Flotation process of copper slag

Abstract

The invention provides a flotation process of copper slag, and belongs to the technical field of resource utilization. Copper slag is sequentially subjected to coarse grinding and grading, magnetic separation, first-series flotation, magnetic copper slag fine grinding 1 + grading, magnetic copper slag fine grinding 2 + grading and second-series flotation processes, and therefore concentrate is obtained. The preparation method of the carbon anode plate for fluorine preparation is simple, the generation of polarization of the carbon anode plate is prevented, and the carbon anode plate has the advantages of low porosity, low ash content, high mechanical strength, high volume density, obviously prolonged service life, low resistivity and the like, and has a wide application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of resource utilization, and in particular to a flotation process for copper slag. Background Art

[0002] With the rapid development of China's industrialization, the demand for copper is increasing. Domestic copper mine resources can no longer meet the demand, and the competition for international copper resources is becoming increasingly fierce. The recycling of recycled copper has become a general trend. Pyrometallurgy is the main method for producing metallic copper. For every ton of copper produced, about 2.2 tons of slag are produced. Therefore, the efficient recovery of copper in copper slag is of great significance.

[0003] At present, copper slag is mainly recovered by beneficiation methods. According to the copper grade and physical characteristics of the slag, it mainly includes one-time grinding + flotation method; step grinding and step separation, gravity flotation combined separation, and magnetic flotation combined process, all of which have achieved good recovery effects. However, the commonality of these processes is that the final flotation tailings with a fineness of less than 0.074mm accounts for more than 92%, the grinding cost is high and the indicators are unstable. Summary of the invention

[0004] The purpose of the present invention is to propose a flotation process for copper slag. In view of the defects of high cost and unstable index in the conventional grinding + flotation process for copper slag in recovering copper, a magnetic and non-magnetic double series grinding + flotation process for copper slag is developed, which is beneficial to improve the machine time, reduce production costs and improve the recovery rate of copper minerals in copper slag, thereby increasing enterprise benefits.

[0005] The technical solution of the present invention is achieved in this way:

[0006] The invention provides a flotation process for copper slag, wherein the copper slag is subjected to coarse grinding + classification, magnetic separation, a first series of flotation, magnetic copper slag fine grinding 1 + classification, magnetic copper slag fine grinding 2 + classification, and a second series of flotation processes in sequence, so as to obtain concentrate.

[0007] As a further improvement of the present invention, the following steps are included:

[0008] (1) Rough grinding + classification: The copper slag is put into the rough grinding operation, and the products after grinding are classified. The classified sediment is returned to the rough grinding for re-grinding, and the overflow product enters the following process;

[0009] (2) Magnetic separation: the overflow product obtained in step (1) is subjected to magnetic separation to obtain magnetic copper slag and non-magnetic copper slag;

[0010] (3) First series flotation: The non-magnetic copper slag obtained in step (2) enters the first series flotation operation, and the flotation adopts a one-roughing and one-fine two-sweeping process; the roughing concentrate enters the fine grinding operation, and the final concentrate is obtained after one fine grinding operation. The fine grinding tailings are returned to the roughing operation, and the roughing tailings enter the scavenging operation. After two scavenging operations, the final tailings are obtained. The concentrates from the two scavenging operations are used as middlings and returned to the classification operation of fine grinding 2;

[0011] (4) Magnetic copper slag fine grinding 1 + classification: The magnetic copper slag obtained in step (2) is put into fine grinding 1, the product after grinding is classified, and the classified sediment is returned to fine grinding 1 for re-grinding;

[0012] (5) Fine grinding 2+classification of magnetic copper slag, the overflow product obtained in step (4) enters the classification operation of fine grinding 2, the classified sedimentation returns to the fine grinding operation 2, and the product after grinding is further classified;

[0013] (6) Second series flotation: The magnetic copper slag obtained in step (5) is fed into the second series flotation operation. The collector is butyl xanthate + butylamine black medicine, and the frother is 2# oil. The flotation adopts a one-roughing, two-fine and four-sweeping process. The roughing concentrate is fed into the first fine grinding operation. The tailings from the first fine grinding operation are returned to the roughing operation. The concentrate is fed into the second fine grinding operation. The tailings from the second fine grinding operation are returned to the first fine grinding operation. The concentrate from the second fine grinding operation is used as the final concentrate. The roughing tailings are fed into the scavenging operation. The final tailings are obtained after four scavenging operations. The concentrate from the four scavenging operations is used as the medium ore and is returned to the classification operation of fine grinding 2.

[0014] As a further improvement of the present invention, the particle size of the copper slag in step (1) is less than 12 mm; the classified overflow fineness is less than 0.074 mm, accounting for 55-60%; the magnetic content of the magnetic copper slag in step (2) is 88-92%, and the magnetic content of the non-magnetic copper slag is 5-8%, and the magnetic field strength used in the magnetic separation operation is 2500-3500GS.

[0015] As a further improvement of the present invention, in step (3), the collectors are butyl xanthate and nanoparticles in a mass ratio of 10:2-3, the foaming agent is 2# oil, and the added amounts of the collectors are: 8-10 g / t for roughing, 4-6 g / t for sweeping, and 1-3 g / t for sweeping. The added amount of the foaming agent is 15-25 g / t for roughing.

[0016] As a further improvement of the present invention, the overflow fineness of the classification in step (4) is less than 0.074 mm, accounting for more than 85%; the overflow fineness of the classification in step (5) is less than 0.074 mm, accounting for more than 95%.

[0017] As a further improvement of the present invention, the addition amount of the collector in step (6) is: 5-8 g / t for roughing, 3-5 g / t for sweep 1, 1-3 g / t for sweep 2, 1-2 g / t for sweep 3, and 0.5-1 g / t for sweep 4; the addition amount of the foaming agent is: 8-10 g / t for roughing, and 3-8 g / t for sweep 3; the collector is a mixture of butyl xanthate, nanoparticles and butylamine black medicine in a mass ratio of 10-15:1-2:4-7; and the foaming agent is 2# oil.

[0018] As a further improvement of the present invention, the preparation method of the nanoparticles is as follows:

[0019] S1. Mix ethanol, water and polyvinyl pyrrolidone to obtain a mixed solution;

[0020] S2. Under the protection of inert gas, styrene, hydroxyethyl methacrylate, 1-vinylimidazole, allylbenzazole, and N-tert-butyl-1,1-dimethylallylamine are added to the mixture to prepare a liquid with a monomer concentration of 30-35wt%, stirred and mixed evenly, an initiator is added, heated and stirred to react, centrifuged, washed, and dried to obtain nanospheres;

[0021] S3. Add the nanospheres into an ethanol aqueous solution, add dimethyl sulfate, heat and stir to react, centrifuge, wash, and dry to obtain nanoparticles.

[0022] As a further improvement of the present invention, the mass ratio of ethanol, water and polyvinyl pyrrolidone in step S1 is 30-40:1-3:0.5-1.

[0023] As a further improvement of the present invention, the mass ratio of styrene, hydroxyethyl methacrylate, 1-vinylimidazole, allylbenzazole, and N-tert-butyl-1,1-dimethylallylamine in step S2 is 10-12:3-5:1-3:2-5:3-6, the initiator is at least one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, sodium persulfate, potassium persulfate, and ammonium persulfate, the amount of the initiator added is 0.5-1wt% of the total mass of the system, the temperature of the heating and stirring reaction is 65-75°C, and the time is 8-10h.

[0024] As a further improvement of the present invention, the ethanol content in the ethanol aqueous solution in step S3 is 40-50wt%, the mass ratio of the nanospheres to dimethyl sulfate is 100:4-7, the temperature of the heating and stirring reaction is 60-80°C, and the time is 1-3h.

[0025] The present invention has the following beneficial effects:

[0026] The present invention aims at the defects of high cost and unstable index in the conventional grinding + flotation process of copper slag in recovering copper, and develops a copper slag magnetic and non-magnetic dual series grinding + flotation process. According to the characteristics of easy crushing, easy single dissociation and easy flotation of non-magnetic minerals in copper slag, the present invention selects less grinding + conventional reagents to shorten the flotation process to produce qualified concentrated tailings products, and according to the characteristics of difficult crushing, difficult dissociation and difficult flotation of magnetic minerals, selects more grinding + combined reagents to extend the flotation process, improves the machine time and reduces the cost while stabilizing the flotation index. In the non-magnetic mineral series, the non-magnetic slag is separated through rough grinding + classification + magnetic separation, and butyl xanthate is used to produce qualified concentrated tailings products through a one-coarse and one-fine two-sweep process; in the magnetic mineral series, the magnetic slag separated through rough grinding + classification + magnetic separation is subjected to two-stage fine grinding to fully dissociate the copper minerals, and a butyl xanthate + butylamine black medicine combined collector is used to produce qualified concentrated tailings products through a one-coarse and two-fine four-sweep process. The present invention makes full use of the difference in the degree of dissociation of magnetic and non-magnetic mineral monomers in copper slag and the selectivity of copper minerals, which is beneficial to improving the production time and reducing production costs, and improving the recovery rate of copper minerals in copper slag, thereby increasing enterprise benefits.

[0027] In the present invention, butyl xanthate has the characteristics of strong collecting ability, wide universality, good water solubility, easy synthesis, low price, etc., and is still one of the main collectors for flotation of copper sulfide ores. However, xanthate has disadvantages such as strong odor and poor flotation selectivity. During use, there are problems such as poor production site environment and low separation efficiency between valuable minerals in the ore.

[0028] The present invention prepares a nanoparticle, which uses styrene as a main monomer, and adds 1-vinyl imidazole, allyl thiazole, and N-tert-butyl-1,1-dimethylallylamine monomers that have good binding ability with copper, wherein the sulfur atom in thiazole has a lone pair of electrons and can chemically adsorb with the active site on the copper surface. For example, the sulfur atom in 2-mercaptobenzothiazole (MBT) can form a chemical bond with the copper atom or copper ion on the copper surface, thereby forming a stable adsorption layer on the copper surface; the amine group can combine with the copper ion through coordination to form a stable complex; the nitrogen atom on the imidazole ring has a lone pair of electrons and can form a coordination bond with the empty orbit on the copper surface, thereby forming a stable adsorption layer on the copper surface. This adsorption can not only inhibit the corrosion of copper, but also can be used to construct a protective film for copper-based materials. Therefore, the prepared nanoparticles have good selectivity for copper and greatly improve the flotation recovery rate. In addition, antioxidant monomers such as hydroxyethyl methacrylate are added to the monomers. The hydroxyl group can react with free radicals by providing hydrogen atoms, thereby removing free radicals, thereby avoiding the oxidation of butyl xanthate, thereby greatly improving the utilization rate of the collector and reducing the amount of collector added, and also having a good flotation recovery rate.

[0029] The surface of copper slag usually has a negative charge, which is because the metal oxides and silicate minerals on its surface easily adsorb or dissociate hydroxide ions (OH - ), resulting in negative charge on the surface. The present invention subjects the prepared nanospheres to a quaternary ammonium reaction, whereby the amine groups form quaternary ammonium salts, so that the surface of the nanoparticles carries a positive charge, thereby facilitating the combination with the copper slag and separation and flotation, thereby greatly improving the flotation recovery rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0031] Figure 1 The present invention is a flow chart of the flotation process of copper slag. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] Preparation Example 1 Preparation of Nanoparticles

[0034] Here’s how:

[0035] S1. 30 g of ethanol, 1 g of water and 0.5 g of polyvinyl pyrrolidone were stirred for 5 min to obtain a mixed solution;

[0036] S2. Under nitrogen protection, 10 g of styrene, 3 g of hydroxyethyl methacrylate, 1 g of 1-vinylimidazole, 2 g of allylbenzazole, and 3 g of N-tert-butyl-1,1-dimethylallylamine were added to the mixture to prepare a liquid with a monomer concentration of 30 wt%, stirred and mixed for 15 min, azobisisoheptanenitrile was added, the amount of azobisisoheptanenitrile added was 0.5 wt% of the total mass of the system, heated to 65 ° C, stirred for 8 h, centrifuged, washed, and dried to obtain nanospheres;

[0037] S3. Add 10 g of nanospheres into 200 mL of 40 wt % ethanol aqueous solution, add 0.4 g of dimethyl sulfate, heat to 60° C., stir to react for 1 h, centrifuge, wash, and dry to obtain nanoparticles.

[0038] Preparation Example 2 Preparation of Nanoparticles

[0039] Here’s how:

[0040] S1. 40 g of ethanol, 3 g of water and 1 g of polyvinyl pyrrolidone were stirred and mixed for 5 min to obtain a mixed solution;

[0041] S2. Under nitrogen protection, 12 g of styrene, 5 g of hydroxyethyl methacrylate, 3 g of 1-vinylimidazole, 5 g of allylbenzazole, and 6 g of N-tert-butyl-1,1-dimethylallylamine were added to the mixture to prepare a liquid with a monomer concentration of 35 wt%, stirred and mixed for 15 min, azobisisovaleronitrile was added, and the amount of azobisisovaleronitrile added was 1 wt% of the total mass of the system, heated to 75 ° C, stirred for 10 h, centrifuged, washed, and dried to obtain nanospheres;

[0042] S3. Add 10 g of nanospheres into 200 mL of 50 wt% ethanol aqueous solution, add 0.7 g of dimethyl sulfate, heat to 80° C., stir to react for 3 h, centrifuge, wash, and dry to obtain nanoparticles.

[0043] Preparation Example 3 Preparation of Nanoparticles

[0044] Here’s how:

[0045] S1. 35 g of ethanol, 2 g of water and 0.7 g of polyvinyl pyrrolidone were stirred and mixed for 5 min to obtain a mixed solution;

[0046] S2. Under nitrogen protection, 11 g of styrene, 4 g of hydroxyethyl methacrylate, 2 g of 1-vinylimidazole, 3.5 g of allylbenzazole, and 4.5 g of N-tert-butyl-1,1-dimethylallylamine were added to the mixture to prepare a liquid with a monomer concentration of 32 wt%, stirred and mixed for 15 min, azobisisobutyronitrile was added, the amount of azobisisobutyronitrile added was 0.7 wt% of the total mass of the system, heated to 70 ° C, stirred for 9 h, centrifuged, washed, and dried to obtain nanospheres;

[0047] S3. Add 10 g of nanospheres into 200 mL of 45 wt% ethanol aqueous solution, add 0.55 g of dimethyl sulfate, heat to 70° C., stir to react for 2 h, centrifuge, wash, and dry to obtain nanoparticles.

[0048] Comparative Preparation Example 1

[0049] Compared with Preparation Example 3, the difference is that step S3 is not performed.

[0050] The details are as follows:

[0051] S1. 35 g of ethanol, 2 g of water and 0.7 g of polyvinyl pyrrolidone were stirred and mixed for 5 min to obtain a mixed solution;

[0052] S2. Under nitrogen protection, 11 g of styrene, 4 g of hydroxyethyl methacrylate, 2 g of 1-vinylimidazole, 3.5 g of allylbenzazole, and 4.5 g of N-tert-butyl-1,1-dimethylallylamine were added to the mixed solution to prepare a liquid with a monomer concentration of 32 wt%. The mixture was stirred for 15 min, and azobisisobutyronitrile was added in an amount of 0.7 wt % of the total mass of the system. The mixture was heated to 70°C, stirred for 9 h, centrifuged, washed, and dried to obtain nanoparticles.

[0053] Comparative Preparation Example 2

[0054] Compared with Preparation Example 3, the difference is that hydroxyethyl methacrylate is not added in step S2.

[0055] The details are as follows:

[0056] S1. 35 g of ethanol, 2 g of water and 0.7 g of polyvinyl pyrrolidone were stirred and mixed for 5 min to obtain a mixed solution;

[0057] S2. Under nitrogen protection, 15 g of styrene, 2 g of 1-vinyl imidazole, 3.5 g of allyl thiazole, and 4.5 g of N-tert-butyl-1,1-dimethylallylamine were added to the mixture to prepare a liquid with a monomer concentration of 32 wt%, stirred and mixed for 15 min, azobisisobutyronitrile was added, and the amount of azobisisobutyronitrile added was 0.7 wt% of the total mass of the system, heated to 70 ° C, stirred for 9 h, centrifuged, washed, and dried to obtain nanospheres;

[0058] S3. Add 10 g of nanospheres into 200 mL of 45 wt% ethanol aqueous solution, add 0.55 g of dimethyl sulfate, heat to 70° C., stir to react for 2 h, centrifuge, wash, and dry to obtain nanoparticles.

[0059] Comparative Preparation Example 3

[0060] Compared with Preparation Example 3, the difference is that hydroxyethyl methacrylate, 1-vinylimidazole, allylbenzazole and N-tert-butyl-1,1-dimethylallylamine are not added in step S2.

[0061] The details are as follows:

[0062] S1. 35 g of ethanol, 2 g of water and 0.7 g of polyvinyl pyrrolidone were stirred and mixed for 5 min to obtain a mixed solution;

[0063] S2. Under nitrogen protection, 25 g of styrene was added to the mixture to prepare a liquid with a monomer concentration of 32 wt%, stirred and mixed for 15 min, azobisisobutyronitrile was added, the amount of azobisisobutyronitrile added was 0.7 wt% of the total mass of the system, heated to 70 ° C, stirred for 9 h, centrifuged, washed, and dried to obtain nanospheres;

[0064] S3. Add 10 g of nanospheres into 200 mL of 45 wt% ethanol aqueous solution, add 0.55 g of dimethyl sulfate, heat to 70° C., stir to react for 2 h, centrifuge, wash, and dry to obtain nanoparticles.

[0065] Example 1

[0066] like Figure 1 The present embodiment provides a flotation process for copper slag, characterized in that it comprises the following steps:

[0067] (1) Rough grinding + classification: Copper slag (particle size less than 12 mm) is put into rough grinding, and the products after grinding are classified. The classified sediment is returned to the rough grinding for re-grinding, and the overflow product enters the following process. The overflow fineness of the classified product is less than 0.074 mm, accounting for 55%;

[0068] (2) Magnetic separation: the overflow product obtained in step (1) is subjected to magnetic separation to obtain magnetic copper slag and non-magnetic copper slag; the magnetic copper slag has a magnetic content of 88%, and the non-magnetic copper slag has a magnetic content of 8%; the magnetic field strength used in the magnetic separation is 2500 GS;

[0069] (3) First series flotation: The non-magnetic copper slag obtained in step (2) enters the first series flotation operation, and the flotation adopts a one-roughing and one-fine two-sweeping process; the roughing concentrate enters the fine grinding operation, and the final concentrate is obtained after one fine grinding operation. The fine grinding tailings are returned to the roughing operation, and the roughing tailings enter the scavenging operation. After two scavenging operations, the final tailings are obtained. The concentrates from the two scavenging operations are used as middlings and returned to the classification operation of fine grinding 2;

[0070] The collectors are butyl xanthate and the nanoparticles prepared in Preparation Example 1, with a mass ratio of 10:2. The foaming agent is 2# oil. The addition amounts of the collectors are: 8g / t for roughing, 4g / t for sweeping, and 1g / t for sweeping. The addition amount of the foaming agent is 15g / t for roughing.

[0071] (4) Magnetic copper slag fine grinding 1 + classification: The magnetic copper slag obtained in step (2) is fed into the fine grinding 1, the product after grinding is classified, and the classified sediment is returned to the fine grinding 1 for re-grinding; the overflow fineness of the classification is less than 0.074 mm, accounting for more than 85%;

[0072] (5) fine grinding 2+classification of the magnetic copper slag, the overflow product obtained in step (4) enters the classification operation of fine grinding 2, the classified sedimentation returns to the fine grinding operation 2, and the product after grinding is further classified; the overflow fineness of the classification is less than 0.074 mm, accounting for more than 95%;

[0073] (6) Second series flotation: The magnetic copper slag obtained in step (5) enters the second series flotation operation, the collector is butyl xanthate + butylamine black medicine, the frother is 2# oil, and the flotation adopts a one-roughing, two-fine and four-sweeping process. The roughing concentrate enters the first cleaning operation, and the tailings after the first cleaning operation are returned to the roughing operation. The concentrate enters the second cleaning operation, and the tailings after the second cleaning operation are returned to the first cleaning operation. The concentrate of the second cleaning operation is used as the final concentrate. The roughing tailings enter the scavenging operation. After four scavenging operations, the final tailings are obtained. The concentrate after four scavenging operations is used as the middling ore and returned to the classification operation of fine grinding 2;

[0074] The added amounts of collectors are: 5 g / t for roughing, 3 g / t for sweep one, 1 g / t for sweep two, 1 g / t for sweep three, and 0.5 g / t for sweep four. The added amounts of foaming agents are: 8 g / t for roughing and 3 g / t for sweep three. The collector is a mixture of butyl xanthate, the nanoparticles obtained in Preparation Example 1, and butylamine black medicine, with a mass ratio of 10:1:4. The foaming agent is 2# oil.

[0075] Example 2

[0076] like Figure 1 The present embodiment provides a flotation process for copper slag, characterized in that it comprises the following steps:

[0077] (1) Rough grinding + classification: copper slag (particle size less than 12 mm) is put into rough grinding, and the products after grinding are classified. The classified sediment is returned to the rough grinding for re-grinding, and the overflow product enters the following process. The overflow fineness of the classified product is less than 0.074 mm, accounting for 60%;

[0078] (2) Magnetic separation: the overflow product obtained in step (1) is subjected to magnetic separation to obtain magnetic copper slag and non-magnetic copper slag; the magnetic copper slag has a magnetic content of 92%, and the non-magnetic copper slag has a magnetic content of 5%; the magnetic field strength used in the magnetic separation is 3500 GS;

[0079] (3) First series flotation: The non-magnetic copper slag obtained in step (2) enters the first series flotation operation, and the flotation adopts a one-roughing and one-fine two-sweeping process; the roughing concentrate enters the fine grinding operation, and the final concentrate is obtained after one fine grinding operation. The fine grinding tailings are returned to the roughing operation, and the roughing tailings enter the scavenging operation. After two scavenging operations, the final tailings are obtained. The concentrates from the two scavenging operations are used as middlings and returned to the classification operation of fine grinding 2;

[0080] The collectors are butyl xanthate and the nanoparticles prepared in Preparation Example 2, with a mass ratio of 10:3. The foaming agent is 2# oil. The addition amounts of the collectors are: 10 g / t for roughing, 6 g / t for sweeping, and 3 g / t for sweeping. The addition amount of the foaming agent is 25 g / t for roughing.

[0081] (4) Magnetic copper slag fine grinding 1 + classification: The magnetic copper slag obtained in step (2) is fed into the fine grinding 1, the product after grinding is classified, and the classified sediment is returned to the fine grinding 1 for re-grinding; the overflow fineness of the classification is less than 0.074 mm, accounting for more than 85%;

[0082] (5) fine grinding 2+classification of the magnetic copper slag, the overflow product obtained in step (4) enters the classification operation of fine grinding 2, the classified sedimentation returns to the fine grinding operation 2, and the product after grinding is further classified; the overflow fineness of the classification is less than 0.074 mm, accounting for more than 95%;

[0083] (6) Second series flotation: The magnetic copper slag obtained in step (5) enters the second series flotation operation, the collector is butyl xanthate + butylamine black medicine, the frother is 2# oil, and the flotation adopts a one-roughing, two-fine and four-sweeping process. The roughing concentrate enters the first cleaning operation, and the tailings after the first cleaning operation are returned to the roughing operation. The concentrate enters the second cleaning operation, and the tailings after the second cleaning operation are returned to the first cleaning operation. The concentrate of the second cleaning operation is used as the final concentrate. The roughing tailings enter the scavenging operation. After four scavenging operations, the final tailings are obtained. The concentrate after four scavenging operations is used as the middling ore and returned to the classification operation of fine grinding 2;

[0084] The added amounts of collectors are: 8 g / t for roughing, 5 g / t for sweep one, 3 g / t for sweep two, 2 g / t for sweep three, and 1 g / t for sweep four. The added amounts of foaming agents are: 10 g / t for roughing and 8 g / t for sweep three. The collector is a mixture of butyl xanthate, the nanoparticles prepared in Preparation Example 2, and butylamine black medicine, with a mass ratio of 15:2:7. The foaming agent is 2# oil.

[0085] Example 3

[0086] like Figure 1 The present embodiment provides a flotation process for copper slag, characterized in that it comprises the following steps:

[0087] (1) Rough grinding + classification: Copper slag (particle size less than 12 mm) is put into rough grinding, and the products after grinding are classified. The classified sediment is returned to the rough grinding for re-grinding, and the overflow product enters the following process. The overflow fineness of the classified product is less than 0.074 mm, accounting for 57%;

[0088] (2) Magnetic separation: the overflow product obtained in step (1) is subjected to magnetic separation to obtain magnetic copper slag and non-magnetic copper slag; the magnetic copper slag has a magnetic content of 90%, and the non-magnetic copper slag has a magnetic content of 6%; the magnetic field strength used in the magnetic separation is 3000 GS;

[0089] (3) First series flotation: The non-magnetic copper slag obtained in step (2) enters the first series flotation operation, and the flotation adopts a one-roughing and one-fine two-sweeping process; the roughing concentrate enters the fine grinding operation, and the final concentrate is obtained after one fine grinding operation. The fine grinding tailings are returned to the roughing operation, and the roughing tailings enter the scavenging operation. After two scavenging operations, the final tailings are obtained. The concentrates from the two scavenging operations are used as middlings and returned to the classification operation of fine grinding 2;

[0090] The collectors are butyl xanthate and the nanoparticles prepared in Preparation Example 3, with a mass ratio of 10:2.5. The foaming agent is 2# oil. The addition amounts of the collectors are: 9g / t for roughing, 5g / t for sweeping, and 2g / t for sweeping. The addition amount of the foaming agent is 20g / t for roughing.

[0091] (4) Magnetic copper slag fine grinding 1 + classification: The magnetic copper slag obtained in step (2) is fed into the fine grinding 1, the product after grinding is classified, and the classified sediment is returned to the fine grinding 1 for re-grinding; the overflow fineness of the classification is less than 0.074 mm, accounting for more than 85%;

[0092] (5) fine grinding 2+classification of the magnetic copper slag, the overflow product obtained in step (4) enters the classification operation of fine grinding 2, the classified sedimentation returns to the fine grinding operation 2, and the product after grinding is further classified; the overflow fineness of the classification is less than 0.074 mm, accounting for more than 95%;

[0093] (6) Second series flotation: The magnetic copper slag obtained in step (5) enters the second series flotation operation, the collector is butyl xanthate + butylamine black medicine, the frother is 2# oil, and the flotation adopts a one-roughing, two-fine and four-sweeping process. The roughing concentrate enters the first cleaning operation, and the tailings after the first cleaning operation are returned to the roughing operation. The concentrate enters the second cleaning operation, and the tailings after the second cleaning operation are returned to the first cleaning operation. The concentrate of the second cleaning operation is used as the final concentrate. The roughing tailings enter the scavenging operation. After four scavenging operations, the final tailings are obtained. The concentrate after four scavenging operations is used as the middling ore and returned to the classification operation of fine grinding 2;

[0094] The added amounts of collectors are: 6 g / t for roughing, 4 g / t for sweep one, 2 g / t for sweep two, 1.5 g / t for sweep three, and 0.7 g / t for sweep four. The added amounts of foaming agents are: 9 g / t for roughing and 5 g / t for sweep three. The collector is a mixture of butyl xanthate, the nanoparticles obtained in Preparation Example 3, and butylamine black medicine, with a mass ratio of 12:1.5:5.5. The foaming agent is 2# oil.

[0095] Comparative Example 1

[0096] Compared with Example 3, the difference is that the nanoparticles are prepared by Comparative Preparation Example 1.

[0097] Comparative Example 2

[0098] Compared with Example 3, the difference is that the nanoparticles are prepared by Comparative Preparation Example 2.

[0099] Comparative Example 3

[0100] Compared with Example 3, the difference is that the nanoparticles are prepared by Comparative Preparation Example 3.

[0101] Comparative Example 4

[0102] The difference compared with Example 3 is that no nanoparticles are added.

[0103] Comparative Example 5

[0104] Compared with Example 3, the difference is that in step (6), the collector is only butyl xanthate.

[0105] Comparative Example 6

[0106] Compared with Example 3, the difference is that step (2) magnetic separation is not performed.

[0107] The details are as follows:

[0108] (1) Rough grinding + classification: Copper slag (particle size less than 12 mm) is put into rough grinding, and the products after grinding are classified. The classified sediment is returned to the rough grinding for re-grinding, and the overflow product enters the following process. The overflow fineness of the classified product is less than 0.074 mm, accounting for 57%;

[0109] (2) First series flotation: The overflow product obtained in step (1) enters the first series flotation operation, and the flotation adopts a one-roughing and one-fine-two-sweeping process; the rougher concentrate enters the fine grinding operation, and the final concentrate is obtained after one fine grinding operation. The fine tailings are returned to the rougher operation, and the rougher tailings enter the scavenging operation. After two scavenging operations, the final tailings are obtained. The concentrates from the two scavenging operations are used as middlings and returned to the classification operation of fine grinding 2;

[0110] The collectors are butyl xanthate and the nanoparticles prepared in Preparation Example 3, with a mass ratio of 10:2.5. The foaming agent is 2# oil. The addition amounts of the collectors are: 9g / t for roughing, 5g / t for sweeping, and 2g / t for sweeping. The addition amount of the foaming agent is 20g / t for roughing.

[0111] (3) Fine grinding 1 + classification: the copper slag obtained in step (2) is fed into the fine grinding 1, the product after grinding is classified, and the classified sediment is returned to the fine grinding 1 for re-grinding; the overflow fineness of the classification is less than 0.074 mm, accounting for more than 85%;

[0112] (4) fine grinding 2 + classification, the overflow product obtained in step (3) enters the classification operation of fine grinding 2, the classified sedimentation returns to the fine grinding operation 2, and the ground product is further classified; the overflow fineness of the classification is less than 0.074 mm, accounting for more than 95%;

[0113] (5) Second series flotation: The copper slag obtained in step (4) enters the second series flotation operation, the collector is butyl xanthate + butylamine black medicine, the frother is 2# oil, and the flotation adopts a one-roughing, two-fine and four-sweeping process. The roughing concentrate enters the first cleaning operation, and the tailings after the first cleaning operation are returned to the roughing operation. The concentrate enters the second cleaning operation, and the tailings after the second cleaning operation are returned to the first cleaning operation. The concentrate of the second cleaning operation is used as the final concentrate. The roughing tailings enter the scavenging operation. After four scavenging operations, the final tailings are obtained. The concentrate after four scavenging operations is used as the medium ore and returned to the classification operation of fine grinding 2;

[0114] The added amounts of collectors are: 6 g / t for roughing, 4 g / t for sweep one, 2 g / t for sweep two, 1.5 g / t for sweep three, and 0.7 g / t for sweep four. The added amounts of foaming agents are: 9 g / t for roughing and 5 g / t for sweep three. The collector is a mixture of butyl xanthate, the nanoparticles obtained in Preparation Example 3, and butylamine black medicine, with a mass ratio of 12:1.5:5.5. The foaming agent is 2# oil.

[0115] Test Example 1

[0116] The concentrates and tailings obtained in Examples 1-3 or Comparative Examples 1-6 were analyzed, and the results are shown in Table 1.

[0117] Table 1

[0118]

[0119] It can be seen from the above table that the concentrate obtained in the flotation process of copper slag in Examples 1-3 of the present invention has a high grade and a high recovery rate.

[0120] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A flotation process for copper slag, characterized in that: The copper slag is sequentially subjected to coarse grinding + classification, magnetic separation, first series of flotation, magnetic copper slag fine grinding 1 + classification, magnetic copper slag fine grinding 2 + classification, and second series of flotation processes to obtain concentrate.

2. The flotation process of copper slag according to claim 1, characterized in that: The following steps are involved: (1) Rough grinding + classification: The copper slag is put into the rough grinding operation, and the products after grinding are classified. The classified sediment is returned to the rough grinding for re-grinding, and the overflow product enters the following process; (2) Magnetic separation: the overflow product obtained in step (1) is subjected to magnetic separation to obtain magnetic copper slag and non-magnetic copper slag; (3) First series flotation: The non-magnetic copper slag obtained in step (2) enters the first series flotation operation, and the flotation adopts a one-roughing and one-fine two-sweeping process; the roughing concentrate enters the fine grinding operation, and the final concentrate is obtained after one fine grinding operation. The fine grinding tailings are returned to the roughing operation, and the roughing tailings enter the scavenging operation. After two scavenging operations, the final tailings are obtained. The concentrates from the two scavenging operations are used as middlings and returned to the classification operation of fine grinding 2; (4) Magnetic copper slag fine grinding 1 + classification: The magnetic copper slag obtained in step (2) is put into fine grinding 1, the product after grinding is classified, and the classified sediment is returned to fine grinding 1 for re-grinding; (5) Fine grinding 2+classification of magnetic copper slag, the overflow product obtained in step (4) enters the classification operation of fine grinding 2, the classified sedimentation returns to the fine grinding operation 2, and the product after grinding is further classified; (6) Second series flotation: The magnetic copper slag obtained in step (5) enters the second series flotation operation, the collector is butyl xanthate + butylamine black medicine, the frother is 2# oil, and the flotation adopts a one roughing, two fines and four sweeping process. The roughing concentrate enters the first concentrating operation, the tailings after the first concentrating operation are returned to the roughing operation, the concentrate enters the second concentrating operation, the tailings after the second concentrating operation are returned to the first concentrating operation, the concentrate of the second concentrating operation is used as the final concentrate, the roughing tailings enter the sweeping operation, the final tailings are obtained after four sweepings, and the concentrate after four sweepings is used as the medium ore and returned to the classification operation of fine grinding 2.

3. The flotation process of copper slag according to claim 1, characterized in that: The particle size of the copper slag in step (1) is less than 12 mm; the overflow fineness of the classification is less than 0.074 mm, accounting for 55-60%; the magnetic content of the magnetic copper slag in step (2) is 88-92%, and the magnetic content of the non-magnetic copper slag is 5-8%, and the magnetic field strength used in the magnetic separation operation is 2500-3500GS.

4. The flotation process of copper slag according to claim 1, characterized in that: In step (3), the collectors are butyl xanthate and nanoparticles in a mass ratio of 10:2-3, and the foaming agent is 2# oil. The added amounts of the collectors are: 8-10 g / t for roughing, 4-6 g / t for sweeping, and 1-3 g / t for sweeping. The added amount of the foaming agent is 15-25 g / t for roughing.

5. The flotation process of copper slag according to claim 1, characterized in that: In step (4), the overflow fineness of the classified product is less than 0.074 mm, accounting for more than 85%; and in step (5), the overflow fineness of the classified product is less than 0.074 mm, accounting for more than 95%.

6. The flotation process of copper slag according to claim 1, characterized in that: In step (6), the addition amount of the collector is: 5-8 g / t for roughing, 3-5 g / t for sweep 1, 1-3 g / t for sweep 2, 1-2 g / t for sweep 3, and 0.5-1 g / t for sweep 4; the addition amount of the foaming agent is: 8-10 g / t for roughing, and 3-8 g / t for sweep 3; the collector is a mixture of butyl xanthate, nanoparticles and butylamine black medicine, with a mass ratio of 10-15:1-2:4-7; and the foaming agent is 2# oil.

7. The flotation process of copper slag according to claim 4 or 6, characterized in that: The preparation method of the nanoparticles is as follows: S1. Mix ethanol, water and polyvinyl pyrrolidone to obtain a mixed solution; S2. Under the protection of inert gas, styrene, hydroxyethyl methacrylate, 1-vinylimidazole, allylbenzazole, and N-tert-butyl-1,1-dimethylallylamine are added to the mixture to prepare a liquid with a monomer concentration of 30-35wt%, stirred and mixed evenly, an initiator is added, heated and stirred to react, centrifuged, washed, and dried to obtain nanospheres; S3. Add the nanospheres into an ethanol aqueous solution, add dimethyl sulfate, heat and stir to react, centrifuge, wash, and dry to obtain nanoparticles.

8. The flotation process of copper slag according to claim 7, characterized in that: The mass ratio of ethanol, water and polyvinyl pyrrolidone in step S1 is 30-40:1-3:0.5-1.

9. The flotation process of copper slag according to claim 7, characterized in that: In step S2, the mass ratio of styrene, hydroxyethyl methacrylate, 1-vinylimidazole, allylbenzazole, and N-tert-butyl-1,1-dimethylallylamine is 10-12:3-5:1-3:2-5:3-6, the initiator is at least one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, sodium persulfate, potassium persulfate, and ammonium persulfate, the amount of the initiator added is 0.5-1wt% of the total mass of the system, the temperature of the heated and stirred reaction is 65-75°C, and the time is 8-10h.

10. The flotation process of copper slag according to claim 7, characterized in that: In step S3, the ethanol content in the ethanol aqueous solution is 40-50wt%, the mass ratio of the nanospheres to dimethyl sulfate is 100:4-7, the temperature of the heating and stirring reaction is 60-80°C, and the time is 1-3h.

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