A grading magnetic-floatation combined beneficiation method for sulfur-oxygen mixed copper ore

Abstract

The application discloses a kind of sulphur oxygen mixed type copper ore grading magnetic-flotation combined beneficiation method, including grinding screening, magnetic separation, grading, copper sulphide flotation, copper oxide roughing, copper oxide strengthening scavenging.The application is by using strong magnetic separation recovery part coarse grain copper oxide in mill grading system, reduce the overgrinding of copper oxide mineral in the process of grinding, realize the ability to collect early collection, improve copper oxide comprehensive recovery rate, while reducing the release of copper ions in the process of grinding, reduce the adverse effect on subsequent copper sulphide flotation.By using sodium sulphide and sodium pyrosulphite to form efficient copper oxide sulphidizing agent, the stability of the film in the sulphidation process is strengthened, and the inhibition of pyrite is also strengthened, improving the separation efficiency of copper oxide flotation.In addition, by using efficient reagents and precise control, the copper oxide concentrate is directly obtained by opening the circuit of copper oxide roughing and strengthening scavenging concentrate, reducing the copper metal loss caused by closed loop circulation.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, specifically to a graded magnetic-flotation combined beneficiation method for sulfur-oxygen mixed copper ore. Background Technology

[0002] Approximately 10%-15% of the world's copper resources consist of copper oxide ores and mixed copper ores, representing important copper mineral resources. For high-grade copper oxide ores, leaching is generally used for recovery. With the continuous exploitation of copper sulfide ores, the proportion of mixed copper ores and low-grade copper oxide ores is constantly expanding, making the development of green and efficient beneficiation processes crucial. In mixed copper oxide ores, a stepwise flotation process is often used to first obtain copper sulfide concentrate, and then recover copper oxide minerals from the tailings via sulfide flotation, thus achieving comprehensive resource utilization. However, in actual production, single flotation has low efficiency in recovering copper oxide. This is partly due to the poor floatability of copper oxide itself, resulting in limited recovery rates via sulfide flotation; and partly because most copper oxide minerals are brittle and easily over-crushed during grinding, leading to extremely low recovery rates of copper oxide in mixed copper ores. In mixed copper oxide ores, the release of copper ions from copper oxide minerals during grinding deteriorates the flotation environment, causing a decline in the flotation performance of copper sulfide.

[0003] Therefore, developing a beneficiation process with good separation effect and strong adaptability will help improve the overall copper recovery rate of sulfur-oxygen mixed copper ore and improve the utilization level of this type of mineral resource. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention aims to provide a graded magnetic-flotation combined beneficiation method for sulfur-oxygen mixed copper ores.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A graded magnetic-flotation combined beneficiation method for sulfur-oxygen mixed copper ore includes the following steps:

[0007] S1. Grinding and screening operation: The crushed raw ore is mixed with water and then ground; the grinding discharge enters a wet screening machine, the oversize product is returned to continue grinding, and the undersize product enters a pulsed high gradient magnetic separator.

[0008] S2. Magnetic separation operation: The undersize product obtained in step S1 is subjected to magnetic separation by a pulsed high gradient magnetic separator to obtain magnetic concentrate and magnetic residue. The magnetic concentrate is copper oxide concentrate.

[0009] S3. Classification operation: The magnetic separation residue obtained in step S2 is mixed with water and fed into a hydrocyclone for classification. The classified sand is returned to step S1 for grinding, and the classified overflow is sent to step S4 for copper sulfide flotation.

[0010] S4. Copper sulfide flotation operation: Calcium oxide, butyl xanthate, butylammonium black powder, and pine oil are added sequentially to the classifying overflow obtained in step S3 for copper sulfide roughing. The roughing concentrate obtained from copper sulfide roughing is then subjected to copper sulfide cleaning. The roughing tailings obtained from copper sulfide roughing are then added sequentially to butyl xanthate, butylammonium black powder, and pine oil for copper sulfide scavenging. The concentrate obtained from copper sulfide cleaning is the copper sulfide concentrate. The cleaning tailings obtained from copper sulfide cleaning and the scavenging concentrate obtained from copper sulfide scavenging are returned to the copper sulfide roughing operation. The scavenging tailings obtained from copper sulfide scavenging are then sent to the copper oxide roughing operation.

[0011] S5. Copper oxide roughing operation: Sulfidating agent, butyl xanthate, butyl ammonium black powder and pine oil are added to the tailings obtained from copper sulfide scavenging in step S4 in sequence, and then copper oxide roughing is carried out. The roughing concentrate obtained from copper oxide roughing is copper oxide concentrate II. The roughing tailings obtained from copper oxide roughing enter the copper oxide enhanced scavenging operation.

[0012] S6. Enhanced copper oxide scavenging: The roughing tailings obtained from the copper oxide roughing in step S5 are sequentially added with activator sodium ethylenediamine phosphate, sulfiding agent, butyl xanthate and butylammonium black powder, and then subjected to enhanced copper oxide scavenging. The scavenging concentrate obtained from the enhanced copper oxide scavenging is copper oxide concentrate three, and the scavenging tailings obtained from the enhanced copper oxide scavenging is the final tailings.

[0013] Furthermore, in step S1, the mass ratio of raw ore to water is 2:1.

[0014] Furthermore, in step S1, the particle size of the product over the sieve is greater than 3 mm, and the particle size of the product under the sieve is less than 3 mm.

[0015] Furthermore, in step S2, the background magnetic field strength is 1.3-1.75T, the pulse frequency is 100-200 times / min, and the magnetic medium is a 5mm rod medium.

[0016] Furthermore, in step S3, the solid-liquid mass ratio between the magnetic separation residue and water is 3:2.

[0017] Furthermore, in step S4, based on the dry weight of each ton of raw ore, in the roughing of copper sulfide, the dosage of calcium oxide is 1000-2000 g / t, the dosage of butyl xanthate is 20-50 g / t, the dosage of butylammonium black is 5-20 g / t, and the dosage of pine oil is 10 g / t; in the scavenging of copper sulfide, the dosage of butyl xanthate is 10 g / t, the dosage of butylammonium black is 5 g / t, and the dosage of pine oil is 5 g / t.

[0018] Furthermore, in step S5, based on the dry weight of each ton of raw ore, the amount of sulfiding agent is 2000-3000 g / t, the amount of butyl xanthate is 50-100 g / t, the amount of butyl ammonium black is 25-50 g / t, and the amount of pine oil is 5-10 g / t.

[0019] Furthermore, in step S6, based on the dry weight of each ton of raw ore, the dosage of sodium ethylenediamine phosphate is 200-500 g / t, the dosage of sulfiding agent is 500-1000 g / t, the dosage of butyl xanthate is 25-50 g / t, and the dosage of butyl ammonium black is 10-30 g / t.

[0020] Further, in steps S5 and S6, the sulfiding agent is a mixture of sodium sulfide and sodium metabisulfite in a mass ratio of 2:1.

[0021] The beneficial effects of this invention are as follows:

[0022] (1) This invention uses strong magnetic separation in the mill classification system to recover some coarse copper oxide particles, which reduces the over-grinding of copper oxide minerals during the grinding process, achieves early recovery, improves the overall recovery rate of copper oxide, and at the same time reduces the release of copper ions during the grinding process, thus mitigating the adverse effects on subsequent copper sulfide flotation.

[0023] (2) The present invention uses sodium sulfide and sodium metabisulfite to form a highly efficient copper oxide sulfiding agent, which enhances the stability of the film during the sulfidation process, strengthens the inhibition of pyrite, and improves the flotation separation efficiency of copper oxide.

[0024] (3) By using efficient reagents and precise control, the present invention directly obtains copper oxide concentrate by opening the cobalt oxide roughing and enhanced scavenging concentrate, thereby reducing the loss of copper metal caused by closed-loop circulation.

[0025] (4) The method of the present invention recovers copper sulfide and copper oxide minerals in sulfur-oxygen mixed copper ore in stages (asynchronous) through magnetic-levitation combination, and strengthens the recovery of fine-grained copper oxide by using a high-efficiency copper oxide modifier, and finally achieves high-efficiency recovery of copper minerals in sulfur-oxygen mixed copper ore, thereby improving resource utilization. Attached Figure Description

[0026] Figure 1 This is a flowchart of the method in Embodiments 1-2 of the present invention. Detailed Implementation

[0027] The present invention will be further described below with reference to the accompanying drawings. It should be noted that this embodiment is based on the present technical solution and provides detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to this embodiment.

[0028] Example 1

[0029] A certain sulfide-oxygen mixed-type copper ore contains 1.53% copper in its raw ore, with a copper oxidation rate of 63.12%. The copper sulfide is mainly composed of chalcocite, while the copper oxide is mainly composed of malachite, chrysocolla, and pseudomalachite. The gangue minerals are primarily quartz and calcite. Due to the high copper oxidation rate, complex types of copper oxide minerals, and high chrysocolla content, the recovery rate of this mine is low.

[0030] This embodiment provides a graded magnetic-levitation combined beneficiation method for sulfur-oxygen mixed copper ore. Experiments were conducted on the aforementioned sulfur-oxygen mixed copper ore, and the process is as follows: Figure 1 As shown. Figure 1 In the diagram, a: 5mm steel rod medium; b: calcium oxide; c: butyl xanthate; d: butyl ammonium black powder; e: pine oil; f: sulfiding agent; g: sodium ethylenediamine phosphate; A: raw ore; B: copper oxide concentrate; C: copper sulfide concentrate; D: tailings.

[0031] The raw ore, crushed to a particle size of -10mm, is fed into a ball mill for grinding. The mill discharge passes through a vibrating screen, and the undersize product with a particle size of less than 3mm is fed into a pulsating high gradient magnetic separator. The background magnetic field strength is 1.75T, the pulsation frequency is 100 times / min, and the magnetic medium is a 5mm rod medium. The result is magnetic concentrate (copper oxide concentrate 1) and magnetic residue.

[0032] The magnetic separation residue is mixed with water at a solid-liquid mass ratio of 3:2 and then fed into a hydrocyclone for classification. The overflow particle size of the classification is -0.074mm, accounting for 65%. The oversize material with a particle size greater than 3mm obtained from the classification sand and vibrating screen is returned to the ball mill for further grinding, and the overflow of the classification enters the copper sulfide flotation operation.

[0033] Add 1000g / t of calcium oxide, 30g / t of butyl xanthate, 15g / t of butylammonium black powder, and 10g / t of pine oil to the staged overflow in sequence for one copper sulfide roughing. The froth from the copper sulfide roughing concentrate enters the copper sulfide cleaning process, and the froth from the copper sulfide cleaning process is the copper sulfide concentrate. Add 10g / t of butyl xanthate, 5g / t of butylammonium black powder, and 5g / t of pine oil to the tailings from the copper sulfide roughing in sequence for one copper sulfide scavenging. The cleaning tailings from the copper sulfide cleaning process and the scavenging concentrate from the copper sulfide scavenging process are returned to the copper sulfide roughing process, and the scavenging tailings from the copper sulfide scavenging process enter the copper oxide roughing process.

[0034] Add 2000g / t of sulfiding agent, 80g / t of butyl xanthate, 40g / t of butylammonium black powder, and 5g / t of pine oil to the tailings obtained from copper sulfide scavenging for a first copper oxide roughing. Add 400g / t of sodium ethylenediamine phosphate, 500g / t of sulfiding agent, 25g / t of butyl xanthate, and 10g / t of butylammonium black powder to the copper oxide roughing tailings for an enhanced copper oxide scavenging. Combine the copper oxide roughing concentrate and the enhanced copper oxide scavenging concentrate to form copper oxide concentrate 2. The enhanced copper oxide scavenging tailings are the final tailings.

[0035] The vulcanizing agent is a mixture of sodium sulfide and sodium metabisulfite in a mass ratio of 2:1.

[0036] The specific process experimental parameters for Example 1 are shown in Table 1.

[0037] Table 1

[0038]

[0039] Example 2

[0040] A certain sulfur-oxygen mixed-type copper ore contains 1.29% copper and has a copper oxidation rate of 48.87%. The copper sulfide is mainly chalcopyrite, while the copper oxide is mainly malachite. The gangue rocks are primarily quartz and feldspar. The ore also has a high sulfur content, reaching 22.78%. Due to the high copper oxidation rate, high sulfur content, and complex grain size distribution, the copper concentrate grade in this mining area is low, and copper-sulfur separation is difficult. The process of this invention was used to conduct experiments on ore samples from this mining area, as shown in Example 2.

[0041] This embodiment provides a graded magnetic-levitation combined beneficiation method for sulfur-oxygen mixed copper ore. Experiments were conducted on the aforementioned sulfur-oxygen mixed copper ore, and the process is as follows: Figure 1 As shown.

[0042] The raw ore, crushed to -10mm, is fed into a ball mill for grinding. The mill discharge passes through a vibrating screen, and the undersize product with a particle size of less than 3mm is fed into a pulsating high gradient magnetic separator. The background magnetic field strength is 1.75T, the pulsation frequency is 100 times / min, and the magnetic medium is a 5mm rod medium. The result is magnetic concentrate (copper oxide concentrate 1) and magnetic residue.

[0043] The magnetic separation residue is mixed with water at a solid-liquid mass ratio of 3:2 and then fed into a hydrocyclone for classification. 70% of the overflow from the classification process has a particle size of -0.074mm. The oversize material with a particle size greater than 3mm obtained from the classification sedimentation and vibrating screen is returned to the ball mill, while the overflow from the classification process enters the copper sulfide flotation operation.

[0044] 2000 g / t of calcium oxide, 20 g / t of butyl xanthate, 10 g / t of butylammonium black powder, and 10 g / t of pine oil are added sequentially to the staged overflow for a first copper sulfide roughing process. The foam from the copper sulfide roughing concentrate enters the copper sulfide cleaning process, and the foam from the copper sulfide cleaning concentrate is the copper sulfide concentrate. 10 g / t of butyl xanthate, 5 g / t of butylammonium black powder, and 5 g / t of pine oil are added sequentially to the copper sulfide roughing tailings for a first copper sulfide scavenging process. The copper sulfide cleaning tailings and copper sulfide scavenging concentrate are returned to the copper sulfide cleaning process, and the copper sulfide scavenging tailings enter the copper oxide roughing process.

[0045] The copper sulfide scavenging tailings are sequentially treated with 3000 g / t of sulfiding agent, 80 g / t of butyl xanthate, 40 g / t of butylammonium black powder, and 5 g / t of pine oil for a primary copper oxide roughing process. The copper oxide roughing tailings are then sequentially treated with 300 g / t of sodium ethylenediamine phosphate, 1000 g / t of sulfiding agent, 25 g / t of butyl xanthate, and 10 g / t of butylammonium black powder for an enhanced copper oxide scavenging process. The copper oxide roughing concentrate and the enhanced copper oxide scavenging concentrate are combined to form copper oxide concentrate 2, and the enhanced copper oxide scavenging tailings are the final tailings. The sulfiding agent is a mixture of sodium sulfide and sodium metabisulfite in a 2:1 mass ratio.

[0046] The specific process experiment parameters for Example 2 are shown in Table 2.

[0047] Table 2

[0048]

[0049] Compared to production targets, the total copper recovery rate of Example 1 increased by 28.84 percentage points, and the total copper recovery rate of Example 2 increased by 27.13 percentage points, showing a significant improvement in recovery rate.

[0050] For those skilled in the art, various corresponding changes and modifications can be made based on the above technical solutions and concepts, and all such changes and modifications should be included within the protection scope of the claims of this invention.

Claims

1. A combined magnetic-flotation method for grading a copper ore of the sulfide-oxide type, characterized in that, The method comprises the following steps: S1, grinding and screening operation: after mixing the crushed raw ore with water, grinding is performed; the grinding discharge is subjected to wet screening, the oversize product is returned to continue grinding, and the undersize product is subjected to pulsed high gradient magnetic separation; S2, magnetic separation operation: the undersize product obtained in step S1 is subjected to pulsed high gradient magnetic separation to obtain a magnetic separation concentrate and a magnetic separation residue, wherein the magnetic separation concentrate is an oxidized copper concentrate I; S3, classification operation: the magnetic separation residue obtained in step S2 is mixed with water and fed into a hydrocyclone for classification, the classified sand return is returned to step S1 for grinding, and the classified overflow is subjected to copper sulfide flotation in step S4; S4, copper sulfide flotation operation: the classified overflow obtained in step S3 is sequentially added with calcium oxide, butyl xanthate, ammonium butyl dithiophosphate and pine oil for copper sulfide roughing, the copper sulfide roughing concentrate is subjected to copper sulfide cleaning, the copper sulfide roughing tailings are sequentially added with butyl xanthate, ammonium butyl dithiophosphate and pine oil for copper sulfide scavenging; the copper sulfide cleaning concentrate is a copper sulfide concentrate, the cleaning tailings and the scavenging concentrate are returned to the copper sulfide roughing operation, and the scavenging tailings are subjected to oxidized copper roughing operation; S5, oxidized copper roughing operation: the scavenging tailings obtained in step S4 are sequentially added with a sulfidizing agent, butyl xanthate, ammonium butyl dithiophosphate and pine oil for oxidized copper roughing, and the roughing concentrate is an oxidized copper concentrate II, and the roughing tailings are subjected to oxidized copper intensive scavenging operation; S6, oxidized copper intensive scavenging operation: the roughing tailings obtained in step S5 are sequentially added with an activator sodium ethylenediamine phosphate, a sulfidizing agent, butyl xanthate and ammonium butyl dithiophosphate for oxidized copper intensive scavenging, the scavenging concentrate is an oxidized copper concentrate III, and the scavenging tailings are final tailings.

2. The method of claim 1, wherein, In step S1, the mass ratio of raw ore to water is 2:

1.

3. The method of claim 1, wherein, In step S1, the particle size of the oversize product is greater than 3 mm, and the particle size of the undersize product is less than 3 mm.

4. The method of claim 1, wherein, In step S2, the magnetic background field strength is 1.3-1.75T, the pulsed frequency is 100-200 times / min, and the magnetic medium is a 5mm rod medium.

5. The method of claim 1, wherein, In step S3, the solid-liquid mass ratio between the magnetic separation residue and water is 3:

2.

6. The method of claim 1, wherein, In step S4, according to the dry ore weight of each ton of raw ore, in the copper sulfide roughing, the dosage of calcium oxide is 1000-2000g / t, the dosage of butyl xanthate is 20-50g / t, the dosage of ammonium butyl dithiophosphate is 5-20g / t, and the dosage of pine oil is 10g / t; in the copper sulfide scavenging, the dosage of butyl xanthate is 10g / t, the dosage of ammonium butyl dithiophosphate is 5g / t, and the dosage of pine oil is 5g / t.

7. The method of claim 1, wherein, In step S5, according to the dry ore weight of each ton of raw ore, the dosage of sulfidizing agent is 2000-3000g / t, the dosage of butyl xanthate is 50-100g / t, the dosage of ammonium butyl dithiophosphate is 25-50g / t, and the dosage of pine oil is 5-10g / t.

8. The method of claim 1, wherein, In step S6, the amount of sodium ethylenediamine phosphate is 200-500 g / t, the amount of sulfidizing agent is 500-1000 g / t, the amount of butyl xanthate is 25-50 g / t, and the amount of butylamine black drug is 10-30 g / t, based on the dry weight of the raw ore per ton of ore.

9. The method of claim 1, wherein, In steps S5 and S6, the sulfidizing agent is a mixture of sodium sulfide and sodium metabisulfite in a mass ratio of 2:1.

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