A method for deep sulfidation of complex copper-lead-zinc oxide surfaces enhanced by synergistic enhancement of mechanochemical and coordination chemistry, and its application.

Abstract

This invention belongs to the field of mineral processing, and specifically relates to a method and application of deep sulfidation on the surface of complex copper-lead-zinc oxide minerals enhanced by a synergistic combination of mechanochemical and coordination chemistry. This invention utilizes a novel combination of copper-ammonia complex ions and ethylenediamine phosphate as activators, combined with ball milling, to facilitate deeper sulfidation on the surface of copper-lead-zinc oxide minerals. This technology, when combined with subsequent flotation reagent formulations, significantly improves copper recovery when applied to the flotation of copper oxide ores. This invention features a rationally designed composition, a simple and controllable preparation process, high recovery rate, and is suitable for industrial application.

Description

Technical Field

[0001] This invention belongs to the field of mineral processing, and in particular relates to a method and application of deep sulfidation on the surface of complex copper-lead-zinc oxide minerals enhanced by synergistic enhancement of mechanochemistry and coordination chemistry. background

[0002] Copper is an important natural resource, widely used in power, construction, engineering, and chemical industries due to its excellent electrical and thermal conductivity and corrosion resistance. It plays a crucial role in modern society, supporting the development of various critical infrastructures and technologies. Copper is widely distributed in the Earth's crust, typically existing as oxide ores and sulfide ores. China is one of the world's largest copper producers, possessing abundant copper resources. Despite its rich copper resources, China's high dependence on imports, particularly for copper ore and concentrate, is due to rapid growth in domestic demand. Therefore, the development and utilization of its vast oxide ores is of great importance. The clean and efficient utilization of these complex oxide copper ores is of significant strategic importance for ensuring my country's economic development and resource security. Due to the complex composition, low grade, high impurity content, and fine particle size of my country's oxide copper ores, traditional gravity and magnetic separation methods are ineffective, while flotation is the most effective method for processing complex oxide copper ores. In recent years, flotation separation practices for complex oxide copper ores have mainly addressed these challenges through changes in flotation processes and reagents, achieving good progress. Methods for flotating oxidized copper ores can be categorized into direct flotation, sulfide flotation, amine flotation, and chelating agent-neutral oil flotation. Currently, the sulfide effect is the most critical factor directly affecting the flotation effect of oxidized copper ores, as sulfide formation on the mineral surface creates a hydrophobic layer that significantly enhances floatability. However, research indicates that the hydrophobic film formed by directly adding sulfide reagents to the pulp is unstable, especially during flotation agitation, and tends to detach, thus affecting flotation efficiency. Therefore, it is crucial to consider surface activation treatment before adding sulfide agents. Commonly used oxidized copper ore activators include copper sulfate, copper chloride, ammonium sulfate, and ethylenediamine phosphate, but all have drawbacks such as high recovery rates, low surface activation levels, and poor collection effects. Therefore, it is necessary to find new activators to enhance flotation. Furthermore, current surface activation processes primarily occur before pulp flotation, often resulting in insufficient surface activation, necessitating updates and iterations to the activation process.

[0003] In view of the shortcomings of the current technology, the purpose of this invention is to provide a new type of copper oxide ore activator, and at the same time improve the activation process, so as to enhance the sulfidation process on the surface of copper oxide ore and improve the concentrate flotation recovery rate. Summary of the Invention

[0004] The technical problem to be solved by this invention is to overcome the insufficient activity and defects of existing copper oxide ore activators. By combining the development of new activators with the improvement of activation processes, complementary advantages can be formed to enhance the sulfidation process on the mineral surface, thereby improving the concentrate recovery rate.

[0005] This invention discloses a method for deep sulfidation of complex copper-lead-zinc oxide minerals with synergistic enhancement of mechanochemical and coordination chemistry, comprising the following steps:

[0006] The copper oxide ore is crushed to the grinding size and then fed into a mill for grinding. An activator is added during the grinding process to carry out a co-grinding reaction.

[0007] Alternatively, the activator and the combined sulfiding agent can be added together during the grinding process to form co-grinding, which can perform deep sulfidation while activating the surface. The combined sulfiding agent is composed of sodium sulfide and sodium polysulfide.

[0008] After grinding, the mass percentage of -74μm in copper oxide ore is 70-90%.

[0009] The activator is composed of copper ammonia complex ions and ethylenediamine phosphate; during grinding, the rotation speed is controlled at 100-200 r / min, preferably 120-200 r / min, and more preferably 150-200 r / min, and the time is greater than or equal to 10 min.

[0010] This invention targets common copper oxide ores (including but not limited to malachite, chrysocolla, azurite, and cuprite). By adding a novel activator (a specific combination of copper ammonia complex ions and ethylenediamine phosphate) to the slurry, the hydrophilic film on the mineral surface is broken, increasing the number of copper sites. The sulfide film formed after adding the sulfiding agent is more stable and has enhanced floatability, thereby improving the recovery rate. The preparation of copper ammonia complex ions mainly involves mixing ammonia water with copper salts (including but not limited to various soluble copper salts and copper oxide minerals), and then adjusting the pH to approximately 6-8.

[0011] In industrial applications, concentrated ammonia (concentration of 8-12 mol / L) can be mixed with a copper source (including but not limited to various soluble copper salts and copper oxide minerals), and then the pH value can be adjusted to about 6-8 to obtain the desired result.

[0012] Alternatively, concentrated ammonia water can be mixed with high-purity copper oxide ore at a ratio of 10-20 mL: 3-5 g to obtain a copper ammonia complex ion solution.

[0013] In practical use, the concentration of the ethylenediamine phosphate solution can be controlled at 0.05-0.07 mol / L. A novel activator can be obtained by mixing the prepared copper ammonia complex ion solution with the ethylenediamine phosphate solution at a volume ratio of 3-5:1-2, preferably 3-5:1.

[0014] In industrial applications, the grinding time is 10-20 minutes, and the mill used is a wet ball mill. The grinding media material is steel balls or corundum, with a ratio of large to small steel balls of 5:1 (large balls with a diameter of 1-2 cm and small balls with a diameter of 3-6 mm). The ball-to-material mass ratio is 5-7:1, and the volume of grinding balls and ore sample is 40%-60% of the volume of the ball mill jar. The amount of novel activator added during co-grinding is 100-220 g / t, preferably 180-220 g / t, and more preferably 190-210 g / t.

[0015] This invention addresses the problems of insufficient and unstable surface activation in current methods by improving the activation process to achieve sulfidation strengthening of mineral surfaces. Specifically, a novel activator is added during the grinding of copper oxide minerals to form a co-grinding process. Under appropriate parameters, the novel activator achieves more thorough contact with the mineral surface. Furthermore, as grinding progresses, active sites are continuously exposed on the mineral surface, which facilitates the adhesion of the novel activator and achieves enhanced activation.

[0016] This invention relates to the application of a deep sulfidation method on the surface of complex copper-lead-zinc oxide minerals, which is enhanced by a combination of mechanochemical and coordination chemical methods.

[0017] Copper oxide ore is crushed to the grinding particle size and then fed into a mill for grinding. An activator is added during the grinding process to induce a co-grinding reaction. After grinding, the mass percentage of -74μm particles in the copper oxide ore is 70-90%. The activator consists of copper ammonia complex ions and ethylenediamine phosphate. During grinding, the rotation speed is controlled at 100-200 r / min, preferably 120-200 r / min, and more preferably 150-200 r / min, for a time of ≥10 min. After grinding, the slurry is adjusted to a mass percentage concentration of 25%-40%, and then a combination of sulfiding agent, a combination of collector, a combination of depressant, and a frother is added sequentially for flotation to obtain copper concentrate.

[0018] or

[0019] Copper oxide ore is crushed to the grinding particle size and then fed into a mill for grinding. During the grinding process, an activator and a combined sulfiding agent are added for co-grinding. After grinding, the mass percentage of -74μm particles in the copper oxide ore is 70-90%. The activator consists of copper ammonia complex ions and ethylenediamine phosphate. During grinding, the rotation speed is controlled at 100-200 r / min, preferably 120-200 r / min, and more preferably 150-200 r / min, for a time of ≥10 min. After grinding, the slurry is adjusted to a mass percentage concentration of 25%-40%, and then a combined collector, a combined depressant, and a frother are added sequentially for flotation to obtain copper concentrate.

[0020] The combined collector is obtained by combining ethyl xanthate, butyl xanthate and benzohydroxyxamic acid in a mass ratio of 5:3:1;

[0021] The combined inhibitor is obtained by combining water glass, sodium hexametaphosphate and carboxymethyl cellulose in a mass ratio of 1:1:3;

[0022] The combined vulcanizing agent is obtained by combining sodium sulfide and sodium polysulfide in a mass ratio of 2:1; the foaming agent is selected from at least one of No. 2 oil and pine oil.

[0023] In this invention, the composition and dosage of the novel activator have a crucial impact on the copper recovery rate. As a preferred embodiment, the amount of novel activator added during the co-grinding reaction is 180-220 g / t, and more preferably 190-210 g / t. The preparation of the novel activator with this dosage is as follows: concentrated ammonia water and copper oxide are mixed at a ratio of 10-20 mL: 3-5 g to obtain a copper-ammonia complex ion solution; and the concentration of the ethylenediamine phosphate solution is controlled at 0.05-0.07 mol / L. The prepared copper-ammonia complex ion solution and the ethylenediamine phosphate solution are mixed at a volume ratio of 3-5:1 (optimal is 3:1) to obtain the novel activator.

[0024] This invention relates to an application of a method for deep sulfidation of complex copper-lead-zinc oxide minerals with synergistic enhancement of mechanochemical and coordination chemistry, wherein 400-800g, preferably 500-750g, of a combined collector is added to 1 ton of raw ore; more preferably 600-750g.

[0025] This invention relates to an application of a method for deep sulfidation of complex copper-lead-zinc oxide minerals with synergistic enhancement of mechanochemical and coordination chemistry, wherein 800-1200g of combined inhibitors are added to 1 ton of raw ore, preferably 900-1100g; and more preferably 1000-1100g.

[0026] This invention relates to an application of a deep sulfidation method for the surface of complex copper-lead-zinc oxide minerals that is synergistically enhanced by mechanochemical and coordination chemistry. The method involves adding 500-1200g of a combined sulfiding agent per ton of raw ore, preferably 800-1200g, and more preferably 1000-1200g.

[0027] Principles and advantages

[0028] To address the issues of insufficient surface activation and inadequate sulfidation in the flotation of copper oxide ore, this study develops novel activators and combines them with mechanical and chemical regulation during grinding to enhance mineral surface sulfidation treatment, thereby improving floatability and recovery rates. During grinding, the mineral surface is continuously subjected to stress and breakage, generating new exposed surfaces and active sites. The addition of the novel activator at this point, due to the continuous grinding process, allows it to continuously adhere to and interact with the mineral surface. Simultaneously, as grinding progresses, the specific surface area of ​​the mineral increases, further increasing the probability of contact with the activator. This disrupts the hydrophilic film on the mineral surface, forming a copper ion activation layer, providing numerous copper sites for subsequent surface-enhanced sulfidation. This facilitates the formation of the surface sulfidation film and creates favorable conditions for subsequent collector collection.

[0029] This invention addresses the problems of low activation efficiency and poor recovery rate of single copper oxide ore activators by innovatively developing a combined activator for activating the surface of copper oxide minerals. The copper-ammonia complex ions increase the number of copper sites on the mineral surface, providing numerous sites for subsequent enhanced sulfidation treatment and improving the stability of surface sulfidation. Furthermore, ethylenediamine phosphate inhibits the floating of slime in the slurry while simultaneously activating sulfide minerals, further enhancing the activation effect. The combination of these two components creates a complementary advantage, significantly improving the activation effect on the surface of copper oxide minerals.

[0030] Current activator addition processes mainly focus on the stage before slurry flotation. However, since the particle size in the slurry is already determined at this stage, i.e., the contact sites are fixed, and the activation time is limited, problems such as insufficient surface activation may occur. To address this, mechanical grinding and chemical regulation are employed, where a combination of activators is co-ground with copper oxide ore to achieve coordination regulation of the activator during the grinding process, thereby enhancing activation. Attached Figure Description

[0031] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0032] In the example:

[0033] Combined collector: Ethyl xanthate, butyl xanthate and benzohydroxyxamic acid are combined in a mass ratio of 5:3:1;

[0034] Combination inhibitor: Water glass, sodium hexametaphosphate, and carboxymethyl cellulose are combined in a mass ratio of 1:1:3;

[0035] Combined vulcanizing agent: Sodium sulfide and sodium polysulfide are combined in a mass ratio of 2:1;

[0036] Foaming agent: One of the following: No. 2 oil or pine oil.

[0037] The experiment explored the following:

[0038] Example 1

[0039] Preparation of copper-ammonia complex sulfide activator: A 10 mol / L concentrated ammonia solution was prepared. The concentrated ammonia solution was mixed with high-purity copper oxide ore at a volume ratio of 20 mL:3 g, and leached to obtain a copper-ammonia complex ion solution. Furthermore, a 0.05 mol / L ethylenediamine phosphate solution was prepared. The prepared copper-ammonia complex ion solution was mixed with the 0.05 mol / L ethylenediamine phosphate solution at a volume ratio of 3:1 to prepare a novel activator.

[0040] 2.0 g of copper oxide ore (particles with a size of -74 μm, accounting for approximately 80% of all particles by mass) was weighed and poured into a flotation cell. 30 mL of deionized water was added, and the slurry was stirred and adjusted for 1 min to bring the pH of the slurry to 6.5. Two experimental groups were set up: the experimental group added 1 mL of a novel activator solution, and the control group added the same amount of copper ammonia complex ion solution. The reaction time was 3 min. Then, 0.4 mL (2 mg of combined sulfiding agent, i.e., 1000 g / t) of combined sulfiding agent and 0.8 mL (1.2 mg of combined collector, i.e., 600 g / t) of combined collector were added sequentially, along with 1 μL of terpineol. The sulfidation and collecting reaction times were both 3 min, the frother reaction time was 1 min, and the frothing time was 4 min. The resulting flotation concentrate was then dried in a 50℃ oven. After drying, the concentrate weight was measured, and the recovery rate was calculated. The results are shown in the table below.

[0041] Table 1 Recovery rate of Example 1

[0042] Add new activator Recovery rate / % Adding copper ammonia complex ions Recovery rate / % Concentrate 91.5％ Concentrate 82.1％

[0043] The results showed that the flotation recovery rate using the new activator was significantly higher, reaching 92.5%, compared with that of a single activator. This indicates that the new activator has a better activation effect and can better enhance the floatability of minerals.

[0044] Example 2

[0045] Preparation of copper-ammonia complex sulfide activator: A 10 mol / L concentrated ammonia solution was prepared. The concentrated ammonia solution was mixed with high-purity copper oxide ore at a volume ratio of 20 mL:3 g, and leached to obtain a copper-ammonia complex ion solution. Furthermore, a 0.05 mol / L ethylenediamine phosphate solution was prepared. The prepared copper-ammonia complex ion solution was mixed with the 0.05 mol / L ethylenediamine phosphate solution at a volume ratio of 3:1 to prepare a novel activator.

[0046] 2.0 g of copper oxide ore (particles with a size of -74 μm, accounting for approximately 80% of all particles by mass) was weighed and poured into a flotation cell. 30 mL of deionized water was added, and the slurry was stirred and adjusted for 1 min to bring the pH of the slurry to 6.5. Two experimental groups were set up: the experimental group added 1 mL of a novel activator solution, and the control group added the same amount of ethylenediamine phosphate solution. The reaction time was 3 min. Then, 0.4 mL (2 mg of combined sulfiding agent, i.e., 1000 g / t) of combined sulfiding agent and 0.8 mL (1.2 mg of combined collector, i.e., 600 g / t) of combined collector were added sequentially, along with 1 μL of terpineol. The sulfidation and collecting reaction times were both 3 min, the frother reaction time was 1 min, and the frothing time was 4 min. The resulting flotation concentrate was then dried in a 50℃ oven. After drying, the concentrate weight was measured, and the recovery rate was calculated. The results are shown in the table below.

[0047] Table 2 Recovery rate of Example 2

[0048] Add new activator Recovery rate / % Add ethylenediamine phosphate Recovery rate / % Concentrate 91.8％ Concentrate 75.4％

[0049] The results showed that, compared with a single activator, the flotation recovery rate using the new activator was significantly higher, reaching 91.8%, which is 16.4 percentage points higher. This indicates that the new activator has a better activation effect and can better enhance the floatability of minerals.

[0050] Example 3

[0051] Preparation of copper-ammonia complex sulfide activator: A 10 mol / L concentrated ammonia solution was prepared. The concentrated ammonia solution was mixed with high-purity copper oxide ore at a volume ratio of 20 mL:3 g, and leached to obtain a copper-ammonia complex ion solution. Furthermore, a 0.05 mol / L ethylenediamine phosphate solution was prepared. The prepared copper-ammonia complex ion solution was mixed with the 0.05 mol / L ethylenediamine phosphate solution at a volume ratio of 3:1 to prepare a novel activator.

[0052] Weigh 2.0g of copper oxide ore (particles with a size of -74μm, accounting for about 80% of all particles by mass) and pour it into a flotation cell. Add 30mL of deionized water and stir for 1min to adjust the slurry pH to 6.5. Two groups of experiments were set up. The experimental group was after the grinding machine was activated (grinding time was 15min, rotation speed was 150r / min, the mill used was a wet ball mill, the grinding media material was steel balls, the ratio of large steel balls to small steel balls was 5:1 (large balls with a diameter of 2cm and small balls with a diameter of 5mm), the ball-to-material ratio was 5:1, the volume of grinding balls and ore sample filled was 40% of the volume of the ball mill jar, and the amount of new activator added during the co-grinding reaction was 200g / t). The control group received the same amount of the novel activator, but without grinding mechanochemical regulation. The reaction time was 3 min. Then, 0.4 mL (2 mg of combined sulfiding agent, i.e., 1000 g / t) of combined sulfiding agent and 0.8 mL (1.2 mg of combined collector, i.e., 600 g / t) of combined collector were added sequentially, along with 1 μL of terpineol. The sulfidation and collecting reaction times were both 3 min, the frother reaction time was 1 min, and the frothing time was 4 min. The resulting flotation concentrate was then dried in an oven at 50℃. After drying, the concentrate was weighed, and the recovery rate was calculated. The results are shown in the table below.

[0053] Table 3 Recovery rate of Example 3

[0054]

[0055] The results showed that the flotation recovery rate was higher (94.7%) with the addition of an activator to the grinding mechanical chemical regulation compared to the method without grinding mechanical chemical regulation. This indicates that adding a novel activator to the grinding mechanical chemical regulation further enhances the activation effect and improves the floatability of minerals.

[0056] Example 4

[0057] The other conditions are the same as in Example 3, except that the prepared copper ammonia complex ion solution is mixed with 0.05 mol / L ethylenediamine phosphate solution at a volume ratio of 5:1 to prepare a novel activator.

[0058] The results after flotation are shown in the table below:

[0059] Table 4 Recovery rate of Example 4

[0060] Novel activator (5:1) Recovery rate % Concentrate 91.2％

[0061] Example 5

[0062] The other conditions are the same as in Example 3, except that the prepared copper ammonia complex ion solution is mixed with 0.05 mol / L ethylenediamine phosphate solution at a volume ratio of 5:2 to prepare a novel activator.

[0063] The results after flotation are shown in the table below:

[0064] Table 5 Recovery rate of Example 5

[0065] Novel activator (5:2) Recovery rate % Concentrate 89.7％

[0066] Example 6

[0067] The other conditions are the same as in Example 3, except that the prepared copper ammonia complex ion solution is mixed with 0.05 mol / L ethylenediamine phosphate solution at a volume ratio of 3:2 to prepare a novel activator.

[0068] The results after flotation are shown in the table below:

[0069] Table 6 Recovery rate of Example 6

[0070] Novel activator (3:2) Recovery rate % Concentrate 86.2％

[0071] Example 7

[0072] Other conditions are the same as in Example 3, except that: the grinding time is 20 min, the rotation speed is 100 r / min, the mill used is a wet ball mill, the grinding media material is steel balls, the ratio of large to small steel balls is 5:1 (large ball diameter 2.5 cm, small ball diameter 6 mm), the ball-to-material mass ratio is 10:1, the volume of grinding balls and ore sample is 40% of the volume of the ball mill jar, and the amount of new activator added during co-grinding reaction is 100 g / t;

[0073] The results after flotation are shown in the table below:

[0074] Table 7 Recovery rate of Example 7

[0075]

[0076]

[0077] Example 8

[0078] Other conditions are the same as in Example 3, except that: the grinding time is 10 min, the rotation speed is 120 r / min, the mill used is a wet ball mill, the grinding media material is steel balls, the ratio of large to small steel balls is 5:1 (large balls are 3 cm in diameter and small balls are 1 cm in diameter), the ball-to-material mass ratio is 15:1, the volume of grinding balls and ore sample is 40% of the volume of the ball mill jar, and the amount of new activator added during co-grinding reaction is 250 g / t.

[0079] The results after flotation are shown in the table below:

[0080] Table 8 Recovery rate of Example 8

[0081] Novel activator (3:2) Recovery rate % Concentrate 89.4％ .

[0082] Example 9

[0083] Preparation of copper-ammonia complex sulfide activator: A 10 mol / L concentrated ammonia solution was prepared. The concentrated ammonia solution was mixed with high-purity copper oxide ore at a volume ratio of 20 mL:3 g, and leached to obtain a copper-ammonia complex ion solution. Furthermore, a 0.05 mol / L ethylenediamine phosphate solution was prepared. The prepared copper-ammonia complex ion solution was mixed with the 0.05 mol / L ethylenediamine phosphate solution at a volume ratio of 3:1 to prepare a novel activator.

[0084] Weigh 2.0g of copper oxide ore (particles with a size of -74μm, comprising approximately 80% of all particles by mass) and pour it into a flotation cell. Add 30mL of deionized water and stir for 1 minute to adjust the slurry pH to 6.5. Add the activator and combined sulfiding agent. Perform wet ball milling (grinding time: 15 minutes, rotation speed: 150 r / min; mill used: wet ball mill; grinding media: steel balls; large to small ball ratio: 5:1 (large ball diameter: 2cm; small ball diameter: 5mm); ball-to-material ratio: 5:1; total volume of grinding balls and ore sample. The ball mill jar volume was 40%. During the co-grinding reaction, the amount of the new activator added was 200 g / t. Then, 0.4 mL (2 mg of combined sulfiding agent) of combined sulfiding agent (1000 g / t) and 0.8 mL (1.2 mg of combined collector) of combined collector (600 g / t) were added sequentially, along with 1 μL of terpineol. The collecting time was 3 min for all reactions, the frother action was 1 min, and the frothing time was 4 min. The resulting flotation concentrate was then dried in an oven at 50℃. After drying, the weight of the concentrate was measured, and the recovery rate was calculated. The results are shown in the table below.

[0085] Table 9 Recovery rate of Example 9

[0086]

Claims

1. Application of a method for deep sulfidation of complex copper oxide mineral surfaces synergistically reinforced by mechanochemistry and coordination chemistry, characterized in that: the copper oxide ore is crushed to a grinding particle size and then placed in a grinding mill for grinding, and an activator is added during the grinding process to perform a co-grinding reaction; after grinding, the pulp is adjusted to a mass percentage concentration of 25-40%, and then a combined sulfidation agent, a combined collector, a combined depressant, and a frother are sequentially added for flotation to obtain a copper concentrate; or the copper oxide ore is crushed to a grinding particle size and then placed in a grinding mill for grinding, and an activator and a combined sulfidation agent are added during the grinding process to perform a co-grinding reaction; after grinding, the pulp is adjusted to a mass percentage concentration of 25-40%, and then a combined collector, a combined depressant, and a frother are sequentially added for flotation to obtain a copper concentrate; after grinding, the mass percentage content of -74 μm in the copper oxide ore is 70-90%; the activator is composed of copper ammonia complex ions and ethylenediamine phosphate; during grinding, the rotational speed is controlled to be 120-200 r / min, and the time is greater than or equal to 10 min; the combined collector is obtained by combining ethyl xanthate, butyl xanthate, and benzohydroxamic acid in a mass ratio of 5:3:1; the combined depressant is obtained by combining water glass, sodium hexametaphosphate, and carboxymethyl cellulose in a mass ratio of 1:1:3; the combined sulfidation agent is obtained by combining sodium sulfide and sodium polysulfide in a mass ratio of 2:1; and the frother is selected from at least one of No. 2 oil and pine oil. The copper ammonia complex ion solution is obtained by mixing concentrated ammonia water with a concentration of 8-12 mol / L and a copper source, and then adjusting the pH value to 6-8; the copper source is a soluble copper salt and / or copper oxide. Alternatively, the copper ammonia complex ion solution is obtained by stirring and mixing concentrated ammonia water with copper oxide at a ratio of 10-20 mL:3-5 g.

3. The application according to claim 2, characterized in that: the concentration of the ethylenediamine phosphate solution is controlled to be 0.05-0.07 mol / L; and the activator is obtained by mixing the prepared copper ammonia complex ion solution and the ethylenediamine phosphate solution in a volume ratio of 3-5:

1.

4. The application according to claim 2, characterized in that: the grinding time is 10-20 min, the grinding mill used is a wet ball mill, the grinding medium material is steel balls or corundum, the mass ratio of large and small steel balls is 5:1, the ball-to-material mass ratio is 5-7:1, the volume of the grinding balls and the mineral sample loaded is 40%-60% of the volume of the ball mill tank; wherein the diameter of the large balls is 1-2 cm and the diameter of the small balls is 3-6 mm. The addition amount of the activator during the co-grinding reaction is 180-220 g / t. 1 ton of raw ore is added with 500-750 g of the combined collector. 1 ton of raw ore is added with 900-1100 g of the combined depressant. 1 ton of raw ore is added with 800-1200 g of the combined sulfidation agent.

2. Use according to claim 1, characterized in that: ​ ​ ​ ​ ​ ​ ​ 5. The use according to claim 1, characterized in that: ​ 6. The use according to claim 1, characterized in that: ​ 7. The use according to claim 1, characterized in that: ​ 8. The use according to claim 1, characterized in that: ​

Images