Composite inhibitor for inhibiting copper ion activated pyrrhotite and application thereof

Abstract

The invention discloses a composite inhibitor for inhibiting copper ion activated pyrrhotite and application of the composite inhibitor. The composite inhibitor is composed of sodium ethylene diamine tetramethylene phosphonate, soluble starch, modified sodium lignin sulfonate and sodium thiosulfate according to a specific mass percentage. The invention further provides a beneficiation method adopting the inhibitor. The beneficiation method comprises the steps of ore grinding, copper-lead bulk flotation, zinc flotation and concentration. The composite inhibitor can efficiently and selectively inhibit the pyrrhotite activated by Cu < 2 + >, especially monoclinic pyrrhotite through multiple synergistic action mechanisms of complexing stripping, shielding covering and hydrophilic film forming, and obviously reduces the entrainment of Cu < 2 + > in concentrates, so that the grade and recovery rate of copper, lead and zinc concentrates are improved. The inhibitor is environmentally friendly and high in applicability, can be directly embedded into an existing priority flotation process, and has important industrial application value.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, specifically to a composite inhibitor for suppressing copper-ion-activated pyrrhotite and its application. Background Technology

[0002] Pyrrhotite is a common iron sulfide mineral and an important raw material for sulfuric acid production and iron and steel smelting. Its crystal structure is complex, mainly comprising hexagonal and monoclinic crystal systems. During flotation, due to the dissociation of the mineral itself or the introduction of exogenous copper sulfate activators, Cu... 2+ It readily adsorbs onto the surface of pyrrhotite, forming an extremely thin and dense, incomplete copper-like (CuS) or chalcocite-like (Cu2S) structure. This structure provides excellent adsorption sites for collectors, which is why pyrrhotite is susceptible to Cu adsorption. 2+ The main reason for the significant improvement in its buoyancy after activation.

[0003] However, pyrrhotite through Cu 2+ After activation, the copper-like / chalcocite capping layer formed on the surface exhibits high stability and is not easily oxidized. Its presence, however, hinders the contact between inhibitor ions and the mineral substrate or residual iron active sites, making it difficult to regulate the surface charge and potential, thus significantly reducing the inhibitory effect. Simultaneously, this dense copper film completely covers the mineral surface, physically enhancing surface stability and inhibiting further oxidation of the pyrrhotite itself. In actual ores, due to the presence of associated copper minerals or Cu in the slurry circulation system... 2+ Due to the accumulation of pyrrhotite, it often undergoes unexpected activation, resulting in its floatability being similar to that of target minerals (such as copper, lead, and zinc minerals), making separation difficult and severely affecting concentrate grade and recovery rate.

[0004] Therefore, for polymetallic sulfide mineral resources rich in pyrrhotite, it is necessary to develop methods that can effectively inhibit Cu... 2+ The new methods and reagents for activating pyrrhotite are of great practical significance for achieving efficient separation of valuable minerals such as copper, lead, and zinc. Summary of the Invention

[0005] Based on the aforementioned technical problems, the purpose of this invention is to provide a composite inhibitor for suppressing copper-activated pyrrhotite and its application. This aims to address the limitations of traditional inhibitors on Cu-activated pyrrhotite. 2+ The problem of poor inhibition effect of activated pyrrhotite, especially in pyrrhotite-rich polymetallic ores with a high proportion of monoclinic pyrrhotite; traditional inhibitors require large amounts, are prone to scaling, and some inorganic inhibitors are toxic and harmful, which do not meet the requirements of green mineral processing.

[0006] This invention protects a composite inhibitor for inhibiting copper-activated pyrrhotite, the composite inhibitor being composed of the following four components in parts by weight: 25-45 parts of sodium ethylenediaminetetramethylenephosphonate, 10-20 parts of soluble starch, 15-30 parts of modified sodium lignin sulfonate, and 30-45 parts of sodium thiosulfate.

[0007] Optimally, the modified sodium lignin sulfonate is preferably at least one of iron-chromium sodium lignin sulfonate or sulfonated sodium lignin sulfonate.

[0008] This invention also protects the application of the aforementioned composite inhibitor in the flotation separation of copper-lead-zinc polymetallic minerals rich in pyrite.

[0009] Furthermore, the application is to suppress pyrrhotite, especially monoclinic pyrrhotite, which is activated by copper ions during the flotation process.

[0010] This invention also protects a mineral processing method for flotation separation of pyrrhotite-type copper-lead-zinc polymetallic ores using the aforementioned composite inhibitor, specifically comprising the following steps: Step 1, Pretreatment: Add water to the pyrrhotite-type copper-lead-zinc-sulfur metal ore to be treated at a solid-liquid ratio of 1:1 to 1:1.5, and grind it to a fineness of -0.074 mm accounting for 65 to 75%, to obtain slurry a; Step 2, Copper-lead mixed flotation: First, add sphalerite inhibitor to the slurry a obtained in Step 1 and stir for 3-5 minutes; then add copper-lead collector and stir for 2-4 minutes; finally, add frother pine oil, stir for 1-2 minutes, and then carry out aeration flotation, skimming the bubbles for 3-5 minutes to obtain copper-lead rough concentrate b and copper-lead tailings c. Step 3, Zinc flotation: Add the composite inhibitor to the copper-lead tailings c obtained in Step 2, and stir for 3-5 minutes; add copper sulfate, the sphalerite activator, and stir for 2-3 minutes; add butyl xanthate, the sphalerite collector, and stir for 2-3 minutes; add pine oil, the frother, and stir for 1-2 minutes, then perform aerated flotation and skim the bubbles for 4-6 minutes to obtain zinc rough concentrate d and zinc tailings e containing pyrrhotite; Step 4, Fine Refinement: The copper-lead crude concentrate b obtained in Step 2 is finely refined three times to obtain copper-lead concentrate; the zinc crude concentrate d obtained in Step 3 is finely refined three times to obtain zinc concentrate.

[0011] Further, in step 2, the sphalerite inhibitor is selected from one or two of zinc sulfate, sodium sulfite, sodium sulfide, and sodium carbonate, and the addition amount is 400~800g / t of raw ore; the copper-lead sulfide collector is selected from any one of Z200 and ethyl xanthate, 25# black powder, and ethyl thiocyanate in a ratio of 1~3:1~4, and the addition amount is 60~70g / t of raw ore; the foaming agent is pine oil, and the addition amount is 0~20g / t of raw ore.

[0012] Further, in step 3, the composite inhibitor is the aforementioned composite inhibitor used to inhibit copper-ion-activated pyrrhotite, and the amount of the composite inhibitor added is 300-500 g / t of raw ore; the amount of the zinc sulfide activator copper sulfate added is 200-300 g / t of raw ore; the amount of the zinc sulfide collector butyl xanthate added is 30-80 g / t of raw ore; and the amount of the frother pine oil added is 30-40 g / t of raw ore.

[0013] Its working principle is as follows: First, it involves complexation and exfoliation, utilizing the selective complexation of Cu in sodium ethylenediaminetetramethylenephosphonate and soluble starch molecules. 2+ and Fe 3+ First, it can selectively integrate, dissolve, or transform copper ions in the surface-activated "copper-sulfur" phase into hydrophilic complexes, fundamentally eliminating the main adsorption sites of the collector. Second, it provides shielding and covering, utilizing the main chain of the molecule or other sterically hindered groups of the polymer to cover the sulfur vacancy surface that has been stripped of copper but still has a certain degree of hydrophobicity through bonds, van der Waals forces, or physical adsorption, forming a stable hydrophilic layer and preventing secondary adsorption of the collector. Third, it utilizes the interaction between the molecule and the Fe on the surface of monoclinic pyrrhotite. 3+ A bonding reaction occurs, forming a hydrophilic film that covers the surface of pyrrhotite, thus achieving an inhibitory effect.

[0014] Compared with existing technologies, the present invention has the following beneficial effects: The composite inhibitor of this invention has a highly effective inhibitory effect on activated pyrrhotite, while having minimal impact on the floatability of target minerals such as chalcopyrite, galena, and sphalerite, significantly improving the grade of copper, lead, and zinc concentrates. It is particularly suitable for minerals with high monoclinic pyrrhotite content and those affected by Cu. 2+ This process is suitable for highly activated complex polymetallic ores and can be directly integrated into existing preferential flotation processes such as "zinc suppression for copper and lead flotation - activated zinc flotation," without altering the main process structure. The main components are biodegradable or low in toxicity, making it more compliant with green mineral processing requirements compared to traditional high-lime processes. Specifically, it selectively complexes and chelates Cu deposits stripped from the surface of pyrrhotite through the strong chelation effect of sodium ethylenediaminetetramethylenephosphonate and soluble starch. 2+ The activated film fundamentally eliminates the collector adsorption sites. Utilizing the steric hindrance effect and polymer adsorption properties of soluble starch and modified sodium lignosulfonate, a stable hydrophilic coating layer is formed on the mineral surface after the activated film is removed, effectively preventing secondary adsorption of the collector. The modified sodium lignosulfonate and other components can react with Fe on the surface of pyrrhotite. 3+ Bonding occurs, forming a hydrophilic film that further enhances the inhibition of the pyrrhotite matrix. Attached Figure Description

[0015] Figure 1 This is a process flow diagram of the composite inhibitor beneficiation method of the present invention. Detailed Implementation

[0016] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention. Example 1

[0017] A composite inhibitor for inhibiting copper-activated pyrrhotite, the composite inhibitor being composed of the following four components in parts by weight: 175 g / t (35%) sodium ethylenediaminetetramethylenephosphonate, 50 g / t (10%) soluble starch, 100 g / t (20%) modified sodium lignin sulfonate, and 175 g / t (35%) sodium thiosulfate. The above raw materials are mixed evenly under a dry environment to obtain the composite inhibitor. Example 2

[0018] A composite inhibitor for inhibiting copper-activated pyrrhotite, the composite inhibitor being composed of the following four components in parts by weight: 100 g / t (25%) sodium ethylenediaminetetramethylenephosphonate, 50 g / t (12.5%) soluble starch, 75 g / t (18.75%) modified sodium lignin sulfonate, and 175 g / t (43.75%) sodium thiosulfate. The above raw materials are mixed evenly under a dry environment to obtain the composite inhibitor. Example 3

[0019] A composite inhibitor for inhibiting copper-activated pyrrhotite, the composite inhibitor being composed of the following four components in parts by weight: 75 g / t (25%) sodium ethylenediaminetetramethylenephosphonate, 50 g / t (16%) soluble starch, 75 g / t (25%) modified sodium lignin sulfonate, and 100 g / t (33.33%) sodium thiosulfate. The above raw materials are mixed evenly under a dry environment to obtain the composite inhibitor. Example 4

[0020] Taking a copper-lead-zinc-sulfur polymetallic mine in Qinghai, my country as an example Properties of the raw ore: The raw material contains 0.2% copper, 3.69% zinc, 22.02% sulfur, and 1.5% lead; the target minerals are mainly galena, sphalerite, chalcopyrite, and pyrrhotite; the gangue minerals are mainly quartz and calcite, with minor amounts of sulphite, chlorite, pyroxene, siderite, talc, muscovite, etc.

[0021] The present invention relates to a mineral processing method for flotation separation of monoclinic pyrrhotite using a composite inhibitor to suppress copper-lead-zinc polymetallic pyrrhotite-type copper-lead-zinc polymetallic pyrrhotite, which specifically includes the following steps: Step 1, Pretreatment: Add water to the pyrrhotite-type copper-lead-zinc-sulfur metal ore to be treated at a solid-liquid ratio of 1:1, and grind it to a fineness of -0.074mm accounting for 65%, to obtain slurry a; Step 2, Copper-Lead Mixed Flotation: To the slurry a obtained in Step 1, first add zinc sulfate (500g / t raw ore), a zinc sphalerite inhibitor, and stir for 3 minutes; then add ethyl xanthate (40g / t raw ore) + Z200 (20g / t raw ore), copper-lead sulfide collectors, and stir for 2 minutes; finally add pine oil (10g / t raw ore), a frother, and stir for 2 minutes. Then, perform aerated flotation and skim flotation for 4 minutes to obtain copper-lead rough concentrate b and copper-lead tailings c. Step 3, Zinc Flotation: Add the composite inhibitor prepared in Example 1 (500g / t raw ore) to the copper-lead tailings c obtained in Step 2, and stir for 3 min; add the zinc sulfide activator copper sulfate (200g / t raw ore), and stir for 3 min; add the zinc sulfide collector butyl xanthate (40g / t raw ore), and stir for 3 min; add the frother pine oil (40g / t raw ore), and stir for 2 min. Perform aerated flotation and skim froth for 4 min to obtain zinc rough concentrate d and zinc tailings e containing pyrrhotite. Step 4, Fine Refinement: The copper-lead crude concentrate b obtained in Step 2 is finely refined three times to obtain copper-lead concentrate; the zinc crude concentrate d obtained in Step 3 is finely refined three times to obtain zinc concentrate.

[0022] The ore beneficiation results are detailed in Table 1. Table 1 Mineral Processing Results Example 5

[0023] Taking copper-lead-zinc ore from a certain region in Tibet, my country as an example Raw material properties: The raw material contains 0.15% copper, 5.75% zinc, 19.08% sulfur, and 2.5% lead; the target minerals are mainly galena, sphalerite, chalcopyrite, and pyrrhotite; the gangue minerals are mainly calcite, with minor amounts of quartz, sulphite, chlorite, pyroxene, siderite, talc, muscovite, etc.

[0024] The present invention relates to a mineral processing method for flotation separation of monoclinic pyrrhotite using a composite inhibitor to suppress copper-lead-zinc polymetallic pyrrhotite-type copper-lead-zinc polymetallic pyrrhotite, which specifically includes the following steps: Step 1, Pretreatment: Add water to the pyrrhotite-type copper-lead-zinc-sulfur metal ore to be treated at a solid-liquid ratio of 1:1, and grind it to a fineness of -0.074mm accounting for 65%, to obtain slurry a; Step 2, Copper-Lead Mixed Flotation: First, add zinc sulfate (600g / t raw ore), a zinc sphalerite inhibitor, to the slurry a obtained in Step 1 and stir for 3 minutes; then add copper-lead collector 25# black powder (40g / t raw ore) + Z200 (30g / t raw ore) and stir for 2 minutes; finally, add frother pine oil (0g / t), stir for 2 minutes, and then perform aerated flotation, skimming the froth for 4 minutes to obtain copper-lead rough concentrate b and copper-lead tailings c; Step 3, Zinc Flotation: Add the composite inhibitor prepared in Example 2 (400g / t raw ore) to the copper-lead tailings c obtained in Step 2, and stir for 3 min; add the zinc sulfide activator copper sulfate (300g / t raw ore), and stir for 3 min; add the zinc sulfide collector butyl xanthate (60g / t raw ore), and stir for 3 min; add the frother pine oil (40g / t raw ore), and stir for 2 min. Perform aerated flotation and skim froth for 4 min to obtain zinc rough concentrate d and zinc tailings e containing pyrrhotite. Step 4, Fine Refinement: The copper-lead crude concentrate b obtained in Step 2 is finely refined three times to obtain copper-lead concentrate; the zinc crude concentrate d obtained in Step 3 is finely refined three times to obtain zinc concentrate.

[0025] The ore beneficiation results are detailed in Table 2. Table 2 Mineral Processing Results Example 6

[0026] Taking copper, lead, and zinc ore from a certain region in Myanmar as an example Properties of the raw ore: The raw material contains 0.32% copper, 2.63% zinc, 16.05% sulfur, and 0.9% lead. The target minerals are mainly galena, sphalerite, chalcopyrite, and pyrrhotite; the gangue minerals are mainly quartz, with minor amounts of shale, chlorite, pyroxene, siderite, talc, and calcite.

[0027] The present invention relates to a mineral processing method for flotation separation of monoclinic pyrrhotite using a composite inhibitor to suppress copper-lead-zinc polymetallic pyrrhotite-type copper-lead-zinc polymetallic pyrrhotite, which specifically includes the following steps: Step 1, Pretreatment: Add water to the pyrrhotite-type copper-lead-zinc-sulfur metal ore to be treated at a solid-liquid ratio of 1:1, and grind it to a fineness of -0.074mm accounting for 75%, to obtain slurry a; Step 2, Copper-Lead Mixed Flotation: To the slurry a obtained in Step 1, first add zinc sulfate (400g / t raw ore), a zinc sphalerite inhibitor, and stir for 3 minutes; then add ethyl thiocyanate (40g / t raw ore) + Z200 (30g / t raw ore), a copper-lead sulfide collector, and stir for 2 minutes; finally add pine oil (10g / t raw ore), a frother, and stir for 2 minutes. Then, perform aerated flotation and skim flotation for 4 minutes to obtain copper-lead rough concentrate b and copper-lead tailings c. Step 3, Zinc Flotation: Add the composite inhibitor prepared in Example 3 (300g / t raw ore) to the copper-lead tailings c obtained in Step 2, and stir for 3 min; add the zinc sulfide activator copper sulfate (200g / t raw ore), and stir for 3 min; add the zinc sulfide collector butyl xanthate (30g / t raw ore), and stir for 3 min; add the frother pine oil (30g / t raw ore), and stir for 2 min. Perform aerated flotation and skim froth for 4 min to obtain zinc rough concentrate d and zinc tailings e containing pyrrhotite. Step 4, Fine Refinement: The copper-lead crude concentrate b obtained in Step 2 is finely refined three times to obtain copper-lead concentrate; the zinc crude concentrate d obtained in Step 3 is finely refined three times to obtain zinc concentrate.

[0028] The ore beneficiation results are detailed in Table 3. Table 3 Mineral Processing Results Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A composite inhibitor for suppressing copper-ion-activated pyrrhotite, characterized in that, The composite inhibitor is composed of the following four components in parts by weight: 25-45 parts of sodium ethylenediaminetetramethylenephosphonate, 10-20 parts of soluble starch, 15-30 parts of modified sodium lignin sulfonate, and 30-45 parts of sodium thiosulfate.

2. The composite inhibitor according to claim 1, characterized in that, The modified sodium lignin sulfonate is at least one of iron-chromium sodium lignin sulfonate or sulfonated sodium lignin sulfonate.

3. The application of the composite inhibitor for inhibiting copper-ion-activated pyrrhotite according to claim 1, characterized in that, Application of the composite inhibitor in the flotation separation of copper-lead-zinc polymetallic minerals rich in pyrite.

4. The application according to claim 3, characterized in that, The application is to suppress pyrrhotite, especially monoclinic pyrrhotite, which is activated by copper ions during the flotation process.

5. A mineral processing method for flotation separation of pyrrhotite-type copper-lead-zinc polymetallic ores using a composite inhibitor, characterized in that, The mineral processing method described in claim 3 is an application of a composite inhibitor for suppressing copper-activated pyrrhotite, and specifically includes the following steps: Step 1, Pretreatment: Add water to the pyrrhotite-type copper-lead-zinc-sulfur metal ore to be treated at a solid-liquid ratio of 1:1 to 1:1.5, and grind it to a fineness of -0.074 mm accounting for 65 to 75%, to obtain slurry a; Step 2, Copper-lead mixed flotation: First, add sphalerite inhibitor to the slurry a obtained in Step 1 and stir for 3-5 minutes; then add copper-lead collector and stir for 2-4 minutes; finally, add frother pine oil, stir for 1-2 minutes, and then carry out aeration flotation, skimming the bubbles for 3-5 minutes to obtain copper-lead rough concentrate b and copper-lead tailings c. Step 3, Zinc flotation: Add the composite inhibitor to the copper-lead tailings c obtained in Step 2, and stir for 3-5 minutes; add copper sulfate, the sphalerite activator, and stir for 2-3 minutes; add butyl xanthate, the sphalerite collector, and stir for 2-3 minutes; add pine oil, the frother, and stir for 1-2 minutes, then perform aerated flotation and skim the bubbles for 4-6 minutes to obtain zinc rough concentrate d and zinc tailings e containing pyrrhotite; Step 4, Fine Refinement: The copper-lead crude concentrate b obtained in Step 2 is finely refined three times to obtain copper-lead concentrate; the zinc crude concentrate d obtained in Step 3 is finely refined three times to obtain zinc concentrate.

6. The mineral processing method according to claim 5, characterized in that, In step 2, the sphalerite inhibitor is selected from one or two of zinc sulfate, sodium sulfite, sodium sulfide, and sodium carbonate, and the addition amount is 400~800g / t of raw ore; the copper-lead sulfide collector is selected from any one of Z200 and ethyl xanthate, 25# black powder, and ethyl thiocyanate in a ratio of 1~3:1~4, and the addition amount is 60~70g / t of raw ore; the foaming agent is pine oil, and the addition amount is 0~20g / t of raw ore.

7. The mineral processing method according to claim 5, characterized in that, In step 3, the composite inhibitor is the composite inhibitor used to inhibit copper-activated pyrrhotite, and the amount of the composite inhibitor added is 300-500 g / t of raw ore; the amount of the zinc sulfide activator copper sulfate added is 200-300 g / t of raw ore; the amount of the zinc sulfide collector butyl xanthate added is 30-80 g / t of raw ore; and the amount of the foaming agent pine oil added is 30-40 g / t of raw ore.

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