Zinc sustained-release material, preparation method therefor, and use thereof

Abstract

The present invention relates to the technical field of sustained-release materials, and provides a zinc sustained-release material, a preparation method therefor, and a use thereof. The zinc sustained-release material of the present invention comprises zinc polyphosphate loaded on a carrier framework, and based on the total mass of the zinc sustained-release material, the loading capacity of the zinc polyphosphate is 55% to 70%. According to the zinc sustained-release material provided by the present invention, sustained-release of zinc ions is achieved by means of a specific loading capacity of zinc polyphosphate, and stable release of 0.02-1 mg / L of zinc ions can be maintained at a flow rate of 4-6 L / min, so that the zinc sustained-release material can be applied to high-flow scenarios such as bathing water, and the defects of existing products are overcome.

Description

Zinc sustained-release material and its preparation method and application

[0001] Cross-references

[0002] This application claims priority to Chinese patent application No. 202311702959.5, filed on December 12, 2023, entitled “Zinc sustained-release material, preparation method and application thereof,” and all disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present invention relates to the technical field of sustained-release materials, and in particular to a zinc sustained-release material and a preparation method and application thereof. Background Art

[0004] Zinc is one of the essential trace elements for the human body. It has functions such as maintaining normal appetite and enhancing human immunity. Zinc ions also have antibacterial effects in water. Some zinc preparations are also used in medicine or beauty cosmetics.

[0005] However, the existing technical solutions can only achieve stable sustained release of zinc ions under small flow rates, and the amount of zinc ion dissolution is low, which cannot be applied to scenarios with high flow rates such as bathing water flow rates (4-6L / min).

[0006] Summary of the Invention

[0007] The present invention aims to solve at least one of the technical problems existing in the related art. To this end, the present invention provides a zinc sustained-release material that can maintain a stable release of 0.02-1 mg / L zinc ions at a flow rate of 4-6 L / min.

[0008] The invention also provides a method for preparing the zinc sustained-release material.

[0009] The invention also provides an application of the zinc slow-release material.

[0010] In a first aspect, the present invention provides a zinc slow-release material, comprising zinc polyphosphate loaded on a carrier skeleton, wherein the loading amount of the zinc polyphosphate is 55%-70% based on the total mass of the zinc slow-release material.

[0011] According to the zinc slow-release material provided by the present invention, the carrier skeleton is quartz sand with a mesh size of 100-120.

[0012] According to the zinc slow-release material provided by the present invention, the zinc slow-release material is in granular form with a particle size of 1-4 mm.

[0013] According to the zinc slow-release material provided by the present invention, the zinc slow-release material is made of the following raw materials in parts by weight:

[0014] The molar ratio of zinc element to phosphate ion is controlled at 1:0.5-1:0.8.

[0015] According to the zinc sustained-release material provided by the present invention, the phosphate is selected from one or more of sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, magnesium phosphate, magnesium hydrogen phosphate, and magnesium dihydrogen phosphate.

[0016] In one embodiment of the present application, the phosphate is selected from one or more of calcium phosphate, calcium hydrogen phosphate, and calcium dihydrogen phosphate.

[0017] In one embodiment of the present application, the phosphate is selected from one or both of calcium hydrogen phosphate and calcium dihydrogen phosphate.

[0018] According to the zinc slow-release material provided by the present invention, the flux is selected from one or more of boron oxide, calcium oxide, and phosphorus oxide.

[0019] In one embodiment of the present application, the flux is selected from one or both of boron oxide and calcium oxide.

[0020] In a second aspect, the present invention provides a method for preparing the above-mentioned zinc sustained-release material, comprising:

[0021] The carrier skeleton, zinc oxide, phosphate and flux are mixed evenly, water is added to form a wet powder, granulated to obtain granules with a diameter of 3-5 mm, and then dried, melt-calcined, cooled and crushed to obtain a granular zinc slow-release material.

[0022] According to the preparation method provided by the present invention, the drying temperature is 110-130°C, and the temperature of the melt calcination is controlled at 1500-1800°C.

[0023] In a third aspect, the present invention provides use of the above-mentioned zinc slow-release material in purifying bathing water.

[0024] According to the application provided by the present invention, the zinc slow-release material is loaded into a filter element, and tap water is passed through the filter element at a flow rate of 4-6 L / min.

[0025] The above one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects:

[0026] The zinc sustained-release material provided by the present invention achieves sustained release of zinc ions through a specific loading amount of zinc polyphosphate, and can maintain a stable release of 0.02-1 mg / L zinc ions at a flow rate of 4-6 L / min, so it can be applied to high-flow scenarios such as bathing water, making up for the shortcomings of existing products.

[0027] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG1 is a schematic diagram of a process for preparing a zinc sustained-release material according to an embodiment of the present invention;

[0029] FIG2 is a microscopic morphology of the zinc sustained-release material obtained in an embodiment of the present invention;

[0030] FIG3 is a physical picture of the zinc sustained-release material obtained in an embodiment of the present invention. DETAILED DESCRIPTION

[0031] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0032] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the embodiment of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0033] In a first aspect, the present invention provides a zinc slow-release material, comprising zinc polyphosphate loaded on a carrier skeleton, wherein the loading amount of the zinc polyphosphate is 55-70% based on the total mass of the zinc slow-release material.

[0034] As is well known in the art, zinc ion has the effect of sterilization and disinfection, and under the environment of static liquid immersion or dynamic liquid flow through / flushing, stably releases as time goes by, just can realize long-acting bactericidal effect.In the prior art, zinc oxide is usually adopted as the release source material of zinc ion, but in fact, it is very poor to release the source material release effect using zinc oxide, and it is the zinc ion stabilization long-term release that can not satisfy concentration and is 0.02-1mg / L.In order to overcome this problem, the method that zinc oxide is made into zinc oxide nanorod coating is arranged in the prior art, but the process of preparing zinc oxide nanorod coating is comparatively complicated, and the zinc ion release rate can be too fast like this, thereby needing zinc oxide part to be converted into zinc phosphate to reduce the release rate of zinc ion, referring to CN115501392A, it is too loaded down with trivial details to summarize in words this method.

[0035] During the development of this invention, the conventional idea of ​​using zinc oxide as the release source material was broken, and zinc polyphosphate loaded on the carrier skeleton was used as the zinc release source material. By controlling the loading amount of zinc polyphosphate, it is possible to achieve a stable release of 0.02-1 mg / L zinc ions at a flow rate of 4-6 L / min, so that it can be used in high-flow scenarios such as bathing water, making up for the lack of products in this aspect.

[0036] Among them, 1 mg / L meets the upper limit of 1000 ppb specified in the sanitary standards for drinking water, and the significance of 0.02 mg / L, i.e. 20 ppb, is that the minimum inhibitory concentration of zinc ions is 6.5 ppb. The sustained-release concentration of the present invention can reach above this index value within a water flow of 25 t, and has an antibacterial effect.

[0037] The carrier skeleton of the present invention can be a conventional carrier that provides a skeleton structure, such as a ceramic matrix, quartz sand, and the like.

[0038] In some embodiments of the present invention, the carrier skeleton is 100-120 mesh quartz sand. Quartz sand is quartz particles obtained by crushing quartz stone. Quartz stone is a non-metallic mineral, a hard, wear-resistant, and chemically stable silicate mineral. Quartz stone comes in a variety of common sizes. The present invention uses 100-120 mesh quartz sand, which facilitates rapid melting during heating.

[0039] In some embodiments of the present invention, the zinc sustained-release material is in granular form with a particle size of 1-4 mm.

[0040] In some embodiments of the present invention, the zinc sustained-release material is made of the following raw materials in parts by weight:

[0041] Among them, the molar ratio of zinc element to phosphate ion should be controlled at 1:0.5-1:0.8.

[0042] In some embodiments of the present invention, the phosphate is selected from one or more of sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, magnesium phosphate, magnesium hydrogen phosphate, and magnesium dihydrogen phosphate.

[0043] In some embodiments of the present invention, the phosphate is selected from one or more of calcium phosphate, calcium hydrogen phosphate, and calcium dihydrogen phosphate.

[0044] In one embodiment of the present invention, the phosphate is selected from calcium hydrogen phosphate and calcium dihydrogen phosphate, which can be mixed in any proportion.

[0045] Among them, phosphate reacts with zinc oxide to generate zinc polyphosphate, and the amount of each component is controlled within the above range to obtain a zinc sustained-release material that meets the zinc polyphosphate loading capacity.

[0046] The function of flux is to lower the melting temperature of the material, thereby facilitating melt calcination.

[0047] In some embodiments of the present invention, the flux is selected from one or more of boron oxide, calcium oxide, and phosphorus oxide.

[0048] In one embodiment of the present invention, the flux is selected from boron oxide and calcium oxide, which can be mixed in any proportion.

[0049] In a second aspect, the present invention provides a method for preparing the above-mentioned zinc sustained-release material, comprising:

[0050] The carrier skeleton, zinc oxide, phosphate and flux are mixed evenly, water is added to form a wet powder, granulated to obtain granules with a diameter of 3-5 mm, and then dried, melt-calcined, cooled and crushed to obtain a granular zinc slow-release material.

[0051] The present invention requires granulation, drying and then calcination and melting, which can make the material melt relatively quickly, greatly shorten the heating time and save energy. If the material is directly mixed and then melted and calcined, a semi-solid is formed, not a liquid with strong fluidity.

[0052] In some embodiments of the present invention, the drying temperature is 110-130°C. In one embodiment of the present invention, the drying temperature is 120°C.

[0053] In some embodiments of the present invention, the temperature of the melt calcination is controlled at 1500-1800°C.

[0054] In a third aspect, the present invention provides use of the above-mentioned zinc slow-release material in purifying bathing water.

[0055] According to the application provided by the present invention, the zinc slow-release material is loaded into a filter element, and tap water is passed through the filter element at a flow rate of 4-6 L / min.

[0056] The filter element of the present invention can be any commercially available filter element with filtering function. It only needs to ensure that the water flow can completely pass through the loaded filter material at the corresponding flow rate, and the filter material will not be washed out of the filter element by the water flow.

[0057] It should be noted that the bathing water mentioned in the present invention is the bathing water before heating, that is, the tap water is heated after being purified by the zinc slow-release material of the present invention. Therefore, when the present invention conducts application tests, only the flow rate of the tap water is considered, and the temperature remains at room temperature.

[0058] Specific embodiments will be described below.

[0059] In the following examples, unless otherwise specified, all materials used can be obtained through regular commercial channels.

[0060] In the following examples, the particle size of the quartz sand used is 100-120 mesh; zinc oxide is a common white powder available on the market; and the raw materials used in the present invention are all commercially available food grade.

[0061] Example 1

[0062] This embodiment provides a zinc sustained-release material, the raw materials for its preparation are the following components in parts by weight:

[0063] The above materials were mixed uniformly, and a small amount of water was added to form a wet powder. After granulation, granules with a diameter of 3-5 mm were formed. The mixture was dried at 120°C, heated to 1500°C in a kiln for melt calcination, and kept at this temperature for 4 hours. After cooling, the mixture was crushed and sieved to obtain granules with a diameter of 1-4 mm. After dust removal by air showering, a granular zinc slow-release material was obtained. The preparation process is shown in Figure 1. Figure 2 is a microscopic morphology of the zinc slow-release material obtained in accordance with the present invention; Figure 3 is a physical image of the zinc slow-release material obtained in accordance with the present invention.

[0064] 100 g of the zinc sustained-release material obtained in this example was loaded into a filter element. Tap water was passed through the filter element at a flow rate of 6 L / min at room temperature. The zinc content in the flow-through liquid of the filter element was tested according to the method of GB / T 5750.6-2023. The test results are shown in Table 1.

[0065] Table 1

[0066] Test results showed that the initial zinc ion concentration of 100g of the zinc sustained-release material was 0.885mg / L, lower than the 1000ppb upper limit specified in the drinking water hygiene standards, demonstrating good safety. Even after 25t of water flow, the sustained-release zinc ion concentration remained at 0.069mg / L, significantly superior to commercially available zinc-rich sustained-release materials.

[0067] Example 2

[0068] This embodiment provides a zinc sustained-release material, the raw materials for its preparation are the following components in parts by weight:

[0069] The above materials are mixed evenly, and a small amount of water is added to prepare a wet powder. After granulation, particles with a diameter of 3-5 mm are formed. The particles are dried at 120°C, transferred to a kiln and heated to 1600°C for melting and calcining. The mixture is kept warm for 3 hours. After cooling, the particles are crushed and sieved to obtain particles with a diameter of 1-4 mm. The particles are then air-showered to remove dust to obtain a granular zinc slow-release material.

[0070] 100 g of the zinc sustained-release material obtained in this example was loaded into a filter element. Tap water was passed through the filter element at a flow rate of 6 L / min at room temperature. The zinc content in the flow-through liquid of the filter element was tested according to the method of GB / T 5750.6-2023. The test results are shown in Table 2.

[0071] Table 2

[0072] Test results showed that the initial zinc ion concentration of 100g of the zinc sustained-release material was 0.692mg / L, lower than the upper limit of 1mg / L specified in the drinking water hygiene standards, demonstrating good safety. Even after 25t of water flow, the sustained-release concentration of zinc ions still reached 0.025mg / L, significantly superior to commercially available zinc-rich sustained-release materials.

[0073] Example 3

[0074] This embodiment provides a zinc sustained-release material, the raw materials for its preparation are the following components in parts by weight:

[0075] The above materials are mixed evenly, and a small amount of water is added to prepare a wet powder. After granulation, particles with a diameter of 3-5 mm are formed. The particles are dried at 120°C, transferred to a kiln and heated to 1800°C for melting and calcining. The mixture is kept warm for 2 hours. After cooling, the particles are crushed and sieved to obtain particles with a diameter of 1-4 mm. The particles are then air-showered to remove dust to obtain a granular zinc slow-release material.

[0076] 100 g of the zinc sustained-release material obtained in this example was loaded into a filter element. Tap water was passed through the filter element at a flow rate of 6 L / min at room temperature. The zinc content in the flow-through liquid of the filter element was tested according to the method of GB / T 5750.6-2023. The test results are shown in Table 3.

[0077] Table 3

[0078] Test results showed that the initial zinc ion concentration of 100g of the zinc sustained-release material was 0.976mg / L, lower than the upper limit of 1mg / L specified in the drinking water hygiene standards, demonstrating good safety. Even after 25t of water flow, the sustained-release concentration of zinc ions still reached 0.020mg / L, significantly superior to commercially available zinc-rich sustained-release materials.

[0079] Comparative Example 1

[0080] This comparative example provides a commercially available zinc-rich slow-release material. 100 g of the commercially available zinc-rich slow-release material of this comparative example was loaded into a filter element. Tap water was passed through the filter element at a flow rate of 6 L / min at room temperature. The zinc content in the flow-through liquid of the filter element was detected according to the GB / T 5750.6-2023 method. The test results are shown in Table 4.

[0081] Table 4

[0082] It can be seen that the zinc ion sustained-release concentration of the commercially available zinc-rich sustained-release material is only 0.012 mg / L after 5 tons of water are passed through it, and no zinc ions are released after 10 tons of water are passed through it, which obviously cannot achieve good stable and continuous release of zinc ions.

[0083] Comparative Example 2

[0084] This comparative example provides an antibacterial composite material disclosed in CN114685185A, and its preparation method is as follows:

[0085] (1) Preparation of ceramic substrate: refer to steps S702, S704 and S706.

[0086] (2) Preparing a soluble antimicrobial glass melt: Weighing raw materials according to a mass ratio of zinc oxide: boron oxide: calcium oxide: phosphorus oxide = 10:20:30:40 and mixing the raw materials to obtain a mixture; melting the mixture to obtain a soluble antimicrobial glass melt. See steps S302 and S304.

[0087] (3) The antibacterial glass melt is applied to the surface of the ceramic core. Referring to step S106, the weight proportion of zinc oxide in the entire antibacterial composite material is 10%.

[0088] 100 g of the antibacterial material of this comparative example was loaded into a filter element. Tap water was passed through the filter element at a flow rate of 6 L / min at room temperature. The zinc content in the flow-through liquid of the filter element was detected according to the GB / T 5750.6-2023 method. The test results are shown in Table 5.

[0089] Table 5

[0090] It can be seen that the sustained-release concentration of zinc ions in the antibacterial composite material is only 0.025 mg / L after 5t of water is passed through it, and no sustained-release of zinc ions is achieved after 15t of water is passed through it, which obviously fails to achieve a good stable and sustained release of zinc ions.

[0091] Comparative Example 3

[0092] In this comparative example, 200 g of the antibacterial material of Comparative Example 2 was loaded into a filter element. Tap water was passed through the filter element at a flow rate of 6 L / min at room temperature. The zinc content in the flow-through liquid of the filter element was detected according to the GB / T 5750.6-2023 method. The test results are shown in Table 6.

[0093] Table 6

[0094] It can be seen that even if the dosage of the antibacterial composite material is increased, the sustained-release concentration of zinc ions is only 0.026 mg / L after 5 tons of water is passed through, and no zinc ions are released after 15 tons of water is passed through. It is obviously impossible to achieve a good stable and continuous release of zinc ions.

[0095] Comparative Example 4

[0096] This comparative example provides an antibacterial phosphate glass. The raw materials (calculated by weight) are prepared as follows: 23.26 parts of boric acid, 65.97 parts of sodium dihydrogen phosphate, 0.89 parts of copper oxide, 1.05 parts of silver oxide, 2.0 parts of four-needle zinc oxide whiskers, and 6.83 parts of calcium oxide. The raw materials are mixed evenly and passed through a 60-mesh standard sieve to obtain a mixture. The mixture is placed in a quartz crucible, heated to 900°C at a rate of 7°C / min, kept warm for 50 minutes, and subjected to a fusion reaction to obtain a glass melt, i.e., a melt. The glass melt is poured into a homemade mold to form and cool to obtain an antibacterial phosphate glass. The antibacterial phosphate glass is poured into a ball mill, and a stainless steel ball (or porcelain ball) stirrer is added. The speed is set to 45 rpm and ground for about 30 minutes. Burrs and burrs are removed by friction and impact of the glass particles themselves. After grinding, the mixture is passed through a 40-mesh standard sieve to obtain a finished glass product.

[0097] 100 g of the antibacterial phosphate glass of this comparative example was loaded into a filter element. Tap water was passed through the filter element at a flow rate of 6 L / min at room temperature. The zinc content in the filter element flowthrough was detected according to the GB / T 5750.6-2023 method. The test results are shown in Table 7.

[0098] Table 7

[0099] It can be seen that the sustained-release concentration of zinc ions in the antibacterial phosphate glass was only 0.003 mg / L after 5t of water flow, and no sustained-release of zinc ions was observed after 10t of water flow, which obviously failed to achieve a good stable and sustained release of zinc ions.

[0100] Finally, it should be noted that the above embodiments are intended to illustrate the present invention only and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications, or equivalent substitutions of the technical solutions of the present invention do not depart from the spirit and scope of the technical solutions of the present invention and are intended to be encompassed by the claims of the present invention. Industrial Applicability

[0101] The present invention provides a zinc sustained-release material, a preparation method, and applications thereof. The zinc sustained-release material comprises zinc polyphosphate loaded on a carrier skeleton, with the zinc polyphosphate loading being 55%-70% based on the total mass of the zinc sustained-release material. The zinc sustained-release material provided by the present invention achieves sustained release of zinc ions through a specific loading of zinc polyphosphate, maintaining a stable release of 0.02-1 mg / L of zinc ions at a flow rate of 4-6 L / min. This material can be applied to high-flow scenarios such as bathing water, addressing the shortcomings of existing products and exhibiting good economic value and application prospects.

Claims

1. A zinc sustained-release material, characterized in that: The invention comprises zinc polyphosphate loaded on a carrier skeleton, and the loading amount of the zinc polyphosphate is 55%-70% based on the total mass of the zinc sustained-release material.

2. The zinc sustained-release material according to claim 1, characterized in that: The carrier skeleton is quartz sand of 100-120 meshes.

3. The zinc sustained-release material according to claim 1 or 2, characterized in that: The zinc sustained-release material is in granular form with a particle size of 1-4 mm.

4. The zinc sustained-release material according to any one of claims 1 to 3, characterized in that: The zinc sustained-release material is made of the following raw materials in parts by weight: 22-32 parts of quartz sand Zinc oxide 28-40 parts Phosphate 20-55 parts 8-12 parts of flux, Among them, the molar ratio of zinc element to phosphate ion is controlled at 1:0.5-1:0.

8.

5. The zinc sustained-release material according to claim 4, characterized in that: The phosphate is selected from one or more of sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, magnesium phosphate, magnesium hydrogen phosphate, and magnesium dihydrogen phosphate.

6. The zinc sustained-release material according to claim 5, wherein: The phosphate is selected from one or more of calcium phosphate, calcium hydrogen phosphate, and calcium dihydrogen phosphate.

7. The zinc sustained-release material according to claim 6, wherein: The phosphate is selected from one or both of calcium hydrogen phosphate and calcium dihydrogen phosphate.

8. The zinc sustained-release material according to any one of claims 4 to 7, characterized in that: The flux is selected from one or more of boron oxide, calcium oxide and phosphorus oxide.

9. The zinc sustained-release material according to claim 8, characterized in that: The flux is selected from one or both of boron oxide and calcium oxide.

10. The method for preparing the zinc sustained-release material according to any one of claims 1 to 9, characterized in that: include: The carrier skeleton, zinc oxide, phosphate and flux are mixed evenly, water is added to form a wet powder, granulated to obtain granules with a diameter of 3-5 mm, and then dried, melt-calcined, cooled and crushed to obtain a granular zinc slow-release material.

11. The preparation method according to claim 10, characterized in that: The drying temperature is 110-130°C, and the melting calcination temperature is controlled at 1500-1800°C.

12. Use of the zinc sustained-release material according to any one of claims 1 to 9 in purifying bathing water.

13. The use according to claim 12, characterized in that: The zinc slow-release material is loaded into a filter element, and tap water is passed through the filter element at a flow rate of 4-6 L / min.

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