Anti-agglomeration preparation device and method for nanoscale ultrafine powder

Abstract

The invention belongs to the technical field of nano material preparation, and particularly relates to an anti-agglomeration preparation device and method for nanoscale ultrafine powder. Nanoscale hydroxyapatite is named as nHA for short, is nanoscale ultrafine powder, is easy to agglomerate in a normal-temperature and normal-pressure air exposure environment, and agglomerates into a substance with larger granularity. The modified casein is used as the filler, so that the nHA particles are compounded and dispersed in the filler, and the nano agglomeration effect is effectively prevented. The method is relatively low in cost and suitable for large-scale industrial application.

Description

Technical Field

[0001] The present invention relates to the field of nanomaterials, and in particular to an anti-agglomeration preparation device and method for nano-level ultrafine powder. Background Art

[0002] Nanoagglomeration refers to the phenomenon that nanoparticles connect with each other to form larger particle agglomerates during the preparation, separation, processing and storage process.

[0003] Nano-hydroxyapatite (nHA) is a highly effective calcium supplement with high absorption and safety. However, as a nano-powder, nHA inevitably undergoes nanoagglomeration. This agglomeration of nHA increases particle size, significantly reducing its absorption rate. Addressing the agglomeration issue of nHA requires considering both the cost of making it viable for large-scale industrial production and the safety of its absorption by the human body.

[0004] Current methods to address nanoaggregation primarily rely on the use of inert gas for storage, which is inefficient, costly, and impractical for large-scale industrial production. This invention uses modified casein as a filler, with nHA particles dispersed throughout the filler, effectively preventing the nanoaggregation effect. Furthermore, casein, a major component of cow's milk, is widely available and safe for the human body. Summary of the Invention

[0005] In view of the above deficiencies in the prior art, the purpose of the embodiments of the present invention is to provide an anti-agglomeration preparation device and method for nano-scale ultrafine powders, which can solve the problems of low efficiency, high cost and inability to achieve large-scale industrial production in the prior art.

[0006] 1. In a first aspect of the present invention, a device for preparing nano-scale ultrafine powders to prevent agglomeration is provided. The device comprises a pre-treatment system, a composite dispersion system, a forming and drying system, and a detection and analysis platform.

[0007] The pre-treatment system includes a nano-crushing unit, a vacuum drying oven, a low-temperature plasma surface treatment device and a casein modification device;

[0008] The composite dispersion system includes a high-pressure homogenization unit and an ultrasonic-microwave synergistic generator;

[0009] The drying and molding system includes a vacuum freeze drying system and a fluidized bed coating device;

[0010] The nano-crushing unit is provided with a coarse particle inlet, which is used to input animal bone coarse particles, and the nano-crushing unit is crushed into nano-grade hydroxyapatite ultrafine powder (abbreviated as nHA);

[0011] The vacuum drying oven performs surface water adsorption treatment on the nHA;

[0012] The low-temperature plasma surface treatment device performs surface etching on the nHA;

[0013] The casein modification device is provided with a casein feed port, and the casein feed port is used to input casein particles;

[0014] The casein modification device performs casein enzymatic hydrolysis (casein hydrolysis) on the casein particles;

[0015] The casein modification device performs thiol modification on the casein particles to form modified casein;

[0016] Mixing the nHA with Tris-HCl buffer to form an nHA suspension;

[0017] Slowly injecting the modified casein into the nHA suspension to form a mixed solution of nHA and modified casein;

[0018] The jet of the high-pressure homogenizing unit forms a velocity gradient difference in the homogenizing valve or the flow-limiting gap, which causes the bubbles in the nHA and modified casein mixture to burst due to a sudden pressure drop, resulting in a cavitation effect and a collision effect between the material particles (referring to the nHA and the modified casein);

[0019] The ultrasonic-microwave cooperative reactor generates ultrasonic waves and utilizes the cavitation effect of the ultrasonic waves to disperse and emulsify the material particles.

[0020] The nHA and modified casein mixture is quickly frozen to below the eutectic point (usually -30°C to -50°C) using a vacuum freeze-drying system. Water forms an ice crystal skeleton, locking the original structure of the nHA-modified casein mixture to form nHA and casein mixed ice crystals.

[0021] A fluidized bed coating device is used to coat the entire surface of the nHA and casein mixed ice crystals without any dead corners; the solvent (water / organic phase) is volatilized simultaneously to achieve dynamic drying and molding.

[0022] A second aspect of the present invention provides a method for preparing nano-scale ultrafine powders with anti-agglomeration properties, which is applied to the above-mentioned device for preparing nano-scale ultrafine powders with anti-agglomeration properties, comprising:

[0023] S1: The nano-crusher unit crushes the coarse particles of hydroxyapatite into nano-sized hydroxyapatite (nHA for short).

[0024] S2: The vacuum dryer performs surface water adsorption treatment on the nHA;

[0025] S3: The low-temperature plasma surface treatment device performs surface etching on the nHA;

[0026] S4: performing enzymatic hydrolysis (casein hydrolysis) on the casein by the casein modification device: decomposing the macromolecular casein into small molecular peptides and amino acids by trypsin;

[0027] S5: performing thiolation modification (Thiolation) on the casein by the casein modification device to introduce thiol groups (-SH) into the casein molecules by a chemical method;

[0028] S6: Mix the nHA with Tris-HCl buffer to obtain an nHA suspension.

[0029] S7: slowly injecting the modified casein into the nHA suspension to obtain a mixed solution of nHA and modified casein.

[0030] S8: utilizing the velocity gradient difference, cavitation effect, and collision effect of the high-pressure homogenization unit, the material particles (referring to the nHA and the modified casein) are fully mixed.

[0031] S9: utilizing the ultrasonic-microwave synergistic reactor to generate cavitation, thereby dispersing and emulsifying the material particles, adding trehalose, and reducing the interfacial energy of the dispersed phase, so that the nHA and modified casein mixture forms a sufficient, uniform, and stable mixture.

[0032] S10: Using the vacuum freeze-drying system, the nHA and modified casein mixture is quickly frozen to below the eutectic point, so that water forms an ice crystal skeleton, locking the original structure of the nHA and modified casein mixture.

[0033] S11: Using the fluidized bed coating equipment, dynamic drying and molding of the nHA and modified casein mixture is achieved.

[0034] The beneficial effects brought about by the technical solution provided by the embodiment of the present invention include at least:

[0035] In the embodiment of the present invention, modified casein is used as a filler, and nHA particles are compositely dispersed in the filler, which effectively prevents the occurrence of nano-agglomeration effect. At the same time, casein is the main component of cow's milk, has a wide source and is safe for the human body. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The accompanying drawings are only for the purpose of illustrating specific embodiments and are not to be considered as limiting the present invention. Throughout the drawings, the same reference symbols represent the same components. Obviously, the drawings described below are only some embodiments of the present invention. It is clear that those skilled in the art can derive other drawings based on these drawings without inventive effort.

[0037] Figure 1 Schematic diagram of the structure of an anti-agglomeration preparation device for nano-scale ultrafine powder provided by an embodiment of the present invention;

[0038] Figure 2 This is a scanning electron microscope observation image of a nano-level ultrafine powder provided by an embodiment of the present invention;

[0039] Figure 3 The present invention provides a flow chart of a method for preparing nano-scale ultrafine powder with anti-agglomeration properties.

[0040] Explanation of the accompanying drawings: 1-nano-crushing unit; 2-vacuum drying oven; 3-low-temperature plasma surface treatment device; 4-casein modification device; 5-high-pressure homogenization unit; 6-ultrasonic-microwave co-reactor; 7-vacuum freeze-drying system; 8-fluidized bed coating equipment. DETAILED DESCRIPTION

[0041] In order to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the embodiments described are part of the embodiments of the present invention, rather than all of the embodiments. It should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work should fall within the scope of protection of the present invention.

[0042] Furthermore, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessarily obscuring the concepts disclosed in the present invention.

[0043] Exemplary embodiments are described in detail herein, with examples illustrated in the accompanying drawings. When the following description refers to the drawings, identical numerals in different figures represent identical or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments are not intended to represent all embodiments consistent with the present invention.

[0044] Reference Manual Figure 1 , shows a structural schematic diagram of an anti-agglomeration preparation device for nano-scale ultrafine powder provided by an embodiment of the present invention.

[0045] An embodiment of the present invention provides a device for preparing nano-scale ultrafine powder, including: 1-a nano-crushing unit; 2-a vacuum drying oven; 3-a low-temperature plasma surface treatment device; 4-a casein modification device; 5-a high-pressure homogenization unit; 6-an ultrasonic-microwave co-reactor; 7-a vacuum freeze-drying system; and 8-a fluidized bed coating device.

[0046] The pre-treatment system includes a nano-crushing unit, a vacuum drying oven, a low-temperature plasma surface treatment device and a casein modification device;

[0047] The composite dispersion system includes a high-pressure homogenization unit and an ultrasonic-microwave synergistic generator;

[0048] The drying and molding system includes a vacuum freeze drying system and a fluidized bed coating device;

[0049] The nano-crushing unit is provided with a coarse particle inlet, which is used to input animal bone coarse particles, and the nano-crushing unit is crushed into nano-grade hydroxyapatite ultrafine powder (abbreviated as nHA);

[0050] The vacuum drying oven performs surface water adsorption treatment on the nHA;

[0051] The low-temperature plasma surface treatment device performs surface etching on the nHA;

[0052] The casein modification device is provided with a casein feed port, and the casein feed port is used to input casein particles;

[0053] The casein modification device performs casein enzymatic hydrolysis (casein hydrolysis) on the casein particles;

[0054] The casein modification device performs thiol modification on the casein particles to form modified casein;

[0055] Mixing the nHA with Tris-HCl buffer to form an nHA suspension;

[0056] Slowly injecting the modified casein into the nHA suspension to form a mixed solution of nHA and modified casein;

[0057] The jet of the high-pressure homogenizing unit forms a velocity gradient difference in the homogenizing valve or the flow-limiting gap, which causes the bubbles in the nHA and modified casein mixture to burst due to a sudden pressure drop, resulting in a cavitation effect and a collision effect between the material particles (referring to the nHA and the modified casein);

[0058] The ultrasonic-microwave cooperative reactor generates ultrasonic waves and utilizes the cavitation effect of the ultrasonic waves to disperse and emulsify the material particles.

[0059] The nHA and modified casein mixture is quickly frozen to below the eutectic point (usually -30°C to -50°C) using a vacuum freeze-drying system. Water forms an ice crystal skeleton, locking the original structure of the nHA-modified casein mixture to form nHA and casein mixed ice crystals.

[0060] A fluidized bed coating device is used to coat the entire surface of the nHA and casein mixed ice crystals without any dead corners; the solvent (water / organic phase) is volatilized simultaneously to achieve dynamic drying and molding.

[0061] The beneficial effects brought about by the technical solution provided by the embodiment of the present invention include at least:

[0062] In the embodiment of the present invention, modified casein is used as a filler, and nHA particles are compositely dispersed in the filler, which effectively prevents the occurrence of nano-agglomeration effect. At the same time, casein is the main component of cow's milk, has a wide source and is safe for the human body.

[0063] In a possible implementation, the low-temperature plasma surface treatment device releases plasma oxygen atoms to perform surface etching on the nHA.

[0064] The casein modification device decomposes macromolecular casein into small molecular peptide segments and amino acids through trypsin.

[0065] The chemical method for thiol modification of the casein modification device is specifically hydroxylamine (NH2OH) treatment, hydrolysis to remove the acetyl group and release free -SH.

[0066] The modified casein is injected into the nHA suspension by a reverse addition method to form a mixed solution of nHA and modified casein.

[0067] The solid-to-liquid ratio of the nHA suspension to the modified casein is 1:0.8.

[0068] The pressure of the high-pressure homogenization three-stage treatment of the high-pressure homogenization unit is from 1000 bar to 1500 bar and then to 800 bar.

[0069] It should be noted that 0.05% trehalose was added as a lyoprotectant. The hydroxyl groups (-OH) of trehalose form strong hydrogen bonds with water molecules, reconstructing the hydration layer at the interface and forming a high-density hydration shell. Simultaneously, temperature control reduces the interfacial energy of the dispersed phase, improving the stability of the mixture under temperature fluctuations (such as freeze-thaw cycles).

[0070] The cold trap temperature of the vacuum freeze-drying system is ≤-50°C.

[0071] The coating solution formula is 1% hydroxypropyl methylcellulose + 0.2% lecithin.

[0072] Reference Manual Figure 2 , shows a scanning electron microscope observation image of a nano-scale ultrafine powder provided by an embodiment of the present invention.

[0073] Check whether the finished product meets the expected standards. There are two main indicators. The main control particle size, the diameter range of mHA particles, less than 10nm is considered to meet the definition of nano-sized nHA. The distribution width, which represents the statistically significant uniformity of the particle distribution.

[0074] The mixed nHA-casein suspension was diluted with Tris-HCl buffer (pH 7.4) to a solids content of 0.01-0.1% to minimize multiple scattering. Large particles were removed by pre-filtration through a 0.22 μm PVDF filter. 0.1% polyoxyethylene and sorbitan were added to suppress bubble formation. Automatic sampling was performed every 5 minutes for 1 hour, and the median value was used as the final test result.

[0075] The sample was a mixed nHA-casein suspension using a SU8010 scanning electron microscope with an accelerating voltage of 5.0 kV. The distance from the sample to the objective aperture was 14.0 mm, and the secondary electron image was taken at a magnification of 18,000 times. Figure 2 As shown, the distribution of nHA and casein is sufficient, uniform and stable, and the particle size of casein is about 1.5 to 2 times that of nHA.

[0076] The core test result parameter values ​​are as follows:

[0077] Main particle size:

[0078] D50(LD)5-8nm

[0079] Characterizing the distribution width:

[0080] Span value <1.2((D90-D10) / D50)

[0081] The test result parameters meet the set values.

[0082] Reference Manual Figure 3 , which shows a schematic flow chart of an anti-agglomeration preparation method for nano-scale ultrafine powder provided by an embodiment of the present invention.

[0083] An embodiment of the present invention provides a method for preparing nano-scale ultrafine powders with anti-agglomeration properties, which is applied to the above-mentioned device for preparing nano-scale ultrafine powders with anti-agglomeration properties, comprising:

[0084] S1: The nano-crusher unit crushes the coarse particles of hydroxyapatite into nano-sized hydroxyapatite (nHA for short).

[0085] S2: The vacuum dryer performs surface water adsorption treatment on the nHA;

[0086] S3: The low-temperature plasma surface treatment device performs surface etching on the nHA;

[0087] S4: performing enzymatic hydrolysis (casein hydrolysis) on the casein by the casein modification device: decomposing the macromolecular casein into small molecular peptides and amino acids by trypsin;

[0088] S5: performing thiolation modification (Thiolation) on the casein by the casein modification device to introduce thiol groups (-SH) into the casein molecules by a chemical method;

[0089] S6: mixing the nHA with Tris-HCl buffer to obtain an nHA suspension;

[0090] S7: slowly injecting the modified casein into the nHA suspension to obtain a mixture of nHA and modified casein;

[0091] S8: utilizing the velocity gradient difference, cavitation effect, and collision effect of the high-pressure homogenization unit to fully mix the material particles (referring to the nHA and the modified casein);

[0092] S9: utilizing the ultrasonic-microwave synergistic reactor to generate cavitation, thereby dispersing and emulsifying the material particles. Adding trehalose and reducing the interfacial energy of the dispersed phase allows the nHA and modified casein mixture to form a sufficient, uniform, and stable mixture;

[0093] S10: using the vacuum freeze-drying system, quickly freezing the nHA and modified casein mixture to below the eutectic point, so that water forms an ice crystal skeleton, locking the original structure of the nHA and modified casein mixture;

[0094] S11: using the fluidized bed coating equipment to achieve dynamic drying and molding of the nHA and modified casein mixture;

[0095] The beneficial effects brought about by the technical solution provided by the embodiment of the present invention include at least:

[0096] In the embodiment of the present invention, modified casein is used as a filler, and nHA particles are compositely dispersed in the filler, which effectively prevents the occurrence of nano-agglomeration effect. At the same time, casein is the main component of cow's milk, has a wide source and is safe for the human body.

[0097] The present invention encompasses any alternatives, modifications, equivalents, and solutions that fall within the spirit and scope of the present invention. While specific details are described in detail in the preferred embodiments to provide a thorough understanding of the present invention, those skilled in the art will be able to fully understand the present invention without these details. Furthermore, to avoid unnecessary confusion regarding the essence of the present invention, well-known methods, processes, procedures, components, and circuits have not been described in detail.

[0098] Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the embodiments of the present invention, and are not intended to limit them. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they may still modify the technical solutions described in the aforementioned embodiments, or replace some of the technical features therein with equivalents; and such modifications or replacements do not deviate from the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention. Any changes or replacements that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be covered by the scope of protection of the present invention.

Claims

1. A device for preparing nano-scale ultrafine powders to prevent agglomeration, characterized in that: The preparation device is a set of combined equipment, including pre-treatment system, compound dispersion system, molding and drying system and detection and analysis platform; The pre-treatment system includes a nano-crushing unit, a vacuum drying oven, a low-temperature plasma surface treatment device and a casein modification device; The composite dispersion system includes a high-pressure homogenization unit and an ultrasonic-microwave synergistic generator; The drying and molding system includes a vacuum freeze drying system and a fluidized bed coating device; The nano-crushing unit is provided with a coarse particle inlet, which is used to input animal bone coarse particles, and the nano-crushing unit is crushed into nano-grade hydroxyapatite ultrafine powder (abbreviated as nHA); The vacuum drying oven performs surface water adsorption treatment on the nHA; The low-temperature plasma surface treatment device performs surface etching on the nHA; The casein modification device is provided with a casein feed port, and the casein feed port is used to input casein particles; The casein modification device performs casein enzymatic hydrolysis (casein hydrolysis) on the casein particles; The casein modification device performs thiol modification on the casein particles to form modified casein; Mixing the nHA with Tris-HCl buffer to form an nHA suspension; Slowly injecting the modified casein into the nHA suspension to form a mixed solution of nHA and modified casein; The jet of the high-pressure homogenizing unit forms a velocity gradient difference in the homogenizing valve or the flow-limiting gap, which causes the bubbles in the nHA and modified casein mixture to burst due to a sudden pressure drop, resulting in a cavitation effect and a collision effect between the material particles (referring to the nHA and the modified casein); The ultrasonic-microwave cooperative reactor generates ultrasonic waves and utilizes the cavitation effect of the ultrasonic waves to disperse and emulsify the material particles. The nHA and modified casein mixture is quickly frozen to below the eutectic point (usually -30°C to -50°C) using a vacuum freeze-drying system. Water forms an ice crystal skeleton, locking the original structure of the nHA-modified casein mixture to form nHA and casein mixed ice crystals. A fluidized bed coating device is used to coat the entire surface of the nHA and casein mixed ice crystals without any dead corners; the solvent (water / organic phase) is volatilized simultaneously to achieve dynamic drying and molding.

2. The anti-agglomeration preparation device for nano-scale ultrafine powder according to claim 1, characterized in that: The low-temperature plasma surface treatment device releases plasma oxygen atoms to perform surface etching on the nHA.

3. The anti-agglomeration preparation device for nano-scale ultrafine powder according to claim 1, characterized in that: The casein modification device decomposes macromolecular casein into small molecular peptide segments and amino acids through trypsin.

4. The device for preventing agglomeration of nano-scale ultrafine powder according to claim 1, characterized in that: The chemical method for thiol modification of the casein modification device is specifically hydroxylamine (NH2OH) treatment, hydrolysis to remove the acetyl group and release free -SH.

5. The anti-agglomeration preparation device for nano-scale ultrafine powder according to claim 1, characterized in that: The modified casein is injected into the nHA suspension by a reverse addition method to form a mixed solution of nHA and modified casein.

6. The device for preventing agglomeration of nano-scale ultrafine powder according to claim 1, characterized in that: The solid-to-liquid ratio of the nHA suspension to the modified casein is 1:0.

8.

7. The device for preventing agglomeration of nano-scale ultrafine powders according to claim 1, characterized in that: The pressure of the high-pressure homogenization three-stage treatment of the high-pressure homogenization unit is from 1000 bar to 1500 bar and then to 800 bar.

8. The device for preventing agglomeration of nano-scale ultrafine powders according to claim 1, characterized in that: 0.05% trehalose was added as a lyoprotectant.

9. The device for preventing agglomeration of nano-scale ultrafine powders according to claim 1, characterized in that: The cold trap temperature of the vacuum freeze-drying system is ≤-50°C.

10. The device for preventing agglomeration of nano-scale ultrafine powders according to claim 1, characterized in that: The coating solution formula is 1% hydroxypropyl methylcellulose + 0.2% lecithin.

11. A method for preparing nano-scale ultrafine powders with anti-agglomeration properties, applied to the device for preparing nano-scale ultrafine powders with anti-agglomeration properties according to any one of claims 1 to 10, characterized in that: include: S1: The nano-crusher unit crushes the coarse particles of hydroxyapatite into nano-sized hydroxyapatite (nHA for short). S2: The vacuum dryer performs surface water adsorption treatment on the nHA; S3: The low-temperature plasma surface treatment device performs surface etching on the nHA; S4: performing enzymatic hydrolysis (casein hydrolysis) on the casein by the casein modification device: decomposing the macromolecular casein into small molecular peptides and amino acids by trypsin; S5: performing thiolation modification (Thiolation) on the casein by the casein modification device to introduce thiol groups (-SH) into the casein molecules by a chemical method; S6: Mix the nHA with Tris-HCl buffer to obtain an nHA suspension. S7: slowly injecting the modified casein into the nHA suspension to obtain a mixed solution of nHA and modified casein. S8: utilizing the velocity gradient difference, cavitation effect, and collision effect of the high-pressure homogenization unit, the material particles (referring to the nHA and the modified casein) are fully mixed. S9: utilizing the ultrasonic-microwave synergistic reactor to generate cavitation, thereby dispersing and emulsifying the material particles, adding trehalose, and reducing the interfacial energy of the dispersed phase, so that the nHA and modified casein mixture forms a sufficient, uniform, and stable mixture. S10: Using the vacuum freeze-drying system, the nHA and modified casein mixture is quickly frozen to below the eutectic point, so that water forms an ice crystal skeleton, locking the original structure of the nHA and modified casein mixture. S11: Using the fluidized bed coating equipment, dynamic drying and molding of the nHA and modified casein mixture is achieved.

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