A magnesium reduction inhibitor for copper-nickel sulfide ore flotation and a preparation method and application thereof

Abstract

This invention discloses a magnesium-reducing inhibitor for the flotation of copper-nickel sulfide ore, its preparation method, and its application, relating to the field of mineral flotation inhibitor technology. The raw materials for the magnesium-reducing inhibitor for the flotation of copper-nickel sulfide ore include component A, water glass, an organic macromolecular thickener, and water; the mass ratio of component A, water glass, and the organic macromolecular thickener is 1~5:2:1~2; the mass ratio of the total mass of component A and the organic macromolecular thickener to the mass of water is 1:0.5~2. The magnesium-reducing inhibitor for the flotation of copper-nickel sulfide ore of this invention can be used for the flotation separation of copper-nickel sulfide ore. Through the core inhibition of component A and the synergistic effect of the combination of water glass and the organic macromolecular thickener, it can efficiently inhibit magnesium-containing silicates such as talc and serpentine, significantly reducing the MgO content of the concentrate. Simultaneously, it has weak inhibition on sulfide minerals (nickel pyrite, chalcopyrite, etc.), ensuring a high recovery rate.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation inhibitor technology, and in particular to a magnesium-reducing inhibitor for the flotation of copper-nickel sulfide ores, its preparation method, and its application. Background Technology

[0002] Nickel is a cornerstone material for modern industry, especially high-end manufacturing and green energy transformation (stainless steel, new energy batteries). Its properties are difficult to be completely replaced by other metals. Global economic development and technological progress are highly dependent on it. It is widely used in industrial production fields such as alloys, electroplating, catalysis, batteries, dyes, and ceramics.

[0003] Nickel-bearing metal deposits are mainly copper-nickel sulfide deposits, characterized by low grades, complex associated components, and high content of magnesium silicate gangue minerals, including talc, serpentine, chlorite, olivine, amphibole, and phlogopite, with talc and serpentine being the most abundant. These gangue minerals severely disrupt the selectivity of the flotation process through multiple mechanisms such as slime covering, heterogeneous agglomeration, natural floatability, interference from dissolved ions, and similar flotation behavior, resulting in: (1) difficulty in improving concentrate grades, especially with severely excessive magnesium oxide (MgO) content (usually >10%); (2) loss of recovery rates of valuable metals such as nickel and copper; (3) increased consumption of flotation reagents (especially inhibitors); and (4) deterioration of foam stability. Excessive MgO content is a key bottleneck restricting the efficient utilization of copper-nickel sulfide resources, making it impossible for concentrates to meet the requirements of modern efficient and low-consumption smelting processes, and greatly reducing the economic benefits of resource utilization. Therefore, developing efficient and selective technologies to suppress magnesium silicate gangue minerals is a core challenge in the flotation of copper-nickel sulfide ores.

[0004] Currently, improvements are mainly achieved through optimizing grinding and classification, optimizing flotation processes, and adding magnesium-reducing inhibitors. Among these, developing highly selective magnesium-reducing inhibitors is the most direct, efficient, and economical way to improve concentrate quality (magnesium reduction) and metal recovery rate. Organic macromolecular inhibitors (such as sodium carboxymethyl cellulose) are currently widely used magnesium-reducing agents, but they still have significant shortcomings: (1) The inhibitory selectivity needs to be improved: while inhibiting talc and serpentine, they also inhibit sulfide minerals (nickel pyrite, chalcopyrite, etc.) to a certain extent, affecting the recovery rate; (2) Poor solubility and workability: the dissolution rate is slow and it is easy to clump, affecting the uniformity and stability of on-site preparation and administration; (3) There are many types of agents and the dosage is large: they often need to be used in combination with dispersants, resulting in a complex agent formulation and a high total dosage; (4) The effect is unstable: the adaptability to changes in ore properties is sometimes poor.

[0005] Therefore, there is an urgent need to develop a new type of inhibitor that can efficiently and selectively inhibit magnesium silicate gangue minerals such as talc and serpentine, with minimal impact on the floatability of sulfide minerals, and is also highly soluble, requires only a small dosage, is easy to use, and is environmentally friendly. Summary of the Invention

[0006] The purpose of this invention is to provide a magnesium-reducing inhibitor for the flotation of copper-nickel sulfide ore, its preparation method and application, so as to solve the problems existing in the prior art.

[0007] To achieve the above objectives, the present invention provides the following solution:

[0008] One of the technical solutions of the present invention is a magnesium-reducing inhibitor for flotation of copper-nickel sulfide ore, the raw materials of which include component A, water glass, organic macromolecular thickener and water;

[0009] The mass ratio of component A, water glass and organic macromolecular thickener is 1~5:2:1~2;

[0010] The total mass ratio of component A and the organic macromolecular thickener to the mass ratio of water is 1:0.5~2;

[0011] The structural formula of component A is: ;

[0012] In the formula, R is selected from H, -CH2-COOH, and -CH2-COO. - or n is an integer ≥ 100, and M is an integer ≥ 1.

[0013] The magnesium-reducing depressant for copper-nickel sulfide ore flotation of the present invention is a compound depressant, wherein component A has a large molecular weight, a special spatial structure, and is rich in polar groups (-OH, -COO). - -NH2, -NH-, -NR3 + (Quaternary ammonium groups) efficiently suppress magnesium-containing silicate minerals such as talc and serpentine through multiple synergistic mechanisms, as detailed below:

[0014] (1) Hydrogen bonding: Abundant hydroxyl groups (-OH) form hydrogen bonds with Si-O or Mg-O on the surface of talc, covering its hydrophobic surface with a hydrophilic layer, which hinders the adhesion of bubbles.

[0015] (2) Steric hindrance effect: A dense adsorption layer is formed on the surface of talc, which physically blocks the collector molecules from approaching the surface of talc and inhibits its hydrophobicity.

[0016] (3) Flocculation effect: The cationic groups (-NH2, -NH-, -NR3) on the molecular chain + It can promote the flocculation and sedimentation of fine-grained talc, serpentine, etc., reducing their mechanical entrainment into the concentrate.

[0017] Through the above mechanism, component A exhibits a strong inhibitory effect on magnesium-containing silicate gangue minerals such as talc and serpentine, while showing a weak inhibitory effect on target minerals such as copper sulfide and nickel sulfide, demonstrating good selectivity. It should be particularly noted that component A, as the core inhibitory component, achieves its optimal inhibitory effect only in a compound system. Specifically, when component A is compounded with water glass and an organic macromolecular thickener in the above proportions, the inhibitory effect on magnesium-containing gangue minerals (especially talc and serpentine) is significantly better than that of a single component or a combination of both, exhibiting a strong synergistic effect, mainly reflected in:

[0018] (1) Synergistic enhancement of inhibition effect: The strong specific adsorption inhibition of component A, the inhibition and dispersion effect of silicate ions provided by water glass, and the auxiliary inhibition / steric stabilization effect of organic macromolecular thickener promote each other and jointly build a more efficient and longer-lasting inhibition barrier.

[0019] (2) Improved solubility and workability: The hydrophilicity and specific structure of component A can effectively improve the solubility and dispersibility of organic macromolecular thickeners (such as sodium carboxymethyl cellulose (CMC)) in water, solve the problems of slow dissolution and easy agglomeration, make compound agents easier to prepare and use in mineral processing operations, and ensure the uniformity and stability of drug administration.

[0020] (3) Simplified formulation and reduced dosage: The single compound formulation system of the present invention can replace the traditional combination of water glass + organic inhibitor (such as CMC) and CMC + dispersant, reducing the types of on-site agents and reducing the total amount of agents used.

[0021] Furthermore, the preparation steps of component A include: mixing glacial acetic acid solution, component B, component C and glutaraldehyde aqueous solution, reacting them to obtain component A;

[0022] The structural formula of component B is: In the formula, R is selected from H, -CH2-COOH, and -CH2-COO. - or M is an integer ≥ 1;

[0023] The structural formula of component C is: In the formula, n is an integer ≥ 100.

[0024] The added glutaraldehyde aqueous solution plays a cross-linking role in the reaction between component B and component C; at the same time, the reaction is carried out in glacial acetic acid solution, which can promote the complete reaction of component B and component C.

[0025] Furthermore, the concentration of the glacial acetic acid solution is 2 wt%.

[0026] Furthermore, the concentration of the glutaraldehyde aqueous solution is 5 wt%.

[0027] Furthermore, the mass ratio of component B to component C is 1:0.5~2.

[0028] Furthermore, the volume ratio of the glacial acetic acid solution to the glutaraldehyde aqueous solution is 1:0.1~0.5.

[0029] Furthermore, the ratio of component B to the glutaraldehyde aqueous solution is 1~10g:10~15mL.

[0030] Furthermore, the reaction temperature is 30~50℃ and the time is 1~4h.

[0031] Preferably, the number-average molecular weight of component C is 600~750000 g / mol, more preferably 10000~60000 g / mol.

[0032] Furthermore, the modulus of the water glass is 2.0 to 3.5.

[0033] Furthermore, the organic macromolecular thickener includes one or more of sodium carboxymethyl cellulose (CMC), sodium carboxymethyl starch, gum arabic, xanthan gum, and carrageenan.

[0034] The second technical solution of the present invention: a method for preparing the above-mentioned magnesium-reducing inhibitor for flotation of copper-nickel sulfide ore, comprising the following steps: mixing component A and water glass, adding an organic macromolecular thickener and water under stirring conditions, and continuing to stir until completely dissolved to obtain the magnesium-reducing inhibitor for flotation of copper-nickel sulfide ore.

[0035] The third technical solution of the present invention: the application of the above-mentioned magnesium-reducing inhibitor in the flotation separation of copper-nickel sulfide ore.

[0036] Furthermore, the magnesium reduction inhibitor for copper-nickel sulfide ore flotation is used in the roughing stage of copper-nickel sulfide ore flotation separation; when the roughing operation is performed once, the amount of magnesium reduction inhibitor added is 100~300g / t; when the roughing operation is performed twice, the amount of magnesium reduction inhibitor added in roughing I is 100~300g / t, and the amount of magnesium reduction inhibitor added in roughing II is 50~200g / t.

[0037] Furthermore, the magnesium reduction inhibitor for copper-nickel sulfide ore flotation is used in the roughing and cleaning stages of copper-nickel sulfide ore flotation separation. When the cleaning operation is performed three times, the amount of magnesium reduction inhibitor added in cleaning stage I is 50-200 g / t, in cleaning stage II it is 0-100 g / t, and in cleaning stage III it is 0-50 g / t. When the cleaning operation is performed once or twice, the magnesium reduction inhibitor is not added.

[0038] The present invention discloses the following technical effects:

[0039] (1) High efficiency in reducing magnesium content and high selectivity: This invention can effectively inhibit magnesium silicates such as talc and serpentine by using the core inhibition of component A and the synergistic combination of water glass and organic macromolecular thickener, significantly reducing the MgO content of concentrate. At the same time, it has weak inhibition on sulfide minerals (nickel pyrite, chalcopyrite, etc.), ensuring a high recovery rate.

[0040] (2) Synergistic effect: The combination of component A, water glass and organic macromolecular thickener in this invention produces a significant synergistic inhibitory effect, which is better than that of single component or traditional combination.

[0041] (3) Improved solubility and workability: The compound system of the present invention solves the problems of poor solubility and easy agglomeration of organic macromolecules (such as CMC), making the agent easier to prepare and use.

[0042] (4) Simplify the drug formulation and reduce the total dosage: The single compound drug of the present invention can replace the traditional combination of "dispersant + inhibitor", reduce the types of drugs and reduce the total dosage.

[0043] (5) Stable properties and easy to use: The inhibitor of the present invention is stable, safe and non-toxic, easily soluble in water, and easy to apply on site.

[0044] (6) Improve economic benefits: This invention can improve the quality of concentrate (reduce MgO content) to meet smelting requirements; at the same time, it can improve the recovery rate of nickel and copper and reduce reagent costs. Attached Figure Description

[0045] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0046] Figure 1 This is a process flow diagram of closed-circuit flotation used in an application example of the present invention.

[0047] Figure 2 The image shows the infrared absorption spectrum of component A-1 prepared in Example 1.

[0048] Figure 3 The image shows the infrared absorption spectrum of component A-2 prepared in Example 2. Detailed Implementation

[0049] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0050] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0051] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0052] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This specification and embodiments are merely exemplary.

[0053] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0054] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0055] As a first aspect of the present invention, the present invention provides a magnesium reduction inhibitor for flotation of copper-nickel sulfide ore, the raw materials of which include component A, water glass, organic macromolecular thickener and water;

[0056] The mass ratio of component A, water glass and organic macromolecular thickener is 1~5:2:1~2 (the specific ratio needs to be adjusted according to the properties of the ore).

[0057] The total mass ratio of component A and the organic macromolecular thickener to the mass ratio of water is 1:0.5~2;

[0058] The structural formula of component A is: ;

[0059] In the formula, R is selected from H, -CH2-COOH, and -CH2-COO. - or n is an integer ≥ 100, and M is an integer ≥ 1.

[0060] As an embodiment of the present invention, the preparation steps of component A include: mixing glacial acetic acid solution, component B, component C and glutaraldehyde aqueous solution, reacting to obtain component A;

[0061] The structural formula of component B is: In the formula, R is selected from H, -CH2-COOH, and -CH2-COO. - or M is an integer ≥ 1;

[0062] The structural formula of component C is: In the formula, n is an integer ≥ 100.

[0063] The synthetic route for component A is as follows:

[0064] .

[0065] In a preferred embodiment of the present invention, the concentration of the glacial acetic acid solution is 2 wt%.

[0066] In a preferred embodiment of the present invention, the concentration of the glutaraldehyde aqueous solution is 5 wt%.

[0067] In a preferred embodiment of the present invention, the mass ratio of component B to component C is 1:0.5~2.

[0068] In a preferred embodiment of the present invention, the volume ratio of the glacial acetic acid solution to the glutaraldehyde aqueous solution is 1:0.1~0.5.

[0069] In a preferred embodiment of the present invention, the ratio of component B to the glutaraldehyde aqueous solution is 1~10g:10~15mL.

[0070] In a preferred embodiment of the present invention, the reaction temperature is 30~50℃ and the time is 1~4h.

[0071] In a preferred embodiment of the present invention, component C is added in the form of an aqueous solution, and the concentration of the aqueous solution of component C is 0.1 g / mL.

[0072] In a preferred embodiment of the present invention, mixing the glacial acetic acid solution, component B, component C, and glutaraldehyde aqueous solution includes: adding component B to the glacial acetic acid solution and dissolving it completely to form a hydrogel; dissolving component C completely in water and adding it to the hydrogel, stirring; and adding the glutaraldehyde aqueous solution dropwise to the hydrogel at 30-50°C.

[0073] In a preferred embodiment of the present invention, the number-average molecular weight of component C is 600~750000 g / mol, preferably 10000~60000 g / mol.

[0074] In a preferred embodiment of the present invention, the modulus (molar ratio of SiO2 to Na2O) of the water glass is 2.0 to 3.5.

[0075] In a preferred embodiment of the present invention, the organic macromolecular thickener includes one or more of sodium carboxymethyl cellulose (CMC), sodium carboxymethyl starch, gum arabic, xanthan gum, and carrageenan.

[0076] As a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned magnesium-reducing inhibitor for flotation of copper-nickel sulfide ore, comprising the following steps: mixing component A and water glass, adding an organic macromolecular thickener and water under stirring conditions, and continuing to stir until completely dissolved to obtain the magnesium-reducing inhibitor for flotation of copper-nickel sulfide ore.

[0077] As a third aspect of the present invention, the present invention provides an application of the above-mentioned magnesium-reducing inhibitor for flotation of copper-nickel sulfide ores in the flotation separation of copper-nickel sulfide ores.

[0078] In a preferred embodiment of the present invention, the magnesium reduction inhibitor for copper-nickel sulfide ore flotation is used in the roughing stage of copper-nickel sulfide ore flotation separation. When the roughing operation is performed once, the amount of magnesium reduction inhibitor added is 100~300g / t (the total amount added is 100~300g / t, which means that 100~300g of magnesium reduction inhibitor is added to 1t of copper-nickel sulfide ore flotation, the same below). When the roughing operation is performed twice, the amount of magnesium reduction inhibitor added in roughing I is 100~300g / t, and the amount added in roughing II is 50~200g / t.

[0079] In a preferred embodiment of the present invention, the magnesium reduction inhibitor for copper-nickel sulfide ore flotation is used in the roughing and cleaning stages of copper-nickel sulfide ore flotation separation. When the cleaning operation is performed three times, the amount of magnesium reduction inhibitor added in cleaning stage I is 50-200 g / t, the total amount added in cleaning stage II is 0-100 g / t, and the total amount added in cleaning stage III is 0-50 g / t. When the cleaning operation is performed once or twice, the magnesium reduction inhibitor for copper-nickel sulfide ore flotation is not added.

[0080] In a preferred embodiment of the present invention, the magnesium-reducing inhibitor for copper-nickel sulfide ore flotation is used in the first and second roughing stages and the third cleaning stage of copper-nickel sulfide ore flotation separation.

[0081] In a preferred embodiment of the present invention, the flotation separation step of the copper-nickel sulfide ore includes: grinding the copper-nickel sulfide ore and then subjecting it to 1-2 roughing stages, 1-2 scavenging stages, and 2-3 cleaning stages to obtain copper-nickel concentrate. During the roughing and cleaning stages, magnesium-reducing depressants, collectors, and frothers are added as needed. The roughing, scavenging, and cleaning stages are all conventional flotation processes and do not require special treatment.

[0082] In a preferred embodiment of the present invention, the grinding specifically involves grinding until the mineral particles with a fineness of <0.074 mm account for 70-80 wt%.

[0083] In a preferred embodiment of the present invention, the time for each coarse selection is 3-6 minutes, the time for each sweep selection is 2-4 minutes, and the time for each fine selection is 3-6 minutes.

[0084] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0085] In the following embodiments and application examples of the present invention, room temperature refers specifically to 20~30℃.

[0086] All raw materials used in the following embodiments and application examples of the present invention are commercially available products, wherein the modulus of water glass is 2.3.

[0087] The grades of the actual copper-nickel sulfide ores used in the following embodiments and application examples of this invention are merely illustrative and do not constitute essential features for implementing the technical solutions of this invention.

[0088] Example 1

[0089] (1) Synthesis of component A (denoted as A-1):

[0090] The synthetic route for component A-1 is as follows:

[0091] ;

[0092] The specific synthesis steps are as follows:

[0093] 1g of chitosan (compound 1 in the synthetic route, i.e., structural formula) was added. Compound R=H (with a number-average molecular weight of 30,000 g / mol and CAS number 9012-76-4) was added to 50 mL of 2 wt% glacial acetic acid solution and dissolved completely to form a chitosan hydrogel, which was then poured into a 250 mL three-necked flask. 1 g of polyethyleneimine (compound 2 in the synthetic route, with a number-average molecular weight of 20,000 g / mol and CAS number 9002-98-6) was dissolved completely in 10 mL of deionized water and added to the chitosan hydrogel. Stirring was continued for 1 h. At 40 °C, 10 mL of 5 wt% glutaraldehyde aqueous solution was added dropwise to the chitosan hydrogel (approximately 1 drop / 10 s, completed in about 1 h). After the addition was complete, the reaction was continued at 40 °C for 2 h to obtain a viscous product, which is component A-1.

[0094] The infrared absorption spectrum of component A-1 is as follows: Figure 2 As shown, the wave number is 3433 cm⁻¹. -1 The peak at this point is a characteristic absorption peak of the OH stretching vibration and the NH stretching vibration; wavenumber 2918 cm⁻¹. -1 2854cm -1 The peak at this point is a characteristic absorption peak of the stretching vibrations of -CH and -CH2; wavenumber 1655 cm⁻¹. -1 The peak at 1575 cm⁻¹ is the characteristic absorption peak of the stretching vibration of C=O; -1 The peak at this point is the characteristic absorption peak of the bending vibration of amide-NH-; wavenumber 1404 cm⁻¹. -1 The peak at 1058 cm⁻¹ is the characteristic absorption peak of the stretching vibration of CN; -1 The peak at 1404 cm⁻¹ is a characteristic absorption peak of COC. -1 The peak at that point is the characteristic absorption peak of the stretching vibration of CN, which proves the crosslinking of chitosan and polyethyleneimine.

[0095] (2) Preparation of compound magnesium-reducing inhibitors for flotation of copper-nickel sulfide ores:

[0096] Take 5g of component A-1 and 10g of water glass in a 250mL beaker, add 5g of sodium carboxymethyl cellulose and 6g of water while stirring, and continue stirring until completely dissolved to form a homogeneous, viscous colloidal solution, which is the compounded magnesium-reducing inhibitor for copper-nickel sulfide ore flotation. The absence of clumping during the stirring and dissolution process indicates that the compounded magnesium-reducing inhibitor for copper-nickel sulfide ore flotation in this embodiment has good solubility.

[0097] Application Example 1

[0098] Taking a copper-nickel sulfide ore in Qinghai as an example (ore properties are shown in Table 1), the flotation separation of copper-nickel sulfide ore was carried out through a closed-circuit flotation test with two tailings (process flow is as follows). Figure 1 (As shown) to verify the magnesium-lowering effect of the inhibitor on concentrate.

[0099] Table 1 Ore Properties

[0100]

[0101] The specific implementation steps are as follows:

[0102] 1. Grinding: For each closed-circuit flotation, weigh 800g of copper-nickel sulfide ore and grind it until the mineral particles with a diameter of less than 0.074mm account for 73wt%.

[0103] 2. Flotation process: In the roughing flotation operation, according to... Figure 1 The dosing regimen shown includes an inhibitor (different inhibitors were used in the control and experimental groups), the activator copper sulfate (CuSO4), and the collector butyl xanthate. The mixture undergoes two 4-minute roughing stages and two 4-minute roughing-scavenging stages to obtain a rough concentrate and roughing-scavenging tailings. In the fine flotation operation, according to… Figure 1 The dosing regime shown involves adding inhibitors and the collector butyl xanthate, followed by a 3-stage, 4-minute cleaning process to obtain concentrate; and a 3-stage, 4-minute scavenging process to obtain scavenging tailings. Closed-circuit flotation yields three products: concentrate, scavenging tailings, and roughing tailings.

[0104] 3. Dosing regimen (the key difference lies in the different inhibitors):

[0105] Control Group 1: The total amount of inhibitor added in the roughing stage (roughing I: water glass added 100g / t, CMC added 220g / t; roughing II: CMC added 200g / t; total addition in the roughing stage: water glass 100g / t + CMC 420g / t) and the cleaning stage (cleaning I: water glass added 50g / t, CMC added 100g / t; cleaning II: CMC added 80g / t; cleaning III: CMC added 50g / t; total addition in the cleaning stage: water glass 50g / t + CMC 230g / t) was 150g / t water glass + 650g / t CMC (total 800g / t).

[0106] Experimental Group 1: The compound magnesium-reducing inhibitor for flotation of copper-nickel sulfide ore prepared in Example 1 was used. The total amount of inhibitor added in the roughing stage (250 g / t for roughing I, 150 g / t for roughing II, and a total of 400 g / t for the roughing stage) and the cleaning stage (150 g / t for cleaning I, 80 g / t for cleaning II, and 40 g / t for cleaning III, and a total of 270 g / t for the cleaning stage) was 670 g / t.

[0107] Except for the inhibitor, the types, dosages, and addition locations of other agents, such as activators and collectors, were exactly the same in control group 1 and experimental group 1. All other conditions, except for the agents, were also identical.

[0108] 4. Results and Analysis: Each group of closed-circuit flotation reached equilibrium after two cycles. After multiple cycles, the grade and recovery rate of concentrate and tailings were tested. The results were the average of the items after five cycles, as shown in Table 2.

[0109] Table 2 Comparison of Closed-Circuit Flotation Results

[0110]

[0111] Analyze the experimental data of experimental group 1 and control group 1:

[0112] Magnesium reduction effect: The MgO content in the concentrate remained basically the same (4.17% vs 4.16%); Metal recovery rate significantly improved: Using the compound inhibitor prepared in Example 1, the nickel recovery rate increased by 3.74% (73.69% vs 69.95%), and the copper recovery rate increased by 3.49% (68.50% vs 65.01%); Concentrate grade: The nickel grade slightly increased (12.25% vs 12.15%), and the copper grade slightly decreased (2.80% vs 2.85%), with the overall metal enrichment effect being comparable; Tailings grade: The nickel grade in the tailings from the scavenging process significantly decreased (0.36% vs 0.59%), and the total tailings nickel grade significantly decreased (0.23% vs 0.25%), indicating a reduction in valuable metal loss; Reagent dosage: The total inhibitor dosage decreased by 130 g / t (670 g / t vs 4.16%). 800g / t), simplifying the drug formulation (single drug vs. combination of two drugs, control group 1 is the addition of two drugs separately).

[0113] Conclusion: In Application Example 1, while maintaining the MgO content of the concentrate at the required level and slightly increasing the nickel grade, the compound inhibitor of this invention significantly improved the recovery rates of nickel and copper metals, reduced the metal grade of the tailings from the scavenging process, and decreased the total reagent dosage. Although the absolute value of MgO did not decrease, the MgO level was maintained while significantly improving the recovery rate, and the nickel grade of the tailings from the scavenging process was reduced. The overall effect was better than that of Experimental Group 1 using water glass + CMC.

[0114] Example 2

[0115] (1) Synthesis of component A (denoted as A-2):

[0116] The synthetic route for component A-2 is as follows:

[0117] ;

[0118] The specific synthesis steps are as follows:

[0119] 10g of carboxymethylated chitosan (compound 3 in the synthetic route, i.e., structural formula) was added. R=CH2COO - A chitosan hydrogel (compound 4 in the synthetic route, with a number-average molecular weight of 100,000 g / mol and CAS number 83512-85-0) was added to 100 mL of a 2 wt% glacial acetic acid solution and dissolved completely to form a chitosan hydrogel, which was then poured into a 250 mL three-necked flask. 10 g of polyethyleneimine (compound 4 in the synthetic route, with a number-average molecular weight of 10,000 g / mol) was dissolved completely in 100 mL of deionized water and added to the chitosan hydrogel, and the mixture was stirred for 1 h. At 40 °C, 15 mL of a 5 wt% glutaraldehyde aqueous solution was added dropwise to the chitosan hydrogel (approximately 1.5 h, at a rate of about 1 drop / 10 s). After the addition was complete, the reaction was continued at 40 °C for 2 h to obtain a viscous product, which is component A-2.

[0120] The infrared absorption spectrum of component A-2 is as follows: Figure 3 As shown, the wavenumber is 3426 cm⁻¹. -1 The peak at this point is a characteristic absorption peak of the OH stretching vibration and the NH stretching vibration; wavenumber 2929 cm⁻¹. -1 2852cm -1 The peak at this point is a characteristic absorption peak of the stretching vibrations of -CH and -CH2; wavenumber 1645 cm⁻¹. -1 The peak at 1577 cm⁻¹ is the characteristic absorption peak of the stretching vibration of C=O; -1 The peak at this point is the characteristic absorption peak of the bending vibration of amide-NH-; wavenumber 1403 cm⁻¹. -1 The peak at 1049 cm⁻¹ is the characteristic absorption peak of the stretching vibration of CN; -1 The peak at 1403 cm⁻¹ is a characteristic absorption peak of COC.-1 The peak at that point is the characteristic absorption peak of the stretching vibration of CN, which proves the crosslinking of carboxymethyl chitosan and polyethyleneimine.

[0121] (2) Preparation of compound magnesium-reducing inhibitors for flotation of copper-nickel sulfide ores:

[0122] Take 5g of component A-2 and 10g of water glass in a 250mL beaker, add 5g of gum arabic and 10g of water while stirring, and continue stirring until completely dissolved to form a homogeneous colloidal solution with a certain viscosity. This is the compounded magnesium-reducing inhibitor for copper-nickel sulfide ore flotation. The absence of clumping during the stirring and dissolution process indicates that the compounded magnesium-reducing inhibitor for copper-nickel sulfide ore flotation in this embodiment has good solubility.

[0123] Application Example 2

[0124] Taking a copper-nickel sulfide ore in Qinghai as an example (ore properties are shown in Table 3, with lower nickel grade and higher magnesium oxide content), the flotation separation of copper-nickel sulfide ore was carried out through a closed-circuit flotation test with two tailings (process flow is as follows). Figure 1 (As shown) to verify the magnesium-lowering effect of the inhibitor on concentrate.

[0125] Table 3 Ore Properties

[0126]

[0127] The specific implementation steps are as follows:

[0128] 1. Grinding: For each closed-circuit flotation, weigh 800g of copper-nickel sulfide ore and grind it until the mineral particles with a diameter of less than 0.074mm account for 73wt%.

[0129] 2. Flotation process: Same as in application example 1.

[0130] 3. Dosing regimen (the key difference lies in the different inhibitors):

[0131] Control Group 2: The total amount of inhibitor added in the roughing stage (roughing I: water glass added 100g / t, CMC added 300g / t; roughing II: CMC added 200g / t; total addition in the roughing stage: water glass 100g / t + CMC 500g / t) and the cleaning stage (cleaning I: water glass added 50g / t, CMC added 130g / t; cleaning II: CMC added 80g / t; cleaning III: CMC added 50g / t; total addition in the cleaning stage: water glass 50g / t + CMC 260g / t) was 150g / t water glass + 760g / t CMC (total 910g / t).

[0132] Experimental Group 2: The compound magnesium-reducing inhibitor for flotation of copper-nickel sulfide ore prepared in Example 2 was used. The total amount of inhibitor added in the roughing stage (300 g / t for roughing I, 160 g / t for roughing II, and a total of 460 g / t for the roughing stage) and the cleaning stage (120 g / t for cleaning I, 80 g / t for cleaning II, and 40 g / t for cleaning III, and a total of 240 g / t for the cleaning stage) was 700 g / t.

[0133] Except for the inhibitor, the types, dosages, and addition locations of other agents, such as activators and collectors, were exactly the same in control group 2 and experimental group 2. All other conditions, except for the agents, were also identical.

[0134] 4. Results and Analysis: Each group of closed-circuit flotation reached equilibrium after two cycles. After multiple cycles, the grade and recovery rate of concentrate and tailings were tested. The results were the average of the values ​​of each item after five cycles, as shown in Table 4.

[0135] Table 4 Comparison of Closed-Circuit Flotation Results

[0136]

[0137] Analyze the experimental data of experimental group 2 and control group 2:

[0138] Significant magnesium reduction effect: The MgO content of the concentrate in experimental group 2 decreased from 2.77% to 2.16% (a decrease of 0.61%), which was far better than that in control group 2 and met the smelting requirements (MgO<6%). Metal recovery rate was improved across the board: the nickel recovery rate increased by 1.68% (69.51% vs 67.83%) and the copper recovery rate increased by 1.20% (55.39% vs 54.19%).

[0139] Concentrate grades improved in two ways: nickel grade increased by 0.38% (7.88% vs 7.50%), and copper grade increased by 0.34% (1.73% vs 1.39%); tailings metal loss decreased: nickel grade in coarse scavenging tailings decreased by 0.02% (0.12% vs 0.14%), and the overall nickel content in tailings decreased simultaneously; reagent economy was optimized: total reagent usage decreased by 210g / t (700g / t vs 910g / t), simplifying the on-site reagent preparation process and the reagent system (single reagent vs two reagent combinations).

[0140] Conclusion: The compound inhibitor prepared in Example 2 exhibits the following characteristics in low-grade, high-magnesium ores: synergistic magnesium reduction: the compounding of component A-2 with water glass and gum arabic significantly enhances the inhibition of talc / serpentine; cost-effectiveness: achieving simultaneous improvement in metal recovery rate and concentrate grade with lower dosage (30% reduction in reagent dosage); and wide adaptability: maintaining stable effects even on refractory ores with a MgO content of nearly 30%.

[0141] Example 3

[0142] (1) Synthesis of component A (denoted as A-2):

[0143] Same as Example 2.

[0144] (2) Preparation of compound magnesium-reducing inhibitors for flotation of copper-nickel sulfide ores:

[0145] Take 8g of component A-2 and 10g of water glass in a 250mL beaker, add 5g of gum arabic, 5g of sodium carboxymethyl cellulose, and 15g of water while stirring, and continue stirring until completely dissolved to form a homogeneous colloidal solution with a certain viscosity. This is the compounded magnesium-reducing inhibitor for copper-nickel sulfide ore flotation. No clumping occurred during the stirring and dissolution process, indicating that the compounded magnesium-reducing inhibitor for copper-nickel sulfide ore flotation in this embodiment has good solubility.

[0146] Application Example 3

[0147] Taking a copper-nickel sulfide ore in Qinghai as an example (ore properties are shown in Table 5), the flotation separation of copper-nickel sulfide ore was carried out through a closed-circuit flotation test with two tailings (process flow is as follows). Figure 1 (As shown) to verify the magnesium-lowering effect of the inhibitor on concentrate.

[0148] Table 5 Ore Properties

[0149]

[0150] The specific implementation steps are as follows:

[0151] 1. Grinding: For each closed-circuit flotation, weigh 800g of copper-nickel sulfide ore and grind it until the mineral particles with a diameter of less than 0.074mm account for 73wt%.

[0152] 2. Flotation process: Same as in application example 1.

[0153] 3. Dosing regimen (the key difference lies in the different inhibitors):

[0154] Control Group 3: The total amount of inhibitor added in the roughing stage (roughing I: water glass added 100g / t, CMC added 400g / t; roughing II: CMC added 280g / t; total addition in the roughing stage: water glass 100g / t + CMC 680g / t) and the cleaning stage (cleaning I: water glass added 50g / t, CMC added 180g / t; cleaning II: CMC added 100g / t; cleaning III: CMC added 40g / t; total addition in the cleaning stage: water glass 50g / t + CMC 320g / t) was 150g / t water glass + 1000g / t CMC (total 1150g / t).

[0155] Experimental Group 3: The compound magnesium-reducing inhibitor for flotation of copper-nickel sulfide ore prepared in Example 3 was used. The total amount of inhibitor added in the roughing stage (300 g / t for roughing I, 150 g / t for roughing II, and a total of 450 g / t for the roughing stage) and the cleaning stage (200 g / t for cleaning I, 50 g / t for cleaning II, and 40 g / t for cleaning III, and a total of 290 g / t for the cleaning stage) was 740 g / t.

[0156] Except for the inhibitor, the types, dosages, and addition locations of other agents, such as activators and collectors, were exactly the same in control group 3 and experimental group 3. All other conditions, except for the agents, were also identical.

[0157] 4. Results and Analysis: Each group of closed-circuit flotation reached equilibrium after two cycles. After multiple cycles, the grade and recovery rate of concentrate and tailings were tested. The results were the average of the values ​​of each item after five cycles, as shown in Table 6.

[0158] Table 6 Comparison of Closed-Circuit Flotation Results

[0159]

[0160] Analyze the experimental data of experimental group 3 and control group 3:

[0161] Significant magnesium reduction effect: Compared with control group 3, the MgO content of concentrate in experimental group 3 decreased from 9.40% to 7.08% (a decrease of 24.68%), which was far better than control group 3; Improved metal recovery rate: Nickel recovery rate increased by 0.57% (80.97% vs 80.40%), and copper recovery rate decreased by 0.86% (64.43% vs 65.29%).

[0162] Concentrate grades improved in two ways: nickel grade increased by 0.75% (10.76% vs 10.01%), and copper grade increased by 0.08% (1.35% vs 1.27%). Tailings metal loss decreased: nickel grade in fine scavenging tailings decreased by 0.05% (0.24% vs 0.29%), nickel grade in coarse scavenging tailings decreased by 0.01% (0.15% vs 0.16%), and overall nickel grade in tailings decreased by 0.02% (0.17% vs 0.19%). Reagent economics were optimized: total reagent usage decreased by 410g / t (740g / t vs 1150g / t), simplifying the on-site reagent preparation process and the reagent formulation (single reagent vs two reagent combinations).

[0163] Conclusion: Under the premise of maintaining a certain useful metal recovery rate, the compound inhibitor prepared in Example 3 can significantly improve the concentrate grade and significantly reduce the magnesium oxide content in the concentrate. Simultaneously, it significantly reduces the metal content in both the roughing and finishing tailings, resulting in reduced useful metal loss in the tailings. Economical and efficient: It achieves simultaneous improvement in metal recovery rate and concentrate grade with a lower dosage (35.7% reduction in reagent dosage).

[0164] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A magnesium-reducing inhibitor for the flotation of copper-nickel sulfide ores, characterized in that, The raw materials include ingredient A, water glass, organic macromolecular thickener, and water; The mass ratio of component A, water glass and organic macromolecular thickener is 1~5:2:1~2; The total mass ratio of component A and the organic macromolecular thickener to the mass ratio of water is 1:0.5~2; The structural formula of component A is: ; In the formula, R is selected from H, -CH2-COOH, and -CH2-COO. - or n is an integer ≥ 100, and M is an integer ≥ 1; The organic macromolecular thickener includes one or more of sodium carboxymethyl cellulose, sodium carboxymethyl starch, gum arabic, xanthan gum, and carrageenan.

2. The magnesium-reducing depressant for copper-nickel sulfide ore flotation as described in claim 1, characterized in that, The preparation steps of component A include: mixing glacial acetic acid solution, component B, component C and glutaraldehyde aqueous solution, reacting to obtain component A; The structural formula of component B is: In the formula, R is selected from H, -CH2-COOH, and -CH2-COO. - or M is an integer ≥ 1; The structural formula of component C is: In the formula, n is an integer ≥ 100.

3. The magnesium-reducing depressant for flotation of copper-nickel sulfide ore as described in claim 2, characterized in that, The concentration of the glacial acetic acid solution is 2 wt%; And / or, the concentration of the glutaraldehyde aqueous solution is 5 wt%; And / or, the mass ratio of component B to component C is 1:0.5~2; And / or, the volume ratio of the glacial acetic acid solution to the glutaraldehyde aqueous solution is 1:0.1~0.5; And / or, the ratio of component B to the aqueous glutaraldehyde solution is 1~10g:10~15mL.

4. The magnesium-reducing depressant for flotation of copper-nickel sulfide ore as described in claim 2, characterized in that, The reaction is carried out at a temperature of 30-50°C for 1-4 hours.

5. The magnesium-reducing depressant for flotation of copper-nickel sulfide ore as described in claim 1, characterized in that, The modulus of the water glass is 2.0 to 3.

5.

6. A method for preparing a magnesium-reducing inhibitor for flotation of copper-nickel sulfide ore as described in any one of claims 1-5, characterized in that, The process includes the following steps: mixing component A and water glass, adding an organic macromolecular thickener and water under stirring conditions, and continuing to stir until completely dissolved to obtain the magnesium-reducing inhibitor for the flotation of copper-nickel sulfide ore.

7. The application of a magnesium-reducing inhibitor for copper-nickel sulfide ore flotation as described in any one of claims 1-5 in the flotation separation of copper-nickel sulfide ore.

8. The application of the magnesium-reducing inhibitor for copper-nickel sulfide ore flotation as described in claim 1 in the flotation separation of copper-nickel sulfide ore, characterized in that, The magnesium reduction inhibitor for copper-nickel sulfide ore flotation is used in the roughing stage of copper-nickel sulfide ore flotation separation. When the roughing operation is performed once, the amount of magnesium reduction inhibitor added is 100~300g / t. When the roughing operation is performed twice, the amount of magnesium reduction inhibitor added in roughing I is 100~300g / t, and the amount added in roughing II is 50~200g / t.

9. The application of the magnesium-reducing inhibitor for copper-nickel sulfide ore flotation as described in claim 8 in the flotation separation of copper-nickel sulfide ore, characterized in that, The magnesium reduction inhibitor for copper-nickel sulfide ore flotation is used in the roughing and cleaning stages of copper-nickel sulfide ore flotation separation. When the cleaning operation is performed three times, the amount of magnesium reduction inhibitor added in cleaning I is 50~200g / t, the amount added in cleaning II is 0~100g / t, and the amount added in cleaning III is 0~50g / t.

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