A method for separating copper-molybdenum mixed concentrate by advanced oxidation flotation

Abstract

The application discloses a method for separating copper-molybdenum mixed concentrate by advanced oxidation flotation, which comprises the following steps: S1, adding the copper-molybdenum mixed concentrate into a flotation tank with water, and adding peroxysulfate; S2, adding a divalent iron salt to the treated ore pulp, and then adding a collector and a foaming agent, so as to obtain a molybdenum rough concentrate and a copper rough concentrate by flotation; and S3, obtaining a molybdenum concentrate by 4-5 times of cleaning of the molybdenum rough concentrate, and obtaining a copper concentrate by 2-3 times of scavenging of the copper rough concentrate. By adding the peroxysulfate and the divalent iron salt, the application can generate sulfate radicals SO4 ‑ · and hydroxyl radicals ·OH, which have the characteristics of high activity and strong oxidizing property, can effectively decompose organic collectors in the copper-molybdenum mixed concentrate, and can reduce the difficulty of copper-molybdenum separation; and can also oxidize chalcopyrite to generate hydrophilic substances such as oxides and sulfates on the surface of the chalcopyrite, so that the chalcopyrite is inhibited; and the hydrophobicity of molybdenite can be restored by adding the collector, so that the copper-molybdenum efficient and clean flotation separation can be realized.

Description

Technical Field

[0001] This invention belongs to the field of mineral processing and sorting technology, specifically relating to a method for separating copper-molybdenum mixed concentrate using advanced oxidative flotation. Background Technology

[0002] Molybdenum is an important rare metal and strategic resource with excellent physical, chemical, and mechanical properties, and is widely used in aerospace, electronics, and machinery manufacturing industries. Molybdenum is mainly extracted from molybdenum-bearing minerals, with molybdenite being the most industrially valuable. Molybdenite is often found as an associated mineral in copper-molybdenum deposits.

[0003] In copper-molybdenum ores, chalcopyrite and molybdenite are associated minerals. These two minerals have similar properties and good floatability, making flotation separation of copper and molybdenum a persistent global challenge. With my country's increasing demand for copper and molybdenum resources, easily beneficiated copper-molybdenum ores are becoming increasingly scarce, while the proportion of difficult-to-beneficiate ores is rising. Therefore, developing efficient copper-molybdenum flotation separation technology is becoming increasingly important. Since most copper-molybdenum deposits have low copper and molybdenum grades, a mixed flotation process is generally used to obtain a mixed copper-molybdenum concentrate, which is then subjected to copper-molybdenum separation. This process incorporates strong collectors, such as butyl xanthate, during the mixed flotation stage. The copper and molybdenum sulfides adsorbed by these collectors become even more difficult to separate. In the flotation separation of copper-molybdenum rough concentrates, a "copper-suppressing, molybdenum-floating" process is often used. This requires the addition of large amounts of copper inhibitors, such as sodium sulfide, sodium hydrosulfide, sodium mercaptoacetate, and cyanide. Some of these flotation reagents are highly toxic, impacting the environment and human health, while others are expensive, leading to high production costs.

[0004] Therefore, a method for separating copper-molybdenum mixed concentrates using advanced oxidative flotation with minimal environmental impact is urgently needed. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a method for separating copper-molybdenum mixed concentrates using advanced oxidative flotation.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] This invention provides a method for separating copper-molybdenum mixed concentrates using advanced oxidative flotation, comprising the following steps:

[0008] S1. Add water to the copper-molybdenum mixed concentrate and put it into the flotation cell. Adjust the pH of the slurry to the range of 5 to 8, add persulfate, and stir for 2 minutes.

[0009] S2. Add ferrous salt to the slurry after step S1, stir for 10 minutes, then add collector, stir for 2-3 minutes, then add frother and stir for 1-2 minutes, and obtain molybdenum crude concentrate and copper crude concentrate by flotation.

[0010] S3. Molybdenum rough concentrate is obtained by 4-5 beneficiation processes. The middlings from the first beneficiation process are returned to the roughing process. The middlings from the second, third, fourth, and fifth beneficiation processes are returned to the previous beneficiation process in sequence. Copper rough concentrate is obtained by 2-3 scavenging processes. The middlings from the first scavenging process are returned to the roughing process. The middlings from the second and third scavenging processes are returned to the previous scavenging process in sequence.

[0011] Preferably, in step S1, the molybdenum grade of the copper-molybdenum mixed concentrate is 0.2-1.2%, the copper grade is 16%-26%, and the weight of the copper-molybdenum mixed concentrate with a fineness of less than 74 micrometers accounts for 70%-90% of the total weight of the copper-molybdenum mixed concentrate.

[0012] Preferably, in step S1, the mass ratio of copper-molybdenum mixed concentrate to water is 1:(3-5), the persulfate includes at least one of potassium persulfate and sodium persulfate, and the amount of persulfate used is 4-6 kg / t.

[0013] Preferably, the adjusting agent used to adjust the pH of the slurry in step S1 is sulfuric acid and lime.

[0014] Preferably, the ferrous salt in step S2 includes at least one of ferrous chloride and ferrous sulfate, and the amount of ferrous salt used is 2-4 kg / t.

[0015] Preferably, in step S2, the collector is kerosene, the amount of the collector is 50-80 g / t, the foaming agent is No. 2 oil, and the amount of the foaming agent is 20-30 g / t.

[0016] Preferably, in step S3, the first selection adds 2-3 kg / t of persulfate and 1-2 kg / t of ferrous salt; the second selection adds 1-1.5 kg / t of persulfate and 0.5-1 kg / t of ferrous salt; the third selection adds 0.5-0.75 kg / t of persulfate and 0.25-0.5 kg / t of ferrous salt; and no reagents are added in the fourth and fifth selections. In the first scavenging, 15-30 g / t of kerosene and 10-15 g / t of No. 2 oil are added; and in the second scavenging, 5-10 g / t of kerosene are added.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] This invention involves adding persulfate and ferrous salt during the flotation separation of copper-molybdenum mixed concentrate. The ferrous salt activates the persulfate to generate sulfate radicals (SO4). -• Hydroxyl radicals (·OH). On the one hand, these two free radicals are highly reactive and have strong oxidizing properties, effectively decomposing organic collectors in copper-molybdenum mixed concentrates, thus reducing the difficulty of copper-molybdenum separation. On the other hand, these two free radicals can also oxidize chalcopyrite, inhibiting the formation of hydrophilic substances such as oxides and sulfates on its mineral surface. Simultaneously, these two free radicals have a relatively small oxidizing effect on the surface of molybdenite; by adding kerosene, a collector for molybdenite, its surface hydrophobicity can be restored, thereby achieving efficient and clean flotation separation of copper and molybdenum. Attached Figure Description

[0019] Figure 1 This is a flowchart of the process of a method for separating copper-molybdenum mixed concentrate using oxidative flotation according to the present invention. Detailed Implementation

[0020] The preferred embodiments of the present invention are described below. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0021] Example 1

[0022] like Figure 1 As shown, this embodiment provides a method for separating copper-molybdenum mixed concentrate using advanced oxidative flotation. The raw material, copper-molybdenum mixed concentrate, has a copper grade of 19.57% and a molybdenum grade of 0.67%. The copper mineral is mainly chalcopyrite, and the molybdenum mineral is mainly molybdenite, with 80% of the concentrate being below 74 micrometers. The specific steps are as follows:

[0023] Add 500g of copper-molybdenum mixed concentrate to 1500g of water and place it in a flotation cell. Adjust the pH of the slurry to 7.3 with lime, add 4.4kg / t of potassium persulfate, and stir for 2 minutes.

[0024] Add 2.4 kg / t ferrous sulfate to the flotation cell and stir for 10 minutes. Add 60 g / t kerosene and stir for 2 minutes. Then add 2... # 25g / t of oil was stirred for 1 minute, followed by aeration flotation to obtain rough concentrate and tailings.

[0025] For the first cleaning of the rough concentrate, 2.2 kg / t of potassium persulfate and 1.2 kg / t of ferrous sulfate are added. For the second cleaning, 1.1 kg / t of potassium persulfate and 0.6 kg / t of ferrous sulfate are added. For the third cleaning, 0.6 kg / t of potassium persulfate and 0.3 kg / t of ferrous sulfate are added. No reagents are added for the fourth and fifth cleanings. The middlings from the first cleaning are returned to the rougher, and the middlings from the second, third, fourth, and fifth cleanings are returned to the previous cleaning in sequence. For the tailings, 20 g / t of kerosene and 10 g / t of No. 2 oil are added for the first scavenging. 10 g / t of kerosene is added for the second scavenging. The middlings from the first scavenging are returned to the rougher, and the middlings from the second and third scavengings are returned to the previous scavenging in sequence. Finally, a molybdenum concentrate with a molybdenum grade of 48.32% and a molybdenum recovery rate of 88.67% can be obtained.

[0026] Example 2

[0027] like Figure 1 As shown, this embodiment provides a method for separating copper-molybdenum mixed concentrate using advanced oxidative flotation. The raw material, copper-molybdenum mixed concentrate, has a copper grade of 21.25% and a molybdenum grade of 1.06%. The copper mineral is mainly chalcopyrite, and the molybdenum mineral is mainly molybdenite, with 80% of the concentrate being below 74 micrometers. The specific steps are as follows:

[0028] Add 500g of copper-molybdenum mixed concentrate to 1750g of water and place it in a flotation cell. Adjust the pH of the slurry to 7.8 with lime, add 5.6kg / t of potassium persulfate, and stir for 2 minutes.

[0029] Add 2.8 kg / t of ferrous sulfate to the flotation cell and stir for 10 minutes. Add 70 g / t of kerosene and stir for 2 minutes. Then add 2... # 20g / t of oil was stirred for 1 minute, followed by aeration flotation to obtain rough concentrate and tailings.

[0030] For the first cleaning of the rough concentrate, 2.8 kg / t of potassium persulfate and 1.4 kg / t of ferrous sulfate were added. For the second cleaning, 1.4 kg / t of potassium persulfate and 0.7 kg / t of ferrous sulfate were added. For the third cleaning, 0.7 kg / t of potassium persulfate and 0.4 kg / t of ferrous sulfate were added. No reagents were added for the fourth and fifth cleanings. For the tailings, 20 g / t of kerosene and 10 g / t of No. 2 oil were added for the first scavenging. 10 g / t of kerosene was added for the second scavenging. The middlings from the first scavenging were returned to the roughing process. The middlings from the second and third scavengings were returned to the previous scavenging processes in turn. Finally, a molybdenum concentrate with a molybdenum grade of 50.95% and a molybdenum recovery rate of 86.59% was obtained.

[0031] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for separating copper-molybdenum mixed concentrate using advanced oxidative flotation, characterized in that, Includes the following steps: S1. Add water to the copper-molybdenum mixed concentrate and put it into the flotation cell. Adjust the pH of the slurry to the range of 5 to 8, add persulfate, and stir for 2 minutes. S2. Add ferrous salt to the slurry after step S1, stir for 10 minutes, then add collector, stir for 2-3 minutes, then add frother and stir for 1-2 minutes, and obtain molybdenum crude concentrate and copper crude concentrate by flotation. S3. Molybdenum rough concentrate is obtained by 4-5 beneficiation processes. The middlings from the first beneficiation process are returned to the roughing process. The middlings from the second, third, fourth, and fifth beneficiation processes are returned to the previous beneficiation process in sequence. Copper rough concentrate is obtained by 2-3 scavenging processes. The middlings from the first scavenging process are returned to the roughing process. The middlings from the second and third scavenging processes are returned to the previous scavenging process in sequence.

2. The method for separating copper-molybdenum mixed concentrate by oxidative flotation according to claim 1, characterized in that, In step S1, the molybdenum grade of the copper-molybdenum mixed concentrate is 0.2-1.2%, the copper grade is 16%-26%, and the weight of the copper-molybdenum mixed concentrate with a fineness of less than 74 micrometers accounts for 70%-90% of the total weight of the copper-molybdenum mixed concentrate.

3. The method for separating copper-molybdenum mixed concentrate by oxidative flotation according to claim 1, characterized in that, In step S1, the mass ratio of copper-molybdenum mixed concentrate to water is 1:(3-5), the persulfate includes at least one of potassium persulfate and sodium persulfate, and the amount of persulfate used is 4-6 kg / t.

4. The method for separating copper-molybdenum mixed concentrate by oxidative flotation according to claim 1, characterized in that, The pH adjusters used in step S1 to adjust the slurry pH are sulfuric acid and lime.

5. The method for separating copper-molybdenum mixed concentrate by oxidative flotation according to claim 1, characterized in that, In step S2, the ferrous salt includes at least one of ferrous chloride and ferrous sulfate, and the amount of ferrous salt used is 2-4 kg / t.

6. The method for separating copper-molybdenum mixed concentrate by oxidative flotation according to claim 1, characterized in that, In step S2, the collector is kerosene, and the amount of the collector is 50-80 g / t. The foaming agent is No. 2 oil, and the amount of the foaming agent is 20-30 g / t.

7. The method for separating copper-molybdenum mixed concentrate by oxidative flotation according to claim 1, characterized in that, In step S3, the first selection adds 2-3 kg / t of persulfate and 1-2 kg / t of ferrous salt; the second selection adds 1-1.5 kg / t of persulfate and 0.5-1 kg / t of ferrous salt; the third selection adds 0.5-0.75 kg / t of persulfate and 0.25-0.5 kg / t of ferrous salt; no reagents are added in the fourth and fifth selections. The first scavenging adds 15-30 g / t of kerosene and 10-15 g / t of No. 2 oil; the second scavenging adds 5-10 g / t of kerosene.

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