Flotation collecting agent for refractory copper oxide ore and preparation method of flotation collecting agent

Abstract

The invention relates to the technical field of beneficiation collecting agents, and discloses a flotation collecting agent for refractory copper oxide ore and a preparation method of the flotation collecting agent. The flotation collecting agent comprises, by mass, 59.3% of a chelating main agent, 19.76% of dimethyl phthalate, 15.81% of a pH response type segmented copolymer, 3.95% of 0 # light diesel oil, 0.24% of a quantum dot additive, 0.4% of shell source polypeptide, 0.08% of a magnetic recycling agent, 1.19% of an emulsion stabilizer, 0.04% of a calcium ion activating agent, 0.4% of tetrabutylammonium bromide and 23.73% of deionized water. Wherein the total mass percentage of other components except the deionized water is 100%, and the deionized water is independently added into the solid formula as a solvent to form the flotation collecting agent for the refractory copper oxide ore. According to the flotation collecting agent for the refractory copper oxide ore and the preparation method of the flotation collecting agent, through the design of multi-active-group collaboration, an intelligent carrier and the like, the flotation efficiency and selectivity of the refractory copper oxide ore are improved, prevulcanization is not needed, agent recovery and environmental protection are achieved, and a new scheme is provided for complex ore development.

Description

Technical Field

[0001] This invention relates to the field of mineral processing collectors, and in particular to a flotation collector for refractory copper oxide ores and its preparation method. Background Technology

[0002] The flotation recovery of refractory copper oxide ores has always been a key focus and challenge in the efficient utilization of mineral resources. These ores have complex mineral compositions, often containing multiple copper oxide minerals such as malachite, azurite, and chrysocolla, and are frequently closely associated with gangue minerals such as calcium magnesium silicates and carbonates. Their fine particle size and tendency to form hydrophilic oxide films on the surface make it difficult for conventional collectors to adhere effectively. Traditional processing methods, such as the sulfidation-xanthate method, require large amounts of sulfidating agents like sodium sulfide, resulting in high reagent consumption and insufficient recovery rates for refractory minerals like chrysocolla, and are easily affected by polymetallic ions in the pulp. While fatty acid collectors can directly act on some copper oxide minerals, their selectivity is extremely poor, easily undergoing non-specific adsorption with alkaline gangues such as calcite and dolomite, leading to low concentrate grades. Hydroxime acid reagents offer some improvement in selectivity, but their synthesis process is complex and costly, and they exhibit poor dispersibility in high-slim environments, making it difficult to control foam stability and unsuitable for the separation of complex polymetallic ores.

[0003] Meanwhile, existing collectors generally suffer from problems such as a narrow pH range, a sharp drop in activity at low temperatures, and difficulty in recovering reagent residues. Some reagents containing heavy metals or highly toxic components can also cause environmental pollution, which contradicts the development concept of green mineral processing. As high-grade copper oxide ore resources become increasingly depleted, the demand for the development and utilization of low-grade, complex, and difficult-to-process copper oxide ores is becoming more and more urgent. Developing new flotation collectors that do not require pre-sulfurization treatment, have broad-spectrum collecting ability for a variety of copper oxide minerals, are highly selective, environmentally friendly, and recyclable has become the key to breaking through existing technological bottlenecks and improving the utilization rate of difficult-to-process copper oxide ore resources. Summary of the Invention

[0004] This invention provides a flotation collector for refractory oxidized copper ore and its preparation method. Through the synergistic design of multiple active groups and intelligent carriers, the flotation efficiency and selectivity of refractory oxidized copper ore are improved. It does not require pre-sulfurization, realizes reagent recovery, and is green and environmentally friendly, providing a new solution for the development of complex mines.

[0005] This invention provides a flotation collector for refractory copper oxide ores, comprising the following components by mass percentage:

[0006]

[0007]

[0008] The solid formulation comprises a total mass percentage of 100% consisting of the chelating agent, dimethyl phthalate, pH-responsive block copolymer, 0# light diesel oil, quantum dot additive, shell-derived polypeptide, magnetic recovery agent, emulsifying stabilizer, calcium ion activator, and tetrabutylammonium bromide. Deionized water is added separately as a solvent to the solid formulation to form a flotation collector for refractory copper oxide ores.

[0009] Furthermore, the chelating agent comprises 2-mercapto-5-trifluoromethylpyridineimidazole and dibutyl dithiophosphate ammonium, wherein 2-mercapto-5-trifluoromethylpyridineimidazole accounts for 27.67% and dibutyl dithiophosphate ammonium accounts for 31.63%.

[0010] Furthermore, the pH-responsive block copolymer is a PEG-PAA-b-PDMS block copolymer with PEG M=600, PAA M=2000, and PDMS M=1500. When pH>8.5, the PAA chain extends and the steric hindrance layer thickens to 12nm.

[0011] Furthermore, the quantum dot additive is ZnS-coated CdSe quantum dots with a -COOH surface modification. The CdSe core / ZnS shell thickness ratio in the quantum dots is 1:0.5, and the quantum dot size is 3.5 nm. This is combined with 0# light diesel oil to reduce Cu content. 2+ The reduction barrier is 0.15 eV.

[0012] Furthermore, the magnetic recovery agent is Fe3O4@SiO2-NH2 nanoparticles with a particle size of 50 nm and an amino density ≥5 μmol / g.

[0013] Furthermore, the emulsifying stabilizer is Tween-80, and the calcium ion activator is a 1mM CaCl2 solution.

[0014] Furthermore, it also includes a pH adjuster, which is a 10% NaOH solution, added as needed to the formulation of the flotation collector for refractory copper oxide ores to control the reaction pH to 8.5–9.0.

[0015] This invention also provides a method for preparing a flotation collector for refractory copper oxide ores. Based on the flotation collector for refractory copper oxide ores described above, the preparation method specifically includes:

[0016] S1. Prepare the following ingredients according to the mass percentage of the flotation collector for the refractory copper oxide ore: 2-mercapto-5-trifluoromethylpyridine imidazole, dibutyl dithiophosphate, dimethyl phthalate, pH-responsive block copolymer, 0# light diesel oil, quantum dot additive, shell-derived polypeptide, Fe3O4@SiO2-NH2 nanoparticles, Tween-80, CaCl2 solution, tetrabutylammonium bromide, and deionized water.

[0017] S2. In a nitrogen-protected reactor, add 2-mercapto-5-trifluoromethylpyridine imidazole, propylene oxide, and tetrabutylammonium bromide. Heat to 118±1℃ and stir at 250 rpm for 3.5 hours. Cool to 50℃ to obtain the trifluoromethylpyridine modified product.

[0018] S3. First, dibutyl dithiophosphate and dimethyl phthalate are added to the trifluoromethylpyridine modified product, then Fe3O4@SiO2-NH2 magnetic nanoparticles are added, and finally 10% NaOH solution is added dropwise to maintain pH = 8.7±0.1. Nitrogen gas is introduced at a rate of 1.2 L / min, and the reaction is carried out at 50°C for 4.5 hours to generate a copolymer with dual active groups containing magnetic support.

[0019] S4. Mix 0# light diesel oil with carboxylated CdSe / ZnS quantum dots and ultrasonically disperse at 40kHz and 300W for 20 minutes to form a diesel oil phase with uniformly dispersed quantum dots.

[0020] S5. Add 1 mM CaCl2 solution to the PEG-PAA-b-PDMS block copolymer and stir at 60°C for 1 hour to induce pre-activation of the peptide binding sites to obtain the smart carrier.

[0021] S6. Add the dual-active group copolymer containing magnetic carrier generated in step S3, the diesel phase with uniformly dispersed quantum dots formed in step S4, and the smart carrier formed in step S5 to the emulsification tank, and then add Tween-80, shell-derived peptides, and 40℃ deionized water. First, mix at 8000 rpm for 5 min, and then mix again at 12000 rpm for 15 min to enhance the dispersion of quantum dots. The emulsion particle size D90 ≤ 180 nm and the Zeta potential ≤ -45 mV are detected to obtain the flotation collector for difficult-to-process copper oxide ore.

[0022] The beneficial effects of this invention are as follows:

[0023] This invention significantly improves the flotation performance of refractory copper oxide ores through innovative multi-active group synergistic design and intelligent carrier technology. The trifluoromethylpyridine imidazole in the chelating agent forms a dual-site action mechanism with dibutyldithiophosphate, exhibiting strong collection capabilities for various copper oxide minerals such as malachite, azurite, and chrysocolla, achieving efficient recovery without pre-sulfurization. The pH-responsive block copolymer intelligently regulates surface properties in the slurry, enhancing selective adsorption and inhibiting gangue mineral flotation. The combination of quantum dot additives and magnetic recovery agents not only lowers the copper ion reduction barrier but also enables magnetic separation, recovery, and reuse of the reagents, significantly reducing reagent consumption. The shell-derived peptide biomimetic inhibitor exhibits highly selective inhibition of calcium-magnesium gangue minerals, significantly improving concentrate grade. Microemulsion dispersion technology ensures uniform distribution and stability of the reagents in the slurry, maintaining good activity even at low temperatures. The overall process is green and environmentally friendly, free of heavy metals and toxic components, meeting sustainable development requirements and providing a novel solution for the efficient development of complex and refractory copper oxide resources. Attached Figure Description

[0024] Figure 1 This is a schematic flowchart of the method for preparing flotation collectors for refractory copper oxide ores according to the present invention.

[0025] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0026] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0027] This invention provides a flotation collector for refractory copper oxide ores, comprising the following components by mass percentage:

[0028] a. Chelating agents, accounting for 59.3%, include: (1) 2-mercapto-5-trifluoromethylpyridine imidazole, accounting for 27.67%, used to regulate electron cloud density with strong electron-withdrawing groups (-CF4) and increase chelation energy to -248kJ / mol. (2) dibutyl dithiophosphate ammonium, accounting for 31.63%, used to provide thiophosphate groups (-P(=S)OR).

[0029] b. Dimethyl phthalate, accounting for 19.76%, acts as a crosslinking agent, serving as a bridge to promote the formation of amide bonds between molecules in the collector system.

[0030] c. pH-responsive block copolymer, accounting for 15.81%, is a PEG-PAA-b-PDMS block copolymer with PEG M=600, PAA M=2000, and PDMS M=1500. When pH>8.5, the PAA chain extends and the steric hindrance layer thickens to 12nm.

[0031] d.0# light diesel oil, accounting for 3.95%, is used as a catalytic co-solvent.

[0032] e. Quantum dot additive, accounting for 0.24%, consists of ZnS-coated CdSe quantum dots (surface-COOH modified), with a CdSe core / ZnS shell thickness ratio of 1:0.5. 2 + Dissolution rate < 0.1 ppm, quantum dot size 3.5 nm, combined with 0# light diesel oil to reduce Cu 2+ The reduction barrier is 0.15 eV.

[0033] f. Shell-derived polypeptide (H2N-Gly-Pro-Hyp-Gly-Glu-Ser-COOH), accounting for 0.4%, acts as a biomimetic inhibitor, forming a β-folded mineralization film (contact angle > 90°) on the surface of calcium magnesium minerals.

[0034] g. Magnetic recycling agent, accounting for 0.08%, is Fe3O4@SiO2-NH2 nanoparticles with a particle size of 50nm and an amino density ≥5μmol / g.

[0035] h. Emulsifying stabilizer, accounting for 1.19%, is Tween-80.

[0036] i. Calcium ion activator, 0.04%, is CaCl2 (1mM solution). 2+ It induces peptide prefolding to maintain its active conformation.

[0037] j. Tetrabutylammonium bromide, accounting for 0.4%, is used as a catalyst for alkoxylation reaction.

[0038] k. Deionized water, accounting for 23.73%, was used as the reaction medium and dispersion medium.

[0039] l. pH adjuster, which is a 10% NaOH solution, is added to the flotation collector formulation for difficult-to-process copper oxide ores as needed to control the reaction pH to 8.5-9.0.

[0040] The above components a to j constitute a 100% solid formulation by mass. Deionized water k is added separately to the solid formulation as a solvent to form a flotation collector for refractory copper oxide ores. pH adjuster l is added as needed to the flotation collector formulation for refractory copper oxide ores to control the reaction pH to 8.5 to 9.0.

[0041] like Figure 1 As shown, the present invention also provides a method for preparing a flotation collector for refractory copper oxide ores. Based on the flotation collector for refractory copper oxide ores described above, the preparation method specifically includes:

[0042] S1. Preparation of each component

[0043] Prepare the following ingredients in the specified mass percentages according to the flotation collector for the refractory copper oxide ore: 2-mercapto-5-trifluoromethylpyridinium imidazole, dibutyl dithiophosphate, dimethyl phthalate, pH-responsive block copolymer, 0# light diesel oil, quantum dot additive, shell-derived polypeptide, Fe3O4@SiO2-NH2 nanoparticles, Tween-80, CaCl2 solution, tetrabutylammonium bromide, and deionized water.

[0044] S2, Alkoxylation Pretreatment

[0045] In a nitrogen-protected reactor, 2-mercapto-5-trifluoromethylpyridine imidazole, propylene oxide, and tetrabutylammonium bromide were added, heated to 118±1℃ (precise temperature control), stirred at 250 rpm for 3.5 hours, and cooled to 50℃ to obtain the trifluoromethylpyridine modified product.

[0046] S3, Low-temperature copolymerization reaction

[0047] Dibutyl dithiophosphate and dimethyl phthalate were first added to the trifluoromethylpyridine modified product, followed by Fe3O4@SiO2-NH2 magnetic nanoparticles. Finally, 10% NaOH solution was added dropwise to maintain pH = 8.7±0.1, nitrogen gas was introduced at a rate of 1.2 L / min, and the reaction was carried out at 50 °C for 4.5 hours to generate a copolymer with dual active groups containing a magnetic support.

[0048] S4, Catalytic Cosolvent Premix

[0049] 0# light diesel oil was mixed with carboxylated CdSe / ZnS quantum dots and ultrasonically dispersed at 40kHz and 300W for 20 minutes to form a diesel oil phase with uniformly dispersed quantum dots.

[0050] S5, Intelligent Carrier Activation

[0051] 1 mM CaCl2 solution was added to the PEG-PAA-b-PDMS block copolymer (PEG M=600, PAA M=2000, PDMS M=1500), and the mixture was stirred at 60°C for 1 hour to induce pre-activation of the peptide binding sites, thus obtaining the smart carrier.

[0052] S6, Microemulsion Dispersion

[0053] The dual-active group copolymer containing magnetic carrier generated in step S3, the diesel phase with uniformly dispersed quantum dots formed in step S4, and the smart carrier formed in step S5 are added to an emulsification tank. Then, Tween-80, shell-derived peptides, and 40°C deionized water are added. The mixture is first initially mixed at 8000 rpm for 5 min, and then mixed a second time at 12000 rpm for 15 min to enhance the dispersion of quantum dots. The emulsion particle size D90 is ≤180 nm and the Zeta potential is ≤-45 mV to obtain a flotation collector for difficult-to-process copper oxide ore.

[0054] In the chelating agent, 2-mercapto-5-trifluoromethylpyridineimidazole contains N and S heterocycles and an electron-withdrawing group (-CF3), which enhances the selective chelation of copper ions; dibutyl dithiophosphate provides a thiophosphate ester group (-P=S), which forms a stable five-membered ring structure with copper ions.

[0055] In the smart carrier, the pH-responsive block copolymer (PEG-PAA-b-PDMS) provides water solubility and dispersibility through PEG segments; PAA segments (polyacrylic acid) dissociate into carboxylate groups (-COO-) under alkaline conditions (pH>8.5), which are adsorbed onto the mineral surface through electrostatic interaction; and PDMS segments (polydimethylsiloxane) enhance hydrophobicity and promote bubble adhesion.

[0056] Quantum dot additives (ZnS-coated CdSe) reduce Cu content by reacting with the hydroxyl groups on the mineral surface via surface carboxyl groups (-COOH). 2 +Reduction barrier; Shell-derived peptides form a selective inhibition film on the surface of gangue minerals through specific amino acid sequences (such as Gly-Pro-Hyp).

[0057] Through the above innovative multi-active group (chelating agent, smart carrier, quantum dot additive, shell-derived peptide) synergistic design and smart carrier technology, the flotation performance of difficult-to-process copper oxide ores has been significantly improved.

[0058] The trifluoromethylpyridine imidazole in the chelating agent forms a two-site action mechanism with dibutyldithiophosphate, exhibiting strong collection ability for various copper oxide minerals such as malachite, azurite, and chrysocolla, achieving efficient recovery without pre-sulfurization. The pH-responsive block copolymer can intelligently regulate surface properties in the slurry, enhancing selective adsorption and inhibiting gangue mineral flotation. The combination of quantum dot additives and magnetic recovery agents not only lowers the copper ion reduction barrier but also enables magnetic separation, recovery, and reuse of the reagents, significantly reducing reagent consumption. The shell-derived peptide biomimetic inhibitor has a highly selective inhibitory effect on calcium and magnesium gangue minerals, significantly improving concentrate grade. The microemulsion dispersion technology ensures the uniform distribution and stability of the reagents in the slurry, maintaining good activity even at low temperatures.

[0059] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, apparatus, article, or method that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, apparatus, article, or method. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, apparatus, article, or method that includes that element.

[0060] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A flotation collector for refractory copper oxide ores, characterized in that, Includes the following components by mass percentage: The solid formulation comprises a total mass percentage of 100% consisting of the chelating agent, dimethyl phthalate, pH-responsive block copolymer, 0# light diesel oil, quantum dot additive, shell-derived polypeptide, magnetic recovery agent, emulsifying stabilizer, calcium ion activator, and tetrabutylammonium bromide. Deionized water is added separately as a solvent to the solid formulation to form a flotation collector for refractory copper oxide ores.

2. The flotation collector for refractory copper oxide ores according to claim 1, characterized in that, The chelating agents include 2-mercapto-5-trifluoromethylpyridineimidazole and dibutyl dithiophosphate ammonium, wherein 2-mercapto-5-trifluoromethylpyridineimidazole accounts for 27.67% and dibutyl dithiophosphate ammonium accounts for 31.63%.

3. The flotation collector for refractory copper oxide ores according to claim 1, characterized in that, The pH-responsive block copolymer is a PEG-PAA-b-PDMS block copolymer with PEG M=600, PAA M=2000, and PDMS M=1500. When pH>8.5, the PAA chain extends and the steric hindrance layer thickens to 12nm.

4. The flotation collector for refractory copper oxide ores according to claim 1, characterized in that, The quantum dot additive consists of ZnS-coated CdSe quantum dots with a -COOH surface modification. The CdSe core / ZnS shell thickness ratio in the quantum dots is 1:0.5, and the quantum dot size is 3.5 nm. It is combined with 0# light diesel oil to reduce Cu content. 2+ The reduction barrier is 0.15 eV.

5. The flotation collector for refractory copper oxide ores according to claim 1, characterized in that, The magnetic recovery agent is Fe3O4@SiO2-NH2 nanoparticles with a particle size of 50 nm and an amino density ≥5 μmol / g.

6. The flotation collector for refractory copper oxide ores according to claim 1, characterized in that, The emulsifying stabilizer is Tween-80, and the calcium ion activator is a 1mM CaCl2 solution.

7. The flotation collector for refractory copper oxide ores according to claim 1, characterized in that, It also includes a pH adjuster, which is a 10% NaOH solution, added as needed to the formulation of the flotation collector for refractory copper oxide ores to control the reaction pH to 8.5-9.

0.

8. A method for preparing a flotation collector for refractory copper oxide ores, characterized in that, The preparation method of the flotation collector for refractory copper oxide ores according to claim 7 specifically includes: S1. Prepare the following ingredients according to the mass percentage of the flotation collector for the refractory copper oxide ore: 2-mercapto-5-trifluoromethylpyridine imidazole, dibutyl dithiophosphate, dimethyl phthalate, pH-responsive block copolymer, 0# light diesel oil, quantum dot additive, shell-derived polypeptide, Fe3O4@SiO2-NH2 nanoparticles, Tween-80, CaCl2 solution, tetrabutylammonium bromide, and deionized water. S2. In a nitrogen-protected reactor, add 2-mercapto-5-trifluoromethylpyridine imidazole, propylene oxide, and tetrabutylammonium bromide. Heat to 118±1℃ and stir at 250 rpm for 3.5 hours. Cool to 50℃ to obtain the trifluoromethylpyridine modified product. S3. First, dibutyl dithiophosphate and dimethyl phthalate are added to the trifluoromethylpyridine modified product, then Fe3O4@SiO2-NH2 magnetic nanoparticles are added, and finally 10% NaOH solution is added dropwise to maintain pH = 8.7±0.

1. Nitrogen gas is introduced at a rate of 1.2 L / min, and the reaction is carried out at 50°C for 4.5 hours to generate a copolymer with dual active groups containing magnetic support. S4. Mix 0# light diesel oil with carboxylated CdSe / ZnS quantum dots and ultrasonically disperse at 40kHz and 300W for 20 minutes to form a diesel oil phase with uniformly dispersed quantum dots. S5. Add 1 mM CaCl2 solution to the PEG-PAA-b-PDMS block copolymer and stir at 60°C for 1 hour to induce pre-activation of the peptide binding sites to obtain the smart carrier. S6. Add the dual-active group copolymer containing magnetic carrier generated in step S3, the diesel phase with uniformly dispersed quantum dots formed in step S4, and the smart carrier formed in step S5 to the emulsification tank, and then add Tween-80, shell-derived peptides, and 40℃ deionized water. First, mix at 8000 rpm for 5 min, and then mix again at 12000 rpm for 15 min to enhance the dispersion of quantum dots. The emulsion particle size D90 ≤ 180 nm and the Zeta potential ≤ -45 mV are detected to obtain the flotation collector for difficult-to-process copper oxide ore.

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