A copper-zinc sulphide ore flotation separation organic combination inhibitor and application thereof

Abstract

The application discloses a kind of copper-zinc sulphide ore flotation separation organic combination inhibitor and its application, belong to mineral processing technical field.The organic combination inhibitor of the application includes phosphonic acid inhibitor and succinate inhibitor, wherein the mass ratio of phosphonic acid inhibitor and succinate inhibitor is 1:1~5:1, the organic combination inhibitor can selectively inhibit sphalerite in copper-zinc sulphide ore;The organic combination inhibitor of the application can form hydrophilic complex on the surface of sphalerite, reduce its floatability, and can selectively inhibit sphalerite under low alkalinity system, and has no inhibiting effect on chalcopyrite;The organic combination inhibitor of the application is stable in nature, easy to use, less in amount, and has significant selective inhibition effect, strong applicability, especially suitable for copper-activated sphalerite and chalcopyrite flotation separation.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, specifically to an organic combination inhibitor for the flotation separation of copper-zinc sulfide ores and its application. Background Technology

[0002] Copper-zinc sulfide minerals are one of the important raw materials for smelting copper and zinc metals. Flotation is the most important method for recovering copper-zinc sulfide minerals. However, because copper-zinc sulfide ores are often densely coexisting with fine-grained inclusions, and are often associated with minerals such as pyrite, sericite, and quartz, and because copper ions dissolved from copper minerals have a significant activating effect on sphalerite during flotation, the floatability of copper and zinc minerals is similar, making their flotation separation extremely difficult.

[0003] The flotation separation of copper-zinc sulfide ores often employs a preferential flotation process that suppresses zinc and floats copper, making the selection of depressants particularly crucial. Commonly used depressants for sphalerite in production practice are primarily inorganic, such as zinc sulfate, lime, sodium hydroxide, sodium sulfide, sodium sulfite, and cyanide. In practice, zinc sulfate is often used as the primary depressant, with lime and sodium sulfite used as auxiliary depressants to form a combined depressant combination for better inhibition. While cyanide has good inhibition effects, it is no longer used in production due to its high toxicity. Inorganic depressants often suffer from problems such as large reagent dosage, high cost, and environmental unfriendliness, and are difficult to achieve good separation results for complex and difficult-to-process copper-zinc ores. Therefore, it is necessary to develop a new, highly efficient copper-zinc sulfide ore depressant with low reagent dosage, good selective inhibition effect, safe application, and strong adaptability, which is of great significance for improving the quality and recovery rate of copper concentrate products. Summary of the Invention

[0004] The purpose of this invention is to provide a novel organic combination inhibitor for the flotation separation of copper-zinc sulfide ores, which has low reagent dosage, good selective inhibition effect, safe application, and strong adaptability. The organic combination inhibitor includes phosphonic acid inhibitors and succinate inhibitors, wherein the mass ratio of phosphonic acid inhibitors to succinate inhibitors is 1:1 to 5:1. This organic combination inhibitor can selectively inhibit sphalerite in copper-zinc sulfide ores.

[0005] The phosphonic acid inhibitor is one of diethylenetriaminepentamethylenephosphonic acid, sodium diethylenetriaminepentamethylenephosphonate, dihexenetriaminepentamethylenephosphonic acid, sodium dihexenetriaminepentamethylenephosphonate, or a combination of one of diethylenetriaminepentamethylenephosphonic acid, sodium diethylenetriaminepentamethylenephosphonate, and one of dihexenetriaminepentamethylenephosphonate.

[0006] When the phosphonic acid inhibitor is a combination of two, the mass ratio of one of diethylenetriaminepentamethylenephosphonic acid and sodium diethylenetriaminepentamethylenephosphonic acid to one of dihexenetriaminepentamethylenephosphonic acid and sodium dihexenetriaminepentamethylenephosphonic acid is 1:1 to 5:1.

[0007] The succinate inhibitor is one or both of sodium iminodisuccinate and sodium (2R,3R)-2,3-dihydroxysuccinate.

[0008] When the succinate inhibitor is a combination of two, the mass ratio of tetrasodium iminodisuccinate to sodium (2R,3R)-2,3-dihydroxysuccinate is 3:1 to 5:1.

[0009] Another object of the present invention is to provide an application of the organic combination inhibitor: applying the organic combination inhibitor to the flotation separation of chalcopyrite and sphalerite in copper-zinc sulfide ores.

[0010] Furthermore, the specific process of using organic combination inhibitors for the flotation separation of sphalerite and zinc in copper-zinc sulfide chalcopyrite is as follows: the copper-zinc sulfide ore is ground to the required fineness, the pulp concentration and pH value are adjusted, organic combination inhibitors are added at each stage of flotation, stirred for 3 minutes, and then collectors and frothers are added as needed. The copper-zinc sulfide ore is subjected to 1-2 roughing, 2-3 scavenging, and 2-3 cleaning to obtain copper concentrate.

[0011] Preferably, the organic combination inhibitors of the present invention are added to the roughing, cleaning and scavenging stages respectively.

[0012] Preferably, the total amount of organic combination inhibitors added in the roughing stage is 1000-1500 g / t, and the mass ratio of organic combination inhibitors added in roughing stage I and roughing stage II is 2:1-4:1.

[0013] Preferably, the total amount of organic combination inhibitor added in the scavenging stage is 100-300 g / t, and the mass ratio of organic combination inhibitor added in scavenging I, scavenging II and scavenging III during the three scavenging stages is 2:2:1.

[0014] Preferably, the total amount of organic combination inhibitors added in the refining stage is 100-300 g / t. During the three refining stages, the organic combination inhibitors are added only in refining stage I, and not in refining stages II and III.

[0015] Preferably, the grinding fineness of the present invention is 70% to 90% -0.074 mm.

[0016] Preferably, the slurry concentration of the present invention is 30% to 45% by mass percentage.

[0017] Preferably, the pH value of the slurry in this invention is 8 to 11.

[0018] Preferably, the total amount of the organic combination inhibitor added according to the present invention is 1200-2100 g / t.

[0019] The beneficial effects of this invention are as follows:

[0020] (1) The phosphonic acid inhibitor and succinic acid inhibitor in the organic combination inhibitors described in this invention can react with the zinc active sites on the surface of zinc sphalerite or with Zn in the slurry. 2+ A chelation reaction occurs, and a hydrophilic chelate film is formed on the surface of sphalerite through multilayer assembly using zinc as a crosslinking agent. This enhances the hydrophilicity of the sphalerite surface and hinders the adsorption of collectors on the sphalerite surface, thus reducing its floatability.

[0021] (2) The organic combination inhibitor described in this invention can selectively inhibit sphalerite in a low alkalinity environment, while having virtually no effect on the flotation of chalcopyrite.

[0022] (3) The organic combination inhibitor described in this invention has a small dosage, is safe and non-toxic, has stable physicochemical properties, is easy to add in actual production, is convenient to use, can effectively improve the quality of copper concentrate products, and has broad application prospects. Detailed Implementation

[0023] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the content described.

[0024] Example 1

[0025] An organic combination inhibitor for flotation separation of copper-zinc sulfide ore, comprising a phosphonic acid inhibitor and a succinate inhibitor; the phosphonic acid inhibitor is diethylenetriaminepentamethylenephosphonic acid, and the succinate inhibitor is tetrasodium iminodisuccinate; the mass ratio of the phosphonic acid inhibitor to the succinate inhibitor is 1:1; the total amount of the organic combination inhibitor is 1200 g / t; and the organic combination inhibitor is added to the pulp during flotation.

[0026] When the above-mentioned organic combination of inhibitors is used in the flotation of copper-zinc sulfide ores, the separation of sphalerite and chalcopyrite is achieved.

[0027] In this embodiment, the copper-zinc sulfide ore processed has the following composition: Cu grade 0.50 wt%, Zn grade 2.89 wt%, copper-bearing minerals mainly chalcopyrite, and zinc-bearing minerals mainly sphalerite. The flotation steps are as follows:

[0028] (1) Grind the copper-zinc sulfide ore to a fineness of -0.074 mm, accounting for 70%, adjust the slurry concentration to 30%, and adjust the slurry pH to 8.

[0029] (2) The slurry obtained in step (1) is subjected to flotation through a closed-loop process of “one roughing, two scavenging, two cleaning, and middlings return in sequence”.

[0030] The specific process for the primary roughing stage is as follows: 1000 g / t of organic combined inhibitors are added (including 500 g / t of diethylenetriaminepentamethylenephosphonic acid and 500 g / t of tetrasodium iminodisuccinate). The slurry pH is adjusted to 8 with lime, stirred for 3 minutes, and then 150 g / t of collector butyl xanthate and 2 g / t of frother are added. # 20g / t of oil, stir for 3 minutes and then carry out rough selection.

[0031] The specific process for the two scavenging processes is as follows: The organic combination inhibitor is added at a rate of 100 g / t, of which 50 g / t of inhibitor is added in Scavenging I (including 25 g / t of diethylenetriaminepentamethylenephosphonic acid and 25 g / t of tetrasodium iminodisuccinate), butyl xanthate (50 g / t) is added as the collector, and 2 molting agents are added. # Add oil (10g / t), stir for 3 minutes, and then perform scavenging operation; the dosage and operation steps of scavenging II are the same as those of scavenging I.

[0032] The specific process for the two selection steps is as follows: the amount of organic combination inhibitor added is 100g / t. For selection step I, 100g / t of inhibitor is added and stirred for 3 minutes before selection. For selection step II, no reagent is added.

[0033] The copper concentrate product obtained after the above flotation operation is shown in Table 1, and its grade and recovery rate are shown in Table 1.

[0034] Example 2

[0035] An organic combination inhibitor for the flotation separation of copper-zinc sulfide ore, comprising a phosphonic acid inhibitor and a succinate inhibitor; the phosphonic acid inhibitor is dihexenetriaminepentamethylenephosphonic acid, and the succinate inhibitor is sodium (2R,3R)-2,3-dihydroxysuccinate; the mass ratio of the phosphonic acid inhibitor to the succinate inhibitor is 4:1; the total amount of the organic combination inhibitor is 1650 g / t; and the organic combination inhibitor is added to the pulp during flotation.

[0036] When the above-mentioned organic combination of inhibitors is used in the flotation of copper-zinc sulfide ores, the separation of sphalerite and chalcopyrite is achieved.

[0037] In this embodiment, the copper-zinc sulfide ore processed has the following composition: Cu grade 0.87 wt%, Zn grade 4.12 wt%, copper-bearing mineral is mainly chalcopyrite, and zinc-bearing mineral is mainly sphalerite. The flotation steps are as follows:

[0038] (1) Grind the copper-zinc sulfide ore to a fineness of -0.074 mm, accounting for 80%, adjust the slurry concentration to 35%, and adjust the slurry pH to 10.

[0039] (2) The slurry obtained in step (1) is subjected to flotation through a closed-loop process of “two roughing, three scavenging, two cleaning, and middlings return in sequence”.

[0040] The specific process for the two roughing processes is as follows: The amount of organic combined inhibitor added is 1200 g / t. The mass ratio of inhibitors added in roughing process I and roughing process II is 2:1. Roughing process I adds 800 g / t of inhibitor (including 640 g / t of dihexenetriamine pentamethylphosphonic acid and 160 g / t of sodium (2R,3R)-2,3-dihydroxysuccinate). The pH of the pulp is adjusted to 10 with lime, stirred for 3 minutes, and then 150 g / t of collector butyl xanthate and 2 g / t of frother are added. # 20 g / t of oil was added, and after stirring for 3 minutes, roughing was carried out. For roughing stage II, 400 g / t of inhibitor was added (including 320 g / t of dihexenetriamine pentamethylphosphonic acid and 80 g / t of sodium (2R,3R)-2,3-dihydroxysuccinate). The pulp pH was adjusted to 10 with lime, and the mixture was stirred for 3 minutes. Then, 70 g / t of collector butyl xanthate and 2 g / t of frother were added. # 10g / t of oil, stir for 3 minutes and then perform coarse selection.

[0041] The specific process for the three-stage scavenging is as follows: The organic combination inhibitor is added at a rate of 250 g / t, of which scavenging I involves 100 g / t of inhibitor (including 80 g / t of diethylenetriaminepentamethylenephosphonic acid and 20 g / t of tetrasodium iminodisuccinate), butyl xanthate as a collector (added at a rate of 50 g / t), and 2 molting agents. # Oil (addition amount 10g / t), stir for 3 minutes and then carry out scavenging operation; the dosage and operation steps of scavenging II are the same as those of scavenging I; the dosage of inhibitor for scavenging III is 50g / t, and the other operation steps are the same as those of scavenging I.

[0042] The specific process for the two selection steps is as follows: the amount of organic combination inhibitor added is 200g / t. For selection step I, 200g / t of inhibitor is added and stirred for 3 minutes before selection. For selection step II, no reagent is added.

[0043] The copper concentrate product obtained after the above flotation operation is shown in Table 1, and its grade and recovery rate are shown in Table 1.

[0044] Example 3

[0045] An organic combination inhibitor for the flotation separation of copper-zinc sulfide ore, comprising a phosphonic acid inhibitor and a succinate inhibitor; the phosphonic acid inhibitor is sodium diethylenetriaminepentamethylenephosphonate and sodium dihexenetriaminepentamethylenephosphonate (mass ratio of the two is 1:1), the succinate inhibitor is tetrasodium iminodisuccinate, the mass ratio of the phosphonic acid inhibitor to the succinate inhibitor is 5:1, the total amount of the organic combination inhibitor is 2100 g / t, and the organic combination inhibitor is added to the pulp during flotation.

[0046] When the above-mentioned organic combination of inhibitors is used in the flotation of copper-zinc sulfide ores, the separation of sphalerite and chalcopyrite is achieved.

[0047] In this embodiment, the copper-zinc sulfide ore processed has the following composition: Cu grade 1.24 wt%, Zn grade 6.68 wt%, copper-bearing minerals mainly chalcopyrite, and zinc-bearing minerals mainly sphalerite. The flotation steps are as follows:

[0048] (1) Grind the copper-zinc sulfide ore to a fineness of -0.074 mm (90%), adjust the slurry concentration to 45%, and adjust the slurry pH to 11.

[0049] (2) The slurry obtained in step (1) is subjected to flotation through a closed-circuit process of “two roughing, three scavenging, three cleaning, and middlings return in sequence”.

[0050] The specific process for the two roughing stages is as follows: The organic combination inhibitor is added at a rate of 1500 g / t, with an inhibitor mass ratio of 4:1 between roughing stage I and roughing stage II. Roughing stage I involves adding 1200 g / t of inhibitor (500 g / t of sodium diethylenetriaminepentamethylphosphonate, 500 g / t of sodium dihexenetriaminepentamethylphosphonate, and 200 g / t of tetrasodium iminodisuccinate). The pulp pH is adjusted to 11 using lime, stirred for 3 minutes, and then 180 g / t of collector butyl xanthate and 2 g / t of frother are added. # After stirring for 3 minutes, 20 g / t of oil is added to the roughing process. For roughing II, 300 g / t of inhibitor is added (125 g / t of sodium diethylenetriaminepentamethylenephosphonate, 125 g / t of sodium dihexenetriaminepentamethylenephosphonate, and 50 g / t of tetrasodium iminodisuccinate). The pulp pH is adjusted to 11 with lime, stirred for 3 minutes, and then 90 g / t of collector butyl xanthate and 2 g / t of frother are added. # 10g / t of oil, stir for 3 minutes and then perform coarse selection.

[0051] The specific process for the three-stage scavenging is as follows: The organic combination inhibitor is added at a rate of 300 g / t, of which scavenging I involves adding 120 g / t of inhibitor (50 g / t of sodium diethylenetriaminepentamethylphosphonate, 50 g / t of sodium dihexenetriaminepentamethylphosphonate, and 20 g / t of tetrasodium iminodisuccinate), 80 g / t of butyl xanthate as a collector, and 2 g / t of frother. # Oil (addition amount 10g / t), stir for 3 minutes and then perform scavenging operation; the dosage and operation steps of scavenging II are the same as those of scavenging I; the dosage of inhibitor added to scavenging III is 60g / t, and other operation steps are the same as those of scavenging I.

[0052] The specific process for the three-stage selection is as follows: the amount of organic combination inhibitor added is 300g / t. In selection I, 300g / t of inhibitor is added and stirred for 3 minutes before selection. Selection II and selection III are carried out without adding any reagents.

[0053] The copper concentrate product obtained after the above flotation operation is shown in Table 1, and its grade and recovery rate are shown in Table 1.

[0054] Example 4

[0055] An organic combination inhibitor for the flotation separation of copper-zinc sulfide ores, comprising a phosphonic acid inhibitor and a succinate inhibitor; the phosphonic acid inhibitor is sodium diethylenetriaminepentamethylenephosphonate and sodium dihexenetriaminepentamethylenephosphonate (mass ratio of the two is 3:1), the succinate inhibitor is tetrasodium iminodisuccinate and sodium (2R,3R)-2,3-dihydroxysuccinate (mass ratio of the two is 3:1), the mass ratio of the phosphonic acid inhibitor to the succinate inhibitor is 3:1, the total amount of the organic combination inhibitor is 1600 g / t, and the organic combination inhibitor is added to the pulp during flotation.

[0056] When the above-mentioned organic combination of inhibitors is used in the flotation of copper-zinc sulfide ores, the separation of sphalerite and chalcopyrite is achieved.

[0057] In this embodiment, the copper-zinc sulfide ore processed has the following composition: Cu grade 0.95 wt%, Zn grade 4.54 wt%, copper-bearing minerals are mainly chalcopyrite, and zinc-bearing minerals are mainly sphalerite. The flotation steps are as follows:

[0058] (1) Grind the copper-zinc sulfide ore to a fineness of -0.074 mm, accounting for 85%, adjust the slurry concentration to 40%, and adjust the slurry pH to 10.

[0059] (2) The slurry obtained in step (1) is subjected to flotation through a closed-circuit process of “two roughing, three scavenging, three cleaning, and middlings return in sequence”.

[0060] The specific process for the two roughing stages is as follows: the amount of organic combined inhibitor added is 1200 g / t, and the mass ratio of inhibitors in roughing stage I and roughing stage II is 3:1.

[0061] In the roughing process, 900 g / t of inhibitors (506.25 g / t of sodium diethylenetriaminepentamethylphosphonate, 168.75 g / t of sodium dihexenetriaminepentamethylphosphonate, 168.75 g / t of tetrasodium iminodisuccinate, and 56.25 g / t of sodium (2R,3R)-2,3-dihydroxysuccinate) were added. The pH of the slurry was adjusted to 10 with lime, and the mixture was stirred for 3 minutes. Then, 150 g / t of collector butyl xanthate and 2 g of frother were added. # 15 g / t of oil was added, and after stirring for 3 minutes, roughing was carried out. For roughing stage II, 300 g / t of inhibitor was added, along with (168.75 g / t of sodium diethylenetriaminepentamethylphosphonate, 56.25 g / t of sodium dihexenetriaminepentamethylphosphonate, 56.25 g / t of tetrasodium iminodisuccinate, and 18.75 g / t of sodium (2R,3R)-2,3-dihydroxysuccinate). The pulp pH was adjusted to 10 with lime, and the mixture was stirred for 3 minutes. Then, 70 g / t of collector butyl xanthate and 2 g / t of frother were added. # 10g / t of oil, stir for 3 minutes and then perform coarse selection.

[0062] The specific process for the three-stage scavenging is as follows: The organic combination inhibitor is added at a rate of 250 g / t, of which scavenging I involves adding 100 g / t of inhibitor (56.25 g / t of sodium diethylenetriaminepentamethylphosphonate, 18.75 g / t of sodium dihexenetriaminepentamethylphosphonate, 18.75 g / t of tetrasodium iminodisuccinate, and 6.25 g / t of sodium (2R,3R)-2,3-dihydroxysuccinate), butyl xanthate (50 g / t of collector), and 2% foaming agent. # Oil (addition amount 10g / t), stir for 3 minutes and then carry out scavenging operation; the dosage and operation steps of scavenging II are the same as those of scavenging I; the dosage of inhibitor for scavenging III is 50g / t, and the other operation steps are the same as those of scavenging I.

[0063] The specific process for the three-stage selection is as follows: the amount of organic combination inhibitor added is 150g / t. In selection I, 150g / t of inhibitor is added and the selection operation is carried out after stirring for 3 minutes; selection II and selection III are carried out without adding any reagents.

[0064] The copper concentrate product obtained after the above flotation operation is shown in Table 1, and its grade and recovery rate are shown in Table 1.

[0065] Example 5

[0066] An organic combination inhibitor for the flotation separation of copper-zinc sulfide ores, comprising a phosphonic acid inhibitor and a succinate inhibitor; the phosphonic acid inhibitor is sodium diethylenetriaminepentamethylenephosphonate, and the succinate inhibitor is tetrasodium iminodisuccinate and sodium (2R,3R)-2,3-dihydroxysuccinate (mass ratio of the two is 5:1), the mass ratio of the phosphonic acid inhibitor to the succinate inhibitor is 4:1, the total amount of the organic combination inhibitor is 1700 g / t, and the organic combination inhibitor is added to the pulp during flotation.

[0067] When the above-mentioned organic combination of inhibitors is used in the flotation of copper-zinc sulfide ores, the separation of sphalerite and chalcopyrite is achieved.

[0068] In this embodiment, the copper-zinc sulfide ore processed has the following composition: Cu grade 0.73 wt%, Zn grade 5.72 wt%, copper-bearing minerals are mainly chalcopyrite, and zinc-bearing minerals are mainly sphalerite. The flotation steps are as follows:

[0069] (1) Grind the copper-zinc sulfide ore to a fineness of -0.074 mm, accounting for 85%, adjust the slurry concentration to 40%, and adjust the slurry pH to 9.

[0070] (2) The slurry obtained in step (1) is subjected to flotation through a closed-loop process of “two roughing, two scavenging, three cleaning, and middlings return in sequence”.

[0071] The specific process for the two roughing stages is as follows: 1200 g / t of organic combined inhibitor is added, with an inhibitor mass ratio of 3:1 between roughing stage I and roughing stage II. Roughing stage I includes 900 g / t of inhibitor (720 g / t sodium diethylenetriaminepentamethylphosphonate, 150 g / t tetrasodium iminodisuccinate, and 30 g / t sodium (2R,3R)-2,3-dihydroxysuccinate). The pulp pH is adjusted to 9 with lime, stirred for 3 minutes, and then 100 g / t of collector butyl xanthate and 2 g / t frother are added. # After stirring for 3 minutes, 15 g / t of oil is added for roughing. For roughing stage II, 300 g / t of inhibitor, (240 g / t of sodium diethylenetriaminepentamethylphosphonate, 50 g / t of tetrasodium iminodisuccinate, and 10 g / t of sodium (2R,3R)-2,3-dihydroxysuccinate) are added. The pulp pH is adjusted to 9 with lime, stirred for 3 minutes, and then 50 g / t of collector butyl xanthate and 2 g / t of frother are added. # 10g / t of oil, stir for 3 minutes and then perform coarse selection.

[0072] The specific process for the two scavenging processes is as follows: The organic combination inhibitor is added at a rate of 300 g / t, of which scavenging I involves adding 150 g / t of inhibitor (120 g / t of sodium diethylenetriaminepentamethylphosphonate, 25 g / t of tetrasodium iminodisuccinate, and 5 g / t of sodium (2R,3R)-2,3-dihydroxysuccinate), 30 g / t of butyl xanthate as a collector, and 2 g / t of frother. # Add oil (10g / t), stir for 3 minutes, and then perform scavenging operation; the dosage and operation steps of scavenging II are the same as those of scavenging I.

[0073] The specific process for the three-stage selection is as follows: the amount of organic combination inhibitor added is 200g / t. In selection I, 200g / t of inhibitor is added and the selection operation is carried out after stirring for 3 minutes; selection II and selection III are carried out without adding any reagents.

[0074] The copper concentrate product obtained after the above flotation operation is shown in Table 1, and its grade and recovery rate are shown in Table 1.

[0075] Example 6

[0076] An organic combination inhibitor for the flotation separation of copper-zinc sulfide ores is disclosed, comprising a phosphonic acid inhibitor and a succinate inhibitor. The phosphonic acid inhibitor is sodium diethylenetriaminepentamethylenephosphonate and sodium dihexenetriaminepentamethylenephosphonate (mass ratio of 5:1), and the succinate inhibitor is tetrasodium iminodisuccinate and sodium (2R,3R)-2,3-dihydroxysuccinate (mass ratio of 4:1). The mass ratio of the phosphonic acid inhibitor to the succinate inhibitor is 2:1. The total amount of the organic combination inhibitor is 1845 g / t, and the organic combination inhibitor is added to the pulp during flotation.

[0077] When the above-mentioned organic combination of inhibitors is used in the flotation of copper-zinc sulfide ores, the separation of sphalerite and chalcopyrite is achieved.

[0078] In this embodiment, the copper-zinc sulfide ore processed has the following composition: Cu grade 0.94 wt%, Zn grade 6.08 wt%, copper-bearing minerals mainly chalcopyrite, and zinc-bearing minerals mainly sphalerite. The flotation steps are as follows:

[0079] (1) Grind the copper-zinc sulfide ore to a fineness of -0.074 mm, accounting for 80%, adjust the slurry concentration to 45%, and adjust the slurry pH to 10.

[0080] (2) The slurry obtained in step (1) is subjected to flotation through a closed-circuit process of “two roughing, three scavenging, three cleaning, and middlings return in sequence”.

[0081] The specific process for the two roughing processes is as follows: The amount of organic combined inhibitor added is 1440 g / t, and the mass ratio of inhibitors in roughing process I and roughing process II is 3:1. Roughing process I adds 1080 g / t of inhibitor (600 g / t of sodium diethylenetriaminepentamethylphosphonate, 120 g / t of sodium dihexenetriaminepentamethylphosphonate, 288 g / t of tetrasodium iminodisuccinate, and 72 g / t of sodium (2R,3R)-2,3-dihydroxysuccinate). The slurry pH is adjusted to 10 with lime, stirred for 3 minutes, and then 120 g / t of collector butyl xanthate and 2 g / t of frother are added. # After stirring for 3 minutes, 20 g / t of oil is added for roughing. For roughing stage II, 360 g / t of inhibitor, (200 g / t of sodium diethylenetriaminepentamethylphosphonate, 40 g / t of sodium dihexenetriaminepentamethylphosphonate, 96 g / t of tetrasodium iminodisuccinate, and 24 g / t of sodium (2R,3R)-2,3-dihydroxysuccinate) are added. The pulp pH is adjusted to 10 with lime, stirred for 3 minutes, and then 60 g / t of collector butyl xanthate and 2 g / t of frother are added. # 10g / t of oil, stir for 3 minutes and then perform coarse selection.

[0082] The specific process for the three-stage scavenging is as follows: The amount of organic combination inhibitor added is 225 g / t, of which 90 g / t of inhibitor is added in scavenging I (50 g / t of sodium diethylenetriaminepentamethylphosphonate, 10 g / t of sodium dihexenetriaminepentamethylphosphonate, 24 g / t of tetrasodium iminodisuccinate, and 6 g / t of sodium (2R,3R)-2,3-dihydroxysuccinate), 40 g / t of butyl xanthate collector is added, and 2 g / t of foaming agent is added. # Add 10g / t of oil, stir for 3 minutes, and then perform scavenging operation; the dosage and operation steps for scavenging II are the same as those for scavenging I; add 45g / t of inhibitor for scavenging III, and perform other operation steps as for scavenging I.

[0083] The specific process for the three-stage selection is as follows: the amount of organic combination inhibitor added is 180g / t. In selection I, 180g / t of inhibitor is added and the selection operation is carried out after stirring for 3 minutes; selection II and selection III are carried out without adding any reagents.

[0084] The copper concentrate product obtained after the above flotation operation is shown in Table 1, and its grade and recovery rate are shown in Table 1.

[0085] Comparative Example 1

[0086] The processing conditions in this embodiment are the same as in Example 1, except that only conventional inorganic inhibitor ZnSO4 is added, and no organic inhibitor is added. The amount of inorganic inhibitor added in each flotation stage is 1.5 times that in Example 1, and the total amount is 1800 g / t.

[0087] Comparative Example 2

[0088] The processing conditions in this embodiment are the same as in Example 1, except that only the organic inhibitor diethylenetriaminepentamethylenephosphonic acid is added, and the organic inhibitor tetrasodium iminodisuccinate is not added. The amount of diethylenetriaminepentamethylenephosphonic acid added in each flotation stage is the same as the total amount of inhibitor added in Example 1, which is 1200 g / t.

[0089] Comparative Example 3

[0090] The processing conditions in this embodiment are the same as in Example 1, except that only the organic inhibitor tetrasodium iminodisuccinate is added. The amount of tetrasodium iminodisuccinate added in each flotation stage is the same as the total inhibitor amount in Example 1, which is 1200 g / t.

[0091] Table 1. Test Results of Examples

[0092]

[0093] Table 2. Test results of comparative examples

[0094]

[0095] As shown in Table 1, when the organic combination inhibitor for copper-zinc sulfide ore flotation separation of the present invention is added during the flotation separation process of copper-zinc sulfide ore, the zinc content in the copper concentrate products obtained in each embodiment is significantly reduced, and the zinc grade is less than or equal to the maximum value specified in the non-ferrous metal industry standard (YS / T318-2007). Moreover, the copper recovery rate is greater than 90%, effectively realizing the flotation separation of chalcopyrite and sphalerite.

[0096] As shown in Table 2, the comparative data reveals that using inorganic depressants alone, or single phosphonic acid or succinic acid depressants, results in higher reagent dosages. Furthermore, the grade and recovery rate of the copper concentrate are not as high as when using a combination of organic depressants. The zinc content in the copper concentrate is greater than or close to 10%, exceeding the maximum value specified in the YS / T318-2007 standard, leading to unsatisfactory copper-zinc separation. Therefore, the combined use of organophosphonic acid and succinic acid depressants can effectively solve these problems, resulting in more thorough copper-zinc flotation separation and reducing the amount of depressant required to some extent.

[0097] The organic combination inhibitor described in this invention can interact with zinc active sites on the surface of zinc sphalerite or with Zn in the slurry. 2+ The reaction forms chelates that adsorb onto the surface of sphalerite, enhancing its hydrophilicity and hindering the adsorption of collectors, thus reducing its floatability and effectively achieving the flotation separation of copper-zinc sulfide ores. The combined use of organophosphonic acid and succinic acid inhibitors can further reduce the amount of inhibitor required. The organic combination inhibitor described in this invention is applicable to a wide range of pulp pH values ​​(pH 8–11), exhibits strong selective inhibition of sphalerite, and has virtually no inhibitory effect on the flotation of chalcopyrite, effectively achieving the separation of chalcopyrite and sphalerite. The organic combination inhibitor described in this invention is stable, has good selective inhibition, requires small dosage, is safe to use, has strong adaptability, and has broad application prospects.

[0098] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall fall within the scope of the technical solution of the present invention.

Claims

1. A copper-zinc sulphide ore flotation separation organic combination depressant characterised in that, The organic combination inhibitors include phosphonic acid inhibitors and succinate inhibitors, wherein the mass ratio of phosphonic acid inhibitors to succinate inhibitors is 1:1 to 5:

1. The phosphonic acid inhibitors are one of diethylenetriaminepentamethylenephosphonic acid, sodium diethylenetriaminepentamethylenephosphonate, dihexenetriaminepentamethylenephosphonic acid, and sodium dihexenetriaminepentamethylenephosphonate, or a combination of one of diethylenetriaminepentamethylenephosphonic acid and sodium dihexenetriaminepentamethylenephosphonate with one of dihexenetriaminepentamethylenephosphonic acid and sodium dihexenetriaminepentamethylenephosphonate. The succinate inhibitors are one or two of iminodisuccinate tetrasodium and (2R,3R)-2,3-dihydroxysuccinate sodium.

2. The organic combination depressant for the flotation separation of copper-zinc sulphide ores according to claim 1, characterized by: When the phosphonic acid inhibitor is a combination of two, the mass ratio of one of diethylenetriaminepentamethylenephosphonic acid and sodium diethylenetriaminepentamethylenephosphonic acid to one of dihexenetriaminepentamethylenephosphonic acid and sodium dihexenetriaminepentamethylenephosphonic acid is 1:1 to 5:

1.

3. The organic combination inhibitor for the flotation separation of copper-zinc sulfide ores according to claim 1, characterized in that: When the succinate inhibitor is a combination of two, the mass ratio of tetrasodium iminodisuccinate to sodium (2R,3R)-2,3-dihydroxysuccinate is 3:1 to 5:

1.

4. The application of the organic combination inhibitor for the flotation separation of copper-zinc sulfide ores according to any one of claims 1 to 3, characterized in that, Organic combination inhibitors were used for the flotation separation of sphalerite and chalcopyrite in copper-zinc sulfide ores.

5. The application of the organic combination inhibitor for the flotation separation of copper-zinc sulfide ores according to claim 4, characterized in that: The specific process is as follows: the copper-zinc sulfide ore is ground to the required fineness, the pulp concentration and pH value are adjusted, and organic combination inhibitors are added in the roughing, cleaning and scavenging stages respectively. The copper-zinc sulfide ore is subjected to 1-2 roughing, 2-3 scavenging and 2-3 cleaning to obtain copper concentrate.

6. The application of the organic combination inhibitor for the flotation separation of copper-zinc sulfide ores according to claim 5, characterized in that: The total amount of organic combination inhibitors added in the roughing stage is 1000-1500 g / t. During the two roughing stages, the mass ratio of organic combination inhibitors added in roughing stage I and roughing stage II is 2:1-4:

1.

7. The application of the organic combination inhibitor for the flotation separation of copper-zinc sulfide ores according to claim 5, characterized in that: The total amount of organic combination inhibitors added during the selection stage is 100-300 g / t. During the three selection stages, the organic combination inhibitors are added only in the first stage of selection, and not in the second and third stages.

8. The application of the organic combination inhibitor for the flotation separation of copper-zinc sulfide ores according to claim 5, characterized in that: The total amount of organic combination inhibitor added in the scavenging stage is 100-300 g / t. During the three scavenging stages, the mass ratio of organic combination inhibitor added in scavenging I, scavenging II, and scavenging III is 2:2:

1.

9. The application of the organic combination inhibitor for the flotation separation of copper-zinc sulfide ores according to claim 5, characterized in that: The total amount of organic combination inhibitor added during the roughing, cleaning and scavenging stages is 1200-2100 g / t.

10. The application of the organic combination inhibitor for the flotation separation of copper-zinc sulfide ores according to claim 5, characterized in that: The copper-zinc sulfide ore is ground to a thickness of -0.074 mm, with 70% to 90% of the ore being fined. The slurry mass percentage concentration is 30% to 45%, and the slurry pH value is 8 to 11.

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