Kaolinite AL-O surface targeted chelating collector as well as preparation and application thereof

Abstract

The invention provides a kaolinite AL-O surface targeted chelating collector and preparation and application thereof, and relates to the technical field of chelating collectors, the kaolinite AL-O surface targeted chelating collector comprises the following components by weight: 30-50 parts of alkyl hydroxamic acid, 40-60 parts of kerosene, 10-30 parts of D-limonene, 2-8 parts of a biquaternary ammonium salt gemini surfactant, and 0.5-5 parts of 18-crown-6. A hydration film on the surface of kaolinite is destroyed by utilizing the strong charge density of the ionic liquid, precise targeted recognition of an Al-O surface is realized by matching with the electrostatic anchoring effect of the biquaternary ammonium salt gemini surfactant, and D-limonene is induced to generate molecular configuration fine adjustment under the assistance of ultraviolet light, so that Van der Waals' force and space interlocking among components are increased, and the sensitivity of the kaolinite is improved. The micellar structure is reinforced on the molecular level, the shear stability and permeation efficiency of the collecting agent in the complex hydraulic environment are improved, and efficient hydrophobization separation of the micro-fine particle kaolinite is achieved.

Description

Technical Field

[0001] This invention relates to the field of chelating collectors, and more particularly to a kaolinite AL-O surface-targeted chelating collector and its preparation and application. Background Technology

[0002] Chelating collectors mainly utilize specific coordinating functional groups in organic molecules (such as isohydroxamic acid groups, phosphonic acid groups, carboxylic acid groups, etc.) to undergo specific coordination reactions with the active sites of metal cations on the mineral surface, thereby forming stable insoluble hydrophobic chelates or adsorption layers on the mineral surface.

[0003] Current technology involves directly dissolving chelating agents in hydrocarbon oils. However, this method is susceptible to interference from high concentrations of unavoidable metal ions such as calcium and magnesium in the mineral slurry environment. This causes the active functional groups in the agent to be consumed by free ions in the solution before reaching the mineral surface, reducing the effective concentration and selectivity of the agent. Furthermore, due to the strong hydrophilic hydration film on the kaolinite surface, traditional non-polar hydrocarbon oil droplets struggle to overcome the barrier effect of the hydration layer, resulting in weak adsorption and binding of the agent on the surface of fine-grained minerals, making it prone to detachment under strong turbulent agitation. Single surfactant systems often fail to form stable micelle structures, frequently exhibiting stratification, precipitation, or degradation of active components during long-term storage or transportation, leading to fluctuations in agent performance. Therefore, improvements are needed. Summary of the Invention

[0004] The purpose of this invention is to address the shortcomings of existing technologies by proposing a kaolinite AL-O surface-targeted chelating collector and its preparation and application.

[0005] To achieve the above objectives, the present invention employs the following technical solution: a kaolinite AL-O surface-targeted chelating collector, wherein the kaolinite AL-O surface-targeted chelating collector comprises the following components in parts by weight: Alkyl isohydroxamic acid 30-50 parts, kerosene 40-60 parts, D-limonene 10-30 parts, bisquaternary ammonium salt gemini surfactant 2-8 parts, 18-crown-6 0.5-5 parts, bioglycolipid surfactant 2-10 parts, hydrophobic room temperature ionic liquid 1-6 parts.

[0006] Preferably, the alkyl hydroxamic acid is a C5-9 alkyl hydroxamic acid.

[0007] Preferably, the hydrophobic room temperature ionic liquid comprises 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, N-butylpyridine hexafluorophosphate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and tetrabutylphosphine bromide.

[0008] Preferably, the bio-glycolipid surfactant includes phycolipid, erythritol, subtilisin, and lichenin.

[0009] This invention also provides a method for preparing a kaolinite AL-O surface-targeted chelating collector, comprising the following steps: S1, Microwave pre-activation of ionic liquid: Hydrophobic room temperature ionic liquid is loaded into the reaction chamber of a microwave chemical synthesizer and heated by microwave to obtain a high temperature and high activity ionic liquid premix. S2, Cold Phase Mixing and Bioprotection: In a stirred reactor with a circulating cooling water jacket, cooling water at 5-15°C is introduced to maintain a low-temperature environment. The frame stirrer of the stirred reactor is turned on and the speed is set to 400-600 r / min. The formulated amounts of kerosene, D-limonene, bisquaternary ammonium salt gemini surfactant, and bioglycolipid surfactant are added sequentially to the reactor. The mixture is stirred for 10-20 min to form a uniform cold oil phase substrate. While maintaining the stirring state, the high-temperature and high-activity ionic liquid premix prepared in step S1 is injected into the cold oil phase substrate through a metering pump at a flow rate of 10-20 mL / min. The heat carried by the ionic liquid is dispersed by the heat sink effect of a large amount of cold oil phase. The mixture is stirred continuously for 15-25 min until the system temperature reaches equilibrium at 20-30°C, thus obtaining a multiphase bioprotection suspension mixture. S3, Construction of ultrasonic cavitation microemulsion: The multiphase biological protective suspension mixture is pumped into the flow cell of an ultrasonic disperser, and the ultrasonic generator is turned on to obtain a nanostructured chelated microemulsion system. S4, Photochemical structural reinforcement: The nanostructured chelated microemulsion system is transferred to a photochemical reactor equipped with an ultraviolet LED array for irradiation and stirring to obtain a photosensitive enhanced stable collector fluid. S5, Stabilization and Aging: The photosensitive enhanced stabilized collector fluid is transported through a pipeline to an aging tank for storage, thereby obtaining kaolinite AL-O surface-targeted chelating collector.

[0010] Preferably, step S1 specifically includes: A hydrophobic room-temperature ionic liquid is loaded into the reaction chamber of a microwave chemical synthesizer. The stirring rate of the microwave chemical synthesizer is set to 300-500 r / min. The microwave heating program is turned on, and the microwave emission power is controlled between 400-800 W. The hydrophobic room-temperature ionic liquid is heated to 60-80℃ and kept at a constant temperature. Alkyl isohydroxamic acid and 18-crown-6 are added to the reaction chamber in sequence. Microscopic hot spots are generated by utilizing the high absorption cross-section characteristics of the ionic liquid to microwaves. The irradiation treatment is continued for 5-10 min, which promotes the dissolution of solid powder in the ionic liquid medium and completes the pre-assembly between molecules and the activation of complexation sites. Microwave irradiation is stopped after the solution changes from turbid to clear and transparent, thus obtaining a high-temperature and highly active ionic liquid premix.

[0011] Preferably, step S3 specifically includes: The multiphase biological protective suspension mixture is pumped into the flow tank of an ultrasonic disperser. The ultrasonic generator is turned on, and the ultrasonic frequency is set to 20-28 kHz, with an ultrasonic power density of 50-80 W / cm³. 2 The ultrasonic amplitude transformer generates a cavitation effect at the top of the ultrasonic amplitude transformer. The high-pressure jet generated at the moment of cavitation bubble collapse breaks and shears the hydrophobic room temperature ionic liquid phase and the bio-glycolipid surfactant phase, forcing the hydrophobic room temperature ionic liquid to form a dispersed phase core, and the bio-glycolipids to be oriented at the interface to form a protective shell. At the same time, alkyl isohydroxamic acid is induced to anchor on the droplet surface. The material is circulated 3-5 times or the residence time of a single treatment is controlled at 20-40 minutes, so that the system changes from turbid to semi-transparent, thus obtaining a nanostructured chelated microemulsion system.

[0012] Preferably, step S4 specifically includes: The nanostructured chelated microemulsion system was transferred to a photochemical reactor equipped with a UV LED array. The stirrer was turned on, and the rotation speed was set to 80-150 r / min to maintain stable liquid flow. A UV LED light source with a wavelength of 250-370 nm was turned on, and the light radiation intensity was adjusted to 30-60 mW / cm². 2 The microemulsion system was continuously irradiated at room temperature for 30-60 minutes. The ultraviolet light energy was used to excite the double bonds of D-limonene molecules in the microemulsion to undergo configurational fine-tuning and isomerization, which enhanced the van der Waals forces and spatial interlocking between the ionic liquid core and the gemini surfactant layer, and finally obtained a photosensitive enhanced stable collector fluid.

[0013] Preferably, step S5 specifically includes: The photosensitive enhanced stabilized collector fluid was transported to an aging tank through a pipeline and placed in the dark at an ambient temperature controlled at 18-25°C for 12-24 hours. This allowed the interfacial film structure of the microemulsion to eliminate internal stress and reach the lowest thermodynamic energy state under Brownian motion. During this period, samples were taken from the bottom of the tank every 2-4 hours to detect the viscosity change rate and stratification. After confirming that there was no precipitation, no phase separation, and the system transmittance was stable, mechanical impurities were removed by filtering through a 200-400 mesh filter to obtain the kaolinite AL-O surface-targeted chelating collector.

[0014] This invention also provides an application of a kaolinite AL-O surface-targeted chelating collector, which is used as a collector for the separation of kaolinite in coal slurry water.

[0015] Compared to existing technologies, this invention utilizes the high microwave absorption cross-section of a hydrophobic room-temperature ionic liquid to generate localized high thermal energy at the microscale. This directionally activates the chelating active sites of alkyl isohydroxamic acid and promotes the pre-formation of a stable complex structure with 18-crown 6, effectively shielding the interference of calcium and magnesium ions in the slurry. By injecting the high-temperature ionic liquid phase into a cold oil-phase substrate containing D-limonene and bio-glycolipid surfactants, the heat is dispersed using the heat sink effect. While retaining the surface activity of the biological components, the high-viscosity ionic liquid and hydrophilic glycolipids are sheared and recombined using the high-energy ultrasonic cavitation effect. A nanoscale microemulsion system with an ionic liquid core, a bio-glycolipid shell, and isohydroxamic acid for directional anchoring was constructed. This system utilizes the strong charge density of the ionic liquid to disrupt the hydration film on the surface of kaolinite, combined with the electrostatic anchoring effect of the bisquaternary ammonium salt gemini surfactant, to achieve precise targeted recognition of the Al-O facet. In addition, ultraviolet light induces molecular configuration fine-tuning of D-limonene, increasing van der Waals forces and spatial interlocking between components, thereby strengthening the micelle structure at the molecular level and improving the shear stability and permeation efficiency of the collector under complex hydraulic environments, achieving efficient hydrophobic separation of fine-grained kaolinite.

[0016] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0017] 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 only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 The present invention provides a method for preparing a kaolinite AL-O surface-targeted chelating collector, and the preparation steps are shown in the figure. Detailed Implementation

[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Example 1: A kaolinite AL-O surface-targeted chelating collector, comprising the following components by weight: 30 parts alkyl isohydroxamic acid, 40 parts kerosene, 10 parts D-limonene, 2 parts bisquaternary ammonium salt gemini surfactant, 0.5 parts 18-crown-6, 2 parts bioglycolipid surfactant, and 1 part hydrophobic room temperature ionic liquid.

[0021] Alkyl isohydroxamic acids are C5-9 alkyl hydroxamic acids.

[0022] Hydrophobic room temperature ionic liquids include 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, N-butylpyridine hexafluorophosphate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and tetrabutylphosphine bromide.

[0023] Bioactive glycolipid surfactants include phycolipids, erythritol, subtilisin, and lichenin.

[0024] This embodiment provides a method for preparing a kaolinite AL-O surface-targeted chelating collector, comprising the following steps: S1, Microwave pre-activation of ionic liquid: Hydrophobic room temperature ionic liquid is loaded into the reaction chamber of a microwave chemical synthesizer and heated by microwave to obtain a high temperature and high activity ionic liquid premix. S2, Cold Phase Mixing and Bioprotection: In a stirred reactor with a circulating cooling water jacket, 5°C cooling water is introduced to maintain a low-temperature environment. The frame stirrer of the stirred reactor is turned on and the speed is set to 400 r / min. The formulated amounts of kerosene, D-limonene, bisquaternary ammonium salt gemini surfactant, and bioglycolipid surfactant are added to the reactor in sequence. The mixture is stirred for 10 min to form a uniform cold oil phase substrate. While maintaining the stirring state, the high-temperature and high-activity ionic liquid premix prepared in step S1 is injected into the cold oil phase substrate through a metering pump at a flow rate of 10 mL / min. The heat carried by the ionic liquid is dispersed by the heat sink effect of a large amount of cold oil phase. The mixture is stirred for 15 min until the system temperature reaches equilibrium at 20°C, thus obtaining a multiphase bioprotection suspension mixture. S3, Construction of ultrasonic cavitation microemulsion: A multiphase biological protective suspension mixture is pumped into the flow cell of an ultrasonic disperser, and the ultrasonic generator is turned on to obtain a nanostructured chelated microemulsion system. S4, Photochemical Structure Strengthening: The nanostructured chelated microemulsion system is transferred to a photochemical reactor equipped with an ultraviolet LED array for irradiation and stirring to obtain a photosensitive enhanced stable collector fluid; S5, Stabilization and Aging: The photosensitive enhanced stabilized collector fluid is transported through pipelines to an aging tank for storage, resulting in kaolinite AL-O surface-targeted chelating collector.

[0025] Step S1 is as follows: A hydrophobic room-temperature ionic liquid was loaded into the reaction chamber of a microwave chemical synthesizer. The stirring rate of the microwave chemical synthesizer was set to 300 r / min, the microwave heating program was turned on, and the microwave emission power was controlled to be between 400 W. The hydrophobic room-temperature ionic liquid was heated to 60 °C and kept at a constant temperature. Alkyl isohydroxamic acid and 18-crown-6 were added to the reaction chamber in sequence. Microscopic hot spots were generated by utilizing the high absorption cross-section characteristics of the ionic liquid to microwaves. The irradiation treatment was continued for 5 min to promote the dissolution of the solid powder in the ionic liquid medium and to complete the pre-assembly between molecules and the activation of complexation sites. Microwave irradiation was stopped after the solution changed from turbid to clear and transparent, thus obtaining a high-temperature and high-activity ionic liquid premix.

[0026] The specific steps in S3 are as follows: The multiphase biological protective suspension was pumped into the flow tank of an ultrasonic disperser. The ultrasonic generator was turned on, and the ultrasonic frequency was set to 20 kHz and the ultrasonic power density to 50 W / cm³. 2 The ultrasonic amplitude transformer generates a cavitation effect at the top of the ultrasonic amplitude transformer. The high-pressure jet generated at the moment of cavitation bubble collapse breaks and shears the hydrophobic room temperature ionic liquid phase and the bio-glycolipid surfactant phase, forcing the hydrophobic room temperature ionic liquid to form a dispersed phase core, and the bio-glycolipids to be oriented at the interface to form a protective shell. At the same time, alkyl isohydroxamic acid is induced to anchor on the droplet surface. The material is circulated 3 times or the residence time is controlled at 20 minutes for a single cycle, so that the system changes from turbid to semi-transparent, thus obtaining a nanostructured chelated microemulsion system.

[0027] The specific steps in S4 are as follows: The nanostructured chelated microemulsion system was transferred to a photochemical reactor equipped with a UV LED array. The stirrer was turned on and the rotation speed was set to 80 r / min to maintain stable liquid flow. A 250 nm UV LED light source was activated, and the light radiation intensity was adjusted to 30 mW / cm². 2 The microemulsion system was continuously irradiated at room temperature for 30 min. The ultraviolet light energy was used to excite the double bonds of D-limonene molecules in the microemulsion to undergo configurational fine-tuning and isomerization, which enhanced the van der Waals forces and spatial interlocking between the ionic liquid core and the gemini surfactant layer, and finally obtained a photosensitive enhanced stable collector fluid.

[0028] The S5 steps are as follows: The photosensitive enhanced stabilized collector fluid was transported to an aging tank through a pipeline and placed in a dark environment at a controlled temperature of 18°C ​​for 12 hours. This allowed the interfacial film structure of the microemulsion to eliminate internal stress and reach the lowest thermodynamic energy state under Brownian motion. During this period, samples were taken from the bottom of the tank every 2 hours to detect the viscosity change rate and stratification. After confirming that there was no precipitation, no phase separation, and the system transmittance was stable, mechanical impurities were removed by filtering through a 200-mesh filter, thus obtaining the kaolinite AL-O surface-targeted chelating collector.

[0029] Example 2: A kaolinite AL-O surface-targeted chelating collector, comprising the following components by weight: 50 parts of alkyl isohydroxamic acid, 60 parts of kerosene, 30 parts of D-limonene, 8 parts of bisquaternary ammonium salt gemini surfactant, 5 parts of 18-crown-6, 10 parts of bioglycolipid surfactant, and 6 parts of hydrophobic room temperature ionic liquid.

[0030] Alkyl isohydroxamic acids are C5-9 alkyl hydroxamic acids.

[0031] Hydrophobic room temperature ionic liquids include 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, N-butylpyridine hexafluorophosphate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and tetrabutylphosphine bromide.

[0032] Bioactive glycolipid surfactants include phycolipids, erythritol, subtilisin, and lichenin.

[0033] This embodiment provides a method for preparing a kaolinite AL-O surface-targeted chelating collector, comprising the following steps: S1, Microwave pre-activation of ionic liquid: Hydrophobic room temperature ionic liquid is loaded into the reaction chamber of a microwave chemical synthesizer and heated by microwave to obtain a high temperature and high activity ionic liquid premix. S2, Cold Phase Mixing and Bioprotection: In a stirred reactor with a circulating cooling water jacket, 15°C cooling water is introduced to maintain a low-temperature environment. The frame stirrer of the stirred reactor is turned on and the speed is set to 600 r / min. The formulated amounts of kerosene, D-limonene, bisquaternary ammonium salt gemini surfactant, and bioglycolipid surfactant are added to the reactor in sequence. The mixture is stirred for 20 min to form a uniform cold oil phase substrate. While maintaining the stirring state, the high-temperature and high-activity ionic liquid premix prepared in step S1 is injected into the cold oil phase substrate through a metering pump at a flow rate of 20 mL / min. The heat carried by the ionic liquid is dispersed by the heat sink effect of a large amount of cold oil phase. The mixture is stirred for 25 min until the system temperature reaches equilibrium at 30°C, thus obtaining a multiphase bioprotection suspension mixture. S3, Construction of ultrasonic cavitation microemulsion: A multiphase biological protective suspension mixture is pumped into the flow cell of an ultrasonic disperser, and the ultrasonic generator is turned on to obtain a nanostructured chelated microemulsion system. S4, Photochemical Structure Strengthening: The nanostructured chelated microemulsion system is transferred to a photochemical reactor equipped with an ultraviolet LED array for irradiation and stirring to obtain a photosensitive enhanced stable collector fluid; S5, Stabilization and Aging: The photosensitive enhanced stabilized collector fluid is transported through pipelines to an aging tank for storage, resulting in kaolinite AL-O surface-targeted chelating collector.

[0034] Step S1 is as follows: A hydrophobic room-temperature ionic liquid was loaded into the reaction chamber of a microwave chemical synthesizer. The stirring rate of the microwave chemical synthesizer was set to 500 r / min, the microwave heating program was turned on, and the microwave emission power was controlled at 4800 W. The hydrophobic room-temperature ionic liquid was heated to 80°C and kept at a constant temperature. Alkyl isohydroxamic acid and 18-crown-6 were added to the reaction chamber in sequence. Microscopic hot spots were generated by utilizing the high absorption cross-section characteristics of the ionic liquid to microwaves. The irradiation treatment was carried out for 10 min to promote the dissolution of the solid powder in the ionic liquid medium and complete the pre-assembly between molecules and the activation of complexation sites. Microwave irradiation was stopped after the solution changed from turbid to clear and transparent, thus obtaining a high-temperature and high-activity ionic liquid premix.

[0035] The specific steps in S3 are as follows: The multiphase biological protective suspension was pumped into the flow tank of an ultrasonic disperser. The ultrasonic generator was turned on, and the ultrasonic frequency was set to 28 kHz and the ultrasonic power density to 80 W / cm³. 2 The ultrasonic amplitude transformer generates a cavitation effect at the top of the ultrasonic amplitude transformer. The high-pressure jet generated at the moment of cavitation bubble collapse breaks and shears the hydrophobic room temperature ionic liquid phase and the bio-glycolipid surfactant phase, forcing the hydrophobic room temperature ionic liquid to form a dispersed phase core, and the bio-glycolipids to be oriented at the interface to form a protective shell. At the same time, alkyl isohydroxamic acid is induced to anchor on the droplet surface. The material is circulated 5 times or the residence time is controlled at 40 minutes for a single cycle, so that the system changes from turbid to semi-transparent, thus obtaining a nanostructured chelated microemulsion system.

[0036] The specific steps in S4 are as follows: The nanostructured chelated microemulsion system was transferred to a photochemical reactor equipped with a UV LED array. The stirrer was turned on and the rotation speed was set to 150 r / min to maintain stable liquid flow. A 370 nm UV LED light source was activated, and the light radiation intensity was adjusted to 60 mW / cm². 2The microemulsion system was continuously irradiated at room temperature for 60 min. The ultraviolet light energy was used to excite the double bonds of D-limonene molecules in the microemulsion to undergo configurational fine-tuning and isomerization, which enhanced the van der Waals forces and spatial interlocking between the ionic liquid core and the gemini surfactant layer, and finally obtained a photosensitive enhanced stable collector fluid.

[0037] The S5 steps are as follows: The photosensitive enhanced stabilized collector fluid was transported to an aging tank through a pipeline and placed in a dark environment at a controlled temperature of 25°C for 24 hours. This allowed the interfacial film structure of the microemulsion to eliminate internal stress and reach the lowest thermodynamic energy state under Brownian motion. During this period, samples were taken from the bottom of the tank every 4 hours to detect the viscosity change rate and stratification. After confirming that there was no precipitation, no phase separation, and the system transmittance was stable, mechanical impurities were removed by filtering through a 400-mesh filter, thus obtaining the kaolinite AL-O surface-targeted chelating collector.

[0038] Experimental methods: Single mineral flotation recovery determination method: This experiment used an XFG hanging-tank flotation machine for micro-flotation experiments to determine the percentage of kaolinite mineral recovered during flotation under a specific reagent regime. First, the raw ore was crushed by a jaw crusher, then wet-ground using a ceramic ball mill, and sieved using a standard test sieve. Samples with a particle size of -0.074 mm were selected as flotation feed and dried in a vacuum drying oven at 60°C for later use. For each experiment, 2.0 g of the dried ore sample was weighed and placed in the flotation tank, along with 30 ml of deionized water. The stirring speed was adjusted to 1800 rpm, and the slurry was stirred for 3 minutes to ensure sufficient dispersion and a fresh surface of the mineral particles. Subsequently, the pH of the slurry was precisely adjusted to 8.0 using dilute hydrochloric acid or sodium hydroxide solution. The adjustment process required real-time monitoring with a precision pH meter, followed by stable stirring for 2 minutes. Next, a predetermined dose of collector (comparative or example sample) was added using a micro-syringe, and the slurry was stirred for 3 minutes to ensure the reagent molecules were fully dispersed in the slurry and adsorbed onto the mineral surface. Then, a frother (such as 2-octanol) was added and stirred for 1 minute. The aeration switch was turned on, and the aeration rate was controlled at 0.1 cubic meters per hour. Manual frothing was performed for 5 minutes, maintaining consistent scraping depth and uniform frothing frequency throughout the process. After flotation, the froth product (concentrate) and the product in the tank (tailings) were filtered, dried to constant weight, and weighed using a 0.01% electronic balance. The final kaolinite recovery rate was calculated as follows: the dry weight of the concentrate was divided by the sum of the dry weights of the concentrate and tailings, and the quotient was multiplied by 100% to obtain the recovery rate under those conditions.

[0039] Contact angle measurement experimental method: This experiment used a JY-82C video optical contact angle meter to measure the change in wettability of the kaolinite surface before and after treatment with the collector using the seat drop method, in order to characterize the hydrophobic modification ability of the collector. First, high-purity kaolinite samples were selected and cut into 1 cm square blocks using a diamond cutter. Then, an automatic polishing machine was used to successively polish the blocks with 400, 800, 1500, and 2000 grit silicon carbide sandpaper. Fine polishing with alumina polishing liquid was then applied to a polishing cloth until the mineral surface achieved a bright mirror finish with no obvious scratches under a microscope. The prepared polished sheets were placed in an ultrasonic cleaner and sequentially cleaned with ethanol and deionized water to remove surface oil and impurities, and then dried in a low-temperature vacuum drying oven. Next, the optical sheet was immersed in a prepared 50 mg / L sample collector solution and treated for 30 minutes at 25°C and 120 rpm in a constant-temperature shaker. After removal, the surface was gently rinsed with deionized water to remove unadsorbed reagent, dried with high-purity nitrogen, and placed on the stage of the measuring instrument. The measurement software was started, and a 2 μL droplet of deionized water was added to the mineral surface through a micro-syringe. After the droplet morphology stabilized (approximately 5 seconds), an image of the droplet was captured using a CCD camera. The droplet profile was fitted and analyzed using the tangent method or circle fitting method in the software, and the angle value at the liquid-gas-solid three-phase interface was read. Each sample required at least 5 measurements at different locations. After discarding the maximum and minimum values, the arithmetic mean was taken as the final contact angle data. The larger the value, the stronger the hydrophobicity of the mineral surface after reagent modification.

[0040] Determination of resistance to calcium ion interference and reagent stability: This experiment consists of two parts, which quantitatively evaluate the chemical resistance to interference and physical storage stability of the reagents. The first part is a calcium ion interference resistance test. Based on the aforementioned flotation recovery determination procedure, a high-hardness simulated mineral slurry containing 500 mg / L calcium chloride was prepared. Under the same pH value and reagent dosage, flotation experiments were conducted using deionized water and high-hardness water, respectively, and the concentrate recovery rates under the two water quality conditions were recorded. The calcium ion interference resistance (recovery rate decay value) was calculated by subtracting the recovery rate under high-hardness water conditions from the recovery rate under deionized water conditions; the absolute value of the difference is the decay value. The smaller this value, the less the chelating groups in the reagent are affected by the competitive adsorption of calcium ions. The second part is a reagent centrifugal stability test. 20 mL of the collector sample was injected into a dedicated stoppered graduated centrifuge tube, and the initial liquid level was recorded. The centrifuge tube was symmetrically placed in the rotor of a high-speed refrigerated centrifuge, and the centrifugation speed was set to 3000 rpm for 30 minutes, with the temperature controlled at 25 degrees Celsius. After centrifugation, remove the test tube and observe for oil-water separation, bottom sedimentation, or top oil separation. Read the scale at the separation interface and calculate the separation volume. The method for calculating the separation rate of the reagent is as follows: divide the volume of the separated clear liquid or oil phase by the total sample volume before centrifugation, and then multiply by 100%. This index is used to simulate the stability of the reagent under long-term gravity settling or transportation vibrations; the closer the value is to zero, the more robust the microemulsion structure.

[0041] Experiments were conducted on the finished materials prepared in Examples 1-2, where Comparative Example 1 used a chelating collector prepared according to Chinese Invention Publication No. CN105880034A. The experimental results are as follows: Table 1 Performance Test Data As can be seen from Table 1, Examples 1-2 mainly benefit from their unique component synergy and innovative preparation process. The combination of hydrophobic room-temperature ionic liquid and microwave pre-activation process fully activates the chelating activity of alkyl isohydroxamic acid by utilizing the "micro-hot spot" effect, and pre-assembles it with 18-crown-6. This allows Examples 1-2 to be prepared in environments containing a large amount of Ca. 2 The ⁺-type ion maintained extremely low recovery rate decay (only 1.8-2.3%) in simulated hard water (calcium resistance test), demonstrating that the crown ether effectively shielded interfering ions and ensured that isohydroxamic acid could specifically attack the Al-O facet of kaolinite.

[0042] The "ionic liquid core-bioglycolipid shell" nanoemulsion structure constructed by the bisquaternary ammonium salt gemini surfactant and bioglycolipid under ultrasonic cavitation improves the spreading efficiency and contact angle of the agent on the mineral surface (increased to over 80°), which is impossible to achieve with traditional mechanically mixed agents (Comparative Example 1).

[0043] The photochemical consolidation of D-limonene under ultraviolet light is equivalent to locking the micelle structure at the molecular level, resulting in almost no stratification (stratification rate <0.5%) during high-speed centrifugation at 3000 rpm in Examples 1-2. This completely solves the problems of easy stratification and poor stability of traditional agents, ensuring consistent efficacy in industrial applications. These characteristics work together to achieve efficient and targeted harvesting of fine-grained kaolinite.

Claims

1. A kaolinite AL-O surface-targeted chelating collector, characterized in that, The kaolinite AL-O surface-targeted chelating collector comprises the following components in parts by weight: Alkyl isohydroxamic acid 30-50 parts, kerosene 40-60 parts, D-limonene 10-30 parts, bisquaternary ammonium salt gemini surfactant 2-8 parts, 18-crown-6 0.5-5 parts, bioglycolipid surfactant 2-10 parts, hydrophobic room temperature ionic liquid 1-6 parts.

2. The kaolinite AL-O surface-targeted chelating collector according to claim 1, characterized in that: The alkyl isohydroxamic acid is a C5-9 alkylhydroxamic acid.

3. The kaolinite AL-O surface-targeted chelating collector according to claim 1, characterized in that: The hydrophobic room temperature ionic liquid includes 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, N-butylpyridine hexafluorophosphate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, and tetrabutylphosphine bromide.

4. The kaolinite AL-O surface-targeted chelating collector according to claim 1, characterized in that: The bio-glycolipid surfactants include trehalose, erythritol, subtilisin, and lichenin.

5. A method for preparing a kaolinite AL-O surface-targeted chelating collector, characterized in that, Includes the following steps: S1, Microwave pre-activation of ionic liquid: Hydrophobic room temperature ionic liquid is loaded into the reaction chamber of a microwave chemical synthesizer and heated by microwave to obtain a high temperature and high activity ionic liquid premix. S2, Cold Phase Mixing and Bioprotection: In a stirred reactor with a circulating cooling water jacket, cooling water at 5-15°C is introduced to maintain a low-temperature environment. The frame stirrer of the stirred reactor is turned on and the speed is set to 400-600 r / min. The formulated amounts of kerosene, D-limonene, bisquaternary ammonium salt gemini surfactant, and bioglycolipid surfactant are added sequentially to the reactor. The mixture is stirred for 10-20 min to form a uniform cold oil phase substrate. While maintaining the stirring state, the high-temperature and high-activity ionic liquid premix prepared in step S1 is injected into the cold oil phase substrate through a metering pump at a flow rate of 10-20 mL / min. The heat carried by the ionic liquid is dispersed by the heat sink effect of a large amount of cold oil phase. The mixture is stirred continuously for 15-25 min until the system temperature reaches equilibrium at 20-30°C, thus obtaining a multiphase bioprotection suspension mixture. S3, Construction of ultrasonic cavitation microemulsion: The multiphase biological protective suspension mixture is pumped into the flow cell of an ultrasonic disperser, and the ultrasonic generator is turned on to obtain a nanostructured chelated microemulsion system. S4, Photochemical structural reinforcement: The nanostructured chelated microemulsion system is transferred to a photochemical reactor equipped with an ultraviolet LED array for irradiation and stirring to obtain a photosensitive enhanced stable collector fluid. S5, Stabilization and Aging: The photosensitive enhanced stabilized collector fluid is transported through a pipeline to an aging tank for storage, thereby obtaining kaolinite AL-O surface-targeted chelating collector.

6. The preparation method of the kaolinite AL-O surface-targeted chelating collector according to claim 5, characterized in that: The specific steps in S1 are as follows: A hydrophobic room-temperature ionic liquid is loaded into the reaction chamber of a microwave chemical synthesizer. The stirring rate of the microwave chemical synthesizer is set to 300-500 r / min. The microwave heating program is turned on, and the microwave emission power is controlled between 400-800 W. The hydrophobic room-temperature ionic liquid is heated to 60-80℃ and kept at a constant temperature. Alkyl isohydroxamic acid and 18-crown-6 are added to the reaction chamber in sequence. Microscopic hot spots are generated by utilizing the high absorption cross-section characteristics of the ionic liquid to microwaves. The irradiation treatment is continued for 5-10 min, which promotes the dissolution of solid powder in the ionic liquid medium and completes the pre-assembly between molecules and the activation of complexation sites. Microwave irradiation is stopped after the solution changes from turbid to clear and transparent, thus obtaining a high-temperature and highly active ionic liquid premix.

7. The preparation method of the kaolinite AL-O surface-targeted chelating collector according to claim 5, characterized in that: The specific steps in S3 are as follows: The multiphase biological protective suspension mixture is pumped into the flow tank of an ultrasonic disperser. The ultrasonic generator is turned on, and the ultrasonic frequency is set to 20-28 kHz, with an ultrasonic power density of 50-80 W / cm³. 2 The ultrasonic amplitude transformer generates a cavitation effect at the top of the ultrasonic amplitude transformer. The high-pressure jet generated at the moment of cavitation bubble collapse breaks and shears the hydrophobic room temperature ionic liquid phase and the bio-glycolipid surfactant phase, forcing the hydrophobic room temperature ionic liquid to form a dispersed phase core, and the bio-glycolipids to be oriented at the interface to form a protective shell. At the same time, alkyl isohydroxamic acid is induced to anchor on the droplet surface. The material is circulated 3-5 times or the residence time of a single treatment is controlled at 20-40 minutes, so that the system changes from turbid to semi-transparent, thus obtaining a nanostructured chelated microemulsion system.

8. The preparation method of the kaolinite AL-O surface-targeted chelating collector according to claim 5, characterized in that: The S4 step is specifically as follows: The nanostructured chelated microemulsion system was transferred to a photochemical reactor equipped with an ultraviolet LED array. The stirrer was turned on, and the rotation speed was set to 80-150 r / min to maintain stable liquid flow. An ultraviolet LED light source with a wavelength of 250-370 nm was turned on, and the light radiation intensity was adjusted to 30-60 mW / cm². 2 The microemulsion system was continuously irradiated at room temperature for 30-60 minutes. The ultraviolet light energy was used to excite the double bonds of D-limonene molecules in the microemulsion to undergo configurational fine-tuning and isomerization, which enhanced the van der Waals forces and spatial interlocking between the ionic liquid core and the gemini surfactant layer, and finally obtained a photosensitive enhanced stable collector fluid.

9. The preparation method of the kaolinite AL-O surface-targeted chelating collector according to claim 5, characterized in that: The specific steps in S5 are as follows: The photosensitive enhanced stabilized collector fluid was transported to an aging tank through a pipeline and placed in the dark at an ambient temperature controlled at 18-25°C for 12-24 hours. This allowed the interfacial film structure of the microemulsion to eliminate internal stress and reach the lowest thermodynamic energy state under Brownian motion. During this period, samples were taken from the bottom of the tank every 2-4 hours to detect the viscosity change rate and stratification. After confirming that there was no precipitation, no phase separation, and the system transmittance was stable, mechanical impurities were removed by filtering through a 200-400 mesh filter to obtain the kaolinite AL-O surface-targeted chelating collector.

10. The application of a kaolinite AL-O surface-targeted chelating collector, characterized in that: It was used as a collector in the separation of kaolinite from coal slurry water.

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