A method for preparing a rare earth antibacterial carrier
By preparing a rare earth zirconium zinc phosphate composite antibacterial carrier, the problems of long reaction time and high temperature in the preparation of inorganic zirconium phosphate carriers were solved, and a rare earth antibacterial carrier with large specific surface area and high metal ion loading was obtained, which is suitable for medical, food packaging and water treatment fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HANGZHOU BAOTOU RARE EARTH TECH DEV CO LTD
- Filing Date
- 2025-05-15
- Publication Date
- 2026-05-26
AI Technical Summary
Existing inorganic zirconium phosphate supports suffer from problems such as long reaction time, high temperature, high energy consumption, difficulty in washing and filtering materials, small specific surface area, and low metal ion loading, which limit their application in ceramics, textiles, paints, coatings and other fields.
A method for preparing a rare earth zirconium zinc phosphate composite antibacterial carrier was adopted. The rare earth chloride, zinc chloride and zirconium oxychloride were mixed into an aqueous solution, heated and then PEG and glacial acetic acid were added to adjust the pH value. The precipitate was filtered and dried. Then concentrated phosphoric acid and 1-butyl-3-methylimidazolium phosphate dibutyl ester salt were added, reacted and filtered to obtain a porous needle-like rare earth antibacterial carrier.
It achieves the effects of simple operation, short reaction time, low reaction temperature, easy filtration of reactants, large specific surface area, and high metal ion loading, thereby improving the antibacterial properties of the carrier.
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Figure CN120477209B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of rare earth material preparation technology, and more specifically to a method for preparing a rare earth antibacterial carrier. Background Technology
[0002] Inorganic ion antibacterial technology utilizes the antibacterial properties of metal ions such as silver, copper, zinc, and rare earth elements, and is widely used in fields such as medical treatment, food packaging, textiles, and water treatment. For example, silver ions are the most common due to their potent antibacterial ability; they can disrupt bacterial cell membranes and interfere with DNA replication, effectively combating a variety of bacteria. Copper and rare earth ions damage bacterial cell structures by generating reactive oxygen species, while zinc and rare earth ions exert their antibacterial 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] Traditional inorganic ion antibacterial materials typically use inorganic materials such as zeolite, clay minerals, and silicate minerals as carriers. By loading antibacterial active ions such as silver, zinc, copper, and rare earth elements, they can achieve antibacterial and bacteriostatic effects. However, these materials generally have high impurity content, and silicate mineral carriers have poor heat resistance and are prone to discoloration, which limits their application in ceramics, textiles, paints, coatings, and other fields.
[0005] Inorganic zirconium phosphate, as an important inorganic carrier material, has attracted widespread attention in the field of antibacterial applications in recent years due to its unique layered structure, high ion exchange capacity, and good chemical stability. The layered structure of zirconium phosphate allows it to load antibacterial ions such as silver, copper, and zinc through ion exchange and achieve controlled release, thus exerting a long-lasting antibacterial effect. Furthermore, zirconium phosphate itself possesses good biocompatibility and thermal stability, making it widely applicable in medical, food packaging, and water treatment fields.
[0006] However, the preparation of inorganic zirconium phosphate supports generally involves high temperatures and long cycles.
[0007] CN 115849325 A discloses a method for preparing cubic sodium zirconium phosphate carrier and its silver-zinc-loaded antibacterial powder. This method further improves upon CN102763678A and CN 110934153 A, but the antibacterial powder prepared by this method has a high viscosity and is prone to agglomeration during drying, requiring further pulverization before use. Furthermore, the morphology remains cubic with a small specific surface area, which affects the antibacterial effect in subsequent use. CN 115517268 A discloses a method for preparing silver-zinc-copper monolayer zirconium phosphate nanosheets. The zirconium phosphate prepared 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 silver-doped zinc oxide antibacterial and antiviral nanoparticles, products, and applications. The prepared antibacterial agent is unstable, and the silver oxide obtained by directly precipitating silver is prone to discoloration and blackening during subsequent use. CN114698649A discloses a rare earth antibacterial material, its preparation method and application. Although the prepared antibacterial material is dispersed, the tetra-needle-shaped zinc oxide whiskers, lanthanum oxide and cerium oxide in the raw materials are insoluble in water. Even after dispersion, there is still a problem of uneven composition.
[0008] Therefore, developing a method for preparing a cerium zirconium zinc phosphate antibacterial carrier that is simple to operate, has a short reaction time, low reaction temperature, allows the reactants to be easily washed and filtered, has a large specific surface area of the carrier, and a high metal ion loading capacity is an urgent problem that needs to be solved by those skilled in the art. Summary of the Invention
[0009] This invention overcomes the drawbacks in the preparation and application of inorganic zirconium phosphate antibacterial carriers by proposing a method for preparing a rare earth zirconium-zinc phosphate composite antibacterial carrier. This method features simple operation, short reaction time, low reaction temperature, easy washing and filtration of reactants, large specific surface area of the carrier, and high metal ion loading.
[0010] To achieve the above objectives, the present invention provides a method for preparing a rare earth antibacterial carrier, the specific steps of which are as follows:
[0011] (1) Prepare a mixed aqueous solution of rare earth chloride, zinc chloride and zirconium oxychloride;
[0012] (2) Heat the mixed aqueous solution, add PEG and glacial acetic acid, mix well, adjust the pH of the mixed solution to 6.7-7, filter the precipitate, dry at 80℃ to obtain the first reactant;
[0013] (3) The first reactant was slurried with deionized water, and concentrated phosphoric acid and 1-butyl-3-methylimidazolium dibutyl phosphate were added. The reaction was carried out, the precipitate was filtered, and dried at 80°C to obtain a porous needle-like morphology with a specific surface area >100m². 2 / g, with an active metal ion adsorption capacity of 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 the PEG is 2000-10000, and more preferably 6000.
[0019] Preferably, in step (2), the heating is carried out to 40-80°C, more preferably 60°C; the pH value is adjusted by adding 2.53 mol / L ammonium bicarbonate solution to the mixed solution.
[0020] Furthermore, the method for preparing the ammonium bicarbonate solution is as follows: prepare a 2.53 mol / L ammonium bicarbonate solution, and add citric acid or tartaric acid to the ammonium bicarbonate solution, wherein 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, and more preferably 1:5.
[0022] Preferably, in step (3), the mass ratio of concentrated phosphoric acid to the first reactant is 0.2-0.3:1, more preferably 0.25:1; the mass ratio of 1-butyl-3-methylimidazolium dibutyl phosphate to the first reactant is 0.001-0.01:1.
[0023] Preferably, in step (3), the reaction temperature is 60-90℃ and the time is 0.5-2h.
[0024] As can be seen from the above technical solution, compared with the prior art, the beneficial effects achieved by the present invention are as follows: Unlike the shortcomings of the prior art in the preparation of inorganic zirconium phosphate support, such as long reaction time, high temperature, high energy consumption, and difficulty in washing and filtering materials, the present invention has the characteristics of simple operation, short reaction time, low reaction temperature, easy water washing and filtration of reactants, large specific surface area of the support, and high metal ion loading. Attached Figure Description
[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0026] Figure 1 The image shows the SEM image of the antibacterial carrier provided in Example 1.
[0027] Figure 2 SEM image of the antibacterial carrier provided for Comparative Example 2. Detailed Implementation
[0028] 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.
[0029] Experimental materials: The rare earth chloride used in the experiment contains water of crystallization, with a water content of 56%-57% per 100g of rare earth chloride.
[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 (ammonium bicarbonate concentration 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 of the system is 6.7-7. Centrifuge and dry at 80 °C to obtain the first reactant.
[0033] 20g of the first reactant was mixed with 100g of water to form a slurry. 5g of concentrated phosphoric acid was added, followed by 0.05g of 1-butyl-3-methylimidazolium dibutyl phosphate. The mixture was reacted at 60℃ for 2 hours, filtered, washed, and dried at 80℃ to obtain a porous needle-like morphology with a specific surface area of 126 m². 2 / g, active metal ion Ag + An antibacterial carrier with an adsorption capacity of 3.5g / 100g.
[0034] Comparative Example 1
[0035] Take 78.25g of cerium chloride, 6.8g of zinc chloride, and 64.5g of zirconium oxychloride, add 300mL of water, heat to 60℃, add 1.5g of PEG6000, add 2g of glacial acetic acid, and add ammonium bicarbonate solution (concentration of ammonium bicarbonate solution is 2.53mol / L) until the pH of the system is 6.7-7. Centrifuge and dry at 80℃ to obtain the first reactant.
[0036] 20g of the first reactant was mixed with 100g of water to form a slurry. 5g of concentrated phosphoric acid was added, followed by 0.05g of 1-butyl-3-methylimidazolium dibutyl phosphate. The mixture was reacted at 60℃ for 2 hours, filtered, washed, and dried at 80℃ to obtain a porous needle-like morphology with a specific surface area of 96 m². 2 / g, active metal ion Ag + An 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 organic complexes with metal ions during the precipitation process, reduce the agglomeration between 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 (ammonium bicarbonate concentration 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 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, mix it with 100g of water to form a slurry, add 5g of concentrated phosphoric acid, react at 60℃ for 1h, filter, wash, and dry at 80℃ to obtain a blocky morphology with a specific surface area of 58m². 2 / g, active metal ion Ag + An antibacterial carrier with an adsorption capacity of 1.2g / 100g.
[0041] Example 2
[0042] Preparation method of rare earth antibacterial carrier:
[0043] Take 93.9g of cerium chloride, 9.2g of zinc chloride, and 76.6g of zirconium oxychloride, add 400mL of water, heat to 60℃, add 2.4g of PEG4000, add 3g of glacial acetic acid, and add ammonium bicarbonate solution (ammonium bicarbonate solution concentration is 2.53mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:2) until the pH of the system is 6.7-7, centrifuge, and dry at 80℃ to obtain the first reactant.
[0044] 40g of the first reactant was mixed with 200g of water to form a slurry, 8.6g of concentrated phosphoric acid was added, and 0.25g of 1-butyl-3-methylimidazolium dibutyl phosphate was added. The mixture was reacted at 60℃ for 1.5h, filtered, washed, and dried at 80℃ to obtain a blocky morphology with a specific surface area of 143m². 2 / g, active metal ion Ag + An antibacterial carrier with an adsorption capacity of 3.8g / 100g.
[0045] Example 3
[0046] Take 93.9g of lanthanum chloride, 5g of zinc chloride, and 50g of zirconium oxychloride, add 500mL of water, heat to 50℃, add 1.4g of PEG4000, add 1.8g of glacial acetic acid, and add ammonium bicarbonate solution (ammonium bicarbonate solution concentration is 2.53mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:1) until the pH of the system is 6.7-7. Centrifuge, filter, and dry at 80℃ to obtain the first reactant.
[0047] Take 30g of the first reactant and mix it with 240g of water to form a slurry. Add 6g of concentrated phosphoric acid and 0.1g of 1-butyl-3-methylimidazolium dibutyl phosphate. React at 80℃ for 2 hours. Filter, wash, and dry at 80℃ to obtain a blocky morphology with a specific surface area of 136m². 2 / g, active metal ions Zn 2+ An antibacterial carrier with an adsorption capacity of 3.5g / 100g.
[0048] Example 4
[0049] Take 120g of lanthanum chloride, 13.6g of zinc chloride, and 96.7g of zirconium oxychloride, add 500mL of water, heat to 60℃, add 1.2g of PEG6000, add 6.2g of glacial acetic acid, and add ammonium bicarbonate solution (ammonium bicarbonate solution concentration is 2.53mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:2) until the pH of the system is 6.7-7. Centrifuge, filter, and dry at 80℃ to obtain the first reactant.
[0050] Take 50g of the first reactant and mix it with 350g of water to form a slurry. Add 12g of concentrated phosphoric acid and 0.2g of 1-butyl-3-methylimidazolium dibutyl phosphate. React at 90℃ for 1.5h. Filter, wash, and dry at 80℃ to obtain a blocky morphology with a specific surface area of 148m². 2 / g, active metal ions Zn 2+ An antibacterial carrier with an adsorption capacity of 3.7g / 100g.
[0051] Example 5
[0052] Take 120g of lanthanum chloride, 12g of zinc chloride, and 100g of zirconium oxychloride, add 600mL of water, heat to 60℃, add 4.2g of PEG4000, add 4.2g of glacial acetic acid, and add ammonium bicarbonate solution (ammonium bicarbonate solution concentration is 2.53mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:2) until the pH of the system is 6.7-7. Centrifuge, filter, and dry at 80℃ to obtain the first reactant.
[0053] Take 50g of the first reactant and mix it with 400g of water to form a slurry. Add 12.5g of concentrated phosphoric acid and 0.5g of 1-butyl-3-methylimidazolium dibutyl phosphate. React at 80℃ for 2 hours. Filter, wash, and dry at 80℃ to obtain a blocky morphology with a specific surface area of 158m². 2 / g, active metal ions Zn 2+ An antibacterial carrier with an adsorption capacity of 4.0 g / 100 g.
[0054] The above description of the disclosed embodiments enables those skilled in the art to make or use the 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 invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded 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 as follows: (1) Prepare a mixed aqueous solution of rare earth chloride, zinc chloride and zirconium oxychloride; (2) Heat the mixed aqueous solution, add PEG and glacial acetic acid, mix well, adjust the pH of the mixed solution to 6.7-7, filter the precipitate, dry it, and obtain the first reactant; (3) The first reactant was mixed with water to form a slurry, and concentrated phosphoric acid and 1-butyl-3-methylimidazolium dibutyl phosphate were added. The reaction was carried out, the precipitate was filtered and dried to obtain a rare earth antibacterial carrier. 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). The concentration of rare earth ions in the mixed aqueous solution is 0.3-0.9 mol / L; The rare earth chloride is lanthanum chloride, cerium chloride, or lanthanum-cerium chloride. In step (2), the heating is carried out to 40-80℃, and the pH value is adjusted by adding 2.53 mol / L ammonium bicarbonate solution to the mixed solution; 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. The method for preparing the ammonium bicarbonate solution is as follows: prepare a 2.53 mol / L ammonium bicarbonate solution, add 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. In step (3), the mass ratio of the first reactant to the water is 1:3-8; In step (3), the mass ratio of concentrated phosphoric acid to the first reactant is 0.2-0.3:1, and the mass ratio of 1-butyl-3-methylimidazolium dibutyl phosphate to the first reactant is 0.001-0.01:
1.
2. 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℃ and the time is 0.5-2h.