Coarse-grained ilmenite flotation electrostatic assembly collector and preparation method and application thereof

Abstract

The application discloses a coarse-grained ilmenite flotation electrostatic assembly collector and a preparation method and application thereof. The electrostatic assembly collector is a structural compact macromolecular substance formed by electrostatic force assembly of fatty acid methyl ester sulfonate and alkyl hydroxamic acid under the action of hyperbranched quaternary ammonium salt as an initiator. The electrostatic assembly collector can fully exert the synergistic effect of multifunctional groups of sulfonic acid groups, hydroxamic acid groups and amine groups, has the characteristics of strong selectivity of collecting low dissociation coarse-grained ilmenite, strong adaptability, small dosage, low cost, non-toxicity and non-pollution, and the electrostatic assembly preparation method has the advantages of simple process, mild reaction condition and low cost. The electrostatic assembly collector can be widely applied to the fluidized flotation separation process of coarse-grained ilmenite, fundamentally solves the problems of low recovery rate and low flotation efficiency of coarse-grained ilmenite flotation caused by weak bubble adhesion force, effectively improves the flotation recovery rate and concentrate grade, efficiently recovers ilmenite conjoined bodies, and significantly reduces the mineral processing cost.

Description

Technical Field

[0001] This invention belongs to the field of mineral flotation technology, specifically relating to an electrostatically assembled collector for coarse-grained ilmenite flotation, its preparation method, and its application. Background Technology

[0002] Ilmenite is an important strategic metal oxide ore, and flotation is the most common method for recovering ilmenite. Since the upper limit of the particle size requirement for ilmenite in flotation is generally 0.1-0.15mm, the flotation effect of coarse ore exceeding the upper limit is poor. Before flotation, grinding is required to reduce the particle size of the ore, but grinding consumes a lot of energy. Therefore, carrying out coarse particle flotation is of great practical significance for reducing the cost of grinding operations and realizing the pre-disposal of coarse gangue.

[0003] Current research on ilmenite flotation collectors focuses on the fine-particle size, primarily using fatty acids and hydroxamic acid to enhance the hydrophobicity of the ilmenite surface for flotation. However, research on coarse-particle ilmenite flotation is limited, and research on collectors suitable for coarse-particle ilmenite flotation is currently lacking. In recent years, a series of fluidized bed flotation devices for coarse particles have emerged. Their working principle is as follows: based on traditional flotation equipment, an upward flow of water is introduced, relying on bubbles and the upward flow to form a fluidized bed, thereby overcoming the gravity of the coarse particles to achieve flotation. This has a significant promoting effect on the recovery of coarse particles through flotation. However, due to the relatively low liberation degree of valuable minerals in ilmenite, the interaction between existing collectors and the active sites on the surface of coarse ilmenite is relatively weak and their adaptability is poor when using existing fine-grained ilmenite flotation collectors. Compound collectors obtained through simple mixing offer limited improvement in selective collecting ability, resulting in problems such as weak particle hydrophobicity, weak particle-bubble adhesion, easy particle detachment, and high collector dosage during the coarse-grained ilmenite flotation process. This leads to low coarse particle recovery and low flotation efficiency. Therefore, developing highly efficient collectors with strong selective collecting ability and enhanced surface hydrophobicity of ilmenite is an effective way to improve the recovery rate of coarse-grained ilmenite in fluidized bed flotation. Summary of the Invention

[0004] To address the problems of weak hydrophobicity of particles, low ilmenite recovery rate, and low flotation efficiency in traditional fluidized bed flotation processes for coarse-grained ilmenite, one objective of this invention is to provide a collector with extremely strong selective collecting ability for coarse-grained ilmenite with low liberation degree, which is beneficial for significantly improving concentrate grade and flotation recovery rate, and is highly adaptable, requires low dosage, is low in cost, and is non-toxic and pollution-free. Another objective of this invention is to provide a collector preparation method with a simple process, mild reaction conditions, and low cost. A third objective of this invention is to provide a collector application suitable for fluidized bed flotation of coarse-grained ilmenite, in particular, which significantly reduces beneficiation costs.

[0005] To achieve the above-mentioned technical objectives, the technical solution adopted by the present invention to solve its technical problems is as follows:

[0006] An electrostatically assembled collector for coarse-grained ilmenite flotation is composed of fatty acid methyl ester sulfonate and alkyl hydroxamic acid, electrostatically assembled with a hyperbranched quaternary ammonium salt as an initiator. The hyperbranched quaternary ammonium salt has the following molecular structure:

[0007] In the above formula, R is an alkyl group.

[0008] Furthermore, the longer the carbon chain of the fatty acid methyl ester sulfonate R1CH(SO3M)COOCH3, the stronger the collecting ability, but the selectivity for iron ore will decrease. Therefore, R1 is preferably an alkyl group with C=16-18 and M is a monovalent metal ion.

[0009] Furthermore, M is sodium or potassium.

[0010] Furthermore, the longer the carbon chain of the alkyl hydroxamic acid, the stronger its collecting ability, but the selectivity for iron ore will decrease. Therefore, the preferred alkyl hydroxamic acid is a C7-12 alkyl hydroxamic acid.

[0011] Furthermore, the ratio of fatty acid methyl ester sulfonate to alkyl hydroxamic acid is related to the degree of dissociation of coarse-grained ilmenite ore, therefore the molar ratio of fatty acid methyl ester sulfonate to alkyl hydroxamic acid is preferably 1:(3-5).

[0012] Furthermore, the longer the carbon chain of the hyperbranched quaternary ammonium salt, the stronger its collecting ability, but the selectivity for iron ore will decrease. Therefore, the R of the hyperbranched quaternary ammonium salt is preferably an alkyl group with C=12 to 18.

[0013] Furthermore, in order to obtain suitable electrostatic assembly efficiency while taking into account the macromolecular compactness of the collector, the molar ratio of the hyperbranched quaternary ammonium salt to the alkyl hydroxamic acid is preferably 1:(10-20).

[0014] Furthermore, the hyperbranched quaternary ammonium salt is formed by reacting alkyl tertiary amines with epichlorohydrin, and has amine groups that can interact with active particles on the surface of ilmenite, and the nonpolar groups have strong hydrophobicity.

[0015] Furthermore, the molar ratio of the alkyl tertiary amine to epichlorohydrin is 1:(1 to 1.2).

[0016] A method for preparing an electrostatically assembled collector for the flotation of coarse-grained ilmenite includes: reacting fatty acid methyl ester sulfonate and alkyl hydroxamic acid thoroughly, then slowly adding hyperbranched quaternary ammonium salt, adding electrolyte to carry out an electrostatic reaction, and after the electrostatic reaction is completed, taking the product for crystallization and drying to obtain the electrostatically assembled collector.

[0017] Furthermore, the fatty acid methyl ester sulfonate and alkyl hydroxamic acid are stirred and reacted for 10-15 minutes.

[0018] Furthermore, the dropping rate of the hyperbranched quaternary ammonium salt is no higher than 0.02 g / s.

[0019] Furthermore, the electrolyte is potassium nitrate.

[0020] Furthermore, the electrostatic reaction is carried out in an electrostatic reaction vessel at a temperature of 50–80°C for 30–40 minutes.

[0021] Furthermore, the method includes preparing hyperbranched quaternary ammonium salts: after thoroughly dissolving an alkyl tertiary amine by stirring, the temperature is raised to 80–90°C, and epichlorohydrin is slowly added dropwise. After the addition is complete, the mixture is stirred and kept at 80–90°C for 3–4 hours. Then, a vacuum is drawn, and a solvent is slowly added dropwise. A catalyst is added, and the temperature is raised to 90–95°C. The reaction is carried out for 5–6 hours. The solvent is removed by rotary evaporation to obtain a viscous liquid. The viscous liquid is dialyzed and then dried under vacuum to obtain the hyperbranched quaternary ammonium salt.

[0022] Furthermore, the dropping rate of the epichlorohydrin is not higher than 0.04 g / s.

[0023] Furthermore, the solvent is N,N-dimethylformamide, and the dropping rate is not higher than 0.02 g / s.

[0024] An application of an electrostatically assembled collector for coarse-grained ilmenite flotation, the application method of which includes: using the electrostatically assembled collector as a collector for waste products from coarse-grained ilmenite flotation, wherein the mass ratio of fatty acid methyl ester sulfonate to alkyl hydroxamic acid is negatively correlated with the degree of ilmenite liberation.

[0025] Furthermore, the coarse-grained ilmenite has a particle size of less than 1 mm.

[0026] Furthermore, the proportion of -0.8mm particles in the coarse-grained ilmenite is not less than 60%.

[0027] Furthermore, the degree of liberation of the coarse-grained ilmenite is not less than 10%.

[0028] Furthermore, the amount of electrostatic assembly collector used is positively correlated with the flotation throughput of coarse ilmenite and the grade of ilmenite, while the amount of electrostatic assembly collector used is negatively correlated with the degree of ilmenite liberation.

[0029] Furthermore, the flotation waste is fluidized flotation waste, which plays an important role in promoting the recovery of coarse particles through flotation.

[0030] Furthermore, the fluidized flotation waste disposal involves taking the reagent including the electrostatic assembly collector and fully mixing it with coarse ilmenite to obtain a slurry. The slurry is then placed in a flotation column with a gas-liquid-solid three-phase composite fluidized bed formed by rising water flow and bubbles for flotation, thereby overcoming the gravity of the coarse particles and further improving the flotation performance.

[0031] Furthermore, to ensure adequate slurry preparation, the slurry preparation time shall not be less than 10 minutes.

[0032] Furthermore, the slurry is neutral and alkaline, within which good flotation performance can be achieved; therefore, the pH value is preferably 7 to 10.

[0033] Furthermore, if the reagent concentration of the slurry is too low, the water consumption will be too high, reducing the flotation efficiency; if it is too high, the solubility will be reduced, which is not conducive to reagent dissolution. Therefore, the reagent mass concentration is preferably 2 to 10%.

[0034] Furthermore, the reagent also includes one or more of a pH adjuster, inhibitor, and frother to further optimize flotation parameters.

[0035] Compared with the prior art, the beneficial effects of the present invention are:

[0036] (1) The electrostatic assembly collector of the present invention differs from traditional mixed agents. It utilizes the negatively charged fatty acid methyl ester sulfonate and alkyl hydroxyxamic acid, and the positively charged hyperbranched quaternary ammonium salt as an initiator. After electrostatic attraction, it can form a dense macromolecular substance:

[0037] Among them, the sulfonic acid group of fatty acid methyl ester sulfonate, the hydroxamic acid group of alkyl hydroxamic acid, and the amine group of hyperbranched quaternary ammonium salt can all interact with the active particles on the surface of ilmenite, exerting the synergistic effect of multiple functional groups of macromolecules. They have strong adaptability and are therefore suitable for the flotation of ilmenite with low degree of liberation, and have extremely strong selective collection ability for coarse-grained ilmenite.

[0038] Meanwhile, fatty acid methyl ester sulfonates, alkyl hydroxamic acids, and hyperbranched quaternary ammonium salts have strong nonpolar hydrophobicity. In particular, hyperbranched quaternary ammonium salts have excellent hydrophobicity. When assembled into macromolecules, they have excellent performance, low dosage, low cost, and are non-toxic and pollution-free. Synergistically, they can significantly enhance the hydrophobicity of ilmenite surface, thereby greatly improving the grade and recovery rate of ilmenite flotation concentrate. This fundamentally solves the problem of low recovery rate and low flotation efficiency caused by weak bubble adhesion and easy detachment in the flotation of coarse-grained ilmenite.

[0039] By optimizing the carbon chain length and the ratio of fatty acid methyl ester sulfonate, alkyl hydroxamic acid, and hyperbranched quaternary ammonium salt, the collection capacity and selectivity for coarse-grained ilmenite can be further enhanced.

[0040] (2) The electrostatic assembly collector preparation method of the present invention synthesizes hyperbranched quaternary ammonium salt by catalytic reaction of alkyl tertiary amine and epichlorohydrin under suitable temperature, ratio and addition method. After the reaction of fatty acid methyl ester sulfonate and alkyl hydroxamic acid, the electrostatic reaction is further carried out by an initiator to obtain a macromolecular electrostatic assembly collector with dense structure and excellent performance. It has the advantages of simple process, mild reaction conditions and low cost, which is conducive to large-scale production.

[0041] (3) The electrostatic assembly collector of the present invention is different from the existing fine-particle flotation of 0.1-0.15mm. It can be applied to fluidized flotation of low-dissociation coarse-particle ilmenite with a particle size of less than 1mm and a particle size of -0.8mm of not less than 60%, avoiding the phenomenon of weak particle-bubble adhesion and easy particle detachment. By optimizing the composition ratio and dosage of the collector, the flotation index is improved. The TiO2 recovery rate of the concentrate can reach more than 90%, which significantly reduces the grinding requirements and thus significantly reduces the beneficiation cost. Attached Figure Description

[0042] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0043] Figure 1 This is the 1H NMR spectrum of the hyperbranched quaternary ammonium salt described in this invention.

[0044] Figure 2 This is a process flow diagram of the application of the electrostatic assembly collector described in this invention. Detailed Implementation

[0045] The embodiments of the present invention are described in detail below. The embodiments described with reference to the accompanying drawings are exemplary and intended to explain the present invention, but should not be construed as limiting the present invention.

[0046] Example 1:

[0047] A preferred embodiment of the coarse-grained ilmenite flotation electrostatic collector of the present invention includes the following preparation method:

[0048] Preparation of hyperbranched quaternary ammonium salt: 1 mol of dodecyl tertiary amine was added to a 500 mL four-necked round-bottom flask equipped with a magnetic stirrer and thermometer. The mixture was stirred thoroughly until the dodecyl tertiary amine dissolved, and then heated to 80 °C. 1 mol of epichlorohydrin was slowly added dropwise to the dodecyl tertiary amine at a rate of 0.04 g / s. After the addition was complete, the mixture was stirred and kept at 80 °C for 3 h. Then, under vacuum, N,N-dimethylformamide was slowly added dropwise at a rate of 0.02 g / s to dissolve the solution. The amount of solvent added depended on the dissolution process. Copper chloride catalyst was then added, and the temperature was raised to 90 °C. The reaction was carried out for 5 h. The solvent was removed by rotary evaporation to obtain a viscous liquid. The viscous liquid was dialyzed using a dialysis bag with a molecular weight cutoff of 2000 D. The retained product was then vacuum dried to obtain the hyperbranched quaternary ammonium salt. The hyperbranched quaternary ammonium salt was characterized by nuclear magnetic resonance (NMR). The results are as follows: Figure 1 As shown, the signal peaks of each chemical shift indicate that the obtained structure is indeed a hyperbranched quaternary ammonium salt of dodecyl.

[0049] Preparation of electrostatic assembly collector: Sodium alkyl fatty acid methyl ester sulfonate (R1 = C=18) and octylalkyl hydroxamic acid were reacted in a stirred container at a molar ratio of 1:3 for 10 min. Then, the above hyperbranched quaternary ammonium salt was slowly added dropwise at a dropping rate of 0.02 g / s, with a molar ratio of hyperbranched quaternary ammonium salt to octyl hydroxamic acid of 1:10 and a concentration of 10. -3 A solution of potassium nitrate (mol / L) was electrostatically reacted in an electrostatic reaction vessel at 50°C for 30 min. After the electrostatic reaction was completed, the product was crystallized and dried to obtain an electrostatic assembly collector.

[0050] Taking the processing of Panzhihua ilmenite as an example, the raw material has a TiO2 grade of 20.97%, the main titanium mineral is ilmenite, and the gangue minerals are pyroxene, calcite, and garnet, etc., the ore particle size is less than 1 mm, of which the -0.8 mm particle size accounts for 60%, and the ilmenite liberation degree is 20%. Figure 2 As shown, a preferred embodiment of the above-mentioned electrostatic assembly collector application includes:

[0051] Based on the relative addition of reagents to the raw ore, 100 g / t water glass was used as a depressant, 280 g / t of the obtained electrostatically assembled collector was used as a flotation collector, and 20 g / t pine oil was used as a frother. These were thoroughly mixed with the Panzhihua ilmenite to obtain a slurry. The slurry was then placed in a fluidized bed flotation machine, where it was floated using a flotation column formed by the rising water flow and air bubbles creating a gas-liquid-solid three-phase composite fluidized bed. The concentrate and tailings were collected. The flotation test results for Panzhihua ilmenite are shown in Table 1 below.

[0052] Table 1 Results of flotation tests for ilmenite in Panzhihua

[0053] product Yield / % <![CDATA[TiO2 grade / %]]> <![CDATA[TiO2 recovery rate / %]]> Concentrate 64.33 29.68 91.04 Tailings 35.67 5.27 8.96 raw ore 100.00 20.97 100.00

[0054] The experiment yielded a concentrate with a TiO2 grade of 29.68% and a TiO2 recovery rate of 91.04%. This demonstrates that the electrostatically assembled collector has a strong selective collecting ability for coarse-grained ilmenite with low liberation degree, significantly improving the concentrate grade and flotation recovery rate, and achieving efficient collection of coarse-grained ilmenite intergrowths.

[0055] Example 2:

[0056] A preferred embodiment of the coarse-grained ilmenite flotation electrostatic collector of the present invention includes the following preparation method:

[0057] Preparation of hyperbranched quaternary ammonium salt: 1 mol of dodecyl tertiary amine was added to a 500 mL four-necked round-bottom flask equipped with a magnetic stirrer and thermometer. After thorough stirring until the dodecyl tertiary amine dissolved, the temperature was raised to 85 °C. 1.1 mol of epichlorohydrin was slowly added dropwise to the dodecyl tertiary amine at a rate of 0.03 g / s. After the addition was complete, the mixture was stirred and kept at 85 °C for 3.5 h. Then, under vacuum, N,N-dimethylformamide was slowly added dropwise at a rate of 0.015 g / s to dissolve the solution. The amount of solvent added depended on the dissolution process. Then, copper chloride catalyst was added, and the temperature was raised to 90 °C for 6 h. The solvent was removed by rotary evaporation to obtain a viscous liquid. The viscous liquid was dialyzed using a dialysis bag with a molecular weight cutoff of 2000 D. The retained material was then vacuum dried to obtain the hyperbranched quaternary ammonium salt. The hyperbranched quaternary ammonium salt was characterized by nuclear magnetic resonance. The results are as follows: Figure 1 As shown, the signal peaks of each chemical shift indicate that the obtained structure is indeed a hyperbranched quaternary ammonium salt of dodecyl.

[0058] Preparation of electrostatic assembly collector: Sodium alkyl fatty acid methyl ester sulfonate (R1 = C=16) and dodecyl hydroxamic acid were reacted in a stirred container at a molar ratio of 1:4 for 15 min. Then, the above hyperbranched quaternary ammonium salt was slowly added dropwise at a dropping rate of 0.01 g / s, with a molar ratio of hyperbranched quaternary ammonium salt to dodecyl hydroxamic acid of 1:15 and a concentration of 10... -3 Potassium nitrate electrolyte (mol / L) was electrostatically reacted in an electrostatic reaction vessel at 80℃ for 40 min. After the electrostatic reaction was completed, the product was crystallized and dried to obtain an electrostatically assembled collector.

[0059] Taking the ilmenite mine in Chengde, Hebei Province, with a raw material TiO2 grade of 11.68%, the main titanium mineral is ilmenite, and the gangue minerals are pyroxene and quartz, etc. The ore particle size is less than 1mm, of which -0.8mm particles account for 70%, and the ilmenite liberation degree is 35%. For example, Figure 2 As shown, a preferred embodiment of the above-mentioned electrostatic assembly collector application includes:

[0060] Based on the relative addition of reagents to the raw ore, 80 g / t of soda ash was used as a pH adjuster, 120 g / t of water glass as a depressant, 240 g / t of the obtained electrostatically assembled collector as a flotation collector, and 30 g / t of pine oil as a frother. These were thoroughly mixed with the ilmenite from Chengde, Hebei Province, to obtain the slurry. The slurry was then placed in a fluidized bed flotation machine, where it was floated using a flotation column formed by the rising water flow and air bubbles creating a gas-liquid-solid three-phase composite fluidized bed. The concentrate and tailings were collected. The flotation test results for the ilmenite from Chengde, Hebei Province are shown in Table 2 below.

[0061] Table 2 Results of flotation tests on ilmenite from Chengde, Hebei Province

[0062] product Yield / % <![CDATA[TiO2 grade / %]]> <![CDATA[TiO2 recovery rate / %]]> Concentrate 46.77 23.55 94.30 Tailings 53.23 1.25 5.70 raw ore 100.00 11.68 100.00

[0063] The experiment yielded a concentrate with a TiO2 grade of 23.55% and a TiO2 recovery rate of 94.30%. This demonstrates that the electrostatically assembled collector has a strong selective collecting ability for coarse-grained ilmenite with low liberation degree, significantly improving the concentrate grade and flotation recovery rate, and achieving efficient collection of coarse-grained ilmenite intergrowths.

[0064] Example 3:

[0065] A preferred embodiment of the coarse-grained ilmenite flotation electrostatic collector of the present invention includes the following preparation method:

[0066] Preparation of hyperbranched quaternary ammonium salt: 1 mol of octadecyl tertiary amine was added to a 500 mL four-necked round-bottom flask equipped with a magnetic stirrer and thermometer. After stirring thoroughly until the octadecyl tertiary amine dissolved, the temperature was raised to 90 °C. 1.2 mol of epichlorohydrin was slowly added dropwise to dodecyl tertiary amine at a rate of 0.02 g / s. After the addition was complete, the mixture was stirred and kept at 90 °C for 4 h. Then, a vacuum was drawn, and N,N-dimethylformamide was slowly added dropwise at a rate of 0.02 g / s to dissolve the amine. Then, copper chloride catalyst was added, and the temperature was raised to 95 °C for 6 h. The solvent was removed by rotary evaporation to obtain a viscous liquid. The viscous liquid was dialyzed using a dialysis bag with a molecular weight cutoff of 2000 D. The retained material was then vacuum dried to obtain the hyperbranched quaternary ammonium salt. The hyperbranched quaternary ammonium salt was characterized by nuclear magnetic resonance. The signal peaks of each chemical shift indicated that the obtained product was indeed a hyperbranched quaternary ammonium salt with R being octadecyl.

[0067] Preparation of electrostatic assembly collector: Sodium alkyl fatty acid methyl ester sulfonate (R1 = C=18) and dodecyl hydroxamic acid were reacted in a stirred container at a molar ratio of 1:5 for 15 min. Then, the above hyperbranched quaternary ammonium salt was slowly added dropwise at a dropping rate of 0.02 g / s. The molar ratio of hyperbranched quaternary ammonium salt to dodecyl hydroxamic acid was 1:20, and the concentration of the added salt was 10. -3 Potassium nitrate electrolyte (mol / L) was electrostatically reacted in an electrostatic reaction vessel at 80℃ for 40 min. After the electrostatic reaction was completed, the product was crystallized and dried to obtain an electrostatically assembled collector.

[0068] Taking the processing of an ilmenite ore deposit in Shaanxi Province as an example, the raw material has a TiO2 grade of 20.84%, the main titanium mineral is ilmenite, and the gangue minerals are calcite, quartz, and pyroxene, etc. The ore particle size is less than 1 mm, of which -0.8 mm particles account for 75%, and the ilmenite liberation degree is 40%. Figure 2 As shown, a preferred embodiment of the above-mentioned electrostatic assembly collector application includes:

[0069] Based on the relative addition of reagents to the raw ore, 120 g / t water glass was used as a depressant, 240 g / t of the obtained electrostatically assembled collector was used as a flotation collector, and 30 g / t pine oil was used as a frother. These were thoroughly mixed with Panzhihua ilmenite to obtain a slurry. The slurry was then placed in a fluidized bed flotation machine, where it was floated using a flotation column formed by the rising water flow and air bubbles creating a gas-liquid-solid three-phase composite fluidized bed. The concentrate and tailings were collected. The flotation test results for an ilmenite ore mine in Shaanxi are shown in Table 3 below.

[0070] Table 3. Flotation test results of an ilmenite ore mine in Shaanxi Province

[0071] product Yield / % <![CDATA[TiO2 grade / %]]> <![CDATA[TiO2 recovery rate / %]]> Concentrate 61.22 31.44 92.35 Tailings 38.78 4.11 7.65 raw ore 100.00 20.84 100.00

[0072] The experiment yielded a concentrate with a TiO2 grade of 31.44% and a TiO2 recovery rate of 92.35%. This demonstrates that the electrostatically assembled collector has a strong selective collecting ability for coarse-grained ilmenite with low liberation degree, significantly improving the concentrate grade and flotation recovery rate, and achieving efficient collection of coarse-grained ilmenite intergrowths.

[0073] The detailed descriptions listed above are merely specific illustrations of feasible embodiments of the present invention and are not intended to limit the scope of protection of the present invention. All equivalent embodiments or modifications made without departing from the spirit of the present invention should be included within the scope of protection of the present invention.

Claims

1. A coarse-grained ilmenite flotation electrostatic assembly collector characterized by, The electrostatic force assembly is formed by fatty acid methyl ester sulfonate and alkyl hydroxamic acid under the initiation of hyperbranched quaternary ammonium salt, and the hyperbranched quaternary ammonium salt has the following molecular structure: in the above formula, R is an alkyl group.

2. A coarse-grained ilmenite flotation electrostatic assembly collector according to claim 1, characterized by The fatty acid methyl ester sulfonate is R1CH(SO3M)COOCH3, R1 is C=16-18 alkyl, and M is a positive monovalent metal ion.

3. A coarse-grained ilmenite flotation electrostatic assembly collector according to claim 1, characterized by, The alkyl hydroxamic acid is C7-12 alkyl hydroxamic acid, and the molar ratio of the fatty acid methyl ester sulfonate to the alkyl hydroxamic acid is 1:(3-5).

4. A coarse-grained ilmenite flotation electrostatic assembly collector according to claim 1, characterized by, R of the hyperbranched quaternary ammonium salt is C=12-18 alkyl, and the molar ratio of the hyperbranched quaternary ammonium salt to the alkyl hydroxamic acid is 1:(10-20).

5. A coarse-grained ilmenite flotation electrostatic assembly collector according to claim 4, characterised in that, The hyperbranched quaternary ammonium salt is formed by reacting alkyl tertiary amine with epichlorohydrin at a molar ratio of 1:(1-1.2).

6. A process for the preparation of a coarse-grained ilmenite flotation electrostatic assembly collector according to any one of claims 1 to 5, characterized by, The method comprises: fully reacting fatty acid methyl ester sulfonate and alkyl hydroxamic acid, then slowly adding hyperbranched quaternary ammonium salt, adding electrolyte, and performing electrostatic reaction at a temperature of 50-80℃ for 30-40min, and then crystallizing and drying the product to obtain the electrostatic assembly collector.

7. The method of claim 6, wherein the method further comprises the step of: The method comprises preparing the hyperbranched quaternary ammonium salt: fully stirring and dissolving alkyl tertiary amine, heating to 80-90℃, slowly adding epichlorohydrin, stirring and keeping warm at 80-90℃ for 3-4h after the addition is completed, slowly adding a solvent under vacuum, adding a catalyst, heating to 90-95℃, and then reacting for 5-6h, and then removing the solvent by rotary evaporation to obtain a viscous liquid, dialyzing the viscous liquid, and then vacuum drying to obtain the hyperbranched quaternary ammonium salt. ​ 8. Use of a collector according to any one of claims 1 to 5 for the flotation of coarse grained ilmenite, characterized in that, The application method comprises: using the electrostatic assembly collector as a collector for rough particle ilmenite flotation and waste disposal, and the mass ratio of the fatty acid methyl ester sulfonate to the alkyl hydroxamic acid is negatively correlated with the dissociation degree of ilmenite.

9. Use of a coarse ilmenite flotation electrostatic assembly collector according to claim 8, characterized in that, The ore particle size of the rough particle ilmenite is less than 1mm, the particle size of -0.8mm accounts for not less than 60%, and the dissociation degree is not less than 10%. The amount of the electrostatic assembly collector is positively correlated with the ilmenite grade of the rough particle ilmenite and the flotation treatment amount of the rough particle ilmenite, and is negatively correlated with the dissociation degree of ilmenite.

10. Use of a coarse ilmenite flotation electrostatic assembly collector according to claim 8, characterized in that, The flotation and waste disposal comprises: fully mixing reagents including the electrostatic assembly collector with rough particle ilmenite to obtain ore slurry, and then placing the ore slurry in a flotation column in which an upward water flow and bubbles form a gas-liquid-solid three-phase complex flow interference bed for flotation. The pH value of the ore slurry is 7-10, and the mass concentration of the reagents is 2-10%.

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