Classification magnetic-flotation combined beneficiation method for sulfur-oxygen mixed type copper ore

Abstract

The invention discloses a grading magnetic-flotation combined beneficiation method for sulfur-oxygen mixed copper ore. The grading magnetic-flotation combined beneficiation method comprises the steps of ore grinding and screening, magnetic separation, grading, copper sulfide flotation, copper oxide roughing and copper oxide enhanced scavenging. According to the method, strong magnetic separation is adopted in the mill grading system to recover part of coarse-grain copper oxide, excessive grinding of copper oxide minerals in the ore grinding process is reduced, early recovery can be achieved, the comprehensive recovery rate of copper oxide is increased, meanwhile, release of copper ions in the ore grinding process is reduced, and the adverse effect on follow-up copper sulfide flotation is relieved. The efficient copper oxide vulcanizing agent is composed of sodium sulfide and sodium pyrosulfite, the stability of a film in the vulcanizing process is enhanced, meanwhile, the inhibition effect on pyrite is enhanced, and the flotation separation efficiency of copper oxide is improved. In addition, by adopting an efficient reagent and precise regulation and control, copper oxide concentrate is directly obtained through open circuit of copper oxide roughing and enhanced scavenging concentrate, and the copper metal falling loss caused by closed cycle is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of mineral processing, and in particular to a classification magnetic-flotation combined beneficiation method for sulfur-oxygen mixed copper ore. Background Art

[0002] About 10%-15% of the world's copper resources are oxidized copper ores and mixed copper ores, which are important copper mineral resources. For high-grade oxidized copper ores, leaching processes are generally used for recovery. With the continuous exploitation of sulfide copper ore resources, the proportion of mixed copper ore and low-grade oxidized copper ore resources continues to expand. It is of great significance to develop green and efficient beneficiation processes. In sulfide-oxygen mixed copper ores, a step-by-step flotation process is often used to first obtain copper sulfide concentrate, and then sulfide flotation is used to recover oxidized copper minerals from tailings, thereby realizing the comprehensive utilization of resources. However, in actual production, the recovery efficiency of copper oxide by single flotation is low. On the one hand, the floatability of copper oxide itself is poor, and the recovery rate of sulfide flotation is limited. On the other hand, most of the oxidized copper minerals are brittle and easily over-crushed during the grinding process, resulting in extremely low recovery rate of copper oxide in mixed copper ores. In sulfide-oxygen mixed copper ores, the release of copper ions from oxidized copper minerals during the grinding process deteriorates the flotation environment, resulting in poor flotation indicators of copper sulfide.

[0003] Therefore, developing a mineral processing technology with good separation effect and strong adaptability will help to improve the comprehensive copper recovery rate of sulfur-oxygen mixed copper ore and improve the utilization level of this type of mineral resources. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide a classification magnetic-flotation combined beneficiation method for sulfur-oxygen mixed copper ore.

[0005] In order to achieve the above object, the present invention adopts the following technical solution:

[0006] A method for classifying magnetic-flotation combined beneficiation of sulfur-oxygen mixed copper ore, comprising the following steps:

[0007] S1. Grinding and screening: The crushed raw ore is mixed with water and then ground; the grinding discharge enters the wet screening, the screened product is returned for further grinding, and the screened product enters the pulsating high gradient magnetic separator;

[0008] S2, magnetic separation operation: the undersize product obtained in step S1 is subjected to magnetic separation by a pulsating high gradient magnetic separator to obtain a magnetic separation concentrate and a magnetic separation residue, wherein the magnetic separation concentrate is a 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 obtained classified sand is returned to step S1 for grinding, and the obtained classified overflow enters step S4 for copper sulfide flotation;

[0010] S4, copper sulfide flotation operation: calcium oxide, butyl xanthate, butyl ammonium nitropropane and pine oil are sequentially added to the classified overflow obtained in step S3, and then copper sulfide roughing is carried out; the roughing concentrate obtained from the copper sulfide roughing is subjected to copper sulfide cleaning; butyl xanthate, butyl ammonium nitropropane and pine oil are sequentially added to the roughing tailings obtained from the copper sulfide roughing, and then copper sulfide scavenging is carried out; the concentrate obtained from the copper sulfide cleaning is the copper sulfide concentrate, the cleaned tailings obtained from the copper sulfide cleaning and the scavenged concentrate obtained from the copper sulfide scavenging are returned to the copper sulfide roughing operation together, and the scavenged tailings obtained from the copper sulfide scavenging enter the copper oxide roughing operation;

[0011] S5, copper oxide roughing operation: adding sulfiding agent, butyl xanthate, butyl ammonium black medicine and pine oil to the scavenging tailings obtained from the copper sulfide scavenging in step S4 in sequence, and then performing copper oxide roughing. The roughing concentrate obtained from the copper oxide roughing is the copper oxide concentrate II. The roughing tailings obtained from the copper oxide roughing enter the copper oxide enhanced scavenging operation;

[0012] S6, copper oxide enhanced scavenging operation: the roughing tailings obtained by the copper oxide roughing in step S5 are sequentially added with an activator, sodium ethylenediamine phosphate, a sulfiding agent, butyl xanthate and butyl ammonium black medicine, and then copper oxide enhanced scavenging is performed. The scavenged concentrate obtained by the enhanced scavenging of copper oxide is copper oxide concentrate III, and the scavenged tailings obtained by the enhanced scavenging of copper oxide are the final tailings.

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

[0014] Furthermore, in step S1, the particle size of the product on 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 magnetic separation background field strength is 1.3-1.75 T, the pulsation frequency is 100-200 times / min, and the magnetic medium is a 5 mm rod medium.

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

[0017] Further, in step S4, based on the dry ore weight per ton of raw ore, in the roughing of copper sulfide, the amount of calcium oxide is 1000-2000 g / t, the amount of butyl xanthate is 20-50 g / t, the amount of butyl ammonium black medicine is 5-20 g / t, and the amount of pine oil is 10 g / t; in the scavenging of copper sulfide, the amount of butyl xanthate is 10 g / t, the amount of butyl ammonium black medicine is 5 g / t, and the amount 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 used is 2000-3000 g / t, the amount of butyl xanthate used is 50-100 g / t, the amount of butyl ammonium black medicine used is 25-50 g / t, and the amount of pine oil used is 5-10 g / t.

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

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

[0021] The beneficial effects of the present invention are:

[0022] (1) The present invention adopts strong magnetic separation in the mill classification system to recover part of the coarse copper oxide, thereby reducing the over-grinding of the copper oxide minerals during the grinding process, achieving early recovery, and improving the comprehensive recovery rate of copper oxide. At the same time, the release of copper ions during the grinding process is reduced, thereby reducing the adverse effect on the subsequent flotation of copper sulfide.

[0023] (2) The present invention uses sodium sulfide and sodium pyrosulfite to form a high-efficiency copper oxide sulfiding agent, which enhances the stability of the film during the sulfidation process, while enhancing the inhibitory effect on pyrite and improving the flotation separation efficiency of copper oxide.

[0024] (3) The present invention adopts high-efficiency reagents and precise control to directly obtain copper oxide concentrate by opening the copper oxide roughing and enhanced scavenging concentrate, thereby reducing the copper metal drop loss caused by closed-loop circulation.

[0025] (4) The method of the present invention recovers copper sulfide and copper oxide minerals in the sulfur-oxygen mixed copper ore in stages (asynchronously) by magnetic-flotation combination, and uses a high-efficiency copper oxide regulator to enhance the recovery of fine-grained copper oxide, thereby ultimately achieving efficient recovery of copper minerals in the sulfur-oxygen mixed copper ore and improving resource utilization. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a flow chart of the method of Embodiment 1-2 of the present invention. DETAILED DESCRIPTION

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

[0028] Example 1

[0029] A certain sulfur-oxygen mixed copper mine has a copper content of 1.53% in the original ore and a copper oxidation rate of 63.12%. The copper sulfide is mainly chalcocite, the copper oxide is mainly malachite, chrysocolla and pseudomalachite, and the gangue is mainly quartz, calcite, etc. The mining area has a high copper oxidation rate, complex types of copper oxide minerals, and a high content of chrysocolla, resulting in a low recycling rate.

[0030] This embodiment provides a classification magnetic-flotation combined beneficiation method for sulfur-oxygen mixed copper ore. The above sulfur-oxygen mixed copper ore is tested. The process is as follows: Figure 1 shown. Figure 1 In the figure, a: 5mm steel rod medium; b: calcium oxide; c: butyl xanthate; d: butyl ammonium xanthate; e: pine oil; f: vulcanizing 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 ore discharged from the mill is passed through a vibrating screen, and the undersize product with a particle size of less than 3mm is fed into a pulsating high-gradient strong magnetic separator. The background magnetic field strength is 1.75T, the pulsation frequency is 100 times / min, and the magnetic medium uses a 5mm rod medium to obtain a magnetic concentrate (copper oxide concentrate 1) and a magnetic residue.

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

[0033] 1000 g / t of calcium oxide, 30 g / t of butyl xanthate, 15 g / t of butyl ammonium black powder and 10 g / t of pine oil are added to the classification overflow in sequence to carry out a copper sulfide roughing selection. The copper sulfide roughing concentrate foam enters the copper sulfide concentration, and the concentrate foam obtained by the copper sulfide concentration is the copper sulfide concentrate; 10 g / t of butyl xanthate, 5 g / t of butyl ammonium black powder and 5 g / t of pine oil are added to the copper sulfide roughing tailings in sequence to carry out a copper sulfide scavenging selection. The selected tailings obtained by the copper sulfide concentration and the scavenged concentrate obtained by the copper sulfide scavenging are returned to the copper sulfide roughing selection, and the scavenged tailings obtained by the copper sulfide scavenging enter the copper oxide roughing operation.

[0034] To the scavenging tailings obtained from copper sulfide scavenging, 2000 g / t of sulfiding agent, 80 g / t of butyl xanthate, 40 g / t of butyl ammonium black medicine and 5 g / t of pine oil were added in sequence to carry out a primary copper oxide roughing. To the copper oxide roughing tailings, 400 g / t of sodium ethylenediamine phosphate, 500 g / t of sulfiding agent, 25 g / t of butyl xanthate and 10 g / t of butyl ammonium black medicine were added in sequence to carry out copper oxide enhanced scavenging. The copper oxide roughing concentrate and the copper oxide enhanced scavenging concentrate were combined into copper oxide concentrate 2, and the copper oxide enhanced scavenging tailings were the final tailings.

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

[0036] Example 1 Specific process experimental indicators are shown in Table 1.

[0037] Table 1

[0038]

[0039] Example 2

[0040] A certain sulfur-oxygen mixed copper ore, the original ore contains 1.29% copper, the copper oxidation rate is 48.87%, wherein the copper sulfide is mainly chalcopyrite, the copper oxide ore is mainly malachite, the gangue is mainly quartz and feldspar, and the original ore contains high sulfur, reaching 22.78%. Due to the high copper oxidation rate, high sulfur content, and complex embedded particle size, the copper concentrate grade is low and the separation of copper and sulfur is difficult. The ore sample of the mining area was tested by the process of the present invention, as shown in Example 2.

[0041] This embodiment provides a classification magnetic-flotation combined beneficiation method for sulfur-oxygen mixed copper ore. The above sulfur-oxygen mixed copper ore is tested. The process is as follows: Figure 1 shown.

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

[0043] The residue from magnetic separation is mixed with water at a solid-liquid mass ratio of 3:2 and then fed into a hydrocyclone for classification. The fineness of the classified overflow is -0.074mm, accounting for 70%. The materials on the screen with a particle size greater than 3mm obtained by the classified sand settling and vibrating screen are returned to the ball mill, and the classified overflow enters the copper sulfide flotation operation.

[0044] 2000 g / t of calcium oxide, 20 g / t of butyl xanthate, 10 g / t of butyl ammonium black powder and 10 g / t of pine oil are sequentially added to the classification overflow to carry out a copper sulfide roughing operation. The copper sulfide roughing concentrate foam enters the copper sulfide concentration operation. The copper sulfide concentration concentrate foam is the copper sulfide concentrate. 10 g / t of butyl xanthate, 5 g / t of butyl ammonium black powder and 5 g / t of pine oil are sequentially added to the copper sulfide roughing tailings to carry out a copper sulfide scavenging operation. The copper sulfide concentration tailings and the copper sulfide scavenging concentrate are returned to the copper sulfide concentration operation. The copper sulfide scavenging tailings enter the copper oxide roughing operation.

[0045] To the copper sulfide scavenging tailings, 3000 g / t of sulfiding agent, 80 g / t of butyl xanthate, 40 g / t of butyl ammonium black medicine, and 5 g / t of pine oil were added in sequence to perform a copper oxide roughing, and 300 g / t of sodium ethylenediamine phosphate, 1000 g / t of sulfiding agent, 25 g / t of butyl xanthate, and 10 g / t of butyl ammonium black medicine were added in sequence to the copper oxide roughing tailings to perform copper oxide enhanced scavenging, and the copper oxide roughing concentrate and the copper oxide enhanced scavenging concentrate were combined into copper oxide concentrate 2, and the copper oxide enhanced scavenging tailings were the final tailings. The sulfiding agent is a mixture of sodium sulfide and sodium pyrosulfite in a mass ratio of 2:1.

[0046] The specific process experimental indicators of Example 2 are shown in Table 2.

[0047] Table 2

[0048]

[0049] Compared with the production index, 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, and the recovery rate was significantly improved.

[0050] For those skilled in the art, various corresponding changes and modifications can be made according to the above technical solutions and concepts, and all of these changes and modifications should be included in the protection scope of the claims of the present invention.

Claims

1. A method for classifying magnetic-flotation combined beneficiation of sulfur-oxygen mixed copper ore, characterized in that: The following steps are involved: S1. Grinding and screening: The crushed raw ore is mixed with water and then ground; the grinding discharge enters the wet screening, the screened product is returned for further grinding, and the screened product enters the pulsating high gradient magnetic separator; S2, magnetic separation operation: the undersize product obtained in step S1 is subjected to magnetic separation by a pulsating high gradient magnetic separator to obtain a magnetic separation concentrate and a magnetic separation residue, wherein the magnetic separation concentrate is a copper oxide concentrate. S3, classification operation: the magnetic separation residue obtained in step S2 is mixed with water and fed into a hydrocyclone for classification, the obtained classified sand is returned to step S1 for grinding, and the obtained classified overflow enters step S4 for copper sulfide flotation; S4, copper sulfide flotation operation: calcium oxide, butyl xanthate, butyl ammonium nitropropane and pine oil are sequentially added to the classified overflow obtained in step S3, and then copper sulfide roughing is carried out; the roughing concentrate obtained from the copper sulfide roughing is subjected to copper sulfide cleaning; butyl xanthate, butyl ammonium nitropropane and pine oil are sequentially added to the roughing tailings obtained from the copper sulfide roughing, and then copper sulfide scavenging is carried out; the concentrate obtained from the copper sulfide cleaning is the copper sulfide concentrate, the cleaned tailings obtained from the copper sulfide cleaning and the scavenged concentrate obtained from the copper sulfide scavenging are returned to the copper sulfide roughing operation together, and the scavenged tailings obtained from the copper sulfide scavenging enter the copper oxide roughing operation; S5, copper oxide roughing operation: adding sulfiding agent, butyl xanthate, butyl ammonium black medicine and pine oil to the scavenging tailings obtained from the copper sulfide scavenging in step S4 in sequence, and then performing copper oxide roughing. The roughing concentrate obtained from the copper oxide roughing is the copper oxide concentrate II. The roughing tailings obtained from the copper oxide roughing enter the copper oxide enhanced scavenging operation; S6, copper oxide enhanced scavenging operation: the roughing tailings obtained by the copper oxide roughing in step S5 are sequentially added with an activator, sodium ethylenediamine phosphate, a sulfiding agent, butyl xanthate and butyl ammonium black medicine, and then copper oxide enhanced scavenging is performed. The scavenged concentrate obtained by the enhanced scavenging of copper oxide is copper oxide concentrate III, and the scavenged tailings obtained by the enhanced scavenging of copper oxide are the final tailings.

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

1.

3. The method according to claim 1, characterized in that In step S1, the particle size of the product on the sieve is greater than 3 mm, and the particle size of the product under the sieve is less than 3 mm.

4. The method according to claim 1, characterized in that: In step S2, the background field strength of the magnetic separation is 1.3-1.75 T, the pulsation frequency is 100-200 times / min, and the magnetic medium is a 5 mm rod medium.

5. The method according to claim 1, characterized in that In step S3, the solid-liquid mass ratio between the magnetic separation residue and water is 3:

2.

6. The method according to claim 1, characterized in that In step S4, based on the dry ore weight per ton of raw ore, in the roughing of copper sulfide, the amount of calcium oxide is 1000-2000 g / t, the amount of butyl xanthate is 20-50 g / t, the amount of butyl ammonium black medicine is 5-20 g / t, and the amount of pine oil is 10 g / t; in the scavenging of copper sulfide, the amount of butyl xanthate is 10 g / t, the amount of butyl ammonium black medicine is 5 g / t, and the amount of pine oil is 5 g / t.

7. The method according to claim 1, characterized in that In step S5, based on the dry weight of each ton of raw ore, the amount of sulfiding agent used is 2000-3000 g / t, the amount of butyl xanthate used is 50-100 g / t, the amount of butyl ammonium black medicine used is 25-50 g / t, and the amount of pine oil used is 5-10 g / t.

8. The method according to claim 1, characterized in that: In step S6, based on the dry weight of each ton of raw ore, the amount of ethylenediamine sodium phosphate is 200-500 g / t, the amount of vulcanizing agent is 500-1000 g / t, the amount of butyl xanthate is 25-50 g / t, and the amount of butyl ammonium black medicine is 10-30 g / t.

9. The method according to claim 1, characterized in that: In steps S5 and S6, the vulcanizing agent is a mixture of sodium sulfide and sodium metabisulfite in a mass ratio of 2:1.

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