CN113061738B - Method for comprehensively recovering multiple valuable metals in copper slag floating copper tailings - Google Patents

Method for comprehensively recovering multiple valuable metals in copper slag floating copper tailings Download PDF

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CN113061738B
CN113061738B CN202110285498.0A CN202110285498A CN113061738B CN 113061738 B CN113061738 B CN 113061738B CN 202110285498 A CN202110285498 A CN 202110285498A CN 113061738 B CN113061738 B CN 113061738B
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copper
slag
iron
copper slag
tailings
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CN113061738A (en
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雷鹰
雍超
李�雨
刘瑞
杨皓月
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Anhui University of Technology AHUT
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/018—Mixtures of inorganic and organic compounds
    • 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
    • C22B1/02—Roasting 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
    • C22B13/025—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
    • 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
    • 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
    • C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/007—Modifying reagents for adjusting pH or conductivity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/04—Frothers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/06—Depressants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores
    • 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
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working

Abstract

The invention discloses a method for comprehensively recovering various valuable metals in copper slag floating copper tailings, and belongs to the technical field of metal element recovery. The method comprises the following steps: direct reduction roasting, magnetic separation and reverse flotation. According to the invention, by introducing mixed gas of methane, hydrogen and argon for direct reduction roasting, magnetite in the mixed gas can be completely converted into metallic iron, and the fayalite in the mixed gas is dissociated by matching with a composite additive, so that the purpose of resource mineral phase reconstruction is achieved, the phase composition in the copper slag is improved, the iron phase in the slag is subjected to decomposition reaction, and lead and zinc are gasified in the form of metal steam, so that comprehensive recovery of various valuable metals in the copper slag is realized. And meanwhile, the roasted product is treated by magnetic separation and reverse flotation, so that the grade of the iron ore concentrate is effectively improved, the effective utilization rate of resources is higher, the recovery process is simple, the energy consumption is lower, and the economic benefit is higher.

Description

Method for comprehensively recovering multiple valuable metals in copper slag floating copper tailings
Technical Field
The invention belongs to the technical field of metal element recovery, and particularly relates to a method for comprehensively utilizing and recovering valuable metals in copper slag by a combined process.
Background
The metallurgical slag is solid waste discharged after valuable metals are extracted from metal-containing minerals or semi-finished products in metallurgical production. The copper slag is solid waste left after smelting copper ore. Copper is a metal element widely stored in the earth's crust and oceans, and accounts for about 0.01% of the earth. Copper, as a material, has been used in various forms in human society since ancient times, and has become an integral part of the development of human society. The smelting technology of copper is mature, and is mainly divided into pyrometallurgy and wet smelting, but 80% of copper in the world comes from pyrometallurgy, and the wet smelting is not widely applied at present. The copper slag is a product in the matte smelting and matte converting processes of copper smelting. The different smelting processes are different, and the material elements and the composition components of the copper slag are different. The copper slag is divided into slow-cooling slag and water-quenching slag according to different cooling modes; according to copper production equipment, the method comprises the following steps of dividing the copper into reflection slag, blast furnace slag, converter slag and flash smelting slag; according to the copper smelting process, the method can be divided into blowing slag, smelting slag and the like[4]. With the development of metallurgical technology, the copper yield is rapidly increasing, and more copper slag is conceivable to be produced therewith. The data show that the copper yield in 2019 reaches 978.4 ten thousand tons, the copper yield in China reaches 744.9 ten thousand tons in 1-9 months in 2020, the future increase is expected to continue, 2.2 tons of copper slag are produced according to each 1 ton of copper, and the amount of the copper slag produced in 2020 exceeds 1800 ten thousand tons.
Along with the development of metallurgical technology, mineral resources are increasingly depleted and depleted, and China still faces a series of mineral resources problems such as more lean ores, less rich ores, low ore grade, large processing difficulty and the like, so that the recycling of secondary resources such as copper slag and the like is not slow. The copper slag, which is the most important solid waste in the copper metallurgy industry, contains a large amount of valuable metal elements such as copper, iron and the like, and the valuable metal grade is higher than that of common ore resources, so that the copper slag is an artificial ore in a certain sense. Therefore, the development and utilization of copper slag resources become very important, and the comprehensive recovery of copper and iron in the copper slag has very important practical significance and considerable economic benefit at the present stage.
Research shows that the copper slag has extremely complex composition, consists of a plurality of compounds and is accompanied with highly toxic element substances such as arsenic, lead and the like. Iron in the copper slag is mainly distributed in an olivine phase and a magnetic iron oxide phase, and the combination form of copper is complex and is mainly uniformly dispersed in fine particles. The structure is compact, hard and crisp, the density is large, the ore grinding work index is higher, the valuable metal has more coarse and fine grades, and the intermediate granularity is less. The properties of the copper smelting slag are closely related to the properties of the copper concentrate entering the furnace, the components of the flux, the smelting process, the slag cooling system and the like, and the factors determine the process flow and the resource value of the comprehensive utilization of the copper smelting slag, so that the comprehensive recovery of the metal in the copper slag is difficult and the cost is high. The method has the advantages that the conventional sorting process cannot effectively recover valuable metals, the comprehensive utilization rate is extremely low, a large amount of copper slag generated every year is accumulated for a long time, a large part of land resources are occupied, the problem of serious environmental pollution is caused, and the continuous healthy development of the copper metallurgy industry is influenced to a great extent. Aiming at resource research and utilization of copper slag, the main methods are wet extraction, pyrogenic dilution and mineral separation.
In the aspect of wet extraction, the aged will be bushy[15]Combining with kinetic analysis, carrying out experimental study on the sulfating leaching of the desiliconized copper slag, and mainly investigating the influence of sulfuric acid concentration, leaching time, liquid-solid ratio, temperature and particle size on the leaching rate of copper and zinc. The results show that: under mechanical stirring, the concentration of sulfuric acid is 2.5mol/L, the leaching time is 120min, the liquid-solid ratio is 4:1, the temperature is 70 ℃, and the leaching rates of copper and zinc are highest when the particle size is 200 meshes, wherein the leaching rates are respectively 76.2% and 98.3%. Research on modification of copper slag and recovery of copper and iron on Otemet (Jenseng. Otemet)]Wuhan university of science and technology 2015.) iron in certain copper slag was recovered by roasting-leaching-magnetic separation using coal powder as a reducing agent. The influence of factors such as roasting temperature, roasting time, coal powder consumption, sodium carbonate consumption and the like on iron recovery is discussed, and under the optimal process conditions: roasting temperature is 800 ℃, roasting time is 60min, coal powder dosage is 1%, and sodium carbonate dosage is 1%Calcine is obtained under 10 percent, and iron concentrate with the iron grade of 62.53 percent and the iron recovery rate of 70.82 percent can be obtained through further dilute acid leaching and magnetic separation. However, although the processes can effectively recover copper and iron in the copper slag, on one hand, the leaching process has high requirements on equipment and seriously affects the service life of production equipment; on the other hand, the leaching and other processes are easy to cause secondary pollution and are not environment-friendly.
In the fire method dilution aspect, Zdongyang and the discipline (Zdongyang, the discipline and the waste scrap copper smelting slag dilution research [ J ] and Chinese metal report, 2017(07):66-67.) carry out fire method dilution research on the waste scrap copper smelting slag according to the copper slag fire method dilution principle. Under the experimental conditions of the heat preservation temperature of 1300 ℃ and the heat preservation time of 60min, the experimental atmosphere is explored, and the influence of different additives on the dilution effect is explored. The test result shows that: the reducing atmosphere is necessary for the pyrogenic depletion of the slag from the copper smelting by the FRHC method, river sand and fluorite are favorable for the depletion of the copper slag, and sodium salt is harmful for the depletion of the copper slag. The recovery rate of copper obtained by the experiment reaches more than 99 percent, and the copper content in the depleted slag is 0.97 percent. Experiments prove that the method can effectively dissolve and extract the copper mixed in the slag. But on one hand, the high temperature has a great influence on the service life of the smelting furnace and has higher requirements on equipment, and on the other hand, the energy consumption generated by high-temperature dilution is too high and is irrevocable when being applied to the actual industry.
In the aspect of mineral separation, the optimization of the reinforced flotation recovery process of the monoplasm copper phase in copper smelting slag and the production practice [ J ]. nonferrous metal (mineral separation part), 2020(06):36-40+70.) optimize and recover the monoplasm copper phase in the reinforced copper smelting slag from three aspects of ore grinding fineness, collecting agent type and flotation concentration. Under the optimal condition, the recovery rates of copper, gold and silver of the obtained copper concentrate are respectively 93.64%, 83.30% and 93.65%, the copper grade in the tailings is reduced to 0.22%, the flotation recovery of the simple substance copper phase is effectively enhanced, and the aims of reducing the content of the simple substance copper phase in the tailings and improving the recovery rate of copper are achieved. However, the grade of the concentrate obtained by recovering valuable metals by adopting a beneficiation method is still not high, the chemical quantity consumed by direct flotation is too large, the yield is lower, the problem of high energy consumption is caused by further reducing the fineness of grinding, and the valuable metals in the copper slag cannot be effectively recovered.
As can be seen from the above documents, many scholars have studied on the recovery of valuable metals from copper slag, but most of them have studied more deeply on the recovery method of single valuable metals from copper slag, and the research on the comprehensive utilization of multiple metals from copper slag is less. The copper slag not only contains copper, but also contains more iron and valuable metal elements such as zinc, lead and the like. The loss of the metal elements also causes great resource waste, and the copper slag cannot achieve the purpose of effective resource utilization. And in general, the direct reduction of copper smelting slag in a molten state can lead to the content of residual copper exceeding 0.5 wt%, zinc and lead oxides remaining in the reduced slag exceeding 1 wt%, and some harmful trace elements such as antimony, arsenic and bismuth are not reduced to harmless concentrations.
Through retrieval, related patent publications on the utilization of iron in copper slag are provided, for example, a patent with application number 200910163234.7 proposes a method for extracting iron from copper slag through smelting reduction by blowing inert gas, the method proposes that discharged high-temperature copper slag, a certain amount of reducing agent and slag former are added into a reducing furnace for carrying out high-temperature reduction iron-making reaction, the temperature is kept for 20min under the condition of 1540 ℃, and inert gas is used for blowing and stirring, so that high-temperature molten iron is finally obtained, and the purpose of recovering iron in copper slag is achieved. In the reaction process, after waste heat recovery, high-temperature flue gas secondary combustion is carried out, dust collection and washing treatment are carried out, after the requirement of evacuation is met, the flue gas is discharged into the atmosphere, and the calculated result shows that the recovery rate of iron in the copper slag is higher and reaches 91.9%. For another example, the application No. 201510283249.2 proposes a system and a method for recovering iron from molten copper slag by step reduction and recovering waste heat by coal gasification, in which molten copper slag at 1200-1300 ℃ discharged from a copper smelting furnace flows into a reduction iron extracting furnace, CO is injected at 1450-1500 ℃ to perform CO reduction reaction on the copper slag, limestone is added after the reaction is finished, and coal powder is injected for 30min to obtain molten iron. The method can effectively recover the iron in the copper slag, and the iron recovery rate reaches over 90 percent. However, when the iron in the copper slag is reduced in the two applications, the reduction temperature exceeds 1000 ℃, the energy consumption is high, and the economic benefit is relatively poor.
Disclosure of Invention
1. Technical problems to be solved by the invention
The invention aims to overcome the defects that when the existing method is used for recycling copper slag, the types of the recycled valuable metals are single, the comprehensive recycling of the valuable metal elements such as iron, zinc, lead and the like is difficult, the resource waste is easily caused, and the effective resource utilization of the copper slag cannot be realized, and provides a method for comprehensively recycling a plurality of valuable metals in copper slag floating tailings. The technical scheme of the invention can effectively solve the problems, fully recover more valuable metals in the copper slag, and has the advantages of high effective utilization rate of resources, simple recovery process, low energy consumption, environmental friendliness and high economic benefit.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to a method for comprehensively recovering various valuable metals in copper slag floating copper tailings, which comprises the following steps:
step one, direct reduction
Uniformly mixing the copper flotation tailings with a composite additive of calcium oxide and sodium carbonate, and introducing a mixed gas of methane, hydrogen and argon for reduction roasting;
step two, wet magnetic separation
Carrying out magnetic separation on the copper flotation tailings after the reduction roasting treatment to obtain iron ore concentrate, and filtering and drying the iron ore concentrate;
step three, reverse flotation
And adding a collecting agent, a foaming agent, a pH regulator and an inhibitor to perform a reverse flotation experiment on the magnetic concentrate, and further separating and removing impurities to obtain an iron concentrate product with qualified quality.
Furthermore, in the step one, the addition amount of the composite additive is 10-25% of the total amount of the copper dross and the composite additive, and the CaO in the composite additive is Na2CO3＝1.5～3。
Further, in the first step, after the copper flotation tailings are dried, the composite additive is added and mixed uniformly, then the temperature is raised to the reduction temperature under the protection of inert gas, and finally the mixed gas is introduced for reduction roasting, wherein the reduction roasting temperature is 700-900 ℃, and the roasting time is 90-120 min.
Furthermore, in the first step, under the protection of inert gas, the temperature is increased from room temperature to 400 ℃ at the speed of 7-10 ℃/min, and then the temperature is increased to the reduction temperature at the speed of 3-5 ℃/min.
Furthermore, in the first step, the total flow rate of the introduced mixed gas is 700-900 mL/min, wherein the volume fraction of argon is 50%, the volume fraction of used methane is 5-15%, and the volume fraction of hydrogen is 35-45%.
Furthermore, in the second step, the magnetic separation strength is controlled to be 1200-1800 Gs.
Furthermore, in the third step, dodecylamine is used as a collecting agent, and the using amount of the dodecylamine is 500-900 g/t; the foaming agent is No. 2 oil, and the dosage of the oil is 20-30 g/t; lime is adopted as the pH regulator, and the dosage of the lime is 1000-1300 g/t; the inhibitor is causticized starch, and the dosage of the causticized starch is 800-1200 g/t.
Furthermore, in the third step, during the flotation, the mixture is stirred for three minutes, then the pH regulator is added to adjust the pH value of the ore pulp, the inhibitor is added after three minutes, the collector is added after five minutes, then the foaming agent is added after three minutes, and the iron concentrate product is obtained by blowing and scraping after three minutes and performing flotation for three minutes.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the method for comprehensively recovering various valuable metals in copper slag and copper floating tailings comprises the steps of uniformly mixing the copper floating tailings with a composite additive of calcium oxide and sodium carbonate, introducing mixed gas for reduction roasting, and comprehensively recovering the copper slag through wet magnetic separation and reverse flotation. According to the invention, the whole recovery process is optimally designed, and particularly, the mixed gas is introduced at the medium and low temperature to reduce the copper slag, so that on one hand, iron, lead and zinc in the copper slag floating tailings can be effectively and comprehensively recovered, and harmful trace elements are reduced to harmless concentration, thereby achieving the purpose of comprehensively recovering various valuable metal elements in the copper slag and improving the resource utilization rate of the copper slag. On the other hand, the reduction temperature can be effectively reduced, the treatment energy consumption is greatly reduced, and the economic benefit is higher.
(2) According to the method for comprehensively recovering multiple valuable metals in the copper slag floating tailings, the composition and content of the reducing atmosphere adopted in the direct reduction, the reducing roasting temperature and the reduction roasting time length are optimally designed, so that on one hand, the content of the valuable metal elements in the copper slag can be well reduced, the elements such as iron, lead and zinc can be effectively recycled, the harmful elements such as antimony, arsenic and bismuth can be reduced to harmless concentration, and the environment-friendly policy is maintained. On the other hand, during reduction, excessive deposition of soot in the reduction process can be effectively avoided, and the recovery effect of metal elements such as zinc, lead and the like is further improved.
(3) According to the method for comprehensively recovering various valuable metals in the copper slag floating copper tailings, the temperature of the reduction treatment environment is much lower than that of other methods, the copper slag recovery cost is greatly reduced, and the problem of high energy consumption of copper slag recovery can be effectively solved. Meanwhile, the introduced mixed gas consists of methane, hydrogen and argon, and the mass fraction ratio of the mixed gas is optimally designed, so that magnetite in the copper slag can be completely reduced into metallic iron at a medium-low temperature, and other impurities such as zinc, lead and the like in the copper slag are further decomposed and reduced according to different driving forces of reduction reactions of various impurities such as oxides at a low temperature, and then the oxides are evaporated from the slag in the form of metal steam to enter flue gas for recovery. On one hand, the method can completely recover the valuable metal elements with lower boiling points, such as zinc, lead and the like in the copper slag, thereby achieving the purpose of resource utilization. On the other hand, the problem of high content of zinc and other impurity elements in the iron ore concentrate in the subsequent process is solved, so that the obtained iron ore concentrate can be directly used as an iron-making raw material.
(4) The method for comprehensively recovering various valuable metals in copper slag floating copper tailings is characterized by optimally designing the components and the proportion of the composite additive, specifically, by adopting CaO and Na2CO3When reducing, can be achieved inThe phase composition in the copper slag is improved at medium and low temperature, iron oxide combined in the fayalite phase is dissociated, a new mineral phase is generated, the resource reconstruction of the mineral phase of the copper slag is realized, and the recovery difficulty of the copper slag is reduced.
(5) According to the method for comprehensively recovering multiple valuable metals in copper slag and copper flotation tailings, the roasted product is subjected to magnetic separation assisted by a mineral separation technology and reverse flotation to obtain iron ore concentrate, impurities in the iron ore concentrate are further removed, the grade of the iron ore concentrate is improved, and the iron ore concentrate with qualified quality and high metal iron content is sorted out. The reverse flotation process is optimized, specifically, the collecting agent adopts dodecylamine, the foaming agent adopts No. 2 oil, the pH regulator adopts lime, the inhibitor adopts causticized starch, and the addition amount of each reagent is designed, so that iron ore concentrate obtained after reverse flotation can be directly used as a blast furnace raw material, tailings obtained by mineral separation can be used as a raw material for preparing building materials such as cement, and the copper slag can be utilized most effectively, and the requirements of secondary resource utilization and economic development in China can be met.
Drawings
FIG. 1 is a schematic flow chart of a method for comprehensively recovering a plurality of valuable metals in copper slag floating copper tailings according to the invention;
FIG. 2 is a schematic diagram of the flow of the mixed gas during the direct reduction process of the present invention.
Detailed Description
The invention relates to a method for comprehensively recovering various valuable metals in copper slag floating copper tailings, which comprises the following steps:
step one, direct reduction
After some copper slag and copper floating tailings are dried at the temperature of 100 ℃, the copper floating tailings and a compound additive of calcium oxide and sodium carbonate are uniformly mixed and then are put into a tube furnace, the temperature is slowly raised under the protection of inert gas (argon gas), the mixed gas is continuously introduced for reduction roasting when the isothermal period is reached, magnetite in the copper slag is completely converted into elemental iron, harmful impurities such as zinc, lead and the like in slag removal are removed, and zinc and lead are recycled and used as raw materials for lead and zinc smelting. In the step, CaO and Na are adopted as the composite additive2CO3Mixture ofThe addition amount of the additive is 10-25% of the total amount of the copper dross and the composite additive, and the additive is CaO and Na2CO31.5 to 3. When the temperature is increased, the temperature is increased from room temperature to 400 ℃ at the speed of 7-10 ℃/min, and then is increased to the reduction temperature at the speed of 3-5 ℃/min. The introduced mixed gas is mixed gas of methane, hydrogen and argon, the total flow rate of the gas is 700-900 mL/min, wherein the volume fraction of the argon is 50%, the volume fraction of the used methane is 5-15%, and the volume fraction of the hydrogen is 35-45%. And during reduction roasting, the temperature is 700-900 ℃, and the roasting time is 90-120 min.
On the one hand, because the copper slag contains a large amount of iron, copper, and precious metals and rare metals such as gold, silver, cobalt, nickel and the like, the copper slag has extremely complicated compositions, mostly fayalite and hercynite, and secondly magnetite, copper sulfide and metallic copper, and is accompanied with highly toxic elements such as arsenic, lead and the like, so that the copper slag is difficult to effectively utilize, the comprehensive recovery difficulty is high, and the cost is high. Therefore, currently, most of the methods are more deeply researched for recovering the single valuable metal of the copper slag, and the research on the comprehensive utilization of the multiple metals of the copper slag is less. However, the loss of valuable metal elements such as iron, zinc, lead and the like with a large content in the copper slag causes great resource waste, and the copper slag cannot achieve the purpose of effective resource utilization. On the other hand, particularly valuable elements left after copper slag copper flotation tailings are recovered, the copper flotation tailings are finer in granularity due to the recovery of copper in the copper slag, the phase structure group becomes more complex, and the difficulty of comprehensive recovery is further increased, so that research effort must be increased in the aspect of comprehensive recovery of the copper slag copper flotation tailings, valuable components in the copper slag are recovered as far as possible, and a good and complete recycling process is formed.
According to the invention, the mixed gas of methane, hydrogen and argon is introduced into the copper floating tailings of the copper slag to carry out direct reduction to remove harmful impurities such as zinc, lead and the like, and the harmful impurities are recovered. And (3) extracting iron by magnetic separation and reverse flotation, wherein iron, lead and zinc in the copper slag are comprehensively recovered by different processes according to different properties of various valuable metal elements in the copper slag, so that the purpose of comprehensively recovering various valuable metal elements in the copper slag is achieved, and the copper slag can be effectively recycled. The invention provides a new method for treating copper slag at a low temperature and recovering the high zinc content in the iron ore concentrate, and provides a new choice for the process flow of comprehensively recovering various valuable metals from the copper slag.
In particular, the direct reduction of copper smelting slag in the molten state usually results in a residual copper content of more than 0.5 wt.%, and the zinc and lead oxides remaining in the reduced slag are more than 1 wt.%, while some harmful trace elements, such as antimony, arsenic and bismuth, are not reduced to harmless concentrations. In the reduction roasting process, the selected gaseous methane is a reducing agent which is stronger than pure gaseous hydrogen or solid carbon. In methane cracking reactions, the chemical activity of the locally formed carbon exceeds that of the stabilization reaction due to the slow decomposition kinetics of methane at high temperatures: CH (CH)4(g)＝C(s)+2H2(g) In that respect Therefore, the content of valuable metal elements in the copper slag can be well reduced, so that elements such as iron, lead, zinc and the like can be effectively recycled, harmful elements such as antimony, arsenic, bismuth and the like can be reduced to harmless concentration, and the environment-friendly policy is maintained. In addition, the inventor carries out optimization design on the substance type and the mixture ratio of the composite additive, the composition and the content of the mixed gas, the reduction roasting temperature and the reduction roasting time length through experimental study, thereby further ensuring the effect of direct reduction treatment. Meanwhile, the selected methane gas can avoid excessive deposition of soot in the reduction process, and can effectively recover metal elements such as zinc, lead and the like. Since the reduction of the oxides by methane is carried out at high temperatures by decomposition of the oxides and on the metal surface, the main chemical reaction equation as in the reaction is: MeOx+CH4(g)＝(1-x)C(s)+xCO(g)+2H2(g) + Me, but at low temperatures several hundred degrees above the decomposition temperature of pure 1atm methane, the decomposition is kinetically slow, with little or possibly no soot formation, such as: MeOx+xCH4(g)＝xCO(g)+2xH2(g)+Me。
It should also be noted that the reduction treatment environment of the invention is much lower than the temperature of other existing treatment methods, thereby greatly reducing the cost of copper slag recovery, effectively solving the problem of high energy consumption of copper slag recovery, and having higher economic benefit. The mixed gas of methane, hydrogen and argon is introduced to ensure that magnetite in the copper slag can be completely reduced into metallic iron at medium and low temperature, and the impurities such as zinc, lead and other oxides in the copper slag are further decomposed and reduced aiming at different driving forces of reduction reactions of various impurities and oxides at low temperature, and then the impurities and other oxides are evaporated from the slag in the form of metal vapor to enter flue gas for recycling.
In addition, the invention adds CaO and Na as composite additives2CO3And the mixture ratio is optimized, so that the phase composition in the copper slag can be improved as far as possible under the condition of medium and low temperature, the iron oxide combined in the fayalite phase is dissociated, a new mineral phase is generated, and the mineral phase resource reconstruction of the copper slag is realized. The addition of CaO in the reduction process can effectively reduce Fe2SiO4Thereby improving the reduction capability and improving Fe2SiO4The reducing property of (2). The silicate formed by combining the sodium carbonate as an alkaline oxide and the silicon dioxide can destroy the fayalite structure of the copper slag and improve the activity of FeO, thereby accelerating the reduction of the iron oxide and promoting the decomposition of the fayalite:
Fe2SiO4(s)+2C(s)＝2Fe(s)+2CO(g)+SiO2(s)
Fe2SiO4(s)+2CaO(s)+2C(s)＝2Fe(s)+Ca2SiO4(s)+2CO(g)
Na2CO3(s)+SiO2(s)＝Na2SiO3(s)+CO2(g)
moreover, reactions also occur at high temperatures:
2FeO(s)+SiO2(s)＝2FeO·SiO2(s)
while adding Na2CO3Na formed at high temperature2SiO3Ratio FeO SiO2More stable, can prevent iron oxide from regenerating into iron silicate as far as possibleThe recovery rate of iron in the copper slag is improved.
According to the process flow, mixed gas of methane, hydrogen and argon is introduced at medium and low temperature for direct reduction for a long time, on one hand, valuable metal elements such as zinc, lead and the like with low boiling points in copper slag copper flotation tailings are effectively recycled, so that magnetite in the copper slag copper flotation tailings is completely converted into metallic iron, and the concentration of harmful elements such as antimony, arsenic, bismuth and the like in the copper slag copper flotation tailings can be effectively reduced, and a part of impurities are removed; on the other hand, the added composite additive is matched to modify and reduce the copper slag, so that fayalite in the copper slag is decomposed and converted into a new iron phase as far as possible, the recovery rate of iron is improved, and the aim of comprehensively utilizing the copper slag in a multi-metal resource mode is fulfilled.
Step two, wet magnetic separation
Carrying out magnetic separation on the copper flotation tailings subjected to reduction roasting treatment by using a wet-type low-intensity magnetic separator, controlling the magnetic separation strength to be 1200-1800 Gs, obtaining iron ore concentrate, filtering and drying;
step three, reverse flotation
And (2) carrying out reverse flotation experiments on the magnetic concentrate by taking dodecylamine as a collecting agent, oil No. 2 as a foaming agent and lime as a pH regulator, wherein the addition amount of the dodecylamine is 500-900 g/t, the addition amount of the oil No. 2 is 20-30 g/t, the addition amount of the lime is 1000-1300 g/t, and the addition amount of starch inhibition is 800-1200 g/t.
According to the invention, iron is extracted by magnetic separation-reverse flotation, different auxiliary reagents are adopted according to different properties of various valuable metal elements in the copper slag, and the addition amount of each reagent is optimally designed, so that iron, lead and zinc in the copper slag can be comprehensively recovered, the purpose of comprehensively recovering various valuable metal elements in the copper slag is achieved, and the copper slag can be effectively recycled.
For a further understanding of the invention, reference will now be made in detail to specific embodiments of the invention.
Example 1
As shown in fig. 1 and 2, the method for comprehensively recovering a plurality of valuable metals in copper dross and copper tailings in the embodiment comprises the following steps:
step one, direct reduction
Adding composite additive (CaO: Na) of calcium oxide and sodium carbonate2CO32) mixing the copper slag with the mixture accounting for 10 percent, putting the mixture into a tubular furnace, introducing a gas mixture of methane, hydrogen and argon for reduction roasting, wherein the roasting temperature is 700 ℃, the roasting time is 120min, the constant volume fraction of dry argon of the mixed gas is 50 percent, the concentrations of the used methane and hydrogen are selected to be 5vol percent and 45vol percent, the total flow rate of introducing the mixed gas into the tubular furnace is 800mL/min, removing harmful impurities such as zinc, lead and the like in slag, and recovering zinc and lead, wherein the grade of lead and zinc in the obtained smoke dust is more than 30 percent, and the smoke dust can be used as a raw material for lead and zinc smelting;
step two, wet magnetic separation
Carrying out magnetic separation on the copper flotation tailings subjected to reduction roasting treatment by using a wet low-intensity magnetic separator, wherein the magnetic separation strength is 1200Gs, obtaining iron ore concentrate, and filtering and drying the iron ore concentrate;
step three, reverse flotation
And performing a reverse flotation experiment on the magnetic concentrate by taking dodecylamine as a collecting agent, No. 2 oil as a foaming agent and lime as a pH regulator, wherein the addition amount of the dodecylamine is 500g/t, the addition amount of the No. 2 oil is 20g/t, the addition amount of the lime is 1000g/t, and the addition amount of the starch inhibitor is 800 g/t. During flotation, the ore pulp is stirred for three minutes, then a pH regulator is added to adjust the pH value of the ore pulp, an inhibitor is added after three minutes, a collector is added after five minutes, a foaming agent is added after three minutes, air blowing and foam scraping are carried out after three minutes, flotation is carried out for three minutes, and further separation and impurity removal are carried out, so that an iron concentrate product with the iron grade of 62.38% and the recovery rate of 71.54% is obtained.
Example 2
As shown in fig. 1 and 2, the method for comprehensively recovering a plurality of valuable metals in copper dross and copper tailings in the embodiment comprises the following steps:
step one, direct reduction
Adding composite additive (CaO: Na) of calcium oxide and sodium carbonate2CO31.5) mixing the copper slag with 15 percent of the mixture uniformly, putting the mixture into a tubular furnace, introducing a gas mixture of methane, hydrogen and argon for reduction roasting, wherein the roasting temperature is 800 ℃, the roasting time is 100min, the constant volume fraction of dry argon of the mixed gas is 50 percent, the concentration of the used methane and hydrogen is selected to be 10vol percent and 40vol percent, the total flow rate of the mixed gas introduced into the tubular furnace is 800mL/min, removing harmful impurities such as zinc, lead and the like in slag, recovering zinc and lead, and obtaining smoke with lead-zinc grade of more than 30 percent which can be used as a raw material for lead-zinc smelting;
step two, wet magnetic separation
Carrying out magnetic separation on the copper flotation tailings subjected to reduction roasting treatment by using a wet low-intensity magnetic separator, wherein the magnetic separation strength is 1400Gs, so as to obtain iron ore concentrate, and filtering and drying the iron ore concentrate;
step three, reverse flotation
And performing a reverse flotation experiment on the magnetic concentrate by using lauryl amine as a collecting agent, No. 2 oil as a foaming agent and lime as a pH adjusting agent, wherein the addition amount of lauryl amine is 600g/t, the addition amount of No. 2 oil is 20g/t, the addition amount of lime is 1100g/t, and the addition amount of starch inhibition is 900 g/t. During flotation, the ore pulp is stirred for three minutes, then a pH regulator is added to adjust the pH value of the ore pulp, an inhibitor is added after three minutes, a collector is added after five minutes, a foaming agent is added after three minutes, air blowing and foam scraping are carried out after three minutes, flotation is carried out for three minutes, and then separation and impurity removal are further carried out, so that an iron concentrate product with the iron grade of 63.69% and the recovery rate of 71.83% is obtained.
Example 3
As shown in fig. 1 and 2, the method for comprehensively recovering multiple valuable metals in copper slag floating copper tailings of the embodiment comprises the following steps:
step one, direct reduction
Adding composite additive (CaO: Na) of calcium oxide and sodium carbonate2CO32) the mixture accounting for 15 percent of the total weight is uniformly mixed with copper slag and then put into a tube furnace, and a gas mixture of methane, hydrogen and argon is introduced for reduction roasting at the roasting temperature of 900 ℃ for 90min, wherein the dry argon of the mixed gas has a constant volumeThe percentage is 50%, the concentration of the used methane and hydrogen is selected to be 15 vol% and 35 vol%, the total flow rate of the mixed gas introduced into the tubular furnace is 700mL/min, harmful impurities such as zinc, lead and the like in slag are removed, zinc and lead are recovered, the grade of the obtained smoke dust lead and zinc is more than 30%, and the smoke dust lead and zinc can be used as a raw material for lead and zinc smelting;
step two, wet magnetic separation
Carrying out magnetic separation on the copper flotation tailings subjected to reduction roasting treatment by using a wet-type low-intensity magnetic separator, wherein the magnetic separation strength is 1600Gs, obtaining iron ore concentrate, and filtering and drying the iron ore concentrate;
step three, reverse flotation
And performing a reverse flotation experiment on the magnetic concentrate by using dodecylamine as a collecting agent, No. 2 oil as a foaming agent and lime as a pH adjusting agent, wherein the addition amount of the dodecylamine is 700g/t, the addition amount of the No. 2 oil is 20g/t, the addition amount of the lime is 1200g/t, and the addition amount of the starch inhibitor is 1000 g/t. During flotation, stirring for three minutes, adding a pH regulator to adjust the pH value of the ore pulp, adding an inhibitor after three minutes, adding a collecting agent after five minutes, adding a foaming agent after three minutes, blowing, scraping and foaming after three minutes, carrying out flotation for three minutes, and further separating and removing impurities to obtain an iron concentrate product with an iron grade of 64.75% and a recovery rate of 73.62%.
Example 4
As shown in fig. 1 and 2, the method for comprehensively recovering a plurality of valuable metals in copper dross and copper tailings in the embodiment comprises the following steps:
step one, direct reduction
Adding composite additive (CaO: Na) of calcium oxide and sodium carbonate2CO33) mixing the copper slag with 20 percent of the mixture uniformly, putting the mixture into a tubular furnace, introducing a gas mixture of methane, hydrogen and argon for reduction roasting, roasting at 900 ℃ for 90min, wherein the constant volume fraction of dry argon of the mixed gas is 50 percent, the concentrations of the used methane and hydrogen are selected to be 15vol percent and 35vol percent, the total flow rate of the mixed gas introduced into the tubular furnace is 900mL/min, so as to remove harmful impurities such as zinc, lead and the like in slag, recover zinc and lead, and obtain smoke dust with the lead-zinc grade of more than 30 percent, which can be used as a raw material for lead-zinc smelting;
step two, wet magnetic separation
Carrying out magnetic separation on the copper flotation tailings subjected to reduction roasting treatment by using a wet-type low-intensity magnetic separator, wherein the magnetic separation strength is 1800Gs, obtaining iron ore concentrate, and filtering and drying the iron ore concentrate;
step three, reverse flotation
And performing a reverse flotation experiment on the magnetic concentrate by using dodecylamine as a collecting agent, No. 2 oil as a foaming agent and lime as a pH adjusting agent, wherein the addition amount of the dodecylamine is 800g/t, the addition amount of the No. 2 oil is 25g/t, the addition amount of the lime is 1200g/t, and the addition amount of the starch inhibitor is 1200 g/t. During flotation, stirring for three minutes, adding a pH regulator to adjust the pH value of the ore pulp, adding an inhibitor after three minutes, adding a collecting agent after five minutes, adding a foaming agent after three minutes, blowing, scraping and foaming after three minutes, carrying out flotation for three minutes, and further separating and removing impurities to obtain an iron concentrate product with the iron grade of 66.71% and the recovery rate of 75.37%.
Example 5
As shown in fig. 1 and 2, the method for comprehensively recovering a plurality of valuable metals in copper dross and copper tailings in the embodiment comprises the following steps:
step one, direct reduction
Adding composite additive (CaO: Na) of calcium oxide and sodium carbonate2CO32) uniformly mixing 25% of mixture with copper slag, putting the mixture into a tubular furnace, introducing a gas mixture of methane, hydrogen and argon for reduction roasting, wherein the roasting temperature is 750 ℃, the roasting time is 110min, the constant volume fraction of dry argon of the mixed gas is 50%, the concentration of the used methane and hydrogen is selected to be 15 vol% and 35 vol%, the total flow rate of the mixed gas introduced into the tubular furnace is 800mL/min, so as to remove harmful impurities such as zinc, lead and the like in slag, recover zinc and lead, and obtain smoke dust with the lead-zinc grade of more than 30%, wherein the smoke dust can be used as a raw material for lead-zinc smelting;
step two, wet magnetic separation
Carrying out magnetic separation on the copper flotation tailings subjected to reduction roasting treatment by using a wet low-intensity magnetic separator, wherein the magnetic separation strength is 1500Gs, obtaining iron ore concentrate, and filtering and drying the iron ore concentrate;
step three, reverse flotation
And performing a reverse flotation experiment on the magnetic concentrate by using dodecylamine as a collecting agent, No. 2 oil as a foaming agent and lime as a pH adjusting agent, wherein the addition amount of the dodecylamine is 900g/t, the addition amount of the No. 2 oil is 30g/t, the addition amount of the lime is 1300g/t, and the addition amount of the starch inhibitor is 900 g/t. During flotation, the ore pulp is stirred for three minutes, then a pH regulator is added to adjust the pH value of the ore pulp, an inhibitor is added after three minutes, a collector is added after five minutes, a foaming agent is added after three minutes, air blowing and foam scraping are carried out after three minutes, flotation is carried out within three minutes, and then separation and impurity removal are further carried out, so that an iron concentrate product with the iron grade of 65.75% and the recovery rate of 73.92% is obtained.
Comparative example 1
The method for comprehensively recovering various valuable metals from the copper slag in the comparative example comprises the following steps:
step one, direct reduction
Carbon powder 20%, calcium oxide and sodium carbonate composite additive (CaO: Na)2CO32) uniformly mixing the copper slag and the proportion accounting for 20 percent of the total weight of the copper slag, and putting the mixture into a muffle furnace for reduction roasting at the roasting temperature of 900 ℃ for 90 min;
step two, wet magnetic separation
Carrying out magnetic separation on the copper flotation tailings subjected to reduction roasting treatment by using a wet-type low-intensity magnetic separator, wherein the magnetic separation strength is 1800Gs, obtaining iron ore concentrate, and filtering and drying the iron ore concentrate;
step three, reverse flotation
And (2) carrying out reverse flotation experiments on the magnetic concentrate by using dodecylamine as a collecting agent, No. 2 oil as a foaming agent and lime as a pH adjusting agent, wherein the addition amount of the dodecylamine is 800g/t, the addition amount of the No. 2 oil is 20g/t, the addition amount of the lime is 1200g/t, the addition amount of starch is 1200g/t, and further carrying out separation and impurity removal to obtain an iron concentrate product with the iron grade of 57.87% and the recovery rate of 63.19%.

Claims (5)

1. A method for comprehensively recovering various valuable metals in copper slag floating copper tailings is characterized by comprising the following steps:
step one, direct reduction
Mixing the copper tailing with the composite additive of calcium oxide and sodium carbonateAfter mixing evenly, introducing a mixed gas of methane, hydrogen and argon for reduction roasting; wherein the addition amount of the composite additive is 10-25% of the total amount of the copper flotation tailings and the composite additive, and CaO in the composite additive is Na2CO31.5-3; the total flow rate of the introduced mixed gas is 700-900 mL/min, wherein the volume fraction of argon is 50%, the volume fraction of used methane is 5-15%, and the volume fraction of hydrogen is 35-45%;
drying the copper flotation tailings, adding a composite additive, uniformly mixing, heating to a reduction temperature under the protection of inert gas, and introducing mixed gas for reduction roasting, wherein the reduction roasting temperature is controlled to be 700-900 ℃, and the roasting time is 90-120 min;
step two, wet magnetic separation
Carrying out magnetic separation on the copper flotation tailings after the reduction roasting treatment to obtain iron ore concentrate, and filtering and drying the iron ore concentrate;
step three, reverse flotation
And adding a collecting agent, a foaming agent, a pH regulator and an inhibitor to perform a reverse flotation experiment on the magnetic concentrate, and further separating and removing impurities to obtain an iron concentrate product with qualified quality.
2. The method for comprehensively recovering multiple valuable metals in copper slag and copper tailings according to claim 1, which is characterized by comprising the following steps: in the first step, under the protection of inert gas, the temperature is increased from room temperature to 400 ℃ at the speed of 7-10 ℃/min, and then the temperature is increased to the reduction temperature at the speed of 3-5 ℃/min.
3. The method for comprehensively recovering multiple valuable metals in copper dross and copper tailings according to any one of claims 1-2, wherein the method comprises the following steps: in the second step, the magnetic separation strength is controlled to be 1200-1800 Gs.
4. The method for comprehensively recovering multiple valuable metals in copper slag and copper tailings according to claim 3, which is characterized by comprising the following steps: in the third step, the collecting agent adopts dodecylamine, and the using amount of the dodecylamine is 500-900 g/t; the foaming agent is No. 2 oil, and the dosage of the foaming agent is 20-30 g/t; lime is adopted as the pH regulator, and the dosage of the lime is 1000-1300 g/t; the inhibitor is causticized starch, and the dosage of the inhibitor is 800-1200 g/t.
5. The method for comprehensively recovering multiple valuable metals in copper slag and copper tailings according to claim 4, which is characterized by comprising the following steps: and in the third step, stirring for three minutes, adding the pH regulator, adding the inhibitor after three minutes, adding the collecting agent after five minutes, adding the foaming agent after three minutes, blowing, scraping and foaming after three minutes, and performing flotation for three minutes to obtain the iron concentrate product.
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