Flotation reagent and method for recovering copper component in copper slag

Abstract

The invention relates to the technical field of flotation, in particular to a flotation reagent and method for recycling copper components in copper slag. The invention provides a flotation reagent for recycling copper components in copper slag. The flotation reagent comprises a composite activating agent and a composite collecting agent. The composite activating agent is prepared from 2, 5-dimercaptothiadiazole and a modifier I; the first modifier is selected from at least one of copper sulfate, copper chloride, copper nitrate, lead nitrate and lead chloride; the composite collecting agent is composed of xanthate and a second modifier. The modifier II is selected from at least one of black powder, thionocarbamate compounds, fatty acid compounds and hydroximic acid. According to the invention, the composite activator highly matched with the copper oxide component in the copper slag is constructed, so that the active sites on the surface of the copper oxide are fully exposed and directionally strengthened; and meanwhile, a composite collecting agent with ultrahigh selectivity on the copper component is introduced, so that copper oxide and copper sulfide are efficiently and synchronously collected in the same process, and deep enrichment and comprehensive recovery of the copper component in the copper slag are achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of flotation technology, in particular to a flotation reagent and method for recovering copper components in copper slag. BACKGROUND

[0002] As an important strategic metal resource, copper has an irreplaceable position in the fields of energy and power, national defense and military industry, and mechanical manufacturing due to its excellent electrical and thermal conductivity. At present, more than 80% of global copper production is produced through pyrometallurgical process, however, a large amount of copper slag is inevitably produced in the process of copper smelting by fire. According to statistics, about 2-3 tons of copper slag will be produced for every ton of copper. In 2023, the global copper production reached 22 million tons, resulting in more than 45 million tons of copper slag. It is worth noting that previous studies have shown that in addition to the huge annual production, a large amount of copper slag has not been resourceized and is stored in slag yards. According to reports, the global copper slag stockpile has exceeded 300 million tons.

[0003] The main components of copper slag are fayalite and magnetite, and it also contains valuable metal elements such as Cu, Co, Ag, and Zn, and toxic and harmful elements such as Pb and As. Among them, the copper content is generally 0.5%-2%. Therefore, the large-scale storage of copper slag brings double problems: the infiltration of toxic elements into the environment will cause serious ecological harm, and the unutilized copper content means a huge waste of resources. Efficient recovery of copper elements in slag can not only solve the environmental problem, but also alleviate the current shortage of copper resources, providing an effective way for secondary recovery of metal resources.

[0004] Copper in copper slag mainly exists in the form of copper sulfide, with a small amount of copper oxide. Copper sulfide has strong floatability and can be recovered by using only a collector, while the recovery of copper oxide is significantly increased due to its high density and strong hydrophilicity. It is worth noting that studies have shown that as the storage time of copper slag increases, the copper sulfide component gradually oxidizes to copper oxide, which increases the oxidation rate of a large amount of long-term stored copper slag and reduces the flotation recovery efficiency. At present, the efficient copper recovery method for high oxidation rate and long-term storage of copper slag still needs to be developed. Therefore, improving the recovery efficiency of copper oxide phase in copper slag is of great significance for the resource disposal of long-term storage of difficult-to-handle copper slag.

[0005] The copper furnace slag has fine dissemination size, and therefore, the crushing fineness is usually required to be high in the copper furnace slag flotation process. In order to avoid the agglomeration of the fine particles and the slimes, the water glass is usually added as a dispersant in the copper furnace slag flotation process. The copper in the copper furnace slag mainly exists in the form of copper sulfide minerals such as chalcopyrite, bornite and chalcocite. Therefore, the collector used in the copper furnace slag flotation is similar to the collector used in the flotation of copper sulfide minerals. At present, the types of the collector used in the copper furnace slag flotation are few. The common copper furnace slag flotation collectors can be roughly divided into three categories: xanthate collectors such as butyl xanthate and amyl xanthate; black drug collectors such as butyl amine black drug; and lipid collectors such as Z200.

[0006] The recovery of the oxidized copper component in the copper furnace slag mainly adopts the sulfidation flotation technology, that is, the artificial sulfidation film is formed on the surface of the oxidized copper by the sulfidation agent to enhance the hydrophobicity, so as to improve the flotation recovery rate. However, in industrial applications, the sulfidation flotation effect is often not ideal, resulting in low recovery efficiency. Usually, the copper grade of the tailings of the copper furnace slag flotation is still more than 0.2%, and part of the copper resources in the slag is lost in the tailings, causing the waste of copper resources. In addition, the types of the flotation reagents for the oxidized copper component in the copper furnace slag are few, and all of them have the defects such as poor activation effect or high price. SUMMARY

[0007] In view of the defects in the prior art, the present application provides a flotation reagent and method for recovering copper components in copper furnace slag. The present application realizes the full exposure and directional strengthening of the active sites on the surface of the oxidized copper by constructing a composite activator highly adapted to the oxidized copper component in the copper furnace slag. At the same time, the composite collector with ultra-high selectivity to the copper component is introduced, so that the oxidized copper and the copper sulfide are efficiently and synchronously collected in the same process, and the deep enrichment and comprehensive recovery of the copper components in the copper furnace slag are realized by the combined action of the two.

[0008] In order to achieve the above purpose, the technical scheme adopted by the present application is: The first object of the present application is to provide a flotation reagent for recovering copper components in copper furnace slag, comprising a composite activator and a composite collector; the composite activator is composed of 2,5-dimercaptothiadiazole and a first modifier, the mass ratio of 2,5-dimercaptothiadiazole to the first modifier is 1:0.2-5; the first modifier is selected from at least one of copper sulfate, copper chloride, copper nitrate, lead nitrate and lead chloride; the composite collector is composed of xanthate and a second modifier, the mass ratio of xanthate to the second modifier is 1:1-10; the second modifier is selected from at least one of black drug, sulfonamide compounds, fatty acid compounds and hydroxamic acid. In the composite activator, when the first modifier is lower than the mass ratio, effective modification effect cannot be formed, and when the first modifier is higher than the mass ratio, the composite collector is consumed due to the reaction between the first modifier and the composite collector, thereby reducing the flotation index; in the composite collector, when the amount of the second modifier is lower than the mass ratio, the modification effect is not obvious, and when the amount of the second modifier is too high, the grade of the flotation concentrate is reduced.

[0009] When the copper components in the copper furnace slag are recovered, rapid flotation, roughing, scavenging and cleaning are sequentially performed; in the rapid flotation, the amount of the composite collector is 50g / t-200g / t based on the mass of the copper furnace slag; in the roughing, the amount of the composite activator is 20g / t-250g / t and the amount of the composite collector is 50g / t-200g / t based on the mass of the copper furnace slag; in the scavenging, the amount of the composite activator is 10g / t-125g / t and the amount of the composite collector is 25g / t-100g / t based on the mass of the copper furnace slag.

[0010] Preferably, in the composite activator, the mass ratio of 2,5-dimercaptothiadiazole to the first modifier is 1:0.2-2.

[0011] Preferably, the mass ratio of xanthate to the second modifier is 1:1-5.

[0012] Preferably, the flotation reagent for recovering copper components in copper furnace slag further comprises a frother, and the frother is selected from pinol oil or methyl isobutyl carbinol.

[0013] Preferably, in the rapid flotation, the amount of the composite collector is 50g / t-150g / t based on the mass of the copper furnace slag; in the roughing, the amount of the composite activator is 50g / t-200g / t and the amount of the composite collector is 50g / t-150g / t based on the mass of the copper furnace slag; in the scavenging, the amount of the composite activator is 10g / t-100g / t and the amount of the composite collector is 50g / t-80g / t based on the mass of the copper furnace slag.

[0014] Preferably, in the cleaning, the amount of the composite activator is 0g / t-5g / t and the amount of the composite collector is 0g / t-20g / t based on the mass of the copper furnace slag.

[0015] Preferably, in order to fully dissociate the copper components from other gangue components in the copper furnace slag, the mass percentage of the copper furnace slag with a particle size of ≤0.045 mm in the copper furnace slag is ≥75%.

[0016] A second object of the present application is to provide a flotation method for copper components in copper furnace slag, which recovers copper oxide by using the flotation reagent for recovering copper components in copper furnace slag described above, and comprises the following steps: S1, grinding the copper furnace slag to obtain ore materials; mixing the ore materials with water to obtain an ore slurry.

[0017] S2, rapid flotation treatment: adjusting the pH of the ore slurry to 8-10 to ensure the activity of the collector and the activator in the ore slurry environment, then adding a composite collector and a foaming agent, and then performing a scraping bubble treatment to obtain a copper concentrate and a flotation tailing.

[0018] S3, roughing: adding a composite activator, a composite collector and a foaming agent to the flotation tailing, and performing a scraping bubble treatment to obtain a roughing concentrate and a roughing tailing.

[0019] S4, scavenging: adding a composite activator, a composite collector and a foaming agent to the roughing tailing, and performing a scraping bubble treatment to obtain a first scavenging concentrate and a first scavenging tailing, and the first scavenging concentrate is returned to the roughing step to form a closed loop.

[0020] S5, cleaning: adding a composite activator, a composite collector and a foaming agent to the first scavenging tailing, and performing a scraping bubble treatment to obtain a second scavenging concentrate and a second scavenging tailing; the second scavenging concentrate is returned to the first scavenging step to form a closed loop.

[0021] S6, performing a scraping bubble flotation on the roughing concentrate to obtain a first cleaning concentrate and a first cleaning middling, and the first cleaning middling is returned to the roughing step to form a closed loop.

[0022] S7, performing a scraping bubble flotation on the first cleaning concentrate without adding reagents to obtain a copper concentrate and a second cleaning middling, and the second cleaning middling is returned to the first cleaning step to form a closed loop to obtain the copper concentrate.

[0023] S8, the scavenging and cleaning form a closed loop.

[0024] Preferably, the foaming agent is selected from pinol oil or methyl isobutyl carbinol.

[0025] Preferably, in the rapid flotation, the amount of the foaming agent is 50g / t-200g / t based on the mass of the copper furnace slag; in the roughing, the amount of the foaming agent is 5g / t-20g / t; in the scavenging, the amount of the foaming agent is 1g / t-10g / t; and in the cleaning, the amount of the foaming agent is 0g / t-5g / t.

[0026] Preferably, the pH of the ore pulp is adjusted by using a pH regulator selected from at least one of hydrochloric acid, sulfuric acid, sodium hydroxide, sodium carbonate, calcium oxide, calcium hydroxide, and ammonia.

[0027] Preferably, the mass fraction of the copper slag in the ore pulp is 35% to 45%.

[0028] Compared with the prior art, the present application has the following advantages: 1. The present application provides a flotation reagent for recovering copper components in copper slag, which comprises a composite activator and a composite collector, the composite activator is composed of 2,5-dimercaptothiadiazole and a first modifier, the mass ratio of 2,5-dimercaptothiadiazole to the first modifier is 1:0.2-5; the composite collector is composed of sodium butyl xanthate and a second modifier, the mass ratio of sodium butyl xanthate to the second modifier is 1:1-10; the first modifier is selected from at least one of copper sulfate, copper chloride, copper nitrate, lead nitrate, and lead chloride; the second modifier is selected from at least one of xanthate, sulfonamide compounds, fatty acid compounds, and hydroxamic acid; when recovering copper components in copper slag, rapid flotation, roughing, scavenging, and cleaning are sequentially performed; in the rapid flotation, the dosage of the composite collector is 50g / t-200g / t based on the mass of the copper slag; in the roughing, the dosage of the composite activator is 20g / t-250g / t and the dosage of the composite collector is 50g / t-200g / t based on the mass of the copper slag; in the scavenging, the dosage of the composite activator is 10g / t-125g / t and the dosage of the composite collector is 25g / t-100g / t based on the mass of the copper slag.

[0029] Compared with the traditional xanthate method, the flotation method of the present application can obtain a flotation copper concentrate with higher grade and higher recovery rate. Since 2,5-dimercaptothiadiazole is relatively expensive, its use in flotation has a high cost, and the present application can form more active reaction sites on the surface of copper oxide in copper slag by adding a first modifier, so that 2,5-dimercaptothiadiazole is more likely to react with the surface of copper oxide, thereby reducing the dosage of 2,5-dimercaptothiadiazole in the flotation process, significantly reducing the cost of reagents, and enhancing the activation effect. In addition, sodium butyl xanthate has the problem of insufficient selectivity in the copper slag flotation process, and the present application enhances the selectivity of the collector in the copper slag flotation process by adding a second modifier to improve the grade of the concentrate.

[0030] 2, the invention also provides a kind of flotation reagent and method for recovering copper component in copper furnace slag, copper furnace slag is crushed, the particle size is less than or equal to 0.045mm and the proportion is greater than or equal to 75%, and copper furnace slag is obtained;Copper furnace slag and water are mixed to obtain ore pulp;The mass fraction of copper furnace slag in the ore pulp is 35% to 45%;Fast flotation treatment: first, the pH of the ore pulp is adjusted to 8 to 10 using a pH adjuster, then a composite collector and a foaming agent are added, and then a scraping bubble treatment is performed to obtain a copper concentrate and a flotation tailings;Coarse selection: composite activator, composite collector and foaming agent are added to the flotation tailings, and the scraping bubble treatment is performed to obtain a rough concentrate and a rough tailings;Scavenging: composite activator, composite collector and foaming agent are added to the rough tailings, and the scraping bubble treatment is performed to obtain a first scavenging concentrate and a first scavenging tailings, and the first scavenging concentrate is returned to the coarse selection to form a closed loop;Concentration: composite activator, composite collector and foaming agent are added to the first scavenging tailings, and the scraping bubble treatment is performed to obtain a second scavenging concentrate and a second scavenging tailings;The second scavenging concentrate is returned to the first scavenging step to form a closed loop;The rough concentrate is subjected to scraping bubble flotation to obtain a primary concentration concentrate and a primary concentration middlings, and the primary concentration middlings are returned to the coarse selection step to form a closed loop;The primary concentration concentrate is subjected to scraping bubble flotation without adding reagent to obtain a copper concentrate and a secondary concentration middlings, and the secondary concentration middlings are returned to the primary concentration step to form a closed loop, and the copper concentrate is obtained;Scavenging and concentration form a closed loop.

[0031] 3, compared with the traditional sulfidized xanthate method, the flotation method of the present application can obtain a flotation copper concentrate with higher grade and higher recovery rate. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The copper furnace slag flotation process flowchart of the embodiment of the present application. DETAILED DESCRIPTION

[0033] The technical solutions of the present application will be described in detail below in combination with the data in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0034] It should be noted that the professional terms used in the present application are only for the purpose of describing the specific embodiments, and are not intended to limit the protection scope of the present application. Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the following embodiments of the present application can be purchased from the market or prepared by the existing method. Among them, the grade of copper in the smelting slag of a certain smelting plant is 2.11%~3.77%, mainly exists in the form of copper sulfide ore, and contains part of copper oxide, which exists in glass body and is partly wrapped by gangue minerals. Sodium butyl xanthate is purchased from Shanghai Mailer Biochemical Technology Co., Ltd.; Butylamine black medicine is purchased from Liaoning Chihong Technology Co., Ltd.; Ethion is purchased from Shandong Xinchang Chemical Technology Co., Ltd.; 2,5-dimercaptothiadiazole is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Sodium sulfide is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Sodium hydroxide is purchased from Shanghai Yinn Chemical Technology Co., Ltd.; Sodium carbonate is purchased from Shanghai Yinn Chemical Technology Co., Ltd.; Calcium oxide is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0035] In the prior art, the recovery of copper oxide components in copper slag mainly adopts sulfidation flotation technology, that is, through the sulfidation agent to form an artificial sulfidation film on the surface of copper oxide to enhance the hydrophobicity, so as to improve the flotation recovery rate. However, in industrial applications, the effect of sulfidation flotation is often not ideal, resulting in low recovery efficiency, and the copper grade of copper slag flotation tailings is still more than 0.2%, part of the copper resources in the slag is lost in the tailings, causing waste of copper resources. Moreover, the research and development of flotation reagents for copper oxide components in copper slag is relatively less, and the types of flotation reagents for copper oxide components in copper slag are less, and there are also disadvantages such as poor activation effect or high price. The grade and recovery rate of the flotation copper concentrate obtained by the traditional sulfidation xanthate method are not ideal, and 2,5-dimercaptothiadiazole is expensive, and the cost of using it alone in flotation is high. At the same time, butyl xanthate shows the problem of insufficient selectivity in the copper slag flotation process, which affects the grade of the concentrate copper.

[0036] In view of the problems existing in the prior art, the present application provides a flotation reagent and method for recovering copper components in copper slag, which utilizes a high-matching composite activator for copper oxide components in copper slag, i.e. composed of 2,5-dimercaptothiadiazole and a first modifier, and a composite collector, i.e. composed of butyl xanthate and a second modifier, to deeply enrich and comprehensively recover the copper oxide components in copper slag, thereby overcoming the defects.

[0037] In order for those skilled in the art to more clearly understand the technical solutions of the present application, the following will be described in detail in combination with specific embodiments: Embodiment 1 A flotation reagent and method for recovering copper components in copper slag, comprising the following steps: S1, 700 g of copper slag with a copper grade of 2.11% is crushed to a particle size of less than 0.045 mm, accounting for 75%, to obtain copper slag; the copper slag is injected into a flotation machine and water is added to adjust the pulp concentration to 40%.

[0038] S2, NaOH solution is added to the pulp to adjust the pH value to 8, then 100 g / t of a composite collector compounded by butyl sodium xanthate and ethyl thiourea at a volume ratio of 1:1 and 20 g / t of pine oil are added, and the froth is scraped for 2 min to separate copper concentrate and flotation tailings.

[0039] S3, 100 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and copper sulfate at a mass ratio of 1:1, 100 g / t of a composite collector compounded by butyl sodium xanthate and ethyl thiourea at a volume ratio of 1:1 and 10 g / t of pine oil are added to the flotation tailings, and the froth is scraped for 5 min to separate the roughing concentrate and the roughing tailings.

[0040] S4, 50 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and copper sulfate at a mass ratio of 1:1, 50 g / t of a composite collector compounded by butyl sodium xanthate and ethyl thiourea at a volume ratio of 1:1 and 5 g / t of pine oil are added to the roughing tailings, and the froth is scraped for 4 min to separate the first scavenging tailings and the first scavenging concentrate; the first scavenging concentrate returns to the roughing operation in step S3 to form a closed loop.

[0041] S5, 25 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and copper sulfate at a mass ratio of 1:1, 25 g / t of a composite collector compounded by butyl sodium xanthate and ethyl thiourea at a volume ratio of 1:1 and 2.5 g / t of pine oil are added to the first scavenging tailings, and the froth is scraped for 3 min to separate the second scavenging tailings and the second scavenging concentrate; the second scavenging concentrate returns to the first scavenging in step S4 to form a closed loop.

[0042] S6, the roughing concentrate is floated without adding reagents, and the primary cleaning concentrate and the primary cleaning middlings are separated; the primary cleaning middlings return to the roughing operation in step S3 to form a closed loop.

[0043] S7, the primary cleaning concentrate is floated without adding reagents, and the final copper concentrate and the secondary cleaning middlings are separated; the secondary cleaning middlings return to the first cleaning in step S6 to form a closed loop; the final copper concentrate has a copper grade of about 23% and a copper recovery rate of about 93%.

[0044] Example 2 A flotation reagent and method for recovering copper components from copper slag, comprising the following steps: S1, 700 g of copper slag with a copper grade of 3.77% is crushed to a particle size of less than 0.045 mm, accounting for 75%, to obtain copper slag; the copper slag is injected into a flotation machine and water is added to adjust the pulp concentration to 40%.

[0045] S2, Na2CO3 is added to the pulp to adjust the pH value to 7, then 150 g / t of a composite collector compounded by butyl xanthate sodium and ethyl thiourea in a volume ratio of 1:1 and 20 g / t of pine oil are added, and the froth is scraped for 2 min to separate copper concentrate and flotation tailings.

[0046] S3, 120 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and lead nitrate in a mass ratio of 1:0.2, 150 g / t of a composite collector compounded by butyl xanthate sodium and butylamine black in a volume ratio of 1:2 and 10 g / t of pine oil are added to the flotation tailings, the froth is scraped for 5 min, and the roughing concentrate and roughing tailings are separated.

[0047] S4, 60 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and lead nitrate in a mass ratio of 1:0.2, 75 g / t of a composite collector compounded by butyl xanthate sodium and butylamine black in a volume ratio of 1:1 and 5 g / t of pine oil are added to the roughing tailings, the froth is scraped for 4 min, and the first scavenging tailings and the first scavenging concentrate are separated; the first scavenging concentrate returns to the roughing operation in step S3 to form a closed circuit.

[0048] S5, 30 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and lead nitrate in a mass ratio of 1:0.2, 37.5 g / t of a composite collector compounded by butyl xanthate sodium and butylamine black in a volume ratio of 1:1 and 2.5 g / t of pine oil are added to the first scavenging tailings, the froth is scraped for 3 min, and the second scavenging tailings and the second scavenging concentrate are obtained; the second scavenging concentrate returns to the first scavenging in step S4 to form a closed circuit.

[0049] S6, the roughing concentrate is floated without adding reagents, and the primary concentration concentrate and the primary concentration middlings are separated; the primary concentration middlings return to the roughing operation in step S3 to form a closed circuit.

[0050] S7, the primary concentration concentrate is floated without adding reagents, and the final copper concentrate and the secondary concentration middlings are separated; the secondary concentration middlings return to the first concentration in step S6 to form a closed circuit; the final copper concentrate has a copper grade of about 19% and a copper recovery rate of about 94%.

[0051] Example 3 A flotation reagent and method for recovering copper components from copper slag, comprising the following steps: S1, 700 g of copper slag with a copper grade of 2.81% is crushed to a particle size of less than 0.045 mm, accounting for 75%, to obtain copper slag; the copper slag is injected into a flotation machine and water is added to adjust the pulp concentration to 40%.

[0052] S2, CaO is added to the pulp to adjust the pH value to 8, then 120 g / t of a composite collector compounded by butyl sodium xanthate and ethion with a volume ratio of 1:0.5 and 20 g / t of pine oil are added, the froth is scraped for 2 min, and the copper concentrate and flotation tailings are separated.

[0053] S3, 90 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and copper chloride with a mass ratio of 1:0.5, 120 g / t of a composite collector compounded by butyl sodium xanthate and ethion with a volume ratio of 1:0.5 and 10 g / t of pine oil are added to the flotation tailings, the froth is scraped for 5 min, and the roughing concentrate and roughing tailings are separated.

[0054] S4, 45 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and copper chloride with a mass ratio of 1:0.5, 60 g / t of a composite collector compounded by butyl sodium xanthate and ethion with a volume ratio of 1:0.5 and 5 g / t of pine oil are added to the roughing tailings, the froth is scraped for 4 min, and the first scavenging tailings and the first scavenging concentrate are separated; the first scavenging concentrate returns to the roughing operation in step S3 to form a closed circuit.

[0055] S5, 22.5 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and copper chloride with a mass ratio of 1:0.5, 30 g / t of a composite collector compounded by butyl sodium xanthate and ethion with a volume ratio of 1:0.5 and 2.5 g / t of pine oil are added to the first scavenging tailings, the froth is scraped for 3 min, and the second scavenging tailings and the second scavenging concentrate are obtained; the second scavenging concentrate returns to the first scavenging in step S4 to form a closed circuit.

[0056] S6, the roughing concentrate is floated without adding reagents, and the primary concentration concentrate and the primary concentration middlings are separated; the primary concentration middlings return to the roughing operation in step S3 to form a closed circuit.

[0057] S7, the primary concentration concentrate is floated without adding reagents, and the final copper concentrate and the secondary concentration middlings are separated; the secondary concentration middlings return to the first concentration in step S6 to form a closed circuit; the final copper concentrate has a copper grade of about 22% and a copper recovery rate of about 95%.

[0058] Comparative Example 1 A flotation reagent and method for recovering copper components from copper slag, comprising the following steps: S1, 700g of copper slag with a copper grade of 2.11% is crushed to a particle size of less than 0.045mm, accounting for 75%, to obtain copper slag; the copper slag is injected into a flotation machine and adjusted with water to obtain a slurry, and the concentration of the slurry is 40%.

[0059] S2, NaOH solution is added to the slurry to adjust the pH value to 8, then 100g / t of sodium butyl xanthate and 20g / t of pine oil are added, and the foam is scraped for 2min to separate the copper concentrate and the flotation tailings.

[0060] S3, 100g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and copper sulfate at a mass ratio of 1:1, 100g / t of sodium butyl xanthate and 10g / t of pine oil are added to the flotation tailings, and the foam is scraped for 5min to separate the roughing concentrate and the roughing tailings.

[0061] S4, 50g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and copper sulfate at a mass ratio of 1:1, 50g / t of sodium butyl xanthate and 5g / t of pine oil are added to the roughing tailings, and the foam is scraped for 4min to separate the first scavenging tailings and the first scavenging concentrate; the first scavenging concentrate returns to the roughing operation in step S3 to form a closed loop.

[0062] S5, 25g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and copper sulfate at a mass ratio of 1:1, 25g / t of sodium butyl xanthate and 2.5g / t of pine oil are added to the first scavenging tailings, and the foam is scraped for 3min to separate the second scavenging tailings and the second scavenging concentrate; the second scavenging concentrate returns to the first scavenging in step S4 to form a closed loop.

[0063] S6, the roughing concentrate is floated without adding reagents, and the primary cleaning concentrate and the primary cleaning middlings are separated; the primary cleaning middlings return to the roughing operation in step S3 to form a closed loop.

[0064] S7, the primary cleaning concentrate is floated without adding reagents, and the final copper concentrate and the secondary cleaning middlings are separated; the secondary cleaning middlings return to the first cleaning in step S6 to form a closed loop; the final copper concentrate has a copper grade of about 18% and a copper recovery rate of about 90%.

[0065] Comparative Example 2 A flotation reagent and method for recovering copper components from copper slag, comprising the following steps: S1, 700g of copper slag with a copper grade of 2.11% is crushed to a particle size of less than 0.045mm, accounting for 75%, to obtain copper slag; the copper slag is injected into a flotation machine and adjusted with water to obtain a slurry, and the concentration of the slurry is 40%.

[0066] S2, NaOH solution is added to the ore pulp to adjust the pH value to 8, then 100 g / t of a composite collector compounded by butyl xanthate sodium and ethiofencat in a volume ratio of 1:1 and 20 g / t of pine oil are added, and the froth is scraped for 2 min, and the copper concentrate and flotation tailings are separated.

[0067] S3, 100 g / t of sodium sulfide, 100 g / t of a composite collector compounded by butyl xanthate sodium and ethiofencat in a volume ratio of 1:1 and 10 g / t of pine oil are added to the flotation tailings, and the froth is scraped for 5 min, and the roughing concentrate and roughing tailings are separated.

[0068] S4, 50 g / t of sodium sulfide, 50 g / t of a composite collector compounded by butyl xanthate sodium and ethiofencat in a volume ratio of 1:1 and 5 g / t of pine oil are added to the roughing tailings, and the froth is scraped for 4 min, and the first scavenging tailings and the first scavenging concentrate are separated; the first scavenging concentrate returns to the roughing operation in step S3 to form a closed circuit.

[0069] S5, 25 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and copper sulfate in a mass ratio of 1:1, 25 g / t of a composite collector compounded by butyl xanthate sodium and ethiofencat in a volume ratio of 1:1 and 2.5 g / t of pine oil are added to the first scavenging tailings, and the froth is scraped for 3 min, and the second scavenging tailings and the second scavenging concentrate are separated; the second scavenging concentrate returns to the first scavenging in step S4 to form a closed circuit.

[0070] S6, the roughing concentrate is floated without adding reagents, and the once-concentrate and the once-concentrate middlings are separated; the once-concentrate middlings return to the roughing operation in step S3 to form a closed circuit.

[0071] S7, the once-concentrate is floated without adding reagents, and the final copper concentrate and the twice-concentrate middlings are separated; the twice-concentrate middlings return to the first concentration in step S6 to form a closed circuit; the final copper concentrate has a copper grade of about 20% and a copper recovery rate of about 92%.

[0072] Comparative Example 3 A flotation reagent and method for recovering copper components in copper slag, comprising the following steps: S1, 700 g of copper slag with a copper grade of 3.77% is crushed to a fineness of less than 0.045 mm, and 75% of the particles are obtained, to obtain copper slag; the copper slag is injected into a flotation machine and water is added to adjust the concentration to obtain an ore pulp with a concentration of 40%.

[0073] S2, Na2CO3 is added to the ore pulp to adjust the pH value to 7, then 150 g / t of butyl xanthate sodium and 20 g / t of pine oil are added, and the froth is scraped for 2 min, and the copper concentrate and flotation tailings are separated.

[0074] S3, 120 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and lead nitrate at a mass ratio of 1:0.2, 150 g / t of sodium butyl xanthate and 10 g / t of pine oil were added into the flotation tailings, the froth was scraped for 5 min, and the roughing concentrate and the roughing tailings were separated.

[0075] S4, 60 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and lead nitrate at a mass ratio of 1:0.2, 75 g / t of sodium butyl xanthate and 5 g / t of pine oil were added into the roughing tailings, the froth was scraped for 4 min, and the first scavenging tailings and the first scavenging concentrate were separated; the first scavenging concentrate was returned to the roughing operation in step S3 to form a closed circuit.

[0076] S5, 30 g / t of a composite activator compounded by 2,5-dimercaptothiadiazole and lead nitrate at a mass ratio of 1:0.2, 37.5 g / t of sodium butyl xanthate and 2.5 g / t of pine oil were added into the first scavenging tailings, the froth was scraped for 3 min, and the second scavenging tailings and the second scavenging concentrate were separated; the second scavenging concentrate was returned to the first scavenging operation in step S4 to form a closed circuit.

[0077] S6, the roughing concentrate was subjected to scraping flotation without adding reagents, and the once-concentrating concentrate and the once-concentrating middlings were separated; the once-concentrating middlings were returned to the roughing operation in step S3 to form a closed circuit.

[0078] S7, the once-concentrating concentrate was subjected to scraping flotation without adding reagents, and the final copper concentrate and the twice-concentrating middlings were separated; the twice-concentrating middlings were returned to the first concentrating operation in step S6 to form a closed circuit; the final copper concentrate had a copper grade of about 14% and a copper recovery rate of about 86%.

[0079] Comparative Example 4 A flotation reagent and method for recovering copper components in copper slag, comprising the following steps: S1, 700 g of copper slag with a copper grade of 3.77% was crushed to a fineness of less than 0.045 mm, and 75% of the particles were obtained, to obtain copper slag; the copper slag was injected into a flotation machine and water was added to adjust the pulp to a concentration of 40%.

[0080] S2, Na2CO3 was added to the pulp to adjust the pH value to 7, then 150 g / t of a composite collector compounded by sodium butyl xanthate and butylamine black at a mass ratio of 2:1 and 20 g / t of pine oil were added, the froth was scraped for 2 min, and the copper concentrate and the flotation tailings were separated.

[0081] S3, 120 g / t of sodium sulfide, 150 g / t of a composite collector compounded by sodium butyl xanthate and butylamine black at a mass ratio of 2:1 and 10 g / t of pine oil were added into the flotation tailings, the froth was scraped for 5 min, and the roughing concentrate and the roughing tailings were separated.

[0082] S4, 45 g / t of the composite activator compounded by 2,5-dimercaptothiadiazole and copper chloride at a mass ratio of 1:0.5, 60 g / t of butyl xanthate sodium and 5 g / t of pine oil were added into the roughing tailings, and scraping and foaming for 4 min, to separate the first scavenging tailings and the first scavenging concentrate; the first scavenging concentrate returned to the roughing operation of step S3 to form a closed circuit.

[0083] S5, 30 g / t of sodium sulfide, 37.5 g / t of the composite collector compounded by butyl xanthate sodium and butylamine black medicine at a mass ratio of 2:1 and 2.5 g / t of pine oil were added into the first scavenging tailings, and scraping and foaming for 3 min, to separately obtain the second scavenging tailings and the second scavenging concentrate; the second scavenging concentrate returned to the first scavenging of step S4 to form a closed circuit.

[0084] S6, the roughing concentrate was subjected to scraping and foaming flotation without adding reagents, to separate the once-concentrating concentrate and the once-concentrating middlings; the once-concentrating middlings returned to the roughing operation of step S3 to form a closed circuit.

[0085] S7, the once-concentrating concentrate was subjected to scraping and foaming flotation without adding reagents, to separate the final copper concentrate and the twice-concentrating middlings; the twice-concentrating middlings returned to the first concentrating of step S6 to form a closed circuit; the final copper concentrate had a copper grade of about 13% and a copper recovery rate of about 88%.

[0086] Comparative Example 5 A flotation reagent and method for recovering copper components in copper slag, comprising the following steps: S1, 700 g of copper slag with a copper grade of 2.81% was crushed to a fineness of 75% of particles less than 0.045 mm to obtain the copper slag; the copper slag was injected into a flotation machine and water was added to adjust to obtain a slurry with a concentration of 40%.

[0087] S2, CaO was added to the slurry to adjust the pH value to 8, followed by adding 120 g / t of butyl xanthate sodium and 20 g / t of pine oil, and scraping and foaming for 2 min to separate the copper concentrate and the flotation tailings.

[0088] S3, 90 g / t of the composite activator compounded by 2,5-dimercaptothiadiazole and copper chloride at a mass ratio of 1:0.5, 120 g / t of butyl xanthate sodium and 10 g / t of pine oil were added into the flotation tailings, and scraping and foaming for 5 min to separate the roughing concentrate and the roughing tailings.

[0089] S4, 45 g / t of the composite activator compounded by 2,5-dimercaptothiadiazole and copper chloride at a mass ratio of 1:0.5, 60 g / t of butyl xanthate sodium and 5 g / t of pine oil were added into the roughing tailings, and scraping and foaming for 4 min to separate the first scavenging tailings and the first scavenging concentrate; the first scavenging concentrate returned to the roughing operation of step S3 to form a closed circuit.

[0090] S5, adding 22.5 g / t of a composite activator compounded from 2, 5-dimercaptothiadiazole and copper chloride at a mass ratio of 1:0.5, 30 g / t of sodium butyl xanthate, and 2.5 g / t of pine oil to the first-time scavenging tailings, scraping for 3 min, to obtain second-time scavenging tailings and second-time scavenging concentrate respectively; the second-time scavenging concentrate returns to the first-time scavenging in step S4 to form a closed circuit.

[0091] S6, scraping and floating the roughing concentrate without adding reagents to separate a first cleaning concentrate and a first cleaning middlings; the first cleaning middlings returns to the roughing in step S3 to form a closed circuit.

[0092] S7, scraping and floating the first cleaning concentrate without adding reagents to separate a final copper concentrate and a second cleaning middlings; the second cleaning middlings returns to the first cleaning in step S6 to form a closed circuit; the final copper concentrate has a copper grade of about 20% and a copper recovery rate of about 90%.

[0093] Comparative Example 6 A flotation reagent and method for recovering copper components from copper slag, comprising the following steps: S1, crushing 700 g of copper slag with a copper grade of 2.81% to a particle size of less than 0.045 mm, accounting for 75%, to obtain copper slag; the copper slag is injected into a flotation machine and water is added to adjust to obtain a slurry with a concentration of 40%.

[0094] S2, adding CaO to the slurry to adjust the pH value to 8, then adding 120 g / t of a composite collector compounded from sodium butyl xanthate and ethyldithiurea at a volume ratio of 1:0.5 and 20 g / t of pine oil, scraping for 2 min, and separating to obtain a copper concentrate and a flotation tailings.

[0095] S3, adding 90 g / t of sodium sulfide, 120 g / t of a composite collector compounded from sodium butyl xanthate and ethyldithiurea at a volume ratio of 1:0.5, and 10 g / t of pine oil to the flotation tailings, scraping for 5 min, and separating to obtain a roughing concentrate and a roughing tailings.

[0096] S4, adding 45 g / t of sodium sulfide, 60 g / t of a composite collector compounded from sodium butyl xanthate and ethyldithiurea at a volume ratio of 1:0.5, and 5 g / t of pine oil to the roughing tailings, scraping for 4 min, and separating to obtain first-time scavenging tailings and first-time scavenging concentrate; the first-time scavenging concentrate returns to the roughing in step S3 to form a closed circuit.

[0097] S5, adding 22.5g / t of sodium sulfide, 30g / t of a composite collector compounded by sodium butyl xanthate and ethyldithiurea at a volume ratio of 1:0.5 and 2.5g / t of pine oil to the first-time scavenging tailings, scraping bubbles for 3min, to obtain the second-time scavenging tailings and the second-time scavenging concentrate respectively; the second-time scavenging concentrate returns to the first-time scavenging in step S4 to form a closed loop.

[0098] S6, scraping bubble flotation of the roughing concentrate without adding reagents to separate the first-time cleaning concentrate and the first-time cleaning middlings; the first-time cleaning middlings return to the roughing operation in step S3 to form a closed loop.

[0099] S7, scraping bubble flotation of the first-time cleaning concentrate without adding reagents to separate the final copper concentrate and the second-time cleaning middlings; the second-time cleaning middlings return to the first-time cleaning in step S6 to form a closed loop; the final copper concentrate has a copper grade of about 17% and a copper recovery rate of about 87%.

[0100] Table 1: flotation method conditions for recovering copper components in copper slag in examples 1-3 and comparative examples 1-6 Examples 1, 2 and 3 are compared with comparative examples 1, 2, 3, 4, 5 and 6 respectively; it is concluded from Table 1 that compared with the traditional copper slag flotation collector xanthate and the traditional activator sodium sulfide, the composite activator or the composite collector can improve the grade and recovery rate of the copper concentrate, and the effect is more significant when used together. Therefore, the composite activator and the composite collector provided by the present application can achieve the effect of deep copper selection and improve the recovery rate of the copper concentrate.

[0101] It should be noted that when numerical ranges are involved in the present application, both endpoints of each numerical range and any number between the two endpoints can be selected. Since the same steps and examples are used, the preferred embodiments are described in the present application to prevent redundancy. Although the preferred embodiments of the present application have been described, those skilled in the art can make further changes and modifications to the embodiments once they understand the basic inventive concept. Therefore, the appended claims are intended to include the preferred embodiments and all changes and modifications falling within the scope of the present application.

Claims

1. A flotation reagent for recovering copper components from copper furnace slag, characterized in that, Including compound activators and compound collectors; The composite activator consists of 2,5-dimercaptothiadiazole and a first modifier, with a mass ratio of 2,5-dimercaptothiadiazole to the first modifier of 1:0.2~5. Modifier No. 1 is selected from at least one of copper sulfate, copper chloride, copper nitrate, lead nitrate, and lead chloride; The compound collector is composed of xanthate and No. 2 modifier, with a mass ratio of xanthate to No. 2 modifier of 1:1~10; Modifier No. 2 is selected from at least one of black powder, thiocyanate compounds, fatty acid compounds, and hydroxamic acid; When recovering copper components from copper slag, rapid flotation, roughing, scavenging, and cleaning were carried out sequentially. In rapid flotation, the dosage of the composite collector was 50 g / t to 200 g / t based on the weight of copper slag. In roughing, the dosage of the composite activator was 20 g / t to 250 g / t and the dosage of the composite collector was 50 g / t to 200 g / t based on the weight of copper slag. In scavenging, the dosage of the composite activator was 10 g / t to 125 g / t and the dosage of the composite collector was 25 g / t to 100 g / t based on the weight of copper slag.

2. The flotation reagent for recovering copper components from copper slag according to claim 1, characterized in that, The mass ratio of 2,5-dimercaptothiadiazole to modifier No. 1 is 1:0.2~2.

3. The flotation reagent for recovering copper components from copper slag according to claim 1, characterized in that, The mass ratio of xanthate to modifier No. 2 is 1:1~5.

4. The flotation reagent for recovering copper components from copper slag according to claim 1, characterized in that, In rapid flotation, the dosage of the composite collector is 50 g / t to 150 g / t based on the mass of copper slag; in roughing, the dosage of the composite activator is 50 g / t to 200 g / t and the dosage of the composite collector is 50 g / t to 150 g / t based on the mass of copper slag; in scavenging, the dosage of the composite activator is 10 g / t to 100 g / t and the dosage of the composite collector is 50 g / t to 80 g / t based on the mass of copper slag.

5. The flotation reagent for recovering copper components from copper slag according to claim 1, characterized in that, Based on the quality of copper slag, the dosage of composite activator in the fine-grained process is 0g / t to 5g / t, and the dosage of composite collector is 0g / t to 20g / t.

6. The flotation reagent for recovering copper components from copper slag according to claim 1, characterized in that, In copper slag, the mass percentage of copper slag with a particle size ≤0.045mm is ≥75wt%.

7. A flotation method for recovering copper components from copper furnace slag, characterized in that, The flotation reagent for recovering copper components from copper slag according to claim 1 includes the following steps: Copper slag and water are mixed to obtain a slurry; Rapid flotation treatment: Adjust the pH of the pulp to 8-10, then add a composite collector and a frother, and then perform a frothing treatment to obtain copper concentrate and flotation tailings; Roughing: A composite activator, a composite collector, and a frother are added to the flotation tailings. After frothing treatment, roughing concentrate and roughing tailings are obtained. Scavenging: A composite activator, a composite collector and a frother are added to the roughing tailings. After the frothing treatment, the first scavenging concentrate and the first scavenging tailings are obtained. The first scavenging concentrate is returned to the roughing to form a closed loop. Fine sieving: A composite activator, a composite collector, and a frother are added to the tailings from the first scavenging process. After frothing treatment, the second scavenging concentrate and the second scavenging tailings are obtained. The second scavenging concentrate is returned to the first scavenging step to form a closed loop. The roughing concentrate is subjected to flotation to obtain a primary cleaning concentrate and a primary cleaning middlings. The primary cleaning middlings are returned to the roughing step to form a closed loop. The primary concentrate is subjected to flotation without reagents to obtain copper concentrate and middlings from secondary concentrate. The middlings from secondary concentrate are returned to the primary concentrate step to form a closed loop, resulting in copper concentrate.

8. The flotation method for recovering copper components from copper slag according to claim 7, characterized in that, The foaming agent is selected from pine oil or methyl isobutyl alcohol.

9. The flotation method for recovering copper components from copper slag according to claim 7, characterized in that, Based on the mass of copper slag, the dosage of frother in rapid flotation is 50g / t to 200g / t; in roughing, it is 5g / t to 20g / t; in scavenging, it is 1g / t to 10g / t; and in cleaning, it is 0g / t to 5g / t.

10. The flotation method for recovering copper components from copper slag according to claim 7, characterized in that, The mass fraction of copper slag in the slurry is 35% to 45%.

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