CN112374519A - Preparation method and application of micro-nano natural shell calcitonin powder - Google Patents
Preparation method and application of micro-nano natural shell calcitonin powder Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
- A23L5/276—Treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
Abstract
The invention belongs to the technical field of preparation of micro-nano natural shell calcium powder, and particularly relates to a preparation method and application of micro-nano natural shell calcium powder. The preparation method comprises the following steps: purifying and crushing shells, calcining, puffing, and finally crushing to obtain powdery micro-nano natural conchiolin powder, wherein the purification is to purify the shells in subcritical water. The technical process for subcritical water treatment of the shell raw material can remove more than 90% of heavy metals in the raw material with the shell layer structure, eliminates potential safety hazards, can remove fruit and vegetable pesticide residues and aflatoxin with a removal rate of more than 99%, and has high removal efficiency.
Description
Technical Field
The invention belongs to the technical field of preparation of micro-nano natural shell calcium powder, and particularly relates to a preparation method and application of micro-nano natural shell calcium powder.
Background
China is a big agricultural country, and the use of pesticide amount is in the top of the world. The large-scale application of a plurality of related pesticides, especially the excessive application of organophosphorus pesticides, and pesticide residue in food is inevitable. Pesticide residues are seriously threatening or endangering the health of everyone. Related reports reveal that: more than 92 kinds of pesticides and 90% of pesticides can cause cancers. The residual pesticide is 40 to 50 percent of the inducement of children leukemia patients in China. The residual pesticide can cause brain development disorder of children before 7 years old. The toxicity of the residual pesticide can cause the symptoms of sexual precocity, cancer, congenital malformation of fetus, and the like. The related researches further reveal that the residual pesticide is one of the main causes of infertility of more than 10%, so that the removal of the residual pesticide in food is not slow.
A safe, green, natural and pollution-free food pesticide residue scavenger and an aflatoxin scavenger are directions of great concern in the field of food safety. In the existing market, various fruit and vegetable pesticide residue cleaning agents are available, most of which are prepared by taking a chemically synthesized surfactant as a main component, but the fruit and vegetable pesticide residue cleaning agents have strong surface decontamination capability, but cannot effectively decompose the fruit and vegetable pesticide residue, have limited effect on removing the fruit and vegetable pesticide residue, further have the risks of causing secondary pollution and still having potential serious health hazards after long-term use, and have influence on environmental ecology. In order to realize a safe, green and pollution-free pesticide residue remover, a plurality of researchers carry out continuous research and development work to develop a series of fruit and vegetable cleaning agents, but at present, patents related to invention of shell raw materials mostly exist, and a simple, convenient and efficient removing method for harmful substances such as heavy metals, surface sediments, symbiotic attached organic matters and the like which are integrally enriched in shells of shellfish organisms in water environment is still lacking, and development and utilization of the shell raw materials are severely restricted. At present, aflatoxin scavengers are available in the market.
For example, patent CN110205207A discloses a fruit and vegetable cleaning agent based on shell, a preparation method and an application method thereof, which are prepared by using calcined shell powder, essence, calcium chloride, citric acid and other additives according to a certain proportion. In this patent, calcined shell powder is prepared by the following method: soaking shell with hydrochloric acid, and drying; and then crushing the dried shell, and then calcining the crushed shell in a nitrogen atmosphere to obtain calcined shell powder.
In addition, patent CN 104388208A-discloses a method for preparing pesticide-removing fruit and vegetable cleaning agent based on shell powder, which comprises the following steps: the preparation method of the micro-nano shell powder comprises the following steps: performing desalting and degreasing treatment, drying treatment, coarse crushing treatment, calcining and puffing treatment, cooling treatment and micro-nano crushing treatment on shells to obtain micro-nano shell powder; adding a natural auxiliary agent: and adding a natural additive into the micro-nano shell powder to obtain the pesticide-removing fruit and vegetable cleaning agent. Wherein, the method for desalting and degreasing the shells adopts hydrochloric acid solution or sodium hydroxide solution for soaking. The method can be used for preparing powder with particle size of 50-1000 nm. However, the method for preparing the shell powder has the following two problems: 1) hydrochloric acid and/or sodium hydroxide are/is adopted for surface layer cleaning treatment, so that not only is secondary pollution inevitable during acid treatment or alkali treatment exist, but also the requirements of a clean production process which is green, safe, ecological and environment-friendly and suitable for large-scale industrialization are difficult to meet; 2) only organic matters on the surfaces of the shells can be removed, but the heavy metal removal capacity is limited, and the prepared scavenger still has certain potential safety hazard due to an exogenous heavy metal source.
Therefore, the research and development of a method suitable for large-scale preparation of the safe micro-nano natural kakolin powder capable of efficiently removing pesticide residues on the surfaces of food materials and the aflatoxin scavenger are urgently needed.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a micro-nano natural conchiolin powder production method which is environment-friendly, simple, convenient and economical to operate and suitable for large-scale production, and particularly is used for removing pesticide residues and aflatoxin on the surface of food materials.
The invention also aims to provide application of the micro-nano natural kakolin powder in preparation of fruit and vegetable pesticide residue scavengers and crop aflatoxin scavengers.
In order to achieve the above object, one of the technical solutions of the present invention is:
a preparation method of micro-nano natural conch calcium powder comprises the following steps: purifying and crushing shells, calcining, puffing, and finally crushing to obtain powdery micro-nano natural conchiolin powder, wherein the purification is to purify the shells in subcritical water.
Preferably, the calcination is continuous high-temperature instantaneous rotational flow dynamic calcination; the puffing is the catalytic puffing of fine water mist input by a medium-low pressure water mist spray head.
The subcritical water is a solvent and a reactant, and can realize the efficient removal of organic matters and inorganic matters on the surface of the shell carrier raw material, because on one hand, the density of water is sharply increased along with the rise of pressure and temperature in a subcritical environment, so that the solvating capacity of the water is remarkably improved; on the other hand, under the subcritical high-temperature and high-pressure condition, the ionization degree, the dielectric constant, the viscosity and the ion activity product of water are greatly changed, the intermolecular hydrogen bonding action is weakened, the solubility of the organic matters is increased, the hydrolysis reaction of the organic matters and the water is remarkably catalyzed and accelerated, and the efficient removal of the organic matters on the surface of the shell carrier raw material is realized; furthermore, subcritical water produces H at high temperature and high pressure+The ion product is increased and the shell biomass material is acidic, so that the shell biomass material is subjected to hydrolysis reaction which is equivalent to acid catalysis in subcritical water, and the heavy metal in the shell biomass material is efficiently removed.
Preferably, the pressure condition adopted for the purification treatment in the subcritical water is 0.2MPa-22MPa, and further preferably 0.5MPa-20MPa, 1MPa-20MPa, 5MPa-20MPa, 1.5MPa-18MPa, 1.5MPa-16MPa, 1.5MPa-15MPa, 2MPa-15MPa and 10-20 MPa.
Preferably, the temperature condition for purification treatment in subcritical water is 120 ℃ to 370 ℃, more preferably 150 ℃ to 350 ℃, 180 ℃ to 330 ℃, 200 ℃ to 320 ℃, 200 ℃ to 300 ℃, 220 ℃ to 280 ℃.
Preferably, the subcritical water is subjected to purification treatment under the conditions of set pressure and temperature for 15-120min, and further preferably for 15-100min, 15-80min, 15-60min, 15-40min, 15-30min and 15-20 min.
Preferably, the calcination mode adopts continuous high-temperature instantaneous rotational flow dynamic calcination. The continuous high-temperature instantaneous rotational flow dynamic calcination is to mix the powdery material with heated hot air and flow oppositely to form a heat exchange maximum specific surface to achieve instantaneous calcination.
The traditional calcining mode, such as a muffle furnace, is to calcine materials in batches, cannot realize continuous production, and is long in calcining time. But the adoption of the calcining mode of the invention realizes the continuous production of the calcining process, also realizes the continuous production of the calcining process and the subsequent puffing work, shortens the process time and improves the efficiency of the whole production process. Meanwhile, the calcination process can activate the shells.
Preferably, the temperature of the calcination is from 500 ℃ to 1250 ℃, more preferably from 800 ℃ to 1200 ℃, from 820 ℃ to 1200 ℃, from 880 ℃ to 1200 ℃, from 900 ℃ to 1200 ℃, from 1000 ℃ to 1100 ℃.
Preferably, the puffing refers to inputting water mist to fully contact with calcined conch calcium powder to catalyze and release heat, wherein: the working pressure of the water mist nozzle is 0.5Mpa to 3.0Mpa, the average grain diameter of the water mist droplets is 200 mu m to 600 mu m, and the weight ratio of the input water amount of the water mist to the calcined conch calcium powder is 3:100 to 10: 100. In the contact process of the water mist and the calcium powder, the material is rapidly catalyzed and bulked. Experimental results show that the pressure, the particle size and the temperature of the water mist in the puffing process influence the microstructure of the finally prepared conch calcium powder. The difference of the microstructure can have important influence on the removal effect of the pesticide residue and the aflatoxin.
Preferably, the working pressure of the water mist spray head is 1.0-2.5 MPa; the particle size is 250-500 μm, and the weight ratio of the water mist input water quantity to the calcined conch calcium powder is 5: 100-10: 100.
Preferably, the expanded conch calcium powder is continuously subjected to micro-nano crushing to obtain micro-nano natural conch calcium powder with the particle size of 10 mu m-20 nm.
Preferably, the shell is a natural shell selected from one or more of oyster shell, clam shell, oil clam shell, mussel shell, scallop shell, pearl clam shell and clam shell, which are by-products of bulk aquaculture processes.
Preferably, in the subcritical water treatment process, the weight ratio of the raw shell to water is 1:1 to 1:12, more preferably 1:1 to 1:10, 1:1 to 1:8, 1:1 to 1:6, 1:1 to 1:4, and 1:1 to 1: 2.
The microstructure of the natural shell calcitonin powder prepared by the preparation process provided by the invention is a porous chain-like and multi-cavity layered structure with a larger specific surface.
The invention also provides application of the micro-nano natural conchiolin powder prepared by the method in preparation of a fruit and vegetable pesticide residue remover.
The fruit and vegetable pesticide residue remover can be used for removing harmful substances on the surfaces of fruits and vegetables, such as pesticide residues, chemical waxiness, preservatives, herbicides and the like.
Preferably, when the fruit and vegetable pesticide residue remover is used, water is used as a solvent, and the weight ratio of the powdery micro-nano natural conchiolin powder to the water is 1: 1000-1: 4000; further preferably 1:1000 to 1: 2000.
The natural conch calcium powder is also used for preparing aflatoxin scavenger.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the shell raw material is purified in subcritical water, so that organic matters, symbiotic sediments on the surface of the shell, and proteins, lipid substances, heavy metals and salt substances in the shell can be effectively removed, and the shell raw material after subcritical hydrolysis and purification is further obtained.
(2) The subcritical water provided by the invention has the functions of acid catalysis and alkali catalysis, has the characteristic of simultaneously dissolving organic matters such as keratin and inorganic matters (such as heavy metal), and can enable organic attachments, proteins, heavy metal and the like in the shells to be subjected to decomposition reaction and converted into other products for removal. Acid and alkali are not needed to be added, and the cleaning agent has the advantages of high efficiency, greenness and cleanness.
(3) Micronizing and crushing the shell raw material subjected to subcritical hydrolysis purification, performing rotational flow dynamic high-temperature instant calcination, activation and modification, inputting water mist for catalysis and rapid puffing, and continuously performing micro-nano crushing to obtain micro-nano natural conchiolin powder. The change of the structure of the micro-nano natural shell calcium powder has the characteristics of quantum size effect, surface effect and the like, and has more excellent performance than common shell calcined calcium powder. The micro-nano carrier particles have porous chain type and sheet type structures with large specific surface. In aqueous solution, H adsorbable on the surface2O or OH-The ionic reaction forms OH and OH-reactions with strong oxidationFormation of OH and O with strong oxidation2-Thereby degrading or decomposing the pesticide residue with high efficiency.
(4) The invention adopts rotational flow dynamic calcination, the purified and dried shell powder material is guided into a furnace by a quantitative screw feeder and a gas-solid mixer to be mixed with heated hot air and move in a rotational flow state, after the calcination process is instantly finished, the calcined shell calcium powder is obtained through gas-solid separation without other operations, and the fine water mist catalysis further heat release expansion can be directly carried out, so that the time of calcination and cooling expansion is reduced; the working efficiency is improved; on the other hand, the large-scale continuous production can be realized; moreover, the calcination is directly carried out, and the fine water mist catalytic heat release expansion is beneficial to forming micro-nano particles with more holes and cavity structures.
(5) The technical process for subcritical water treatment of the shell raw material can remove more than 90% of heavy metals in the raw material with the shell layer structure, eliminates potential safety hazards, can remove fruit and vegetable pesticide residues and aflatoxin with a removal rate of more than 99%, and has high removal efficiency.
Drawings
Fig. 1 is a transmission electron microscope image of the micro-nano natural kakolin powder provided in example 3, which shows that the micro-nano particles have a porous chain structure and a sheet structure with a large specific surface and a plurality of holes and cavities inside.
Fig. 2 is a scanning electron microscope image of the micro-nano natural kakolin provided in example 3, which shows that the micro-nano particles are in a sheet structure.
Detailed Description
The method of the present invention is described below with reference to specific examples to make it easier to understand and understand the technical solution of the present invention, but the present invention is not limited thereto. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Washing and draining natural shells, taking clear water as a solvent, and placing the washed and drained shells in subcritical reaction equipment, wherein the weight ratio of the shells to water is 1:1, performing subcritical hydrolysis reaction for 40min under the conditions that the pressure is 2Mpa and the temperature is 210 ℃. Impurities such as heavy metals, organic matters adsorbed on the surface, sediments and the like in the shell are removed efficiently. Cooling, taking out, washing with water to neutrality, oven drying, and pulverizing to 200 mesh to obtain pure natural shell raw material powder. The shell raw material is oyster shell, scallop shell or corbicula fluminea shell.
Introducing pure natural shell raw material powder into a rotational flow dynamic calcining furnace by a quantitative screw feeder in cooperation with a gas-solid mixer, mixing the pure natural shell raw material powder with heated hot air, then enabling the mixture to flow in the same direction to form large-specific surface heat exchange, instantaneously calcining the mixture for 10 seconds at 900 ℃, and then fully contacting the calcined shell powder with water mist to realize synchronous catalytic heat release expansion to ionize and molecularly oxidize the calcined shell powder, wherein the working pressure of the water mist is 0.5 MPa; the grain diameter is 400 mu m; the weight ratio of the input water amount of the water mist to the calcined conch calcium powder is 3:100, and finally, micro-nano pulverization is further carried out to obtain micro-nano natural conch calcium powder with the particle size of 80-900nm, namely the fruit and vegetable pesticide residue scavenger raw material powder, and the fruit and vegetable pesticide residue scavenger product is obtained through bagging sealing or bottling sealing. Preparing 1:1000 aqueous solution of the fruit and vegetable pesticide residue remover.
Example 2
Washing and draining natural shells, taking clear water as a solvent, and placing the washed and drained shells in subcritical reaction equipment, wherein the weight ratio of the shells to water is 1:10, carrying out subcritical hydrolysis reaction for 30min under the conditions that the pressure is 5.0Mpa and the temperature is 250 ℃. Impurities such as heavy metals, organic matters adsorbed on the surface, sediments and the like in the shell are removed efficiently. Cooling, taking out, washing with water to neutrality, drying, and pulverizing to 100 mesh to obtain pure natural shell raw material powder. The shell raw material is oyster shell, scallop shell or corbicula fluminea shell.
Introducing pure natural shell raw material powder into a rotational flow dynamic calcining furnace by a quantitative screw feeder in cooperation with a gas-solid mixer, mixing the pure natural shell raw material powder with heated hot air, then enabling the mixture to flow in the same direction to form large-specific surface heat exchange, instantly calcining the mixture for 12 seconds at 1000 ℃, and then fully contacting the calcined shell powder with water mist to realize synchronous catalytic heat release expansion so as to ionize and molecularly oxidize the calcined shell powder, wherein the working pressure of the water mist is 1.5 MPa; the weight ratio of the input water amount of the water mist with the particle size of 600 mu m to the calcined shell calcium powder is 5:100, and finally micro-nano crushing treatment is carried out to obtain micro-nano natural shell calcium powder with the particle size of 50-800nm, namely the fruit and vegetable pesticide residue scavenger raw material powder, and the fruit and vegetable pesticide residue scavenger product is obtained by bagging and sealing or bottling and sealing. Preparing 1:1500 aqueous solution of the fruit and vegetable pesticide residue remover.
Example 3
Washing and draining natural shells, taking clear water as a solvent, and placing the washed and drained shells in subcritical reaction equipment, wherein the weight ratio of the shells to water is 1: and 5, performing subcritical hydrolysis reaction for 25min under the conditions that the pressure is 10Mpa and the temperature is 300 ℃. Impurities such as heavy metals, organic matters adsorbed on the surface, sediments and the like in the shell are removed efficiently. Cooling, taking out, washing with water to neutrality, drying, and pulverizing to 300 mesh to obtain pure natural shell raw material powder. The shell raw material is oyster shell, scallop shell or mussel shell.
Introducing pure natural shell raw material powder into a rotational flow dynamic calcining furnace by a quantitative screw feeder in cooperation with a gas-solid mixer, mixing the pure natural shell raw material powder with heated hot air, then enabling the mixture to flow in the same direction to form large-specific surface heat exchange, instantaneously calcining the mixture for 12 seconds at 1050 ℃, and then fully contacting the calcined shell powder with water mist to realize synchronous catalytic heat release expansion to ionize and molecularly oxidize the calcined shell powder, wherein the working pressure of the water mist is 1.0 MPa; the grain diameter is 500 mu m; the weight ratio of the input water amount of the water mist to the calcined shell calcitonin powder is 6:100, and finally micro-nano fine crushing is further carried out to obtain micro-nano natural shell calcitonin powder with the particle size of 30-700nm, namely the fruit and vegetable pesticide residue scavenger raw material powder, and the fruit and vegetable pesticide residue scavenger product is obtained by bagging and sealing or bottling and sealing. Preparing 1:2000 aqueous solution of the fruit and vegetable pesticide residue remover.
Example 4
Washing and draining natural shells, taking clear water as a solvent, and placing the washed and drained shells in subcritical reaction equipment, wherein the weight ratio of the shells to water is 1: and 8, performing subcritical hydrolysis reaction for 15min under the conditions that the pressure is 20Mpa and the temperature is 350 ℃. Impurities such as heavy metals, organic matters adsorbed on the surface, sediments and the like in the shell are removed efficiently. Cooling, taking out, washing with water to neutrality, drying, and pulverizing to 100 mesh to obtain pure natural shell raw material powder. The shell raw material is oyster shell, scallop shell or corbicula fluminea shell.
Introducing pure natural shell raw material powder into a rotational flow dynamic calcining furnace by a quantitative screw feeder in cooperation with a gas-solid mixer, mixing the pure natural shell raw material powder with heated hot air, then enabling the mixture to flow in the same direction to form large-specific surface heat exchange, instantly calcining the mixture for 12s at 1150 ℃, and then fully contacting the calcined shell powder with water mist to realize synchronous catalytic heat release expansion so as to ionize and molecularly oxidize the calcined shell powder, wherein the working pressure of the water mist is 1.8 MPa; the grain diameter is 250 mu m; the weight ratio of the input water amount of the water mist to the calcined conch calcium powder is 8:100, and finally micro-nano fine crushing is further carried out to obtain micro-nano natural conch calcium powder with the particle size of 30-600nm, namely the fruit and vegetable pesticide residue scavenger raw material powder, and the fruit and vegetable pesticide residue scavenger product is obtained through bagging sealing or bottling sealing. Preparing 1:4000 aqueous solution of the fruit and vegetable pesticide residue remover.
Example 5
Washing and draining natural shells, taking clear water as a solvent, and placing the washed and drained shells in subcritical reaction equipment, wherein the weight ratio of the shells to water is 1:10, performing subcritical hydrolysis reaction for 60min under the conditions that the pressure is 1.5Mpa and the temperature is 150 ℃. Impurities such as heavy metals, organic matters adsorbed on the surface, sediments and the like in the shell are removed efficiently. Cooling, taking out, washing with water to neutrality, drying, and pulverizing to 300 mesh to obtain pure natural shell raw material powder. The shell raw material is oyster shell, scallop shell or corbicula fluminea shell.
Introducing pure natural shell raw material powder into a rotational flow dynamic calcining furnace by a quantitative screw feeder in cooperation with a gas-solid mixer, mixing the pure natural shell raw material powder with heated hot air, then enabling the mixture to flow in the same direction to form large-specific surface heat exchange, instantaneously calcining the mixture for 10 seconds at 1200 ℃, and then fully contacting the calcined shell powder with water mist to realize synchronous catalytic heat release expansion to ionize and molecularly oxidize the calcined shell powder, wherein the working pressure of the water mist is 2.0 MPa; the grain diameter is 300 mu m; the weight ratio of the input water amount of the water mist to the calcined conch calcium powder is 5:100, and finally micro-nano refinement treatment is carried out to obtain micro-nano natural conch calcium powder with the particle size of 30-600nm, namely the fruit and vegetable pesticide residue scavenger raw material powder, and the fruit and vegetable pesticide residue scavenger product is obtained through bagging sealing or bottling sealing. Preparing 1:1000 aqueous solution of the fruit and vegetable pesticide residue remover.
Example 6
This example differs from example 3 in that: the subcritical water treatment conditions are as follows:
washing and draining natural shells, taking clear water as a solvent, and placing the washed and drained shells in subcritical reaction equipment, wherein the weight ratio of the shells to water is 1: and 5, performing subcritical hydrolysis reaction for 25min under the conditions that the pressure is 50Mpa and the temperature is 300 ℃.
Example 7
This example differs from example 3 in that: the subcritical water treatment conditions are as follows:
washing and draining natural shells, taking clear water as a solvent, and placing the washed and drained shells in subcritical reaction equipment, wherein the weight ratio of the shells to water is 1: and 5, performing subcritical hydrolysis reaction for 25min under the conditions that the pressure is 10Mpa and the temperature is 150 ℃.
Example 8
This example differs from example 3 in that: the subcritical water treatment conditions are as follows:
washing and draining natural shells, taking clear water as a solvent, and placing the washed and drained shells in subcritical reaction equipment, wherein the weight ratio of the shells to water is 1: and 5, performing subcritical hydrolysis reaction for 125min under the conditions that the pressure is 10Mpa and the temperature is 300 ℃. Impurities such as heavy metals, organic matters adsorbed on the surface, sediments and the like in the shell are removed efficiently.
Example 9
This example differs from example 3 in that:
wherein the working pressure of the water mist is 5 MPa; the grain diameter is 500 mu m; the weight ratio of the input water amount of the water mist to the calcined shell calcitonin powder is 6:100, and finally micro-nano fine crushing is further carried out to obtain micro-nano natural shell calcitonin powder with the particle size of 30-700nm, namely the fruit and vegetable pesticide residue scavenger raw material powder, and the fruit and vegetable pesticide residue scavenger product is obtained by bagging and sealing or bottling and sealing. Preparing 1:2000 aqueous solution of the fruit and vegetable pesticide residue remover.
Example 10
This example differs from example 3 in that:
wherein the working pressure of the water mist is 1.0 MPa; the grain diameter is 500 mu m; the weight ratio of the input water amount of the water mist to the calcined shell calcitonin powder is 15:100, and finally micro-nano fine crushing is further carried out to obtain micro-nano natural shell calcitonin powder with the particle size of 30-700nm, namely the fruit and vegetable pesticide residue scavenger raw material powder, and the fruit and vegetable pesticide residue scavenger product is obtained by bagging and sealing or bottling and sealing. Preparing 1:2000 aqueous solution of the fruit and vegetable pesticide residue remover.
Effect test
1. Test of degradation and removal effect of residual pesticide in fruit and vegetable samples
A fruit and vegetable pesticide residue remover aqueous solution prepared by spraying organic phosphorus and pyrethroid pesticides on fruit and vegetable sample samples before picking and using the micro-nano natural conchiolin powder prepared by the embodiments is subjected to untreated and treated comparative tests to further illustrate the effect test of removing fruit and vegetable pesticide residues by decomposing and destroying the fruit and vegetable pesticide residue remover.
Sample preparation and detection results: respectively taking 10 parts of fruit and vegetable sample samples sprayed with organophosphorus and pyrethroid pesticides before picking, wherein each part is divided into 2 parts of 20 parts, 10 parts of fruit and vegetable sample samples are fruit and vegetable original samples (before treatment), and the other 10 parts of fruit and vegetable pesticide residue scavenger aqueous solution prepared by the products of the embodiments of the invention are respectively used for carrying out pesticide residue degradation removal treatment (after treatment); the 20 samples are respectively detected, and the result is as follows: the total amount detection results and pesticide residue removal rate statistics of organophosphorus and pyrethroid pesticides in fruit and vegetable samples before and after treatment (treated by the product of the invention) are shown in the following table 1. The pesticide residue removal rate calculation formula is as follows: (pesticide residue content before treatment-pesticide residue content after treatment)/pesticide residue content before treatment x 100%.
TABLE 1 statistical table of the degradation and removal effects of pesticide residues on fruits and vegetables in each example
2. Test of pesticide degradation and removal effect
By adding an aqueous solution of organophosphorus and pyrethroid pesticides, the micro-nano natural kauri-calcium powder products prepared in the embodiments 1, 3, 7 and 8 of the invention are subjected to untreated and treated comparative tests to further illustrate the effect test of decomposing, destroying and removing the pesticides in the aqueous solution by the fruit and vegetable pesticide residue remover.
Sample preparation and detection results: adding different amounts of organophosphorus and pyrethroid pesticides into 4 parts of 2 liters of water respectively, uniformly stirring, and then correspondingly dividing into 2 parts and 8 parts in total, wherein 4 parts are original solution (before treatment), and the other 4 parts are added with the product of the invention for decomposition treatment (after treatment); the 8 samples are respectively detected, and the result is as follows: the detection results and the pesticide residue removal rate statistics of organophosphorus and pyrethroid pesticide residues in the sample solution before and after treatment (treated by the product of the invention) are shown in the following table 2. The pesticide residue removal rate calculation formula is as follows: (pesticide residue content before treatment-pesticide residue content after treatment)/pesticide residue content before treatment x 100%.
Table 2 statistical table of the effect of degrading and removing pesticide residue in water in each example
Furthermore, to verify whether the added organophosphorus and pyrethroid pesticide sample solution is degraded or damaged after being treated by the product of the invention? Is there a degradation product that is still toxic? The sample solutions treated with the product of the invention were subjected to the following animal toxicity test.
Materials and methods:
test animal and breeding environment
The mouse is 40 mice, SPF grade, ICR species, 18-22g weight, and male and female halves. Production license number SCXK (Min) 2018-. The mice adapt to 3d time in the test environment before the test so as to adapt to the feeding environment, and mice which are unhealthy and have unqualified weight are eliminated.
II, test article
1. And (3) preparing a test sample, namely adding an aqueous solution which is detected to be added with organophosphorus and pyrethroid pesticides and has the total content of 235.8mg/kg into the aqueous solution treated in the embodiment 2 of the invention to serve as the test sample. Comparison: and (5) purifying the water.
Third, test methods and results
Mice were fasted for 6h before the experiment and had free access to water. During the test, mice were randomly divided into 2 groups of 20 mice each, and the mice were half-pushed by females. On the test day, the mice in the test sample group are subjected to intragastric administration of the test sample, the administration volume is 0.04mL/g, the administration is carried out three times within 24h, each time interval is 4h, and the total administration volume within 24h is equal to 0.12 mL/g. The control group was gavaged with purified water of the same volume and the mice were observed for toxic reactions after administration. The observation was continued for 14 days. Results the mice were tested to have no abnormalities in appearance, mental state, behavioral activities, food intake, stool and urine, hair color and respiration, no abnormal secretions in nose, eyes and oral cavity, weight gain, survival of all the mice, and no abnormal pathological changes in internal organs observed by dissection, as shown in Table 3.
TABLE 3 Table for observing and recording the acute toxicity test of the cleaning agent (product) for pesticide residues on fruits and vegetables
Note: p > 0.05 compared to control group
Conclusion
The water solution containing organophosphorus and pyrethroid pesticides is measured by a maximum dose method, and the oral acute toxicity tolerance of the water solution to mice is more than 1200ml/kg (equivalent to 60kg of the water solution which is orally taken by an adult for 7200ml a day) after the water solution is treated by the product (fruit and vegetable pesticide residue remover), and half of the death causing amount LD50 cannot be measured. The results of animal experiments show that the organophosphorus and pyrethroid pesticides in the aqueous solution are decomposed and removed.
3. Heavy metal removal effect
Elemental analysis was performed on the raw shell and the prepared powdery micro-nano natural conchiolin powder in examples 1 to 10, and the test results are shown in tables 4 to 5 below.
TABLE 4 comparison of heavy metal content of shells before and after treatment by the method provided in example 3
TABLE 5 statistics of the heavy metal removal effect of natural conchiolin powder (oyster shell) provided in examples 1, 2, 4-8
4. Test of aflatoxin degradation and removal effect
The micro-nano natural conchiolin powder prepared by the embodiment 3 of the invention is mixed with water in a proportion of 1:1500 or 1:2000, and carrying out untreated and treated comparative tests on the moldy peanut kernels containing the aflatoxin to further illustrate the effect test of decomposing and removing the aflatoxin by using the aflatoxin scavenger.
Sample and detection results: respectively taking 2 parts of mildewed peanut kernel samples, wherein 200 grains are divided into 2 parts respectively, and the 4 parts are totally 4 parts, wherein 2 parts are raw samples and are not processed (before treatment); another 2 parts of the product prepared in the examples 1 to 10 of the present invention were respectively subjected to a soaking washing treatment (after treatment); the 4 samples are respectively detected, and the result is as follows: the results of testing the moldy peanut kernel samples before and after treatment (treated with the product of the present invention) and the aflatoxin removal statistics are shown in table 6. The aflatoxin removal rate calculation formula is as follows: (content of aflatoxin before treatment-content of aflatoxin after treatment)/content of aflatoxin before treatment is multiplied by 100%.
Table 6 statistics of aflatoxin degradation removal effectiveness of scavengers provided in example 3
Meanwhile, the degradation and removal effects of the shell powder on aflatoxin provided by other embodiments are detected and counted, and the results show that the removal rate of the scavenger for aflatoxin provided by the scavengers in embodiments 1-10 on aflatoxin is over 90%.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of micro-nano natural conch calcium powder comprises the following steps: purifying and crushing shells, calcining, puffing, and finally crushing to obtain powdery micro-nano natural conchiolin powder, wherein the purification is to purify the shells in subcritical water.
2. The method for preparing micro-nano natural conchiolin powder according to claim 1, wherein the pressure condition for purification treatment in subcritical water is 0.2MPa-22 MPa.
3. The method for preparing micro-nano natural kakolin powder according to claim 1,
the temperature condition of the subcritical water purification treatment is 120 ℃ to 370 ℃.
4. The method for preparing micro-nano natural kakolin powder according to claim 1,
the calcination is continuous high-temperature instantaneous rotational flow dynamic calcination; the puffing is the catalytic puffing of fine water mist input by a medium-low pressure water mist spray head.
5. The method for preparing micro-nano natural kakolin powder according to claim 1, wherein the calcining temperature is 800 ℃ to 1250 ℃.
6. The preparation method of the micro-nano natural conch calcitonin powder according to claim 1, characterized in that the swelling is realized by fully contacting the calcined conch calcitonin powder with water mist, wherein the weight ratio of the input water amount of the water mist to the calcined conch calcitonin powder is 3:100 to 10: 100.
7. The method for preparing micro-nano natural conchiolin powder according to any one of claims 1 to 6, wherein the particle size of the powdery micro-nano natural conchiolin powder is 10 μm to 20 nm.
8. The method for preparing micro-nano natural conchiolin powder according to any one of claims 1 to 7, wherein the shell is natural shell selected from one or more of oyster shell, clam shell, oil clam shell, mussel shell, scallop shell, pearl clam shell and corbicula fluminea shell which are the bulk aquatic product processing by-products.
9. Use of the micro-nano natural kakolin powder as claimed in any one of claims 1 to 8 in the preparation of a fruit and vegetable pesticide residue remover.
10. Use of the micro-nano natural kakolin powder as claimed in any one of claims 1 to 8 in the preparation of aflatoxin scavengers.
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