CN117618514B

CN117618514B - Preparation method of ultra-high purity nanoscale bamboo leaf total flavone dispersoid

Info

Publication number: CN117618514B
Application number: CN202410107128.1A
Authority: CN
Inventors: 谭卓华; 黄炜岚
Original assignee: Guangzhou Lvhui New Material Research Institute Co ltd
Current assignee: Guangzhou Lvhui New Material Research Institute Co ltd
Priority date: 2024-01-26
Filing date: 2024-01-26
Publication date: 2024-04-12
Anticipated expiration: 2044-01-26
Also published as: CN117618514A

Abstract

Belongs to the technical field of extraction of bamboo leaf total flavonoids, and in particular relates to a preparation method of an ultra-high purity nanoscale bamboo leaf total flavonoids dispersoid, which comprises the following steps: the device comprises an ultra-low temperature freezing auxiliary high-pressure-double vortex counter-flow back pressure cavitation continuous dynamic circulation nanometer grinding wall breaking extraction and filtration integrated device, wherein the ionic liquid functionalized vortex magnetic nanometer elliptic hollow annular sphere is combined with an externally applied rotating magnetic field to perform adsorption separation, and the dynamic elution desorption is performed, so that the low-temperature vacuum evaporation concentration and freeze drying are performed; obtaining D ₅₀ Nano-scale ultra-high purity bamboo leaf total flavone dispersion with purity of 99.7-99.9 percent, wherein the nano-scale ultra-high purity bamboo leaf total flavone dispersion is 0.02-0.08 mu m; solves the limitation of the technology for industrially extracting the bamboo leaf flavone, and industrializes the nanoscale ultra-high purity bamboo leaf total flavone dispersoid in large scale, and is used in the fields of medicines, health products, special food, special functional beverages and cosmetics.

Description

Preparation method of ultra-high purity nanoscale bamboo leaf total flavone dispersoid

Technical Field

The invention relates to a preparation method of an ultra-high purity nanoscale bamboo leaf total flavone dispersion, in particular to a preparation method of an ultra-high purity nanoscale bamboo leaf total flavone dispersion, and belongs to the technical field of extraction of bamboo leaf total flavone.

Background

According to the patent and open literature in the field, the technical condition of extracting bamboo leaf flavone is studied at home and abroad at present:

a method 200910223926.6 for preparing a bamboo leaf flavone extract by column purification shows that the purity of the bamboo leaf flavone is 20.78%; a production method 200610053134.5 for extracting bamboo leaf flavone from bamboo leaves shows that the purity of the bamboo leaf flavone is more than or equal to 24%; a method for separating and purifying flavone and lactone from bamboo leaves based on a microwave-assisted process CN201510481490 shows that the purity of the bamboo leaf flavone is more than or equal to 29%; a method for preparing herba Lophatheri flavone extract 200910223927.0 shows that the purity of herba Lophatheri flavone is 42%; a method 201110003352.9 for extracting flavone from folium Bambusae; the purity of the bamboo leaf flavone is 30-50%; a method 201110406495.4 for extracting bamboo leaf flavone shows that the purity of the bamboo leaf flavone is 30-50%; the production process 200610053436.2 for extracting bamboo leaf flavonoid series products from bamboo leaves shows that the purity of the bamboo leaf flavonoid is 60%; the preparation method 200810195064.6 of the bamboo leaf flavone extract shows that the purity of the bamboo leaf flavone is 40% -65%;

the research progress of flavonoid compounds in bamboo leaves of Tai Yu Ji university shows that the bamboo leaf flavonoid powder with 24 percent of flavonoid content is obtained; the research on the extraction, purification and antioxidant activity of bamboo leaf flavone, which is the university of science and technology of south China, shows that the total flavone content in the obtained product is 36%; the biological activity and application research of the bamboo leaf flavone at the food science and engineering institute of Yangzhou university show that the obtained bamboo leaf flavone content reaches more than 40 percent; the optimization and analysis characteristic research of the adsorbent in the purification of bamboo leaf flavone, which is a food strain of Beijing university student in the biological science and technology college, shows that the purity of the bamboo leaf flavone produced by the process reaches 54.16 percent; a pilot plant test extraction of Nanchang university-phyllostachys pubescens leaf active polysaccharide and flavonoid shows that the purity of phyllostachys pubescens leaf flavone after being refined by AB-8 resin reaches 79.4 percent.

Therefore, according to the conventional technical knowledge and industry consensus in the art, the bamboo leaf flavone is only a conceptual summary, in fact, only a crude extract, the extraction rate is low, and impurities in the extraction are relatively high (such as phenols, saponins, tannins, alkaloids, polysaccharides, proteins, crude fats, chlorophyll, anthraquinone compounds, terpene lactones, inorganic salts, moisture, mineral substances, ash, heavy metals, arsenic, manganese, zinc, selenium and other trace elements, more than 20 mineral elements, 82 aromatic component compounds, 16 amino acids, 53 volatile components, 10 alcohols, 17 aldehydes and the like), and the so-called bamboo leaf flavone is only a part of the contents of these substances, at most only a commodity name.

Based on the knowledge known in the industry, the bamboo leaf flavones with different purities have different effects in different fields; the higher the purity of the bamboo leaf flavone is, the stronger the activity and the polarity of the bamboo leaf flavone are; if the effects of effectively reducing blood fat, preventing cardiovascular diseases and the like, improving anoxia endurance, preventing osteoporosis and the like are to be achieved, the purity is at least 90%; thus, purity determines the physiological activity of a drug; so how to prepare high-purity flavone at low cost is the focus of research by scientists in various countries at present; therefore, how to extract natural substances efficiently, economically and environmentally friendly is a problem to be solved in production of a large amount of high-quality substances.

In summary, although the existing extraction method of bamboo leaf flavone has a certain result, the purity of the flavone products of the existing factories is low, and a lot of troubles are brought to further separation, and the subsequent refining process flow is relatively complicated and time-consuming to operate; the purity can only be used for resisting fatigue and improving the health care function of human body on the market, thereby limiting the further development of the purity in the fields of foods and medicines; there are also certain limitations in industrial use; how to rapidly and efficiently industrialize the production of bamboo leaf flavonoids is the key point of our research.

Disclosure of Invention

Therefore, in actual production, a new process for extracting the effective components of the bamboo leaves with high purity, high efficiency, low cost and small pollution is found, and the method becomes a concern of people; aiming at the problems, in order to overcome the limitation caused by the defects of the prior art at home and abroad at present, the application focuses on developing a new method, and designs a preparation method of an ultra-high purity nanoscale bamboo leaf total flavone dispersion:

(1) the extraction equipment and auxiliary materials are thoroughly reformed, so that the product extraction rate is reasonably and effectively improved greatly, the production cost is reduced, and convenience is provided for industrial production;

(2) The method adopts an orthogonal test analysis method to optimize the process conditions for extracting the total flavonoids of the bamboo leaves, and performs the integrated research between different extraction technologies or between the extraction technologies and the separation technologies according to the characteristics of each extraction technology, so that the extraction technology is diversified and developed, and the technical support is better provided for screening the optimal technology;

the nanometer particle diameter median D is prepared ₅₀ The extraction technology of the nanoscale ultra-high purity bamboo leaf total flavone dispersion with the purity of 99.7-99.9 percent, which is 0.02-0.08 mu m, is not reported yet, and is the first example before the application; provides theoretical reference for better developing and utilizing rich bamboo leaf resources in China.

In order to achieve the above purpose, the technical scheme adopted in the application comprises the following process steps:

step one, an ultra-low temperature freezing auxiliary high-pressure-double vortex counter-flow back pressure cavitation continuous dynamic circulation nano grinding wall breaking extraction and filtration integrated device is used for extracting nanoscale bamboo leaf flavonoid compounds:

inputting a refrigerant into a jacket layer of the integrated device, starting an overlapping ultralow temperature refrigerating system, and adjusting the cooling temperature in a pear-shaped grinding wall breaking extraction tank to be between minus 15 ℃ and minus 50 ℃; putting bamboo leaf powder and 30-90% ethanol solution into a pear-shaped grinding wall breaking extraction tank according to a feed liquid ratio of 1:10-20 g/mL, matching with 4-5 parts of bioflocculant solution and a grinding medium with a filling rate of 70-80 vol%, starting a double-turbine positive and negative two-way vortex countercurrent driving disc, rotating at a high speed of 12-20 m/s, starting a pressure pump, pressing inert gas into the pear-shaped grinding wall breaking extraction tank, adjusting the pressure to 0.5-2.5 MPa, taking part in ultra-low temperature continuous dynamic circulation grinding wall breaking/extraction treatment in the whole process at an air flow rate of 200L/min, and taking part in the whole process total time of 30-50 min; starting a peristaltic pump at 15 th seed of the total treatment time in the whole process, and continuously and dynamically adding 30-90% ethanol solution with a feed liquid ratio of 1:10-20 g/mL in a dropwise manner until the total treatment capacity reaches a feed liquid ratio of 1:20-40 g/mL; then, the pressure is removed, the materials are discharged from a discharge hole of a pear-shaped grinding and wall-breaking extraction tank to a solid-liquid separation nanofiltration layer, high-speed rotation and intermittent compression movement are carried out, under the action of centrifugal force, filtrate passes through a nanofiltration rotary membrane in a tangential manner under the action of a pump and the pressure of 3-5 kg, and flows out from the bottom of an integrated device through a hollow pipeline to achieve solid-liquid separation; obtaining the median diameter D ₅₀ Nano bamboo leaves with the diameter of 0.02-0.08 mu mFlavonoid compound solution and solid bamboo powder precipitate;

the refrigerant is any one of 30-80% ethanol and liquid nitrogen;

the grinding medium is zirconia balls or ceramic balls, and the diameter range of the grinding medium is 0.2-0.4 mm;

the bioflocculant solution is any one of a 1% gelatin solution and a 1% chitosan solution;

the inert gas is any one of carbon dioxide, argon and food grade 99.999% ultra-pure nitrogen;

the nanofiltration rotary membrane is a microporous filter membrane with the aperture of 0.02-0.08 mu m;

step two, carrying out adsorption separation by combining the ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere with an externally applied rotating magnetic field, and dynamically eluting and desorbing:

uniformly mixing the nanoscale bamboo leaf flavonoid compound solution and the ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere in a ratio of 5:1, filling the mixture into a polytetrafluoroethylene pipeline, carrying out ultrasonic treatment at 30 ℃ for 5min, enabling the mixture to flow through a resin column at a flow rate of 3BV/h until adsorption saturation, and closing the external rotating magnetic field after the mixture is subjected to vortex for 20min by means of an external rotating magnetic field which is tightly attached to the annular cylindrical shape of the pipe wall and has a magnetic induction intensity of 1-1.5T; eluting impurities of flavone adsorbate on the resin column by using 5BV distilled water and 5BV 30% ethanol respectively, eluting flavone by using 5BV 50% ethanol and 4BV 70% ethanol respectively, and finally realizing complete desorption, wherein the total eluting desorption time is 25min; combining 50% and 70% ethanol eluates, and then filtering and collecting the desorption solution;

The ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere is Fe ₃ O ₄ @HDI-EMIMLpro and Fe ₃ O ₄ @SiO ₂ Any one of @ HDI-EMIMLpro;

the preparation method of the ionic liquid functionalized vortex magnetic nano elliptic hollow ring ball comprises the following steps:

in a sealed reaction kettle, fe ³⁺ Introducing phosphate and sulfate surfactant as reactant, and under high temperature and high pressure conditions, supersaturating to separate out crystal，PO ₄ ^3- And SO ₄ ^2- Selectively adsorb alpha-Fe respectively ₂ O ₃ On the crystal face of the crystal, the ferric oxide crystal is induced to form a polyhedral structure, the polyhedral structure is dissolved in the long axis direction preferentially to form a hollow structure, and the concentration of reactants and an auxiliary magnetic field are regulated to lead the nanowires to be arranged in an oriented mode, so that the composite particles form a nano elliptic hollow ring sphere with the length-diameter ratio of beta=1.5; further by alpha-Fe ₂ O ₃ Nanometer elliptic hollow ring ball is used as precursor, fe with good dispersivity, high phase purity and magnetic anisotropy is obtained by hydrogen thermal reduction method ₃ O ₄ Vortex magnetic nano elliptic hollow ring ball;

coating silicon dioxide SiO on the surface of the precursor solvent of ethyl orthosilicate ₂ Thin layer to obtain Fe with good dispersibility ₃ O ₄ @SiO ₂ Composite vortex magnetic nano elliptic hollow ring ball;

taking Hexamethylene Diisocyanate (HDI) as a connecting agent, and respectively modifying amino acid ionic liquid 1-ethyl-3-methylimidazole L-proline salt (EMIMLpro) in Fe ₃ O ₄ Vortex magnetic nano elliptic hollow ring sphere and Fe ₃ O ₄ @SiO ₂ The surfaces of the composite vortex magnetic nano elliptic hollow annular spheres are respectively obtained to obtain Fe ₃ O ₄ @HDI-EMIMLpro and Fe ₃ O ₄ @SiO ₂ Two ionic liquid functionalized vortex magnetic nano elliptic hollow ring spheres @ HDI-EMIMLpro; the nanometer elliptic hollow ring sphere with the length-diameter ratio beta=1.5 is an outer long axis a=90-100 nm, an outer short axis b=60-66 nm, an inner long axis a=72-80 nm, an inner short axis b=48-53 nm, and the thickness of the inner diameter and the outer diameter is 9-10 nm;

step three, vacuum evaporation concentration at low temperature:

inputting the desorption solution obtained in the step two into a low-temperature vacuum evaporation concentration device, and removing water and ethanol in the desorption solution to obtain a concentrate;

step four, freeze drying:

freeze drying the concentrate obtained in the step three to obtain the median diameter D ₅₀ Nano-level super-high purity bamboo leaf total flavone with purity of 99.7-99.9% with the purity of 0.02-0.08 mu mA dispersion;

the detection method of the median particle size comprises the steps of adopting a laser particle sizer, and according to GB/T19007: 2016. ISO 13320: 2009. q/0100JWN 001-2018 for wet particle size detection;

the purity detection method comprises the steps of detecting and measuring by adopting a High Performance Liquid Chromatograph (HPLC) according to the high performance liquid chromatograph (the rule 0512 of the year 2020 edition of Chinese pharmacopoeia).

The ultralow temperature freezing auxiliary high-pressure double-vortex counter-flow back pressure cavitation continuous dynamic circulation nano grinding wall breaking extraction and filtration integrated device comprises a pear-shaped grinding wall breaking extraction tank, a jacket layer and a solid-liquid separation nanofiltration layer;

the pear-shaped grinding broken-wall extraction tank adopts a double-turbine positive and negative two-way vortex countercurrent driving movement mode, the inner radius of the container is 60mm, the depth is 938mm, and the specific surface area is 0.01;

the jacket layer is provided with an input sealing cover and an output sealing cover, an electromagnetic valve is arranged on the input sealing cover, a refrigerant is directly communicated into the jacket layer through a pump body, the refrigerant is directly cooled, after the refrigerant absorbs heat, the refrigerant is discharged through the electromagnetic valve arranged on the output sealing cover, and a pear-shaped grinding broken wall extraction tank filled with materials is positioned in a certain constant-temperature low-temperature environment; the temperature is externally controlled, the temperature control precision is +/-0.5 ℃, and the temperature control range is 4-100 ℃;

the solid-liquid separation nanofiltration layer is of a special structure for high-speed rotation and intermittent compression motion filtration.

The freeze drying in the step four is any one of vacuum freeze drying and spray freeze drying.

The nanometer ultra-high purity bamboo leaf total flavone dispersoid is the median diameter D ₅₀ The purity of the product is 99.7-99.9%, and the product can be used in the fields of medicines, health products, special food, special functional beverages and cosmetics according to requirements, wherein the product is 0.02-0.08 mu m.

The solid bamboo powder precipitate is subjected to pressure spray drying or cyclone combined pressure spray drying to form powder, and is applied to the fields of composite materials, bioplastic, motor vehicle shells and inner decorations, paint ink, water source purification, bioethanol, petrochemical industry, tobacco, explosives and nanocellulose products.

Advantageous effects

The application initiates an integrated device for extracting and filtering nanoscale bamboo leaf flavonoid compounds by using ultra-low temperature refrigeration assisted high-pressure double-vortex counter-current back pressure cavitation continuous dynamic circulation nano grinding and wall breaking.

From the structure of plant cells, plant cells have a layer of stronger cell wall structure; as a protective layer for cells, the cell wall effectively prevents the release of numerous intracellular substances; therefore, the effective wall breaking treatment of the plant cells is a key ring capable of releasing and extracting the high value-added substance products contained in the cells; the key to obtaining useful substances inside the cells is the ability to effectively destroy the cell walls.

At present, cell wall breaking by using an ultrasonic method is common only in a laboratory range; however, when a large amount of cells are treated by the ultrasonic wall breaking technology, larger power is required, and because the energy distribution of an ultrasonic field is uneven, the shearing force on the cells is smaller in the area with insufficient energy, the wall breaking effect is not achieved, or the wall breaking rate is low; in the area with overlarge energy, although the requirement of a certain wall breaking rate can be met, the area is easy to heat up too much due to the overlarge energy, and the intracellular substances are damaged; the energy distribution of the ultrasonic field is uneven, so that the overall wall breaking rate is not high, and the damage to useful substances to be extracted is larger; in large-scale industrial production, if an ultrasonic wall breaking method is used alone, the problems of uneven energy distribution and difficult heat dissipation are more serious, and the product is also more influenced; therefore, it has not been industrially applied; for mass production, there is still a need to further solve the problem of enlargement of engineering equipment.

When cell wall breaking is carried out by using an enzymatic hydrolysis method, due to the complex components in the extract, enzymes can react with certain components in the traditional Chinese medicine to generate new chemical substances, thereby affecting the purity and yield of the product; the specificity of the enzyme, the cell wall breaking of different types needs to select different enzymes, so that the universality of the enzyme dissolution method is poor, in addition, the price of the biological enzyme is higher, the production cost is increased, the time required for the cell wall breaking of the enzyme dissolution method is longer, and the factors severely limit the application of the enzyme dissolution method in industrial large-scale treatment; therefore, the enzymatic hydrolysis method is generally only suitable for small-scale experimental wall breaking, and does not have the condition of large-scale industrial production at present.

The chemical permeation method depends on the structural composition of cell walls and the types of chemical reagents, and the different chemical reagents have different effects on different types of cells, namely selectivity, so that the chemical permeation method has poor universality and simultaneously has the problems of long treatment time and low efficiency; the chemical reagents such as acid, alkali or oxidant are easy to damage the products in the cells; in addition, the general chemical reagent has certain toxicity, and in the process of chemical wall breaking treatment, the product is easy to pollute, so that the difficulty in separating or removing the reagents later is increased; the existence of these problems determines that chemical treatment is not suitable for general mass industrial production.

The high-pressure homogenization method is more suitable for the wall breaking condition of microbial cells, however, the difficulty of breaking is definitely determined by the mechanical strength of cell walls; for natural plants, the active ingredients are often embedded in internal parenchyma cells or vacuoles protected by hard or soft epidermis, and the high-pressure homogenization method is difficult to destroy the harder cell walls; the wall breaking is very difficult by the method.

In the conventional rotor-structured bead mill, due to poor flow in the milling cavity, as the cell wall breaking process is continuously carried out, the components in the cells are gradually released due to the rupture of the cell walls; the release of these intracellular viscous materials not only increases the viscosity of the fluid in the milling chamber, but also adheres or coats the surfaces of the stirrer, the milling beads and the inner wall of the milling chamber; the viscosity of the fluid is increased, and the intracellular substances are accumulated on the surfaces of the grinding beads and the like, so that the grinding beads have lubricating and elastic damping effects, the kinetic energy of the grinding beads can be lost, the shearing and extrusion effects of the grinding beads on plant cells are weakened, and the wall breaking efficiency of the bead mill on the cells is reduced; in industrial production, a large amount of intracellular substances accumulate in a grinding cavity to cause blockage and difficult discharge, which is unfavorable for the continuous proceeding of the wall breaking process; therefore, the industrial mass application of the bead grinding method to break the wall of plant cells requires further improvement of the bead grinding method.

The microwave method is limited to polar solvents, the product is easily damaged by the temperature rise in the wall breaking process, and the method can only be applied to the wall breaking of partial cells in a laboratory and is difficult to apply to industry.

Therefore, although the traditional cell wall breaking technology is many and new technologies are continuously appeared, at present, the technologies have more or less problems, and most of the technologies are only suitable for laboratories and are difficult to realize large-scale industrialized application; for developing efficient cell wall breaking techniques, important considerations include: process economy, industrial expandability and product quality reliability.

The application provides an ultra-low temperature freezing-assisted high-pressure double-vortex counter-flow back-pressure cavitation continuous dynamic circulation nano grinding wall breaking extraction and filtration integrated device, which reduces the viscosity of bamboo leaf liquid and cells dispersed in grinding liquid in the process of continuously and dynamically crushing the cells through ultra-low temperature freezing-assisted high-pressure double-vortex counter-flow back-pressure cavitation, increases the fluidity of the grinding liquid, reduces the thick volume of bamboo leaf cells and viscous substances, has the functions of dispersing and reducing the viscosity of organic matters, and increases the circulation of the grinding liquid; therefore, the cell wall breaking efficiency of the device is improved, and meanwhile, emulsification and damage of useful substances released by broken bamboo leaf cells due to long-time wall breaking are avoided; the integrated device has the functions of ultralow-temperature freezing treatment, high-pressure double-vortex countercurrent back-pressure cavitation grinding wall breaking and filtering, and can be used for extracting nanoscale bamboo leaf flavonoid compounds; these efforts can be divided into the following six strategies.

First, the present application employs specific size cans and environmental cryomilling.

Before the plants are extracted, the plants need to be crushed and other treatments; the purpose of crushing is to increase the specific surface area of the plant, so that the plant particles are fully contacted with the solvent, the active ingredients are easier to leach out, and the rate of plant extraction is improved; in general, the harder and more brittle the material, the easier it is to grind, but not all materials exhibit hardness and brittleness at ordinary temperatures.

Therefore, in the freeze-thawing extraction process, the solution freezing process is a key step in determining the final quality of the extract; at present, the related research on the freezing change process of plant grinding fluid in a low-temperature environment is not thorough, and research reports on the relation between the freezing speed and different production process conditions are lacking.

Therefore, the application adopts the extraction process technology of ultralow-temperature freeze grinding to the bamboo leaf grinding liquid, and extracts the active ingredients in the bamboo leaves by using the solution, so that the activity and the original molecular structure of the active ingredients are kept as much as possible: in an ultralow temperature freezing environment, the water-swelling bamboo leaf cells are absorbed, and ice crystals formed in the inside of the cells along with low temperature puncture the bamboo leaf cell membranes, so that the original cell structure is damaged; along with the grinding process of the solution environment, the bamboo leaf cell inner solution can flow into the solution, so that the extraction process of pharmacological molecular substances is realized; the pharmacological activity of the bamboo leaf flavone substance is not affected in the low-temperature freezing and re-melting processes, so the method improves the quality and curative effect of the preparation product.

The method comprises the steps of collecting real-time monitoring data of heat conductivity and fusion temperature in the ultralow-temperature freeze-grinding extraction process of the bamboo leaves, and constructing a numerical model; based on classical theory of computational fluid mechanics, the ultralow-temperature freezing grinding extraction process of the grinding fluid under the conditions of containers with different sizes and environmental freezing temperatures is obtained through simulation calculation; through result analysis, the influence of different freezing container sizes and environmental freezing temperatures on the ultralow temperature freeze-grinding extraction process is compared, and experimental data basis and theoretical analysis basis are provided for the process improvement of the She Chaodi temperature freeze-grinding extraction process.

The simulated process size of the ultralow temperature freeze-grinding extraction process of the bamboo leaves is shown in Table 1

As can be seen from table 1, there is a large difference in specific surface area of the containers under different size conditions, and experimental study in this application found and verified in conjunction with table 1:

the method comprises the steps of performing ultralow-temperature freeze grinding extraction, wherein the final freezing time is gradually reduced along with the increase of a temperature difference T, and the final freezing time is affected by the size of a container: when the specific surface area is larger, the freezing speed is higher, and conversely, the freezing speed is gradually slowed down; the sequence of the freezing time from fast to slow is as follows: d4 C3, F6, B2, A1 and E5.

The specific size of the container plays a more obvious limiting role in the freezing process of the extract:

(1) compared with the condition of the same freezing temperature difference, the influence of the specific size of the container on the grinding liquid freezing process is larger in the ultralow-temperature freezing, grinding and extracting process; in a cylindrical container, the heat transfer direction of the polishing liquid has three directions: a vertical axial direction, a horizontal radial direction and a tangential direction, respectively; it can be seen from experiments that the temperature distribution of each circumference in the horizontal tangential direction is substantially uniform, which means that the heat transfer is mainly in the radial direction and the axial direction during freezing; it can be seen from the temperature results of this experiment that the freezing rate is dependent on the relative ratio between the depth of the container in the inner volume and the length of the radius.

(2) When the depth of the container is smaller than the radius, the freezing time is determined by the axial height of the container; conversely, the freezing time is determined by the radius distance of the container; at this time, the lower the column height, the faster the freezing speed and the shorter the freezing time, under the condition that the internal volume is unchanged.

(3) When the distance proportion is smaller, the freezing time is shorter, otherwise, the freezing time is prolonged, which means that the heat transfer distance directly restricts the process of freezing the grinding fluid; compared with the environment and the freezing temperature of the solution, the grinding liquid freezing process is greatly influenced by the size of the container, the container with a shorter heat transfer distance has better freezing effect, and the influence on the freezing process of the mixed liquid is larger than the influence on the freezing temperature.

(3) The lower the temperature is, the shorter the freezing time is, but the two are not in direct proportion, when the freezing temperature is higher than-50 ℃, the increasing trend of the freezing time is not greatly changed, and the influence of the freezing energy consumption on the production cost is considered.

Therefore, in combination with the energy consumption of the freezing process and the practical need analysis of the application, the optimal freezing process conditions of the grinding fluid are as follows: the cooling temperature is between minus 15 ℃ and minus 50 ℃, the inner radius of the container is 60mm, the depth is 938mm, and the specific surface area is 0.01, and the freezing and grinding time is between 30 and 50 minutes.

Secondly, the pear-shaped tank body with a special geometric structure is adopted, a double-turbine positive and negative two-way vortex countercurrent driving movement mode is combined, high-pressure double-vortex countercurrent back pressure cavitation is continuously and dynamically circulated, nanometer grinding and breaking is carried out, a cell wall is one of the remarkable characteristics of plant cells, the cell wall is composed of a tough cellulose shell and the like, the tissue structure of the cell wall is hard and insoluble in most solvents, the cell wall has strong chemical corrosion resistance and radioactivity resistance, the cell volume is very small, the cell wall is difficult to damage by common physical and chemical method treatment, and most bioactive components or medicinal components exist in the cell, and only a small amount exists in cell gaps. Thus, the cell wall of plants is a major obstacle to leaching of the active ingredients inside the cells.

Acoustic cavitation and hydrodynamic cavitation are hot spots of academic and industrial interest in four modes due to the efficiency of cavitation generation and ease of engineering application.

At present, acoustic cavitation is generally controlled by an ultrasonic generator, acoustic energy generated by high-frequency vibration is transmitted to a liquid medium by a transducer, when the acoustic energy reaches a certain threshold value, cavitation bubbles begin to appear in the liquid, and almost cavitation effect is generated at the same time, but the cavitation efficiency is not increased along with the increase of the acoustic energy, so that the effect is better only under a small container in a laboratory and a limited space, but when the ultrasonic cavitation device is applied to pilot scale or industrialization, the problems of uneven cavitation field, low cavitation efficiency, small flux, large amplification difficulty and the like can appear.

Hydrodynamic cavitation is that a pressure drop is generated when fluid passes through a flow limiting area (such as fluid flowing through a venturi tube), when the pressure drops below cavitation primary pressure, gas dissolved in the fluid is released, and simultaneously the fluid is gasified to generate a large number of cavitation bubbles, and the cavitation bubbles collapse when encountering surrounding pressure change in the process of further flowing along with the fluid; compared with ultrasonic cavitation, the device is simple and low in cost, and can generate large-scale cavitation fields (such as an orifice plate, a venturi tube, a liquid whistle and the like), but the cavitation intensity of the hydraulic cavitation is smaller, the efficiency is lower, and the hydraulic cavitation is often insufficient for triggering or strengthening certain physicochemical reactions.

According to the Venturi principle, the area of the flow passage surface is suddenly reduced, the flow speed is suddenly increased, the pressure in the flow passage is lower than the saturated vapor pressure, cavitation is generated in liquid, and a back pressure cavitation effect is formed; with the release of the high pressure, a strong shock wave (homogeneous) or high-speed jet (heterogeneous) will be formed in the liquid; in extraction, the strong impact flow can effectively reduce and eliminate a blocking layer between a solvent and a water phase, thereby increasing mass transfer rate; at the same time, the impact flow generates a physical shearing force on the animal and plant cell tissues to deform and break the animal and plant cell tissues and release the contents, thereby greatly accelerating the extraction process; in addition, the air flow rate is a key parameter affecting the extraction rate, and directly affects the turbulence, collision and mass transfer of the solvent and the bamboo She Weili; the bubbles are generated on the wall of the container, and the shape of the container can also have a certain influence on the bubble generation amount, thereby influencing the extraction effect; therefore, the double vortex counter-flow back pressure cavitation device,

the adoption of the double turbine discs is different in axes, and the shape of the container is thoroughly changed and the air flow rate is optimized.

Experimental studies in this application found and verified:

when the turbine disk rotates at a high speed with a linear speed of 12-20m/s in a bidirectional opposite direction, two eddies are made to form convection, so that a hydraulic shearing effect is increased, bamboo She Weili and grinding media are accelerated to rotate, and due to the bidirectional opposite direction double eddies, the bamboo She Weili and the grinding media in the cylinder are stirred together by a disperser rotating at a high speed to form vortex and reflux, so that bamboo particles receive more shearing and friction in unit time, the purpose of repeated grinding is achieved, and the bamboo She Weili and the grinding media in the material generate stronger impact force, friction, crushing force and shearing effect, and the bamboo She Weili in the fluid is dispersed, crushed, shaped, coated, modified, depolymerized and homogenized; the physical grinding does not damage the performance of the bamboo leaf material, and the deagglomeration and the real grinding of loose masses are carried out; the aim of accelerating grinding of fine particles and dispersing of aggregates is achieved, the bamboo leaves are ground into uniform slurry, and the discharging is more uniform, so that the active ingredients in the bamboo leaf cells are rapidly released and fully contacted with a solvent to accelerate the dissolution.

When the bamboo She Weili material pulp enters the grinding cavity through the improved flow channel, the flow velocity is suddenly reduced and the flow velocity is suddenly increased, so that the pressure in the flow channel is lower than the saturated vapor pressure, a large amount of cavitation bubbles are generated to generate cavitation phenomena, the cavitation bubbles undergo generation, development and final explosion, and high-speed shock waves and microjet generated during the explosion of the bubbles accelerate the movement of the bamboo leaf particles, so that the bamboo leaf particles have higher speed, the friction and collision are increased, the efficiency of crushing the fine bamboo leaf particles is improved, and the bamboo leaf particles are crushed to the nanometer fineness; simultaneously, as the grinding medium and the bamboo She Weili rub, collide and shear mutually, the bamboo leaf particles generate micro-cracks, and cavitation bubbles are generated in the micro-cracks of the bamboo leaf particles, and the cavitation bubbles generate high-speed shock waves and microjet when collapsing, so that the micro-cracks can be continuously expanded, the bamboo She Weili is fried, the bamboo She Weili is crushed, the material is dispersed, and the crushed bamboo She Weili is prevented from re-agglomerating.

According to the method, the turbine wheel rotates to limit flow and shear multiple modes to induce cavitation, a large amount of cavitation clouds can be generated, the transport property of cavitation is high, the energy consumption is low, the cavitation efficiency is high, the cavitation bubbles collapse when encountering surrounding pressure change in the process of flowing with fluid, cell swelling or breakdown of cell walls is caused, a solvent can be diffused into the bamboo She Weili, collision and mass transfer between an extraction solvent and bamboo leaf particles are improved, and total flavonoids in bamboo leaves can be extracted efficiently.

Under the synergistic effect of the high-pressure double-vortex counter-flow back pressure cavitation, the main movement form of the whole grinding system fluid is turbulence, the mass transfer caused by the strong mixing effect of turbulent eddies is far larger than the effect of molecular movement, the vibration effect and some secondary effects such as diffusion, fragmentation, chemical effect, thermal effect and the like generated by the grinding medium in the bamboo She Weili and the cylinder body can sufficiently loosen the cell wall structure, further expand the effect of cell perforation, cause more cells to generate irreversible breakdown, and strengthen the release and diffusion of substances in the cells

And dissolving, thereby further improving the extraction rate of the total flavonoids of the bamboo She Zhongzhu leaves.

Fifthly, the pear-shaped modeling grinding and wall breaking extraction tank has large specific surface area at the bottom, large air flow rate in the cavitation process, large amount of bubbles generated in unit time on the wall of the tank, good turbulence effect and contribution to collision, turbulence and mass transfer; the radius of the upper part of the equipment tank is smaller, the pressure applied during the rising process of the bubbles is rapidly reduced and is broken, cavitation is generated by the breakdown of the bubbles, the surface of the bamboo She Weili is corroded, the solvent can be diffused into the bamboo She Weili, and the total flavone is transferred into the solvent; compared with the traditional conventional cylindrical cavitation equipment, the method has higher effect and is more suitable for industrialized mass production.

The wall breaking efficiency of the pear-shaped grinding broken wall extraction tank on bamboo leaf cells is obviously improved due to the introduction of double vortex back pressure cavitation; in the early stage of cell wall breaking, larger cells are more easily broken, and at the moment, the cells are mainly broken by extrusion and shearing; along with the progress of the wall breaking process, cells with smaller particle sizes are difficult to break, and the shearing action becomes a main wall breaking mechanism gradually; the extraction rate of the cavitation container with the same shape is always greater than that of the cavitation container with the same shape, the air flow rate is 200mL/min and is always greater than that of the cavitation container with the same shape, and when the air flow rates are 200mL/min, the extraction rate of the pear-shaped grinding wall breaking extraction tank is always greater than that of the cavitation container with the same shape, the total flavone extraction rate is obviously increased from 52.20mg/g to 76.05mg/g, and the cavitation container is beneficial to collision, turbulence and mass transfer due to the large air flow rate, the large bubble quantity generated in unit time and good turbulence effect; the surface of the bamboo She Weili is corroded, the solvent can be diffused into the bamboo She Weili, and the total flavone is transferred into the solvent; when the cavitation time is increased to 70min, the extraction rate is almost equal to that of 50min, so that the pear-shaped grinding wall breaking extraction tank has the best wall breaking effect when the air flow rate is 200mL/min and the cavitation time is 50 min.

And under higher pressure, some cell walls in the bamboo leaves can be damaged, the wetting permeation process is accelerated, so that capillary holes in tissues are filled with the solvent more quickly, subsequent diffusion of solutes is facilitated, a stronger leaching solution is formed, concentration difference is formed between the leaching solution and surrounding solvents, and the leaching speed is improved.

The grains are uniform and fine, and the plant cell walls are damaged; along with the extension of the grinding break-wall time, the grain diameter of the plant becomes smaller, and finally reaches the grinding break-wall to D ₅₀ =0.02 to 0.08 μm (whereas plant cell wall diameter is only 10 μm); the smaller particle size can provide higher specific surface area, and the increase of the specific surface area accelerates the diffusion and mass transfer of the total flavonoids of the bamboo leaves in the cavitation process; thereby shortening the mass transfer path, improving the mass transfer efficiency, and accelerating the diffusion and mass transfer of the total flavonoids of the bamboo leaves in the cavitation process.

According to the method, the influence of main factors (such as stirring linear speed, grinding medium size, feed liquid ratio, grinding time, grinding medium filling rate and the like) on the wall breaking effect of the pear-shaped grinding broken wall extraction tank is researched through single-factor experiments, and the experiments show that:

(1) the size of the grinding medium is one of the important factors influencing the cell wall breaking effect; the smaller the grinding medium size, the greater the number of grinding media under the same grinding medium filling rate; in the pear-shaped modeling grinding broken wall extraction tank with the same volume, the increase of the size of the grinding medium means the reduction of the quantity of the grinding medium, so that the probability of collision between grinding beads in the tank and bamboo leaf cells is reduced, and the cell wall breaking rate is reduced under the same wall breaking time; this shows that the too large size of the grinding medium can seriously affect the wall breaking effect on cells, and the grinding medium with smaller size is easier to obtain higher wall breaking rate faster; however, for the pear-shaped grind break extraction tank of the present application, the smaller the size of the grinding media is not, the better; the smaller the size of the grinding medium is, the smaller the energy carried by a single grinding medium is, when the viscosity and fluidity of the bamboo leaf cell sap are changed, especially when the viscosity of the bamboo leaf cell sap is greatly increased, the kinetic energy carried by the grinding medium is extremely easy to consume, so that the energy required by broken cells cannot be met, and the broken cell rate is reduced.

(2) The wall breaking of the bamboo leaf cells can be realized at a small linear speed, but the stirring linear speed is small (such as 10 m/s), and the wall breaking rate of the bamboo leaf cells is low, so that a long time is required to be spent to reach a certain wall breaking rate; increasing the linear speed of the stirrer of the pear-shaped grinding and wall-breaking extraction tank means that more and more grinding media have enough energy to break the cell wall, so that the wall breaking rate can be rapidly increased; however, when the stirring line speed is too high, the cell wall breaking rate cannot be increased as rapidly as expected; as the linear velocity increases, the wall breaking rate of bamboo leaf cells increases, and when the linear velocity increases to a certain extent (such as 2.3 m/s), the increase of the wall breaking rate of the cells becomes slower, and more disadvantageously, higher stirring linear velocity consumes more energy; this indicates that proper stirring line speed should be selected during the process of breaking the wall of the bamboo leaf cells.

(3) In the early stage of bamboo leaf cell wall breaking, the pear-shaped grinding and wall breaking extraction tank has high wall breaking rate, namely, a large cell wall breaking rate is obtained in a short time, for example, the cell wall breaking rate reaches 61.7% in 5 min; the pear-shaped grinding broken wall extraction tank has stronger cell wall breaking capacity; however, as the wall breaking time increases, the wall breaking rate decreases, and it can be seen that at 10min, the cell wall breaking rate reaches 79.9%, and only 18.2% of the wall breaking rate increases as compared with the case of 5min, and the wall breaking rate gradually increases with time; the change is that on one hand, the residual cells which are not broken are less and less, on the other hand, the release of substances in the cells leads to the change of the viscosity and the fluidity of the bamboo leaf cell fluid in the grinding cavity, and the occurrence probability of the broken cells is reduced; in addition, after a long time of wall breaking, the cell wall breaking rate can finally reach a larger value, namely, the cell wall breaking rate reaches 97.4% when the wall breaking treatment is carried out for 45 min; the prolonged wall breaking time means an increase in energy consumption while also reducing production efficiency; further, the long-term grinding is not only easy to cause excessive generation of fine cell fragments, but also unfavorable for the separation of the products at the later stage.

As can be known from comprehensive comparison of the three groups of optimal parameters, the stirring linear speed, the wall breaking time and the grinding medium filling rate of the grinding wall breaking extraction tank for the shape modeling are properly increased, the size of the grinding medium and the proper feed-liquid ratio are reduced, and the larger cell wall breaking rate is facilitated; through orthogonal experiments, the cell wall breaking rate and the cell fluid viscosity are comprehensively considered, and the optimized wall breaking parameter combination is as follows: namely, the linear speed is 12-20m/s, the diameter of the grinding medium is 0.2-0.4 mm, the filling rate of the grinding medium is 70-80 vol%, the wall breaking time is 30-50 min, the feed-liquid ratio is 1:20-40, the regulating pressure is 0.5-2.5 MPa, and the air flow rate is 200L/min; experiments show that under the process conditions, the bamboo leaf cell structure is seriously damaged, cell membranes shrink, cracks appear between cell walls, part of cell membranes are broken, and a 'cavity' phenomenon appears; overall, almost no intact cells are present and the cell wall is severely damaged; the cell wall breaking rate can reach 97.4 percent.

Thirdly, the optimal extraction rate of the nanoscale bamboo leaf flavonoid compound is obtained by adopting different ethanol solution concentrations.

The bamboo leaf plant cell belongs to large particle cell clusters, the wall breaking is only to break cell walls of surface parts of the cell clusters, although the components in the cells can be extracted rapidly, for inner cells and whole cell clusters, more importantly, a solid-liquid contact surface is increased, the extraction and diffusion surface of effective components in the inner cells is accelerated, after one cell wall is broken on the surface of the cell cluster, a plurality of inner cells adjacent to the cell become solid-liquid contact surface cells, the area of the diffusion surface is also increased, and the change of the area of the diffusion surface is related to the number or ratio of the broken cells; ethanol can solubilize the lipids of the cell walls and membranes, thereby bringing a large amount of the cell contents out of or into solution or directly penetrating out of the lysed cells; thereby achieving the purpose of extraction.

The experiment is designed, the concentration of the ethanol solution is fixed, the extraction time is changed, a single factor experiment of the change of the flavone yield along with the time is made, and the result obtained by changing the extraction time is shown in Table 2

From the data in Table 2, the change in flavone yields at different extraction times can be seen:

(1) The flavone yield gradually increases with the increase of the extraction time.

(2) The lower the ethanol concentration, the shorter the equilibration time, the ethanol concentration below 75%, the equilibrium is generally reached for 30-40 min, and the longer the time required for the equilibrium to be reached by the extraction with the increase of the ethanol concentration.

(3) It can be observed in the experiment that, due to the insolubility of chlorophyll in water, the color of the extracted solution gradually changes from yellowish-brown to greenish-black with increasing concentration of ethanol; if 30% ethanol solution is selected as the extraction solvent of bamboo leaf flavone, less chlorophyll is contained in the extract.

(4) When the ethanol concentration ratio is less than 75%, the total flavone yield increases with increasing ethanol concentration; when the ethanol concentration reaches 75%, the ethanol concentration is continuously increased, and the yield is reduced; this is because the dissolution of flavonoids in ethanol solutions follows a similar principle of miscibility, with 75% ethanol concentration having a polarity similar to that of the flavonoids.

Fourth, the application adopts different feed liquid ratios to demonstrate the influence of the feed liquid ratios on the extraction amount of the nanoscale bamboo leaf flavonoid compounds.

The experimental study of the application finds and verifies that along with the continuous dynamic increase of the feed liquid ratio of the bamboo leaf sample and the ethanol water solution, the flavone extraction amount is in a slow increasing trend, but when the feed liquid ratio exceeds 1:40, the extraction amount is hardly changed remarkably; the method is characterized in that as the ratio of feed to liquid is continuously and dynamically increased, the contact area of the material and the solvent is increased, so that the ethanol solution is easier to permeate into bamboo leaf cells, and the extraction amount of flavone is increased; however, the feed liquid ratio is continuously and dynamically increased to a certain extent, the concentration difference between the boundary layer of the material and the solvent is reduced, the diffusion reaches equilibrium, and the content in the solution tends to be stable. Therefore, the final feed-liquid ratio is selected to be 1:20-1:40, and the optimization is reasonable; therefore, the extraction solvent multiple is increased, so that the concentration difference of two phases is increased, and the diffusion power is increased; reducing the grain size of the bamboo She Weili to shorten the diffusion path; therefore, the extraction process can be accelerated by continuously and dynamically increasing the solvent multiple and reducing the grain size of the bamboo She Weili.

Fifthly, the biological flocculant is adopted for removing impurities, so that the purity of the bamboo leaf flavonoid compound is improved.

Tannins are astringent and polyphenol compounds which can generate water insoluble precipitate with alkaloids and proteins, and can be dissolved in water and alcohol and insoluble in benzene, chloroform and other organic solvents, so that a large amount of tannins are often mixed in water or alcohol extract, and the components of the bamboo leaf extract are often greatly affected.

Experimental studies in this application found and verified:

the dosage of the biological flocculant solution has great influence on flocculation impurity removal effect; with the increase of the dosage of the bioflocculant solution, the flavone retention rate of the bamboo leaf extract is continuously reduced, and the light transmittance is in a trend of increasing firstly and then decreasing; the reduction of the retention rate of flavone is probably caused by the addition of the bioflocculant solution, so that the stability of the flavone in the extracting solution is affected to a certain extent, and the flavone is settled out simultaneously with macromolecular substances such as protein, tannic acid and the like; whereas the change in light transmittance can be explained as: when the adding amount of the bioflocculant solution is small, the bioflocculant and substances in the extracting solution can form a complex more quickly and completely, and the complex adsorbs suspended substances in the extracting solution to be precipitated, so that the clarity of the solution is improved; when the bioflocculant solution is excessive, the impurities in the extract are insufficient to form complexes with the bioflocculant, and the excessive bioflocculant is suspended in the solution, so that the clarity of the solution is reduced; considering the flavone retention rate and the light transmittance of the bamboo leaf extract, 4-5 parts of 1% bioflocculant solution is a better dosage.

Sixth, the application provides an ultralow temperature frozen pear form nanometer grinding and wall breaking extraction integrated device with a filtering function, and solid-liquid separation is carried out.

In the prior art, the existing grinding machine lacks the grinding process of materials

Filtering the material, when the grinder grinds the material, a part of the material is not completely ground into particles, but when the material which is not ground is not filtered, the grinding quality of the material is reduced, and the use of the material is affected.

Therefore, the application provides a pear-shaped ultralow-temperature freezing auxiliary high-pressure double-vortex countercurrent back pressure cavitation continuous dynamic circulation nano grinding wall breaking extraction and filtration integrated device with a filtration function, and experimental research shows and verifies a filtration technology adopted by a solid-liquid separation nanofiltration layer of the pear-shaped ultralow-temperature freezing auxiliary high-pressure double-vortex countercurrent back pressure cavitation continuous dynamic circulation nano grinding wall breaking extraction and filtration integrated device:

rotating and filtering: the solid forms turbulence due to high-speed rotation, and the shearing force of the outer wall is improved by 50% compared with the traditional cross-flow filtration; meanwhile, as the turbulent flow continuously washes the surface of the membrane, the solid matters are prevented from staying on the surface of the membrane disc, thus effectively preventing the membrane surface from being blocked and ensuring the normal filtration;

Intermittent compression motion filtering: the ultrathin permeation distance and the permeation distance are not influenced by the solid content of the feed, and the continuous stable filtration time is long, which means high efficiency and high yield; the membrane flux does not decline, and the yield is improved by several times;

centrifugal action: centrifugal force is used as driving, a large-flow circulating pump is not needed to provide flow velocity, and energy is saved by 60% -80%.

According to the method, the special geometry nanoparticle size with the initial modulation is adopted, the novel ionic liquid with the unique magnetic structure-vortex magnetic domain with the magnetization closed distribution is used for functionalizing the vortex magnetic nano elliptic hollow ring sphere, and then the selective separation adsorption and effective enrichment of active substances in new and better natural products are realized.

Although macroporous resin has more reports on flavonoid component separation, a better separation and purification effect is achieved, and a lot of macroporous resin is applied to industrial production; however, the current research is focused on separating flavonoid components in a certain plant, taking content improvement amount and yield as indexes, examining adsorption process conditions, screening resin and process only suitable for the plant, and the selected resin is different; when a new component needs to be separated, a great deal of time is spent on rescreening resin and fumbling, and time and labor are wasted; moreover, the research on the adsorption behavior of the macroporous adsorption resin on flavonoid compounds in the current literature is incomplete, and the influence of the properties of the resin and the structure of the compounds on the adsorption process is also ambiguous; the method has little significance on separation and reference of flavonoid compounds in different plants.

Conventional magnetic nanoparticles, due to the nanoscale effect, exhibit physicochemical characteristics that are distinct from macroscopic magnetic materials, such as: the magnetic nano-particles have the characteristics of large specific surface area, superparamagnetism, capability of forming magnetic liquid, diversified topological magnetic structures and the like, and the surface of the magnetic nano-particles is easy to functionalize, so that the magnetic nano-particles are applied to the fields of separation and adsorption of target objects, effective enrichment and the like.

However, as applications become deeper, traditional superparamagnetic particles, based on their Brownian-Neel relaxation, produce heat

The magnetization intensity value and the specific absorption rate value of the mechanism are in direct proportion to the square of saturation, so that the separation adsorption and effective enrichment effect of a target object are greatly reduced due to the lower magnetization intensity value of the traditional superparamagnetic particles, an external alternating magnetic field with higher field intensity and frequency is required for improving the magnetization intensity value of the traditional superparamagnetic particles, and a high-amplitude high-frequency external field brings higher specific absorption rate value, and meanwhile, the thermal effect of the external alternating magnetic field rapidly forms a high-temperature region, so that bamboo leaf flavone is easily degraded and denatured by heating; at the same time, the transverse relaxation rate of the traditional superparamagnetic particlesr ₂ Has high dependence on the magnetic properties of the particles; for traditional superparamagnetic particles, the saturation magnetization of the particles is caused by the reduction of the volume magnetic anisotropy energy and the surface spin-casting effect Ms value is low, and the transverse relaxation signal is lowr ₂ ) The magnetic response is slow, and the rapid and efficient separation and adsorption and effective enrichment of the target are difficult to realize; if the surface is coated with a non-magnetic modifier, the concentration of particles in unit volume is further diluted, so that the overall magnetic performance is reduced; in addition, the traditional superparamagnetic particles have too small size, are not easy to locate and stay on a target object, are not beneficial to effectively enriching the separation adsorbate, and have increasingly prominent defects such as poor physical and chemical stability; therefore, the defects can be produced to a great extent in the application steps in the fields of separation and adsorption, effective enrichment and the like of active substances in natural productsRestriction and obstruction; affecting and limiting the wide range of applications of conventional superparamagnetic particles in this respect.

Research shows that Fe is affected ₃ O ₄ An important indicator of the magnetic fluid application effect is its magnetic responsiveness; the stronger the magnetic response of the magnetic fluid is, the better the separation effect and the positioning capability in the magnetic field are, and conversely, the worse the separation effect is; the magnetic response of the magnetic material is closely related to the specific saturation magnetization, and the higher the specific saturation magnetization is, the better the magnetic response of the magnetic material is; at present, however, regarding Fe ₃ O ₄ The properties of nanoparticles have little research on their influence on the saturation magnetization and magnetic responsiveness.

Therefore, there is an urgent need to find a kind of magnetic nanoparticles, which have higher saturation magnetization values on one hand and can form stable magnetic fluid on the other hand, so as to well make up for the defects of the traditional superparamagnetic particles, and further realize better separation adsorption and effective enrichment application effects of active substances in natural products.

Compared with superparamagnetic nanoparticles, the application of magnetic vortex nanoparticles in the field of biological medicine is rarely reported at present; the magnetic vortex nano-particles used for biomedical research are mainly developed from iron oxide particles with the shapes of nano-discs, nano-rings and the like, but the magnetic vortex nano-particles with the shapes of other shapes are not reported.

The Fe with the length-diameter ratio of beta=1.5, the outer long axis a=90-100 nm, the outer short axis b=60-66 nm, the inner long axis a=72-80 nm, the inner short axis b=48-53 nm, the inner diameter thickness of 9-10 nm and the optimal adsorption effect on flavonoid substances is successfully prepared and synthesized ₃ O ₄ @SiO ₂ @HDI-EMIMLpro and Fe ₃ O ₄ Two ionic liquids @ HDI-EMIMLpro functionalized vortex magnetic nano elliptic hollow ring sphere.

Experimental studies in this application found and verified:

The magnetic domain structure of the ionic liquid functionalized vortex magnetic nanometer elliptic hollow ring sphere comprises:

the nanometer elliptic hollow ring sphere has the advantages that under the condition that the magnetocrystalline anisotropy energy is negligible, the static magnetic field can interact with exchange energy, so that a unique magnetic vortex structure, namely magnetic moment, is magnetized and distributed in a clockwise or anticlockwise manner along the in-plane direction, and at the central vortex center, the magnetic moment is distributed vertically along the out-of-plane direction to form vortex cores; because magnetic moment is distributed in a closed way, stray fields are reduced, and then magnetic dipole interaction among particles can be effectively weakened, so that particle agglomeration phenomenon is avoided, and the magnetic condition for forming stable magnetic nanometer hollow ring spheres is provided;

as can be seen by lorentz transmission electron microscopy: whether a single particle or a pair or even a plurality of particles, exhibit a magnetization vortex distribution in the remanent magnetic state, which results indicate that: in the residual magnetic state, the magnetic domain structure of the nano ellipsoidal hollow ring sphere is a magnetic vortex domain, which proves that the magnetic vortex structure exists in the nano ellipsoidal particles.

Experimental results show that: the formation of the magnetization vortex state, which is derived from the finite field effect of the specific size and geometry of the particles, is the result of the minimum value of the total free energy in the magnet of the system at the characteristic scale; the unique vortex domain structure of the magnetic nano elliptic hollow ring sphere has obvious shape and size dependence, and the geometrical shape and the particle size of particles have a determining effect on the formation and the stability of a magnetized vortex structure:

(1) Under the same long axis a, ellipsoidal particles with a larger short axis b, the magnetization vortex state dominates in the remanence magnetization configuration; for ellipsoidal particles with smaller short axis b, in the remanence state, the width of the particles is narrowed, the demagnetizing energy is stronger, so that the remanence magnetization configuration of the ellipsoidal particles is easier to form single domain distribution;

(2) the coercive force of the material is smaller under the same short axis dimension b;

(3) particles with the same beta, the field width of the magnetization vortex state of which stably exists in an externally applied rotating magnetic field gradually narrows along with the reduction of the particle size;

(4) vortex magnetic nano elliptic hollow ring ball with different thickness and external diameterβAt=1.5, the sizes of the presence of magnetic vortex states are the same: under the corresponding internal and external diameter ratio, only the vortex magnetic nano elliptic hollow ringThe vortex magnetic nano elliptic hollow ring ball forms a stable magnetic vortex structure only in the inner and outer diameter surface areas of the ball;

(5) when magnetized in an externally applied rotating magnetic field, the magnetic vortex state of the vortex magnetic nano elliptic hollow ring ball can be changed into other states, and the process is closely related to the geometric morphology of particles;

(6) the elliptic hollow ring-ball morphology and larger particle size ensure that the magnetic field has high magnetic susceptibility and magnetization intensity value, and has quicker and stronger magnetic response in a small externally-applied rotating magnetic field; meanwhile, the vortex magnetic nano elliptic hollow ring sphere has higher magnetic susceptibility and saturation magnetization than the traditional superparamagnetic particles due to larger particle size.

According to the vortex magnetic nano elliptic hollow ring sphere surface modification method, the dispersion and magnetic stability in the environment are improved, and the two effects of surface effect and volume effect are improved, so that the specific surface area of the vortex magnetic nano elliptic hollow ring sphere is increased in a specific reaction mode, the functional group density and the selective absorption capacity are increased, the time for achieving adsorption balance is shortened, and the stability of the vortex magnetic nano elliptic hollow ring sphere is greatly improved; the method not only improves the problems of easy agglomeration, insufficient stability of particles and the like caused by the high specific surface area to a great extent, thereby improving the selectivity of the magnetic particles to the target analytes, but also can protect the vortex magnetic nano elliptic hollow ring sphere from being oxidized in an environment matrix, so that the separation and enrichment of the target analytes are more efficient, rapid and convenient.

The addition of the ionic liquid shows strong response to the external magnetic field, has magnetic effect and can lead the application to

The vortex magnetic nano elliptic hollow annular ball is conveniently separated and magnetically guided under the action of an externally applied rotating magnetic field; when a rotating magnetic field is externally applied, the magnetic field has strong magnetism, and when no magnetic field exists, the magnetism quickly disappears; thus, the vortex magnetic nano elliptic hollow ring ball is not permanently magnetized in a magnetic field.

When the vortex magnetic nano elliptic hollow ring ball is placed in an external rotating magnetic field, the vortex magnetic nano elliptic hollow ring ball is magnetized and a magnetic field is induced, and the vortex magnetic nano elliptic hollow ring ball and the magnetic field are overlapped, so that magnetic lines of force near the vortex magnetic nano elliptic hollow ring ball are deformed, and a gradient magnetic field is formed.

The ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere has a hydroxyl group, has a hydrogen bond effect with flavonoid substances, has pi bond on an imidazole ring, and has a five-membered ring formed into conjugation, so that the adsorption effect on the flavonoid compounds is enhanced through pi-pi bond effect; under the action of an externally-applied rotating magnetic field, due to the friction force generated by the flowing of flavonoid compound solution, vortex magnetic nano elliptic hollow annular balls can be disturbed in a microenvironment, so that the vortex magnetic nano elliptic hollow annular balls can cut magnetic lines of force, then an induced magnetic field is generated on a magnetic pipeline, polarities of the magnetic fields on different vortex magnetic nano elliptic hollow annular balls can be different, attraction or repulsion among particles can occur, and meanwhile, the particles can stably suspend by combining the actions of gravity, fluid force and the like, so that gaps among the particles are increased, and the vortex magnetic nano elliptic hollow annular balls are facilitated to adsorb.

The bamboo leaf flavone has phenolic hydroxyl and glucoside chains and certain polarity and hydrophilicity, and the bamboo leaf flavone substance can form hydrogen bonds with solvent molecules and flavone molecules; when an external rotating magnetic field is applied, electrons forming hydrogen bonds are polarized under the action of the magnetic field, induced magnetic moment is generated, energy of the hydrogen bonds is changed, weakening or bending of the hydrogen bonds is caused, accordingly, the viscosity of the bamboo leaf flavone solution is reduced, the diffusion speed is accelerated, and the adsorption rate of the ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere is improved.

⒍ the application provides a preparation method and process of ultra-high purity nanoscale bamboo leaf total flavone dispersion aiming at the defect of single extraction mode in the prior art, and compared with other known methods, the preparation method and process have the following advantages:

the device has the advantages that the device is used for extracting the nanoscale bamboo leaf flavonoid compounds by initiating an ultra-low temperature freezing auxiliary high-pressure double-vortex counter-flow back pressure cavitation continuous dynamic circulation nano grinding wall breaking extraction and filtration integrated device.

(1) Compared with the traditional mechanical grinding method:

in the operation process of the traditional mechanical grinding method, high-frequency impact and friction of grinding balls in a ball milling tank can generate a large amount of heat, so that the temperature in the grinding tank is increased, the longer the grinding time is, the more the heat is, the temperature increase can influence the molecular structure of plant materials, and the plant materials are easy to soften, become sticky, deteriorate and the like, so that part of plant materials can be consumed, and the biological activity of the plant materials per se can be destroyed;

The application adopts an ultralow temperature freezing solution grinding and extracting process: first, when the sample is in a low temperature state, it rapidly cools down and becomes very fragile; the sample is ground by utilizing ultralow temperature freezing force, mechanical impact force and material friction force, so that the sample is easier to crush, the principle is that firstly, substances which are tough and difficult to crush at normal temperature are frozen below an embrittlement point and then are ground to the required fineness in a low-temperature grinding tank, and original components are not damaged; secondly, in the freeze-grinding process, high temperature cannot be generated, and meanwhile, the sample can be subjected to quick and pollution-free grinding treatment by adopting low-temperature freeze-grinding; compared with the traditional mechanical grinding method, the method means that the sample is more stable, cannot be damaged by heat, and retains the original molecular structure as much as possible.

(2) And comparing the grinding particle size and thin layer chromatography with several traditional mechanical extrusion methods and steam explosion methods:

the result shows that the special pear-shaped structure and the structure with specific size of the tank body and the synergistic effect of the double-turbine positive and negative two-way vortex countercurrent driving movement mode are adopted, so that the friction force between grinding media is enhanced, the impact force of the grinding media at the round corners of the tank body is increased, and the grinding time and the fineness distribution interval of concentrated particles can be obviously shortened; compared with the traditional equipment, the nano grinding wall breaking result is more definite, and the uniformity of the particle size distribution of the material is higher; has the advantages of grinding, breaking and dispersing, uniform fineness, good quality, high fineness of products, small influence of active ingredients of total flavonoids of bamboo leaves on heating, and the like; the grinding and wall breaking time can be greatly shortened, and the grinding and wall breaking efficiency is improved; short extraction time, strong continuity and low cost.

At present, most of domestic enterprises for extracting active ingredients from agricultural products use traditional single-tank extraction, and most agricultural product deep processing enterprises and Chinese medicine production enterprises in China basically use single-tank extraction; the TG2022-3 ultralow temperature refrigeration auxiliary high-pressure double-vortex counter-flow back pressure cavitation continuous dynamic circulation nanometer grinding and wall breaking extraction and filtration integrated device manufactured by Shandong Huana intelligent equipment limited company is authorized by the technology of the application company, analysis and organic combination are carried out according to the extraction principle of each component, and the device has the advantages of convenience in use, wide application range, convenience in industrial production and the like; compared with the traditional single-tank extraction equipment, the device has obvious advantages, thereby having good market prospect, and providing huge market space for popularization and application of the extraction equipment; meanwhile, the device also provides a certain technical theoretical basis for development and research of natural product extraction equipment.

The process development and research work related by the application overcomes the defects of large equipment investment, complex process, low yield and difficult industrial production of the traditional solvent method, and develops the innovative preparation, extraction and separation method with low cost, simple process, high mechanization degree, low energy consumption, high product purity and high environmental quality.

The novel ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere with the unique magnetic structure-vortex magnetic domain of magnetization closed distribution is adopted, a method for enriching flavonoid compounds by using a functionalized externally-applied rotating magnetic field pipeline is established, a novel method is provided for enriching and separating active substances in natural products, and further, the selective separation and adsorption, effective enrichment and biomedical application performances of the active substances in the novel and better natural products are realized.

(1) Compared with the traditional superparamagnetic particles, the magnetic vortex particle has the advantages that based on the unique magnetization vortex domain, the annular morphology and the larger particle size, the magnetic vortex particle has higher magnetic susceptibility and saturation magnetization value, has quicker and stronger magnetic response in an external rotating magnetic field with low field intensity, and can remarkably enhance the adsorption degree.

The comparison test result of the application shows that:

the relaxation rate of the ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere and commercial superparamagnetic iron oxide of the application under the condition of a 1.5T external rotating magnetic field is compared with the table option, see table 3

As can be seen from table 3: the application discloses an ionic liquid functional vortex magnetic nano elliptic hollow ring ball r ₂ ^* The transverse relaxation signal value is almost 4 times that of commercial superparamagnetic iron oxide, and the transverse relaxation signalr ₂ ^* Transverse relaxation signalr ₁ And more preferably 2 orders of magnitude higher than commercial superparamagnetic iron oxide. The reasons for this are two: on the one hand, the application has larger size and thus higher saturation magnetization, resulting in transverse relaxation signals thereofr ₂ ^* The value is higher; on the other hand, under the action of an externally applied rotating magnetic field, the vortex magnetic form is converted, and the process has great influence on the inhomogeneity of the local field around the nano ring, thereby also causing the transverse relaxation signalr ₂ ^* The value becomes high. Further indicated is that: the method is used for effective enrichment of separation and adsorption, and has better application advantages and potential than superparamagnetic iron oxide particles.

Secondly, a vibrating sample magnetometer is adopted to measure the traditional superparamagnetic iron oxide nano particle and the ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere, and the hysteresis loop of the two samples is compared, so that the application has higher than the traditional superparamagnetic iron oxide nano particleMs value;

third, the vortex magnetic nano elliptic hollow ring sphere of the present application has the nano particles with a magnetic vortex structure, and because the magnetic moment is distributed in a closed way, the stray field is reduced, and the magnetic interaction between particles can be effectively weakened, thereby avoiding the occurrence of particle agglomeration phenomenon, and having the magnetic condition for forming stable magnetic sol; at the same time, the present application exhibits higher magnetic susceptibility and saturation magnetization than superparamagnetic particles due to the relatively large particle size.

Fourth, with this application ionic liquid functionalization vortex magnetism nanometer ellipse hollow ring ball, load in the pipeline can increase the load capacity, increases elution time, makes the target object more abundant with this application contact to obtain better enrichment separation effect, have advantages such as separation efficiency is high, fast, specific surface area is big, loadability is strong.

(2) Compared with the traditional separation and purification method, such as macroporous resin and the like:

firstly, the ionic liquid functionalized vortex magnetic nano elliptic hollow annular ball replaces common adsorption resin under the action of an externally applied rotating magnetic field, so that the contact area between the ionic liquid functionalized vortex magnetic nano elliptic hollow annular ball and a liquid phase is increased, the treatment capacity is greatly improved by pipeline design, and the magnetic field enhancing effect is added, so that compared with the traditional common adsorption resin, the adsorption capacity of the ionic liquid functionalized vortex magnetic nano elliptic hollow annular ball on bamboo leaf flavone is not reduced by magnetization treatment, and the advantages of the ionic liquid functionalized vortex magnetic nano elliptic hollow annular ball are more embodied in the aspects of treating turbid materials and improving the operation flow rate; this shows that the pretreatment conditions for materials are properly relaxed by utilizing the advantages of the application while the original adsorption performance is better maintained.

Secondly, the specific surface area is large, the loading capacity is strong, so compared with a macroporous resin column, the material consumption is less, and the occupied space is small; the used ionic liquid functionalized vortex magnetic nano elliptic hollow annular ball can be recycled by adopting methods such as ultrasonic cleaning and the like, and magnet assistance is applied in the recycling process, so that the loss is not easy to occur.

Thirdly, the vortex magnetic nano elliptic hollow ring ball surface prepared by the method is modified with rich amino groups, has the most remarkable advantages of strong selectivity, simplicity and convenience in operation, can directly separate the extract from the bamboo leaf flavonoid compound solution, saves time and labor in the whole separation process, is simple and easy to control in operation, can separate the adsorbed extract from the stock solution by externally adding a rotating magnetic field, and is a good separation and purification method; is expected to be applied to extraction and separation systems of flavonoid and organic acid compounds in complex component systems of other traditional Chinese medicinal materials and the like.

(3) Compared with the prior method for carrying out sample pretreatment on the traditional solid phase extraction material:

firstly, the using amount of the extractant is small, and the extraction efficiency is high; the currently commonly used solid phase extractant has larger particle size (tens to hundreds of micrometers), smaller specific surface area, low extraction capacity and small extraction penetration volume and enrichment multiple; the ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere has the advantages of large surface area, high extraction capacity and strong surface adsorption force.

Second, environmental friendliness; in the extraction process, only a small amount of single solvent is consumed, other toxic and harmful substances are not introduced, and the method is environment-friendly.

Thirdly, the operation is simple and convenient, and the extraction speed is high. On one hand, the nano material has small particle size and short diffusion path, so that the balance speed is high; on the other hand, the prepared ionic liquid functionalized vortex magnetic nano elliptic hollow ring ball has good superparamagnetism, and can realize rapid and complete separation of a target object and mother liquor in a very short time by using an external rotating magnetic field, thereby overcoming the defects of larger column passing resistance, time and labor waste and being very suitable for processing large-scale samples during solid phase extraction of common nano materials.

Fourth, the target can be extracted from the complex actual sample without interference; the volume exclusion function of the ionic liquid can ensure that macromolecular substances such as common proteins in an environmental medium cannot enter the ionic liquid functionalized vortex magnetic nano ring sphere, so that the extraction efficiency is affected.

Fifth, the time of the present application is 50min, which is 60-100 less than that of other methods in the whole enrichment process

min, more efficient; compared with the known reported method, the ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere method provided by the application is more rapid, effective, sensitive and reliable in separation adsorption and effective enrichment of active substances from natural products; the separation mode is simple and convenient to operate, high in enrichment efficiency and capable of recycling magnetic materials, overcomes the defects of the traditional separation method, and overcomes the defects of short service life, unrepeatable use and high price of a common solid phase extraction stationary phase to a certain extent.

According to the ampere loop theorem and the Biao-savart law, when current passes through a conductor loop, the strength of a magnetic field linearly increases according to the direction of a symmetry axis and linearly decreases according to the opposite direction, so that a rotating magnetic field is formed; the rotating magnetic field can enable the conductor ring to rotate, and the performance of the ionic liquid functionalized vortex magnetic nano elliptic hollow ring ball is evaluated by analyzing the motion state of the ionic liquid functionalized vortex magnetic nano elliptic hollow ring ball under the rotating magnetic field.

(1) Under a rotating magnetic field, 67.2% of commercially available spherical magnetic composite particles are agglomerated, and the ionic liquid functionalized vortex magnetic nano elliptic hollow annular spheres prepared by the method are basically free from agglomeration; because spherical particles have weaker magnetic anisotropy, the magnetic moment generated under the rotating magnetic field cannot reach the energy required by the rotation of the particles; (2) most spherical particles on the market cannot alone complete a 360 ° rotation; the average effective rotation frequency of the spherical particles is lower than the application due to oscillation and rotation jump; with the increase of the magnetic field intensity, the spherical particles are gathered, and the number of particles capable of independently completing rotation is reduced; the method can spin under a magnetic field with higher intensity, so that aggregation is reduced;

(3) Commercially available spherical particulate magnetic materials are relatively high, about 20 times as much as the present application, and have increased weight and tend to adhere to the bottom of the substrate, affecting rotational inertia. Although the content of the magnetic substance is small, the magnetic substance has better rotation performance in the rotating magnetic field due to the inherent magnetic anisotropy.

(4) In a low-field-intensity rotating magnetic field with different frequencies, the spherical particles can smoothly and continuously rotate along with the magnetic field, cannot continuously rotate and can oscillate back and forth, so that the average effective rotating frequency is reduced; compared with the spherical particles sold in the market, the number of independent rotations can be increased by 68% under the same rotating magnetic field; the magnetic anisotropic material has higher magnetic anisotropy, is easier to control under a low field intensity magnetic field, and has great application potential.

In summary, the application cuts in from the brand new view angle of the nanoparticle with the unique vortex magnetic domain structure, and provides a novel ionic liquid functionalized vortex magnetic nano elliptic hollow ring-ball system, compared with superparamagnetic nanoparticle, the ionic liquid functionalized vortex magnetic nano elliptic hollow ring-ball system has weak inter-particle magnetic interaction and excellent magnetic performance due to unique magnetization closed distribution, larger particle size and magnetization characteristics in an externally applied rotating magnetic field, can have the advantages of superparamagnetic particles in practical application, overcomes inherent defects of the superparamagnetic particles, and shows remarkable separation adsorption of active substances in natural products and effective enrichment application performance advantages and application values. In addition, experimental researches show that the ionic liquid functionalized vortex magnetic nano elliptic hollow ring-ball binding specificity molecules or antibodies can realize targeted enrichment in organisms, and the larger particle size can enable particles to be combined with more biomolecules (drug molecules, fluorescent agents and the like) and can also realize that the particles have high permeability and retention (EPR) at tumor positions, so that the enrichment in tumor tissues and the improvement of tumor treatment effects are facilitated; the method has better application advantages and potential in the biomedical fields such as magnetic resonance imaging, anti-tumor magnetic hyperthermia, clinical diagnosis, enzyme labeling, targeted drug carrier and magnetic control drug release, cell labeling and separation, gene expression regulation and control, immunodetection, bioengineering (enzyme immobilization) and the like.

As a novel magnetic adsorbent, the ionic liquid functionalized vortex magnetic nano elliptic hollow ring ball further enriches members and types of 'magnetic vortex state nanocrystalline family'; the situation of 'universal' of superparamagnetic nano particles in separation adsorption and effective enrichment application can be broken through; meanwhile, fresh blood is injected into biomedical magnetic nanoparticle families, a new way is opened up, and due to the proper biomedical size and good biocompatibility of the biomedical magnetic nanoparticle families, the research results are used for early magnetic mechanism exploration and bedding in the fields of biomedicine and the like in the future; can be widely applied to pretreatment of samples such as medicines, environment, biology and the like.

First example of the application to prepare D ₅₀ Nano-scale ultra-high purity bamboo leaf total flavone dispersion with the purity of 99.7-99.9 percent, wherein the purity is 0.02-0.08 mu m.

(1) According to Noyes-Whitney and 0stwald-Freundlich equation, when the particle size of the drug is reduced to the nanometer level, the surface area is increased, so that the solubility and dissolution rate are remarkably increased, and the drug is easy to absorb; meanwhile, the nano-size medicine has biological adhesion effect, prolongs the gastrointestinal retention time, and has the possibility of other various absorption mechanisms, thereby obviously improving the bioavailability.

In theory, any particle with a nano-scale size can be called as a nano material, the size of the nano particle determines the distribution and metabolism period of the particle in a living body, and the particle with the particle diameter smaller than 10nm has large specific surface area, more active electrons and strong biotoxicity and can be easily cleared through kidneys; while particles with a particle size greater than 200nm will be phagocytized by macrophages and deposited in the spleen; thus, the nanomaterial scale currently used in the biomedical field is mostly controlled between 10-200nm for bioavailability and biosafety.

According to the second part of the Chinese pharmacopoeia 2005 edition: the particle size of 90% of the dispersed phase pellets of the emulsion injection for intravenous use should be below 1 μm, and no pellets larger than 5 μm are required; the superfine powder of traditional Chinese medicine according to Chinese pharmacopoeia is sieved by a 200-mesh sieve (with the aperture of 75 μm), and according to the report, the superfine powder of traditional Chinese medicine is sieved by a 300-mesh sieve (with the aperture of 47 μm). (2) Based on the knowledge in the industry, the higher the purity of the bamboo leaf flavone is, the stronger the activity and the higher the polarity are, and if the effects of effectively reducing blood fat, preventing cardiovascular diseases and the like are to be achieved, the performance of improving hypoxia tolerance, preventing osteoporosis and the like are improved, the purity is at least 90%, so that the purity determines the physiological activity of one medicine.

(3) The research and improvement of the new formulation of the bamboo leaf flavone should be developed towards the directions of high efficiency, quick effect, long effect, low toxicity, easy carrying, convenient administration and easy preservation; the new preparation forms of low dosage, high absorption rate and high utilization rate, long-time required concentration of the bamboo leaf flavone maintained in the body, such as micropills, dripping pills, granules, injection, sustained release preparations, controlled release preparations and targeting preparations, and the novel preparation forms of granulating, tabletting and the like of the bamboo leaf flavone whole powder without auxiliary materials are achieved.

(4) Thus, the first example of the present application produces D ₅₀ The technology of the nano-scale ultra-high purity bamboo leaf total flavone dispersoid with the purity of 99.7-99.9 percent, which is 0.02-0.08 mu m, is effectiveThe components are fully utilized, the requirements of the conditions can be met, and a material basis is provided for developing a new formulation of the total flavonoids of the bamboo leaves; solves the limitation of the technology for industrially extracting the bamboo leaf flavone, and industrializes the nanoscale ultra-high purity bamboo leaf total flavone dispersoid in large scale, and can be used in the fields of medicines, health products, special food, special functional beverages and cosmetics according to the needs.

In conclusion, most of the plants are difficult to enrich due to low content of active ingredients; the system is complex, macromolecules and micromolecules exist together, living and non-living substances exist together, and particularly isomers with similar structures exist, so that the difficulty in separation and purification is high; many natural products are sensitive to heat and easy to hydrolyze, so that the product obtained by the traditional extraction and separation method has the advantages of low yield, low purity, high cost, complex process and usually residual organic solvent; therefore, the basic research of the extraction and separation of natural products is very necessary to be enhanced, and the high-efficiency, low-cost, simple and convenient and high-quality separation and extraction technology is developed to thoroughly change the low-level, extensive and lagging production mode of the development of the Chinese natural products, which has great significance for accelerating the modernization process of Chinese traditional medicines; therefore, research and application of new extraction and separation means and production modes are necessary and necessary.

However, at present, the integrated technology for comprehensively processing the high-purity bamboo leaf flavonoid extract is lacking at home and abroad, the application innovatively provides an ultra-low temperature freezing-assisted high-pressure double-vortex counter-flow back pressure cavitation continuous dynamic circulation nano grinding wall-breaking extraction and filtration integrated device which is used as a technology for extracting the nanoscale bamboo leaf flavonoid compound, particularly an ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere is combined with an externally applied rotating magnetic field to carry out adsorption separation, and a dynamic elution desorption integrated technology, so that the technical problems in the process of nano grinding wall-breaking extraction and separation and functional product development are solved, and a basis is provided for industrial production of nanoscale ultra-high-purity bamboo leaf total flavonoid dispersoids.

Based on the technology of the application, the drug exposure of oral and non-oral dosage forms is increased, the proper formulation of the most common administration route can be determined by using milligram doses of the drug, and another way for screening and identifying excellent new drugs is provided for the research and development of innovative drugs; the popularization and application of the mode have very important significance on the aspects of material basis, pharmacology, prescription compatibility theory, effective quality monitoring and control and the like of other traditional Chinese medicines.

Bamboo powder is the most commonly used bamboo-plastic composite material. The mesh number of the bamboo powder used as filling has important influence on the mechanical property, the flow property and the microstructure of the composite material, and as known from the fiber reinforcement principle, the larger the mesh number of the bamboo powder is, the smaller the particle size is, the more uniform the bamboo powder is dispersed in a polymer matrix, and the better the mechanical property of the composite material is, which is possibly related to the different interface combination of the bamboo powder and matrix plastic, fiber morphology, surface roughness and internal void conditions; therefore, the number of the bamboo powder is an important parameter to be considered in the preparation process of the bamboo-plastic composite material.

According to reports, the highest mesh number of the bamboo powder sold in the market at present is 800 mesh of German technology and 1600 mesh of Chinese technology; therefore, the research of the high-mesh bamboo powder material is still in a starting stage, and the research cannot simultaneously meet the requirements of safety, sanitation, environmental protection, low cost, high mesh number, complex production process and high preparation cost because of the defects of poor performance, insufficient mechanical strength, high manufacturing cost, poor experience, serious operation pollution and the like or other reasons, so that the further popularization and the use are restricted; to date, there is little commercial mass production and practical commercial use.

Median particle diameter D of the present application ₅₀ The solid bamboo powder sediment with the particle diameter of 0.02-0.08 μm can be widely applied to the fields of high added value products such as buildings, industry, traffic, composite materials, bioplastic, motor vehicle shells and inner decorations, paint ink, water source purification, bioethanol, petrochemical industry, tobacco, explosive, nanocellulose and the like by spray drying, and has good economic value.

Detailed Description

The present application is further illustrated by the following examples, which are provided only to illustrate the present application and not to limit the scope of the present application.

Example 1

The preparation process of the super high purity nanometer bamboo leaf total flavone dispersion includes the following steps:

inputting refrigerant ethanol into a jacket layer of an integrated device, starting the device to overlap an ultralow temperature refrigerating system, and adjusting the cooling temperature in a pear-shaped grinding wall-breaking extraction tank to-15 ℃; bamboo leaf powder and 30% ethanol solution are put into a pear-shaped grinding wall breaking extraction tank according to a feed liquid ratio of 1:10g/mL, 5 parts of bioflocculant solution and a grinding medium with a filling rate of 70vol%, a double-turbine forward and reverse vortex countercurrent driving disc is started to rotate at a high speed of 12m/s, a pressure pump is started at the same time, inert gas carbon dioxide is pressed into the pear-shaped grinding wall breaking extraction tank, the pressure is regulated to 0.5MPa, the air flow rate is 200L/min, and the whole process participates in ultra-low temperature continuous dynamic circulation grinding wall breaking/extraction treatment, and the total whole process time is 50min; starting a peristaltic pump at 15 th seed of the total treatment time in the whole process, continuously and dynamically supplementing and adding 50% ethanol solution with the feed-liquid ratio of 1:10g/mL in 30min in a dropwise manner, and finally achieving the feed-liquid ratio of 1:20g/mL of the total treatment capacity; then, the pressure is removed, the materials are discharged from a discharge hole of a pear-shaped grinding and wall-breaking extraction tank to a solid-liquid separation nanofiltration layer, high-speed rotation and intermittent compression movement are carried out, under the action of centrifugal force, filtrate passes through a nanofiltration rotary membrane in a tangential manner under the pressure of a pump and 3kg, and flows out from the bottom of the device through a hollow pipeline; achieving solid-liquid separation to obtain the median D of particle diameter ₅₀ Nano bamboo leaf flavonoid compound solution and solid bamboo powder precipitate of 0.08 mu m;

step two, fe ₃ O ₄ Modified vortex magnetic nano elliptic hollow ring sphere (HDI-EMIMLpro) ionic liquid is combined with an externally applied rotating magnetic field to perform adsorption separation, and dynamic elution and desorption are performed:

mixing the nanometer bamboo leaf flavonoid compound solution and Fe ₃ O ₄ The @ HDI-EMIMLpro ionic liquid functionalized vortex magnetic nano elliptic hollow ring ball is filled in a polytetrafluoroethylene pipeline after being uniformly mixed in a ratio of 5:1, and is subjected to ultrasonic treatment at 30 ℃ for 5min at 3 BV%h, flowing the flow rate through a resin column until adsorption saturation, and closing the external rotating magnetic field after the external rotating magnetic field has the magnetic induction intensity of 1T and vortexes for 20min by means of the annular cylindrical external rotating magnetic field which is tightly attached to the pipe wall; eluting impurities of flavone adsorbate on the resin column by using 5BV distilled water and 5BV 30% ethanol respectively, eluting flavone by using 5BV 50% ethanol and 4BV 70% ethanol respectively, and finally realizing complete desorption, wherein the total eluting desorption time is 25min; combining 50% and 70% ethanol eluates, and then filtering and collecting the desorption solution;

step three, vacuum evaporation concentration at low temperature:

Step four, freeze drying:

the concentrate obtained in the step three is subjected to vacuum freeze drying to obtain the median diameter D ₅₀ Nanoscale ultra-high purity bamboo leaf total flavone dispersion with purity of 99.7% and=0.08 μm;

the solid bamboo powder precipitate is subjected to pressure spray drying to form powder, and is applied to the fields of composite materials, bioplastic, motor vehicle shells and inner decorations, paint and ink, water source purification, bioethanol, petrochemical industry, tobacco, explosive and nanocellulose products.

Example 2

inputting refrigerant ethanol into a jacket layer of an integrated device, starting a cascade ultralow temperature refrigerating system, and adjusting the cooling temperature in a pear-shaped grinding broken-wall extraction tank to minus 30 ℃; mixing folium Bambusae powder and 50% ethanol solution at a ratio of 1:15

g/mL ratio, adding grinding medium with filling rate of 75vol% into pear-shaped grinding mill, mixing with 4.5 parts of bioflocculant solution The wall extraction tank is internally provided with a double-turbine positive and negative two-way vortex countercurrent driving disc which rotates at a high speed of 16m/s, a pressure pump is simultaneously started, inert gas argon is pressed into the pear-shaped grinding wall breaking extraction tank, the pressure is regulated to 1.5MPa, the air flow rate is 200L/min, the whole process participates in ultralow-temperature continuous dynamic circulation grinding wall breaking/extraction treatment, and the whole process total time is 40min; starting a peristaltic pump at 15 th seed of the total treatment time in the whole process, continuously and dynamically supplementing and adding 50% ethanol solution with the feed-liquid ratio of 1:15g/mL in 20min in a dropwise manner, and finally achieving the feed-liquid ratio of 1:30g/mL of the total treatment capacity; then, the pressure is removed, the materials are discharged from a discharge hole of a pear-shaped grinding and wall-breaking extraction tank to a solid-liquid separation nanofiltration layer, high-speed rotation and intermittent compression movement are carried out, under the action of centrifugal force, filtrate passes through a nanofiltration rotary membrane in a tangential manner under the pressure of a pump and 4kg, and flows out from the bottom of the device through a hollow pipeline; achieving solid-liquid separation to obtain the median D of particle diameter ₅₀ Nano bamboo leaf flavonoid compound solution and solid bamboo powder precipitate of 0.039 μm;

step two, fe ₃ O ₄ @SiO ₂ Modified vortex magnetic nano elliptic hollow ring sphere (HDI-EMIMLpro) ionic liquid is combined with an externally applied rotating magnetic field to perform adsorption separation, and dynamic elution and desorption are performed:

Mixing the nanometer bamboo leaf flavonoid compound solution and Fe ₃ O ₄ @SiO ₂ The method comprises the steps of (1) uniformly mixing a functionalized vortex magnetic nano elliptic hollow ring ball of an @ HDI-EMIMLpro ionic liquid in a ratio of 5:1, filling the mixture into a polytetrafluoroethylene pipeline, carrying out ultrasonic treatment at 30 ℃ for 5min, enabling the mixture to flow through a resin column at a flow rate of 3BV/h until adsorption saturation, and closing an external rotating magnetic field after the mixture is subjected to vortex for 20min by means of an annular cylindrical external rotating magnetic field which is tightly attached to the pipe wall and has a magnetic induction intensity of 1.2T; eluting impurities of flavone adsorbate on the resin column by using 5BV distilled water and 5BV 30% ethanol respectively, eluting flavone by using 5BV 50% ethanol and 4BV 70% ethanol respectively, and finally realizing complete desorption, wherein the total eluting desorption time is 25min; combining 50% and 70% ethanol eluates, and then filtering and collecting the desorption solution;

step three, vacuum evaporation concentration at low temperature:

step four, freeze drying:

spray freeze drying the concentrate obtained in the step three to obtain the median diameter D ₅₀ Nanoscale ultra-high purity bamboo leaf total flavone dispersion with purity of 99.8%, 0.039 μm;

The solid bamboo powder precipitate is spray dried to powder through cyclone combined pressure, and is applied to the fields of composite materials, bioplastic, motor vehicle shells and inner decorations, paint and ink, water source purification, bioethanol, petrochemical industry, tobacco, explosive and nanocellulose products.

Example 3

inputting refrigerant liquid nitrogen into a jacket layer of an integrated device, starting the device to overlap an ultralow temperature refrigerating system, and adjusting the cooling temperature in a pear-shaped grinding wall-breaking extraction tank to minus 50 ℃; bamboo leaf powder and 75% ethanol solution are put into a pear-shaped grinding wall breaking extraction tank according to the feed liquid ratio of 1:20g/mL, 4 parts of bioflocculant solution and grinding media with the filling rate of 80vol% are matched, a double-turbine positive and negative two-way vortex countercurrent driving disc is started to rotate at a high speed of 20m/s, meanwhile, a pressure pump is started, inert gas food grade 99.999% ultra-pure nitrogen is pressed into the pear-shaped grinding wall breaking extraction tank, the pressure is regulated to 2.5MPa, the air flow rate is 200L/min, the whole process participates in ultra-low temperature continuous dynamic circulation grinding wall breaking/extraction treatment, and the whole process total time is 30min; starting a peristaltic pump at 15 th seed of the total treatment time in the whole process, and continuously and dynamically adding 75% ethanol solution with a feed-liquid ratio of 1:20g/mL in a dropwise manner until the total treatment capacity reaches a feed-liquid ratio of 1:40 g/mL; the pressure is then released and the pressure is then released, Discharging the material from a discharge hole of a pear-shaped grinding and wall-breaking extraction tank to a solid-liquid separation nanofiltration layer, performing high-speed rotation and intermittent compression movement, enabling filtrate to pass through a nanofiltration rotary membrane in a tangential manner under the action of centrifugal force and under the pressure of a pump and 5kg, and enabling the filtrate to flow out from the bottom of the device through a hollow pipeline; achieving solid-liquid separation to obtain the median D of particle diameter ₅₀ Nano bamboo leaf flavonoid compound solution and solid bamboo powder precipitate of 0.02 μm;

mixing the nanometer bamboo leaf flavonoid compound solution and Fe ₃ O ₄ @SiO ₂ The method comprises the steps of (1) uniformly mixing a functionalized vortex magnetic nano elliptic hollow ring ball of an @ HDI-EMIMLpro ionic liquid in a ratio of 5:1, filling the mixture into a polytetrafluoroethylene pipeline, carrying out ultrasonic treatment at 30 ℃ for 5min, enabling the mixture to flow through a resin column at a flow rate of 3BV/h until adsorption saturation, and closing an external rotating magnetic field after the mixture is subjected to vortex for 20min by means of an annular cylindrical external rotating magnetic field which is tightly attached to the pipe wall and has a magnetic induction intensity of 1.5T; eluting impurities of flavone adsorbate on the resin column by using 5BV distilled water and 5BV 30% ethanol respectively, eluting flavone by using 5BV 50% ethanol and 4BV 70% ethanol respectively, and finally realizing complete desorption, wherein the total eluting desorption time is 25min; combining 50% and 70% ethanol eluates, and then filtering and collecting the desorption solution;

Step three, vacuum evaporation concentration at low temperature:

step four, freeze drying:

spray freeze drying the concentrate obtained in the step three to obtain the median diameter D ₅₀ Nano-scale ultra-high purity bamboo leaf total flavone dispersion with purity of 99.9 percent, which is=0.02 μm;

The present application found and verified through experimental investigation that the purity obtained according to example 3 above was 99.9%, D ₅₀ Nanoscale ultra-high purity bamboo leaf total flavone dispersion = 0.02 μm:

the effect of bamboo leaf flavone samples of different purity on the blood lipid level of mice (x+ -s) is shown in Table 4

Note that: the general bamboo leaf flavone group with the market purity of 50% and the general bamboo leaf flavone group in the embodiment 3 of the application are fed with high-fat feed for 5 weeks; after 5 weeks, 3 mice were randomly bled without fasting, and serum TC, TG were determined;

As can be seen from table 4, the TC and TG levels of the high fat feed group are significantly higher than those of the normal feed group (P < 0.01), indicating that the model of the hyperlipidemia of the mice is successfully modeled, and the high fat feed can completely cause the mice to suffer from hyperlipidemia; compared with a high-fat feed group and a bamboo leaf flavone group with the conventional market purity of 70%, the bamboo leaf total flavone group in the embodiment 3 of the application obviously reduces TC and TG levels (P is less than 0.01) of mice and obviously reduces blood fat; the dosage of the total flavonoids of the bamboo leaves in the embodiment 3 of the application is only 1/4 of that of the general bamboo leaf flavonoids of the bamboo leaves with the market purity of 70%, the effects of reducing TC and TG are better than those of the traditional bamboo leaf flavonoids of the bamboo leaves, and a solid theoretical and large-scale marketable operability foundation is provided for preparing the high-efficiency low-toxicity lipid-lowering medicament by adopting the high-purity nanoscale flavonoids as raw materials for preparing the disease prevention and treatment machine preparation.

Secondly, the surface area, dispersibility, adsorption capacity, surface activity and other comparative raw materials are comprehensively changed; the specific surface area of the nano-scale material preparation is greatly increased, so that the solubility and dissolution rate of the nano-scale material preparation are remarkably increased, the nano-scale material preparation is easy to disperse, is dissolved in gastrointestinal fluid, and the contact area between the nano-scale material preparation and gastrointestinal mucosa is enlarged, so that the retention time of the nano-scale material preparation in the digestive tract is prolonged, the absorption of active ingredients is more sufficient and complete, and the bioavailability and the curative effect of the nano-scale material preparation are greatly improved; local irritation may also be reduced.

All of the foregoing descriptions of specific exemplary embodiments of the present application are presented for purposes of illustration and description; it is not intended to be exhaustive or to limit the application to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching; the exemplary embodiments were chosen and described in order to explain the specific principles of the present application and its practical application to thereby enable one skilled in the art to make and utilize the present application in various exemplary embodiments and with various modifications as are suited to the particular use contemplated; or equivalent replacement of part of the technical features; these modifications, substitutions, and other conceivable alternatives are within the scope of the present application, and do not depart from the spirit and scope of the embodiments of the present application.

Claims

1. The preparation method of the ultra-high purity nanoscale bamboo leaf total flavone dispersoid is characterized by comprising the following process steps of:

Inputting a refrigerant into a jacket layer of the integrated device, starting an overlapping ultralow temperature refrigerating system, and adjusting the cooling temperature in a pear-shaped grinding wall breaking extraction tank to be between minus 15 ℃ and minus 50 ℃; putting bamboo leaf powder and 30-90% ethanol solution into a pear-shaped grinding wall breaking extraction tank according to a feed liquid ratio of 1:10-20 g/mL, matching with 4-5 parts of bioflocculant solution and a grinding medium with a filling rate of 70-80 vol%, starting a double-turbine positive and negative two-way vortex countercurrent driving disc, rotating at a high speed of 12-20 m/s, starting a pressure pump, pressing inert gas into the pear-shaped grinding wall breaking extraction tank, adjusting the pressure to 0.5-2.5 MPa, taking part in ultra-low temperature continuous dynamic circulation grinding wall breaking/extraction treatment in the whole process at an air flow rate of 200L/min, and taking part in the whole process total time of 30-50 min; at the position ofStarting a peristaltic pump in 15 th seed of the total treatment time, continuously and dynamically supplementing and adding 30-90% ethanol solution with a feed liquid ratio of 1:10-20 g/mL in 10-30 min in a dropwise manner, and finally achieving a feed liquid ratio of 1:20-40 g/mL of the total treatment capacity; then, the pressure is removed, the materials are discharged from a discharge hole of a pear-shaped grinding and wall-breaking extraction tank to a solid-liquid separation nanofiltration layer, high-speed rotation and intermittent compression movement are carried out, under the action of centrifugal force, filtrate passes through a nanofiltration rotary membrane in a tangential manner under the action of a pump and the pressure of 3-5 kg, and flows out from the bottom of an integrated device through a hollow pipeline to achieve solid-liquid separation; obtaining the median diameter D ₅₀ Nano bamboo leaf flavonoid compound solution of 0.02-0.08 mu m and solid bamboo powder precipitate;

the refrigerant is any one of 30-80% ethanol and liquid nitrogen;

uniformly mixing the nanoscale bamboo leaf flavonoid compound solution and the ionic liquid functionalized vortex magnetic nano elliptic hollow ring sphere in a ratio of 5:1, filling the mixture into a polytetrafluoroethylene pipeline, carrying out ultrasonic treatment at 30 ℃ for 5min, enabling the mixture to flow through a resin bed at a flow rate of 3BV/h until adsorption saturation, and closing the external rotating magnetic field after the mixture is subjected to vortex for 20min by means of an external rotating magnetic field which is tightly attached to the annular cylindrical shape of the pipe wall and has a magnetic induction intensity of 1-1.5T; eluting impurities of flavone adsorbate on the resin column by using 5BV distilled water and 5BV 30% ethanol respectively, eluting flavone by using 5BV 50% ethanol and 4BV 70% ethanol respectively, and finally realizing complete desorption, wherein the total eluting desorption time is 25min; combining 50% and 70% ethanol eluates, and then filtering and collecting the desorption solution;

in a sealed reaction kettle, fe ³⁺ Introducing phosphate and sulfate surfactant as reactant, and under high temperature and high pressure conditions, supersaturating to separate out crystal and PO ₄ ^3- And SO ₄ ^2- Selectively adsorb alpha-Fe respectively ₂ O ₃ On the crystal face of the crystal, the ferric oxide crystal is induced to form a polyhedral structure, the polyhedral structure is dissolved in the long axis direction preferentially to form a hollow structure, and the concentration of reactants and an auxiliary magnetic field are regulated to lead the nanowires to be arranged in an oriented mode, so that the composite particles form a nano elliptic hollow ring sphere with the length-diameter ratio of beta=1.5; further by alpha-Fe ₂ O ₃ Nanometer elliptic hollow ring ball is used as precursor, fe with good dispersivity, high phase purity and magnetic anisotropy is obtained by hydrogen thermal reduction method ₃ O ₄ Vortex magnetic nano elliptic hollow ring ball;

taking Hexamethylene Diisocyanate (HDI) as a connecting agent, and respectively modifying amino acid ionic liquid 1-ethyl-3-methylimidazole L-proline salt (EMIMLpro) in Fe ₃ O ₄ Vortex magnetic nano elliptic hollow ring sphere and Fe ₃ O ₄ @SiO ₂ The surfaces of the composite vortex magnetic nano elliptic hollow annular spheres are respectively obtained to obtain Fe ₃ O ₄ @HDI-EMIMLpro and Fe ₃ O ₄ @SiO ₂ Two ionic liquid functionalized vortex magnetic nano elliptic hollow ring spheres @ HDI-EMIMLpro; the nanometer elliptic hollow ring sphere with the length-diameter ratio beta=1.5 is an outer long axis a=90-100 nm, and the outer length axis a=90-100 nmShort axis b=60-66 nm, inner long axis a=72-80 nm, inner short axis b=48-53 nm, inner and outer diameter thickness is 9-10 nm;

step three, vacuum evaporation concentration at low temperature:

step four, freeze drying:

freeze drying the concentrate obtained in the step three to obtain the median diameter D ₅₀ Nano-scale ultra-high purity bamboo leaf total flavone dispersion with the purity of 99.7-99.9 percent, which is 0.02-0.08 mu m.

2. The method for preparing the ultra-high purity nanoscale bamboo leaf total flavonoid dispersion according to claim 1, which is characterized in that: the ultralow temperature freezing auxiliary high-pressure double-vortex counter-flow back pressure cavitation continuous dynamic circulation nano grinding wall breaking extraction and filtration integrated device comprises a pear-shaped grinding wall breaking extraction tank, a jacket layer and a solid-liquid separation nanofiltration layer;

3. The method for preparing the ultra-high purity nanoscale bamboo leaf total flavonoid dispersion according to claim 1, which is characterized in that: the freeze drying in the step four is any one of vacuum freeze drying and spray freeze drying.

4. The method for preparing the ultra-high purity nanoscale bamboo leaf total flavonoid dispersion according to claim 1, which is characterized in that: the nanometer ultra-high purity bamboo leaf total flavone dispersoid is the median diameter D ₅₀ =0.02 to 0.08 μm, purity is 99.7 to 99.9%; can be used in the fields of medicine, health products, special food, special functional beverage and cosmetics according to the needs.

5. The method for preparing the ultra-high purity nanoscale bamboo leaf total flavonoid dispersion according to claim 1, which is characterized in that: the solid bamboo powder precipitate is subjected to pressure spray drying or cyclone combined pressure spray drying to form powder, and is applied to the fields of composite materials, bioplastic, motor vehicle shells and inner decorations, paint ink, water source purification, bioethanol, petrochemical industry, tobacco, explosives and nanocellulose products.