CN108079382B - Preparation method of porous hydroxyapatite - Google Patents
Preparation method of porous hydroxyapatite Download PDFInfo
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- CN108079382B CN108079382B CN201711477116.4A CN201711477116A CN108079382B CN 108079382 B CN108079382 B CN 108079382B CN 201711477116 A CN201711477116 A CN 201711477116A CN 108079382 B CN108079382 B CN 108079382B
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/36—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix
- A61L27/3604—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix characterised by the human or animal origin of the biological material, e.g. hair, fascia, fish scales, silk, shellac, pericardium, pleura, renal tissue, amniotic membrane, parenchymal tissue, fetal tissue, muscle tissue, fat tissue, enamel
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/36—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix
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- A61L2430/00—Materials or treatment for tissue regeneration
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
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Abstract
The invention discloses a preparation method of porous hydroxyapatite, which takes shrimp shells and crab shells of biomass materials containing calcium carbonate and organic matters as raw materials, converts the calcium carbonate into the hydroxyapatite, removes organic impurities through calcination, and keeps a natural porous skeleton structure of the materials, wherein phosphate is weighed according to a calcium-phosphorus atomic ratio of 1.67 +/-0.05, and the particle size of the obtained porous hydroxyapatite is 0.01-1.0 um; the invention provides a method for preparing porous hydroxyapatite by taking shrimp and crab shells as raw materials, provides a new way for utilizing waste resources such as the shrimp and crab shells, and the like, and simultaneously prepares the porous hydroxyapatite with a natural biological skeleton structure, and the porous hydroxyapatite has a unique porous structure, excellent biological activity and loading property, communicated pore channels and uniform pore diameter, and is worthy of popularization and application.
Description
Technical Field
The invention belongs to the field of synthesis of hydroxyapatite, and particularly relates to a preparation method of porous hydroxyapatite.
Background
Hydroxyapatite is a bioactive material, has the same components as bones and teeth of human bodies, and has biocompatibility and bioactivity superior to other biological materials. The porous hydroxyapatite has the advantages of good mechanical property, low relative density, high specific surface area, light weight, sound and heat insulation, good permeability and the like. The interconnected void structure has an enhancement effect on the activity of the material, and is a load material with excellent performance. At present, the synthesis of hydroxyapatite cannot solve the problems of strict requirements on raw materials, higher synthesis pressure and temperature, high requirements on equipment, complex process, long synthesis time and the like, and the complex process can damage the natural porous skeleton structure in the raw materials or the prepared product has the defects of single pore-size structure, nonadjustable pore-size and the like, thereby causing the loss of economic value.
The invention provides a simple and efficient hydroxyapatite synthesis method, which adopts a biomass material containing calcium carbonate and organic matters as a raw material, mainly comprises shellfish materials such as shrimp shells, crab shells and the like, converts the calcium carbonate into the hydroxyapatite, removes the organic matters through calcination treatment, retains the natural porous skeleton structure of the material, has simple preparation process, strong operability and short reaction time, can be synthesized under low temperature conditions, retains the natural porous skeleton structure of the biomass materials such as the shrimp and crab shells, has communicated pore passages and uniform pore diameter, is suitable for large-scale production, has high-value economic benefits and social benefits, and is worthy of popularization.
Disclosure of Invention
Aiming at the defects of harsh reaction conditions, complex process and the like existing in the existing preparation of hydroxyapatite, and the defects of easy damage of a natural porous skeleton structure in a raw material or single pore-size structure, non-adjustable pore-size and the like of a prepared product, the invention provides a preparation method of porous hydroxyapatite, and the technical scheme is as follows:
a preparation method of porous hydroxyapatite is characterized by comprising the following steps: the method comprises the following steps of taking shrimp shells and crab shells of biomass materials containing calcium carbonate and organic matters as raw materials, converting the calcium carbonate into hydroxyapatite, removing organic impurities through calcination, and keeping a natural porous skeleton structure of the materials, wherein phosphate is weighed according to a calcium-phosphorus atomic ratio of 1.67 +/-0.05, the particle size of the obtained porous hydroxyapatite is 0.01-1.0 um, and the specific operation steps are as follows:
(1) weighing crushed shrimp and crab shell powder with the particle size larger than 200 meshes, adding the shrimp and crab shell powder and deionized water into the deionized water according to the ratio of 1:10-1:5 for dissolving, and dropwise adding 5% sodium hydroxide solution to adjust the pH and the alkaline protease;
(2) placing the reaction solution obtained in the step (1) in a water bath kettle for heating reaction, cooling, carrying out solid-liquid separation and drying after the water bath reaction is finished, and obtaining deproteinized shrimp and crab shell powder;
(3) weighing deproteinized shrimp and crab shell powder, adding deionized water, and mixing uniformly;
(4) weighing phosphate, adding the phosphate into deionized water for dissolving and heating, and slowly dropwise adding the phosphate into the mixed solution obtained in the step (3);
(5) continuing the dropwise adding of the mixed solution in the step (4) to perform heating reaction in a water bath kettle, and after the reaction is finished, cooling, performing solid-liquid separation and drying to obtain deproteinized shrimp and crab shell powder hydroxyapatite;
(6) and (4) calcining the deproteinized shrimp and crab shell powder hydroxyapatite obtained in the step (5) in a muffle furnace to obtain a final product, namely the hydroxyapatite with a porous structure.
Further, the pH value of the solution in the step (1) is 7-9.
Further, the alkaline protease added in the step (1) accounts for 0.02-0.05% of the mass of the reaction solution.
Further, the water bath reaction temperature in the step (2) is 50-60 ℃.
Further, the water bath reaction time in the step (2) is 3-6 h.
Further, the phosphate is heated to 90 ℃ in the step (4).
Further, the heating reaction time in the step (5) is 4-6 h.
Further, in the step (4), the phosphate is selected from any one of diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
Further, in the step (6), the calcination is carried out for 2h-4h at the temperature of 600 ℃ -800 ℃.
The invention has the following beneficial effects:
the raw material calcium is derived from shrimp and crab shell powder, the raw material source is wide, the material taking is convenient, a new way is provided for the reutilization of waste resources such as shrimp and crab shells, and the waste utilization obtains higher economic value while the environment is protected; meanwhile, the prepared porous hydroxyapatite reserves a natural biological skeleton structure, the unique porous structure of the porous hydroxyapatite enables a product to have excellent bioactivity and load property, and meanwhile, the porous hydroxyapatite has good mechanical property and good performances of low relative density, high specific surface area, light weight, sound insulation, heat insulation and good permeability, can be widely applied to the field of human skeleton and tooth materials, and provides safe and reliable technical support for human health; the preparation method adopted by the invention reduces the temperature required by the reaction, shortens the reaction time, has simple preparation process, strong operability and easy quality control, reduces the production cost, improves the economic benefit and the environmental benefit, is beneficial to realizing large-scale production operation, and is worthy of popularization.
Detailed Description
The invention is further explained below:
a preparation method of porous hydroxyapatite is characterized by comprising the following steps: the method comprises the following steps of taking shrimp shells and crab shells of biomass materials containing calcium carbonate and organic matters as raw materials, converting the calcium carbonate into hydroxyapatite, removing organic impurities through calcination, and keeping a natural porous skeleton structure of the materials, wherein phosphate is weighed according to a calcium-phosphorus atomic ratio of 1.67 +/-0.05, the particle size of the obtained porous hydroxyapatite is 0.01-1.0 um, and the specific operation steps are as follows:
(1) weighing crushed shrimp and crab shell powder with the particle size larger than 200 meshes, adding the shrimp and crab shell powder and deionized water into the deionized water according to the ratio of 1:10-1:5 for dissolving, and dropwise adding 5% sodium hydroxide solution to adjust the pH and the alkaline protease;
(2) placing the reaction solution obtained in the step (1) in a water bath kettle for heating reaction, cooling, carrying out solid-liquid separation and drying after the water bath reaction is finished, and obtaining deproteinized shrimp and crab shell powder;
(3) weighing deproteinized shrimp and crab shell powder, adding deionized water, and mixing uniformly;
(4) weighing phosphate, adding the phosphate into deionized water for dissolving and heating, and slowly dropwise adding the phosphate into the mixed solution obtained in the step (3);
(5) continuing the dropwise adding of the mixed solution in the step (4) to perform heating reaction in a water bath kettle, and after the reaction is finished, cooling, performing solid-liquid separation and drying to obtain deproteinized shrimp and crab shell powder hydroxyapatite;
(6) and (4) calcining the deproteinized shrimp and crab shell powder hydroxyapatite obtained in the step (5) in a muffle furnace to obtain a final product, namely the hydroxyapatite with a porous structure.
Preferably, the pH value of the solution in the step (1) is 7-9.
Preferably, the alkaline protease added in the step (1) is 0.02-0.05% of the mass of the reaction solution.
Preferably, the water bath reaction temperature in the step (2) is 50-60 ℃.
Preferably, the water bath reaction time in the step (2) is 3-6 h.
Preferably, the phosphate is heated to a temperature of 90 ℃ in said step (4).
Preferably, the heating reaction time in the step (5) is 4-6 h.
Preferably, the phosphate in step (4) is selected from any one of diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
Preferably, the calcination in the step (6) is carried out at the temperature of 600-800 ℃ for 2-4 h.
Example 1:
weighing 100g of crab shell powder with a mesh of 200 and 500ml of deionized water, and uniformly stirring and mixing, wherein the ratio of the feed liquid to the feed liquid is 1:10-1:5, adding 5% sodium hydroxide solution to adjust the pH value to 7-9, adding 0.02-0.05% of alkaline protease by mass of the solution, heating in a water bath to 50-60 ℃, reacting for 3-6 hours, cooling, separating solid from liquid, drying to obtain deproteinized crab shell powder, weighing 50g of deproteinized crab shell powder and 300ml of deionized water, stirring and mixing uniformly, weighing 20g of diammonium hydrogen phosphate, adding water to fully dissolve the solution, heating in a water bath to 90 ℃, slowly dropwise adding a diammonium hydrogen phosphate solution, continuing to heat and react for 4-6 hours after dropwise adding is finished, cooling, separating solid from liquid, drying to obtain crab shell powder hydroxyapatite, placing the crab shell powder hydroxyapatite in a muffle furnace at the temperature of 600-800 ℃, calcining for 2-4 hours to obtain a hydroxyapatite product with a porous structure
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (4)
1. A preparation method of porous hydroxyapatite is characterized by comprising the following steps: the method comprises the following steps of taking shrimp shells and crab shells of biomass materials containing calcium carbonate and organic matters as raw materials, converting the calcium carbonate into hydroxyapatite, removing organic impurities through calcination, and keeping a natural porous skeleton structure of the materials, wherein phosphate is weighed according to a calcium-phosphorus atomic ratio of 1.67 +/-0.05, the particle size of the obtained porous hydroxyapatite is 0.01-1.0 um, and the specific operation steps are as follows:
(1) weighing crushed shrimp and crab shell powder with the particle size larger than 200 meshes, adding the shrimp and crab shell powder and deionized water into the deionized water according to the ratio of 1:10-1:5 for dissolving, and dropwise adding 5% sodium hydroxide solution to adjust the pH and the alkaline protease;
(2) placing the reaction solution obtained in the step (1) in a water bath kettle at 50-60 ℃ for heating reaction for 3-6 h, cooling, carrying out solid-liquid separation and drying after the water bath reaction is finished, thus obtaining deproteinized shrimp and crab shell powder;
(3) weighing deproteinized shrimp and crab shell powder, adding deionized water, and mixing uniformly;
(4) weighing phosphate, adding the phosphate into deionized water for dissolving, heating to 90 ℃, and slowly dropwise adding the phosphate into the mixed solution obtained in the step (3);
(5) continuing the dropwise adding of the mixed solution in the step (4) to perform heating reaction in a water bath for 4-6 h, and after the reaction is finished, cooling, performing solid-liquid separation and drying to obtain deproteinized shrimp and crab shell powder hydroxyapatite;
(6) and (3) calcining the deproteinized shrimp and crab shell powder hydroxyapatite obtained in the step (5) in a muffle furnace at the temperature of 600-800 ℃ for 2-4 h to obtain the final product hydroxyapatite with a porous structure.
2. The method for preparing porous hydroxyapatite according to claim 1, characterized in that: the pH value of the solution in the step (1) is 7-9.
3. The method for preparing porous hydroxyapatite according to claim 1, characterized in that: the alkaline protease added in the step (1) accounts for 0.02-0.05% of the mass of the reaction solution.
4. The method for preparing porous hydroxyapatite according to claim 1, characterized in that: and (4) in the step (4), the phosphate is selected from any one of diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
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| CN109329794B (en) * | 2018-11-02 | 2022-04-19 | 江西省农业科学院 | Fishbone nano material and preparation and application thereof |
| CN109457492A (en) * | 2018-11-10 | 2019-03-12 | 四川大学 | A kind of acoustical and thermal material and preparation method thereof and product |
| CN112028620B (en) * | 2020-08-06 | 2021-10-08 | 同济大学 | Porous hydroxyapatite bioactive material and preparation method and application thereof |
| CN113578250A (en) * | 2021-08-11 | 2021-11-02 | 湖南沃邦环保科技有限公司 | Composite ammonia nitrogen remover for treating sewage and wastewater and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| WO2007126211A1 (en) * | 2006-05-03 | 2007-11-08 | Megagen Co., Ltd. | Method for fabricating calcium phosphate and calcium phosphate fabricated by using the same |
| CN104841016A (en) * | 2014-12-19 | 2015-08-19 | 中国科学院深圳先进技术研究院 | Tuna fishbone meal material, preparation method and application thereof |
| CN104862366A (en) * | 2015-06-18 | 2015-08-26 | 鹭燕（福建）生物制品有限公司 | Technology for extracting collagen peptide, dermatan sulfate, hydroxyapatite and melanin from black sharkskin |
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| WO2006086783A2 (en) * | 2005-02-11 | 2006-08-17 | The Regents Of The University Of California | Conversion of sea-shells and other calcite-based and aragonite-based materials with dense structures into synthetic materials for implants and other structures and devices |
| CN105218698B (en) * | 2014-06-06 | 2017-07-07 | 浙江海富海洋生物科技有限公司 | A kind of method for preparing hydroxyapatite and shitosan as raw material with shrimp and crab shells |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007126211A1 (en) * | 2006-05-03 | 2007-11-08 | Megagen Co., Ltd. | Method for fabricating calcium phosphate and calcium phosphate fabricated by using the same |
| CN104841016A (en) * | 2014-12-19 | 2015-08-19 | 中国科学院深圳先进技术研究院 | Tuna fishbone meal material, preparation method and application thereof |
| CN104862366A (en) * | 2015-06-18 | 2015-08-26 | 鹭燕（福建）生物制品有限公司 | Technology for extracting collagen peptide, dermatan sulfate, hydroxyapatite and melanin from black sharkskin |
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