CN108079382A - A kind of preparation method of porous hydroxyapatite - Google Patents
A kind of preparation method of porous hydroxyapatite Download PDFInfo
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- CN108079382A CN108079382A CN201711477116.4A CN201711477116A CN108079382A CN 108079382 A CN108079382 A CN 108079382A CN 201711477116 A CN201711477116 A CN 201711477116A CN 108079382 A CN108079382 A CN 108079382A
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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
- A61L27/50—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
- 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
- A61L27/02—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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- A—HUMAN NECESSITIES
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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
- A61L27/3641—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 site of application in the body
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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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
- 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 kind of preparation methods of porous hydroxyapatite, using the shrimp shell containing calcium carbonate and the biological material of organic matter, crab shell as raw material, calcium carbonate is converted into hydroxyapatite, organic impurities is removed by calcining, the natural porous skeleton structure of reserved materials, phosphate wherein is weighed according to 1.67 ± 0.05 calcium phosphorus atoms ratio, acquired porous hydroxyapatite grain size is 0.01um 1.0um；The present invention provides a kind of method that porous hydroxyapatite is prepared using shrimp and crab shells as raw material, new approach is provided for wasted resources such as shrimp and crab shells, the porous hydroxyapatite with natural biological skeleton structure has been prepared simultaneously, with unique porous structure and excellent bioactivity and loading, duct communicates, uniform pore diameter is worth of widely use.
Description
Technical field
The invention belongs to hydroxyapatites to synthesize field, more particularly to a kind of preparation method of porous hydroxyapatite.
Background technology
Hydroxyapatite is a kind of bioactive materials, identical with human skeleton and dental component, biocompatibility
It is better than other biomaterials with bioactivity.Porous hydroxyapatite has good mechanical performance, and relative density is low, specific surface
The advantages that product is high, light-weight, sound-insulating and heat-insulating, good penetrability.The gap structure being mutually communicated has humidification to its activity, is one
The support materials that kind is had excellent performance.It is harsh that the synthesis of hydroxyapatite at present does not depart from ingredient requirement, synthesis pressure, temperature compared with
The problems such as height, requirement to equipment is high, complex process, generated time is long, and complicated technique can destroy it is natural more in raw material
The defects of hole on framework structure or the product aperture structure produced are single, aperture size is non-adjustable, causes damages to its economic value.
The present invention provides a kind of hydroxyapatite synthetic method being simple and efficient, using containing calcium carbonate and organic matter
Biological material is raw material, mainly including the shell-fish material such as shrimp shell, crab shell, calcium carbonate is converted into hydroxyapatite, is passed through
Calcination processing removes organic matter, and the natural porous skeleton structure of reserved materials, preparation process is simple, can close under cryogenic
Into strong operability, the reaction time is short, and remains the natural porous skeleton structure of the biological materials such as shrimp and crab shells, duct
It communicates, uniform pore diameter, is suitble to large-scale production, the economic benefit and social benefit with high value are worthy to be popularized.
The content of the invention
The shortcomings of for harsh reaction condition existing for hydroxyapatite, complex process is prepared now, and be easily destroyed
Natural porous skeleton structure in raw material or produce product aperture structure is single, the defects of aperture size is non-adjustable, this hair
Bright to propose a kind of preparation method of porous hydroxyapatite, technical solution is as follows：
A kind of preparation method of porous hydroxyapatite, it is characterised in that：With the biomass containing calcium carbonate and organic matter
Shrimp shell, the crab shell of material are raw material, and calcium carbonate is converted into hydroxyapatite, and organic impurities, reserved materials are removed by calcining
Natural porous skeleton structure, wherein weighing phosphate, acquired porous hydroxyapatite according to 1.67 ± 0.05 calcium phosphorus atoms ratio
Apatite grain size is 0.01um-1.0um, and concrete operation step is as follows：
(1) the shrimp and crab shells powder that the grain size that crushed is more than 200 mesh is weighed, according to shrimp and crab shells powder and the ratio of deionized water
For 1:10-1:It is dissolved in 5 addition deionized waters, and 5% sodium hydroxide solution is added dropwise and adjusts pH and alkali protease；
(2) reaction solution in above-mentioned steps (1) is placed in heat in water-bath and is reacted, be cooled to after the completion of water-bath,
Separation of solid and liquid, drying obtain the shrimp and crab shells powder of de- protease；
(3) the shrimp and crab shells powder after de- protease is weighed, deionized water is added in and is uniformly mixed；
(4) weigh phosphate and add in deionized water and dissolve and heat, be slowly added dropwise to the mixing of above-mentioned steps (3)
In liquid；
(5) by the mixed liquor being added dropwise in above-mentioned steps (4) continue water-bath heating reaction, after completion of the reaction by its into
Row cooling, separation of solid and liquid, drying obtain the shrimp and crab shells powder hydroxyapatite of de- protease；
(6) the shrimp and crab shells powder hydroxyapatite for the de- protease for obtaining above-mentioned steps (5), which is placed in Muffle furnace, calcines, and obtains
To the hydroxyapatite of final product porous structure.
Further, solution ph is 7-9 in the step (1).
Further, the alkali protease added in the step (1) is the 0.02%-0.05% of reaction solution quality.
Further, water-bath temperature is 50 DEG C -60 DEG C in the step (2).
Further, the water-bath time is 3h-6h in the step (2).
Further, in the step (4) phosphate heating temperature to 90 DEG C.
Further, the heating reaction time is 4h-6h in the step (5).
Further, in the step (4) phosphate in diammonium hydrogen phosphate and ammonium dihydrogen phosphate any one.
Further, using temperature as 600 DEG C of -800 DEG C of calcining 2h-4h in the step (6).
Beneficial effects of the present invention are as follows：
For raw material calcium source in shrimp and crab shells powder raw material, raw material sources are wide, convenient material drawing, are the sharp again of the waste resources such as shrimp and crab shells
With providing new way, while environmental protection waste utilization achieve higher economic value；Simultaneously prepared by the present invention
Porous hydroxyapatite, remains natural biological skeleton structure, and unique porous structure makes product that there is excellent biology to live
Property and loading, while the good mechanical performance that has of porous hydroxyapatite itself and relative density is low, specific surface area
The performance of high, light-weight, sound-insulating and heat-insulating, good penetrability can be widely applied to skeleton and dental material field, be people
Health provides safe and reliable technical support；The preparation method that the present invention uses reduces the temperature needed for reaction, shortens
In the reaction time, preparation process is simple, strong operability, is easy to quality control, and economic benefit is improved while reducing production cost
And environmental benefit, beneficial to running of accomplishing scale production, it is worthy to be popularized.
Specific embodiment
The present invention will be further explained below：
A kind of preparation method of porous hydroxyapatite, it is characterised in that：With the biomass containing calcium carbonate and organic matter
Shrimp shell, the crab shell of material are raw material, and calcium carbonate is converted into hydroxyapatite, and organic impurities, reserved materials are removed by calcining
Natural porous skeleton structure, wherein weighing phosphate, acquired porous hydroxyapatite according to 1.67 ± 0.05 calcium phosphorus atoms ratio
Apatite grain size is 0.01um-1.0um, and concrete operation step is as follows：
(1) the shrimp and crab shells powder that the grain size that crushed is more than 200 mesh is weighed, according to shrimp and crab shells powder and the ratio of deionized water
For 1:10-1:It is dissolved in 5 addition deionized waters, and 5% sodium hydroxide solution is added dropwise and adjusts pH and alkali protease；
(2) reaction solution in above-mentioned steps (1) is placed in heat in water-bath and is reacted, be cooled to after the completion of water-bath,
Separation of solid and liquid, drying obtain the shrimp and crab shells powder of de- protease；
(3) the shrimp and crab shells powder after de- protease is weighed, deionized water is added in and is uniformly mixed；
(4) weigh phosphate and add in deionized water and dissolve and heat, be slowly added dropwise to the mixing of above-mentioned steps (3)
In liquid；
(5) by the mixed liquor being added dropwise in above-mentioned steps (4) continue water-bath heating reaction, after completion of the reaction by its into
Row cooling, separation of solid and liquid, drying obtain the shrimp and crab shells powder hydroxyapatite of de- protease；
(6) the shrimp and crab shells powder hydroxyapatite for the de- protease for obtaining above-mentioned steps (5), which is placed in Muffle furnace, calcines, and obtains
To the hydroxyapatite of final product porous structure.
Preferably, solution ph is 7-9 in the step (1).
Preferably, the alkali protease added in the step (1) is the 0.02%-0.05% of reaction solution quality.
Preferably, water-bath temperature is 50 DEG C -60 DEG C in the step (2).
Preferably, the water-bath time is 3h-6h in the step (2).
Preferably, in the step (4) phosphate heating temperature to 90 DEG C.
Preferably, the heating reaction time is 4h-6h in the step (5).
Preferably, in the step (4) phosphate in diammonium hydrogen phosphate and ammonium dihydrogen phosphate any one.
Preferably, using temperature as 600 DEG C of -800 DEG C of calcining 2h-4h in the step (6).
Embodiment 1：
Crab shell powder 200 mesh 100g is weighed, deionized water 500ml is uniformly mixed, and wherein feed liquid ratio is 1：10-1：
5, the sodium hydroxide solution for adding 5% adjusts pH to 7-9, adds in the alkali protease of the 0.02%-0.05% of solution quality, water
Bath is heated to 50-60 DEG C, when reaction 3-6 is small, separates solid-liquid after cooling, dry, obtains Deproteinated crab shell powder, weighs
Crab shell powder 50g after de- albumen, deionized water 300ml are uniformly mixed, weigh 20g diammonium hydrogen phosphates, water is added fully to dissolve
Ammonium dibasic phosphate solution is slowly added dropwise to 90 DEG C in heating water bath, continue after being added dropwise heating reaction 4-6 it is small when, it is solid after cooling
Liquid separates, dry, obtains crab shell powder hydroxyapatite, crab shell powder hydroxyapatite is placed in 600-800 DEG C of Muffle furnace and is calcined
When 2-4 is small, the hydroxyapatite product of porous structure is obtained
The above description is merely a specific embodiment, but the protection domain invented is not limited thereto, any ripe
Know those skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in should all be covered
Within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of porous hydroxyapatite, it is characterised in that：With the biological material containing calcium carbonate and organic matter
Shrimp shell, the crab shell of material are raw material, and calcium carbonate is converted into hydroxyapatite, and organic impurities is removed by calcining, reserved materials
Natural porous skeleton structure, wherein weighing phosphate, acquired porous hydroxyapatite phosphorus according to 1.67 ± 0.05 calcium phosphorus atoms ratio
Lime stone grain size is 0.01um-1.0um, and concrete operation step is as follows：
(1) the shrimp and crab shells powder that the grain size that crushed is more than 200 mesh is weighed, is 1 according to the ratio of shrimp and crab shells powder and deionized water:
10-1:It is dissolved in 5 addition deionized waters, and 5% sodium hydroxide solution is added dropwise and adjusts pH and alkali protease；
(2) reaction solution in above-mentioned steps (1) is placed in heat in water-bath and is reacted, is cooled to after the completion of water-bath, solid-liquid
Separation, drying obtain the shrimp and crab shells powder of de- protease；
(3) the shrimp and crab shells powder after de- protease is weighed, deionized water is added in and is uniformly mixed；
(4) weigh phosphate and add in deionized water and dissolve and heat, be slowly added dropwise to the mixed liquor of above-mentioned steps (3)
In；
(5) mixed liquor being added dropwise in above-mentioned steps (4) is continued into water-bath heating reaction, is carried out after completion of the reaction cold
But, separation of solid and liquid, drying obtain the shrimp and crab shells powder hydroxyapatite of de- protease；
(6) the shrimp and crab shells powder hydroxyapatite for the de- protease for obtaining above-mentioned steps (5), which is placed in Muffle furnace, calcines, and obtains most
The hydroxyapatite of final product porous structure.
2. a kind of preparation method of porous hydroxyapatite according to claim 1, it is characterised in that：The step (1)
Middle solution ph is 7-9.
3. a kind of preparation method of porous hydroxyapatite according to claim 1, it is characterised in that：The step (1)
The alkali protease of middle addition is the 0.02%-0.05% of reaction solution quality.
4. a kind of preparation method of porous hydroxyapatite according to claim 1, it is characterised in that：The step (2)
Middle water-bath temperature is 50 DEG C -60 DEG C.
5. a kind of preparation method of porous hydroxyapatite according to claim 1, it is characterised in that：The step (2)
The middle water-bath time is 3h-6h.
6. a kind of preparation method of porous hydroxyapatite according to claim 1, it is characterised in that：The step (4)
Middle phosphate heating temperature is to 90 DEG C.
7. a kind of preparation method of porous hydroxyapatite according to claim 1, it is characterised in that：The step (5)
The middle heating reaction time is 4h-6h.
8. a kind of preparation method of porous hydroxyapatite according to claim 1, it is characterised in that：The step (4)
Middle phosphate in diammonium hydrogen phosphate and ammonium dihydrogen phosphate any one.
9. a kind of preparation method of porous hydroxyapatite according to claim 1, it is characterised in that：The step (6)
In using temperature as 600 DEG C -800 DEG C calcining 2h-4h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109329794A (en) * | 2018-11-02 | 2019-02-15 | 江西省农业科学院 | A kind of fish-bone nano material and its preparation and application |
| 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 |
| CN112028620A (en) * | 2020-08-06 | 2020-12-04 | 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 |
| CN116099488A (en) * | 2021-11-09 | 2023-05-12 | 农业部沼气科学研究所 | Layered nano-structure mineral material prepared by high-temperature sintering of antibiotic fermentation fungus residues, and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109329794A (en) * | 2018-11-02 | 2019-02-15 | 江西省农业科学院 | A kind of fish-bone nano material and its preparation and application |
| 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 |
| CN112028620A (en) * | 2020-08-06 | 2020-12-04 | 同济大学 | Porous hydroxyapatite bioactive material and preparation method and application thereof |
| 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 |
| CN116099488A (en) * | 2021-11-09 | 2023-05-12 | 农业部沼气科学研究所 | Layered nano-structure mineral material prepared by high-temperature sintering of antibiotic fermentation fungus residues, and preparation method and application thereof |
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