CN111733325A - Method for comprehensively recovering valuable metals from copper-based solid waste - Google Patents

Method for comprehensively recovering valuable metals from copper-based solid waste Download PDF

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CN111733325A
CN111733325A CN202010547594.3A CN202010547594A CN111733325A CN 111733325 A CN111733325 A CN 111733325A CN 202010547594 A CN202010547594 A CN 202010547594A CN 111733325 A CN111733325 A CN 111733325A
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copper
slag
smelting
based solid
leaching
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CN111733325B (en
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杨建平
张岭
张乐如
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China Aluminum International Engineering Corp ltd
CINF Engineering Corp Ltd
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China Aluminum International Engineering Corp ltd
CINF Engineering Corp Ltd
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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
    • C22B7/001—Dry 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
    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry 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
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0028—Smelting or converting
    • C22B15/0052—Reduction smelting or converting
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • 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
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C22B25/02—Obtaining tin by dry 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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

Abstract

The invention discloses a method for comprehensively recovering valuable metals from copper-based solid waste, which comprises the following steps: uniformly mixing copper-based solid waste, coal and a flux, and then carrying out reduction smelting to produce crude copper, reducing slag and smoke dust 1; carrying out anode refining on the produced crude copper, wherein the fuel rate is 5-15%, the slag forming rate is 3-30%, and a copper anode plate, refining slag and smoke dust 2 are obtained; and acid leaching the produced refining slag to obtain electrolytic copper and leaching slag 1. The invention can not only separate the copper in the copper-based solid waste with high efficiency, but also treat the heavy metal solid waste such as scrap copper, secondary zinc oxide smoke dust, tin slag and the like, thereby realizing the purpose of step comprehensive high-efficiency recovery of copper, zinc, lead and tin in the whole process.

Description

Method for comprehensively recovering valuable metals from copper-based solid waste
Technical Field
The invention relates to recovery of copper-based solid waste, in particular to a method for comprehensively recovering valuable metals from copper-based solid waste.
Background
The copper-based solid waste has wide sources and mainly comprises various waste residues and waste materials generated by nonferrous smelting, such as copper ash, black copper mud, anode mud, lead copper matte, polymetallic copper matte and the like; the copper-containing waste scrap copper and reclaimed copper after copper use, such as copper-containing electroplating sludge, copper in scrapped wires and cables or circuit boards, and the like are also included. The copper-based solid waste has complex components, not only contains high-value copper, but also contains high-value impurity metals such as lead, zinc, tin and the like, and the environment is greatly damaged due to improper treatment; the copper content in the copper-based solid waste is greatly different, the copper grade of the copper powder, the copper sponge and the copper mud is 60-90%, and the copper content of the electroplating sludge and the environment-friendly mud is mostly below 15% or even lower. At present, valuable metals recovered from copper-based solid wastes have attracted wide attention at home and abroad, and the global reclaimed copper yield in 2016 can meet the market demand of 47.5%. China is the biggest refined copper producing country and consuming country in the world, but the copper consumption ratio of the copper-based solid waste production in China is only 28.57%, and the difference is obvious compared with the advanced level in the world. Therefore, from the viewpoint of environmental protection and resources, the method for treating the copper-based solid waste can relieve the situation of copper-zinc-lead-tin metal shortage in China, has important strategic significance on national economic development, and is a necessary way for the sustainable development of the national heavy nonferrous metal industry.
At present, two methods of treating copper-containing solid waste at home and abroad mainly comprise hydrometallurgy and pyrometallurgy. The Outfront company of the United states adopts a full wet process to treat copper-containing waste residues, and the recovery of copper, gold and silver can reach 99 percent. But the whole wet process has long process flow and poor adaptability to raw materials. The pyrometallurgy can realize the cooperative smelting of copper-based solid wastes and copper concentrate, for example, the American company in Belgium and the Tonghe and Hengkong company in Japan respectively adopt an Isa furnace and an Osmante furnace to treat wastes such as scrap copper, waste circuit boards and the like, the smelting efficiency is high, but the investment is expensive. In order to reduce the cost, the research of domestic pyrometallurgical treatment of copper-containing waste materials mainly focuses on developing recycled copper smelting equipment suitable for the national conditions and the improvement of the traditional smelting equipment. For example, the ruin engineering technology limited company combines the characteristics of a tilting furnace and a rotary anode furnace, develops an NGL furnace suitable for copper-containing waste treatment, and has the advantages of simple structure, high thermal efficiency and convenient charging and slagging. However, the NGL furnace is mainly used for treating scrap copper with grade more than 80 percent at present, and is difficult to treat low-grade copper-based solid waste.
In the prior art, few patents adopt the combination of hydrometallurgy and pyrometallurgy, and a method for recovering metals such as tin, copper, lead, zinc and the like from copper smelting waste residue by combining wet process and dry process is provided in the patent with the publication number of CN 1093756A. The patent adopts electric furnace oxidation smelting to fully feed all valuable metals into the alloy in one step, the electric furnace smelting does not separate copper from other metals, and simultaneously, the electric furnace has high energy consumption. In the patent, an alloy is obtained by smelting, then all metals are leached by sulfating roasting leaching, sulfating roasting is adopted, equipment requires corrosion resistance, the requirement on the equipment is high, the equipment is not suitable for industrial application, the energy consumption is high, the obtained mixed solution contains copper sulfate and ferric sulfate, the leaching rate of copper is 96.5%, the leaching rate of iron is 65%, and further separation is needed subsequently. Meanwhile, the patent can only treat copper slag singly, can not synchronously recover other metals, and is only suitable for treating low-grade copper-containing materials.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for comprehensively recovering valuable metals from copper-based solid waste is characterized in that hydrometallurgy and pyrometallurgy are combined, copper is preferentially enriched through reduction smelting, then anode refining is carried out, copper is directly leached by acid, copper is preferentially recovered, energy consumption is reduced, equipment with high corrosion prevention requirements is avoided, and the method is suitable for industrial application.
The technical scheme adopted by the invention is as follows:
a method for comprehensively recovering valuable metals from copper-based solid wastes is characterized by comprising the following steps:
reduction smelting: and (2) mixing the following components in percentage by mass as 100: 10-20: 2-20 copper-based solid waste, coal and flux are uniformly mixed and proportioned, reduction smelting is carried out, the concentration of oxygen enrichment is 30-75%, the oxygen-material ratio is 100-;
anode refining: carrying out anode refining on the crude copper, wherein the fuel rate is 5-15%, the slagging rate is 3-30%, and a copper anode plate, refining slag and smoke dust 2 are obtained;
and (3) copper smelting by a wet method: and the produced refining slag is subjected to acid leaching, the liquid-solid ratio is controlled to be 1-5L/kg, the concentration of acid is controlled to be 50-200g/L, the leaching temperature is 30-90 ℃, and the leaching time is 1-4h, so that a copper leaching solution and leaching slag 1 are obtained.
According to the invention, copper is preferentially recovered by reduction smelting in the side-blown converter, after anode refining, the refining slag contains 30-35% of copper and 1-3% of iron, most of the copper in the refining slag exists in the form of oxide, so that the copper is easily leached by acid and efficiently recovered, equipment with high corrosion prevention requirements is not required, and the method is suitable for industrial application. Meanwhile, lead and tin are enriched in the leaching residue 1, so that the subsequent recycling of lead and tin is facilitated.
Preferably, the concentration of oxygen-enriched gas in reduction smelting is 40-75%, and the oxygen-material ratio is 100-150Nm3The oxygen-coal ratio of the material/t is expressed by a combustion coefficient, is controlled to be between 0.75 and 0.9, and the reduction temperature is controlled to be 1250-. Further preferably, the oxygen-enriched concentration in the reduction smelting is 60 to 75%.
Preferably, scrap copper is added in the anode refining step, the fuel rate is controlled to be 6-10%, and the slagging rate is controlled to be 3-20%. Further preferably, scrap copper is added in the anode refining step, the fuel rate is controlled to be 6-8%, and the slagging rate is controlled to be 3-15%. The scrap copper is purchased externally, and is treated together, so that the yield of refining slag is increased, and the utilization rate of copper is increased.
Further, the method also comprises the following step of smelting the reducing slag after the reduction smelting: smelting the reducing slag, a vulcanizing agent, tin slag, pulverized coal and a fusing agent, wherein the mass ratio of the reducing slag to the vulcanizing agent to the tin slag to the pulverized coal to the fusing agent is 70-80: 10-20: 10-30:20-30: 10 to 20 percent, 25 to 40 percent of vulcanizing agent by mass, 1 to 8 percent of tin content by mass and 21 to 45 percent of oxygen-enriched concentration by mass, wherein the oxygen-coal ratio is represented by a combustion coefficient and is controlled to be 0.5 to 0.8, the temperature is 1250-. Preferably, the oxygen-enriched concentration in the step of smelting the reducing slag is 21-30%, and the oxygen-coal ratio is represented by a combustion coefficient and is controlled to be 0.65-0.75.
Further, zinc hydrometallurgy is also included after the reduction smelting: and recovering zinc from the smoke 1, the smoke 2 and the smoke 3 by acid leaching, wherein the liquid-solid ratio is controlled to be 1-5L/kg, the acid concentration is controlled to be 30-100g/L, the leaching temperature is 20-80 ℃, and the leaching time is 1-4h, so that the electrolytic zinc and the leaching residue 2 are obtained. Preferably, the liquid-solid ratio is controlled to be 1-4L/kg, the concentration of sulfuric acid is controlled to be 30-80g/L, the leaching temperature is controlled to be 40-80 ℃, and the leaching time is controlled to be 1-3 h.
Further, after zinc hydrometallurgy, the method also comprises the following smelting steps of leaching residues 1 and 2: adding a reducing agent and a fusing agent into the leaching residues 1 and 2 for smelting, wherein the dosage of the reducing agent is 1-5% of the theoretical dosage, the fusing agent rate is 5-15%, the smelting temperature is 1300-1500 ℃, and the lead-tin alloy and the electric furnace slag are obtained after smelting for 3-5 h. The high-grade tin-containing and lead slag is directly smelted to obtain the lead-tin alloy. Preferably, the dosage of the reducing agent is controlled to exceed 1-3% of the theoretical dosage by smelting, the flux rate is 10-15%, and the smelting temperature is 1300-1400 ℃.
Furthermore, before wet copper smelting, the refining slag is crushed and then sieved by a 200-mesh sieve, and the particle size is controlled to be more than 98%.
Further, the smoke 3 is obtained by performing a dust removal step on the reducing slag smelting smoke, and the reducing slag smelting smoke after dust removal is used for leaching refining slag, smoke 1, smoke 2 and smoke 3 after acid making.
Further, the mass percentages of Cu, Pb, Zn and Sn in the copper-based solid waste are respectively 3% -40%, 1% -10%, 2% -30% and 1% -8%, and the copper in the copper-based solid waste exists in the form of oxides.
Wherein, copper-based solid waste side-blown converter reduction smelting, the main reactions are (1) - (3):
2C+O2＝2CO (1)
MeO+C＝Me+CO (2)
MeO+CO＝Me+CO2(3)
me is metal such as Cu, Zn, Sn, Pb, etc
Reducing slag side-blown fuming, vulcanizing and smelting, wherein the main reactions are (4) - (6):
4SnO+3S2＝4SnS+2SO2(4)
PbO+C＝Pb+CO (5)
ZnO+C＝Zn+CO (6)
SnS volatilized from fuming and vulcanizing of the side-blown furnace is oxidized at the secondary combustion part of the flue gas uptake flue, and the main reaction is (7):
2SnS+3O2＝2SnO+2SO2(7)
anode refining of the crude copper, wherein the main reactions are (8) to (9):
2Me+O2＝2MeO (8)
MeO+SiO2＝MeO·SiO2(9)
me is a metal such as Cu, Zn, Sn, Pb, etc.
Copper is leached out from refining slag by a wet method, and the main reaction is as follows (10):
CuO+H2SO4＝CuSO4+H2O (10)
zinc is leached by the smoke 1, the smoke 2 and the smoke 3 through a wet method, and the main reaction is as follows (11): ZnO + H2SO4＝ZnSO4+H2O (11)
Electric furnace smelting, the main reactions are (12) to (13):
SnO+C＝Sn+CO (12)
PbO+C＝Pb+CO (13)
the method has strong raw material applicability, can treat copper-based solid wastes with different grades, such as low grade, medium grade and high grade, can treat scrap copper with different tastes, can directly carry out anode refining on the scrap copper with high grade, and can effectively enrich and separate copper from scrap copper with medium and low grade by carrying out reduction smelting firstly.
The invention has the advantages that the oxygen-enriched side-blown reduction furnace is adopted to preferentially recover copper, the oxygen-enriched side-blown fuming furnace is used for cooperatively treating the reduction slag and the fuming, vulcanizing and volatilizing the tin slag to obtain high-grade tin-containing smoke dust, most of the copper in the refining slag and the zinc in each path of smoke dust exist in the form of oxides, the copper and the zinc in each path of smoke dust are easily leached and efficiently recovered by sulfuric acid, lead and tin are further enriched in the leached slag, the high-grade tin-containing lead slag is smelted by an electric furnace to directly obtain lead-tin alloy, and SO is discharged2The flue gas can be used for leaching copper from refining slag and leaching zinc from smoke dust after acid making, so that the leaching cost is reduced, the generated fuming slag is sent to a cement plant for selling copper matte, and the electric furnace slag returns to a side-blown fuming furnace for proportioning, thereby realizing the step comprehensive high-efficiency recycling of the copper, zinc, lead and tin in the whole process.
Drawings
FIG. 1 is a flow chart of example 1.
Detailed description of the preferred embodiments
In order to better understand the technical solution, the technical solution will be described in detail with reference to the drawings and the specific embodiments.
Example 1
The mass percentage of Cu in the copper-based solid waste selected in the embodiment is 19.5%, 3.2% of Pb, 3.5% of Zn and 3.5% of Sn; the mass percentage of carbon in the coal is 75 percent, and the ash content is less than 10 percent; the flux comprises quartz stone and limestone, wherein more than 90% of the quartz stone is quartz stone, and SiO in the quartz stone2The mass percentage content is 85.5 percent, and the CaO content in the limestone is 51.3 percent; the outsourcing scrap copper contains 80 percent of Cu, 2.5 percent of Pb, 6 percent of Zn and 10 percent of Sn, the vulcanizing agent contains 31.3 percent of S, 1.3 percent of Zn and 61.5 percent of FeO, the tin slag contains 4.5 percent of Sn, 2.6 percent of Pb, 3.5 percent of Cu and 2.5 percent of Zn, and the zinc suboxide smoke dust contains 55 percent of Zn, 2.5 percent of Pb2 and 20.2 percent of FeO.
As shown in FIG. 1, 100kg of copper-based solid waste, 15kg of coal and flux5kg of the above materials are uniformly mixed and added into an oxygen-enriched side-blown furnace for reduction smelting. Blowing oxygen-enriched concentration with oxygen concentration of 65%, i.e. the concentration ratio of oxygen to total gas, and controlling the oxygen-material ratio at 130Nm3The combustion coefficient of the/t material and the oxygen coal is controlled to be 0.75, the reduction smelting temperature is controlled to be 1250 ℃, the smelting is carried out for 2.5h, 20.1kg of blister copper is produced, the blister copper contains 89% of Cu, 4.7% of Pb, 2.1% of Zn and 2.8% of Sn, 79.9kg of reducing slag contains 1.8% of Cu, 1.5% of Pb, 0.6% of Zn and 3.3% of Sn, and the smoke dust 1 contains 11.0kg of Cu, 4.3% of Pb5.5%, 23.9% of Zn and 4.8% of Sn.
79.9kg of reducing slag enters an oxygen-enriched side-blown fuming furnace in a hot state, the top of the oxygen-enriched side-blown fuming furnace is provided with a vulcanizing agent adding port and a tin slag port, 20kg of cold solder tin slag is added through the tin slag port, 15kg of vulcanizing agent and 14.8kg of fusing agent are added through the vulcanizing agent adding port, oxygen-enriched oxygen with the oxygen concentration of 21% is blown, 25kg of pulverized coal is sprayed for fuming, vulcanizing and volatilizing smelting, the combustion coefficient of oxygen coal is controlled to be 0.65, the fuming smelting temperature is 1300 ℃, smelting is carried out for 3 hours, 110kg of smelting slag is produced, the smelting slag contains 0.4% of Cu, 0.3% of Pb, 0.26% of Sn and 13.5kg of matte, the smelting smoke contains 15% of Cu, 35.9% of FeC and 25% of S, the reducing slag smelting smoke is subjected to bag dust removal to obtain smoke dust 3, and the reducing slag smelting smoke. The smoke 3 has a mass of 19.6kg, and contains 0.4% of Cu, 7.0% of Pb, 16.5% of Sn16, and 5% of Zn.
Carrying out anode refining on the blister copper and outsourced scrap copper, adopting heavy oil as fuel, adding SiO and CaO for slagging to obtain a copper anode plate, refining slag and smoke dust 2, wherein the fuel rate is the proportion of the fuel in the total weight of the blister copper and the outsourced scrap copper, the fuel rate is 7%, the slagging rate is the proportion of the prepared refining slag in the total weight of the blister copper and the outsourced scrap copper, the slagging rate is 10%, the copper content of the produced anode copper is more than 98.5%, the copper content of the refining slag is 30%, and the iron content of the refining slag is 1%; the grain size of the crushed refining slag is controlled to be more than 98 percent and the crushed refining slag is sieved by a 200-mesh sieve, the slag after crushing is used for leaching copper by sulfuric acid, the liquid-solid ratio is controlled to be 2L sulfuric acid/kg refining slag, the sulfuric acid concentration is 80g/L, the leaching temperature is 60 ℃, the leaching time is 4h, the leaching rate of copper is 99.5 percent, electrolytic copper is obtained, and lead and tin are enriched in leaching slag 1.
The smoke dust 1, the smoke dust 2, the smoke dust 3 and the zinc hypoxide smoke dust are combined and then zinc is leached by sulfuric acid, the liquid-solid ratio is controlled to be 1L sulfuric acid/kg of smoke dust, the concentration of the sulfuric acid is 50g/L, the leaching temperature is 40 ℃, the leaching time is 3 hours, the leaching rate of zinc is 99.8 percent, and lead and tin are enriched in the leaching residue 2.
And (3) mixing the leached slag 1 and the leached slag 2, then smelting in an electric furnace, wherein the mass percent of lead and tin in the leached slag is 45%, the reducing agent is anthracite or coke, the required dosage is calculated according to chemical reactions (12) and (13), the dosage exceeds 2% of the theoretical dosage, the flux rate is the proportion of the flux to the total weight of the leached slag 1 and the leached slag 2, the flux rate is 12%, the smelting temperature is 1300 ℃, smelting is carried out for 4 hours, the mass percent of the produced lead-tin alloy is 98%, the recovery rate is 95%, the electric furnace slag contains 2.5% of tin, and the mixture returns to the fuming furnace for batching.

Claims (10)

1. A method for comprehensively recovering valuable metals from copper-based solid wastes is characterized by comprising the following steps:
reduction smelting: and (2) mixing the following components in percentage by mass as 100: 10-20: 2-20 copper-based solid waste, coal and flux are uniformly mixed and proportioned for reduction smelting, the concentration of the oxygen-enriched gas is 30-75%, and the oxygen-material ratio is 100-200Nm3The oxygen-coal ratio is represented by a combustion coefficient, the oxygen-coal ratio is controlled to be 0.5-0.9, the reduction temperature is 1150-1350 ℃, the reduction time is 1-3h, and crude copper, reduction slag and smoke dust 1 are produced;
anode refining: carrying out anode refining on the crude copper, wherein the fuel rate is 5-15%, the slagging rate is 3-30%, and a copper anode plate, refining slag and smoke dust 2 are obtained;
and (3) copper smelting by a wet method: and the produced refining slag is subjected to acid leaching, the liquid-solid ratio is controlled to be 1-5L/kg, the concentration of acid is controlled to be 50-200g/L, the leaching temperature is 30-90 ℃, and the leaching time is 1-4h, so that a copper leaching solution and leaching slag 1 are obtained.
2. The method for comprehensively recovering valuable metals from copper-based solid waste according to claim 1, characterized by further comprising the step of smelting the reducing slag after the reduction smelting: smelting the reducing slag, a vulcanizing agent, tin slag, pulverized coal and a fusing agent, wherein the mass ratio of the reducing slag to the vulcanizing agent to the tin slag to the pulverized coal to the fusing agent is 70-80: 10-20: 10-30:20-30: 10 to 20 percent, 25 to 40 percent of vulcanizing agent by mass, 1 to 8 percent of tin content by mass and 21 to 45 percent of oxygen-enriched concentration by mass, wherein the oxygen-coal ratio is represented by a combustion coefficient and is controlled to be 0.5 to 0.8, the temperature is 1250-.
3. The method for comprehensively recovering valuable metals from copper-based solid wastes according to claim 2, characterized by further comprising the steps of hydrometallurgical zinc: and recovering zinc from the smoke 1, the smoke 2 and the smoke 3 by acid leaching, wherein the liquid-solid ratio is controlled to be 1-5L/kg, the acid concentration is controlled to be 30-100g/L, the leaching temperature is 20-80 ℃, and the leaching time is 1-4h, so that the electrolytic zinc and the leaching residue 2 are obtained.
4. The method for comprehensively recovering valuable metals from copper-based solid waste according to claim 3, characterized in that the method further comprises the following steps of smelting leaching residues 1 and 2 after the zinc hydrometallurgy: adding a reducing agent and a fusing agent into the leaching residues 1 and 2 for smelting, wherein the dosage of the reducing agent is 1-5% of the theoretical dosage, the fusing agent rate is 5-15%, the smelting temperature is 1300-1500 ℃, and the lead-tin alloy and the electric furnace slag are obtained after smelting for 3-5 h.
5. The method for comprehensively recovering valuable metals from copper-based solid wastes according to any one of claims 1 to 4, characterized in that before the wet copper smelting, the refining slag is crushed and then sieved by a 200-mesh sieve, and the particle size is controlled to be more than 98%.
6. The method for comprehensively recovering valuable metals from copper-based solid wastes according to claim 2, characterized in that: the smoke 3 is obtained by the dust removal step of the reducing slag smelting smoke, and the reducing slag smelting smoke after dust removal is used for leaching refining slag, smoke 1, smoke 2 and smoke 3 after acid making.
7. The method for comprehensively recovering valuable metals from copper-based solid wastes according to any one of claims 1 to 4, characterized in that: the mass percentages of Cu, Pb, Zn and Sn in the copper-based solid waste are respectively 3% -40%, 1% -10%, 2% -30% and 1% -8%, and the copper in the copper-based solid waste exists in the form of oxides.
8. The method for comprehensively recovering valuable metals from copper-based solid wastes according to any one of claims 1 to 4, characterized in that: the concentration of oxygen enrichment in reduction smelting is 40-75%, and the oxygen-material ratio is 100-150Nm3The oxygen-coal ratio of the material/t is expressed by a combustion coefficient, is controlled to be between 0.75 and 0.9, and the reduction temperature is controlled to be 1250-.
9. The method for comprehensively recovering valuable metals from copper-based solid wastes according to any one of claims 2 to 4, characterized in that: the oxygen-enriched concentration in the step of smelting the reducing slag is 21-30%, and the oxygen-coal ratio is represented by a combustion coefficient and is controlled to be 0.65-0.75.
10. The method for comprehensively recovering valuable metals from copper-based solid wastes according to any one of claims 1 to 4, characterized in that: scrap copper is also added in the anode refining step, the fuel rate is controlled to be 6-10%, and the slagging rate is controlled to be 15-25%.
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Publication number Priority date Publication date Assignee Title
CN113355531A (en) * 2021-05-28 2021-09-07 河南豫光金铅股份有限公司 Production method for directly smelting brass raw material into copper anode plate
CN113699382A (en) * 2021-08-27 2021-11-26 上海中川国宇环境有限公司 Treatment device and treatment process applied to slag recycling
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
CN114410969A (en) * 2021-12-30 2022-04-29 济源豫光有色冶金设计研究院有限公司 Method for recycling copper and arsenic from black copper mud step by step

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