A method for efficiently leaching copper sulfide ore by seawater doped with organic acid and composite ozone micro-nano bubbles

Abstract

This invention belongs to the field of hydrometallurgical technology, specifically relating to a method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles. The method includes: 1) adding copper sulfide ore powder to natural seawater and stirring, then adding inorganic acid to adjust the pH to below 3 to obtain a pretreated slurry; 2) continuously introducing ozone in the form of micro-nano bubbles through a micro-nano bubble generator, adding organic acid, and stirring for leaching; 3) after the leaching reaction, separating the solid and liquid phases to obtain a copper-containing leachate. This invention utilizes micro-nano bubbles to significantly improve the solubility and gas-liquid mass transfer efficiency of ozone, and leverages its interfacial effect to disrupt the passivation layer on the mineral surface. It also utilizes the mixed coordination environment formed by organic acid and chloride ions in natural seawater to selectively complex dissolved copper ions, thereby enhancing leaching. A high copper leaching rate of over 90% can be obtained under normal pressure conditions, offering advantages of high efficiency, environmental friendliness, and low cost.

Description

Technical Field

[0001] This invention belongs to the field of hydrometallurgical technology, specifically relating to a method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles. Background Technology

[0002] Copper is an important strategic resource. Due to its excellent electrical and thermal conductivity, ductility, and relatively low price, copper is widely used in industrial and scientific fields. Copper sulfide ores are the most abundant copper resources, accounting for approximately 70% of the world's total reserves. Currently, copper sulfide ores are mainly processed using pyrometallurgical methods, first improving the ore grade through technologies such as flotation, and then smelting and refining the concentrate. However, pyrometallurgical copper refining produces large amounts of harmful gases such as SO2 and CO2, adversely affecting the atmospheric environment. Currently, global high-grade copper oxide ore resources are gradually depleting, and the grade of copper sulfide ores is generally decreasing. The lower the ore grade, the higher the energy consumption and gas emissions of pyrometallurgical processes. Therefore, with the scarcity of copper resources, the continuous decline in copper ore grades, and increasingly stringent environmental standards, hydrometallurgical copper extraction technology is gradually gaining importance.

[0003] Copper sulfide ores are highly inert to chemical reactions and easily form a passivation layer during leaching, reducing the leaching rate and yield. Therefore, wet processing of copper sulfide ores is very challenging. To reduce passivation and accelerate leaching, oxidants or other methods that increase the redox potential of the solution can be used to enhance leaching. Currently, the main wet extraction methods include acid leaching, such as sulfuric acid leaching using ferric sulfate, hydrogen peroxide, and dichromates as oxidants. However, acid leaching methods suffer from drawbacks such as high acid and oxidant consumption, low leaching rates, and high costs.

[0004] To address the problem of low mass transfer efficiency, micro / nanobubble technology has gained attention in the field of mineral leaching in recent years. Micro / nanobubbles possess characteristics such as a large specific surface area (more than 1000 times that of conventional bubbles), slow rise velocity, and long residence time (up to several hours), which can significantly improve gas-liquid mass transfer efficiency. For example, Chinese invention publication CN116356140A discloses an oxidative leaching method that uses micro / nanobubbles of oxidizing gas for sulfide mineral leaching, demonstrating that micro / nanobubbles can improve oxygen utilization to over 35%. Chinese invention publication CN118649771A designs a micro / nanobubble coupling device that enhances mass transfer through circulating dissolved gas, increasing ozone utilization by 50%. While existing technologies include ultrasonic-enhanced ozone leaching and complexing agent-assisted leaching, ultrasonic equipment has high energy consumption and is difficult to scale up, and the introduction of complexing agents increases subsequent copper recovery costs and wastewater treatment load. Therefore, how to develop a low-cost, low-energy-consumption, green and efficient leaching technology has become an urgent technical problem to be solved in the field of hydrometallurgical processing of copper sulfide ore and other sulfide ores. Summary of the Invention

[0005] The purpose of this invention is to provide a method for the efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles, in order to solve the problems of low leaching rate, low production efficiency, and high leaching cost in existing acid leaching technologies for copper sulfide ore.

[0006] To achieve the above objectives, the present invention provides a method for the efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles, comprising the following steps: S1. Preparation and pretreatment of slurry: Add copper sulfide ore powder to natural seawater, stir and mix to form slurry, then add inorganic acid to adjust the pH of the slurry to below 3 to obtain pretreated slurry; S2, Leaching: Ozone is continuously introduced into the pretreated slurry in the form of micro-nano bubbles through a micro-nano bubble generator. At the same time, organic acid is added to the pretreated slurry to obtain a leaching system, which is then stirred and leached. S3. Solid-liquid separation: After the leaching reaction is completed, solid-liquid separation is performed, and the resulting filtrate is the copper-containing leachate.

[0007] Optionally, in step S1, the particle size of the copper sulfide ore powder is not greater than 100 mesh.

[0008] Optionally, in step S1, the inorganic acid is one or more of hydrochloric acid, sulfuric acid, and nitric acid.

[0009] Optionally, in step S1, the liquid-to-solid ratio between natural seawater and copper sulfide ore powder is (3-20) mL:1 g.

[0010] Optionally, in step S2, the pretreated slurry is placed in a leaching reactor equipped with a filter screen. The solid particles in the pretreated slurry are confined inside the filter screen. The inlet of the micro-nano bubble generator is connected to the part of the leaching reactor where the clear liquid outside the filter screen is located. The air inlet of the micro-nano bubble generator is connected to the ozone generator. The outlet of the micro-nano bubble generator draws the liquid containing ozone gas back to the inside of the filter screen through a pipe.

[0011] Optionally, the flow rate of the liquid containing ozone gas is 0.05 to 2.0 L / (min per liter of natural seawater).

[0012] Optionally, in step S2, the leaching reaction temperature is 20–90°C, and the stirring speed is 50–500 rpm.

[0013] Optionally, in step S2, the organic acid is one or more of oxalic acid, citric acid, formic acid, acetic acid, malic acid, tartaric acid, EDTA, ascorbic acid, and gallic acid.

[0014] Optionally, in step S2, the concentration of the organic acid in the leaching system is 0.01–2.0 mol / L.

[0015] The working principle and beneficial effects of this scheme are as follows: This scheme constructs a synergistic enhanced leaching system of "seawater medium-organic acid complexation-ozone micro-nano bubble oxidation," effectively overcoming the technical bottlenecks of traditional acid leaching methods, such as heavy pollution and poor selectivity, and ozone direct oxidation methods, such as low mass transfer efficiency and easy passivation. Specifically, this scheme utilizes micro-nano bubbles to significantly improve the solubility of ozone in seawater and the gas-liquid mass transfer efficiency, and uses its interface effect to destroy the passivation layer on the mineral surface; secondly, organic acids and chloride ions in seawater form a mixed coordination environment, selectively complexing dissolved copper ions, promoting the rightward shift of the reaction equilibrium, and inhibiting the dissolution of impurities; furthermore, by using natural seawater instead of freshwater, the chloride ions in the seawater are activated by ozone and attack the metal-sulfur bonds. These three factors are interconnected, achieving efficient and selective dissociation of the copper sulfide ore lattice, and obtaining a high copper leaching rate of over 90% under normal pressure conditions, with significant advantages of high efficiency, greenness, and low cost. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the equipment used in a method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles, as described in an embodiment of the present invention. Detailed Implementation

[0017] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0018] First, this invention provides equipment used in a method for the efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles, such as... Figure 1 As shown, it includes: The leaching reactor is a container for holding pretreated slurry. It is equipped with a filter screen and stirring blades inside the filter screen. The mesh size of the filter screen is smaller than the particle size of copper sulfide ore powder, thereby confining the solid particles in the pretreated slurry within the filter screen. The micro-nano bubble generator is used to generate ozone-containing micro-nano bubbles. It has a water inlet, a water outlet, and an air inlet. The water inlet is connected to the part of the leaching reactor outside the filter screen where the clear liquid is located through a pipe. The water outlet leads the ozone-containing liquid back to the inside of the filter screen through a pipe, so that the ozone gas can be continuously introduced and circulated in the leaching system in the form of micro-nano bubbles. An ozone generator, used to produce ozone, has an air inlet and an air outlet. The air outlet of the ozone generator is connected to the air inlet of the micro-nano bubble generator through a pipe. A gas cylinder is used to store oxygen or air. The gas cylinder has an outlet, and the outlet of the gas cylinder is connected to the inlet of the ozone generator through a pipe. A gas flow meter and a valve are installed on the pipe between the outlet of the gas cylinder and the inlet of the ozone generator.

[0019] This invention provides a method for the efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro / nano bubbles, the method comprising the following steps: S1. Slurry Preparation and Pretreatment: Copper sulfide ore powder is added to natural seawater and stirred to form a slurry. Then, an inorganic acid is added to adjust the pH of the slurry to below 3 to obtain a pretreated slurry. The particle size of the copper sulfide ore powder is no greater than 100 mesh; the liquid-to-solid ratio between natural seawater and copper sulfide ore powder is (3–20) mL:1 g; the inorganic acid is one or more of hydrochloric acid, sulfuric acid, and nitric acid.

[0020] S2. Leaching: Ozone is continuously introduced into the pretreated slurry in the form of micro-nano bubbles using a micro-nano bubble generator. Simultaneously, organic acids are added to the pretreated slurry to obtain a leaching system. Leaching is carried out at 20–90°C with stirring at a speed of 50–500 rpm. The flow rate of the ozone-containing liquid is 0.05–2.0 L / (min per liter of natural seawater). The organic acid is one or more of oxalic acid, citric acid, formic acid, acetic acid, malic acid, tartaric acid, EDTA, ascorbic acid, and gallic acid, and the concentration of the organic acid in the leaching system is 0.01–2.0 mol / L.

[0021] S3. Solid-liquid separation: After the leaching reaction is completed, solid-liquid separation is performed, and the resulting filtrate is the copper-containing leachate.

[0022] The copper sulfide ore powder used in Examples 1-12 and the comparative examples below contains 0.34% Cu, 6.72% Fe, 2.77% Al, and 0.28% Ti. The natural seawater comes from the nearshore area of ​​the Yellow Sea near Qingdao, China (the average water depth at the water intake point is about 10 meters, 35°49'12" N, 120°10'48" E). The seawater composition contains 9.62% Na, 18.34% Cl, 1.20% Mg, 0.37% Ca, 0.35% K, 0.76% S, and other trace elements.

[0023] Example 1 This embodiment provides a method for the efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles, comprising the following steps: S1. Preparation and pretreatment of slurry: Take 500 mL of natural seawater and place it in the leaching reactor. Preheat it to 60°C. Then take 50 g of 100-mesh copper sulfide ore powder and place it in the filter screen (the filter screen is 300 mesh). Stir and mix to form a slurry. Then add concentrated sulfuric acid to adjust the pH value of the slurry to 2.0 to obtain the pretreated slurry.

[0024] S2, Leaching: The clear liquid outside the filter screen is pumped into a micro / nano bubble generator (median bubble size 300 nm), while ozone generated by an ozone generator (ozone concentration 80 g / Nm³) is simultaneously introduced. 3 The flow rate of the ozone-containing liquid was controlled at 0.5 L / (min per liter of natural seawater), which is equivalent to a flow rate of 1.0 L / min. Stirring was started at 300 rpm, and citric acid was added to the pretreated slurry inside the filter screen to obtain the leaching system. The concentration of citric acid in the leaching system was 0.2 mol / L, and the leaching reaction was carried out at a constant temperature of 60℃.

[0025] S3. Solid-liquid separation: After leaching for 4 h, 6 h, and 8 h, the solution was filtered, and the copper ion concentration in the filtrate was measured. The copper leaching rate was 92.8% after 4 h, 97.5% after 6 h, and 98.1% after 8 h.

[0026] Example 2 The only difference between this embodiment and Example 1 is that in step S2, the concentration of citric acid in the leaching system is 0.01 mol / L; all other parameters are the same as in Example 1. The copper leaching rate was found to be 64.3% after leaching for 8 hours.

[0027] Example 3 The only difference between this embodiment and Example 1 is that in step S2, the concentration of citric acid in the leaching system is 2.0 mol / L; all other parameters are the same as in Example 1. The copper leaching rate was found to be 98.4% after 8 hours of leaching.

[0028] Example 4 The only difference between this embodiment and Embodiment 1 is that the temperature in steps S1 and S2 is 20°C; all other aspects are the same as in Embodiment 1. After leaching for 6 hours, the copper leaching rate was 55.8%; after extending the leaching reaction to 10 hours, the copper leaching rate was 82.1%.

[0029] Example 5 The only difference between this embodiment and Embodiment 1 is that the temperature in steps S1 and S2 is 40°C; all other aspects are the same as in Embodiment 1. After leaching for 6 hours, the copper leaching rate was 89.6%.

[0030] Example 6 The only difference between this embodiment and Embodiment 1 is that the temperature in steps S1 and S2 is 80°C; all other aspects are the same as in Embodiment 1. After leaching for 6 hours, the copper leaching rate was 96.2%.

[0031] Example 7 The only difference between this embodiment and Embodiment 1 is that the temperature in steps S1 and S2 is 90°C; all other aspects are the same as in Embodiment 1. After leaching for 6 hours, the copper leaching rate was 93.7%.

[0032] Example 8 The only difference between this embodiment and Embodiment 1 is the volume of natural seawater used in step S1. The ratio of the ozone-containing liquid flow rate to the "per liter of natural seawater" remains constant. The volume of natural seawater is 150 mL, meaning the flow rate of the ozone-containing liquid is 3.33 L / min. All other aspects are the same as in Embodiment 1. After 6 hours of leaching, the copper leaching rate was 58.4%.

[0033] Example 9 The only difference between this embodiment and Embodiment 1 is that the volume of natural seawater used in step S1 is different, while the ratio of the flow rate of the ozone-containing liquid to "per liter of natural seawater" remains constant. The volume of natural seawater is 1000 mL, meaning the flow rate of the ozone-containing liquid is 0.5 L / min. All other aspects are the same as in Embodiment 1. After 6 hours of leaching reaction, the copper leaching rate was 91.2%.

[0034] Example 10 The only difference between this embodiment and Example 1 is that oxalic acid is used instead of citric acid in step S2; all other aspects are the same as in Example 1. After leaching for 6 hours, the copper leaching rate was 96.8%.

[0035] Example 11 The only difference between this embodiment and Example 1 is that EDTA is used instead of citric acid in step S2; all other aspects are the same as in Example 1. After leaching for 6 hours, the copper leaching rate was 95.1%.

[0036] Example 12 The only difference between this embodiment and Example 1 is that acetic acid is used instead of citric acid in step S2; all other aspects are the same as in Example 1. After leaching for 6 hours, the copper leaching rate was 71.3%.

[0037] Example 13 The only difference between this embodiment and Example 1 is that in this embodiment, low-grade chalcocite (Cu2S, containing 1.60% Cu, 7.1% Fe, and 2.9% Al) powder is used instead of the copper sulfide powder in Example 1; all other aspects are the same as in Example 1. After leaching for 6 hours, the copper leaching rate was 99.1%.

[0038] Example 14 The only difference between this embodiment and Example 1 is that in this embodiment, low-grade bornite (Cu5FeS4, Cu 0.76%, Fe 10.49%, Al 5.38%) powder is used instead of copper sulfide powder in Example 1; all other aspects are the same as in Example 1. After leaching for 6 hours, the copper leaching rate was 96.3%.

[0039] Example 15 The only difference between this embodiment and Example 1 is that in this embodiment, low-grade complex chalcopyrite (containing gangue, with 1.26% Cu, 13.5% Fe, and 3.87% Al) powder is used instead of the copper sulfide ore powder in Example 1; all other aspects are the same as in Example 1. After leaching for 6 hours, the copper leaching rate was 94.7%.

[0040] Comparative Example 1 The only difference between this comparative example and Example 1 is that citric acid is not added in step S2 in this comparative example; all other aspects are the same as in Example 1. In this comparative example, the copper leaching rate was 58.2% after 6 hours of leaching reaction.

[0041] Comparative Example 2 The only difference between this comparative example and Example 1 is that, in this comparative example, ozone gas was replaced with high-purity nitrogen gas in step S2; all other aspects are the same as in Example 1. In this comparative example, the copper leaching rate was 18.5% after 6 hours of leaching reaction.

[0042] Comparative Example 3 The only difference between this comparative example and Example 1 is that in this comparative example, the micro / nano bubble generator is turned off in step S2, and a common porous ceramic aerator (producing millimeter-sized bubbles) is used to introduce ozone gas at the same flow rate and concentration into the pretreated slurry. All other aspects are the same as in Example 1. In this comparative example, after 6 hours of leaching reaction, the copper leaching rate was 76.8%.

[0043] Comparative Example 4 The only difference between this comparative example and Example 1 is that, in step S1, natural seawater was replaced with an equal volume of deionized water; all other aspects are the same as in Example 1. In this comparative example, after 6 hours of leaching reaction, the copper leaching rate was 79.4%.

[0044] Comparative Example 5 The only difference between this comparative example and Example 1 is that in this comparative example, the micro / nano bubble generator, ozone generator, and gas cylinder are turned off in step S2, and citric acid is not added; otherwise, it is the same as Example 1. In this comparative example, the copper leaching rate is 2.6% after 6 hours of leaching reaction.

[0045] Comparative Example 6 The only difference between this comparative example and Example 1 is that, in step S1, natural seawater was replaced with an 18.34 wt% NaCl solution; all other steps are the same as in Example 1. In this comparative example, after 6 hours of leaching reaction, the copper leaching rate was 88.6%.

[0046] Comparative Example 7 The only difference between this comparative example and Example 1 is that, in step S1, natural seawater is replaced with synthetic seawater. The synthetic seawater contains, in addition to NaCl, MgCl2, CaCl2, and Na2SO4 in proportions equivalent to those in natural seawater; otherwise, it is the same as in Example 1. In this comparative example, after 6 hours of leaching reaction, the copper leaching rate was 85.1%.

[0047] Examples 1-3 and Comparative Example 1 show that when the concentration of organic acid (citric acid) is 0.01 mol / L, the copper leaching rate, although only 64.3%, is still higher than that of Comparative Example 1. This indicates that even a low concentration of organic acid can produce a significant enhanced leaching effect. Moreover, when organic acid complexation is lacking, the dissolved copper ions are prone to redeposition on the surface and cannot effectively inhibit the formation of sulfur or iron oxide passivation layers.

[0048] As can be seen from Examples 1 and 4-7, when the leaching reaction temperature is 20°C, the copper leaching rate is low after 6 hours, but a high copper leaching rate can still be obtained after extending the leaching time. When the leaching reaction temperature reaches 90°C, the copper leaching rate is actually lower after 6 hours than at 80°C. This is because the ozone thermal decomposition is intensified, and the efficiency decreases slightly, but it still maintains a high efficiency, and the high-temperature range is feasible.

[0049] As can be seen from Examples 1, 8, and 9, when the liquid-solid ratio between copper sulfide ore powder and natural seawater is 3 mL:1 g, the slurry is viscous and difficult to stir. The copper leaching rate is only 58.4% after 6 h of leaching reaction, proving that the present invention can still operate under low liquid-solid ratio. When the liquid-solid ratio is 20 mL:1 g, the copper leaching rate after 6 h of leaching reaction is lower than that in Example 1. This is because the reagent concentration is diluted, and the efficiency is slightly reduced, but it is still at a high level.

[0050] As demonstrated in Examples 1, 10-12, oxalic acid, citric acid, and EDTA are more effective than acetic acid in increasing the copper leaching rate in copper sulfide ores. This indicates that organic acids with strong acidity and multidentate complexing ability are more effective.

[0051] As can be seen from Examples 1 and 13-15, the present invention exhibits efficient and universal leaching capabilities for copper sulfide ores with different crystal structures and grades.

[0052] Comparing Example 1 with Comparative Example 2, it can be seen that without a strong oxidant (ozone) to disrupt the sulfide ore lattice, the leaching effect is limited solely by the acidity and complexing ability of organic acids. Comparing Example 1 with Comparative Example 3, it can be seen that micro / nano bubbles, with their large specific surface area and ultra-long liquid phase residence time, significantly improve the dissolution and mass transfer efficiency of ozone, which is unmatched by ordinary bubbling methods. Comparing Example 1 with Comparative Example 4, it can be seen that electrolytes (especially chloride ions) in natural seawater have a crucial synergistic enhancing effect on the oxidative leaching process, which is incomparable to freshwater (deionized water).

[0053] By comparing Examples 1, 1, and 5, it can be found that if the leaching effect of natural seawater + ozone microbubbles + organic acid on copper in copper sulfide ore is simply summed, the expected value should be: copper leaching rate of Comparative Example 5 + (copper leaching rate of Comparative Example 1 - copper leaching rate of Comparative Example 5) + (copper leaching rate of Comparative Example 2 - copper leaching rate of Comparative Example 5) = 2.6% + (58.2% - 2.6%) + (18.5% - 2.6%) = 74.1%, which is much lower than the copper leaching rate of 97.5% in Example 1. Therefore, this shows that the three elements of the present invention produce a synergistic effect, significantly improving the copper leaching rate and achieving unexpected technical effects.

[0054] By comparing Example 1 with Comparative Examples 6 and 7, it can be found that although sodium chloride solution can provide most of the synergistic effect, natural seawater, due to its more complex ionic composition, produces the best overall synergistic effect. The presence of calcium and magnesium ions may slightly complex with organic acids, slightly affecting the efficiency, but overall it is still far superior to freshwater.

[0055] The above are merely embodiments of the present invention. The invention is not limited to the fields covered by these embodiments. Commonly known structures and characteristics are not described in detail here. Those skilled in the art are aware of all common technical knowledge in the field prior to the application date or priority date, are aware of all existing technologies in that field, and have the ability to apply conventional experimental methods prior to that date. Those skilled in the art can improve and implement this solution based on the guidance provided in this application and their own capabilities. Some typical known structures or methods should not be obstacles for those skilled in the art to implement this application. It should be noted that those skilled in the art can make several modifications and improvements without departing from the structure of the present invention. These should also be considered within the scope of protection of the present invention, and will not affect the effectiveness or practicality of the invention. The scope of protection claimed in this application should be determined by the content of its claims. The specific embodiments described in the specification can be used to interpret the content of the claims.

Claims

1. A method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles, characterized in that: Includes the following steps: S1. Preparation and pretreatment of slurry: Add copper sulfide ore powder to natural seawater, stir and mix to form slurry, then add inorganic acid to adjust the pH of the slurry to below 3 to obtain pretreated slurry; S2, Leaching: Ozone is continuously introduced into the pretreated slurry in the form of micro-nano bubbles through a micro-nano bubble generator. At the same time, organic acid is added to the pretreated slurry to obtain a leaching system, which is then stirred and leached. S3. Solid-liquid separation: After the leaching reaction is completed, solid-liquid separation is performed, and the resulting filtrate is the copper-containing leachate.

2. The method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles according to claim 1, characterized in that: In step S1, the particle size of the copper sulfide ore powder is no greater than 100 mesh.

3. The method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles according to claim 1, characterized in that: In step S1, the inorganic acid is one or more of hydrochloric acid, sulfuric acid, and nitric acid.

4. The method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles according to claim 1, characterized in that: In step S1, the liquid-to-solid ratio between natural seawater and copper sulfide ore powder is (3-20) mL:1 g.

5. The method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles according to claim 1, characterized in that: In step S2, the pretreated slurry is placed in a leaching reactor equipped with a filter screen. The solid particles in the pretreated slurry are confined inside the filter screen. The inlet of the micro-nano bubble generator is connected to the part of the leaching reactor where the clear liquid outside the filter screen is located. The air inlet of the micro-nano bubble generator is connected to the ozone generator. The outlet of the micro-nano bubble generator draws the liquid containing ozone gas back to the inside of the filter screen through a pipe.

6. The method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles according to claim 2, characterized in that: The flow rate of the liquid containing ozone gas is 0.05–2.0 L / (min per liter of natural seawater).

7. The method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles according to claim 1, characterized in that: In step S2, the leaching reaction temperature is 20–90°C, and the stirring speed is 50–500 rpm.

8. The method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles according to claim 1, characterized in that: In step S2, the organic acid is one or more of oxalic acid, citric acid, formic acid, acetic acid, malic acid, tartaric acid, EDTA, ascorbic acid, and gallic acid.

9. The method for efficient leaching of copper sulfide ore using seawater-doped organic acid composite ozone micro-nano bubbles according to claim 1, characterized in that: In step S2, the concentration of organic acid in the leaching system is 0.01–2.0 mol / L.

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