Supramolecular polymer collectors for the flotation of fine-grained ilmenite, their preparation methods and applications

Abstract

This invention relates to a supramolecular polymer collector for the flotation of fine-grained ilmenite, its preparation method, and its application. The collector is a quaternary ammonium polymer monomer synthesized by reacting alkyl tertiary amines and acryloyl chloride. The quaternary ammonium polymer monomer is then polymerized with acrylamide to synthesize cationic hydrophobic polyacrylamide. The supramolecular polymer, formed by the self-assembly of dicarboxylic acid and cationic hydrophobic polyacrylamide through intermolecular hydrogen bonding, can exert a synergistic adsorption effect of multiple functional groups such as amine, hydroxyl, amide, and carbonyl groups on the iron and titanium active particles on the surface of ilmenite. It can form a dense hydrophobic film on the surface of ilmenite through a large number of hydrogen bonds, comprehensively enhancing the hydrophobic coverage of the mineral surface. It has the characteristics of extremely strong selective collection ability for fine-grained ilmenite, strong adaptability, small dosage, low cost, and non-toxicity and pollution-free. The preparation method is simple, the reaction conditions are mild, and the cost is low. It can be widely used in the flotation separation process of fine-grained ilmenite to effectively improve the flotation index.

Description

Technical Field

[0001] This invention belongs to the field of mineral flotation technology, specifically relating to a supramolecular polymer collector for the flotation of fine-grained ilmenite, its preparation method, and its application. Background Technology

[0002] Ilmenite is an important mineral resource and a major source of titanium metal. China currently boasts the world's largest titanium resources, with proven reserves of approximately 870 million tons, accounting for about 48% of global titanium reserves. Ilmenite beneficiation processes include gravity separation, magnetic separation, electrostatic separation, and flotation. Among these, flotation is an effective method for recovering fine-grained ilmenite; however, the overall recovery rate of fine-grained ilmenite in my country is relatively low, and flotation efficiency urgently needs improvement. Collectors are the core of ilmenite flotation; therefore, developing new and efficient flotation collectors is of great significance for the flotation recovery of ilmenite.

[0003] Commonly used collectors for ilmenite flotation include fatty acids, hydroxamic acids, and organophosphonic acids, with oleic acid and its salts being the most widely used. However, traditional collectors have poor selectivity and require the addition of large amounts of depressants during use, resulting in low overall titanium recovery rates. Combined collectors utilize two or more reagents to achieve synergistic effects, often resulting in better flotation performance than single reagents. In recent years, the use of mixed reagents for ilmenite flotation has become a major research direction.

[0004] Reported combined collectors in the literature include anionic collector-anionic collector, anionic collector-nonpolar collector, and collector-frother combinations, which have achieved certain separation effects. However, in industrial practice with fine-grained primary ilmenite, the recovery rate remains low. The main reason is that, under the same environmental conditions, ilmenite can only use one of titanium or iron particles as active sites on its surface. Traditional collectors have fewer functional groups, simpler structures, and weaker adaptability, failing to effectively adsorb onto the ilmenite surface by interacting fully with the active sites. Furthermore, the loose structure of traditional mixed reagents prevents the formation of a strongly hydrophobic molecular film on the ilmenite surface, hindering its hydrophobicity and resulting in relatively poor floatability. Secondly, there are also problems such as high reagent dosage, high cost, complex collector preparation and flotation processes, and unsatisfactory production indicators. Therefore, developing macromolecular collectors with multiple functional groups is an effective way to enhance the adsorption capacity and hydrophobicity of collectors, which helps to improve the hydrophobicity of ilmenite surfaces. Summary of the Invention

[0005] To address the problems of weak mineral surface hydrophobicity, low ilmenite recovery rate, and low flotation efficiency in traditional collector flotation processes for fine-grained ilmenite, one objective of this invention is to provide a collector with extremely strong selective collecting ability for fine-grained ilmenite, which is beneficial for significantly improving concentrate grade and flotation recovery rate, 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 the flotation of fine-grained ilmenite, significantly improving flotation indicators.

[0006] To achieve the above-mentioned technical objectives, the technical solution adopted by the present invention to solve its technical problems is as follows:

[0007] A supramolecular polymer collector for the flotation of fine-grained ilmenite is a supramolecular polymer formed by the self-assembly of dicarboxylic acid and cationic hydrophobic polyacrylamide through intermolecular hydrogen bonding. The cationic hydrophobic polyacrylamide has the following molecular structure:

[0008] In the above formula, R is an alkyl group.

[0009] Furthermore, the chemical formula of the dicarboxylic acid is R1(COOH)2. The longer the carbon chain, the stronger the collecting ability, but the selectivity for iron ore will decrease. Therefore, R1 is preferably an alkyl group with C=3 to 10.

[0010] Furthermore, the mass ratio of the dicarboxylic acid to the cationic hydrophobic polyacrylamide is negatively correlated with the grade of ilmenite; therefore, the preferred molar ratio of the dicarboxylic acid to the cationic hydrophobic polyacrylamide is (1-5):1.

[0011] Furthermore, the longer the carbon chain of the cationic hydrophobic polyacrylamide, the stronger its collecting ability, but the selectivity for iron ore will decrease. Therefore, the R of the cationic hydrophobic polyacrylamide is an alkyl group with C=6 to 18 and a weight-average molecular weight of 1200 to 2000.

[0012] Furthermore, the cationic hydrophobic polyacrylamide is formed by reacting acrylamide with quaternary ammonium monomers, and has amine groups, amide groups, carbonyl groups, etc. that can interact with active particles on the surface of ilmenite, and the nonpolar groups have strong hydrophobicity.

[0013] Furthermore, the molar ratio of acrylamide to quaternary ammonium monomer is 1:(1-3).

[0014] Furthermore, the quaternary ammonium polymer monomer is formed by reacting alkyl tertiary amines and acryloyl chloride.

[0015] Furthermore, the molar ratio of the alkyl tertiary amine to acryloyl chloride is 1:(1-2).

[0016] A method for preparing a supramolecular polymer collector for the flotation of fine-grained ilmenite includes: dissolving dicarboxylic acid in water, adjusting the pH to acidic, slowly adding cationic hydrophobic polyacrylamide dropwise under stirring, allowing for full self-assembly reaction, and then taking the product crystallized and dried to obtain the supramolecular polymer collector.

[0017] Furthermore, the dissolution temperature of the dicarboxylic acid is 80–90°C.

[0018] Furthermore, the pH is adjusted by adding hydrochloric acid to adjust the dicarboxylic acid solution to a pH of 3-5.

[0019] Furthermore, the dropping rate of the cationic hydrophobic polyacrylamide is not higher than 0.05 g / s.

[0020] Furthermore, the self-assembly reaction is carried out at a temperature of 50–80°C for 1–2 hours.

[0021] Furthermore, the method includes preparing cationic hydrophobic polyacrylamide: acrylamide and quaternary ammonium polymer monomers are placed in a reaction vessel, vacuumed to remove oxygen, a polymerization initiator is added, and the polymerization reaction is carried out fully. After the reaction is completed, the product is dried, pulverized, and granulated to form a powder, thus obtaining cationic hydrophobic polyacrylamide.

[0022] Furthermore, the amount of the polymerization initiator potassium persulfate is 0.01%-0.03% of the amount of quaternary ammonium monomer used.

[0023] Furthermore, the polymerization reaction is carried out by heating to 50-70°C and reacting for 4-8 hours.

[0024] Furthermore, the method includes preparing quaternary ammonium polymer monomers: alkyl tertiary amines and acryloyl chloride are placed in a reaction vessel, the pH value is adjusted to alkaline, and the reaction is carried out fully. After the reaction is completed, the product is evaporated and crystallized, dried, pulverized and made into powder to obtain quaternary ammonium polymer monomers.

[0025] Furthermore, sodium carbonate was added to adjust the pH of the alkyl tertiary amine and acryloyl chloride to 8–9.

[0026] Furthermore, the reaction is carried out by cooling to 0-10°C and then reacting for 1-2 hours.

[0027] An application of a supramolecular polymer collector for the flotation of fine-grained ilmenite, the application method of which includes: using the supramolecular polymer collector as a collector for the flotation of ilmenite.

[0028] Furthermore, the flotation method includes: thoroughly mixing a reagent comprising the supramolecular polymer collector with a slurry comprising ilmenite, and then performing ilmenite flotation.

[0029] Furthermore, the flotation method includes: after pulp conditioning, the flotation machine is used for roughing, cleaning, and scavenging, with supramolecular polymer collectors added in both the roughing and first scavenging.

[0030] Furthermore, the ilmenite has a particle size of -200 mesh and accounts for 70-85%.

[0031] Furthermore, the mass ratio of the dicarboxylic acid to the cationic hydrophobic polyacrylamide is negatively correlated with the grade of ilmenite, while the amount of the supramolecular polymer collector is positively correlated with the ilmenite flotation throughput and the ilmenite grade.

[0032] Furthermore, the pulp is neutral and alkaline, within which good flotation performance can be achieved; therefore, the pH value is preferably 7 to 11.

[0033] Furthermore, if the collector concentration in 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 the dissolution of the collector. Therefore, the collector mass concentration is preferably 2 to 8%.

[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 supramolecular polymer collector of the present invention differs from traditional mixed agents by utilizing the intermolecular hydrogen bonding of internal functional groups such as amino groups, hydroxyl groups, amide groups, and carbonyl groups of dicarboxylic acid and cationic hydrophobic polyacrylamide to self-assemble into a supramolecular polymer with multiple types of functional groups and a dense structure:

[0037] Among them, the amino, hydroxyl, amide, and carbonyl groups of dicarboxylic acid and cationic hydrophobic polyacrylamide can all interact with the iron and titanium active particles on the surface of ilmenite, exerting the synergistic effect of the multifunctional groups of macromolecules and enhancing the adsorption capacity of the collector. Furthermore, the supramolecular polymer formed by self-assembly has a large number of hydrogen bonds, which can form a dense hydrophobic film on the surface of ilmenite, comprehensively enhancing the hydrophobic coverage of the mineral surface, thereby significantly improving the grade and recovery rate of ilmenite flotation concentrate. This fundamentally solves the problems of low recovery rate and low flotation efficiency caused by the small number of functional groups, simple structure, and difficulty in improving the hydrophobicity of the mineral surface of traditional collectors. Moreover, it is highly adaptable, requires small dosage, is low in cost, and is non-toxic and pollution-free.

[0038] By optimizing the carbon chain length and the ratio of alkyl tertiary amines, acryloyl chloride, acrylamide, and dicarboxylic acid, the harvesting capacity and selectivity of ilmenite can be further enhanced.

[0039] (2) The method for preparing the supramolecular polymer collector of the present invention involves synthesizing a quaternary ammonium polymer monomer by reacting an alkyl tertiary amine with an acryloyl chloride under suitable temperature, ratio and addition method, and then synthesizing a cationic hydrophobic polyacrylamide by polymerizing the quaternary ammonium polymer monomer with an acrylamide. Furthermore, a dense and high-performance macromolecular supramolecular polymer collector is obtained by hydrogen bonding self-assembly reaction of the cationic hydrophobic polyacrylamide with a dicarboxylic acid. It has the advantages of simple process, mild reaction conditions and low cost, which is conducive to large-scale production.

[0040] (3) The supramolecular polymer collector of the present invention can be widely used in the flotation separation process of fine-grained ilmenite through slurry flotation. It can solve the problems of high reagent cost, complex process and unsatisfactory production indicators in the traditional ilmenite flotation process. By optimizing the composition ratio and dosage of the collector, the flotation indicators can be improved. The TiO2 recovery rate of the concentrate can reach more than 90%, which significantly improves the flotation operation indicators. Attached Figure Description

[0041] 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:

[0042] Figure 1 This is the 1H NMR spectrum of the cationic hydrophobic polyacrylamide described in this invention.

[0043] Figure 2 Atomic force microscopy 3D height images of ilmenite surface before and after adsorption of supramolecular polymer collector in Example 1; Figure 2 (a) indicates the state before adsorption; Figure 2 (b) indicates after adsorption.

[0044] Figure 3 This is a process flow diagram of the application of the supramolecular polymer collector described in Example 1 of the present invention.

[0045] Figure 4 This is a process flow diagram of the application of the supramolecular polymer collector described in Example 2 of the present invention.

[0046] Figure 5 This is a process flow diagram of the application of the supramolecular polymer collector described in Example 3 of the present invention. Detailed Implementation

[0047] 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.

[0048] Example 1:

[0049] A preferred embodiment of the fine-grained ilmenite flotation supramolecular polymer collector of the present invention includes the following preparation method:

[0050] Step S1: Preparation of quaternary ammonium polymer monomer: Take 1 mol of dodecyl tertiary amine and 1 mol of acryloyl chloride and place them in a 250 mL reaction vessel. Add sodium carbonate to adjust the pH value to 8. After cooling to 0℃, react for 1 h. After the reaction is completed, take the product, evaporate and crystallize, dry, pulverize and make it into powder to obtain the quaternary ammonium polymer monomer.

[0051] Step S2: Preparation of cationic hydrophobic polyacrylamide: 1 mol of acrylamide and 1 mol of quaternary ammonium monomer obtained in step S1 were placed in a 250 mL reaction vessel. The vessel was evacuated to remove oxygen. 0.01% (by weight of the quaternary ammonium monomer) of potassium persulfate, the polymerization initiator, was added. The temperature was raised to 50 °C, and the polymerization reaction was carried out for 8 hours. After the reaction, the product was dried, pulverized, and granulated to obtain a powder, thus yielding cationic hydrophobic polyacrylamide. The 1H NMR spectrum of the reaction product is shown below. Figure 1 As shown, the characterization results indicate that the reaction produces the expected product with a weight-average molecular weight of approximately 1600.

[0052] Step S3: Preparation of supramolecular polymer collector: Dissolve 3 mol of adipic acid in water at 80°C to obtain an adipic acid solution. Adjust the pH of the adipic acid solution to 3 with hydrochloric acid. Transfer the adipic acid solution to a 500 mL reaction vessel. Then, take 1 mol of the cationic hydrophobic polyacrylamide obtained in step S2 and slowly add it dropwise to the reaction vessel at a rate of 0.05 g / s under stirring. React at 50°C for 2 hours. After the reaction is complete, take the product, crystallize and dry to obtain the supramolecular polymer collector.

[0053] Taking the processing of Panzhihua ilmenite as an example, with a raw material TiO2 grade of 23.21% and a -200 mesh content of 80%, the main titanium mineral is ilmenite, and the gangue minerals are pyroxene, calcite, and garnet, etc. Figure 3 As shown, a preferred embodiment of the application of the above-mentioned supramolecular polymer collector includes:

[0054] Using water glass as a depressant, the supramolecular polymer collector obtained in step S3 as a collector, and pine oil as a frother, the mixture is thoroughly mixed with ilmenite and then fed into a flotation machine for one roughing, three cleaning, and two scavenging processes.

[0055] Roughing: Based on the amount of reagents added relative to the raw ore, water glass 80g / t, collector 240g / t, pine oil 30g / t, collector mass concentration is 5%, pulp pH is 8, roughing yields roughing concentrate and roughing tailings.

[0056] Selected 1: Add 60g / t of water glass to the rough concentrate to obtain refined concentrate and refined tailings. The refined tailings are returned to the rough concentrate.

[0057] Selected 2: Add 30g / t of water glass to the concentrate from Refined 1, and then select Refined 2 concentrate and Refined 2 tailings. The tailings from Refined 2 are returned to Selected 1.

[0058] Selected 3: Without adding any reagents, the refined ore from the second-grade concentrate yields titanium concentrate and the refined ore from the third-grade tailings. The refined ore from the third-grade tailings is returned to the selected ore from the second-grade concentrate.

[0059] Scavenging 1: Add 30g / t of supramolecular polymer collector to the roughing tailings to obtain scavenging concentrate and scavenging tailings. The scavenging concentrate is returned to the roughing.

[0060] Sweep 2: Sweep 1 tailings without adding reagents, and sweep to obtain Sweep 2 concentrate and tailings. Sweep 2 concentrate is returned to Sweep 1.

[0061] The flotation test results of titanium concentrate and tailings from Panzhihua ilmenite are shown in Table 1 below:

[0062] Table 1 Results of flotation tests for ilmenite in Panzhihua

[0063] product Yield / % <![CDATA[TiO2 grade / %]]> <![CDATA[TiO2 recovery rate / %]]> Titanium concentrate 37.22 56.68 90.89 Tailings 62.78 3.37 9.11 raw ore 100.00 23.21 100.00

[0064] like Figure 2 The 3D height images of the ilmenite surface before and after adsorption of the supramolecular polymer collector are shown in the atomic force microscopy. It can be seen that the self-assembled supramolecular polymer can form a dense hydrophobic film on the ilmenite surface, which comprehensively enhances the hydrophobic coverage of the mineral surface. The experiment yielded a titanium concentrate with a TiO2 grade of 56.68% and a TiO2 recovery rate of 90.89%. It can be seen that the supramolecular polymer collector significantly improves the concentrate grade and flotation recovery rate.

[0065] Example 2:

[0066] A preferred embodiment of the fine-grained ilmenite flotation supramolecular polymer collector of the present invention includes the following preparation method:

[0067] Step S1: Preparation of quaternary ammonium polymer monomer: Take 1 mol of octadecyl tertiary amine and 1 mol of acryloyl chloride and place them in a 250 mL reaction vessel. Add sodium carbonate to adjust the pH value to 8. After cooling to 5℃, react for 1.5 h. After the reaction is completed, take the product, evaporate and crystallize, dry, pulverize and make it into powder to obtain the quaternary ammonium polymer monomer.

[0068] Step S2: Preparation of cationic hydrophobic polyacrylamide: 1 mol of acrylamide and 2 mol of quaternary ammonium monomer obtained in step S1 were placed in a 250 mL reaction vessel, and the vessel was evacuated to remove oxygen. 0.02% by mass of potassium persulfate, a polymerization initiator, was added. The temperature was raised to 60 °C and the polymerization reaction was carried out for 6 h. After the reaction was completed, the product was dried, pulverized, and granulated to obtain a powder, which yielded cationic hydrophobic polyacrylamide. Characterization results showed that the reaction produced the expected product with a weight-average molecular weight of about 2000.

[0069] Step S3: Preparation of supramolecular polymer collector: Dissolve 5 mol of glutaric acid in water at 80°C to obtain a glutaric acid solution. Adjust the pH of the glutaric acid solution to 4 with hydrochloric acid. Transfer the glutaric acid solution to a 500 mL reaction vessel. Then, take 1 mol of the cationic hydrophobic polyacrylamide obtained in step S2 and slowly add it dropwise to the reaction vessel at a rate of 0.04 g / s under stirring. React at 80°C for 1 h. After the reaction is complete, take the product, crystallize and dry to obtain the supramolecular polymer collector.

[0070] Taking the processing of ilmenite from Chengde, Hebei Province, with a raw material TiO2 grade of 13.74%, a -200 mesh content of 85%, and ilmenite as the titanium mineral, along with gangue minerals such as ilmenite and quartz, as an example, ... Figure 4 As shown, a preferred embodiment of the application of the above-mentioned supramolecular polymer collector includes:

[0071] Using water glass as a depressant, soda ash as a pH adjuster, and the supramolecular polymer collector obtained in step S3 as a collector, pine oil as a frother, the mixture is thoroughly mixed with ilmenite and then fed into a flotation machine for one roughing, two cleaning, and three scavenging processes:

[0072] Roughing: Based on the amount of reagents added relative to the raw ore, the following parameters are used: soda ash 150g / t, collector 160g / t, pine oil 20g / t, collector concentration 5%, pulp pH 9.5. Roughing yields roughing concentrate and roughing tailings.

[0073] Selected 1: Add 50g / t of water glass to the rough concentrate to obtain refined concentrate and refined tailings. The refined tailings are returned to the rough concentrate.

[0074] Selected 2: Add 30g / t of water glass to the concentrate from Refined 1, and then refine to obtain titanium concentrate and Refined 2 tailings. The Refined 2 tailings are returned to Selected 1.

[0075] Scavenging 1: Add 30g / t of supramolecular polymer collector to the roughing tailings to obtain scavenging concentrate and scavenging tailings. The scavenging concentrate is returned to the roughing.

[0076] Sweep 2: Sweep 1 tailings without adding reagents, and sweep to obtain Sweep 2 concentrate and Sweep 2 tailings. Sweep 2 concentrate is returned to Sweep 1.

[0077] Sweep 3: No reagents are added to the tailings from Sweep 2. Sweep 3 yields concentrate and tailings. The concentrate from Sweep 3 is returned to Sweep 2.

[0078] The flotation test results of titanium concentrate and tailings from ilmenite ore in Chengde, Hebei Province are shown in Table 2 below:

[0079] Table 2 Results of flotation tests on ilmenite from Chengde, Hebei Province

[0080] product Yield / % <![CDATA[TiO2 grade / %]]> <![CDATA[TiO2 recovery rate / %]]> Titanium concentrate 26.46 46.91 90.31 Tailings 73.54 1.81 9.69 raw ore 100.00 13.74 100.00

[0081] The experiment yielded a titanium concentrate with a TiO2 grade of 46.91% and a TiO2 recovery rate of 90.31%, demonstrating that the supramolecular polymer collector significantly improved the concentrate grade and flotation recovery rate.

[0082] Example 3:

[0083] A preferred embodiment of the fine-grained ilmenite flotation supramolecular polymer collector of the present invention includes the following preparation method:

[0084] Step S1: Preparation of quaternary ammonium monomer: Take 1 mol of hexadecyl tertiary amine and 1.5 mol of acryloyl chloride and place them in a 250 mL reaction vessel. Add sodium carbonate to adjust the pH to 9. After cooling to 10 °C, react for 2 h. After the reaction is completed, take the product, evaporate and crystallize it, dry it, pulverize it and make it into powder to obtain the quaternary ammonium monomer.

[0085] Step S2: Preparation of cationic hydrophobic polyacrylamide: 1 mol of acrylamide and 3 mol of quaternary ammonium monomer obtained in step S1 were placed in a 250 mL reaction vessel, and the mixture was evacuated to remove oxygen. 0.03% by mass of potassium persulfate, a polymerization initiator, was added. The mixture was heated to 70 °C and the polymerization reaction was carried out for 4 h. After the reaction was completed, the product was dried, pulverized, and granulated to obtain a powder, which yielded cationic hydrophobic polyacrylamide. Characterization results showed that the reaction produced the expected product with a weight-average molecular weight of about 1800.

[0086] Step S3: Preparation of supramolecular polymer collector: Dissolve 2 mol of octanoic acid in water at 90°C to obtain an octanoic acid solution. Adjust the pH of the octanoic acid solution to 5 with hydrochloric acid. Transfer the octanoic acid solution to a 500 mL reaction vessel. Then, take 1 mol of the cationic hydrophobic polyacrylamide obtained in step S2 and slowly add it dropwise to the reaction vessel at a rate of 0.04 g / s under stirring. React at 80°C for 1.5 h. After the reaction is complete, take the product, crystallize and dry to obtain the supramolecular polymer collector.

[0087] Taking the processing of an ilmenite ore deposit in Shaanxi Province as an example, the raw material has a TiO2 grade of 27.97%, a -200 mesh content of 75%, and the main gangue minerals are calcite, quartz, and pyroxene, etc. Figure 5 As shown, a preferred embodiment of the application of the above-mentioned supramolecular polymer collector includes:

[0088] Using water glass as a depressant, the supramolecular polymer collector obtained in step S3 as a collector, and pine oil as a frother, the mixture is thoroughly mixed with ilmenite and then fed into a flotation machine for one roughing, two cleaning, and two scavenging processes.

[0089] Roughing: Based on the amount of reagents added relative to the raw ore, the collector is 260g / t, the pine oil is 20g / t, the collector mass concentration is 2%, the pulp pH is 7, and the roughing process yields roughing concentrate and roughing tailings.

[0090] Selected 1: Add 80g / t of water glass to the rough concentrate to obtain refined concentrate and refined tailings. The refined tailings are returned to the rough concentrate.

[0091] Selected 2: Add 40g / t of water glass to the concentrate from Refined 1, and then refine to obtain titanium concentrate and Refined 2 tailings. The Refined 2 tailings are returned to Selected 1.

[0092] Scavenging 1: Add 50g / t of supramolecular polymer collector to the roughing tailings to obtain scavenging concentrate and scavenging tailings. The scavenging concentrate is returned to the roughing.

[0093] Sweep 2: Sweep 1 tailings without adding reagents, and sweep to obtain Sweep 2 concentrate and tailings. Sweep 2 concentrate is returned to Sweep 1.

[0094] Table 3 below shows the flotation test results of an ilmenite ore mine in Shaanxi Province, collected from titanium concentrate and tailings.

[0095] Table 3. Flotation test results of an ilmenite ore mine in Shaanxi Province

[0096] product Yield / % <![CDATA[TiO2 grade / %]]> <![CDATA[TiO2 recovery rate / %]]> Titanium concentrate 37.96 66.48 90.22 Tailings 62.04 4.41 9.78 raw ore 100.00 27.97 100.00

[0097] The experiment yielded a titanium concentrate with a TiO2 grade of 66.48% and a TiO2 recovery rate of 90.22%, demonstrating that the supramolecular polymer collector significantly improved the concentrate grade and flotation recovery rate.

[0098] 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 fine-grained ilmenite flotation supramolecular polymer collector, characterized by, The application relates to a supramolecular polymer formed by self-assembly of dicarboxylic acid and cationic hydrophobic polyacrylamide through intermolecular hydrogen bonding, wherein the chemical formula of the dicarboxylic acid is R1(COOH)2, R1 is alkyl with C=3-10; and the cationic hydrophobic polyacrylamide has the following molecular structure. In the above formula, R is an alkyl group of C=6-18.

2. A fine-grained ilmenite flotation supramolecular polymer collector according to claim 1, characterized by, The molar ratio of the dicarboxylic acid to the cationic hydrophobic polyacrylamide is (1-5):

1.

3. A fine-grained ilmenite flotation supramolecular polymer collector according to claim 1, characterized by, The weight average molecular weight of the cationic hydrophobic polyacrylamide is 1200-2000.

4. A fine-grained ilmenite flotation supramolecular polymeric collector according to claim 3, characterized by, The cationic hydrophobic polyacrylamide is formed by reaction of acrylamide and quaternary ammonium polymer monomer at a molar ratio of 1:(1-3).

5. A fine-grained ilmenite flotation supramolecular polymeric collector according to claim 4, characterized by, The quaternary ammonium polymer monomer is formed by reaction of alkyl tertiary amine and acryloyl chloride at a molar ratio of 1:(1-2).

6. The preparation method of the fine-grained ilmenite flotation supramolecular polymer collector according to any one of claims 1-5, characterized in that, The method comprises the following steps: dissolving the dicarboxylic acid in water at a temperature of 80-90 DEG C, adding hydrochloric acid to adjust the pH to 3-5, slowly adding the cationic hydrophobic polyacrylamide under stirring, and performing self-assembly reaction at a temperature of 50-80 DEG C for 1-2 h; and then crystallizing and drying the product to obtain the supramolecular polymer collector.

7. A process for the preparation of a fine-grained ilmenite flotation supramolecular polymer collector according to claim 6, characterized by, The method comprises the following steps: placing acrylamide and quaternary ammonium polymer monomer in a reaction container, removing oxygen by vacuumizing, adding a polymerization initiator potassium persulfate, and performing polymerization reaction at a temperature of 50-70 DEG C for 4-8 h; and then drying, crushing and granulating the product to obtain the cationic hydrophobic polyacrylamide.

8. A process for the preparation of a fine-grained ilmenite flotation supramolecular polymer collector according to claim 7, characterized by, Further, the method comprises the following steps: placing alkyl tertiary amine and acryloyl chloride in a reaction container, adding sodium carbonate to adjust the pH to 8-9, and performing reaction at a temperature of 0-10 DEG C for 1-2 h; and then evaporating, crystallizing, drying and crushing the product to obtain the quaternary ammonium polymer monomer.

9. Use of a fine-grained ilmenite floating supramolecular polymer collector according to any one of claims 1 to 5, characterized in that, The application method comprises the following steps: mixing a medicament comprising the supramolecular polymer collector as a collector with a mineral slurry comprising ilmenite, and performing ilmenite flotation, the particle size of the ilmenite is 70-85% of -200 mesh, the mass ratio of the dicarboxylic acid to the cationic hydrophobic polyacrylamide is negatively correlated with the ilmenite grade, the use amount of the supramolecular polymer collector is positively correlated with the ilmenite flotation treatment amount and the ilmenite grade, and the pH value of the mineral slurry is 7-11 and the mass concentration of the collector is 2-8%.

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