A suppressed zinc blende activator and its application

Abstract

The application discloses a kind of inhibited sphalerite activator and its application, the activator is by ethylenediamine tetraacetic acid, methyl glycine diacetic acid trisodium and copper sulfate composition.For low-grade lead-zinc sulfide ore containing pyrite preferential flotation process, process inhibits sphalerite and pyrite lead selection, lead tailings inhibit pyrite zinc selection.The activator of the application can effectively activate inhibited sphalerite mineral, compared with traditional single activator copper sulfate, with the advantages of good activation effect, low cost and less sphalerite collector dosage, and good applicability for low-grade lead-zinc sulfide ore flotation separation.

Description

Technical Field

[0001] This invention belongs to the field of metallurgical technology, specifically relating to an inhibited sphalerite activator and its application. Background Technology

[0002] In the flotation separation process of lead-zinc sulfide ores, sphalerite activators are necessary to maximize the recovery of sphalerite minerals. This is mainly because, on the one hand, sphalerite has relatively poor floatability compared to galena and other minerals, resulting in a low flotation rate and potentially insufficient collector action; on the other hand, the separation of lead sulfide and zinc sulfide requires the addition of sphalerite depressants. Before flotation, the depressed sphalerite must be activated to enhance the effect of the zinc collector on the sphalerite. Copper sulfate is a commonly used sphalerite activator in the flotation process of lead-zinc sulfide ores, and its main function is to... 2+ Lead-zinc sulfide ore undergoes a displacement reaction with sphalerite, forming a copper sulfide film on its surface. The collector reacts with this film, increasing the hydrophobicity of the sphalerite surface. This film then combines with air bubbles in the pulp to achieve sphalerite flotation and separation from other minerals. However, lead-zinc sulfide ore flotation is often carried out in high-alkalinity pulp using lime as a pyrite depressant. The high pH consumes large amounts of copper sulfate. Furthermore, lead tailings often contain residual lead sulfide collectors, which preferentially react with the activator copper sulfate upon the addition of copper sulfate, resulting in ineffective consumption of copper sulfate. Additionally, the price of copper sulfate is high due to rising copper metal prices. This leads to high copper sulfate usage and reagent costs in lead-zinc sulfide ore flotation, accounting for 40%–80% of the total reagent cost in beneficiation production, severely impacting the economic efficiency of beneficiation plants. Therefore, it is necessary to develop new, highly efficient sphalerite activators to reduce beneficiation reagent costs. Summary of the Invention

[0003] The first objective of this invention is to provide an inhibited zincblende activator; the second objective is to provide the application of the activator.

[0004] The first objective of this invention is achieved by the activator being composed of ethylenediaminetetraacetic acid, trisodium methylglycine diacetate, and copper sulfate.

[0005] The activator described in the application can remove the hydrophilic film generated by the inhibited sphalerite by adding a certain proportion of ethylenediaminetetraacetic acid and trisodium methyl glycine diacetate, and on this basis, a small amount of copper sulfate is added, the copper sulfate reacts with part of the surface of the sphalerite to generate a copper sulfide film, and on this basis, the sphalerite can be fully activated, and the sales unit price of ethylenediaminetetraacetic acid and trisodium methyl glycine diacetate is much lower than that of copper sulfate, so that the activator described in the application not only has high activation efficiency, but also greatly reduces the cost of the reagent, and a certain proportion of ethylenediaminetetraacetic acid and trisodium methyl glycine diacetate can effectively remove the main interfering metal ions in the ore pulp, thereby improving the flotation efficiency of zinc sulfide. The method is more obvious in low-grade lead-zinc sulfide ore flotation separation. The activator of the application can effectively activate the inhibited sphalerite mineral, and compared with the traditional single activator copper sulfate, has the advantages of good activation effect, low cost and less sphalerite collector.

[0006] The second object of the application is achieved by the application of the activator in the preparation of a sphalerite activator.

[0007] The method for activating and beneficiating the inhibited sphalerite of low-grade lead-zinc sulfide ore by using the activator described in the application includes pretreatment and flotation steps, and specifically includes:

[0008] A, pretreatment: a certain proportion of water is added to the inhibited sphalerite of low-grade lead-zinc sulfide ore to be treated according to a solid-liquid ratio of 1:1, and the ore is ground in a mill to a fineness of 60-75% of -0.074 mm to obtain ore slurry a;

[0009] B, flotation:

[0010] 1) The ore slurry a is sequentially added with pyrite depressant, sphalerite depressant, lead sulfide collector, and frother for flotation to obtain lead rough concentrate b and lead tailings c, and the lead rough concentrate b is subjected to three times of cleaning to obtain lead concentrate;

[0011] 2) The lead tailings are sequentially added with pyrite depressant, sphalerite activator, sphalerite collector, and frother for flotation to obtain zinc rough concentrate d and tailings, and the zinc rough concentrate d is cleaned to obtain zinc concentrate.

[0012] The specific operation is as follows:

[0013] 1. The ore and water are put into a mill according to a solid-liquid ratio of 1:1, and the grinding fineness is 60%-75% of -0.074 mm.

[0014] 2. Place the above slurry sample into a flotation machine, add pyrite lime and stir for 3 minutes, add sphalerite inhibitor (zinc sulfate, zinc sulfate + sodium sulfite, sodium sulfide + zinc sulfate, sodium carbonate + zinc sulfate) and stir for 3 minutes, add lead sulfide collector (ethyl xanthate, ethyl xanthate, ethyl xanthate + ethyl xanthate) and stir for 2 minutes, add frother pine oil and stir for 2 minutes, and aerate and skim for 3 minutes to obtain lead rough concentrate. The slurry in the flotation cell is lead tailings.

[0015] 3. Lead concentrate is obtained by three rounds of fine cleaning of lead rough ore.

[0016] 4. Add pyrite inhibitor lime to 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, then aerate and skim for 4 minutes to obtain zinc rough concentrate.

[0017] 5. Zinc concentrate is obtained by three fine-tuning processes from the zinc crude concentrate.

[0018] 6. The above-mentioned sphalerite activator M is: 50%–65% ethylenediaminetetraacetic acid, 25%–30% trisodium methylglycine diacetate, and 5%–25% copper sulfate. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the process flow of the present invention. Detailed Implementation

[0020] The present invention will be further described below with reference to embodiments, but this is not intended to limit the present invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the protection scope of the present invention.

[0021] The activator described in this invention is composed of ethylenediaminetetraacetic acid, trisodium methylglycine diacetate, and copper sulfate.

[0022] The mass ratio of ethylenediaminetetraacetic acid, trisodium methylglycine diacetate and copper sulfate is (50~65):(25~30):(5~25).

[0023] The application of the activator described in this invention is its use in the preparation of a zincblende activator.

[0024] The method for activating and beneficiating inhibited sphalerite in low-grade lead-zinc sulfide ores using the activator described in this invention includes pretreatment and flotation steps, specifically including:

[0025] A. Pretreatment: Water is added to the inhibited sphalerite of the low-grade lead-zinc sulfide ore to be treated at a solid-liquid ratio of 1:1, and the mixture is ground in a mill until the fineness of -0.074mm is 60~75% to obtain slurry a;

[0026] B. Flotation:

[0027] 1) sequentially adding pyrite inhibitor, sphalerite inhibitor, lead sulfide collector, frother into the ore pulp a to carry out flotation to obtain lead rough concentrate b and lead separation tailings c, and the lead rough concentrate b is subjected to three times of cleaning to obtain lead concentrate;

[0028] 2) sequentially adding pyrite inhibitor, sphalerite activator, sphalerite collector and frother into the lead separation tailings to carry out flotation to obtain zinc rough concentrate d and tailings, and the zinc rough concentrate d is subjected to cleaning to obtain zinc concentrate.

[0029] The pyrite inhibitor is lime.

[0030] The frother is pine oil.

[0031] The sphalerite inhibitor in B step 1) is zinc sulfate, zinc sulfate + sodium sulfite, sodium sulfide + zinc sulfate or sodium carbonate + zinc sulfate.

[0032] The lead sulfide collector in B step 1) is ethyl xanthate and / or ethylthiuram.

[0033] The sphalerite collector in B step 2) is butyl xanthate.

[0034] The following further illustrates the present application by specific implementation cases:

[0035] Example 1

[0036] A certain low-grade lead-zinc sulfide ore in Yunnan has a lead grade of 1.04% and a zinc grade of 3.00%, and 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.

[0037] 1. Lead roughing stage: 500g of ore and water are put into a mill at a solid-liquid ratio of 1:1, and the grinding fineness is-0.074mm to 70%.

[0038] 2. The above ore pulp sample is put into a flotation machine, 1000g / t of pyrite lime is added and stirred for 3min, 800g / t of sphalerite inhibitor zinc sulfate is added and stirred for 3min, 20g / t of lead sulfide collector ethyl xanthate + 20g / t of ethylthiuram is added and stirred for 2min, 10g / t of frother pine oil is added and stirred for 2min, and 3min of air scraping is carried out, to obtain lead rough concentrate, and the pulp in the flotation tank is lead separation tailings.

[0039] 3. Add pyrite inhibitor lime 1000g / t in lead ore tailings, stir for 3 min, add sphalerite activator M (ethylenediaminetetraacetic acid 80g / t, methyl glycine diacetic acid trisodium 40g / t, copper sulfate 30g / t) and stir for 3 min, add sphalerite collector butyl xanthate 30g / t and stir for 2 min, add foaming agent pine oil and stir for 2 min, aerate and scrape foam for 4 min, to obtain zinc rough concentrate 1 using activator M.

[0040] 4. Add pyrite inhibitor lime 1000g / t in lead ore tailings, stir for 3 min, add sphalerite activator copper sulfate 150g / t and stir for 3 min, add sphalerite collector butyl xanthate 30g / t and stir for 2 min, add foaming agent pine oil and stir for 2 min, aerate and scrape foam for 4 min, to obtain zinc rough concentrate 2 using activator copper sulfate.

[0041] 5. Add pyrite inhibitor lime 1000g / t in lead ore tailings, stir for 3 min, add sphalerite activator 0g / t and stir for 3 min, add sphalerite collector butyl xanthate 30g / t and stir for 2 min, add foaming agent pine oil and stir for 2 min, aerate and scrape foam for 4 min, to obtain zinc rough concentrate 3 without adding activator.

[0042] Table 1 Comparison of flotation indexes using copper sulfate as sphalerite activator / %

[0043]

[0044] Example 2

[0045] A certain low-grade lead-zinc sulfide ore in Hunan has a lead grade of 2.37% and a zinc grade of 3.78%; the lead oxidation rate is about 7%, and the lead sulfide is galena; the zinc oxidation rate is about 6%, and the zinc sulfide is mainly sphalerite.

[0046] 1. Lead roughing stage: 500g of ore and water are put into the mill at a solid-liquid ratio of 1:1, and the grinding fineness is-0.074mm to 70%.

[0047] 2. Put the above ore slurry sample into the flotation machine, add pyrite lime 1000g / t and stir for 3 min, add sphalerite inhibitor zinc sulfate 1500g / t and stir for 3 min, add lead sulfide collector ethyl xanthate + ethyldithizone (25g / t + 25g / t) and stir for 2 min, add foaming agent pine oil 10g / t and stir for 2 min, aerate and scrape foam for 3 min, to obtain lead rough concentrate, and the slurry in the flotation tank is lead ore tailings.

[0048] 3. Add pyrite inhibitor lime 1000g / t in lead ore tailings, stir for 3 min, add sphalerite activator M (ethylenediaminetetraacetic acid 100g / t, methyl glycine diacetic acid trisodium 50g / t, copper sulfate 50g / t) and stir for 3 min, add sphalerite collector butyl xanthate and stir for 2 min, add foaming agent pine oil and stir for 2 min, aerate and scrape foam for 4 min, to obtain zinc rough concentrate using activator M.

[0049] 4. Add pyrite inhibitor lime 1000g / t in lead ore tailings, stir for 3 min, add sphalerite activator copper sulfate 200g / t and stir for 3 min, add sphalerite collector butyl xanthate and stir for 2 min, add foaming agent pine oil and stir for 2 min, aerate and scrape foam for 4 min, to obtain zinc rough concentrate using activator copper sulfate.

[0050] 5. Add pyrite inhibitor lime 1000g / t in lead ore tailings, stir for 3 min, add sphalerite activator 0g / t and stir for 3 min, add sphalerite collector butyl xanthate 30g / t and stir for 2 min, add foaming agent pine oil and stir for 2 min, aerate and scrape foam for 4 min, to obtain zinc rough concentrate 3 without adding activator.

[0051] Table 2 Comparison of flotation indexes with copper sulfate as sphalerite activator / %

[0052]

[0053] Example 3

[0054] A certain low-grade lead-zinc sulfide ore in Guangxi has 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.

[0055] 1. Lead roughing stage: 500g of ore and water are put into the mill at a solid-liquid ratio of 1:1, and the grinding fineness is-0.074mm to 70%.

[0056] 2. Put the above ore slurry sample into the flotation machine, add pyrite lime 600g / t and stir for 3 min, add sphalerite inhibitor zinc sulfate 1500g / t and stir for 3 min, add lead sulfide collector ethyl xanthate + ethion (15g / t + 15g / t) and stir for 2 min, add foaming agent pine oil 10g / t and stir for 2 min, aerate and scrape foam for 3 min, to obtain lead rough concentrate, and the slurry in the flotation tank is lead ore tailings.

[0057] 3. Add pyrite depressant lime 800 g / t in lead ore dressing tailings, stir for 3 min, sphalerite activator M (50 g / t ethylenediaminetetraacetic acid, 20 g / t methyl glycine diacetic acid trisodium, 30 g / t copper sulfate) stirring for 3 min, sphalerite collector butyl xanthate stirring for 2 min, foaming agent pine oil stirring for 2 min, aerating and scraping foam for 4 min, to obtain zinc rough concentrate using activator M.

[0058] 4. Add pyrite depressant lime 1000 g / t in lead ore dressing tailings, stir for 3 min, sphalerite activator copper sulfate 100 g / t stirring for 3 min, sphalerite collector butyl xanthate stirring for 2 min, foaming agent pine oil stirring for 2 min, aerating and scraping foam for 4 min, to obtain zinc rough concentrate using activator copper sulfate.

[0059] 5. Add pyrite depressant lime 1000 g / t in lead ore dressing tailings, stir for 3 min, sphalerite activator 0 g / t stirring for 3 min, sphalerite collector butyl xanthate 30 g / t stirring for 2 min, foaming agent pine oil stirring for 2 min, aerating and scraping foam for 4 min, to obtain zinc rough concentrate 3 without adding activator.

[0060] Table 3 Comparison of flotation indexes with copper sulfate as sphalerite activator / %

[0061] .

Claims

1. The application of an activator for inhibited sphalerite in low-grade lead-zinc sulfide ores, wherein the activator is composed of ethylenediaminetetraacetic acid, trisodium methylglycine diacetate, and copper sulfate.

2. The application 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. A method for activating and beneficiating low-grade lead-zinc sulfide ore inhibited sphalerite using the low-grade lead-zinc sulfide ore inhibited sphalerite activator described in claim 1 or 2, characterized in that, It includes pretreatment and flotation steps, specifically: A. Pretreatment: Water is added to the inhibited sphalerite of the low-grade lead-zinc sulfide ore to be treated at a solid-liquid ratio of 1:1, and the mixture is ground in a mill until the fineness of -0.074mm is 60~75% to obtain slurry a; B. Flotation: 1) Pyrite inhibitor, sphalerite inhibitor, lead sulfide collector and frother are added to slurry a in sequence for flotation to obtain lead rough concentrate b and lead tailings c. Lead rough concentrate b is then cleaned three times to obtain lead concentrate. 2) Pyrite inhibitor, sphalerite activator, sphalerite collector and frother are added sequentially to lead tailings for flotation to obtain zinc rough concentrate d and tailings. Zinc rough concentrate d is then finely selected to obtain zinc concentrate.

4. The method according to claim 3, characterized in that, The pyrite inhibitor mentioned is lime.

5. The method according to claim 3, characterized in that, The foaming agent is pine oil.

6. The method according to claim 3, characterized in that, The zincblende inhibitor mentioned in step 1) is zinc sulfate, zinc sulfate + sodium sulfite, sodium sulfide + zinc sulfate, or sodium carbonate + zinc sulfate.

7. The method according to claim 3, characterized in that, The lead sulfide collector mentioned in step 1) is ethyl xanthate and / or ethyl thiocyanate.

8. The method according to claim 3, characterized in that, The sphalerite collector mentioned in step 2) is butyl xanthate.

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