Titanium-based particle adsorbent and preparation method thereof

Abstract

The present invention relates to a titanium-based particle adsorbent and a preparation method thereof, and relates to the technical field of titanium-based particle adsorbents. The preparation method of the titanium-based particle adsorbent comprises the following steps: obtaining a lithium metatitanate precursor; adding the lithium metatitanate precursor, an adhesive forming agent, and a pore-forming agent to a first solvent and stirring and mixing them to obtain a first mixture; placing the first mixture in a microwave-ultrasonic composite field for microwave-ultrasonic synergistic treatment to obtain a second mixture; granulating the second mixture, and then acidifying, filtering, and drying it to obtain the titanium-based particle adsorbent. Based on the existing titanium-based particle adsorbent preparation process, the present invention utilizes the synergistic effect of the microwave-ultrasonic composite field to significantly improve the stability of the obtained titanium-based particle adsorbent, so that it has excellent anti-dissolution performance and meets the requirements of multiple recycling in practical applications.

Description

Technical Field

[0001] The present invention relates to the technical field of titanium-based particle adsorbents, and in particular to a titanium-based particle adsorbent and a preparation method thereof. Background Art

[0002] Amidst the global energy transition and the rapid development of new energy industries, demand for lithium, a key raw material for lithium-ion batteries, has exploded. Salt lake brine, a key source of lithium, boasts large reserves and relatively low mining costs. Therefore, efficient lithium extraction from salt lake brine has become a research hotspot.

[0003] Among the technologies for extracting lithium from salt lake brines, adsorption methods are highly favored due to their simplicity, ease of operation, and environmental friendliness. Titanium-based particulate adsorbents, with their excellent chemical stability, high adsorption capacity, and superior ion selectivity, have shown great potential for lithium extraction from salt lake brines.

[0004] However, existing titanium-based particle adsorbents still face several challenges in practical applications, particularly high dissolution rates. Salt lake brine has a complex composition and contains a variety of corrosive ions and impurities. These ions and impurities can easily corrode the adsorbent upon contact, causing structural damage and performance degradation. Consequently, existing titanium-based particle adsorbents often fail to meet the demands of multiple recycling in practical applications, increasing production costs and limiting their widespread application in lithium extraction from salt lake brine.

[0005] Therefore, granulation technology is particularly important in view of the challenges faced by titanium-based particulate adsorbents in industrial application scenarios. The granulation process can convert the original powder material into particles with a certain shape and particle size, thereby significantly improving the material's handling performance and operational convenience. Under industrial equipment conditions, powder materials often have problems such as poor fluidity, easy flying, and difficulty in accurately controlling the amount of feed. These problems not only affect production efficiency, but may also pose a threat to workers' health. Through granulation, these problems can be effectively solved, the bulk density and fluidity of the material can be improved, dust pollution can be reduced, and it is convenient for storage, transportation and processing, thereby optimizing the entire production process.

[0006] For titanium-based granular adsorbents, granulation technology not only improves their physical properties and enhances their stability and durability in industrial applications, but also helps improve their resistance to dissolution and extend their service life, thereby reducing production costs and improving the overall economic benefits of lithium extraction from salt lake brine. Therefore, the development of advanced granulation technology suitable for titanium-based granular adsorbents is of great significance for promoting the industrialization of lithium extraction from salt lake brine and achieving the sustainable development and utilization of lithium resources. Summary of the Invention

[0007] In order to solve the above problems, the present invention provides a titanium-based particle adsorbent and a preparation method thereof.

[0008] In a first aspect, the present invention provides a method for preparing a titanium-based granular adsorbent, the method comprising the following steps:

[0009] Obtaining a lithium metatitanate precursor;

[0010] Adding the lithium metatitanate precursor, the adhesive forming agent and the pore-forming agent into a first solvent and stirring and mixing them to obtain a first mixture;

[0011] placing the first mixed material in a microwave-ultrasonic composite field for microwave-ultrasonic synergistic treatment to obtain a second mixed material;

[0012] granulating the second mixed material, and then performing acidification treatment, filtering and drying to obtain the titanium-based particle adsorbent;

[0013] The working condition parameters of the microwave-ultrasound collaborative treatment include: ultrasonic power of 1500-1800W, and microwave power of 150-220W.

[0014] Furthermore, the ultrasonic power of the microwave-ultrasonic synergistic treatment is 1720-1750W.

[0015] Furthermore, the microwave power of the microwave-ultrasound synergistic treatment is 185-200W.

[0016] Furthermore, the microwave-ultrasound synergistic treatment has a treatment time of 45 to 90 seconds.

[0017] Furthermore, the step of obtaining the lithium metatitanate precursor includes the following process:

[0018] adding a titanium source and a lithium source into a second solvent, stirring and mixing, and then drying, grinding and sintering to obtain the lithium metatitanate precursor;

[0019] The molar ratio of Ti in the titanium source to Li in the lithium source is 1:(2-2.2); the sintering working condition parameters include: temperature of 750-800° C. and time of 12-16 hours.

[0020] Furthermore, the titanium source includes at least one of titanium dioxide and metatitanic acid; the lithium source includes at least one of lithium carbonate, lithium hydroxide and lithium chloride; and the second solvent includes water.

[0021] Furthermore, the weight ratio of the lithium metatitanate precursor, the adhesive forming agent, the pore-forming agent and the first solvent is (68-75):(15-20):(5-10):(100-109);

[0022] The adhesive forming agent comprises at least one of polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl chloride, chlorinated polyvinyl chloride, polyacrylic acid, polyacrylonitrile, polyacrylamide, polymethyl methacrylate, polystyrene, polyamide, polyimide, polyvinylidene fluoride, nitrile rubber, styrene-butadiene rubber, polyvinyl alcohol, polyethylene glycol, chitosan, polysulfone, polyetheretherketone, polytetrafluoroethylene and cellulose acetate butyrate;

[0023] The first solvent includes at least one of dichloromethane, chloroform, carbon tetrachloride, toluene, acetone, ethyl acetate, N,N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

[0024] Furthermore, the adhesive forming agent is composed of polyvinyl butyral and polyvinyl pyrrolidone in a weight ratio of (3-6): (2-4); the pore-forming agent includes at least one of sodium carbonate and potassium carbonate.

[0025] Furthermore, the acidification step includes the following process: adding a hydrochloric acid solution with a molar concentration of 0.2-0.8 mol / L, and then acidifying at a temperature of 40-50° C. for 10-20 hours.

[0026] In a second aspect, the present invention provides a titanium-based particle adsorbent, which is prepared by the preparation method described in any one of the first aspects.

[0027] The above technical solution provided by the embodiment of the present invention has at least the following advantages compared with the prior art:

[0028] An embodiment of the present invention provides a titanium-based particle adsorbent and a preparation method thereof. Based on the existing titanium-based particle adsorbent preparation process, the present invention utilizes the synergistic effect of a microwave-ultrasonic composite field. When microwaves and ultrasonic waves under the above-mentioned specific parameter conditions in the present invention act on the system materials at the same time, the uniform heating and internal heating mechanism provided by the microwaves can accelerate the cavitation and mechanical stirring effects generated by the ultrasonic waves. At the same time, the dispersion and mixing effects of the ultrasonic waves can promote the heating and non-thermal effects of the microwaves, thereby improving the stability of the obtained titanium-based particle adsorbent, making it have excellent anti-dissolution performance, and meeting the needs of multiple recycling in practical applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0031] Figure 1 A schematic flow chart of a method for preparing a titanium-based particle adsorbent provided in an embodiment of the present invention.

[0032] Figure 2 This is the product appearance of the titanium-based particle adsorbent provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0033] To make the purpose, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0034] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0035] In a first aspect, the present invention provides a method for preparing a titanium-based particle adsorbent, such as Figure 1 As shown, the preparation method of the titanium-based particle adsorbent includes the following steps:

[0036] Obtaining a lithium metatitanate precursor;

[0037] Adding the lithium metatitanate precursor, the adhesive forming agent and the pore-forming agent into a first solvent and stirring and mixing them to obtain a first mixture;

[0038] placing the first mixed material in a microwave-ultrasonic composite field for microwave-ultrasonic synergistic treatment to obtain a second mixed material;

[0039] granulating the second mixed material, and then performing acidification treatment, filtering and drying to obtain the titanium-based particle adsorbent;

[0040] The working condition parameters of the microwave-ultrasound collaborative treatment include: ultrasonic power of 1500-1800W, and microwave power of 150-220W.

[0041] An embodiment of the present invention provides a method for preparing a titanium-based granular adsorbent. Based on the existing titanium-based granular adsorbent preparation process, the present invention utilizes the synergistic effect of a microwave-ultrasonic composite field. When microwaves and ultrasonic waves under the above-mentioned specific parameter conditions in the present invention act on the system materials at the same time, the uniform heating and internal heating mechanism provided by the microwaves can accelerate the cavitation and mechanical stirring effects generated by the ultrasonic waves. At the same time, the dispersion and mixing effects of the ultrasonic waves can promote the heating and non-thermal effects of the microwaves, thereby improving the stability of the obtained titanium-based granular adsorbent, making it have excellent anti-dissolution performance, and meeting the needs of multiple recycling in practical applications.

[0042] In some specific embodiments, the "microwave-ultrasonic composite field" in the present invention can be directly carried out using existing ultrasonic microwave coupling equipment, such as the XO-SM series ultrasonic microwave combined reaction system, ultrasonic microwave reactor, etc.

[0043] In some specific embodiments, the ultrasonic power of the microwave-ultrasonic synergistic treatment is 1720-1750W.

[0044] In some specific embodiments, the microwave power of the microwave-ultrasound synergistic treatment is 185-200W.

[0045] In some specific embodiments, the microwave-ultrasound synergistic treatment lasts for 45 to 90 seconds.

[0046] In some specific embodiments, the step of obtaining a lithium metatitanate precursor includes the following process:

[0047] adding a titanium source and a lithium source into a second solvent, stirring and mixing, and then drying, grinding and sintering to obtain the lithium metatitanate precursor;

[0048] The molar ratio of Ti in the titanium source to Li in the lithium source is 1:(2-2.2); the sintering working condition parameters include: temperature of 750-800° C. and time of 12-16 hours.

[0049] In some specific embodiments, the titanium source includes at least one of titanium dioxide and metatitanic acid; the lithium source includes at least one of lithium carbonate, lithium hydroxide and lithium chloride; and the second solvent includes water.

[0050] In some specific embodiments, the weight ratio of the lithium metatitanate precursor, the adhesive forming agent, the pore-forming agent and the first solvent is (68-75):(15-20):(5-10):(100-109);

[0051] The adhesive forming agent comprises at least one of polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl chloride, chlorinated polyvinyl chloride, polyacrylic acid, polyacrylonitrile, polyacrylamide, polymethyl methacrylate, polystyrene, polyamide, polyimide, polyvinylidene fluoride, nitrile rubber, styrene-butadiene rubber, polyvinyl alcohol, polyethylene glycol, chitosan, polysulfone, polyetheretherketone, polytetrafluoroethylene and cellulose acetate butyrate;

[0052] The first solvent includes at least one of dichloromethane, chloroform, carbon tetrachloride, toluene, acetone, ethyl acetate, N,N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

[0053] In some specific embodiments, the adhesive forming agent is composed of polyvinyl butyral and polyvinyl pyrrolidone in a weight ratio of (3-6): (2-4); the pore-forming agent includes at least one of sodium carbonate and potassium carbonate.

[0054] In some specific embodiments, the acidification step includes the following process: adding a hydrochloric acid solution with a molar concentration of 0.2-0.8 mol / L, and then acidifying at a temperature of 40-50° C. for 10-20 hours.

[0055] In a second aspect, based on the same concept, the present invention provides a titanium-based particle adsorbent, which is prepared by the preparation method described in any one of the first aspects.

[0056] The titanium-based particle adsorbent provided by the present invention is produced based on the preparation method described in any one of the first aspects. Therefore, the titanium-based particle adsorbent has at least the beneficial effects of the technical solutions described in any one of the first aspects, which will not be described in detail here.

[0057] It should be noted that the component raw materials involved in the titanium-based particulate adsorbent and the preparation method thereof provided in the embodiments of the present invention, unless otherwise specified or specifically described, can be directly commercially available products or homemade using existing public preparation methods; at the same time, the steps and parameters involved, unless otherwise specified or specifically described, can be carried out in accordance with the existing processing technology of titanium-based particulate adsorbents or directly using existing equipment, and the present invention document will not elaborate on them one by one.

[0058] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the invention. The experimental methods in the following examples where specific conditions are not specified are generally measured in accordance with national standards. If there are no corresponding national standards, then the methods are carried out in accordance with general international standards, conventional conditions, or the conditions recommended by the manufacturer.

[0059] Example 1

[0060] This example provides a titanium-based granular adsorbent, and the preparation method of the titanium-based granular adsorbent includes the following steps:

[0061] Step (1): adding a titanium source (specifically metatitanic acid) and a lithium source (specifically lithium hydroxide) to water and stirring and mixing, then placing in a 75°C environment for vacuum drying and grinding, and sintering the resulting mixture to obtain the lithium metatitanate precursor; wherein the molar ratio of Ti in the titanium source to Li in the lithium source is 1:2.05; the sintering working condition parameters include: temperature of 780°C and time of 14 hours;

[0062] Step (2): adding the lithium metatitanate precursor, the adhesive forming agent and the pore-forming agent obtained in step (1) to N,N-dimethylformamide and stirring and mixing them to obtain a first mixture; wherein the weight ratio of the lithium metatitanate precursor, the adhesive forming agent, the pore-forming agent and the N,N-dimethylformamide is 72:18:7:105; the adhesive forming agent is composed of polyvinyl butyral and polyvinyl pyrrolidone in a weight ratio of 5:3; and the pore-forming agent is sodium carbonate;

[0063] Step (3): placing the first mixed material obtained in step (2) in a microwave-ultrasonic composite field for microwave-ultrasonic synergistic treatment to obtain a second mixed material; wherein the working condition parameters of the microwave-ultrasonic synergistic treatment include: ultrasonic power of 1735W, microwave power of 190W, and treatment time of 60s;

[0064] Step (4): The second mixture obtained in step (3) is extruded into clean water to form spherical particles to obtain spherical particles with a particle size of 2 to 3 mm. The obtained spherical particles are then immersed in a hydrochloric acid solution with a molar concentration of 0.3 mol / L, acidified at a temperature of 48°C for 15 hours, filtered, washed with pure water and dried to obtain the titanium-based particle adsorbent.

[0065] Example 2

[0066] This example provides a titanium-based granular adsorbent, and the preparation method of the titanium-based granular adsorbent includes the following steps:

[0067] Step (1): adding a titanium source (specifically metatitanic acid) and a lithium source (specifically lithium hydroxide) into water and stirring and mixing them, then placing them in a 75°C environment for vacuum drying and grinding, and sintering the resulting mixture to obtain the lithium metatitanate precursor; wherein the molar ratio of Ti in the titanium source to Li in the lithium source is 1:2.05; and the sintering working condition parameters include: temperature of 750°C and time of 16 hours;

[0068] Step (2): adding the lithium metatitanate precursor, the adhesive forming agent and the pore-forming agent obtained in step (1) to N,N-dimethylformamide and stirring and mixing them to obtain a first mixture; wherein the weight ratio of the lithium metatitanate precursor, the adhesive forming agent, the pore-forming agent and the N,N-dimethylformamide is 68:15:5:100; the adhesive forming agent is composed of polyvinyl butyral and polyvinyl pyrrolidone in a weight ratio of 5:3; and the pore-forming agent is sodium carbonate;

[0069] Step (3): placing the first mixed material obtained in step (2) in a microwave-ultrasonic composite field for microwave-ultrasonic synergistic treatment to obtain a second mixed material; wherein the working condition parameters of the microwave-ultrasonic synergistic treatment include: ultrasonic power of 1500W, microwave power of 220W, and treatment time of 45s;

[0070] Step (4): The second mixture obtained in step (3) is extruded into clean water to form spherical particles to obtain spherical particles with a particle size of 2 to 3 mm. The obtained spherical particles are then immersed in a hydrochloric acid solution with a molar concentration of 0.3 mol / L, acidified at a temperature of 48°C for 15 hours, filtered, washed with pure water and dried to obtain the titanium-based particle adsorbent.

[0071] Example 3

[0072] This example provides a titanium-based granular adsorbent, and the preparation method of the titanium-based granular adsorbent includes the following steps:

[0073] Step (1): adding a titanium source (specifically metatitanic acid) and a lithium source (specifically lithium hydroxide) into water and stirring and mixing them, then placing them in a 75°C environment for vacuum drying and grinding, and sintering the resulting mixture to obtain the lithium metatitanate precursor; wherein the molar ratio of Ti in the titanium source to Li in the lithium source is 1:2.05; the sintering working condition parameters include: temperature of 800°C and time of 12 hours;

[0074] Step (2): adding the lithium metatitanate precursor, the adhesive forming agent and the pore-forming agent obtained in step (1) to N,N-dimethylformamide and stirring and mixing them to obtain a first mixture; wherein the weight ratio of the lithium metatitanate precursor, the adhesive forming agent, the pore-forming agent and the N,N-dimethylformamide is 75:20:10:109; the adhesive forming agent is composed of polyvinyl butyral and polyvinyl pyrrolidone in a weight ratio of 5:3; and the pore-forming agent is sodium carbonate;

[0075] Step (3): placing the first mixed material obtained in step (2) in a microwave-ultrasonic composite field for microwave-ultrasonic synergistic treatment to obtain a second mixed material; wherein the working condition parameters of the microwave-ultrasonic synergistic treatment include: ultrasonic power of 1800W, microwave power of 150W, and treatment time of 90s;

[0076] Step (4): The second mixture obtained in step (3) is extruded into clean water to form spherical particles to obtain spherical particles with a particle size of 2 to 3 mm. The obtained spherical particles are then immersed in a hydrochloric acid solution with a molar concentration of 0.3 mol / L, acidified at a temperature of 48°C for 15 hours, filtered, washed with pure water and dried to obtain the titanium-based particle adsorbent.

[0077] Comparative Example 1

[0078] This example provides a titanium-based particulate adsorbent and a preparation method thereof, which differs from Example 1 only in that the microwave-ultrasonic synergistic treatment in step (3) is adjusted to ultrasonic treatment; the remaining steps and parameters are the same.

[0079] The preparation method of the titanium-based particle adsorbent comprises the following steps:

[0080] Step (1): adding a titanium source (specifically metatitanic acid) and a lithium source (specifically lithium hydroxide) to water and stirring and mixing, then placing in a 75°C environment for vacuum drying and grinding, and sintering the resulting mixture to obtain the lithium metatitanate precursor; wherein the molar ratio of Ti in the titanium source to Li in the lithium source is 1:2.05; the sintering working condition parameters include: temperature of 780°C and time of 14 hours;

[0081] Step (2): adding the lithium metatitanate precursor, the adhesive forming agent and the pore-forming agent obtained in step (1) to N,N-dimethylformamide and stirring and mixing them to obtain a first mixture; wherein the weight ratio of the lithium metatitanate precursor, the adhesive forming agent, the pore-forming agent and the N,N-dimethylformamide is 72:18:7:105; the adhesive forming agent is composed of polyvinyl butyral and polyvinyl pyrrolidone in a weight ratio of 5:3; and the pore-forming agent is sodium carbonate;

[0082] Step (3): placing the first mixture obtained in step (2) in an ultrasonic device for ultrasonic treatment to obtain a second mixture; wherein the working condition parameters of the ultrasonic treatment include: ultrasonic power of 1735W, treatment time of 60s;

[0083] Step (4): The second mixture obtained in step (3) is extruded into clean water to form spherical particles to obtain spherical particles with a particle size of 2 to 3 mm. The obtained spherical particles are then immersed in a hydrochloric acid solution with a molar concentration of 0.3 mol / L, acidified at a temperature of 48°C for 15 hours, filtered, washed with pure water and dried to obtain the titanium-based particle adsorbent.

[0084] Comparative Example 2

[0085] This example provides a titanium-based particulate adsorbent and a preparation method thereof. The only difference from Example 1 is that the microwave-ultrasound synergistic treatment in step (3) is adjusted to microwave treatment; the remaining steps and parameters are the same.

[0086] The preparation method of the titanium-based particle adsorbent comprises the following steps:

[0087] Step (1): adding a titanium source (specifically metatitanic acid) and a lithium source (specifically lithium hydroxide) to water and stirring and mixing, then placing in a 75°C environment for vacuum drying and grinding, and sintering the resulting mixture to obtain the lithium metatitanate precursor; wherein the molar ratio of Ti in the titanium source to Li in the lithium source is 1:2.05; the sintering working condition parameters include: temperature of 780°C and time of 14 hours;

[0088] Step (2): adding the lithium metatitanate precursor, the adhesive forming agent and the pore-forming agent obtained in step (1) to N,N-dimethylformamide and stirring and mixing them to obtain a first mixture; wherein the weight ratio of the lithium metatitanate precursor, the adhesive forming agent, the pore-forming agent and the N,N-dimethylformamide is 72:18:7:105; the adhesive forming agent is composed of polyvinyl butyral and polyvinyl pyrrolidone in a weight ratio of 5:3; and the pore-forming agent is sodium carbonate;

[0089] Step (3): placing the first mixed material obtained in step (2) in a microwave device for microwave treatment to obtain a second mixed material; wherein the working condition parameters of the microwave treatment include: microwave power of 190W, treatment time of 60s;

[0090] Step (4): The second mixture obtained in step (3) is extruded into clean water to form spherical particles to obtain spherical particles with a particle size of 2 to 3 mm. The obtained spherical particles are then immersed in a hydrochloric acid solution with a molar concentration of 0.3 mol / L, acidified at a temperature of 48°C for 15 hours, filtered, washed with pure water and dried to obtain the titanium-based particle adsorbent.

[0091] Comparative Example 3

[0092] This example provides a titanium-based particulate adsorbent and a preparation method thereof. The only difference from Example 1 is that the ultrasonic power of the microwave-ultrasonic synergistic treatment in step (3) is adjusted to 1200W, and the microwave power is adjusted to 725W; the remaining steps and parameters are the same.

[0093] The preparation method of the titanium-based particle adsorbent comprises the following steps:

[0094] Step (1): adding a titanium source (specifically metatitanic acid) and a lithium source (specifically lithium hydroxide) to water and stirring and mixing, then placing in a 75°C environment for vacuum drying and grinding, and sintering the resulting mixture to obtain the lithium metatitanate precursor; wherein the molar ratio of Ti in the titanium source to Li in the lithium source is 1:2.05; the sintering working condition parameters include: temperature of 780°C and time of 14 hours;

[0095] Step (2): adding the lithium metatitanate precursor, the adhesive forming agent and the pore-forming agent obtained in step (1) to N,N-dimethylformamide and stirring and mixing them to obtain a first mixture; wherein the weight ratio of the lithium metatitanate precursor, the adhesive forming agent, the pore-forming agent and the N,N-dimethylformamide is 72:18:7:105; the adhesive forming agent is composed of polyvinyl butyral and polyvinyl pyrrolidone in a weight ratio of 5:3; and the pore-forming agent is sodium carbonate;

[0096] Step (3): placing the first mixed material obtained in step (2) in a microwave-ultrasonic composite field for microwave-ultrasonic synergistic treatment to obtain a second mixed material; wherein the working condition parameters of the microwave-ultrasonic synergistic treatment include: ultrasonic power of 1200W, microwave power of 725W, and treatment time of 60s;

[0097] Step (4): The second mixture obtained in step (3) is extruded into clean water to form spherical particles to obtain spherical particles with a particle size of 2 to 3 mm. The obtained spherical particles are then immersed in a hydrochloric acid solution with a molar concentration of 0.3 mol / L, acidified at a temperature of 48°C for 15 hours, filtered, washed with pure water and dried to obtain the titanium-based particle adsorbent.

[0098] Test Example 1

[0099] In this example, the titanium-based particulate adsorbents obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to cyclic adsorption and desorption performance tests based on the existing detection method (performance test method in CN 117899804 A). The number of cycles was 30, and the Ti dissolution rate (%) was calculated. The test results are shown in Table 1.

[0100] Table 1

[0101] Test samples Ti dissolution rate (%) Example 1 0.009 Example 2 0.024 Example 3 0.031 Comparative Example 1 0.678 Comparative Example 2 1.052 Comparative Example 3 0.396

[0102] As shown in Table 1, compared with comparative examples 1 to 3, the titanium-based particle adsorbent provided by the embodiment of the present invention still maintains a low Ti dissolution rate after 50 cycles of adsorption and analytical performance tests, and the Ti dissolution rate of Example 1 can reach 0.009%, which has excellent anti-dissolution performance. In addition, the titanium-based particle adsorbent provided by Examples 1 to 3 of the present invention has the advantages of excellent adsorption capacity performance (Li adsorption capacity ≥ 10.0 mg / g), regular morphology, high molding rate, etc. The actual product appearance is shown in the figure below. Figure 2 As shown, it can meet the needs of multiple cycles in practical applications.

[0103] In summary, the embodiments of the present invention provide a titanium-based particle adsorbent and a preparation method thereof. Based on the existing titanium-based particle adsorbent preparation process, the present invention utilizes the synergistic effect of a microwave-ultrasonic composite field. When microwaves and ultrasonic waves under the above-mentioned specific parameter conditions in the present invention act on the system materials at the same time, the uniform heating and internal heating mechanism provided by the microwaves can accelerate the cavitation and mechanical stirring effects generated by the ultrasonic waves. At the same time, the dispersion and mixing effects of the ultrasonic waves can promote the heating and non-thermal effects of the microwaves, thereby improving the stability of the obtained titanium-based particle adsorbent, making it have excellent anti-dissolution performance, and meeting the needs of multiple cycles in practical applications.

[0104] Various embodiments of the present invention may be presented in the form of a range; it should be understood that the description in a range format is only for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; therefore, the range description should be considered to have specifically disclosed all possible subranges and single numerical values within the range. For example, the description of a range from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated herein, it is intended to include any cited numeral (fractional or integer) within the indicated range.

[0105] The foregoing description is intended only to provide specific embodiments of the present invention, which will enable those skilled in the art to understand and implement the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not intended to be limited to the embodiments shown herein, but is intended to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A method for preparing a titanium-based particle adsorbent, characterized in that: The preparation method of the titanium-based particle adsorbent comprises the following steps: A titanium source and a lithium source are added to a second solvent and stirred and mixed, followed by drying, grinding and sintering to obtain a lithium metatitanate precursor; wherein the molar ratio of Ti in the titanium source to Li in the lithium source is 1:(2-2.2); and the sintering working conditions include: a temperature of 750-800° C. and a time of 12-16 hours; Adding the lithium metatitanate precursor, the adhesive forming agent and the pore-forming agent into a first solvent and stirring and mixing them to obtain a first mixture; placing the first mixed material in a microwave-ultrasonic composite field for microwave-ultrasonic synergistic treatment to obtain a second mixed material; The second mixed material is granulated, and then acidified, filtered, and dried to obtain the titanium-based granular adsorbent; wherein the acidification treatment comprises adding a hydrochloric acid solution having a molar concentration of 0.2-0.8 mol / L and then acidifying at a temperature of 40-50° C. for 10-20 hours; The working condition parameters of the microwave-ultrasound collaborative treatment include: ultrasonic power of 1500-1800W, and microwave power of 150-220W.

2. The method for preparing a titanium-based particulate adsorbent according to claim 1, wherein: The ultrasonic power of the microwave-ultrasonic synergistic treatment is 1720-1750W.

3. The method for preparing a titanium-based particulate adsorbent according to claim 1, wherein: The microwave power of the microwave-ultrasound synergistic treatment is 185-200W.

4. The method for preparing a titanium-based particulate adsorbent according to claim 1, wherein: The microwave-ultrasound synergistic treatment takes 45 to 90 seconds.

5. The method for preparing a titanium-based particulate adsorbent according to claim 1, wherein: The titanium source includes at least one of titanium dioxide and metatitanic acid; the lithium source includes at least one of lithium carbonate, lithium hydroxide and lithium chloride; and the second solvent includes water.

6. The method for preparing a titanium-based particulate adsorbent according to claim 1, wherein: The weight ratio of the lithium metatitanate precursor, the adhesive forming agent, the pore-forming agent and the first solvent is (68-75):(15-20):(5-10):(100-109); The adhesive forming agent comprises at least one of polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl chloride, chlorinated polyvinyl chloride, polyacrylic acid, polyacrylonitrile, polyacrylamide, polymethyl methacrylate, polystyrene, polyamide, polyimide, polyvinylidene fluoride, nitrile rubber, styrene-butadiene rubber, polyvinyl alcohol, polyethylene glycol, chitosan, polysulfone, polyetheretherketone, polytetrafluoroethylene and cellulose acetate butyrate; The first solvent includes at least one of dichloromethane, chloroform, carbon tetrachloride, toluene, acetone, ethyl acetate, N,N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

7. The method for preparing a titanium-based particulate adsorbent according to claim 1, wherein: The adhesive forming agent is composed of polyvinyl butyral ester and polyvinyl pyrrolidone in a weight ratio of (3-6): (2-4); the pore-forming agent includes at least one of sodium carbonate and potassium carbonate.

8. A titanium-based particle adsorbent, characterized in that: The titanium-based particle adsorbent is prepared by the preparation method according to any one of claims 1 to 7.

Images