CN114735669B - Method for extracting hydroxyapatite from fish bones and obtained hydroxyapatite - Google Patents
Method for extracting hydroxyapatite from fish bones and obtained hydroxyapatite Download PDFInfo
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- CN114735669B CN114735669B CN202210209388.0A CN202210209388A CN114735669B CN 114735669 B CN114735669 B CN 114735669B CN 202210209388 A CN202210209388 A CN 202210209388A CN 114735669 B CN114735669 B CN 114735669B
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/327—After-treatment
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The application provides a method for extracting hydroxyapatite from fish bones, which comprises the following steps: adding the fishbone into deionized water, heating and boiling to remove residues on the fishbone, and washing the fishbone for later use; crushing the cleaned fishbone to obtain fishbone powder; putting the fishbone powder into a sodium hydroxide, lithium hydroxide or potassium hydroxide solvent, and performing multiple freeze-thawing cycle treatment; heating the fishbone subjected to repeated freezing-thawing cycle treatment; dialyzing the product to neutrality by deionized water, and freeze-drying to obtain the hydroxyapatite. The method can quickly realize the separation of collagen fibers in the fish bones, and the obtained hydroxyapatite has obviously reduced protein and heavy metal residues and high purity.
Description
Technical Field
The application belongs to the field of preparation of hydroxyapatite, and particularly relates to a method for extracting hydroxyapatite from fish bones and the obtained hydroxyapatite.
Background
Hydroxyapatite is a functional calcium-containing inorganic salt, and has been widely used in the fields of chemical industry, biological medicine, food and the like because of its good biological and chemical activities. At present, most of the common hydroxyapatite in the market is prepared by adopting a chemical synthesis method, and the structure and chemical properties of the hydroxyapatite are difficult to meet the application requirements in the special field.
Thus, more and more researchers are focusing on natural hydroxyapatite synthesized by organisms themselves, and fishbone is one of the important sources. The bones of the fish are mainly composed of collagen and hydroxyapatite, and the hydroxyapatite synthesized by self metabolism has the advantages of low crystallinity, uniform structure, good biocompatibility and the like. The collagen fibers in the fishbone are tightly combined with the hydroxyapatite to form a compact complex, so that the separation and purification of the collagen fibers and the hydroxyapatite are difficult to realize by a soft treatment method.
At present, the extraction method of the hydroxyapatite in the fish bone mainly comprises a calcination method, an enzyme treatment method, an alkali treatment method and the like, harmful substances are easy to remain in the treatment process, the purity of the hydroxyapatite is low, the subsequent application is shadow, and the treatment efficiency is low.
Disclosure of Invention
The application provides a method for extracting hydroxyapatite from fish bones and the obtained hydroxyapatite aiming at the technical problems of low extraction purity and high harmful substance residue of the hydroxyapatite in the prior art.
In order to achieve the above object, the present application provides a method for extracting hydroxyapatite from fish bones, comprising the steps of:
adding the fishbone into deionized water, heating and boiling to remove residues on the fishbone, and washing the fishbone for later use;
crushing the cleaned fishbone to obtain fishbone powder;
putting the fishbone powder into a sodium hydroxide, lithium hydroxide or potassium hydroxide solvent, and performing multiple freeze-thawing cycle treatment;
heating the fishbone subjected to repeated freezing-thawing cycle treatment;
dialyzing the product to neutrality by deionized water, and freeze-drying to obtain the hydroxyapatite.
In some embodiments, the fish bone is heated to boiling time of 1 to 3 hours.
In some embodiments, during the fishbone comminution process, the fishbone is comminuted to a fishbone powder having a particle size in the range of 50 to 300 mesh.
In some embodiments, after the fishbone powder is placed in a sodium hydroxide, lithium hydroxide or potassium hydroxide solvent, the mass fraction of the fishbone powder in the obtained mixture is 3-30wt%, the mass fraction of the sodium hydroxide, lithium hydroxide or potassium hydroxide is 3-20wt%, and the balance is water.
In some embodiments, during the freeze-thaw process: the freezing temperature is 0 to minus 80 ℃ and the freezing time is 3 to 12 hours; the thawing temperature is room temperature, the thawing time is 1-3 h, and the times of freeze-thawing cycle are 1-5 times.
In some embodiments, the heating treatment is microwave heating, water bath heating, air heating, or flame heating.
In some embodiments, the temperature of the heating treatment is 5 to 90 ℃ and the heating time is 1 to 72 hours.
In some embodiments, the fish bone is from golden pomfret, weever, or carp.
In another aspect the application provides a hydroxyapatite extracted from fish bone according to the method of any preceding claim.
In some embodiments, the protein residue in the extracted hydroxyapatite is less than or equal to 0.18wt% and the heavy metal residue is less than or equal to 8 μg/g.
Compared with the prior art, the application has the advantages and positive effects that:
(1) The application can rapidly separate and dissolve collagen fibers in the fishbone by adopting an alkali-freeze thawing method, and alkaline substances can more rapidly and thoroughly separate collagen in the subsequent heating process.
(2) The alkaline substances used in the extraction process of the hydroxyapatite can be recycled, and the whole treatment process is quick and efficient, so that the method accords with the concept of green sustainable development.
(3) The method for extracting the hydroxyapatite from the fishbone has the advantages that the protein and heavy metal residual quantity of the hydroxyapatite is obviously reduced, the high-purity hydroxyapatite can be obtained by utilizing the fishbone waste, the production cost is reduced, and the popularization and the application of the hydroxyapatite are realized.
Drawings
FIG. 1 is an XRD pattern of hydroxyapatite obtained in example 1 of the present application.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In one aspect, the embodiment of the application provides a method for extracting hydroxyapatite from fish bones, which comprises the following steps:
adding the fishbone into deionized water, heating and boiling to remove residues on the fishbone, and washing the fishbone for later use;
crushing the cleaned fishbone to obtain fishbone powder;
putting the fishbone powder into a sodium hydroxide, lithium hydroxide or potassium hydroxide solvent, and performing multiple freeze-thawing cycle treatment;
heating the fishbone subjected to repeated freezing-thawing cycle treatment;
dialyzing the product to neutrality by deionized water, and freeze-drying to obtain the hydroxyapatite.
In the embodiment of the application, the separation and dissolution of the collagen fibers in the fishbone can be rapidly realized by adopting an alkali-freeze thawing method, and the alkaline substances can separate the collagen more rapidly and thoroughly in the subsequent heating process; the alkaline substances used in the extraction process can be recycled, and the whole treatment process is quick and efficient, so that the method accords with the concept of green sustainable development.
The fish bone used for extracting the hydroxyapatite in the embodiment of the application can be fish bone waste, which is boiled by deionized water to remove the residual fish meat and other impurities on the fish bone. In addition, it is understood that the selected fish bones include, but are not limited to, the bones of a variety of fish species such as golden pomfret, weever, or carp bones.
In an alternative embodiment, the fishbone is added to deionized water and heated to boil for 1-3 hours. In this embodiment, the boiling time is limited to the above range to ensure separation of the residue from the fish bone, but it will be understood that the skilled person can adjust the boiling time to the above range according to the actual situation, for example, 1.5h, 2h, 2.5h, etc. and any other point value within the above range.
In an alternative embodiment, during the process of pulverizing the fish bone, the fish bone is pulverized to a particle size in the range of 50 to 300 mesh fish bone powder. In this embodiment, in order to facilitate the subsequent more thorough decomposition of collagen in the fishbone by the alkali-freeze thawing method, the particle size of the pulverized fishbone is limited to the above range, but it will be understood that the skilled person can also adjust the above range according to the conditions of the actual pulverization process and the subsequent treatment process, for example, 80, 100, 150, 180, 200, 250, etc. and any other values in the above range are also possible.
In an alternative embodiment, after the fishbone powder is placed in a sodium hydroxide, lithium hydroxide or potassium hydroxide solvent, the mass fraction of the fishbone powder in the obtained mixture is 3-30%, the mass fraction of the sodium hydroxide, lithium hydroxide or potassium hydroxide is 3-20%, and the balance is water. In this embodiment, it is understood that, in order to make the collagen in the fishbone powder fully contact with the solvent to facilitate the subsequent decomposition, the mass fraction of each substance is limited to the above range, but it is understood that the mass fraction of the fishbone powder may also be 5%, 10%, 15%, 20%, 25%, etc. and any other point value in the range, and the mass fraction of the alkaline solvent may also be 5%, 10%, 12%, 15%, etc. and any other point value in the range, and those skilled in the art may adjust the content of each substance to the above range according to the actual decomposition process.
In an alternative embodiment, during the freeze-thaw process: the freezing temperature is 0 to minus 80 ℃ and the freezing time is 3 to 12 hours; the thawing temperature is room temperature, the thawing time is 1-3 h, and the times of freeze-thawing cycle are 1-5 times. In the embodiment, the freezing and thawing method is adopted to carry out multiple freezing-circulation treatments on the fishbone treated by the alkali solution, so that the separation and dissolution of collagen fibers in the fishbone are realized, the collagen can be separated more rapidly and thoroughly in the subsequent heating process, and the energy loss is reduced. To better achieve the above effects, the parameters are limited to the above ranges, but it is understood that the freezing temperature may be-10 ℃, -20 ℃, -30 ℃, -40 ℃, -50 ℃, -60 ℃, -70 ℃ and the like, the freezing time may be 5h, 6h, 8h, 10h and the like, the thawing time may be 1.5h, 2h, 2.5h and the like, the number of freeze-thaw cycles may be 2 times, 3 times, 4 times and the like, and those skilled in the art may adjust the respective ranges according to actual needs.
In an alternative embodiment, the heating treatment may be selected from microwave heating, water bath heating, air heating or flame heating, as long as the heating purpose can be achieved.
In an alternative embodiment, the heating temperature is 50-90℃and the heating time is 1-72 hours. In this embodiment, the microwave heating method is used to heat the fishbone powder treated by the alkali-freeze thawing method, so that the collagen in the fishbone is decomposed more thoroughly and more rapidly, the temperature and heating time of the microwave heating are limited in the above ranges, but it will be understood that the skilled person can adjust the above ranges according to the heating effect actually required, for example, the temperature of the microwave heating may be 50 ℃, 60 ℃, 70 ℃, 80 ℃ and the like, and any other point value in the above ranges, and the heating time may be 10h, 15h, 24h, 48h, 72h and the like, and any other point value in the above ranges.
Another aspect of an embodiment of the present application provides a hydroxyapatite extracted from fish bone according to the method of any one of the above; wherein the protein residue in the hydroxyapatite is less than or equal to 0.18 percent, and the heavy metal residue is less than or equal to 8 mug/g.
In order to more clearly describe the method for extracting hydroxyapatite from fish bones provided by the embodiment of the present application in detail, the following description will be made with reference to specific embodiments.
Example 1
Adding golden pomfret fishbone waste into deionized water, heating and boiling for 1 hour, removing residual fish meat and other impurities on the fishbone, and washing the obtained product for later use; pulverizing the fishbone to 50 mesh; placing in sodium hydroxide (20wt%) solvent, performing 5 times of freezing-thawing cycles, freezing at-80deg.C for 12 hr, thawing at room temperature for 3 hr; then heating by microwave at 90 ℃ for 1h to remove collagen contained in the fishbone; and finally, dialyzing the obtained product to neutrality by deionized water, and freeze-drying to obtain the fishbone hydroxyapatite.
Example 2
Adding golden pomfret fishbone waste into deionized water, heating and boiling for 2 hours, removing residual fish meat and other impurities on the fishbone, and washing the obtained product for later use; pulverizing the fishbone to 150 mesh; placing in sodium hydroxide (12wt%) solvent, performing 3 times of freezing-thawing cycles, freezing at-30deg.C for 8 hr, thawing at room temperature for 1 hr; then heating by microwave at 70deg.C for 10 hr to remove collagen contained in fish bone; and finally, dialyzing the obtained product to neutrality by deionized water, and freeze-drying to obtain the fishbone hydroxyapatite.
Example 3
Adding golden pomfret fishbone waste into deionized water, heating and boiling for 3 hours, removing residual fish meat and other impurities on the fishbone, and washing the obtained product for later use; pulverizing the fishbone to 300 meshes; placing in a sodium hydroxide (10wt%) solvent, performing 2 times of freezing-thawing cycles, wherein the freezing temperature is 0 ℃, the freezing time is 3 hours, and thawing is performed at room temperature for 2 hours; then heating by microwave at 60deg.C for 24 hr to remove collagen contained in fish bone; and finally, dialyzing the obtained product to neutrality by deionized water, and freeze-drying to obtain the fishbone hydroxyapatite.
Example 4
Adding golden pomfret fishbone waste into deionized water, heating and boiling for 1.5 hours, removing residual fish meat and other impurities on the fishbone, and washing the obtained product for later use; pulverizing the fishbone to 200 mesh; placing in sodium hydroxide (3wt%) solvent, performing 1 time of freezing-thawing treatment, wherein the freezing temperature is-10deg.C, the freezing time is 10h, thawing is performed at room temperature, and the thawing time is 1h; then directly adopting flame heating at 50 ℃ for 72 hours to remove collagen contained in the fishbone; and finally, dialyzing the obtained product to neutrality by deionized water, and freeze-drying to obtain the fishbone hydroxyapatite.
Example 5
Adding weever bone waste into deionized water, heating and boiling for 2.5 hours, removing residual fish meat and other impurities on the fish bone, and washing the obtained product for later use; pulverizing the fishbone to 180 mesh; placing in lithium hydroxide (15 wt%) solvent, performing 2 times of freezing-thawing treatment, freezing at-20deg.C for 6 hr, thawing at room temperature for 2 hr; then heating with air at 60deg.C for 48 hr to remove collagen contained in fish bone; and finally, dialyzing the obtained product to neutrality by deionized water, and freeze-drying to obtain the fishbone hydroxyapatite.
Example 6
Adding carp bone waste into deionized water, heating and boiling for 1.5 hours, removing residual fish meat and other impurities on the fish bone, and washing the obtained product for later use; pulverizing the fishbone to 80 mesh; placing in potassium hydroxide (10wt%) solvent, freezing-thawing for 3 times at-40deg.C for 10 hr, thawing at room temperature for 3 hr; heating in water bath at 80deg.C for 15 hr to remove collagen contained in fish bone; and finally, dialyzing the obtained product to neutrality by deionized water, and freeze-drying to obtain the fishbone hydroxyapatite.
Comparative example 1
Adding carp bone waste into deionized water, heating and boiling for 1.5 hours, removing residual fish meat and other impurities on the fish bone, and washing the obtained product for later use; and (3) crushing the fishbone to 80 meshes, and placing the fishbone in a muffle furnace for high-temperature calcination at 800 ℃ for 1h to obtain the fishbone hydroxyapatite.
Comparative example 2
Adding carp bone waste into deionized water, heating and boiling for 1.5 hours, removing residual fish meat and other impurities on the fish bone, and washing the obtained product for later use; pulverizing the above fishbone to 80 mesh, placing in sodium hydroxide (10wt%) solvent, heating and boiling at 100deg.C for 15 hr, dialyzing the obtained product with deionized water to neutrality, and freeze drying to obtain fishbone hydroxyapatite.
The amounts of residual amounts of protein and heavy metal were measured on the fish bone hydroxyapatite obtained in examples 1 to 6 and comparative examples 1 and 2, and the results are shown in Table 1.
TABLE 1 protein and heavy Metal residues in hydroxyapatite
| Protein residue (wt%) | Residual amount of heavy metal (μg/g) | |
| Example 1 | 0.1 | 2 |
| Example 2 | 0.15 | 5 |
| Example 3 | 0.08 | 3 |
| Example 4 | 0.12 | 8 |
| Example 5 | 0.18 | 7 |
| Example 6 | 0.11 | 4 |
| Comparative example 1 | 0.22 | 50 |
| Comparative example 2 | 0.45 | 30 |
As can be seen from Table 1, the residual amount of heavy metal in the hydroxyapatite obtained in examples 1 to 6 of the present application was 8. Mu.g/g or less, about 1/10 of the residual amount of heavy metal in comparative example 1 and comparative example 2, the residual amount of heavy metal was remarkably reduced, and the residual amount of protein was 0.18wt% or less, so that the purity required for the application of the hydroxyapatite could be satisfied.
Claims (6)
1. A method for extracting hydroxyapatite from fish bones, comprising the steps of:
adding the fishbone into deionized water, heating and boiling to remove residues on the fishbone, and washing the fishbone for later use;
crushing the cleaned fishbone to obtain fishbone powder;
placing fishbone powder into a sodium hydroxide, lithium hydroxide or potassium hydroxide solvent, wherein the mass fraction of the fishbone powder in the obtained mixture is 3-30wt%, the mass fraction of the sodium hydroxide, lithium hydroxide or potassium hydroxide is 3-20wt%, and the balance is water, and performing multiple freeze-thawing cycle treatment; during the freeze-thaw process: the freezing temperature is 0 to minus 80 ℃ and the freezing time is 3 to 12 hours; the thawing temperature is room temperature, the thawing time is 1-3 h, and the number of freeze-thawing cycles is 1-5;
heating the fishbone subjected to repeated freezing-thawing cycle treatment;
dialyzing the product to neutrality by deionized water, and freeze-drying to obtain the hydroxyapatite.
2. The method for extracting hydroxyapatite from fish bone according to claim 1, wherein the fish bone is boiled for 1 to 3 hours.
3. The method for extracting hydroxyapatite from fishbone according to claim 1, wherein in the process of pulverizing fishbone, the fishbone is pulverized to a particle size ranging from 50 to 300 mesh.
4. The method for extracting hydroxyapatite from fish bone according to claim 1, wherein said heating treatment is microwave heating, water bath heating, air heating or flame heating.
5. The method for extracting hydroxyapatite from fish bone according to claim 1, wherein the heating treatment is carried out at a temperature of 5 to 90 ℃ for a period of 1 to 72 hours.
6. The method of extracting hydroxyapatite from fish bone according to claim 1, wherein the fish bone is from golden pomfret, weever or carp.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109393387A (en) * | 2018-12-13 | 2019-03-01 | 青岛蓝色康典海洋生物科技有限公司 | A kind of fish scale processing method and its resulting rich calcium fish scale product |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109393387A (en) * | 2018-12-13 | 2019-03-01 | 青岛蓝色康典海洋生物科技有限公司 | A kind of fish scale processing method and its resulting rich calcium fish scale product |
Non-Patent Citations (4)
| Title |
|---|
| Jayachandran Venkatesan et al..Isolation and Characterization of Nano-Hydroxyapatite from Salmon Fish Bone.《Materials》.2015,第8卷第5426-5439页. * |
| Liquid-Exfoliated Mesostructured Collagen from the Bovine Achilles Tendon as Building Blocks of Collagen Membranes;Ying Pei et al.;《ACS Appl. Mater. Interfaces》;第13卷;第3186-3198页 * |
| R. Bunsiri et al..Synthesis and Characterization of Pure Natural Hydroxyapatite from Fish Bones Bio-Waste.《Advanced Materials Research》.2012,第506卷第206-209页. * |
| Xueke Chen et al..Effects of freezing-thawing pretreatment combined with liquid nitrogen and dilute acid on the gelatinization of collagen.《International Journal of Biological Macromolecules》.2018,第118卷第435-441页. * |
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