Preparation method of rare earth antibacterial carrier

Abstract

The invention belongs to the technical field of rare earth material preparation, and discloses a preparation method of a rare earth antibacterial carrier. The preparation method comprises the following specific steps: (1) preparing rare earth chloride, zinc chloride and zirconium oxychloride into a mixed aqueous solution; (2) heating the mixed aqueous solution, adding PEG and glacial acetic acid, uniformly mixing, adjusting the pH value of the mixed solution to 6.7-7, filtering, precipitating and drying to obtain a first reactant; and (3) carrying out size mixing on the first reactant with water, adding strong phosphoric acid and 1-butyl-3-methylimidazole dibutyl phosphate salt, reacting, filtering, precipitating and drying to obtain the rare earth antibacterial carrier with the ion adsorption capacity of 1g / 100g to 5g / 100g. The method has the characteristics of simplicity in operation, short reaction time, low reaction temperature, easiness in washing and filtering reactants, large specific surface area of the carrier and high metal ion loading capacity.

Description

Technical Field

[0001] The present invention relates to the technical field of rare earth material preparation, and more particularly to a method for preparing a rare earth antibacterial carrier. Background Art

[0002] Inorganic ion antimicrobial technology leverages the antimicrobial properties of metal ions such as silver, copper, zinc, and rare earth ions, and is widely used in healthcare, food packaging, textiles, and water treatment. Silver ions, for example, are the most common due to their potent antimicrobial properties. They can destroy bacterial cell membranes and interfere with DNA replication, effectively combating a wide range of bacteria. Copper and rare earth ions destroy bacterial cell structures by producing reactive oxygen species, while zinc and rare earth ions exert their antimicrobial effects by interfering with bacterial metabolism.

[0003] The advantages of inorganic ion antibacterial materials are that they have a broad antibacterial spectrum, high stability, are not prone to drug resistance, and are relatively safe for the human body.

[0004] The carriers of traditional inorganic ion antibacterial materials are generally inorganic materials such as zeolite, clay minerals, and silicate minerals. By loading antibacterial active ions such as silver, zinc, copper, and rare earth, they can achieve antibacterial and antimicrobial effects. However, these materials as carriers generally have high impurity content, and silicate mineral carriers have poor heat resistance and are easy to discolor, which limits their application in ceramics, textiles, paints, coatings and other fields.

[0005] Inorganic zirconium phosphate, an important inorganic carrier material, has garnered widespread attention in recent years in the antimicrobial field due to its unique layered structure, high ion exchange capacity, and excellent chemical stability. Zirconium phosphate's layered structure enables it to load antimicrobial ions such as silver, copper, and zinc through ion exchange and achieve controlled release, thereby exerting a long-lasting antimicrobial effect. Furthermore, zirconium phosphate exhibits excellent biocompatibility and thermal stability, making it widely applicable in fields such as healthcare, food packaging, and water treatment.

[0006] However, the preparation process of inorganic zirconium phosphate supports generally requires high temperatures and long cycles.

[0007] CN 115849325 A discloses a method for preparing a cubic sodium zirconium phosphate carrier and its silver-zinc-loaded antibacterial powder. This method further improves upon CN 102763678 A and CN 110934153 A. However, the antibacterial powder prepared by this method has a high viscosity and is prone to agglomeration during the drying process, requiring crushing before use. Furthermore, the powder is not cubic in shape and has a small specific surface area, which can affect its antibacterial effect during subsequent use. CN 115517268 A discloses a silver-zinc-copper-loaded single-layer zirconium phosphate nanosheet and its preparation method. The zirconium phosphate obtained by directly adding phosphoric acid and hydrofluoric acid to a soluble zirconium salt is difficult to filter and the method is difficult to operate. CN 114853054 A discloses a method for preparing a silver-doped zinc oxide antibacterial and antiviral nanopowder, its product, and its application. The resulting antibacterial agent is unstable, and the silver oxide obtained by directly precipitating silver tends to discolor and turn black during subsequent use. CN114698649A discloses a rare earth antibacterial material, its preparation method and application. Although the prepared antibacterial material is dispersed, the tetrapod-shaped zinc oxide whiskers, lanthanum oxide and cerium oxide in the raw materials are insoluble in water. Even after dispersion, the problem of uneven composition still exists.

[0008] Therefore, it is an urgent problem for technicians in this field to develop a method for preparing a cerium zirconium zinc phosphate antibacterial carrier with simple operation, short reaction time, low reaction temperature, easy water washing and filtration of reactants, large carrier specific surface area, and high metal ion loading capacity. Summary of the Invention

[0009] To overcome the drawbacks of inorganic zirconium phosphate antimicrobial carrier preparation and application, this invention proposes a method for preparing a rare earth zirconium zinc phosphate composite antimicrobial carrier. This method features simple operation, short reaction time, low reaction temperature, easy washing and filtration of reactants, a large carrier specific surface area, and a high metal ion loading capacity.

[0010] In order to achieve the above object, the present invention provides a method for preparing a rare earth antibacterial carrier, which comprises the following specific steps:

[0011] (1) preparing a mixed aqueous solution of rare earth chloride, zinc chloride and zirconium oxychloride;

[0012] (2) heating the mixed aqueous solution, adding PEG and glacial acetic acid, mixing uniformly, adjusting the pH value of the mixed solution to 6.7-7, filtering the precipitate, and drying at 80° C. to obtain the first reactant;

[0013] (3) The first reactant was slurried with deionized water, concentrated phosphoric acid and 1-butyl-3-methylimidazole dibutyl phosphate were added, reacted, filtered and precipitated, and dried at 80°C to obtain a porous needle-like morphology with a specific surface area of >100m 2 / g, and the active metal ion adsorption capacity is 1g / 100g-5g / 100g rare earth antibacterial carrier.

[0014] Preferably, in step (1), the molar ratio of rare earth ions, zinc ions and zirconium ions in the mixed aqueous solution is (2-8):1:(2-8), and more preferably 2.5:1:2.5.

[0015] Preferably, the concentration of rare earth ions in the mixed aqueous solution is 0.3-0.9 mol / L, more preferably 0.6 mol / L

[0016] Preferably, the rare earth chloride is lanthanum chloride, cerium chloride or lanthanum-cerium chloride.

[0017] Preferably, in step (2), the amount of PEG added is 0.05-2% of the total mass of the rare earth chloride, zinc chloride and zirconium oxychloride, more preferably 1%; the amount of glacial acetic acid added is 1-3% of the total mass of the rare earth chloride, zinc chloride and zirconium oxychloride.

[0018] Preferably, the molecular weight of PEG is 2000-10000, more preferably 6000.

[0019] Preferably, in step (2), the heating is performed to 40-80° C., more preferably 60° C.; and the pH value is adjusted by adding 2.53 mol / L ammonium bicarbonate solution to the mixed solution.

[0020] Furthermore, the preparation method of the ammonium bicarbonate solution is: preparing a 2.53 mol / L ammonium bicarbonate solution, adding citric acid or tartaric acid to the ammonium bicarbonate solution, and the molar ratio of citric acid or tartaric acid to ammonium bicarbonate is 10:1-2.

[0021] Preferably, in step (3), the mass ratio of the first reactant to the water is 1:3-8, more preferably 1:5.

[0022] Preferably, in step (3), the mass ratio of the concentrated phosphoric acid to the first reactant is 0.2-0.3:1, more preferably 0.25:1; the mass ratio of the 1-butyl-3-methylimidazole dibutyl phosphate to the first reactant is 0.001-0.01:1.

[0023] Preferably, in step (3), the reaction temperature is 60-90° C. and the reaction time is 0.5-2 h.

[0024] It can be seen from the above technical solution that compared with the prior art, the beneficial effects achieved by the present invention are: different from the shortcomings of the prior art in the preparation process of inorganic zirconium phosphate carrier, such as long reaction time, high temperature, high energy consumption, and difficult material washing and filtering, the present invention has the characteristics of simple operation, short reaction time, low reaction temperature, easy water washing and filtration of reactants, large carrier specific surface area, and high metal ion loading capacity. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] 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, the drawings described below are merely embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0026] Figure 1 This is the SEM image of the antibacterial carrier provided in Example 1.

[0027] Figure 2 This is the SEM image of the antibacterial carrier provided for Comparative Example 2. DETAILED DESCRIPTION

[0028] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only 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 are within the scope of protection of the present invention.

[0029] Experimental materials: The rare earth chloride used in the experiment contains crystal water, and the water content in every 100g of rare earth chloride reaches 56%-57%.

[0030] Example 1

[0031] Preparation method of rare earth antibacterial carrier:

[0032] Take 78.25 g of cerium chloride, 6.8 g of zinc chloride, and 64.5 g of zirconium oxychloride, add 300 mL of water, heat to 60°C, add 1.5 g of PEG6000, add 2 g of glacial acetic acid, and add ammonium bicarbonate solution (the concentration of ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:1.5) until the pH value of the system is 6.7-7, centrifuge, and dry at 80°C to obtain the first reactant.

[0033] Take 20g of the first reactant and slurry it with 100g of water, add 5g of concentrated phosphoric acid, add 0.05g of 1-butyl-3-methylimidazole dibutyl phosphate, react at 60℃ for 2h, filter, wash, and dry at 80℃ to obtain a porous needle-like morphology with a specific surface area of 126m 2 / g, active metal ion Ag + Antibacterial carrier with an adsorption capacity of 3.5g / 100g.

[0034] Comparative Example 1

[0035] Take 78.25 g of cerium chloride, 6.8 g of zinc chloride, and 64.5 g of zirconium oxychloride, add 300 mL of water, heat to 60°C, add 1.5 g of PEG6000, add 2 g of glacial acetic acid, add ammonium bicarbonate solution (the concentration of ammonium bicarbonate solution is 2.53 mol / L) until the pH value of the system is 6.7-7, centrifuge, and dry at 80°C to obtain the first reactant.

[0036] Take 20g of the first reactant and slurry it with 100g of water, add 5g of concentrated phosphoric acid, add 0.05g of 1-butyl-3-methylimidazole dibutyl phosphate, react at 60℃ for 2h, filter, wash, and dry at 80℃ to obtain a porous needle-like morphology with a specific surface area of 96m 2 / g, active metal ion Ag + Antibacterial carrier with an adsorption capacity of 2.3g / 100g.

[0037] From Example 1 and Comparative Example 1, it can be seen that the addition of tartaric acid or citric acid to the ammonium bicarbonate solution can form an organic complex with the metal ions during the precipitation process, reduce the agglomeration between the powders during the drying process, and increase the specific surface area of the material.

[0038] Comparative Example 2

[0039] Take 78.25 g of cerium chloride, 6.8 g of zinc chloride, and 64.5 g of zirconium oxychloride, add 300 mL of water, heat to 60°C, add 1.5 g of PEG6000, add 2 g of glacial acetic acid, and add ammonium bicarbonate solution (the concentration of ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:1.5) until the pH value of the system is 6.7-7, centrifuge, and dry at 80°C to obtain the first reactant.

[0040] Take 20g of the first reactant and slurry it with 100g of water, add 5g of concentrated phosphoric acid, react at 60℃ for 1h, filter, wash, and dry at 80℃ to obtain a block-like morphology with a specific surface area of 58m 2 / g, active metal ion Ag + Antibacterial carrier with an adsorption capacity of 1.2g / 100g.

[0041] Example 2

[0042] Preparation method of rare earth antibacterial carrier:

[0043] Take 93.9 g of cerium chloride, 9.2 g of zinc chloride, and 76.6 g of zirconium oxychloride, add 400 mL of water, heat to 60°C, add 2.4 g of PEG4000, add 3 g of glacial acetic acid, and add ammonium bicarbonate solution (the concentration of ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:2) until the pH value of the system is 6.7-7, centrifuge, and dry at 80°C to obtain the first reactant.

[0044] Take 40g of the first reactant and slurry it with 200g of water, add 8.6g of concentrated phosphoric acid, add 0.25g of 1-butyl-3-methylimidazole dibutyl phosphate, react at 60℃ for 1.5h, filter, wash, and dry at 80℃ to obtain a block-shaped product with a specific surface area of 143m 2 / g, active metal ion Ag + Antibacterial carrier with an adsorption capacity of 3.8g / 100g.

[0045] Example 3

[0046] Take 93.9 g of lanthanum cerium chloride, 5 g of zinc chloride, and 50 g of zirconium oxychloride, add 500 mL of water, heat to 50°C, add 1.4 g of PEG4000, add 1.8 g of glacial acetic acid, and add ammonium bicarbonate solution (the concentration of ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:1) until the pH value of the system is 6.7-7, centrifuge and filter, and dry at 80°C to obtain the first reactant.

[0047] Take 30g of the first reactant and slurry it with 240g of water, add 6g of concentrated phosphoric acid, add 0.1g of 1-butyl-3-methylimidazole dibutyl phosphate, react at 80℃ for 2h, filter, wash, and dry at 80℃ to obtain a block-like morphology with a specific surface area of 136m 2 / g, active metal ion Zn 2+ Antibacterial carrier with an adsorption capacity of 3.5g / 100g.

[0048] Example 4

[0049] Take 120 g of lanthanum chloride, 13.6 g of zinc chloride, and 96.7 g of zirconium oxychloride, add 500 mL of water, heat to 60 ° C, add 1.2 g of PEG6000, add 6.2 g of glacial acetic acid, and add ammonium bicarbonate solution (the concentration of ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:2) until the pH value of the system is 6.7-7, centrifuge and filter, and dry at 80 ° C to obtain the first reactant.

[0050] Take 50g of the first reactant and slurry it with 350g of water, add 12g of concentrated phosphoric acid, add 0.2g of 1-butyl-3-methylimidazole dibutyl phosphate, react at 90℃ for 1.5h, filter, wash, and dry at 80℃ to obtain a block-shaped product with a specific surface area of 148m 2 / g, active metal ion Zn 2+ Antibacterial carrier with an adsorption capacity of 3.7g / 100g.

[0051] Example 5

[0052] Take 120 g of lanthanum cerium chloride, 12 g of zinc chloride, and 100 g of zirconium oxychloride, add 600 mL of water, heat to 60 ° C, add 4.2 g of PEG4000, add 4.2 g of glacial acetic acid, and add ammonium bicarbonate solution (the concentration of ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:2) until the pH value of the system is 6.7-7, centrifuge and filter, and dry at 80 ° C to obtain the first reactant.

[0053] Take 50g of the first reactant and slurry it with 400g of water, add 12.5g of concentrated phosphoric acid, add 0.5g of 1-butyl-3-methylimidazole dibutyl phosphate, react at 80℃ for 2h, filter, wash, and dry at 80℃ to obtain a block-shaped product with a specific surface area of 158m 2 / g, active metal ion Zn 2+ Antibacterial carrier with an adsorption capacity of 4.0g / 100g.

[0054] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one 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 limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a rare earth antibacterial carrier, characterized in that: The specific steps are: (1) preparing a mixed aqueous solution of rare earth chloride, zinc chloride and zirconium oxychloride; (2) heating the mixed aqueous solution, adding PEG and glacial acetic acid, mixing uniformly, adjusting the pH value of the mixed solution to 6.7-7, filtering the precipitate, and drying to obtain the first reactant; (3) The first reactant is slurried with water, concentrated phosphoric acid and 1-butyl-3-methylimidazole dibutyl phosphate are added, reacted, filtered, precipitated, and dried to obtain a rare earth antibacterial carrier.

2. The method for preparing the rare earth antibacterial carrier according to claim 1, characterized in that: In step (1), the molar ratio of rare earth ions, zinc ions and zirconium ions in the mixed aqueous solution is (2-8):1:(2-8).

3. The method for preparing the rare earth antibacterial carrier according to claim 2, characterized in that: The concentration of rare earth ions in the mixed aqueous solution is 0.3-0.9 mol / L.

4. The method for preparing the rare earth antibacterial carrier according to claim 1, characterized in that: The rare earth chloride is lanthanum chloride, cerium chloride or lanthanum-cerium chloride.

5. The method for preparing the rare earth antibacterial carrier according to claim 1, characterized in that: In step (2), the PEG is 0.05-2% of the total mass of the rare earth chloride, zinc chloride and zirconium oxychloride, and the glacial acetic acid is 1-3% of the total mass of the rare earth chloride, zinc chloride and zirconium oxychloride.

6. The method for preparing the rare earth antibacterial carrier according to claim 1, characterized in that: In step (2), the heating is performed to 40-80° C., and the pH value is adjusted by adding 2.53 mol / L ammonium bicarbonate solution to the mixed solution.

7. The method for preparing the rare earth antibacterial carrier according to claim 6, characterized in that: The ammonium bicarbonate solution is prepared by preparing a 2.53 mol / L ammonium bicarbonate solution, and adding citric acid or tartaric acid to the ammonium bicarbonate solution, wherein the molar ratio of the citric acid or tartaric acid to the ammonium bicarbonate is 10:1-2.

8. The method for preparing the rare earth antibacterial carrier according to claim 1, characterized in that: In step (3), the mass ratio of the first reactant to the water is 1:3-8.

9. The method for preparing the rare earth antibacterial carrier according to claim 1, characterized in that: In step (3), the mass ratio of the concentrated phosphoric acid to the first reactant is 0.2-0.3:1, and the mass ratio of the 1-butyl-3-methylimidazole dibutyl phosphate to the first reactant is 0.001-0.01:

1.

10. The method for preparing the rare earth antibacterial carrier according to claim 1, characterized in that: In step (3), the reaction temperature is 60-90° C. and the reaction time is 0.5-2 h.

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