinc and silver to obtain a refined lead bismuth alloy;
the flux comprises coke, limestone and sodium carbonate, and the addition amount of each component of the flux is calculated by the mass percentage of the copper anode slime smelting waste residue: 5-6% of coke, 15-19% of limestone and 2-4% of sodium carbonate;
transferring the crude lead bismuth alloy melt to an intermediate frequency furnace through a tundish, and keeping the melt temperature at 700 ℃ and 800 ℃ for 0.5 h;
when the copper is removed by liquation, the melt temperature is 600 ℃, and 1-2% of broken coke and 0.05-1% of quartz are added according to the mass percentage of the copper anode mud smelting waste residue for reaction for 1-2 hours;
the temperature of the melt is 350-400 ℃ when the sulfur is added and the nickel is removed, and the sulfur is added for removing the nickel for 2-3h according to 1.5-2 times of the molar weight of the nickel contained in the melt;
when adding zinc and separating silver, the temperature of the melt is 530 ℃ and 560 ℃, zinc particles are added according to 2-4% of the silver content of the melt for removing silver, the silver removing time is 4-6h, and then the temperature is reduced to 400 ℃ for removing slag.
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Publication number Priority date Publication date Assignee Title
CN110760688A (en) * 2019-10-23 2020-02-07 金川集团股份有限公司 Method for deeply removing impurities and enriching precious metals in complex lead-bismuth alloy
CN111549233B (en) * 2020-04-03 2022-02-01 金隆铜业有限公司 Method for recovering lead and bismuth from copper anode mud smelting slag
CN112143915B (en) * 2020-09-28 2022-08-02 云南锡业股份有限公司冶炼分公司 Tin refining nickel removing process and device
CN113981231A (en) * 2021-11-03 2022-01-28 安徽铜冠有色金属(池州)有限责任公司 Process for recovering lead, bismuth, gold and silver from copper anode slime smelting slag
CN114774708B (en) * 2022-03-10 2023-09-22 金川集团股份有限公司 Method for refining copper-removing from copper anode slime leaching slag

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CN101886174A (en) * 2010-06-23 2010-11-17 郴州雄风稀贵金属材料股份有限公司 Process for refining high-purity bismuth from bismuth-containing material generated from anode mud recovery
CN101914694A (en) * 2010-09-08 2010-12-15 江西稀有金属钨业控股集团有限公司 Refining method of crude bismuth containing high silver and high copper
CN102703719A (en) * 2012-07-03 2012-10-03 阳谷祥光铜业有限公司 Technology for recovering valuable metals from noble metal slag
JP2015214760A (en) * 2015-07-30 2015-12-03 住友金属鉱山株式会社 Method for treating copper refining dust

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101245471A (en) * 2008-03-07 2008-08-20 湖南昭山冶金化工有限公司 Method for producing bismuth and enriched silver from high-silver bismuth alloy
CN101886174A (en) * 2010-06-23 2010-11-17 郴州雄风稀贵金属材料股份有限公司 Process for refining high-purity bismuth from bismuth-containing material generated from anode mud recovery
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JP2015214760A (en) * 2015-07-30 2015-12-03 住友金属鉱山株式会社 Method for treating copper refining dust

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