Collecting agent for rapid flotation recovery of ilmenite as well as preparation method and application of collecting agent

Abstract

The invention discloses a collecting agent for rapid flotation recovery of ilmenite as well as a preparation method and application of the collecting agent. The collecting agent is mainly prepared by compounding and reacting the following raw materials: fatty acid salt, alkyl hydroximic acid, alkyl ethoxy polyglycosides and rhamnolipid. The molar ratio of the fatty acid salt to the alkyl hydroximic acid is (2-4): 1; the molar ratio of the compound product of the fatty acid salt and the alkyl hydroximic acid to the alkyl ethoxy polyglycosides to the rhamnolipid is (3-6): 1: 0.5. According to the collecting agent for rapid flotation recovery of the ilmenite, the fatty acid salt, the alkyl hydroximic acid, the alkyl ethoxy polyglycosides and the rhamnolipid which have the synergistic effect are compounded, all the components have the synergistic effect, and the flotation rate, the recovery rate and the grade of the ilmenite are effectively improved.

Description

Technical Field

[0001] This invention belongs to the field of mineral processing, and particularly relates to a collector, its preparation method and application. Background Technology

[0002] Titanium is an important strategic rare metal, widely used in aerospace, marine, pharmaceutical, and catalysis fields, and is hailed as the "metal of the 21st century," with broad development prospects. my country's total titanium reserves rank among the world's top, mainly occurring in the form of ilmenite in the Panxi region within basic to ultrabasic rock bodies, making overall development and utilization quite challenging.

[0003] Currently, the industrial beneficiation of ilmenite mainly employs a combined process of magnetic separation and flotation. Flotation, as a crucial step in improving concentrate grade and recovery rate, directly impacts resource utilization efficiency and economic benefits. Commonly used collectors for ilmenite include fatty acids, phosphates, and hydroxamic acids. While these can achieve flotation recovery of ilmenite to some extent, they generally suffer from insufficient selectivity, slow flotation rates, high dosages, or low recovery rates, severely hindering the efficient utilization of titanium resources.

[0004] In recent years, some studies have attempted to optimize collector systems by employing compound systems, supramolecular structures, or modified organic functional groups to enhance the collection capacity and selectivity for ilmenite. However, these novel collectors generally suffer from problems such as complex synthesis processes, harsh reaction conditions, poor adaptability, or difficulty in matching current industrial acid flotation conditions, hindering their practical application. Therefore, designing a novel composite collector with simple composition, environmental friendliness, and fast flotation response, and developing corresponding preparation methods and application processes, is of great significance for further improving the efficiency of ilmenite beneficiation. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the background art above, and to provide a collector for rapid flotation recovery of ilmenite, its preparation method and application.

[0006] To solve the above-mentioned technical problems, the technical solution proposed by this invention is as follows: A collector for rapid flotation recovery of ilmenite is mainly obtained by the reaction of the following raw materials: fatty acid salt, alkyl hydroxamic acid, alcohol ether glycoside and rhamnolipid; the molar ratio of the fatty acid salt and alkyl hydroxamic acid is (2-4):1; the molar ratio of the compound product of the fatty acid salt and alkyl hydroxamic acid, the alcohol ether glycoside and the rhamnolipid is (3-6):1:0.5.

[0007] In the above-mentioned collectors, preferably, the fatty acid salt has the chemical formula R1COOM, wherein R1 is an alkyl group with C=10-18, and M is a metal cation Na. + Or K + .

[0008] In the above-mentioned collectors, preferably, the alkyl hydroxamic acid has the chemical formula R2CONHOH, wherein R2 is an alkyl group with C=6 to 12.

[0009] In the above-mentioned collectors, preferably, the alcohol ether glycoside is one or more of AEG050, AEG300, AEG1511, AEG1000, AEG2000, and AEG3000.

[0010] In the above-mentioned collectors, preferably, the rhamnolipid is a rhamnolipid having 1-2 glycolipid groups, and the general expression formula of the rhamnolipid is Rha-C10-C10, Rha-Rha-C10, Rha-C10, where Rha is a glycolipid functional group.

[0011] As a general technical concept, the present invention also provides a method for preparing the above-mentioned collector, comprising the following steps: dissolving the fatty acid salt in water, adding the alkyl hydroxamic acid under stirring conditions, reacting the reaction, adding the alcohol ether glycoside and rhamnolipid after the reaction, mixing and reacting in an ultrasonic field, and then drying to precipitate the collector.

[0012] In the above preparation method, preferably, the fatty acid salt is dissolved in water at a temperature of 20-50°C, the addition rate of the alkyl hydroxamic acid does not exceed 5 g / min, and the reaction time between the fatty acid salt and the alkyl hydroxamic acid is 20-50 min.

[0013] In the above preparation method, preferably, the addition rate of the alcohol ether glycoside does not exceed 8 g / min, and the addition rate of the rhamnolipid does not exceed 2 g / min.

[0014] In the above preparation method, preferably, the ultrasonic frequency is 20-80kHz, the temperature is 20-40℃, and the ultrasonic treatment time is 10-30min.

[0015] In the above preparation method, preferably, the drying and precipitation temperature of the collector is 40-80℃ and the time is 1-3h.

[0016] As a general technical concept, the present invention also provides an application of the above-mentioned collector, wherein the collector is used for the flotation recovery of ilmenite in the presence of an inhibitor. Preferably, the inhibitor of the present invention is a combination inhibitor that has a synergistic effect with the collector of the present invention, and this combination inhibitor can be a compound product of small molecule alkanolamines and sulfonated chitosan.

[0017] In the above applications, preferably, the fineness of the ilmenite is 50-65% (-600 mesh), the TiO2 content is 15-20%, the pulp concentration in the flotation process is 20-50%, and the flotation process flow is desulfurization-roughing-cleaning 1-cleaning 2; during roughing, the collector dosage is 1.2-1.6 kg / t, and the frother No. 2 oil dosage is 20-30 g / t; during cleaning 1, only a small amount of frother is added, and the frother No. 2 oil dosage is 10-20 g / t; during cleaning 2, only a small amount of frother is added, and the frother No. 2 oil dosage is 5-10 g / t. Fatty acid salts contain long hydrophobic alkyl chains in their molecular structure, allowing them to rapidly adsorb onto the surface of ilmenite in the pulp, imparting hydrophobicity and facilitating the binding between particles and bubbles, thereby improving collection efficiency. However, fatty acid salt molecules exhibit poor selectivity and readily undergo non-specific adsorption with silicate gangues such as pyroxene and olivine, affecting the grade of the flotation concentrate. In contrast, the hydroxyoxime functional group in alkyl hydroxamic acids has the ability to interact with metal cations (such as Ti...) 4+ Fe 3+ Alkyl hydroxamic acids possess the ability to form chelate coordination, allowing them to specifically bind to the surface of ilmenite and achieve good flotation selectivity. Compared to arsenic acid chelating collectors, alkyl hydroxamic acids are more environmentally friendly. However, due to their overall weak hydrophobicity, their collecting capacity is limited when used alone. By combining fatty acid salts with alkyl hydroxamic acids in a molar ratio of (2–4):1, a hydrophobic coating film and a coordination adsorption layer can be formed simultaneously on the mineral surface. On one hand, the fatty acid salt provides rapid adsorption and hydrophobicity, accelerating the mineral flotation response; on the other hand, an appropriate amount of hydroxamic acid molecules bind to the Ti or Fe active centers on the mineral surface through directional coordination, enhancing the recognition and selective adsorption of ilmenite. Simultaneously, this molar ratio effectively avoids the selectivity reduction problem caused by excessive fatty acid salts, while ensuring sufficient collecting power, balancing flotation speed and separation accuracy.

[0018] The synergistic effect of alcohol ether glycosides and rhamnolipids with fatty acid salts and alkyl hydroxamic acids is the key to improving the overall performance of the collector: (1) The excellent hydrophilicity and surface activity of alcohol ether glycosides first act on the collector itself, which can effectively solubilize and disperse hydrophobic fatty acid salts and alkyl hydroxamic acids in the aqueous phase, forming more stable and uniform micelles or microemulsions. This effect greatly improves the hard water resistance and low temperature adaptability of the composite collector, ensuring the stable performance of the drug in complex slurry environments. (2) Alcohol ether glycosides create conditions for the subsequent function of rhamnolipids. Through intermolecular forces, they form mixed micelles with rhamnolipids, which significantly promotes the dispersion and migration efficiency of rhamnolipids in the slurry, enabling them to reach the bubble interface and mineral surface more quickly and uniformly, thereby amplifying the bubble stabilization and wetting regulation effect of rhamnolipids. (3) As a biosurfactant, the unique amphiphilic structure of rhamnolipids allows them to be tightly arranged on the bubble surface, forming a highly elastic and strong interfacial film. This membrane can effectively prevent bubble coalescence and rupture, providing a more stable and durable rising carrier for hydrophobic particles loaded with ilmenite, which is particularly beneficial for the recovery of fine-grained minerals. (4) The glycosyl part of rhamnolipid may also interact with the fatty acid salt / hydroxyxamic acid hydrophobic layer already adsorbed on the mineral surface through hydrogen bonding and other interactions, further optimizing and consolidating the hydrophobic state of the mineral surface, forming a more complete composite hydrophobic layer, which effectively enhances the effect of the collector. The alcohol ether glycoside and rhamnolipid need to be reasonably controlled, which can avoid the excessive surfactant causing the foam system to become too viscous and the recovery efficiency to decrease, and can achieve good foam control effect on the premise of ensuring the mineral particle carrying efficiency. Therefore, this composite system has a significant synergistic effect in improving the controllability of flotation foam, inhibiting gangue entrainment and improving the flotation separation rate, and can realize the rapid and efficient flotation of fine-grained ilmenite.

[0019] To further enhance the synergistic effect of the composite collector, it was treated with ultrasound at a frequency of 20-80 kHz and a temperature of 20-40 °C for 10-30 min. The cavitation effect under the ultrasonic field induced the intercalation and local rearrangement of the hydrophobic chains of the surfactant, while simultaneously helping to instantly disperse hydrophobic fatty acid salts and alkyl hydroxamic acids into nano-sized droplets, achieving uniform mixing at the molecular level. Furthermore, under the ultrasonic field, the hydroxyl groups of alcohol ether glycosides, the glycosyl groups of rhamnolipids, and the carboxyl groups of fatty acid salts and the hydroxamic acid groups of alkyl hydroxamic acids more easily form dynamic, non-covalent "supramolecular assemblies" through hydrogen bonds and van der Waals forces. This in-situ constructed composite structure exhibits better stability and synergistic efficiency in the slurry compared to simple mechanical mixtures, thus making the composite collector more stable and homogeneous, and resulting in superior flotation efficiency.

[0020] Compared with the prior art, the advantages of the present invention are as follows: 1. The collector for rapid flotation recovery of ilmenite of the present invention is a compound of fatty acid salts, alkyl hydroxamic acids, alcohol ether glycosides and rhamnolipids with synergistic effects. It synergistically combines the strong collecting power of fatty acid salts, the good selectivity of hydroxamic acids, the excellent solubilizing / emulsifying properties / anti-calcium and magnesium ion interference / acid and alkali stability of alcohol ether glycosides, and the excellent foam control and collecting ability of rhamnolipids. The synergistic effect of each component effectively improves the flotation rate, recovery rate and grade of ilmenite.

[0021] 2. The preparation process of the collector of the present invention does not rely on complex conditions such as high temperature and high pressure. It can be completed by aqueous phase reaction and room temperature stirring. The process is simple and suitable for industrial scale-up production.

[0022] 3. The four components used in this invention are all low-toxicity or biodegradable surfactants, and the dosage is lower than that of traditional capture systems, which has good industrial application prospects and environmental advantages.

[0023] 4. The compound collector prepared by this invention is suitable for the flotation of high-concentration ilmenite in the concentration range of 20% to 50%. It can achieve desulfurization, roughing and cleaning under short process conditions, with fast flotation rate and energy-saving and efficient process.

[0024] 5. The collector of this invention exhibits good adaptability to ilmenite of different particle sizes (e.g., -600 mesh accounting for 50-65%) and medium to low grades (TiO2 content 15-20%), enabling efficient utilization of ultrafine raw ore. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 This is a flowchart illustrating the preparation process of the collector of the present invention.

[0027] Figure 2 This is a process flow diagram of the collector of the present invention in the flotation of ilmenite. Detailed Implementation

[0028] To facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments.

[0029] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0030] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0031] Example 1: A collector for rapid flotation recovery of ilmenite is mainly obtained by the reaction of the following components: fatty acid salts, alkyl hydroxyxamic acids, alcohol ether glycosides, and rhamnolipids; such as Figure 1 As shown, its preparation method includes the following steps: Step S1: Weigh 30 mol of sodium fatty acid (carbon chain length C12) and dissolve it in 200 mL of deionized water. Control the water temperature at 40 °C. Under stirring conditions, slowly add 10 mol of alkyl hydroxamic acid (C8) at a rate of 3 g / min and continue stirring for 30 min.

[0032] Step S2: Subsequently, 10 mol of alcohol ether glycoside AEG300 and 5 mol of rhamnolipid (Rha-C10) were added at a rate of 8 g / min and 1 g / min, respectively. After mixing, the mixture was ultrasonically treated at 80 kHz and 30 °C for 10 min. The mixture was then dried at 60 °C for 2 h to obtain the composite collector powder.

[0033] Using a certain ilmenite deposit in the Panzhihua area as raw material, its TiO2 content is 15%, and the content of -600 mesh particles accounts for 55%. The main titanium-containing mineral is ilmenite, and the gangue minerals are pyroxene and forsterite. Figure 2 As shown, the above-mentioned collector is used to enhance the rapid flotation recovery of ilmenite, including the following steps: (1) Desulfurization operation: Take a mineral sample into the flotation machine, the pulp concentration is 40%, the sulfuric acid dosage is 800g / t, the butyl xanthate dosage is 200g / t, the frother is 25g / t, the flotation time is 3min, and the desulfurized product and ilmenite flotation slurry are obtained.

[0034] (2) Roughing of ilmenite: Sulfuric acid, collector and frother are added to the ilmenite flotation slurry in sequence, with sulfuric acid at a dosage of 1600 g / t, collector at a dosage of 1200 g / t, and frother No. 2 oil at a dosage of 20 g / t. The flotation time is 2 min to obtain ilmenite rough concentrate and tailings.

[0035] (3) Ilmenite Concentration 1: The ilmenite rough concentrate is concentrating in two stages. The sulfuric acid dosage is 800 g / t in stage 1 and 400 g / t in stage 2. No collector is added in the concentrating stage, only a small amount of frother is added. The dosage of No. 2 oil in stage 1 is 20 g / t and in stage 2 is 10 g / t. The flotation time is 2 min respectively, to obtain the final ilmenite concentrate and middlings 1 and middlings 2 products.

[0036] Meanwhile, multiple control groups were set up (control groups 1-3 used MOH as the collector in the industrial flotation of ilmenite), namely control group 1-control group 4, wherein: Control group 1 used MOH as the collector, and its dosage and other reagent system were the same as in Example 1. The flotation time was also the same as in Example 1.

[0037] Control group 2 used MOH as the collector, and its dosage and other reagent system were the same as in Example 1. The roughing time for ilmenite was 3 min, the flotation time for the first stage of cleaning was 3 min, and the flotation time for the second stage of cleaning was 3 min.

[0038] Control group 3 used MOH as the collector, and its dosage and other reagent system were the same as in Example 1. The roughing time for ilmenite was 4 min, the flotation time for the first stage of cleaning was 4 min, and the flotation time for the second stage of cleaning was 4 min.

[0039] Control group 4: The collector was prepared according to the collector preparation process of Example 1, but no alcohol ether glycoside was added during the preparation process. Its dosage and other reagent system were the same as in Example 1, and the flotation time was the same as in Example 1.

[0040] Finally, the product was tested and analyzed, and the results are shown in Table 1: Table 1: Flotation Experiment Results of Example 1 and Control Group

[0041] As shown in Table 1, the collector in this embodiment has a good separation effect on fine-grained ilmenite with a -600 mesh content of 55% and a TiO2 grade of 15%. A qualified ilmenite concentrate product with a TiO2 grade of 47.52% and a recovery rate of 72.42% can be obtained by only one roughing and two cleaning processes. Comparison with control groups 1 to 3 shows that the flotation index of the collector in this embodiment is significantly better than that of the existing collector MOH. Furthermore, the existing collector requires more than 3 minutes of flotation time per stage to maintain a good recovery rate, while the collector in this embodiment only requires 2 minutes per stage. Therefore, the collector of this invention can save more than 1 / 3 of the flotation time, greatly improving flotation efficiency and achieving rapid flotation of ilmenite, while obtaining ilmenite concentrate with a TiO2 grade exceeding 47%. Simultaneously, comparison of the experimental results of Example 1 with control group 4 shows that the alcohol ether glycosides in the composite collector of this invention play an important role; their addition can enhance the collecting ability and selectivity of the composite collector, further contributing to improving the titanium concentrate grade and recovery rate.

[0042] Example 2: A collector for rapid flotation recovery of ilmenite is mainly obtained by the compounding reaction of the following components: fatty acid salts, alkyl hydroxamic acids, alcohol ether glycosides, and rhamnolipids; its preparation method includes the following steps: Step S1: Weigh 30 mol of sodium fatty acid (C10 carbon chain length) and dissolve it in 200 mL of deionized water. Control the water temperature at 20℃. Under stirring conditions, slowly add 15 mol of alkyl hydroxamic acid (C12) at a rate of 5 g / min and continue stirring for 20 min.

[0043] Step S2: Subsequently, 15 mol of alcohol ether glycoside AEG1511 and 7.5 mol of rhamnolipid (Rha-Rha-C10) were added at a rate of 5 g / min and 2 g / min, respectively. After mixing, the mixture was ultrasonically treated at 20 kHz and 40 °C for 30 min. The mixture was then dried at 40 °C for 1 h to obtain the composite collector powder.

[0044] Using ilmenite from a certain area in Huili as raw material, its TiO2 content is 20%, and the content of -600 mesh particles accounts for 50%. The main titanium-containing mineral is ilmenite, and the gangue mineral is ilmenite. Figure 2 As shown, the composite collector described in this invention is used to enhance the rapid flotation recovery of ilmenite, comprising the following steps: (1) Desulfurization operation: Take a mineral sample into the flotation machine, the pulp concentration is 20%, the sulfuric acid dosage is 800g / t, the butyl xanthate dosage is 200g / t, the frother is 25g / t, the flotation time is 3min, and the desulfurized product and ilmenite flotation slurry are obtained.

[0045] (2) Roughing of ilmenite: Sulfuric acid, collector and frother are added to the ilmenite flotation slurry in sequence, with sulfuric acid at a dosage of 1000 g / t, collector at a dosage of 1600 g / t, and frother No. 2 oil at a dosage of 30 g / t. The flotation time is 2 min to obtain ilmenite rough concentrate and tailings.

[0046] (3) Ilmenite Refinement 1: The ilmenite rough concentrate is refined in two stages. The sulfuric acid dosage is 500 g / t in the first stage and 250 g / t in the second stage. No collector is added in the refinement stage, only a small amount of frother is added. The dosage of No. 2 oil in the first stage is 15 g / t and the dosage of No. 2 oil in the second stage is 5 g / t. The flotation time is 2 min respectively, and the final ilmenite concentrate and middlings 1 and middlings 2 products are obtained.

[0047] Meanwhile, multiple control groups were set up (control groups 1-3 used MOH as the collector in the industrial flotation of ilmenite), namely control group 1-control group 4, wherein: Control group 1 used MOH as the collector, and its dosage and other reagent system were the same as in Example 2. The flotation time was the same as in Example 1.

[0048] Control group 2 used MOH as the collector, and its dosage and other reagent system were the same as in Example 2. The roughing time for ilmenite was 3 min, the first stage flotation time was 3 min, and the second stage flotation time was 3 min.

[0049] Control group 3 used MOH as the collector, and its dosage and other reagent system were the same as in Example 2. The roughing time for ilmenite was 4 min, the first stage flotation time was 4 min, and the second stage flotation time was 4 min.

[0050] Control group 4: The collector was prepared according to the collector preparation process of Example 2, but rhamnolipid was not added during the preparation process. Its dosage and other reagent system were the same as in Example 2, and the flotation time was the same as in Example 2.

[0051] Finally, the product was tested and analyzed, and the results are shown in Table 2: Table 2: Flotation Experiment Results of Example 2 and Control Group

[0052] As shown in Table 2, the composite collector described in this invention has a good separation effect on fine-grained ilmenite with a -600 mesh content of 50% and a TiO2 grade of 20%. A qualified ilmenite concentrate product with a TiO2 grade of 48.54% and a recovery rate of 80.72% can be obtained by only one roughing and two cleaning processes. Comparison with control groups 1 to 3 shows that the flotation performance of the composite collector described in this invention is significantly better than that of the existing collector MOH. Furthermore, the existing collector requires more than 3 minutes of flotation time per stage to maintain a good recovery rate, while the composite collector proposed in this invention requires only 2 minutes per stage. Therefore, the composite collector proposed in this invention can save more than 1 / 3 of the flotation time, greatly improving flotation efficiency and achieving rapid flotation of ilmenite, while obtaining ilmenite concentrate with a TiO2 grade exceeding 48%. Simultaneously, comparison of the experimental results of Example 2 with control group 4 shows that the rhamnose glycolipid component in the composite collector described in this invention can effectively improve the titanium concentrate yield, concentrate grade, and recovery rate.

[0053] Example 3: A collector for rapid flotation recovery of ilmenite is mainly obtained by the compounding reaction of the following components: fatty acid salts, alkyl hydroxamic acids, alcohol ether glycosides, and rhamnolipids; its preparation method includes the following steps: Step S1: Weigh 48 mol of sodium fatty acid (C18 carbon chain length) and dissolve it in 200 mL of deionized water. Control the water temperature at 50 °C. Under stirring conditions, slowly add 12 mol of alkyl hydroxamic acid (C6) at a rate of 1 g / min and continue stirring for 50 min.

[0054] Step S2: Subsequently, 10 mol of alcohol ether glycoside AEG1000 and 5 mol of rhamnolipid (Rha-C10-C10) were added at rates of 3 g / min and 1 g / min, respectively. After mixing, the mixture was ultrasonically treated at 60 kHz and 20 °C for 25 min. The mixture was then dried at 80 °C for 1 h to obtain the composite collector powder.

[0055] Using an ilmenite mine in Chengde, Hebei Province as raw material, its TiO2 content is 18%, and the content of -600 mesh particles accounts for 65%. The main titanium-containing mineral is ilmenite, and the gangue minerals are pyroxene and garnet, etc. Figure 2 As shown, the composite collector described in this invention is used to enhance the rapid flotation recovery of ilmenite, comprising the following steps: (1) Desulfurization operation: Take a mineral sample into the flotation machine, the pulp concentration is 50%, the sulfuric acid dosage is 800g / t, the butyl xanthate dosage is 200g / t, the frother is 25g / t, the flotation time is 3min, and the desulfurized product and ilmenite flotation slurry are obtained.

[0056] (2) Roughing of ilmenite: Sulfuric acid, collector and frother are added to the ilmenite flotation slurry in sequence, with sulfuric acid amount of 1400 g / t, collector amount of 1400 g / t, frother No. 2 oil amount of 20 g / t, and flotation time of 2 min to obtain ilmenite rough concentrate and tailings.

[0057] (3) Ilmenite Refinement 1: The ilmenite rough concentrate is refined in two stages. The sulfuric acid dosage is 700 g / t in the first stage and 350 g / t in the second stage. No collector is added in the refinement stage, only a small amount of frother is added. The dosage of No. 2 oil in the first stage is 10 g / t and the dosage of No. 2 oil in the second stage are 10 g / t. The flotation time is 2 min respectively, and the final ilmenite concentrate and middlings 1 and middlings 2 products are obtained.

[0058] Meanwhile, multiple control groups were set up (control groups 1-3 used MOH as the collector in the industrial flotation of ilmenite), namely control group 1 to control group 5, wherein: Control group 1 used MOH as the collector, and its dosage and other reagent system were the same as in Example 1. The flotation time was also the same as in Example 1.

[0059] Control group 2 used MOH as the collector, and its dosage and other reagent system were the same as in Example 1. The roughing time for ilmenite was 3 min, the flotation time for the first stage of cleaning was 3 min, and the flotation time for the second stage of cleaning was 3 min.

[0060] Control group 3 used MOH as the collector, and its dosage and other reagent system were the same as in Example 1. The roughing time for ilmenite was 4 min, the flotation time for the first stage of cleaning was 4 min, and the flotation time for the second stage of cleaning was 4 min.

[0061] Control group 4: The collector was prepared according to the collector preparation process of Example 3, but no alcohol ether glycoside was added during the preparation process. Its dosage and other reagent system were the same as in Example 3, and the flotation time was the same as in Example 3.

[0062] Control group 5: The collector was prepared according to the collector preparation process of Example 3, but the ultrasonic treatment was not used in the preparation process. Its dosage and other reagent system were the same as in Example 3, and the flotation time was the same as in Example 3.

[0063] Finally, the product was tested and analyzed, and the results are shown in Table 3: Table 3: Flotation Experiment Results of Example 3 and Control Group

[0064] As shown in Table 3, the composite collector described in this invention has a good separation effect on fine-grained ilmenite with a -600 mesh content of 65% and a TiO2 grade of 18%. A qualified ilmenite concentrate product with a TiO2 grade of 48.15% and a recovery rate of 76.88% can be obtained by only one roughing and two cleaning processes. Comparison with control groups 1 to 3 shows that the flotation performance of the composite collector described in this invention is significantly better than that of the existing collector MOH. Existing collectors require more than 3 minutes of flotation time per stage to maintain a good recovery rate, while the composite collector proposed in this invention only requires 2 minutes per stage. Therefore, the composite collector proposed in this invention can save more than 1 / 3 of the flotation time, greatly improving flotation efficiency and achieving rapid flotation of ilmenite, while obtaining ilmenite concentrate with a TiO2 grade exceeding 48%. Comparison of the experimental results of Example 3 with control group 4 shows that alcohol ether glycosides play an important role in the composite collector described in this invention. Their addition can enhance the collecting ability and selectivity of the composite collector, further contributing to improving the yield, grade, and recovery rate of titanium concentrate. Furthermore, comparison of the experimental results of Example 3 with control group 5 shows that ultrasonic treatment can further improve the activity of the composite collector described in this invention, thereby increasing the yield, grade, and recovery rate of titanium concentrate.

[0065] Example 4: Compared to Example 1, the sulfuric acid was replaced by a combined inhibitor consisting of small molecule alkanolamine 2 and sulfonated chitosan in a mass ratio of 5:1. The dosage of the combined inhibitor in the roughing stage (compared to the raw ore) was 600 g / t, the dosage in the cleaning stage 1 was 300 g / t, and the dosage in the cleaning stage 2 was 100 g / t. Other conditions remained unchanged.

[0066] The structural formula of small molecule alcoholamine 2 is as follows: .

[0067] Sulfonated chitosan is prepared by a nucleophilic addition reaction of 1,3-propanesulfonyl lactone and chitosan with a free amine. Specifically, it includes the following steps: [The text abruptly ends here, so the translation also ends here.] 5 Chitosan from Da was swollen in an appropriate amount of dimethylformamide, followed by the addition of 1,3-propanesulfonyl lactone. The mixture was stirred at 50°C for 10 hours. After the reaction was completed, unreacted substances were removed by repeated precipitation and washing with ethanol or ether. The mixture was then washed with deionized water until neutral and freeze-dried to obtain the final product.

[0068] In addition, control groups 1 and 2 are set up based on this embodiment, as follows: Control Group 1: Compared to Example 4, the inhibitor used was not sulfonated chitosan, but only small molecule alcoholamine 2, and the amount of sulfonated chitosan was replaced by small molecule alcoholamine 2. Other conditions remained unchanged.

[0069] Control group 2: Compared with Example 4, no alcohol ether glycosides were added to the compound collector used, and other conditions remained unchanged.

[0070] The experimental results of Example 4 and Control Groups 1-2 are shown in Table 4: Table 4: Flotation Experiment Results of Example 4 and Control Group

[0071] The results in Table 4 show that replacing sulfuric acid with a combined inhibitor composed of small molecule alkanolamines and sulfonated chitosan can achieve titanium selection indicators superior to those of the traditional sulfuric acid flotation system. The titanium concentrate yield, grade, and recovery rate are all improved to a certain extent. This can reduce the use of sulfuric acid and help solve many drawbacks of traditional acid flotation, such as increased collector dosage, pipe blockage, equipment corrosion, and acidic wastewater hazards. Specifically, the technical principle of the inhibitor of this invention is to achieve precise adsorption and superhydrophilic modification of gangue mineral surfaces through the synergistic effect of a two-component system of highly flexible long-chain sulfonated chitosan and small molecule alkanolamines, thereby significantly improving the flotation selectivity of useful minerals such as ilmenite: (1) Flexible long-chain polymer interface coverage and spatial shielding effect: preferably using a molecular weight of 2×10 5 -8×10 5 Da's chitosan, through a mild sulfonation modification process (40-60℃, 6-12h), maintains the integrity of its main chain and molecular flexibility. The resulting sulfonated chitosan has good long-chain extensibility and hydrophilicity, and can be adsorbed and spread on the surface of gangue minerals such as pyroxene and olivine to form a dense and stable hydrophilic polymer protective film. The steric hindrance and interfacial shielding effect of this film effectively isolate the collector from the contact between the active sites on the mineral surface, thus playing an interfacial passivation role. (2) Functional group specific adsorption and synergistic adsorption: The -SO3 introduced by sulfonated chitosan - The group can react with Ca exposed on the mineral surface 2+ / Mg 2+ The isocations undergo coordination adsorption, thus firmly adsorbing onto the gangue surface. Simultaneously, this invention uses small-molecule alkanolamines, whose amino and hydroxyl groups can react with the -SO3 groups on the chitosan molecular chain. - Groups such as -NH2 form multi-point hydrogen bonds and ion pairs, constructing a stable intermolecular complex network, making the macromolecular inhibition layer more compact and more resistant to desorption. (3) Intermolecular synergistic construction of superhydrophilic interface effect: The flexible long chain structure of sulfonated chitosan provides a continuous adsorption framework, and small molecule amines can quickly diffuse into its incompletely covered or surface defect areas, achieving complementary adsorption and cross-linking stability through multiple hydrogen bonds / coordination with the mineral surface or between chitosan chains. The synergistic effect of the two leads to the introduction of a large amount of -SO3 on the surface of gangue minerals. -Hydrophilic functional groups such as -NH2 and -OH significantly enhance the thickness and stability of the surface hydration film, forming an energy-uniform and strongly hydrophilic interface layer. Compared with the use of chitosan or sulfonated chitosan or small molecule amines alone, the synergistic effect of the two can significantly improve the structural stability and coverage integrity of the inhibition layer, enhance the wettability of gangue minerals and significantly reduce their floatability, thus achieving selective inhibition of gangue minerals.

[0072] Meanwhile, the relevant results further indicate that there is a synergistic effect between the collector component and the inhibitor component described in this invention, and their combined use can further improve the ilmenite separation index. When the component is missing, the flotation index will decrease significantly.

[0073] The synergistic effect of the collector and inhibitor in this invention is as follows: The collector is a compound of fatty acid salts, alkyl hydroxamic acids, alcohol ether glycosides, and rhamnolipids in a specific molar ratio, exhibiting strong collecting ability and dispersibility; while the inhibitor is a compound of small-molecule alkanolamines and sulfonated chitosan with a specific molecular weight range, capable of selectively inhibiting the flotation of gangue minerals. Both exhibit a significant synergistic effect during flotation: the polar groups in the collector efficiently bind to the active sites on the ilmenite surface, while the sulfonated chitosan in the inhibitor, through the synergistic effect of its sulfonic acid groups and alkanolamines, forms a hydrophilic adsorption layer on the gangue surface, effectively blocking the non-selective adsorption of the collector. To achieve better synergistic effects, the structural compatibility of each component is crucial. The alcohol ether glycosides and rhamnolipids in the collector can regulate interfacial behavior, enhancing the dispersibility of the collector and inhibitor in the pulp; the molecular weight of the chitosan in the inhibitor is controlled at 2 × 10⁻⁶. 5 -8×10 5 Within the specified molecular weight range, the sulfonated chitosan possesses both sufficient adsorption group density and moderate molecular chain flexibility, thereby maximizing the difference in adsorption selectivity on the surfaces of ilmenite and gangue. If the molecular weight of chitosan is too low (chain length too short), the steric hindrance of the inhibitor is insufficient, resulting in weak gangue inhibition and easy adsorption of the collector. When the molecular weight is too high, the chains become too entangled, and the steric hindrance is too great, leading to mineral particle dispersion and weakened collector adsorption, thus affecting the synergistic interfacial behavior with the collector.

Claims

1. A collector for rapid flotation recovery of ilmenite, characterized in that, It is mainly obtained by the reaction of the following raw materials: fatty acid salt, alkyl hydroxamic acid, alcohol ether glycoside and rhamnolipid; the molar ratio of the fatty acid salt and alkyl hydroxamic acid is (2-4):1; the molar ratio of the compound product of the fatty acid salt and alkyl hydroxamic acid, the alcohol ether glycoside and the rhamnolipid is (3-6):1:0.

5.

2. The collector according to claim 1, characterized in that, The fatty acid salt has the chemical formula R1COOM, where R1 is an alkyl group with C=10 to 18 and M is a metal cation Na. + Or K + .

3. The collector according to claim 1, characterized in that, The alkyl hydroxamic acid has the chemical formula R2CONHOH, where R2 is an alkyl group with C=6 to 12.

4. The collector according to claim 1, characterized in that, The alcohol ether glycoside is one or more of AEG050, AEG300, AEG1511, AEG1000, AEG2000, and AEG3000.

5. The collector according to claim 1, characterized in that, The rhamnolipid is a rhamnolipid with 1-2 glycolipid groups, and the general expression formula of the rhamnolipid is Rha-C10-C10, Rha-Rha-C10, Rha-C10, where Rha is a glycolipid functional group.

6. A method for preparing a collector as described in any one of claims 1-5, characterized in that, The process includes the following steps: dissolving the fatty acid salt in water, adding the alkyl hydroxamic acid under stirring conditions, reacting the reaction, adding the alcohol ether glycoside and rhamnolipid after the reaction, mixing the mixture and reacting it in an ultrasonic field, and then drying it to precipitate the collector.

7. The preparation method according to claim 6, characterized in that, The fatty acid salt is dissolved in water at a temperature of 20–50°C, the alkyl hydroxamic acid is added at a rate not exceeding 5 g / min, and the reaction time between the fatty acid salt and the alkyl hydroxamic acid is 20–50 min.

8. The preparation method according to claim 6, characterized in that, The addition rate of the alcohol ether glycoside shall not exceed 8 g / min, and the addition rate of the rhamnolipid shall not exceed 2 g / min.

9. The preparation method according to claim 6, characterized in that, The ultrasonic field has an ultrasonic frequency of 20-80kHz, a temperature of 20-40℃, and an ultrasonic treatment time of 10-30min.

10. The application of a collector as described in any one of claims 1-5 or a collector prepared by the method described in any one of claims 6-9, characterized in that, The collector is used for the flotation recovery of ilmenite in the presence of an inhibitor.

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