CN105347322B - Spherical nano-porous hydroxylapatite prepared through shells and preparation method thereof - Google Patents
Spherical nano-porous hydroxylapatite prepared through shells and preparation method thereof Download PDFInfo
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- CN105347322B CN105347322B CN201510900375.8A CN201510900375A CN105347322B CN 105347322 B CN105347322 B CN 105347322B CN 201510900375 A CN201510900375 A CN 201510900375A CN 105347322 B CN105347322 B CN 105347322B
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 41
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000001509 sodium citrate Substances 0.000 claims abstract description 8
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 8
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 241000237536 Mytilus edulis Species 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 235000020638 mussel Nutrition 0.000 claims description 10
- 241001417490 Sillaginidae Species 0.000 claims description 7
- 238000005703 Whiting synthesis reaction Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000013505 freshwater Substances 0.000 claims description 3
- 230000001413 cellular effect Effects 0.000 claims description 2
- 239000000052 vinegar Substances 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 210000000988 bone and bone Anatomy 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- 239000002244 precipitate Substances 0.000 abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 abstract 1
- 239000001639 calcium acetate Substances 0.000 abstract 1
- 229960005147 calcium acetate Drugs 0.000 abstract 1
- 235000011092 calcium acetate Nutrition 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 235000011007 phosphoric acid Nutrition 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 6
- 235000019263 trisodium citrate Nutrition 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000000316 bone substitute Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000007541 cellular toxicity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000820 toxicity test Toxicity 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000490567 Pinctada Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses spherical nano-porous hydroxylapatite prepared through shells and a preparation method thereof, and belongs to the technical field of material preparation. According to the hydroxylapatite prepared through the method, the hydroxylapatite is in a spherical shape, the diameter is 4-5 micrometers, the dispersity is good, the specific surface area is 270 cm<2>/g, the average pore diameter is 18 nm, carbonate radicals are contained, the components are similar to those of hydroxylapatite in the bones, and the biocompatibility is good. The preparation method comprises the following steps that the shells are washed, dried and ground, acetic acid with the concentration of 0.1 g/mL is added to fully react with the ground shells, an H3PO4 solution is dropwise added into a prepared calcium acetate solution, trisodium citrate is added, urea is added after reacting under stirring are performed, a prepared solution is stirred to be subjected to a reaction for 5 min in a water bath at the temperature of 80 DEG C-90 DEG C, standing is performed until precipitates occur, and the obtained precipitates are filtered, washed, dried and then collected. According to the method, shell powder does not need to be calcined, the reaction time is short, the pH does not need to be adjusted, operation is easy, the repeatability is good, the raw materials are easy to obtain, and not only is waste utilization achieved, but also energy conservation and emission reduction are facilitated.
Description
Technical field
The invention belongs to the preparation method technical field of hydroxyapatite, and in particular to prepared by a kind of utilization shell spherical
Nanoporous hydroxyapatite and preparation method thereof.
Technical background
Hydroxyapatite is a kind of important medical material, the sclerous tissues with human body, such as bone, tooth in composition and knot
Consistent on structure, it has good biocompatibility and chemical stability, bone tissue medicament slow release, bone substitute, hard group
The aspects such as reparation, carrier material are knitted with important application.Research finds that hydroxyapatite can also adsorb the heavy metal in water
Ion and some organic matters.
With the development of China's marine aquaculture, in coastal area substantial amounts of discarded shell, substantial amounts of shell are generated
Accumulation had both caused environmental pollution, resource is effectively utilized again.Hydroxyapatite is prepared using shell both to alleviate
Environmental problem, can make full use of waste resource again, turn waste into wealth.
The main inorganic composition of Mussel shell be calcium carbonate (95%), also some organic substances (protein and polysaccharide) and
Other metal ions.The ball shaped hydroxy-apatite prepared using waste shell is non-stoichiometric, because there is its micro
His ion is (such as Fe2+、Mg2+、Si2+、F-) crystal structure is entered into, make the Ca/P ＜ 1.67 of the hydroxyapatite of final synthesis.In
State's patent (application number 201410074680.1) discloses a kind of hydroxyapatite preparation method, and the method is using discarded ocean
Shell prepares hydroxyapatite for raw material, and it is 10nm～80nm to have obtained particle diameter, and reaction need to be carried out under the conditions of 100～200 DEG C,
Need to adjust pH in preparation process, particle diameter distribution is uneven, and method is complex.Amin Shavandi etc. are with Mussel shell
Raw material is prepared for nanometer hydroxyapatite (Materials Chemistry and Physics 149-150 by microwave method
(2015) 607-616), obtained particle is bar-shaped, and width is 15～20nm, and length is what is mentioned in 30～70nm, but article
Method needs to make CaCO therein in 900 DEG C of calcining Mussel shells3It is changed into CaO, energy is thus wasted in preparation process
Source.
The present invention is not required to calcined shell with discarded shell resource as raw material in preparation process, be not required to adjust pH, reacts bar
Part is gentle, and method is simple, and preparation time is short, has both realized twice laid, and energy-saving and emission-reduction, the hydroxyapatite of preparation are conducive to again
Grain biocompatibility is good, can be used for bone substitute, hard tissue repair etc., can be also used in catalyst, water heavy metal from
The adsorbent of son.
The content of the invention
The wasting of resources and Utilizing question for shell, it is an object of the invention to provide ball prepared by a kind of utilization shell
Shape nanoporous hydroxyapatite and preparation method thereof.
The present invention is using the spherical nanoporous hydroxyapatite material that shell is prepared by raw material, the material granule surface
In cellular nano loose structure, grain diameter is 4～5 μm, and specific area is 270cm2/ g, particle surface has bore dia average
For the loose structure of 18nm.
Preferably, described hydroxyapatite is the hydroxyapatite containing carbonate.Prepare the raw material used by the material
For shell, the shell is mussel shell, oyster shell, pearl shell, pearl oyster shell, one or more in freshwater mussel shell.
Present invention also offers a kind of preparation side of the spherical nanoporous hydroxyapatite material of utilization shell preparation
Method, comprises the steps：
1) dry under the conditions of 50～70 DEG C after shell is cleaned up, grinding is into the powder that granularity is 100～400 mesh；
2) 0.5～1.0g oyster shell whitings are taken, 20～40mL concentration is added for the spirit of vinegar of 0.1g/mL, 1～2h of reaction, centrifugation
After take supernatant, deionized water is diluted to 50～100mL；
3) with the rate of addition of 10～20 drop/min by the H of 50～100mL3PO4Solution is added to step 2) solution in,
Need to be stirred continuously during dropwise addition；The H3PO4The concentration of solution is 0.06～0.12mol/L；
4) to step 3) in solution in add 0.4～1.0mmol trisodium citrate, after addition continue react 10～
30min；
5) to step 4) in solution in add 4～8g urea, it is stirring while adding；
6) by step 5) in solution 5～10min is stirred under 80～90 DEG C of water bath condition, stand to occur precipitation；
7) precipitation for obtaining is filtered, is washed with deionized 2～3 times, then washed with ethanol 2～3 times；
8) particle for obtaining is dried into 24h at 70～100 DEG C.
The present invention has prepared spherical nanoporous hydroxyapatite by raw material of shell.
The present invention has advantages below：
(1) present invention has prepared spherical nanoporous hydroxyapatite by raw material of shell, realizes the money of shell
Sourceization is utilized, and raw materials used cheap and easy to get, preparation condition is gentle.
(2) ball shaped hydroxy-apatite Ca/P ＜ 1.67 prepared by the present invention, and have carbonate substitute phosphate radical, in bone
The composition of hydroxyapatite is similar.
(3), without the need for calcined shell, without the need for adjusting pH, the requirement to laboratory apparatus is low, and method is simply easily operated for the present invention,
The particle for obtaining is spherical, and epigranular, good dispersion, specific surface area is big.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture of embodiment product.
Fig. 2 is the XRD spectrum of embodiment product.
Fig. 3 is the FTIR collection of illustrative plates of embodiment product.
Fig. 4 is the TG collection of illustrative plates of embodiment product.
Fig. 5 is the nitrogen adsorption desorption isotherm picture of embodiment product.
Fig. 6 is the cell toxicity test to Gegenbaur's cell MTT of embodiment product.
Specific embodiment
In order that present invention may be readily understood, the present invention will be expanded on further by the following examples, it should be appreciated that real below
Apply example to be only illustrative of the invention and is not intended to limit the scope of the invention, NM specific experiment side in example below
Method, is generally carried out according to normal experiment method.
Embodiment 1
After mussel shell cleaning, being dried, grinding takes 0.5g oyster shell whitings and is added in beaker into the powder that granularity is 100 mesh；
The acetum that 20mL concentration is 0.1g/mL is added, 1h is reacted, supernatant is taken after centrifugation, deionized water is diluted to 50mL；Take
The 0.06mol/L H of 50mL3PO4Solution, while stirring with the speed of 10 drop/min by H3PO4Solution is added drop-wise in solution；Then
0.4mmol trisodium citrates, stirring reaction 30min is added to add 6g urea in mixed solution；Obtained mixed liquor is put
In entering 90 DEG C of water-bath, stirring reaction 5min is stood to appearance precipitation；Finally the precipitation for obtaining is filtered, is washed with deionized water
Wash 2 times, ethanol is washed 2 times, 24h is dried under the conditions of 70 DEG C and obtains ball shaped hydroxy-apatite particle.
The spherical nanoporous hydroxyapatite is characterized as：Grain diameter is 4～5 μm, and specific area is 270cm2/ g,
Grain surface has the loose structure of bore dia average out to 18nm.
The scanning electron microscopic picture of the spherical nanoporous hydroxyapatite is shown in Fig. 1；XRD spectrum is shown in Fig. 2；FTIR collection of illustrative plates is shown in
Fig. 3；TG collection of illustrative plates is shown in Fig. 4；Nitrogen adsorption desorption isotherm picture is shown in Fig. 5；Fig. 6 is shown in the cell toxicity test of Gegenbaur's cell MTT.
Embodiment 2
After mussel shell cleaning, being dried, grinding takes 0.5g oyster shell whitings and is added in beaker into the powder that granularity is 100 mesh；
The acetum that 20mL concentration is 0.1g/mL is added, 1h is reacted, supernatant is taken after centrifugation, deionized water is diluted to 50mL；Take
The 0.12mol/L H of 50mL3PO4Solution, while stirring with the speed of 10 drop/min by H3PO4Solution is added drop-wise in solution；Then
0.4mmol trisodium citrates, stirring reaction 30min is added to add 6g urea in mixed solution；Obtained mixed liquor is put
In entering 90 DEG C of water-bath, stirring reaction 5min is stood to appearance precipitation；Finally the precipitation for obtaining is filtered, is washed with deionized water
Wash 2 times, ethanol is washed 2 times, 24h is dried under the conditions of 70 DEG C and obtains ball shaped hydroxy-apatite particle.
Embodiment 3
After oyster shell cleaning, being dried, grinding takes 0.5g oyster shell whitings and is added in beaker into the powder that granularity is 200 mesh；
The acetum that 20ml concentration is 0.1g/mL is added, 1h is reacted, supernatant is taken after centrifugation, deionized water is diluted to 50mL；Take
The 0.06mol/L H of 50mL3PO4Solution, while stirring with the speed of 20 drop/min by H3PO4Solution is added drop-wise in solution；Then
0.6mmol trisodium citrates, stirring reaction 30min is added to add 6g urea in mixed solution；Obtained mixed liquor is put
In entering 80 DEG C of water-bath, stirring reaction 5min is stood to appearance precipitation；Finally the precipitation for obtaining is filtered, is washed with deionized water
Wash 2 times, ethanol is washed 2 times, 24h is dried under the conditions of 70 DEG C and obtains ball shaped hydroxy-apatite particle.
Embodiment 4
After pearl shell cleaning, being dried, grinding takes 0.5g oyster shell whitings and is added to beaker into the powder that granularity is 100 mesh
In；The acetum that 20mL concentration is 0.1g/mL is added, 1h is reacted, supernatant is taken after centrifugation, deionized water is diluted to
50mL；Take the 0.06mol/L H of 50mL3PO4Solution, while stirring with the speed of 20 drop/min by H3PO4Solution is added drop-wise to solution
In；Then 0.6mmol trisodium citrates, stirring reaction 30min is added to add 8g urea in mixed solution；Will be obtained
Mixed liquor is put in 80 DEG C of water-bath, stirring reaction 5min, is stood to appearance precipitation；Finally the precipitation for obtaining is filtered, is spent
Ion water washing 2 times, ethanol is washed 2 times, 24h is dried under the conditions of 70 DEG C and obtains ball shaped hydroxy-apatite particle.
Embodiment 5
After the cleaning of freshwater mussel shell, being dried, grinding takes 1.0g oyster shell whitings and is added in beaker into the powder that granularity is 400 mesh；
The acetum that 40mL concentration is 0.1g/mL is added, 2h is reacted, supernatant is taken after centrifugation, deionized water is diluted to 100mL；
Take the 0.12mol/L H of 100mL3PO4Solution, while stirring with the speed of 20 drop/min by H3PO4Solution is added drop-wise in solution；
Then 1.0mmol trisodium citrates, stirring reaction 30min is added to add 8g urea in mixed solution；By obtained mixing
Liquid is put in 80 DEG C of water-bath, stirring reaction 5min, is stood to appearance precipitation；Finally the precipitation for obtaining is filtered, deionization is used
Water washing 2 times, ethanol is washed 2 times, 24h is dried under the conditions of 70 DEG C and obtains ball shaped hydroxy-apatite particle.
The spherical nanoporous hydroxyapatite that embodiment 2,3,4 and 5 is obtained is respectively provided with spherical with what embodiment 1 was obtained
Nanoporous hydroxyapatite identical characteristic parameter.
Claims (4)
1. a kind of utilization shell is spherical nanoporous hydroxyapatite material prepared by raw material, it is characterised in that：Material
Grain surface is in cellular nano loose structure, and grain diameter is 4～5 μm, and specific area is 270 cm2/ g, particle surface has hole
The loose structure of the nm of diameter average out to 18.
2. the spherical nanoporous hydroxyapatite material that prepared by a kind of utilization shell according to claim 1, it is special
The hydroxyapatite levied described in being is the hydroxyapatite containing carbonate.
3. the spherical nanoporous hydroxyapatite material that prepared by a kind of utilization shell according to claim 1, it is special
It is that to prepare raw material used by the material be shell to levy, and the shell is mussel shell, oyster shell, pearl shell, in freshwater mussel shell
One or more.
4. the spherical nanoporous hydroxy-apatite stone material that prepared by a kind of utilization shell according to any one of claim 1-3
Material, it is characterised in that its preparation method comprises the steps：
1）Dry under the conditions of 50～70 DEG C after shell is cleaned up, grinding is into the powder that granularity is 100～400 mesh；
2）0.5～1.0 g oyster shell whitings are taken, the spirit of vinegar that 20～40 mL concentration are 0.1 g/mL is added, 1～2 h, centrifugation is reacted
After take supernatant, deionized water is diluted to 50～100 mL；
3）With the rate of addition of 10～20 drop/min by the H of 50～100 mL3PO4Solution is added to step 2）Solution in, be added dropwise
During need to be stirred continuously；The H3PO4The concentration of solution is 0.06～0.12 mol/L；
4）To step 3）In solution in add 0.4～1.0 mmol trisodium citrate, after addition continue react 10～30
min；
5）To step 4）In solution in add 4～8 g urea, it is stirring while adding；
6）By step 5）In solution 5～10 min are stirred under 80～90 DEG C of water bath condition, stand to occur precipitation；
7）The precipitation for obtaining is filtered, is washed with deionized 2～3 times, then washed with ethanol 2～3 times；
8）By the particle for obtaining at 70～100 DEG C be dried 24 h.
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| CN106698380B (en) * | 2017-02-20 | 2018-12-18 | 福建吉特瑞生物科技有限公司 | A kind of hydroxyapatite and preparation method thereof using shell preparation |
| CN113260592A (en) * | 2018-12-27 | 2021-08-13 | 白石钙新加坡有限公司 | Hydroxyapatite particles |
| CN110256241B (en) * | 2019-05-27 | 2021-10-15 | 浙江工业大学 | Method for preparing nano calcium lactate by taking shells as calcium source |
| CN111995514B (en) * | 2019-05-27 | 2022-07-08 | 浙江工业大学 | Method for preparing nano-scale calcium acetate from shells |
| CN110272032B (en) * | 2019-07-10 | 2022-08-12 | 福州大学 | Preparation method of magnesium-doped hydroxyapatite drug-loaded microspheres |
| TWI791260B (en) * | 2021-08-12 | 2023-02-01 | 行政院農業委員會 | Two-stage sintering method for preparing porous biphasic calcium phosphate ceramic from calcium-containing biological waste |
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