A beneficiation process for recovering copper from iron tailings

Abstract

This invention relates to the field of mineral processing technology and discloses a beneficiation process for recovering copper from iron tailings. The process includes: performing copper-sulfur mixed flotation on the iron tailings slurry to obtain a mixed concentrate; physically dehydrating and de-removing the mixed concentrate to remove some residual flotation reagents; wet grinding the concentrated slurry; and, under lime-free conditions, adding a pyrite inhibitor and a copper collector, sequentially performing roughing, scavenging, and cleaning operations to finally obtain a copper concentrate. The pyrite inhibitor is a compound composed of sodium glyceroxanthate, carboxymethyl chitosan, sodium tripolyphosphate, and ethylenediaminetetraacetate. This invention achieves efficient copper-sulfur separation under naturally neutral pH conditions through the synergistic effect of the dehydration and de-removal process and the quaternary compound inhibitor. This not only avoids the equipment scaling problem caused by the high alkalinity of traditional lime flotation but also eliminates the inhibition of associated precious metals, significantly improving the overall recovery rate of associated gold and silver while ensuring the grade of the copper concentrate.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, specifically to a mineral processing technology for recovering copper from iron tailings. Background Technology

[0002] Iron tailings are solid waste generated after iron ore processing and extraction. They often contain small amounts of valuable metallic minerals such as copper, gold, and silver. Separating and recycling these associated metals is a crucial step in the comprehensive development of mineral resources. Flotation is a common separation process for treating metallic sulfide minerals. The process involves adding reagents to alter the hydrophilic state of the mineral surface, causing the target mineral to adhere to air bubbles and float to the surface of the slurry, ultimately extracting the target product.

[0003] The core of copper recovery from iron tailings lies in copper-sulfur separation, which involves separating copper-bearing minerals from associated pyrite. This separation relies on the differences in the physicochemical properties of the different mineral surfaces. During the flotation stage, operators add collectors and depressants to the pulp. The collectors specifically target the copper-bearing mineral surface, increasing its hydrophobicity; the depressants act on the pyrite surface, creating a hydrophilic coating that prevents pyrite particles from binding with air bubbles. As air bubbles carry the copper-bearing minerals to the surface, the pyrite continues to settle at the bottom of the pulp, completing the mineral separation.

[0004] Current copper-sulfur separation processes involve the addition of large amounts of lime to create a highly alkaline slurry environment. This strong alkalinity not only causes scaling on equipment and pipelines but also inhibits the flotation of associated precious metals such as gold and silver, resulting in low overall recovery rates. The potent collectors added during the initial mixed flotation stage leave residues in the slurry upon entering subsequent separation operations. These residues directly interfere with the pyrite inhibition process, reducing the differences in floatability between minerals. Furthermore, traditional processes often use single-component pyrite inhibitors, which fail to eliminate the activation interference of free metal ions in the slurry and the capping interference of fine slime on the target minerals. This prevents the formation of a stable hydrophilic network coating on the pyrite surface, making pyrite easily activated and carried to the surface, thus lowering the copper concentrate grade and disrupting the separation process.

[0005] Therefore, the purpose of this invention is to provide a beneficiation process for recovering copper from iron tailings, in order to overcome the shortcomings of the prior art. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a mineral processing technology for recovering copper from iron tailings. This technology solves the problems in existing copper-sulfur separation processes, such as the addition of large amounts of lime causing equipment scaling and inhibiting the recovery of associated precious metals, interference of residual collectors in front-end flotation with separation, and the inability of a single inhibitor to eliminate metal ion activation and fine mud covering leading to pyrite flotation and lower copper concentrate grades.

[0007] To achieve the above objectives, the present invention provides the following technical solution: A mineral processing technology for recovering copper from iron tailings includes the following steps: Iron tailings slurry is introduced into a mechanically stirred flotation machine, and copper-sulfur collector and frother are added in sequence to carry out copper-sulfur mixed flotation. The frothy product is scraped off to obtain copper-sulfur mixed concentrate, and the bottom flow in the tank is mixed tailings. The obtained copper-sulfur mixed concentrate slurry is introduced into a centrifuge, thickener, or hydrocyclone for physical dewatering and dereticling, removing some water and carrying away some dissolved residual flotation reagents with the discharged aqueous phase, until the mass concentration of the underflow slurry reaches 30wt% to 45wt%. The concentrated slurry is fed into a wet ball mill for wet grinding to produce copper flotation slurry. The finely ground copper flotation slurry is introduced into the flotation machine, and pyrite inhibitor and copper collector are added sequentially under lime-free conditions to carry out roughing operations, thereby obtaining copper rough concentrate and copper roughing tailings. A copper collector is added to the copper roughing tailings for mechanical flotation scavenging, and the concentrate obtained from the scavenging is returned to the roughing section in sequence. Pyrite inhibitors are added to the copper rough concentrate for mechanical flotation and cleaning. The cleaned tailings are returned to the previous operation section in sequence, and the final froth product is the final copper concentrate. The raw materials for preparing pyrite inhibitors include sodium glyceroxanthate, carboxymethyl chitosan, sodium tripolyphosphate, and ethylenediaminetetraacetic acid.

[0008] By adopting the above technical solution, due to the use of a system process involving mixed flotation, dehydration and de-reagenting, regrinding and separation, and the synergistic effect of multi-component compound inhibitors, the technical effect of separating copper and sulfur and producing qualified copper concentrate under natural neutral pH conditions is achieved.

[0009] Preferably, the raw materials for preparing the pyrite inhibitor include the following components in parts by weight: 50-60 parts of sodium glyceroxanthate, 15-20 parts of carboxymethyl chitosan, 10-20 parts of sodium tripolyphosphate, and 10-20 parts of ethylenediaminetetraacetic acid.

[0010] By adopting the above technical solution, relatively good synergistic effects of the reagents are achieved. The content of ethylenediaminetetraacetic acid (EDTA) can adapt to the complex metal ion concentration in conventional iron tailings slurry; sodium glyceroxanthate serves as the dominant adsorbent, providing binding groups; an appropriate amount of carboxymethyl chitosan constructs a steric hindrance network; and a suitable amount of sodium tripolyphosphate acts as a dispersant, dispersing the slurry and eliminating the covering interference of fine mineral slime. Mixing these four components in this proportion reduces the dosage of individual reagents while minimizing the tendency for flocculation and settling.

[0011] Preferably, the specific preparation process of the pyrite inhibitor is as follows: sodium glyceroxanthate, carboxymethyl chitosan, sodium tripolyphosphate and ethylenediaminetetraacetic acid are placed in a dry powder mixer and mechanically stirred at room temperature for 30 minutes until they are uniformly mixed to obtain a pyrite inhibitor dry powder mixture; then, the obtained dry powder mixture is slowly added to a stirring tank containing room temperature deionized water and stirred continuously until the solid is completely dissolved to prepare an aqueous solution of pyrite inhibitor with a mass concentration of 2wt% to 5wt%.

[0012] By adopting the above technical solution, the steps of first mechanically dry mixing and then preparing with a low-concentration aqueous solution promote the uniform distribution of the four powders with different forms and densities during the mixing process. Mechanical dry mixing helps reduce the probability of the polymer forming insoluble encapsulated clumps when it comes into contact with water. Using room temperature deionized water to prepare a low-concentration solution of 2wt% to 5wt% keeps the carboxymethyl chitosan in an extended chain state, guiding the polymer to disperse after entering the slurry and perform its function of capturing the surface of the target mineral.

[0013] Preferably, the copper-sulfur collector is one of sodium butylxanthate and ammonium dibutyldithiophosphate, or a mixed copper-sulfur collector in a 1:1 mass ratio; the frother is one of pine oil and methyl isobutyl methanol, or a mixed frother in a 1:1 mass ratio. In the copper-sulfur mixed flotation operation, the feed rate of the copper-sulfur collector is 50–150 g / t, and the feed rate of the frother is 10–30 g / t.

[0014] By adopting the above technical solution, when sodium butyl xanthate and dibutyl dithiophosphate are used in combination, collectors with different carbon chain lengths generate complementary adsorption on the mineral surface, which expands the collection range for particles of varying sizes and is conducive to improving the recovery rate in the mixed flotation stage.

[0015] Preferably, the performance parameters of the copper flotation slurry obtained by wet grinding are in the range of 80wt% to 95wt% with a fineness of -38μm particles.

[0016] By employing the above technical solution, controlling the fineness within the specified range enables the dissociation of finely embedded copper sulfides into individual particles. Simultaneously, it controls the micro-sludge formation caused by over-grinding, reducing the likelihood of sludge covering the surface of coarse mineral particles and hindering reagent adsorption.

[0017] Preferably, the lime-free conditions controlled in the roughing operation are to control the natural pH of the slurry to 7 to 8; the copper collector is one of ethyl thiocyanate and thiocyanate propionitrile, or a mixed copper collector in a 1:1 mass ratio. In the roughing operation, the feed rate of pyrite inhibitor is 50–150 g / t, and the feed rate of copper collector is 10–50 g / t; the roughing operation specifically involves 1–2 roughing operations.

[0018] By adopting the above technical solution, the natural neutral pH environment maintains the stability of the active groups in the structure of the pyrite inhibitor, alleviating the corrosion and scaling problems of equipment caused by the strong alkaline environment. Ethiocyanate and thiocyanate have the ability to adsorb copper minerals. Under the condition that pyrite is shielded by the compound inhibitor, a lower dosage can be used to make the copper minerals hydrophobically float.

[0019] Preferably, in the scavenging operation, the amount of copper collector added to the ore feed is 5-25 g / t, and the scavenging operation specifically involves 1-2 mechanical flotation scavenging operations; in the cleaning operation, the amount of pyrite inhibitor added to the ore feed is 10-30 g / t, and the cleaning operation specifically involves 3-5 mechanical flotation cleaning operations.

[0020] By adopting the above technical solution, the multi-stage selection process with appropriate addition of inhibitors helps to enhance the separation of hydrophilic and hydrophobic minerals in the flotation froth layer. The addition of a small amount of collector in the scavenging stage promotes the return and re-selection of intergrowth minerals, thus balancing the concentrate grade and recovery rate of the final product.

[0021] Preferably, in the copper-sulfur mixed flotation operation and the roughing operation, each reagent is stirred for 2 minutes before the subsequent flotation operation is carried out.

[0022] By adopting the above technical solution, the stirring time is set so that the macromolecular compounds in the compound inhibitor have time to complete the diffusion, collision and chemical adsorption process to the mineral interface, promote the development of the capping layer and maintain the stability of the separation process.

[0023] This invention provides a mineral processing technology for recovering copper from iron tailings. It has the following beneficial effects: 1. This invention avoids the scaling problem in equipment and pipelines caused by the high alkalinity environment of traditional lime by setting the separation operation under neutral lime-free conditions and using a pyrite inhibitor composed of sodium glycero-xanthate, carboxymethyl chitosan, sodium tripolyphosphate and ethylenediaminetetraacetate. At the same time, it eliminates the inhibitory effect of high alkalinity slurry on the flotation of associated precious metals, and improves the comprehensive recovery index of associated gold and silver in iron tailings while ensuring the grade of copper concentrate.

[0024] 2. The pyrite inhibitor used in this invention utilizes the synergistic physicochemical effects of four components at the mineral interface to achieve highly efficient shielding of pyrite. Specifically, ethylenediaminetetraacetate preferentially complexes free activated metal ions in the slurry to eliminate activation interference; sodium glyceroxanthate provides a bottom-layer fixation base on the pyrite surface through chemical bonding; carboxymethyl chitosan further constructs a sterically hindered hydrophilic network coating layer on the surface; and sodium tripolyphosphate, as a highly efficient dispersant, effectively disperses the slurry system, eliminates the capping phenomenon of fine mineral slime on the pyrite surface, and increases the hydrophilicity of the pyrite surface. The combination of these four components alters the hydrophobic state of pyrite, achieving synergistic effects of small molecule adhesion, macromolecular cross-linking film formation, dispersion, and complexation, while simultaneously ensuring the stability of the separation operation.

[0025] 3. This invention introduces a dewatering and dereagent removal process between mixed flotation and grinding separation, allowing the copper-sulfur mixed concentrate to be processed by a centrifuge, thickener, or hydrocyclone. This not only adjusts the feed concentration for subsequent grinding but, more importantly, removes the potent collectors remaining in the pulp from the mixed flotation stage with the discharged water phase. This eliminates the adverse interference of residual reagents on the subsequent inhibition of pyrite, widens the differences in floatability between minerals, and creates the prerequisites for obtaining high-grade copper concentrate. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the process flow of the present invention; Figure 2 This is a comparison of the intensity of infrared absorption peaks on the surface of pyrite under different reagent systems according to the present invention. Figure 3 This is a comparison of the Zeta potential test results on the pyrite surface under different reagent treatments according to the present invention; Figure 4 This is a comparison of the contact angle test results for the wettability of pyrite surface under different reagent treatments according to the present invention; Figure 5 This is a comparison chart showing the test results of the absorbance of Cu-EDTA complexes and the amount of copper adsorbed on mineral surfaces in different reagent systems according to the present invention; Figure 6 This is a comparison chart of the core technical indicators of copper flotation in the embodiments and comparative examples of the present invention. Detailed Implementation

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] In all embodiments and comparative examples of the present invention, unless otherwise stated, the dosage of reagents is based on the dry basis of the active ingredient; "g / t feed" refers to the mass of dry ore in the slurry of the corresponding operation; and "mg / L" in the test examples refers to the mass concentration of the dry basis of the active ingredient in the solution.

[0029] Preparation Examples 1-3: Preparation Example 1: This preparation example provides a method for preparing a pyrite inhibitor, including the following steps: Weigh out 55 parts of sodium glyceroxanthate, 20 parts of carboxymethyl chitosan, 10 parts of sodium tripolyphosphate, and 10 parts of ethylenediaminetetraacetic acid (EDTA). Place the above four powdered raw materials in a dry powder mixer and mechanically stir at room temperature for 30 minutes until uniformly mixed to obtain a pyrite inhibitor dry powder mixture. Then, slowly add the obtained dry powder mixture to a stirring tank containing room temperature deionized water and continue stirring until the solid is completely dissolved to prepare a 3 wt% pyrite inhibitor aqueous solution for later use.

[0030] Preparation Example 2: This preparation example provides a method for preparing a pyrite inhibitor, including the following steps: Weigh out 50 parts of sodium glyceroxanthate, 15 parts of carboxymethyl chitosan, 15 parts of sodium tripolyphosphate, and 20 parts of ethylenediaminetetraacetic acid (EDTA). Place the above four powdered raw materials in a dry powder mixer and mechanically stir at room temperature for 30 minutes until uniformly mixed to obtain a pyrite inhibitor dry powder mixture. Then, slowly add the obtained dry powder mixture to a stirring tank containing room temperature deionized water and continue stirring until the solid is completely dissolved to prepare a 2 wt% pyrite inhibitor aqueous solution for later use.

[0031] Preparation Example 3: This preparation example provides a method for preparing a pyrite inhibitor, including the following steps: Weigh out 60 parts of sodium glyceroxanthate, 15 parts of carboxymethyl chitosan, 20 parts of sodium tripolyphosphate, and 10 parts of ethylenediaminetetraacetic acid (EDTA). Place the above four powdered raw materials in a dry powder mixer and mechanically stir at room temperature for 30 minutes until uniformly mixed to obtain a pyrite inhibitor dry powder mixture. Then, slowly add the obtained dry powder mixture to a stirring tank containing room temperature deionized water and continue stirring until the solid is completely dissolved to prepare a 5 wt% pyrite inhibitor aqueous solution for later use.

[0032] Examples 1-4: Example 1:

[0033] This embodiment provides a mineral processing technology for recovering copper from iron tailings, including the following steps: (1) Copper-sulfur mixed flotation: The iron tailings slurry is introduced into a mechanically stirred flotation machine, and 80g / t of copper-sulfur collector sodium butyl xanthate and 20g / t of frother pine oil are added in sequence. Each reagent is stirred for 2 minutes after addition, and then copper-sulfur mixed flotation is carried out. The frothy product is scraped off to obtain copper-sulfur mixed concentrate, and the bottom flow in the tank is mixed tailings.

[0034] (2) Concentration and de-reagent removal: The obtained copper-sulfur mixed concentrate slurry is introduced into a centrifuge for physical dehydration and de-reagent removal, removing some water and carrying away some dissolved residual flotation reagents with the discharged water phase until the mass concentration of the underflow slurry reaches 35wt%.

[0035] (3) Grinding of mixed concentrate: The concentrated slurry is fed into a wet ball mill for wet grinding to obtain a copper flotation slurry with a particle size of -38μm accounting for 85wt%.

[0036] (4) Roughing operation: The finely ground copper flotation slurry is introduced into the flotation machine and carried out under natural pH conditions without lime (the natural pH of the slurry is 7 to 8). 80 g / t of pyrite inhibitor prepared by the method in Preparation Example 1 and 30 g / t of copper collector ethyl thiocyanate are added sequentially, and the mixture is stirred for 2 min after each addition. Then, one roughing operation is performed to obtain copper rough concentrate and copper roughing tailings.

[0037] (5) Scavenging operation: Add 10g / t of copper collector ethyl thiocyanate to the copper roughing tailings and carry out one mechanical flotation scavenging operation. The concentrate obtained from the scavenging is returned to the roughing operation section in sequence.

[0038] (6) Cleaning operation: 20 g / t of pyrite inhibitor prepared by the method of Preparation Example 1 is added to the copper rough concentrate, and four mechanical flotation cleaning operations are carried out. The cleaned tailings are returned to the previous operation section in sequence, and the final froth product is the final copper concentrate. Example 2:

[0039] This embodiment provides a mineral processing technology for recovering copper from iron tailings, including the following steps: (1) Copper-sulfur mixed flotation: The iron tailings slurry is introduced into a mechanically stirred flotation machine, and copper-sulfur collector 50g / t of dibutyl dithiophosphate and frother 10g / t of methyl isobutyl methanol are added in sequence. Each reagent is stirred for 2 minutes after addition, and then copper-sulfur mixed flotation is carried out. The frothy product is scraped off to obtain copper-sulfur mixed concentrate, and the bottom flow in the tank is mixed tailings.

[0040] (2) Thickening and de-reagent removal: The obtained copper-sulfur mixed concentrate slurry is introduced into a thickener for physical dehydration and de-reagent removal, removing some water and carrying away some dissolved residual flotation reagents with the discharged water phase until the mass concentration of the underflow slurry reaches 30wt%.

[0041] (3) Grinding of mixed concentrate: The concentrated slurry is fed into a wet ball mill for wet grinding to obtain a copper flotation slurry with a particle size of -38μm accounting for 80wt%.

[0042] (4) Roughing operation: The finely ground copper flotation slurry is introduced into the flotation machine and carried out under natural pH conditions without lime (the natural pH of the slurry is 7 to 8). 50 g / t of pyrite inhibitor prepared by the method in Preparation Example 2 and 10 g / t of copper collector thiopropionitrile are added sequentially, with stirring for 2 min after each addition. Then, one roughing operation is performed to obtain copper rough concentrate and copper roughing tailings.

[0043] (5) Scavenging operation: Add 5g / t of copper collector thiopropionitrile to the copper roughing tailings and carry out one mechanical flotation scavenging operation. The concentrate obtained from the scavenging is returned to the roughing operation section in sequence.

[0044] (6) Cleaning operation: Add 10g / t of pyrite inhibitor prepared by the method in Preparation Example 2 to the copper rough concentrate, and carry out three mechanical flotation cleaning operations. The cleaned tailings are returned to the previous operation section in sequence, and the final froth product is the final copper concentrate. Example 3:

[0045] This embodiment provides a mineral processing technology for recovering copper from iron tailings, including the following steps: (1) Copper-sulfur mixed flotation: The iron tailings slurry is introduced into a mechanically stirred flotation machine, and 150g / t of copper-sulfur collector sodium butyl xanthate and 30g / t of frother pine oil are added in sequence. Each reagent is stirred for 2 minutes after addition, and then copper-sulfur mixed flotation is carried out. The frothy product is scraped off to obtain copper-sulfur mixed concentrate, and the bottom flow in the tank is mixed tailings.

[0046] (2) Concentration and de-reagent removal: The obtained copper-sulfur mixed concentrate slurry is introduced into a hydrocyclone for physical dewatering and de-reagent removal, removing some water and carrying away some dissolved residual flotation reagents with the discharged water phase until the mass concentration of the underflow slurry reaches 45wt%.

[0047] (3) Grinding of mixed concentrate: The concentrated slurry is fed into a wet ball mill for wet grinding to obtain a copper flotation slurry with a particle size of -38μm accounting for 95wt%.

[0048] (4) Roughing operation: The finely ground copper flotation slurry is introduced into the flotation machine and carried out under natural pH conditions without lime (the natural pH of the slurry is 7 to 8). 150 g / t of pyrite inhibitor prepared by the method in Preparation Example 3 and 50 g / t of copper collector ethyl thiocyanate are added sequentially, and the mixture is stirred for 2 min after each addition. Two roughing operations are then performed to obtain copper rough concentrate and copper roughing tailings.

[0049] (5) Scavenging operation: Add 25g / t of copper collector ethyl thiocyanate to the copper roughing tailings and carry out two mechanical flotation scavenging operations. The concentrate obtained from the scavenging is returned to the roughing operation section in sequence.

[0050] (6) Cleaning operation: Add 30g / t of pyrite inhibitor prepared by the method of Preparation Example 3 to the copper rough concentrate, and carry out 5 mechanical flotation cleaning operations. The cleaned tailings are returned to the previous operation section in sequence. The final froth product is the final copper concentrate. Example 4:

[0051] This embodiment provides a mineral processing technology for recovering copper from iron tailings, including the following steps: (1) Copper-sulfur mixed flotation: The iron tailings slurry is introduced into a mechanically stirred flotation machine, and 100g / t of mixed copper-sulfur collector (sodium butyl xanthate and dibutyl dithiophosphate mixed in a mass ratio of 1:1) and 25g / t of mixed frother (pine oil and methyl isobutyl methanol mixed in a mass ratio of 1:1) are added in sequence. Each reagent is stirred for 2 minutes after addition, and then copper-sulfur mixed flotation is carried out. The frothy product is scraped off to obtain copper-sulfur mixed concentrate, and the bottom flow in the tank is mixed tailings.

[0052] (2) Concentration and de-reagent removal: The obtained copper-sulfur mixed concentrate slurry is introduced into a centrifuge for physical dehydration and de-reagent removal, removing some water and carrying away some dissolved residual flotation reagents with the discharged water phase until the mass concentration of the underflow slurry reaches 40wt%.

[0053] (3) Grinding of mixed concentrate: The concentrated slurry is fed into a wet ball mill for wet grinding to obtain a copper flotation slurry with a particle size of -38μm accounting for 90wt%.

[0054] (4) Roughing operation: The finely ground copper flotation slurry is introduced into the flotation machine and carried out under natural pH conditions without lime (the natural pH of the slurry is 7 to 8). 100 g / t of pyrite inhibitor prepared by the method in Preparation Example 1 and 35 g / t of mixed copper collector (acetylene and thiopropionitrile are mixed at a mass ratio of 1:1) are added sequentially, stirring for 2 min after each addition. Then, one roughing operation is carried out to obtain copper rough concentrate and copper rough tailings.

[0055] (5) Scavenging operation: Add 15g / t of the above-mentioned mixed copper collector to the copper roughing tailings and carry out one mechanical flotation scavenging operation. The concentrate obtained from the scavenging is returned to the roughing operation section in sequence.

[0056] (6) Cleaning operation: 25 g / t of pyrite inhibitor prepared by the method of Preparation Example 1 is added to the copper rough concentrate, and four mechanical flotation cleaning operations are carried out. The cleaned tailings are returned to the previous operation section in sequence, and the final froth product is the final copper concentrate.

[0057] Comparative Examples 1-5: Comparative Example 1: Compared with Example 1, the difference is that the pyrite inhibitor prepared in Example 1 is not used in the roughing and cleaning operations. Instead, the conventional inhibitor lime is added to the slurry to adjust the alkalinity (pH value greater than 12). All other aspects are the same.

[0058] Comparative Example 2: Compared with Example 1, the difference is that the concentration and descaling process in step (2) is omitted, and the copper-sulfur mixed concentrate obtained in step (1) is directly fed into step (3) for wet grinding to obtain a copper flotation slurry with a mass concentration of 15%. In addition, in the roughing and cleaning operations, the feed rate of the new pyrite inhibitor is increased to 120 g / t and 40 g / t, respectively, while the rest are the same.

[0059] Comparative Example 3: Compared with Example 1, the difference is that the pyrite inhibitor formulation used removes ethylenediaminetetraacetic acid (EDTA) and is made only from 55 parts of sodium glyceroxanthate, 20 parts of carboxymethyl chitosan, and 15 parts of sodium tripolyphosphate. This formulation is not recalculated to 100 parts (or total parts). When using it, the actual dosage of the retained components is consistent with the corresponding components in Example 1, and all other aspects are the same.

[0060] Comparative Example 4: Compared with Example 1, the difference is that the pyrite inhibitor formulation used removes carboxymethyl chitosan and is made only of 55 parts of sodium glyceroxanthate, 15 parts of sodium tripolyphosphate and 10 parts of ethylenediaminetetraacetate. This formulation is not recalculated to 100 parts. When using it, the actual dosage of the retained components is consistent with the corresponding components in Example 1, and all other components are the same.

[0061] Comparative Example 5: Compared with Example 1, the difference is that the sodium glycero-xanthate was removed from the pyrite inhibitor formulation used, and it was made only from 20 parts of carboxymethyl chitosan, 15 parts of sodium tripolyphosphate and 10 parts of ethylenediaminetetraacetic acid. The formulation was not recalculated to 100 parts, and the actual dosage of the retained components was consistent with the corresponding components in Example 1. All other aspects were the same.

[0062] Test Examples 1-5: Test Example 1: Adsorption Infrared Spectroscopy Test on Pyrite Surface (1) Select high-purity pyrite lumps, artificially crush and grind them in an agate bowl, and obtain powder with a particle size of -38μm by sieving through a standard sieve. Use it as a test sample of pure pyrite mineral.

[0063] (2) Accurately weigh 2.0g of pure pyrite mineral sample and place it in a beaker. Add 40mL of deionized water and adjust the pH of the slurry to 7.5 using dilute hydrochloric acid or sodium hydroxide solution to prepare a mineral suspension.

[0064] (3) The pyrite inhibitor used in Example 1 and Comparative Examples 3 to 5 was added to different beakers at a dosage concentration of 80 mg / L. A blank group was set up with no inhibitor added. Each beaker was placed on a magnetic stirrer and stirred continuously at room temperature for 30 min.

[0065] (4) After stirring, the mineral suspension is filtered to separate the solid and liquid components. The retained solid residue is rinsed three times with deionized water to remove any free reagents that have not been adsorbed on the mineral surface.

[0066] (5) Place the rinsed mineral sample into a vacuum drying oven and dry it at 40°C for 24 hours to obtain the dried sample to be tested.

[0067] (6) Weigh 1 mg of dried sample and mix it with 100 mg of spectroscopically pure KBr powder. Grind the mixture evenly and press it into a transparent sheet. Use a Fourier transform infrared spectrometer at 4000 cm⁻¹. -1 Up to 400cm -1 The infrared transmission spectrum of the sample was tested within the wavenumber range, and the absorption peak intensity data of the target characteristic functional groups were extracted.

[0068] Table 1. Intensity data of infrared absorption peaks of characteristic functional groups on the surface of pyrite after treatment with different reagents. Blank pyrite 0.014 0.026 Example 1 Inhibitor Treatment 0.431 0.385 Comparative Example 3 Inhibitor Treatment 0.417 0.392 Comparative Example 4 Inhibitor Treatment 0.462 0.073 Comparative Example 5 Inhibitor Treatment 0.051 0.368 Conclusions and Analysis: Based on Table 1 and Figure 2 The test results show that the blank pyrite surface did not exhibit obvious C=S and -COO- characteristic absorption peaks. After treatment with the reagent in Example 1, the pyrite surface simultaneously showed C=S absorption peaks and -COO- absorption peaks with absorption intensities of 0.431 and 0.385, respectively, indicating that sodium glyceroxanthate and carboxymethyl chitosan adhered to the pyrite interface at the same time. In Comparative Example 3, no ethylenediaminetetraacetic acid salt was added, and the corresponding two absorption peak intensities were similar to those in Example 1, indicating that ethylenediaminetetraacetic acid salt did not directly participate in the chemical adsorption process on the pyrite surface.

[0069] The test results of Comparative Example 4 show that the removal of carboxymethyl chitosan from the formulation caused a sharp drop in the intensity of the -COO- absorption peak to 0.073, while the intensity of the C=S absorption peak remained at 0.462, exhibiting only the isolated adhesion characteristics of sodium glyceroxanthate. Under the test conditions of Comparative Example 5, sodium glyceroxanthate was removed. Figure 2 The column height representing the C=S absorption peak decreased to 0.051, and only the -COO- absorption peak with an intensity of 0.368 was retained in the spectrum. According to Table 1 and... Figure 2 Test data shows that sodium glycero-xanthate and carboxymethyl chitosan can independently exhibit adhesion behavior on pyrite surfaces, and no significant competitive desorption phenomenon occurs when they are used in combination.

[0070] Based on the variation patterns of the infrared absorption spectrum, the quaternary inhibitor system provided by this invention achieves co-immobilization of small-molecule drugs and large-molecule polymers at the pyrite interface. Sodium glyceroxanthate chemically bonds with the mineral surface through its xanthate groups, providing the underlying immobilization basis. Carboxymethyl chitosan then further forms a network covering on the basis of the underlying small molecules through its long molecular chain and multifunctional structure. The above data confirm the co-adsorption phenomenon of the drug components at the mineral interface, explaining the reason why the inhibitor system changes the hydrophobic state of pyrite at the molecular bonding level.

[0071] Test Example 2: Potential dynamics test of pyrite surface (1) High-purity pyrite ore blocks were selected and artificially ground in an agate mortar. Mineral powder with a particle size of -5μm was obtained by sedimentation or centrifugation as the test object.

[0072] (2) Accurately weigh 0.05g of pyrite mineral powder and place it in a beaker. Add 50mL of potassium nitrate solution with a concentration of 0.001mol / L as a supporting electrolyte to prepare a mineral suspension.

[0073] (3) Add the pyrite inhibitor used in Example 1 and Comparative Examples 3 to 5 to different beakers respectively, and control the drug concentration to 60 mg / L. At the same time, a sample without the inhibitor was set up as a blank control group.

[0074] (4) Use hydrochloric acid and sodium hydroxide solutions with a concentration of 0.1 mol / L to adjust and stabilize the pH values ​​of different groups of mineral suspensions at 6.0 and 8.0 respectively.

[0075] (5) Place the mineral suspension with the pH value adjusted on a magnetic stirrer and stir at room temperature for 15 minutes. After stirring, let it stand for 5 minutes.

[0076] (6) Use a pipette to extract the upper suspension and inject it into the sample cell of the Zeta potential meter. Test and record the Zeta potential values ​​on the surface of pyrite particles under different treatment conditions.

[0077] Table 2. Data on Zeta potential of pyrite surface after treatment with different reagents. Blank pyrite -11.2 -17.8 Example 1 Inhibitor Treatment -39.1 -46.3 Comparative Example 3 Inhibitor Treatment -38.4 -45.7 Comparative Example 4 Inhibitor Treatment -27.5 -32.1 Comparative Example 5 Inhibitor Treatment -22.8 -29.6 Conclusions and Analysis: Based on Table 2 and Figure 3 The data shows that the Zeta potential on the blank pyrite surface was -11.2 mV and -17.8 mV at pH values ​​of 6.0 and 8.0, respectively. After adding the reagent from Example 1, the corresponding Zeta potential values ​​decreased to -39.1 mV and -46.3 mV, respectively. The negative shift of the Zeta potential indicates that the reagent molecules containing xanthic acid and carboxyl groups were adsorbed on the pyrite surface, increasing the amount of negative charge on the mineral surface.

[0078] Comparing the test data of Comparative Example 3, the Zeta potential values ​​were -38.4mV and -45.7mV, which are close to the test results of Example 1. This indicates that removing ethylenediaminetetraacetic acid (EDTA) from the formulation did not change the charge adhesion state of the agent at the pyrite interface, and EDTA did not participate extensively in the direct adsorption process on the surface.

[0079] In Comparative Example 4, carboxymethyl chitosan was removed from the formulation, and in Comparative Example 5, sodium glyceroxanthate was removed from the formulation. The Zeta potentials of the two test groups at pH 8.0 were -32.1 mV and -29.6 mV, respectively. Compared with the test data of Example 1, the degree of negative shift was weakened. This indicates that the adhesion amount of a single component on the pyrite surface is limited. Combining sodium glyceroxanthate with carboxymethyl chitosan can further reduce the surface potential and produce a stronger electrochemical alteration effect.

[0080] According to Table 2 and Figure 3 The data shows that the decrease in the Zeta potential value of pyrite surface reflects the presence of anionic groups on the surface. The increase in surface negative charge can enhance the interaction between mineral particles and water molecules, causing pyrite particles to exhibit a hydrophilic state in aqueous solution and reducing the probability of mineral particles being captured by bubbles. The potential change data confirms the physicochemical mechanism of the compound agent in destroying the floatability of pyrite from the charge dimension.

[0081] Test Example 3: Contact Angle Test for Wettability of Pyrite Surface (1) Select high-purity pyrite ore blocks and cut them into sheet samples with dimensions of 10mm×10mm×5mm using a diamond cutter. The test surfaces of the sheet samples were polished with silicon carbide wet sandpaper of different grits in turn, and then polished with alumina suspension to obtain smooth pyrite sheets. The sheets were ultrasonically cleaned alternately with deionized water and anhydrous ethanol and then dried in a vacuum drying oven.

[0082] (2) Prepare an accurate sodium butyl xanthate collector solution with a mass concentration of 100 mg / L. Completely immerse the pyrite slices in the collector solution and let them stand at room temperature for 15 min to simulate the hydrophobic effect of the collector on pyrite in the flotation pulp. After soaking, remove the slices and rinse the surface with deionized water.

[0083] (3) Prepare pyrite inhibitor solutions for Examples 1 and Comparative Examples 3 to 5, respectively, and control the mass concentration to 80 mg / L. Immerse the pyrite slices treated with the collector into the different inhibitor solutions and let them stand for 20 min. At the same time, set up a control group with a sample immersed in pure deionized water.

[0084] (4) Take out the pyrite blanks under different treatment conditions and slowly blow dry the surface moisture with high-purity nitrogen.

[0085] (5) Place the prepared pyrite sheet on the horizontal stage of the contact angle measuring instrument. Use a micro-syringe to drop 2 μL of deionized water onto the surface of the sheet. Use a high-speed camera system to capture the droplet morphology and measure and record the static contact angle values ​​at 1s and 10s when the droplet contacts the surface.

[0086] Table 3. Data on contact angle of pyrite surface after treatment with different reagents. Collector treatment only 83.2 81.5 Example 1 Inhibitor Treatment 22.5 15.3 Comparative Example 3 Inhibitor Treatment 24.1 17.4 Comparative Example 4 Inhibitor Treatment 46.8 39.2 Comparative Example 5 Inhibitor Treatment 52.7 44.6 Conclusions and Analysis: Based on Table 3 and Figure 4 The test results show that the contact angles of the pyrite test surface treated with the collector alone were 83.2° and 81.5° at 1s and 10s, respectively. Due to the adhesion of sodium butyl xanthate to the mineral interface, the pyrite exhibits a hydrophobic state. After treatment with the agent in Example 1, the contact angle of the pyrite surface decreased to 22.5° and 15.3° at 1s and 10s, respectively. The decrease in the contact angle value indicates that molecules containing hydrophilic groups adhere to the pyrite interface, forming a hydrophilic film layer that covers the underlying hydrophobic structure.

[0087] The test results of Comparative Example 3 were observed. The measured contact angle values ​​were 24.1° and 17.4°, which were close to the data of Example 1. The results showed that the removal of ethylenediaminetetraacetic acid salt in the formulation did not change the ability of the agent to build a hydrophilic film on the pyrite surface. ethylenediaminetetraacetic acid salt does not directly participate in the construction process of the surface hydrophilic wetting film.

[0088] Comparative Example 4's formulation removed carboxymethyl chitosan, and Comparative Example 5's formulation removed sodium glyceroxanthate. Tests showed that the contact angles at 1 second for the two groups were 46.8° and 52.7°, respectively. Compared to the data from Example 1, the decrease in contact angle for these two groups was smaller. The test data indicates that the hydrophilic coverage formed by a single component on the pyrite surface is limited and fails to completely isolate the underlying hydrophobic substances. Combining sodium glyceroxanthate with carboxymethyl chitosan can further reduce the surface contact angle value.

[0089] According to Table 3 and Figure 4 The data shows that the decrease in the contact angle value reflects that water molecules are more likely to spread on the surface of mineral particles. The wettability test data proves from the perspective of physical properties the mechanism by which the composite agent changes the hydrophilic state of the pyrite interface and blocks the adhesion of mineral particles and air bubbles.

[0090] Test Example 4: UV-Vis spectrum and adsorption capacity test of inhibitor against copper ion activation (1) High-purity pyrite ore blocks were selected for crushing and grinding, and powder with a particle size of -38μm was screened out as a mineral test sample.

[0091] (2) Prepare Cu 2+ A copper sulfate solution with a mass concentration of 10 mg / L was used to simulate the unavoidable activation of metal ions present in flotation pulp. 1.0 g of pyrite powder was weighed into a beaker, and 50 mL of the above copper sulfate solution was added to prepare a mineral suspension containing free copper ions.

[0092] (3) The inhibitor used in Preparation Example 1 and the pyrite inhibitor used in Comparative Examples 3 to 5 were added to different mineral suspensions at a dosage concentration of 600 mg / L. A group of suspensions without added inhibitors was set up as a blank group.

[0093] (4) Place all beakers on a magnetic stirrer and stir at room temperature for 20 minutes.

[0094] (5) After stirring, the suspension is centrifuged. The supernatant is extracted and placed in a cuvette. A UV-Vis spectrophotometer is used to scan the solution in the wavelength range of 700 nm to 750 nm and the absorbance values ​​of the characteristic peaks of the Cu-EDTA complex are recorded.

[0095] (6) The total concentration of residual copper ions in the supernatant was determined using atomic absorption spectrometry. Combined with Cu 2+ The initial total amount of copper ions added and the mass of pyrite powder were used to calculate the amount of copper adsorbed on the mineral surface.

[0096] Table 4. Test data of absorbance of complexes and copper adsorption on mineral surfaces under different reagent systems. Blank group 0.015 0.432 Example 1 Inhibitor Treatment 0.724 0.053 Comparative Example 3 Inhibitor Treatment 0.021 0.418 Comparative Example 4 Inhibitor Treatment 0.695 0.076 Comparative Example 5 Inhibitor Treatment 0.681 0.084 Conclusions and Analysis: Based on Table 4 and Figure 5 The test results showed that the absorbance of the complex characteristic peak in the blank solution was 0.015, and the copper adsorption on the mineral surface was 0.432 mg / g. Without the addition of an inhibitor, a large amount of free copper ions in the solution adhered to the pyrite surface. After adding the reagent from Example 1, a complex characteristic peak with an absorbance of 0.724 was detected in the solution, and the copper adsorption on the pyrite surface decreased to 0.053 mg / g. The increase in solution absorbance and the decrease in surface copper adsorption indicate that at the above-mentioned dosage concentration, the ethylenediaminetetraacetic acid salt in the inhibitor formulation reacts with the initial Cu... 2+ It is at a molar quantity level where sufficient complexation can occur, and it can react with free copper ions in solution to form complexes, thereby reducing the amount of copper ions adhering to the mineral interface.

[0097] Observing the test data of Comparative Example 3, the inhibitor formulation removed ethylenediaminetetraacetic acid (EDTA). The absorbance of the solution was 0.021 and the copper adsorption on the mineral surface was 0.418 mg / g. Both test values ​​were close to those of the blank group. The test results show that when EDTA is absent, free copper ions will attach to the pyrite interface, triggering the activation of the mineral.

[0098] In Comparative Examples 4 and 5, ethylenediaminetetraacetic acid (EDTA) was retained, while carboxymethyl chitosan and sodium glyceroxanthate were removed, respectively. The absorbance values ​​of the two sets of tests were 0.695 and 0.681, respectively, and the surface copper adsorption amounts were 0.076 mg / g and 0.084 mg / g, respectively. Compared with the test data of Example 1, it was found that removing the other two components did not significantly weaken the ability of the agent to bind free copper ions in solution.

[0099] Combined with Table 4 Figure 5 The absorbance and adsorption data show that the composite formulation provided by this invention has the effect of resisting the interference of metal ion activation. Ethylenediaminetetraacetic acid salt preferentially combines with free copper ions in the solution to form a water-soluble complex. This reaction consumes the free activated ions in the system, blocks the adsorption channels of copper ions on the pyrite surface, and maintains the initial physicochemical state of the pyrite surface.

[0100] Test Example 5: Comparative Test of Technical Indicators for the Entire Mineral Processing Flotation Process (1) Iron tailings from an iron ore beneficiation plant were used as the test object. The iron tailings were the tailings discharged during the production process of the beneficiation plant, which mainly uses magnetic separation technology to recover iron. The initial Cu content of the iron tailings was 0.045%, S content was 0.54%, Au content was 0.078 g / t, Ag content was 0.18 g / t, and the fineness was -74 μm particles, accounting for 35%. The copper minerals in the tailings were mainly chalcopyrite, with generally fine and highly dispersed particle sizes, mainly distributed between 10 and 50 μm, mostly associated with pyrite, amphibole, chlorite and other minerals; other metal sulfides were mainly pyrite; the main gangue minerals were quartz, feldspar, mica, chlorite and other minerals.

[0101] (2) The iron tailings slurry was fed into a single-cell flotation machine in batches, and flotation tests were carried out according to the process parameters and reagent system set in Examples 1 to 4 and Comparative Examples 1 to 5, respectively.

[0102] (3) During the experiment, for Examples 1 to 4 and Comparative Examples 1, 3 to 5, which include concentration and de-doping processes, centrifuges, thickeners or hydrocyclones were used for concentration and de-doping to remove some water and carry away some dissolved residual flotation reagents with the discharged water phase, and the mass concentration of the underflow slurry was controlled to reach the set range; Comparative Example 2 was directly ground.

[0103] (4) After being finely ground by a wet ball mill, the corresponding inhibitors and copper collectors are added under neutral or high alkalinity conditions and stirred. The stirring time is controlled at 2 minutes for each agent. Then, roughing, scavenging and fine selection are carried out in sequence.

[0104] (5) Collect the final foam product (i.e., the final copper concentrate) and the bottom flow residue (i.e., the final tailings) of each test group, filter the products, dry them in a 105°C drying oven, and weigh the total mass.

[0105] (6) The Cu, Au and Ag grades in the dried copper concentrate and tailings samples were analyzed by atomic absorption spectrometry, ICP-OES, ICP-MS or general chemical multi-element analysis methods. The comprehensive flotation recovery rate of copper, gold and silver was calculated based on the material balance principle (for copper-sulfur mixed concentrate).

[0106] Table 5. Comparative Data of Flotation Technical Indicators between Examples and Comparative Examples Example 1 16.82 89.41 2.98 63.51 85.64 68.17 Example 2 15.64 87.27 2.81 61.12 83.65 66.25 Example 3 17.51 89.92 3.14 64.44 87.31 69.31 Example 4 16.25 88.41 2.91 62.15 84.93 67.93 Comparative Example 1 13.64 81.33 2.25 42.53 68.15 45.26 Comparative Example 2 16.24 86.53 2.83 60.18 83.25 65.84 Comparative Example 3 15.68 86.51 2.69 61.06 82.53 65.67 Comparative Example 4 15.35 85.64 2.61 59.47 81.22 64.22 Comparative Example 5 14.67 83.41 2.52 58.91 79.18 62.18 Conclusions and Analysis: Based on Table 5 and Figure 6The test results show that, after adopting the established process flow and composite reagents in Examples 1 to 4, the copper grade in the copper concentrate ranged from 15.64% to 17.51%, corresponding to a copper recovery rate of 87.27% to 89.92%. Simultaneously, the recovery rate of associated gold ranged from 61.12% to 64.44%, and the recovery rate of associated silver ranged from 66.25% to 69.31%. The test values ​​demonstrate that under the set process parameters and reagent ratios, normal copper-sulfur separation can be achieved, and efficient recovery of associated precious metals can be accomplished.

[0107] Comparing the data from Example 1 and Comparative Example 1, Comparative Example 1 used lime to adjust the high alkalinity of the slurry. The tests showed that the copper grade in the copper concentrate was 13.64%, and the copper recovery rate was 81.33%, while the gold and silver recoveries decreased to 42.53% and 45.26%, respectively. Furthermore, the Au and Ag grades in the concentrate also decreased significantly. The comparative results indicate that the high alkalinity environment created by lime has an inhibitory effect on associated gold and silver minerals. Using natural pH flotation conditions, while ensuring the copper separation index, the recovery index of precious metals can be significantly improved.

[0108] Comparing Example 1 and Comparative Example 2 in Table 5, Comparative Example 2 eliminated the pre-concentration and de-reagent process. The data shows that the copper grade in the copper concentrate decreased to 16.24%, and the copper recovery rate decreased to 86.53%. The reason for the decrease in indicators is that there are collectors remaining in the pulp after mixed flotation. There is a lack of physical de-reagent separation. The remaining collectors will affect the subsequent copper-sulfur separation, causing pyrite to enter the frothy product and reducing the quality of the concentrate.

[0109] Comparing the test data of Example 1 with those of Comparative Examples 3 to 5, when ethylenediaminetetraacetic acid (EDTA), carboxymethyl chitosan, or sodium glyceroxanthate were removed from the reagent formulation, the copper grade of the copper concentrate decreased to 15.68%, 15.35%, and 14.67%, respectively. The fluctuations in the test data reflect the synergistic effect of the various components in the composite reagent. Removing the complexing component inevitably leads to the activation of pyrite by free metal ions in the slurry; removing the macromolecular or small-molecule inhibitory components prevents the formation of a complete hydrophilic coating layer on the pyrite surface. The four components work together: the small-molecule reagent adheres to the bottom layer, the macromolecular polymer cross-links to form a film, and the complexing and dispersing agents eliminate activation interference and fine mud covering, achieving highly efficient inhibition of pyrite under lime-free conditions and ensuring the comprehensive beneficiation indicators of the concentrate.

Claims

1. A beneficiation process for recovering copper from iron tailings, characterized by, Includes the following processes: Iron tailings slurry is introduced into a mechanically stirred flotation machine, and copper-sulfur collector and frother are added in sequence to carry out copper-sulfur mixed flotation. The frothy product is scraped off to obtain copper-sulfur mixed concentrate, and the bottom flow in the tank is mixed tailings. The obtained copper-sulfur mixed concentrate slurry is introduced into a centrifuge, thickener, or hydrocyclone for physical dewatering and dereticling, removing some water and carrying away some dissolved residual flotation reagents with the discharged aqueous phase, until the mass concentration of the underflow slurry reaches 30wt% to 45wt%. The concentrated slurry is fed into a wet ball mill for wet grinding to produce copper flotation slurry. The finely ground copper flotation slurry is introduced into the flotation machine, and pyrite inhibitor and copper collector are added sequentially under lime-free conditions to carry out roughing operations, thereby obtaining copper rough concentrate and copper roughing tailings. A copper collector is added to the copper roughing tailings for mechanical flotation scavenging, and the concentrate obtained from the scavenging is returned to the roughing section in sequence. Pyrite inhibitors are added to the copper rough concentrate for mechanical flotation and cleaning. The cleaned tailings are returned to the previous operation section in sequence, and the final froth product is the final copper concentrate. The raw materials for preparing the pyrite inhibitor include sodium glyceroxanthate, carboxymethyl chitosan, sodium tripolyphosphate, and ethylenediaminetetraacetic acid.

2. The beneficiation process according to claim 1, characterized in that, The raw materials for preparing the pyrite inhibitor include the following components in parts by weight: 50-60 parts of sodium glyceroxanthate, 15-20 parts of carboxymethyl chitosan, 10-20 parts of sodium tripolyphosphate, and 10-20 parts of ethylenediaminetetraacetic acid.

3. The beneficiation process according to claim 2, characterized in that, The specific preparation process of the pyrite inhibitor is as follows: Sodium glyceroxanthate, carboxymethyl chitosan, sodium tripolyphosphate and ethylenediaminetetraacetate were placed in a dry powder mixer and mechanically stirred at room temperature for 30 minutes until they were mixed evenly to obtain a pyrite inhibitor dry powder mixture. Subsequently, the obtained dry powder mixture was slowly added to a stirring tank containing room temperature deionized water, and stirring was continued until the solid was completely dissolved, thus preparing an aqueous solution of pyrite inhibitor with a mass concentration of 2wt% to 5wt%.

4. The beneficiation process according to claim 1, characterized in that, The copper-sulfur collector is one of sodium butyl xanthate and ammonium dibutyl dithiophosphate, or a mixed copper-sulfur collector in a mass ratio of 1:

1. The foaming agent is one of pine oil and methyl isobutyl methanol, or a mixed foaming agent in a mass ratio of 1:

1.

5. The beneficiation process according to claim 4, characterized in that, In the copper-sulfur mixed flotation operation, the feed rate of the copper-sulfur collector is 50-150 g / t, and the feed rate of the frother is 10-30 g / t.

6. The beneficiation process according to claim 1, characterized in that, The performance parameter range of the copper flotation slurry obtained by the wet grinding is as follows: The particle size of -38μm accounts for 80wt% to 95wt%.

7. The beneficiation process according to claim 1, characterized in that, The lime-free conditions controlled in the roughing operation are to control the natural pH value of the slurry to be 7 to 8; The copper collector is one of ethyl thiocyanate and thiocyanate propionitrile, or a mixed copper collector in a mass ratio of 1:

1.

8. The beneficiation process according to claim 7, characterized in that, In the roughing operation, the feed rate of the pyrite inhibitor is 50-150 g / t, and the feed rate of the copper collector is 10-50 g / t. The coarse selection operation specifically involves performing one to two coarse selection operations.

9. The beneficiation process according to claim 1, characterized in that, In the aforementioned scavenging operation, the amount of copper collector added to the ore feed is 5-25 g / t, and the scavenging operation specifically involves performing 1-2 mechanical flotation scavenging operations; In the aforementioned beneficiation process, the amount of pyrite inhibitor added to the feed is 10-30 g / t, and the beneficiation process specifically involves 3-5 mechanical flotation beneficiation operations.

10. The beneficiation process according to claim 1, characterized in that, In the copper-sulfur mixed flotation operation and roughing operation, each reagent is stirred for 2 minutes before the subsequent flotation operation is carried out.

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