Copper sulfide ore ammonia process low-temperature dump leaching method

Abstract

The invention discloses an ammonia-process dump leaching method for copper sulphide ore, which comprises the following steps: treating the copper sulphide ore by adopting a dump leaching mode at a leaching agent temperature of-10-4 DEG C, taking an ammonium salt solution as a leaching agent, controlling the total ammonia concentration of the leaching agent to be 0.5-5mol / L and the pH range to be 7.5-9.5, adding the leaching agent into the copper sulphide ore by adopting a dripping leaching mode, and the copper-containing leachate is extracted and then returned to the leaching process, and ammonia and the ammonia leaching accelerant in the copper-containing leachate are recycled. The temperature of the leaching agent is controlled to be-10-4 DEG C for leaching, the ammonia consumption in the ammonia leaching process can be remarkably reduced, the leaching efficiency of copper under the low-temperature condition can be improved by adding the ammonia leaching accelerant, meanwhile, the copper-containing leachate is returned to the leaching process after being extracted, ammonia and the ammonia leaching accelerant in the copper-containing leachate are recycled, the purpose of effectively leaching chalcopyrite under the low ammonia consumption is achieved, and the method is suitable for large-scale industrial production. And a new technology is provided for development and utilization of low-grade primary copper sulphide ore in alpine regions.

Description

Technical Field

[0001] The invention relates to the technical field of copper sulfide ore leaching, and in particular to a method for low-temperature heap leaching of copper sulfide ore using an ammonia process. Background Art

[0002] At present, many copper mines are located in low-temperature and high-altitude cold areas, and many low-grade copper sulfide ore resources are difficult to develop and utilize. Bio-heap leaching technology is an effective means to recover low-grade copper sulfide ore sources, but the microbial activity in high-altitude cold areas is low, and it is almost powerless against the difficult-to-leach chalcopyrite. Therefore, it is urgent to develop new technologies for recovering copper sulfide ore that can adapt to high-altitude cold areas.

[0003] Ammonia can complex most transition metals, and does not complex with iron, calcium and magnesium, and has strong selectivity; the ammonia leaching process has been industrially applied to recover copper, nickel, cobalt and zinc. The industrial practice of recovering copper by ammonia leaching has a history of more than 100 years. The first ammonia copper leaching project began in 1915, using a stirring leaching process to treat copper oxide ore; the Arbiter stirring ammonia leaching process was used to treat copper sulfide concentrate in 1970, and cathode copper was produced by extraction-electrode after ammonia leaching. These ammonia copper leaching plants have been closed one after another. The possible reasons are attributed to the difficulty and high cost of recovering ammonia by ammonia evaporation, high production costs caused by high temperature or even high pressure leaching, and leaching kinetics that did not meet expectations.

[0004] In order to save investment and reduce operating costs, CN1718786A discloses a method for normal temperature stirring ammonia leaching-slag flotation of copper oxide ore, in which ammonia is not evaporated after extraction of the leaching solution and it is recycled, but the solid-liquid separation operation after stirring leaching will inevitably lead to water expansion, so the problem of high ammonia consumption has not been solved; CN102703701A discloses a method for treating copper oxide by combining stirring ammonia leaching with ammonia leaching in a percolation tank, which adopts a full process closed method to reduce ammonia volatilization loss, but the ammonia loss problem caused by water expansion cannot be solved due to the use of stirring leaching process. In order to improve the efficiency of ammonia leaching of copper oxide ore, CN113088690A discloses a method for stirring ammonia leaching of copper oxide ore with the addition of EDTA, but no measures to reduce ammonia consumption are found; CN102703700A proposes a method for segmented ammonia leaching and diversion extraction of copper oxide ore, which reduces ammonia consumption, but still cannot solve the ammonia loss problem caused by water expansion.

[0005] Primary copper sulfide ore with chalcopyrite as the main copper mineral is the most important raw material for copper smelting. At present, it is mainly recovered by traditional flotation-pyrometallurgy process, but due to the high cost of traditional process, it is not suitable for low-grade copper sulfide ore. Low-cost bio-heap leaching technology has been successfully applied to the recovery of secondary copper sulfide ore resources, but due to the slow leaching kinetics of chalcopyrite in acidic high-iron medium, the bio-heap leaching technology of primary copper sulfide ore has not yet been widely used in commercial applications. However, the leaching kinetics of chalcopyrite in alkaline ammonium salt medium is significantly higher than that in acidic high-iron medium, which shows good prospects for the application of ammonia copper leaching technology in the recovery of primary copper sulfide ore.

[0006] Ammonia leaching of chalcopyrite faces the common challenge of ammonia process - high ammonia consumption, and the problem of chalcopyrite leaching rate. In order to improve the copper leaching rate, CN1320137C proposed a method for leaching chalcopyrite with a composite leaching agent composed of a leaching agent, an oxidant, and a pulp potential control agent; CN111549220A proposed a method for ammonia leaching of sulfide copper-nickel ore with the addition of a reducing agent; CN101730753A discloses a method for first aging and then ammonia leaching of copper, nickel, zinc and other metals; CN1327012C proposed an ammonia leaching method with the addition of a strong oxidant, sodium hypochlorite, to strengthen the leaching of chalcopyrite in oxygen-sulfur mixed ores. These methods can all increase the leaching rate of chalcopyrite, but none of them proposes effective measures to reduce ammonia consumption. Summary of the invention

[0007] In view of the deficiencies of the prior art, the present invention aims to provide a low-temperature heap leaching method for copper sulfide ore using an ammonia process.

[0008] In order to achieve the above object, the present invention adopts the following technical solution:

[0009] A method for heap leaching copper sulfide ore by ammonia method comprises the following steps:

[0010] S1. Under the low temperature condition of -10 to 4°C, the copper sulfide ore is leached by heap leaching; the leaching agent is an ammonium salt solution, which is added to the copper sulfide ore by dripping; an ammonia leaching accelerator is added to the leaching agent;

[0011] S2. After the copper-containing leaching solution obtained by leaching is extracted, the organic phase is washed with water and then stripped, and the raffinate is returned to prepare the leaching agent, and the ammonia and ammonia leaching accelerator therein are recycled.

[0012] Furthermore, the copper sulfide ore includes any one of primary copper sulfide ore, secondary copper sulfide ore, copper-nickel-cobalt sulfide ore, and oxygen-sulfur mixed ore, with a Cu content of 0.1-3% and a particle size of 3mm-300mm.

[0013] Further, in step S1, the temperature of the leaching agent is the temperature of the natural environment and / or achieved by a refrigeration system and / or achieved by a heating system.

[0014] Furthermore, in step S1, the ammonium salt includes one or more of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium hypochlorite, ammonium fluoride, ammonia water, and minerals containing ammonium ions, and the total ammonia concentration in the leaching agent is controlled at 0.5-5 mol / L.

[0015] Furthermore, in step S1, the pH value of the leaching agent is adjusted to 7.5-9.5 by using a pH regulator, and the pH regulator includes any one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, ammonium carbonate, ammonium bicarbonate, and ammonia water.

[0016] Furthermore, in step S1, the ammonia leaching accelerator includes any one or more of sodium hydroxyethylidene diphosphonate HEDP·Na, sodium benzene sulfonate, sodium gluconate, and sodium ethylenediamine di-o-phenylacetate EDDHA·Na, and the concentration of the ammonia leaching accelerator in the leaching agent is controlled at 0.5-5 mmol / L.

[0017] Furthermore, in step S2, the extractant used for extraction is any one of LIX84-1, LIX54 and LIX984N.

[0018] The beneficial effect of the present invention is that: in the method of the present invention, the copper sulfide ore is treated by heap leaching at a leaching agent temperature of -10 to 4°C, an ammonium salt solution is used as a leaching agent, the total ammonia concentration of the leaching agent is controlled to be 0.5-5 mol / L, the pH range is 7.5-9.5, the leaching agent is added to the copper sulfide ore by dripping, and the copper-containing leaching solution is returned to the leaching process after extraction, and the ammonia and ammonia leaching promoter therein are recycled. Controlling the leaching agent temperature to leach at -10 to 4°C can significantly reduce the ammonia consumption of the ammonia leaching process, and adding an ammonia leaching promoter can improve the leaching efficiency of copper under low temperature conditions. At the same time, the copper-containing leaching solution is returned to the leaching process after extraction, and the ammonia and ammonia leaching promoter therein are recycled, so as to achieve the purpose of effectively leaching chalcopyrite under low ammonia consumption, and provide new technology for the development and utilization of low-grade primary copper sulfide ores in high-cold areas. DETAILED DESCRIPTION

[0019] The present invention will be further described below. It should be noted that this embodiment is based on the technical solution and provides a detailed implementation method and a specific operation process, but the protection scope of the present invention is not limited to this embodiment.

[0020] Example 1

[0021] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0022] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of leaching, the copper leaching rate is 78.5%, and the ammonia consumption is 8.5 kg / t.

[0023] Example 2

[0024] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0025] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached at a low temperature of -10°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of testing, the copper leaching rate was 45.1%, and the ammonia consumption was 3.0 kg / t.

[0026] Example 3

[0027] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0028] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 0°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of testing, the copper leaching rate was 60.4%, and the ammonia consumption was 5.5 kg / t.

[0029] Example 4

[0030] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0031] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 5 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and ammonia is recycled. After 300 days of testing, the copper leaching rate was 86.4%, and the ammonia consumption was 8.2 kg / t.

[0032] Example 5

[0033] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0034] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 0.5 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of testing, the copper leaching rate was 68.1% and the ammonia consumption was 8.3 kg / t.

[0035] Example 6

[0036] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0037] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium hydroxyethylidene diphosphonate HEDP·Na, with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of testing, the copper leaching rate was 76.5%, and the ammonia consumption was 8.6 kg / t.

[0038] Example 7

[0039] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0040] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium gluconate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and ammonia is recycled. After 300 days of testing, the copper leaching rate was 77.2% and the ammonia consumption was 8.7 kg / t.

[0041] Example 8

[0042] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0043] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is ethylenediamine di-o-phenylacetic acid sodium EDDHA·Na, with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of testing, the copper leaching rate was 75.8% and the ammonia consumption was 8.4 kg / t.

[0044] Example 9

[0045] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0046] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 0.5 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of testing, the copper leaching rate was 58.4%, and the ammonia consumption was 2.8 kg / t.

[0047] Example 10

[0048] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0049] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 5 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 150 days of testing, the copper leaching rate was 82.5%, and the ammonia consumption was 10.5 kg / t.

[0050] Embodiment 11

[0051] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0052] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 7.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of testing, the copper leaching rate was 65.4%, and the ammonia consumption was 5.5 kg / t.

[0053] Example 12

[0054] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0055] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 9.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of testing, the copper leaching rate was 88.4%, and the ammonia consumption was 11.5 kg / t.

[0056] Embodiment 13

[0057] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0058] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. A mixed solution of ammonium carbonate and ammonium bicarbonate is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of testing, the copper leaching rate was 82.4%, and the ammonia consumption was 12.1 kg / t.

[0059] Embodiment 14

[0060] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =10mm sample.

[0061] In this embodiment, a column leaching system is used to simulate heap leaching, and the primary copper sulfide ore is leached under the condition of a low temperature of 4°C. Among them, ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent, and the ammonia is recycled. After 300 days of testing, the copper leaching rate was 65.4%, and the ammonia consumption was 8.7 kg / t.

[0062] Comparative Example 1

[0063] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0064] The column leaching system simulates heap leaching, and the primary copper sulfide ore is leached at a low temperature of 30°C. Ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent to recycle ammonia. After 300 days of testing, the copper leaching rate was 85.2%, and the ammonia consumption was 160.6 kg / t.

[0065] Comparative Example 2

[0066] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0067] The column leaching system simulates heap leaching, and the primary copper sulfide ore is leached at a low temperature of 20°C. Ammonium sulfate solution is used as the leaching agent, the total ammonia concentration is 2 mol / L, and the ammonia leaching promoter is sodium benzenesulfonate with a concentration of 2 mmol / L to promote copper leaching. Sodium hydroxide is added to adjust the pH of the leaching agent to 8.5, and the leaching agent is added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate are sampled and analyzed during the leaching process. The copper-containing leachate is extracted with LIX84-1 extractant, and the raffinate is returned to the configuration of the leaching agent to recycle ammonia. After 300 days of testing, the copper leaching rate was 80.8%, and the ammonia consumption was 101.3 kg / t.

[0068] Comparative Example 3

[0069] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0070] The column leaching system was used to simulate heap leaching, and the primary copper sulfide ore was leached at a low temperature of 4°C. Ammonium sulfate solution was used as the leaching agent, and the total ammonia concentration was 2 mol / L. No ammonia leaching promoter was added in the experiment. Sodium hydroxide was added to adjust the pH of the leaching agent to 8.5, and the leaching agent was added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate were sampled and analyzed during the leaching process. The copper-containing leachate was extracted with LIX84-1 extractant, and the raffinate was returned to the leaching agent to recycle ammonia. After 300 days of the experiment, the copper leaching rate was 55%, and the ammonia consumption was 9.0 kg / t.

[0071] Comparative Example 4

[0072] The ore sample is a primary copper sulfide ore, with chalcopyrite as the main copper mineral, containing a small amount of bornite and chalcocite; other sulfide minerals are mainly pyrite; the gangue minerals are mainly quartz, chlorite and dolomite. The main chemical composition of the ore is: Cu 1.5%, S 2- 6.74%, Fe 7.12%, CaO 10.09%, MgO 11.25%. The original copper sulfide ore is crushed to obtain a particle size of P 80 =3mm sample.

[0073] The column leaching system was used to simulate heap leaching, and the primary copper sulfide ore was leached at a low temperature of -10°C. Ammonium sulfate solution was used as the leaching agent, and the total ammonia concentration was 2 mol / L. No ammonia leaching promoter was added in the experiment. Sodium hydroxide was added to adjust the pH of the leaching agent to 8.5, and the leaching agent was added to the primary copper sulfide ore by dripping. The copper concentration and ammonia concentration in the leachate were sampled and analyzed during the leaching process. The copper-containing leachate was extracted with LIX84-1 extractant, and the raffinate was returned to the leaching agent to recycle ammonia. After 300 days of the experiment, the copper leaching rate was 28.4%, and the ammonia consumption was 3.2 kg / t.

[0074] 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 heap leaching copper sulfide ore by ammonia method, characterized in that: The steps include: S1. Under the low temperature condition of -10 to 4°C, the copper sulfide ore is leached by heap leaching; the leaching agent is an ammonium salt solution, which is added to the copper sulfide ore by dripping; an ammonia leaching accelerator is added to the leaching agent; S2. After the copper-containing leaching solution obtained by leaching is extracted, the organic phase is washed with water and then stripped, and the raffinate is returned to prepare the leaching agent, and the ammonia and ammonia leaching accelerator therein are recycled.

2. The method according to claim 1, characterized in that The copper sulfide ore includes any one of primary copper sulfide ore, secondary copper sulfide ore, copper-nickel-cobalt sulfide ore and oxygen-sulfur mixed ore, with a Cu content of 0.1-3% and a particle size of 3mm-300mm.

3. The method according to claim 1, characterized in that Step S1, the temperature of the leaching agent is the temperature of the natural environment and / or achieved by a refrigeration system and / or achieved by a heating system.

4. The method according to claim 1, characterized in that In step S1, the ammonium salt includes one or more of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium hypochlorite, ammonium fluoride, ammonia water, and minerals containing ammonium ions, and the total ammonia concentration in the leaching agent is controlled at 0.5-5 mol / L.

5. The method according to claim 1, characterized in that In step S1, the pH value of the leaching agent is adjusted to 7.5-9.5 by using a pH regulator, and the pH regulator includes any one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, ammonium carbonate, ammonium bicarbonate, and ammonia water.

6. The method according to claim 1, characterized in that In step S1, the ammonia leaching accelerator includes any one or more of sodium hydroxyethylidene diphosphonate (HEDP·Na), sodium benzene sulfonate, sodium gluconate, and sodium ethylenediamine di-o-phenylacetate (EDDHA·Na), and the concentration of the ammonia leaching accelerator in the leaching agent is controlled at 0.5-5 mmol / L.

7. The method according to claim 1, characterized in that In step S2, the extractant used for extraction is any one of LIX84-1, LIX54 and LIX984N.