A ternary associated collector for strengthening micro-fine spodumene flotation and a preparation method and application thereof

Abstract

The application discloses a kind of reinforced microfine particle lepidolite flotation ternary associated body collector and its preparation method and application, lepidolite flotation field.The ternary associated body collector is formed by the metal organic complex of A ligand, C ligand and metal ion M coordination assembly;Wherein, A ligand is carboxylic acid ligand and / or sulfonic acid ligand;C ligand is amine ligand or quaternary ammonium salt ligand;M is selected from divalent metal cation above.This application collector is used for microfine particle lepidolite flotation, can be efficiently floated under neutral condition;Ternary associated body collector significantly enhances the collection ability and selectivity to microfine particle lepidolite, and concentrate grade and recovery rate are obviously improved.

Description

Technical Field

[0001] This invention belongs to the field of lepidolite flotation, and relates to a ternary associative collector for enhancing the flotation of fine-particle lepidolite, its preparation method and application. Background Technology

[0002] Lithium is an important energy metal, widely used in new energy batteries, aerospace, nuclear industry and other fields. With the rapid development of the new energy vehicle industry, the demand for lithium resources has increased dramatically, and the development and utilization of low-grade associated fine-grained lepidolite deposits has received attention.

[0003] The flotation recovery of fine-grained lepidolite (typically referring to mineral particles with a diameter of less than 38 μm) faces numerous challenges. For example, fine particles have small mass, large specific surface area, and high surface energy, resulting in a low probability of collision with air bubbles and poor adhesion efficiency; sludge covers the surface of lepidolite, hindering effective adsorption by collectors; conventional collectors have poor selectivity for fine particles, leading to low concentrate grade and low recovery rate; and traditional desliming operations inevitably result in the loss of some fine-grained lepidolite in tailings, causing significant resource waste.

[0004] Existing lepidolite flotation collectors mainly include single-cationic collectors, combined anion-cationic collectors, and synergistic collectors activated by metal ions. However, these collectors all have certain limitations. For example, single-cationic collectors have poor selectivity for fine particles when used under acidic or alkaline conditions, resulting in high foam viscosity and unsatisfactory separation effects; while combined anion-cationic collectors are only binary compounds, limiting their enhancement effect on fine-grained lepidolite; and using Pb... 2+ Fe 3+ Metal ions are used to pre-activate the mineral surface, but there is a lack of directional association between the metal ions and the collector, resulting in unstable activation effects. Furthermore, metal ions readily undergo non-selective adsorption with gangue minerals.

[0005] Chinese patent application CN115646660A discloses a compound collector for lepidolite flotation based on cation-anion interactions, achieving efficient recovery through the interaction of cation and anion compounds. However, it does not involve the introduction of metal ions, resulting in limited enhancement of the collection effect on fine particles. Similarly, Chinese patent application CN115350817A discloses a lepidolite flotation collector and beneficiation method using a compound of multiple surfactants. Although it achieves flotation of all particle sizes under neutral conditions, it also does not involve a ternary association system involving metal ions.

[0006] Therefore, there is an urgent need to develop a new type of collector that can enhance the flotation of fine-grained lepidolite in order to achieve efficient and selective collection of fine-grained lepidolite. Summary of the Invention

[0007] To address the problems in existing technologies, such as the stepwise addition of metal ions and collectors in the flotation cell, lack of directional association, and the fact that the anion-cation mixture is only a binary system, resulting in insufficient collection capacity and selectivity for fine-grained lepidolite, the first objective of this invention is to provide a ternary associative collector for enhanced flotation of fine-grained lepidolite. By pre-mixing and forming a stable ternary associative collector, under neutral flotation conditions, the influence of fine lepidolite slime is avoided, while significantly enhancing the collection capacity and selectivity for fine-grained lepidolite.

[0008] The second objective of this invention is to provide a method for preparing a ternary associated collector for enhancing the flotation of fine-particle lepidolite. This method involves first mixing anionic and cationic collectors to form a binary mixed collector solution, and then adding a metal ion solution dropwise into the solution, allowing the metal ions to gradually associate with the binary system under controlled conditions to obtain a stable ternary associated collector solution.

[0009] The third objective of this invention is to provide a ternary associative collector for the flotation of fine-grained lepidolite, which can significantly improve the grade and recovery rate of fine-grained lepidolite under neutral slurry conditions without desliming.

[0010] To achieve the above-mentioned technical objectives, the present invention provides a ternary associated collector for enhancing the flotation of fine-particle lepidolite. The collector is a metal-organic complex formed by coordination assembly of ligand A, ligand C, and metal ion M. Wherein, ligand A is a carboxylic acid ligand and / or a sulfonic acid ligand; ligand C is an amine ligand or a quaternary ammonium salt ligand; and metal ion M is selected from divalent or higher metal cations.

[0011] In the technical solution of this invention, the formation mechanism of the ternary associative collector is as follows: First, the A ligand of a carboxylic acid ligand and / or a sulfonic acid ligand is mixed with the C ligand of an amine ligand or a quaternary ammonium salt ligand in a solution. The anions and cations form a binary pre-associated structure through electrostatic interaction and hydrophobic association. Then, a metal ion solution is slowly added dropwise to the above binary mixed system under ultrasonic conditions. The metal ions gradually insert into the anion-rich region of the binary pre-associated structure at a low local concentration. The anions and cation collectors are bridged through coordination, and finally a stable ternary associative collector is formed.

[0012] The flotation of lepidolite is mainly carried out in a neutral environment, where lepidolite is negatively charged. However, the ternary associative collector of the present invention exhibits a positive charge in the solution. Therefore, the ternary associative collector of the present invention can have excellent flotation ability for lepidolite in a neutral environment.

[0013] Furthermore, experiments revealed that if the three components are added stepwise in the flotation cell without pre-mixing and compounding, the metal ions and collectors encounter each other randomly, making it difficult to form a stable and ordered associated structure. Moreover, the metal ions easily react with gangue components to form insoluble precipitates, resulting in losses and a significant reduction in the collection enhancement effect. The ternary associated structure in this invention refers to the associated structure formed during the pre-mixing and compounding process of metal ions, A ligands, and C ligands, where metal ions bridge A ligands and C ligands. This is distinct from the simple coexistence of the three components in the flotation pulp.

[0014] As a preferred embodiment, the molar ratio of ligand A to ligand C to metal ion M is (1~2):(1~2):1. Within the preferred molar ratio range of this invention, the three ligands can form a stable ternary associated structure.

[0015] As a preferred embodiment, the metal ion M is selected from Pb. 2+ Fe 3+ Al 3+ Ca 2+ and Mg 2+ At least one of the following. The preferred divalent or higher metal cations of this invention have a high charge number, resulting in strong electrostatic and coordination interactions with the anion collector, which is beneficial for forming a stable pre-associated complex. Further preferred is Mg. 2+ and / or Fe 3+ .

[0016] In this invention, the metal ions are mainly added in the form of soluble metal salts, which are selected from at least one of lead nitrate, ferric chloride, ferric sulfate, aluminum chloride, calcium nitrate, and magnesium chloride. Adding them in the form of soluble salts allows the metal ions to fully dissociate in the solution, facilitating their directional association with the anion collector.

[0017] This invention also provides a method for preparing a ternary associated collector to enhance the flotation of fine-particle lepidolite. The method involves mixing an anionic collector and a cationic collector to obtain a binary mixed collector solution; then adding a metal ion solution dropwise to the binary mixed collector solution to obtain the final product. The anionic collector is a carboxylic acid collector and / or a sulfonic acid collector; the cationic collector is an amine collector and / or a quaternary ammonium salt collector.

[0018] In this invention, a binary mixed system of anions and cations is first formed, and then metal ions are introduced by dropwise addition. This keeps the local concentration of metal ions at a low level, avoiding the formation of insoluble precipitates with the anion collector due to instantaneous excess of metal ions. This is conducive to the orderly and stable formation of ternary associative compounds.

[0019] As a preferred embodiment, the anionic collector is selected from at least one of sodium oleate, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium naphthenate, sodium N-oleoyl-N-methyltaurate, sodium N-lauroyl-N-methyltaurate, and oxidized paraffin soap. More preferably, sodium dodecyl sulfonate (SDS) and / or sodium oleate are used.

[0020] As a preferred embodiment, the cationic collector is selected from at least one of dodecylamine (DDA), cocoylamine, octadecylamine, ether diamine, and quaternary ammonium salt collectors. More preferably, it is dodecylamine and / or ether diamine.

[0021] As a preferred embodiment, the concentration of the metal ion solution is 1-5 wt%. Within this concentration range, the volume of the metal ion solution is moderate, and the local concentration can be controlled during dropwise addition. This avoids the formation of insoluble precipitates due to local excess of metal ions, while also ensuring that the associative products achieve a suitable concentration.

[0022] As a preferred embodiment, the mass concentration of the binary mixed collector solution is 5-15 wt%. Within this concentration range, the anionic and cationic collectors are fully dissolved and pre-associated, providing a suitable reaction environment for bridging metal ions.

[0023] As a preferred embodiment, during the dropping process, under ultrasonic conditions, the dropping rate is 1-3 mL / min, and ultrasonication continues for 10-30 min after the dropping is completed. The dispersing effect of ultrasound ensures rapid and uniform dispersion of the added metal ions, promoting the uniform formation of the aggregates; continued ultrasonication after the dropping is completed allows the association to become more complete and the system to become more stable. During this process, the solution dropping rate should not be too fast, otherwise it will lead to excessively high local concentrations of metal ions, which may instantly form insoluble metal salt precipitates with the anion collector near the dropping port, resulting in incomplete ternary association reaction and a decrease in the effective concentration of the collector.

[0024] As a preferred embodiment, the anionic collector accounts for 28-60% of the total mass of the collector, the cationic collector accounts for 14-30% of the total mass of the collector, and the metal ion solution accounts for 15-50% of the total mass of the collector, wherein the mass of the metal ion solution is calculated based on metal ions.

[0025] In this invention, the dosage of the three collectors directly affects the formation of the ternary aggregate. When the metal ion solution dosage is too high, the concentration of free metal ions in the solution increases, making it easier to form insoluble metal salt precipitates with the anionic collector, resulting in a decrease in the effective concentration of the collector and a reduction in the selectivity of flotation. Conversely, when the metal ion dosage is too low, there are insufficient metal ions available for coordination in the binary pre-association, resulting in weak bridging and incomplete formation of the ternary aggregate, significantly reducing the collecting capacity. When the anionic collector dosage is too high, it will precipitate with the metal ion generator, destroying the ternary aggregate structure. When the anionic collector dosage is too low, there are insufficient negative charge sites in the binary system, making it impossible to effectively complex metal ions, resulting in poor stability of the ternary aggregate and insufficient density of hydrophobic groups, making it difficult to form a dense hydrophobic film on the surface of lepidolite. In addition, when the amount of cationic collector is too high, the foam is too stable, carrying a large amount of gangue minerals and reducing the grade of concentrate; while when the amount is too low, the number of hydrophobic tail chains is small, the degree of hydrophobicity is insufficient, and fine minerals are difficult to adhere to the bubbles.

[0026] Finally, this invention also provides an application of a ternary associative collector in the flotation of fine-grained lepidolite, the steps of which include:

[0027] S1 processes lepidolite ore by crushing, grinding, and slurry preparation to obtain a slurry; the grinding particle size is controlled to be -0.074mm, accounting for 70%~85%;

[0028] S2 adds flotation reagents, including ternary associative collectors, to the slurry for flotation separation to obtain lepidolite concentrate and flotation tailings.

[0029] The ternary associative collector of this invention can significantly enhance the flotation of fine-particle lepidolite. The principle is as follows: compared to simple binary anion-cation complex systems, the ternary associative collector, through the introduction of metal ions, achieves a larger molecular weight and stronger hydrophobicity, reducing the critical micelle concentration and enhancing the stability of the associative collector. Furthermore, the metal ions can act as "molecular bridges," directionally connecting the anion and cation collectors to form an ordered adsorption layer. On the surface of fine-particle lepidolite, the cation portion adsorbs onto the negatively charged region through electrostatic interactions, while the metal ions coordinate with active sites such as Al-O and Si-O, achieving a synergistic effect of electrostatic and chemical adsorption. Simultaneously, the high-density hydrophobic groups forming a dense hydrophobic film enhance the hydrophobicity effect, and the metal ions further enhance the hydrophobicity of the Al-O and Si-O sites on the lepidolite surface. 3+ The selective adsorption at the site endows it with high selectivity for gangue minerals. The macromolecular structure of the ternary association can also penetrate or replace the capping sludge, restoring the floatability of the minerals. In addition, the low surface tension and high surface activity of the ternary association can reduce the bubble size, increase the specific surface area of ​​the bubble, improve the collision probability between fine mineral particles and bubbles, enhance the adhesion strength of bubble-mineral particles and reduce detachment, and optimize the foam structure to make the foam layer have a moderate water content, which is conducive to the enrichment of fine lepidolite particles.

[0030] As a preferred embodiment, the pulp concentration is 25-35 wt%, the pulp pH is 6-9, and the amount of the ternary associative collector relative to the raw ore is 200-800 g / t. This invention achieves good flotation performance within the aforementioned neutral pH range without the need for large amounts of additional acid-base adjusters, resulting in a simple and environmentally friendly process.

[0031] As a preferred embodiment, the flotation includes one roughing, one sweeping, and at least two cleaning processes.

[0032] As a preferred method, in the roughing stage, the ternary associative collector is added at a rate of 200-500 g / t of raw ore, stirred for 2-3 minutes, and then floated for 3-5 minutes. In the scavenging stage, the ternary associative collector is added to the roughing tailings at a rate of 50-200 g / t of raw ore, stirred for 1-2 minutes, and then floated for 2-4 minutes. In the cleaning stage, no reagents are added, and the floatation is carried out for 3-5 minutes. This staged addition of reagents ensures sufficient collector concentration in the roughing stage, recovers fine-grained lepidolite lost in the tailings through scavenging, and improves concentrate grade by eliminating reagents in the cleaning stage.

[0033] As a preferred embodiment, the fine-grained lepidolite refers to lepidolite with a particle size of -74 μm. More preferably, it is lepidolite with a particle size of -19 μm.

[0034] Compared with the prior art, the present invention has at least the following beneficial effects:

[0035] (1) The ternary associative collector provided by the present invention, through the metal ion bridging of the anionic collector and the cationic collector to form a stable ternary associative agent in advance, significantly enhances the collection ability and selectivity of fine-particle lepidolite.

[0036] (2) The preparation method provided by the present invention first prepares a binary mixed collector solution and then adds a metal ion solution dropwise under ultrasound, so that the metal ions gradually associate under controlled low local concentration, avoiding the instantaneous excessive generation of insoluble precipitates by metal ions, which is conducive to obtaining a stable and uniform associative solution.

[0037] (3) The ternary associative collector of the present invention can significantly improve the grade and recovery rate of fine-grained lepidolite under neutral slurry conditions without desliming treatment. The process is simple and environmentally friendly. Attached Figure Description

[0038] Figure 1 is a flow chart of the flotation process of the ternary associative collector of the present invention in fine-grained lepidolite.

[0039] Figure 2 The graph shows the relationship between the zeta potential and pH value of lepidolite in a ternary collector system. Detailed Implementation

[0040] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0041] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0042] Test ore sample: A lepidolite ore from Jiangxi Province, with a Li₂O grade of 0.58% and a -0.038mm particle size content of 35wt%, belonging to a typical fine-grained lepidolite ore; the main gangue minerals are quartz, feldspar, and muscovite. Unless otherwise stated, the following examples and comparative examples all use this ore sample.

[0043] In the embodiments and comparative examples of this invention, the total mass of the collector only considers the amount of metal ion collector, anion collector, and cationic collector added, and does not consider the mass of the solution.

[0044] Example 1

[0045] This embodiment provides a ternary associative collector, which is pre-mixed and compounded from the following components: lead nitrate (Pb(NO3)2, with Pb... 2+ (Total) 50wt%, Sodium dodecyl sulfonate (SDS) 28.6wt%, Dodecylamine (DDA) 21.4wt%;

[0046] The preparation of the ternary associative collector is as follows:

[0047] (1) Pb(NO3)2, with Pb 2+ 10g was dissolved in 200mL of deionized water to prepare a 5wt% lead nitrate solution (as a metal ion solution).

[0048] (2) Dissolve 5.71g of SDS and 4.29g of DDA in 100mL of deionized water to prepare a 10wt% SDS and DDA binary mixed collector solution.

[0049] (4) Under ultrasonic conditions, lead nitrate solution was added dropwise to the binary mixed collector solution of SDS and DDA at a rate of 2 mL / min. After the addition was completed, ultrasonication was continued for 20 min to obtain a ternary associated collector solution, wherein the molar ratio of A ligand to C ligand to metal ion M was 2:1:1.

[0050] The obtained ternary associative collector solution was applied to the flotation of lepidolite, and the specific steps are as follows:

[0051] (1) Crush and grind the ore to -0.074mm (80wt%), add water to make a 30wt% slurry with a natural pH of 7.5;

[0052] (2) Primary roughing: Add 350 g / t of ternary associative collector, stir for 2 min, and float for 4 min to obtain primary roughing concentrate and roughing tailings;

[0053] (3) First scavenging: Add 100g / t of ternary associative collector to the roughing tailings, stir for 1.5min, and float for 3min to obtain scavenging concentrate and tailings;

[0054] (4) Two-stage cleaning: The rough concentrate and scavenging concentrate are combined and cleaned twice without adding reagents. Each flotation lasts for 4 minutes to obtain the final concentrate and cleaned tailings.

[0055] Experimental results: The final concentrate had a Li2O grade of 3.12 wt% and a recovery rate of 91.35%.

[0056] Example 2

[0057] This embodiment provides a ternary associative collector, which is pre-mixed and compounded from the following components (mass percentage): ferric chloride (FeCl3, with Fe...). 3+ (Total) 23.1 wt%, sodium oleate 53.8 wt%, cocoamine 23.1 wt%.

[0058] The preparation method is the same as in Example 1, except that the metal ions, anion collectors, and cationic collectors are replaced with the components described above, specifically:

[0059] (1) Take 75g of FeCl3·6H2O (in Fe... 3+ Dissolve 23.1 g of the sample in 200 mL of deionized water to prepare a ferric chloride solution with a concentration of approximately 3.75 wt%.

[0060] (2) Dissolve 53.8g sodium oleate and 23.1g cocoamine in 100mL of deionized water to prepare a binary mixed collector solution;

[0061] (3) Under ultrasonic conditions, ferric chloride solution was added dropwise to the binary mixed collector solution at a rate of 2 mL / min. After the addition was completed, ultrasonication was continued for 20 min to obtain a ternary associated collector solution, wherein the molar ratio of A ligand to C ligand to metal ion M was 2:1:1.

[0062] The obtained ternary associative collector solution was used to float lepidolite using the same flotation process as in Example 1.

[0063] Experimental results: The final concentrate Li2O grade was 2.98 wt%, and the recovery rate was 89.72%.

[0064] Example 3

[0065] This embodiment provides a ternary associative collector, which is pre-mixed and compounded from the following components (mass percentage): aluminum chloride (AlCl3, in Al...). 3+ 16.7 wt% of N-octadecyl-N-1,2-dicarboxyethyl sulfonated succinamide tetrasodium salt, 55.6 wt% of N-cocoyl-1,3-propanediamine (CAS No. 61791-63-7), and 27.7 wt% of N-cocoyl-1,3-propanediamine (CAS No. 61791-63-7).

[0066] The preparation method is the same as in Example 1, except that the metal ions, anion collectors and cationic collectors are replaced with the above components to obtain a ternary associated collector solution, wherein the molar ratio of ligand A to ligand C to metal ion M is 2:1:1.

[0067] The obtained ternary associative collector solution was used to float lepidolite using the same flotation process as in Example 1.

[0068] Experimental results: The final concentrate had a Li2O grade of 2.85 wt% and a recovery rate of 87.64%.

[0069] Example 4

[0070] This embodiment provides a ternary associative collector, which is pre-mixed and compounded from the following components (mass percentage): magnesium chloride (MgCl2, in mg...). 2+ (Total) 27.2 wt%, sodium oleate 57.8 wt%, cocoamine 15.0 wt%.

[0071] The preparation method is the same as in Example 1, except that the metal ions, anion collectors and cationic collectors are replaced with the above components to obtain a ternary associated collector solution, wherein the molar ratio of ligand A to ligand C to metal ion M is 2:1:1.

[0072] The obtained ternary associative collector solution was used to float lepidolite using the same flotation process as in Example 1.

[0073] Experimental results: The final concentrate Li2O grade was 2.95 wt%, and the recovery rate was 90.64%.

[0074] Example 5

[0075] The only difference between this embodiment and Example 1 is that the lead nitrate dropping rate is changed to 1 mL / min and the ultrasonic time is 30 min in the preparation of the ternary associative collector. All other steps and conditions are the same.

[0076] The obtained ternary associative collector solution was used to float lepidolite using the same flotation process as in Example 1.

[0077] Experimental results: The final concentrate Li2O grade was 3.08 wt%, and the recovery rate was 90.85%.

[0078] Example 6

[0079] The only difference between this embodiment and Embodiment 1 is that the ore is ground to -0.074mm to 90wt% during the flotation process, and the amount of ternary associative collector used in the roughing process is changed to 500g / t. All other steps and conditions are the same.

[0080] Experimental results: The final concentrate had a Li2O grade of 3.25 wt% and a recovery rate of 88.12%.

[0081] Example 7

[0082] This embodiment provides a ternary associative collector, which is pre-mixed and compounded from the following components (mass percentage): lead nitrate (Pb(NO3)2, with Pb... 2+ 20wt% of sodium dodecyl sulfonate (SDS), 55wt% of dodecylamine (DDA), and 25wt% of sodium dodecyl sulfonate (SDS).

[0083] The difference between this embodiment and Embodiment 1 is that the amount of metal ions used is lower and the amount of anions used is higher, while the rest of the preparation steps and flotation process are the same.

[0084] Experimental results: The final concentrate Li2O grade was 2.78 wt%, and the recovery rate was 84.56%.

[0085] The results indicate that when the amount of metal ions is insufficient, the bridging effect of the ternary associative system weakens, and the collection capacity and selectivity decrease, but it is still better than the binary complex system of Comparative Example 2.

[0086] Comparative Example 1

[0087] Dodecylamine was used as a single cationic collector, and flotation was carried out at pH 7.5. The reagent dosage and process flow were the same as in Example 1.

[0088] Experimental results: The final concentrate Li2O grade was 2.15 wt%, and the recovery rate was 72.36%.

[0089] Comparative Example 2

[0090] A binary collector was obtained by combining SDS and DDA of the same mass as in Example 1, without the addition of metal ions, and under the same conditions as in Example 1.

[0091] Experimental results: The final concentrate Li2O grade was 2.56 wt%, and the recovery rate was 81.24%.

[0092] Comparative Example 3

[0093] First, add 50 g / t of Pb(NO3)2 to the slurry for 5 minutes to activate it. Then, add the same mass ratio of SDS and DDA binary compound collector as in Example 1. The total amount of collector is the same as in Example 1.

[0094] Experimental results: The final concentrate Li2O grade was 2.71 wt%, and the recovery rate was 84.58%.

[0095] Comparative Example 4

[0096] The only difference between this comparative example and Example 1 is that the lead nitrate is not added dropwise, but rather poured in quickly in one go (addition time <5s), followed by sonication for 20 minutes. All other steps and conditions are the same.

[0097] Experimental results: The final concentrate Li2O grade was 2.68 wt%, and the recovery rate was 82.35%.

[0098] The results indicate that rapid addition of metal ions in a single step leads to excessively high local concentrations, resulting in the formation of a large amount of Pb(DS)2 precipitate, incomplete formation of ternary aggregates, and a significant decrease in the collection efficiency.

[0099] Comparative Example 5

[0100] The only difference between this comparative example and Example 1 is that the pre-prepared ternary associative collector is not used during flotation. Instead, the three components (Pb(NO3)2, SDS, and DDA) are directly added to the pulp (in the order of addition: Pb is added first). 2+ Then add SDS, and finally add DDA, and stir for 2 minutes each. The total amount used is the same as in Example 1.

[0101] Experimental results: The final concentrate Li2O grade was 2.62 wt%, and the recovery rate was 80.18%.

[0102] The results indicate that when the three components are added to the slurry separately, a stable ternary associated structure cannot be formed due to the lack of a pre-association process. The metal ions and collectors act independently, the synergistic effect is lost, and the flotation effect is significantly worse than that of the pre-combined ternary associated structure.

[0103] Table 1 Summary of flotation results from the examples and comparative examples

[0104]

[0105] Example 8

[0106] The flotation concentrates and tailings from Example 1 and Comparative Example 2 were screened to investigate the recovery of lepidolite of different particle sizes.

[0107] Table 2. Experimental data for different particle sizes in Example 1 and Comparative Example 2.

[0108]

[0109] As shown in Table 2, the recovery rate of Comparative Example 2 decreased significantly with decreasing particle size, while the ternary associative collector of Example 1 had a significantly higher recovery rate for fine particles (-38 μm, especially -19 μm), proving that the ternary associative collector of the present invention has a significant enhanced collection effect on fine-particle lepidolite.

[0110] Example 9

[0111] To prove that a ternary associated structure does exist, rather than a simple physical mixture of three components, this embodiment takes Example 4 as the research object and measures the potential relationship between pure lepidolite mineral Zeta and pH value under the ternary collector system.

[0112] Experimental methods: A Malvern Zetasizer Nano ZS90 nanoparticle size potentiometer was used, at a 1×10⁻⁶ Ω·cm. -3 Under mol / L Cl background electrolyte and 25°C conditions, the potential kinetics of individual components, binary mixtures, and ternary associated systems were measured. Each sample was measured in triplicate, and the average value was taken.

[0113] Results Analysis

[0114] The results are as follows Figure 2 As shown, lepidolite alone exhibits negative potentials under all pH conditions. After introducing a binary collector (cation and anion), the potential kinetics on the lepidolite surface shifts significantly negatively. However, after introducing the ternary associated collector prepared in Example 4, the potential kinetics on the lepidolite surface shifts significantly upward compared to the case with the binary collector, demonstrating that the ternary collector exists in an associated form and is adsorbed onto the lepidolite surface with a positive charge.

Claims

1. A ternary associative collector for enhancing the flotation of fine-particle lepidolite, characterized in that: Organometallic complexes formed by coordination assembly of A ligand, C ligand and metal ion M; Among them, ligand A is a carboxylic acid ligand and / or a sulfonic acid ligand; ligand C is an amine ligand or a quaternary ammonium salt ligand; and metal ion M is selected from divalent or higher metal cations.

2. The ternary associative collector for enhancing the flotation of fine-particle lepidolite according to claim 1, characterized in that: The molar ratio of A ligand, C ligand to metal ion M is (1~2):(1~2):

1.

3. A ternary associative collector for enhancing the flotation of fine-particle lepidolite according to claim 1 or 2, characterized in that: The metal ion M is selected from Pb. 2+ Fe 3+ Al 3+ Ca 2+ and Mg 2+ At least one of them.

4. A method for preparing a ternary associative collector for enhancing the flotation of fine-particle lepidolite as described in any one of claims 1 to 3, characterized in that: An anionic collector and a cationic collector are mixed to obtain a binary mixed collector solution; then a metal ion solution is added dropwise to the binary mixed collector solution to obtain the final product. The anionic collector is a carboxylic acid collector and / or a sulfonic acid collector; The cationic collector is an amine collector and / or a quaternary ammonium salt collector.

5. The method for preparing the ternary associative collector for enhancing the flotation of fine-particle lepidolite according to claim 4, characterized in that: The anionic collector is selected from at least one of sodium oleate, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium naphthenate, sodium N-oleoyl-N-methyl taurate, tetrasodium N-octadecyl-N-1,2-dicarboxyethyl sulfonated succinate, sodium N-lauroyl-N-methyl taurate, and oxidized paraffin soap.

6. The method for preparing the ternary associative collector for enhancing the flotation of fine-particle lepidolite according to claim 4, characterized in that: The cationic collector is selected from at least one of dodecylamine, octadecylamine, ether diamine, and quaternary ammonium salt collectors.

7. A method for preparing a ternary associative collector for enhancing the flotation of fine-particle lepidolite according to claim 5 or 6, characterized in that: The concentration of the metal ion solution is 1~5 wt%; The mass concentration of the binary mixed collector solution is 5-15 wt%; During the dripping process, under ultrasonic conditions, the dripping rate is 1~3 mL / min, and ultrasonication continues for 10~30 min after the dripping is completed; The anionic collector accounts for 28-60% of the total mass of the collector, the cationic collector accounts for 14-30% of the total mass of the collector, and the metal ion solution accounts for 15-50% of the total mass of the collector, wherein the mass of the metal ion solution is calculated based on metal ions.

8. The application of a ternary associative collector as described in any one of claims 1 to 3 in the flotation of fine-particle lepidolite, characterized in that: step include: S1 involves crushing, grinding, and slurry preparation of lepidolite ore to obtain a slurry; the particle size of the ground ore is controlled to be -0.074 mm, accounting for 70%~85 wt%. S2 adds flotation reagents, including ternary associative collectors, to the slurry for flotation separation to obtain lepidolite concentrate and flotation tailings.

9. The application of the ternary associative collector according to claim 8 in the flotation of fine-grained lepidolite, characterized in that: The concentration of the slurry is 25-35 wt%, the pH of the slurry is 6-9, and the amount of the ternary associative collector relative to the raw ore is 200-800 g / t.

10. The application of the ternary associative collector according to claim 8 or 9 in the flotation of fine-particle lepidolite, characterized in that: The flotation process includes one roughing, one sweeping, and at least two cleaning processes.

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