Suppression sphalerite activating agent and application thereof

Abstract

The invention discloses an inhibited sphalerite activating agent and application thereof. The activating agent is prepared from ethylenediaminetetraacetic acid, trisodium methylglycine diacetate and copper sulfate. Aiming at the low-grade lead-zinc sulfide ore containing the pyrite, the process inhibits zinc blende and pyrite lead separation, and the lead separation tailings inhibits the pyrite zinc separation. The activating agent can effectively activate inhibited sphalerite minerals, has the advantages of being good in activating effect, low in cost and small in using amount of a sphalerite collecting agent compared with a traditional single activating agent copper sulfate, and is good in applicability to flotation separation of low-grade lead-zinc sulfide ore.

Description

Technical Field

[0001] The invention belongs to the technical field of metallurgy, and in particular relates to an inhibited sphalerite activator and application thereof. Background Art

[0002] In the flotation separation process of lead-zinc sulfide ores, sphalerite activators must be used to achieve the maximum recovery of sphalerite minerals. This is mainly because, on the one hand, the floatability of sphalerite is relatively poor compared to galena, resulting in a low flotation rate and insufficient collector action; on the other hand, the separation of lead sulfide and zinc sulfide requires the addition of sphalerite inhibitors. Before flotation of sphalerite, the inhibited sphalerite must be activated to enhance the effect of the zinc collector on sphalerite. Copper sulfate is a commonly used sphalerite activator in the flotation process of lead-zinc sulfide ores. Its main function is Cu 2+ It undergoes a replacement reaction with sphalerite, and forms a copper sulfide film on the surface of sphalerite. The collector reacts with the copper sulfide film to increase the hydrophobicity of the sphalerite surface, and combines with the bubbles in the slurry to achieve sphalerite flotation and separation from other minerals. However, the flotation of lead-zinc sulfide ores is often carried out in high-alkalinity slurries using lime as a pyrite depressant. The high pH will consume a large amount of copper sulfate. At the same time, a certain amount of lead sulfide collector often remains in the lead tailings. When copper sulfate is added, it will preferentially react with the activator copper sulfate, which also causes ineffective consumption of copper sulfate. In addition, as the price of copper metal rises, the unit price of copper sulfate is high. This leads to a high dosage of copper sulfate and reagent cost during the flotation of lead-zinc sulfide ores, accounting for 40% to 80% of the cost of ore dressing reagents in production, which seriously affects the economic benefits of the concentrator. Therefore, it is necessary to develop a new and efficient activator for sphalerite to reduce the cost of ore dressing reagents. Summary of the invention

[0003] The first object of the present invention is to provide a suppressed sphalerite activator; the second object is to provide the application of the activator.

[0004] The first object of the present invention is achieved in that the activator is composed of ethylenediaminetetraacetic acid, trisodium methylglycine diacetate and copper sulfate.

[0005] In the activator described in the present invention, adding a certain proportion of ethylenediaminetetraacetic acid and trisodium methylglycine diacetate can remove the hydrophilic film generated by sphalerite due to inhibition, and on this basis, adding a small amount of copper sulfate, copper sulfate and part of the sphalerite surface undergo a replacement reaction to generate a copper sulfide film, on this basis, full activation of sphalerite can be achieved, and the sales unit price of ethylenediaminetetraacetic acid and trisodium methylglycine diacetate is much lower than copper sulfate, so the activator described in the present invention not only plays an efficient activation role but also greatly reduces the cost of the agent, and at the same time, a certain proportion of ethylenediaminetetraacetic acid and trisodium methylglycine diacetate can effectively remove the main interfering metal ions in the pulp and improve the flotation efficiency of zinc sulfide. The method is more suitable for flotation separation of low-grade lead-zinc sulfide ores, and the effect is more obvious. The activator of the present invention can effectively activate the inhibited sphalerite mineral, and compared with the traditional single activator copper sulfate, it has the advantages of good activation effect, low cost and less sphalerite collector dosage.

[0006] The second object of the present invention is achieved by using the activator in the preparation of sphalerite activator.

[0007] The method for activating and beneficiating low-grade lead-zinc sulfide ore suppressed sphalerite using the activator of the present invention comprises pretreatment and flotation steps, specifically comprising: A. Pretreatment: Add water to the suppressed sphalerite of the low-grade lead-zinc sulfide ore to be treated at a solid-liquid ratio of 1:1, grind it to a fineness of -0.074mm of 60-75% to obtain slurry a; B. Flotation: 1) Adding pyrite inhibitor, sphalerite inhibitor, lead sulfide collector and frother to the pulp a in sequence for flotation to obtain lead rough concentrate b and lead tailings c; the lead rough concentrate b is subjected to three rounds of concentration to obtain lead concentrate; 2) Pyrite depressant, sphalerite activator, sphalerite collector and frother are sequentially added to the lead tailings for flotation to obtain zinc rough concentrate d and tailings. The zinc rough concentrate d is beneficiated to obtain zinc concentrate.

[0008] The specific operations are as follows: 1. Place ore and water into the mill at a solid-liquid ratio of 1:1, and the grinding fineness ranges from -0.074mm to 60%~75%.

[0009] 2. Put the above pulp samples into the flotation machine, add pyrite lime and stir for 3 minutes, stir sphalerite inhibitor (zinc sulfate, zinc sulfate + sodium sulfite, sodium sulfide + zinc sulfate, sodium carbonate + zinc sulfate) for 3 minutes, stir lead sulfide collector (ethyl xanthate, ethyl thiocyanate, ethyl xanthate + ethyl thiocyanate) for 2 minutes, stir frother pine oil for 2 minutes, aerate and scrape for 3 minutes to obtain lead rough concentrate. The pulp in the flotation tank is the lead tailings.

[0010] 3. The lead concentrate is obtained by three rounds of concentration.

[0011] 4. Add pyrite inhibitor lime to the lead tailings and stir for 3 minutes, sphalerite activator M and stir for 3 minutes, sphalerite collector butyl xanthate and stir for 2 minutes, frother pine oil and stir for 2 minutes, aerate and scrape for 4 minutes to obtain zinc crude concentrate.

[0012] 5. The zinc concentrate is obtained by three rounds of concentration.

[0013] 6. The above-mentioned sphalerite activator M is: 50% to 65% ethylenediaminetetraacetic acid, 25% to 30% trisodium methylglycine diacetate, and 5% to 25% copper sulfate. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a schematic diagram of the process flow of the present invention. DETAILED DESCRIPTION

[0015] The present invention is further described below in conjunction with the embodiments, but the present invention is not limited in any way. Any changes or substitutions made based on the teachings of the present invention belong to the protection scope of the present invention.

[0016] The activator of the invention is composed of ethylenediaminetetraacetic acid, trisodium methylglycine diacetate and copper sulfate.

[0017] The mass ratio of ethylenediaminetetraacetic acid, trisodium methylglycine diacetate and copper sulfate is (50-65): (25-30): (5-25).

[0018] The application of the activator described in the present invention is the application of the activator in preparing sphalerite activator.

[0019] The method for activating and beneficiating low-grade lead-zinc sulfide ore suppressed sphalerite using the activator of the present invention comprises pretreatment and flotation steps, specifically comprising: A. Pretreatment: Add water to the suppressed sphalerite of the low-grade lead-zinc sulfide ore to be treated at a solid-liquid ratio of 1:1, grind it to a fineness of -0.074mm of 60-75% to obtain slurry a; B. Flotation: 1) Adding pyrite inhibitor, sphalerite inhibitor, lead sulfide collector and frother to the pulp a in sequence for flotation to obtain lead rough concentrate b and lead tailings c; the lead rough concentrate b is subjected to three rounds of concentration to obtain lead concentrate; 2) Pyrite depressant, sphalerite activator, sphalerite collector and frother are sequentially added to the lead tailings for flotation to obtain zinc rough concentrate d and tailings. The zinc rough concentrate d is beneficiated to obtain zinc concentrate.

[0020] The pyrite inhibitor is lime.

[0021] The foaming agent is pine oil.

[0022] B. The sphalerite inhibitor in step 1) is zinc sulfate, zinc sulfate + sodium sulfite, sodium sulfide + zinc sulfate or sodium carbonate + zinc sulfate.

[0023] B. The lead sulfide collector described in step 1) is ethyl xanthate and / or ethyl thiocyanate.

[0024] B. The sphalerite collector described in step 2) is butyl xanthate.

[0025] The present invention is further described below with specific implementation cases: Example 1 A low-grade lead-zinc sulfide ore in Yunnan, with a lead grade of 1.04% and a zinc grade of 3.00%; the lead oxidation rate is about 15%, the lead sulfide is galena, the zinc oxidation rate is about 8%, and the zinc sulfide is mainly sphalerite.

[0026] 1. Lead roughing stage: 500g of ore and water are put into the mill in a solid-liquid ratio of 1:1, and the grinding fineness ranges from -0.074mm to 70%.

[0027] 2. Put the above pulp sample into the flotation machine, add pyrite lime 1000g / t and stir for 3min, add sphalerite inhibitor zinc sulfate 800g / t and stir for 3min, add lead sulfide collector ethyl xanthate + ethylthiocyanate (20g / t+20g / t) and stir for 2min, add frother pine oil 10g / t and stir for 2min, aerate and scrape for 3min to obtain lead rough concentrate. The pulp in the flotation tank is the lead tailings.

[0028] 3. Add pyrite inhibitor lime 1000g / t into the lead tailings and stir for 3min, sphalerite activator M (ethylenediaminetetraacetic acid 80g / t, methylglycine diacetate trisodium 40g / t, copper sulfate 30g / t) and stir for 3min, sphalerite collector butyl xanthate 30g / t and stir for 2min, frother pine oil and stir for 2min, aerate and scrape for 4min to obtain zinc crude concentrate 1 using activator M.

[0029] 4. Add 1000 g / t of lime, a pyrite inhibitor, into the lead tailings and stir for 3 min, 150 g / t of copper sulfate, a sphalerite activator, and stir for 3 min, 30 g / t of butyl xanthate, a sphalerite collector, and stir for 2 min, and pine oil, a foaming agent, and aerate and scrape for 4 min to obtain a coarse concentrate 2 using an activator copper sulfate zinc.

[0030] 5. Add 1000 g / t of pyrite depressant lime to the lead tailings and stir for 3 min, 0 g / t of sphalerite activator and stir for 3 min, 30 g / t of sphalerite collector butyl xanthate and stir for 2 min, pine oil as a foaming agent and stir for 2 min, aerate and scrape for 4 min to obtain a zinc crude concentrate 3 without adding an activator.

[0031] Table 1 Comparison of flotation indexes of sphalerite with copper sulfate as activator / %

[0032] Example 2 A low-grade lead-zinc sulfide ore in Hunan, with a lead grade of 2.37% and a zinc grade of 3.78%; the lead oxidation rate is about 7%, the lead sulfide is galena, the zinc oxidation rate is about 6%, and the zinc sulfide is mainly sphalerite.

[0033] 1. Lead roughing stage: 500g of ore and water are put into the mill in a solid-liquid ratio of 1:1, and the grinding fineness ranges from -0.074mm to 70%.

[0034] 2. Put the above pulp sample into the flotation machine, add pyrite lime 1000g / t and stir for 3min, add sphalerite inhibitor zinc sulfate 1500g / t and stir for 3min, add lead sulfide collector ethyl xanthate + ethylthiocyanate (25g / t+25g / t) and stir for 2min, add frother pine oil 10g / t and stir for 2min, aerate and scrape for 3min to obtain lead rough concentrate. The pulp in the flotation tank is the lead tailings.

[0035] 3. Add pyrite inhibitor lime 1000g / t into the lead tailings and stir for 3min, sphalerite activator M (ethylenediaminetetraacetic acid 100g / t, methylglycine diacetate trisodium 50g / t, copper sulfate 50g / t) and stir for 3min, sphalerite collector butyl xanthate and stir for 2min, frother pine oil and stir for 2min, aerate and scrape for 4min to obtain the trial activator M zinc crude concentrate.

[0036] 4. Add 1000 g / t of pyrite depressant lime to the lead tailings and stir for 3 minutes, add 200 g / t of sphalerite activator copper sulfate and stir for 3 minutes, add sphalerite collector butyl xanthate and stir for 2 minutes, add frother pine oil and stir for 2 minutes, and aerate and scrape for 4 minutes to obtain a coarse concentrate of copper sulfate zinc using an activator.

[0037] 5. Add 1000 g / t of pyrite depressant lime to the lead tailings and stir for 3 min, 0 g / t of sphalerite activator and stir for 3 min, 30 g / t of sphalerite collector butyl xanthate and stir for 2 min, pine oil as a foaming agent and stir for 2 min, aerate and scrape for 4 min to obtain a zinc crude concentrate 3 without adding an activator.

[0038] Table 2 Comparison of flotation indexes of sphalerite with copper sulfate as activator / %

[0039] Example 3 A low-grade lead-zinc sulfide ore in Guangxi, with a lead grade of 0.88% and a zinc grade of 1.72%; the lead oxidation rate is about 5%, and the lead sulfide is galena; the zinc oxidation rate is about 9%, and the zinc sulfide is mainly sphalerite.

[0040] 1. Lead roughing stage: 500g of ore and water are put into the mill in a solid-liquid ratio of 1:1, and the grinding fineness ranges from -0.074mm to 70%.

[0041] 2. Put the above pulp sample into the flotation machine, add pyrite lime 600g / t and stir for 3min, add sphalerite inhibitor zinc sulfate 1500g / t and stir for 3min, add lead sulfide collector ethyl xanthate + ethylthiocyanate (15g / t+15g / t) and stir for 2min, add frother pine oil 10g / t and stir for 2min, aerate and scrape for 3min to obtain lead rough concentrate, and the pulp in the flotation tank is lead tailings.

[0042] 3. Add 800 g / t of lime, a pyrite inhibitor, to the lead tailings and stir for 3 min, add sphalerite activator M (50 g / t of ethylenediaminetetraacetic acid, 20 g / t of trisodium methylglycine diacetate, 30 g / t of copper sulfate) and stir for 3 min, add sphalerite collector butyl xanthate and stir for 2 min, add frother pine oil and stir for 2 min, and aerate and scrape for 4 min to obtain zinc crude concentrate using activator M.

[0043] 4. Add 1000 g / t of pyrite depressant lime to the lead tailings and stir for 3 minutes, 100 g / t of sphalerite activator copper sulfate and stir for 3 minutes, sphalerite collector butyl xanthate and stir for 2 minutes, frother pine oil and stir for 2 minutes, aerate and scrape for 4 minutes to obtain a coarse concentrate of copper sulfate zinc using an activator.

[0044] 5. Add 1000 g / t of pyrite depressant lime to the lead tailings and stir for 3 min, 0 g / t of sphalerite activator and stir for 3 min, 30 g / t of sphalerite collector butyl xanthate and stir for 2 min, pine oil as a foaming agent and stir for 2 min, aerate and scrape for 4 min to obtain a zinc crude concentrate 3 without adding an activator.

[0045] Table 3 Comparison results of flotation indexes of sphalerite with copper sulfate as activator / % .

Claims

1. An activator, characterized in that The activator is composed of ethylenediaminetetraacetic acid, trisodium methylglycine diacetate and copper sulfate.

2. The activator according to claim 1, characterized in that The mass ratio of ethylenediaminetetraacetic acid, trisodium methylglycine diacetate and copper sulfate is (50-65): (25-30): (5-25).

3. Use of an activator according to claim 1 or 2, characterized in that: The activator is used in preparing sphalerite activator.

4. A method for activating and beneficiating low-grade lead-zinc sulfide ore suppressed sphalerite using the activator described in any one of claims 1 to 3, characterized in that: It includes pre-treatment and flotation steps, specifically including: A. Pretreatment: Add water to the suppressed sphalerite of the low-grade lead-zinc sulfide ore to be treated at a solid-liquid ratio of 1:1, grind it to a fineness of -0.074mm of 60-75% to obtain slurry a; B. Flotation: 1) Adding pyrite inhibitor, sphalerite inhibitor, lead sulfide collector and frother to the pulp a in sequence for flotation to obtain lead rough concentrate b and lead tailings c; the lead rough concentrate b is subjected to three rounds of concentration to obtain lead concentrate; 2) Pyrite depressant, sphalerite activator, sphalerite collector and frother are sequentially added to the lead tailings for flotation to obtain zinc rough concentrate d and tailings. The zinc rough concentrate d is beneficiated to obtain zinc concentrate.

5. The method according to claim 4, characterized in that The pyrite inhibitor is lime.

6. The method according to claim 4, characterized in that The foaming agent is pine oil.

7. The method according to claim 4, characterized in that B. The sphalerite inhibitor in step 1) is zinc sulfate, zinc sulfate + sodium sulfite, sodium sulfide + zinc sulfate or sodium carbonate + zinc sulfate.

8. The method according to claim 4, characterized in that B. The lead sulfide collector described in step 1) is ethyl xanthate and / or ethyl thiocyanate.

9. The method according to claim 4, characterized in that B. The sphalerite collector described in step 2) is butyl xanthate.

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