CN108584899A - A kind of porous prilled nanometer hydroxyapatite and preparation method thereof - Google Patents
A kind of porous prilled nanometer hydroxyapatite and preparation method thereof Download PDFInfo
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- CN108584899A CN108584899A CN201810864165.1A CN201810864165A CN108584899A CN 108584899 A CN108584899 A CN 108584899A CN 201810864165 A CN201810864165 A CN 201810864165A CN 108584899 A CN108584899 A CN 108584899A
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- presoma
- preparation
- nanometer hydroxyapatite
- porous prilled
- porous
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- 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
- C01B25/325—Preparation by double decomposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- 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
Abstract
The present invention relates to a kind of porous prilled nanometer hydroxyapatites and preparation method thereof.Its technical solution is：Amount ratio according to Ca: P substance is 1.67: 1 dispensings, is mixed to get presoma I；The ammonium hydroxide of a concentration of 4.0~5.0wt% is added in flotation device mixing bunker, under rotation condition, it is 9.50~11.00 to add presoma I to pH value, continues 0.5~1.5h of mixing to get presoma II.Presoma II is placed in closed container, 20~25h is aged under the conditions of 18~28 DEG C, is filtered to get presoma III.Presoma III is refrigerated to solid-state, 24~36h is freeze-dried under the conditions of 40 DEG C to get presoma IV.Presoma IV is roasted into 2~3h under the conditions of 650~750 DEG C, porous prilled nanometer hydroxyapatite is made.The present invention has the characteristics that simple for process, of low cost, environmentally protective and raw material availability is high, prepared porous prilled nanometer hydroxyapatite purity height, the uniform large specific surface area of particle diameter distribution.
Description
Technical field
The invention belongs to porous nano hydroxyapatite technical fields.More particularly to a kind of porous prilled nano hydroxyapatite
Lime stone and preparation method thereof.
Background technology
Porous nano hydroxyapatite has the ability of good biocompatibility and stronger absorption heavy metal ion, should
Nano material can be used for the raw material, pharmaceutical carrier or bioceramic of artificial skelecton as biomaterial；As environment functional material
It can be used for the processing to the sewage containing heavy metal ion.Porous nano hydroxyapatite belongs to a kind of of low cost and derives from a wealth of sources
Multi-functional nanometer material.
People have carried out many researchs for preparing porous nano hydroxyapatite at present.
" a kind of PEG compound systems hydrothermal preparing process of nanometer hydroxyapatite " (CN201410787214.8) is used
Double-template hydrothermal preparing process, obtains nanometer hydroxyapatite, though have the advantages that simple for process, of low cost, green safe.
But due to handling hydroxyapatite using the method for high temperature drying, there are very havoc, obtained hydroxyl phosphorus to the structure of material
Lime stone appearance and size is inhomogenous, porosity is small and no relatively rich pore structure.
" a kind of preparation method of nano hydroxyapatite powder " (CN200910265055.4), hydroxyl is prepared using template
Base apatite, is dried with freeze-drying, obtains the spherical shape or rod-like nano hydroxy apatite powder of good dispersion, though system
Preparation Method is simple, with short production cycle and nontoxic and pollution-free.But the hydroxyapatite appearance and size of this method preparation is inhomogenous, hole
Rate is small and aperture structure is single.
" a kind of preparation method of porous hydroxyapatite " (CN201711477116.4), hydroxyl is prepared using biological organic matter
Base apatite obtains the hydroxyapatite of uniform pore diameter though preparation process natural green, preparation process are simple, before this method
Phase processing biomass material needs to consume more energy, increases manufacturing cost, and can not ensure the purity of hydroxyapatite.
Invention content
The present invention is directed to overcome prior art defect, it is therefore an objective to provide it is a kind of simple for process, of low cost, environmentally protective and
The preparation method of the high porous prilled nanometer hydroxyapatite of raw material availability, the porous prilled nanometer prepared with this method
Hydroxyapatite purity height, the uniform large specific surface area of particle diameter distribution.
To achieve the above object, the present invention comprising the concrete steps that using technical solution：
Step 1: according to Ca: the amount ratio of the substance of P is 1.67: 1, and calcium salt soln and phosphate solution are mixed to get preceding
Drive body I.
Step 2: the ammonium hydroxide of a concentration of 4.0~5.0wt% is added in flotation device mixing bunker, rotating speed be 1000~
Under conditions of 2000r/min, then it is 9.50~11.00 that the presoma I to pH value, which is added, into flotation device mixing bunker, is then mixed
0.5~1.5h of stirring is closed to get presoma II.
Step 3: the presoma II is placed in closed container, it is aged 20~25h under the conditions of 18~28 DEG C, filters,
Up to presoma III.
Step 4: the presoma III is refrigerated to solid-state, then it is placed in freeze drier, is freezed under the conditions of -40 DEG C
Dry 24~36h is to get presoma IV.
Step 5: the presoma IV is roasted 2~3h under the conditions of 650~750 DEG C, porous prilled nanometer hydroxyl is made
Base apatite.
The calcium salt soln is calcium nitrate solution or is calcium chloride solution.
The phosphate solution is one kind in ammonium dihydrogen phosphate, ammonium phosphate solution and ammonium hydrogen phosphate solution.
Due to the adoption of the above technical scheme, the beneficial effects of the invention are as follows：
The present invention uses the preparation flow of air Aerated stirring-ageing-drying-roasting, simple for process.It is anti-in preparation process
Answer object contact abundant, the reaction was complete, and preparation process only has hydroxyapatite and the waste liquid containing ammonium nitrate, no other impurities to interfere,
Product purity is high.The ammonium nitrate that the present invention generates does not influence preparation process of the present invention, and ammonium nitrate can not only recycle profit
With also as the raw material for preparing chemical fertilizer.Therefore entire invention preparation process is environmentally protective, raw material availability is high and production cost
It is low.
The present invention is stirred using inflatable and is combined with sol-gel chemistries preparation, by using the inflation of flotation device high speed
Stirring replaces tradition machinery to stir so that abundant, the prepared porous prilled nanometer hydroxyapatite grain of preparation process reaction
Diameter is evenly distributed, and grain size is 60~180nm, and specific surface area is 20~25m2/g.In addition, present invention employs freeze-drying skills
Art has protective effect for the porous structure of porous prilled nanometer hydroxyapatite.
In conclusion the present invention has the characteristics that simple for process, of low cost, environmentally protective and raw material availability is high, institute
The porous prilled nanometer hydroxyapatite purity height of preparation, the uniform large specific surface area of particle diameter distribution.
Description of the drawings
Fig. 1 is a kind of SEM figures of porous prilled nanometer hydroxyapatite prepared by the present invention.
Specific implementation mode
The present invention is further illustrated with reference to the accompanying drawings and detailed description, not to the limit of its protection domain
System.
Embodiment 1
A kind of porous prilled nanometer hydroxyapatite and preparation method thereof.The specific step of preparation method described in the present embodiment
Suddenly it is：
Step 1: according to Ca: the amount ratio of the substance of P is 1.67: 1, and calcium salt soln and phosphate solution are mixed to get preceding
Drive body I.
Step 2: the ammonium hydroxide of a concentration of 4.0~5.0wt% is added in flotation device mixing bunker, rotating speed be 1000~
Under conditions of 1400r/min, then it is 9.50~10.00 that the presoma I to pH value, which is added, into flotation device mixing bunker, is then mixed
0.5~0.8h of stirring is closed to get presoma II.
Step 3: the presoma II is placed in closed container, it is aged 22~25h under the conditions of 18~22 DEG C, filters,
Up to presoma III.
Step 4: the presoma III is refrigerated to solid-state, then it is placed in freeze drier, is freezed under the conditions of -40 DEG C
Dry 24~28h is to get presoma IV.
Step 5: the presoma IV is roasted 2~3h under the conditions of 650~680 DEG C, porous prilled nanometer hydroxyl is made
Base apatite.
The calcium salt soln is calcium nitrate solution.
The phosphate solution is ammonium dihydrogen phosphate.
Porous prilled nanometer hydroxyapatite particle diameter distribution manufactured in the present embodiment is uniform, and grain size is 100~180nm,
Specific surface area is 20~23m2/g。
Embodiment 2
A kind of porous prilled nanometer hydroxyapatite and preparation method thereof.In addition to calcium salt soln, remaining is the same as embodiment 1：
The calcium salt soln is calcium chloride solution.
Porous prilled nanometer hydroxyapatite particle diameter distribution manufactured in the present embodiment is uniform, and grain size is 120~180nm,
Specific surface area is 20~22m2/g。
Embodiment 3
A kind of porous prilled nanometer hydroxyapatite and preparation method thereof.The specific step of preparation method described in the present embodiment
Suddenly it is：
Step 1: according to Ca: the amount ratio of the substance of P is 1.67: 1, and calcium salt soln and phosphate solution are mixed to get preceding
Drive body I.
Step 2: the ammonium hydroxide of a concentration of 4.0~5.0wt% is added in flotation device mixing bunker, rotating speed be 1400~
Under conditions of 1700r/min, then it is 10.0~10.5 that the presoma I to pH value, which is added, into flotation device mixing bunker, is then mixed
0.8~1.2h of stirring is closed to get presoma II.
Step 3: by the presoma II be placed in closed container in, under the conditions of 22~25 DEG C be aged 21~for 24 hours, filtering,
Up to presoma III.
Step 4: the presoma III is refrigerated to solid-state, then it is placed in freeze drier, is freezed under the conditions of -40 DEG C
Dry 28~32h is to get presoma IV.
Step 5: the presoma IV is roasted 2~3h under the conditions of 680~720 DEG C, porous prilled nanometer hydroxyl is made
Base apatite.
The calcium salt soln is calcium nitrate solution.
The phosphate solution is ammonium phosphate solution.
Porous prilled nanometer hydroxyapatite particle diameter distribution manufactured in the present embodiment is uniform, and grain size is 80~160nm, than
Surface area is 21~24m2/g。
Embodiment 4
A kind of porous prilled nanometer hydroxyapatite and preparation method thereof.In addition to calcium salt soln, remaining is the same as embodiment 3：
The calcium salt soln is calcium chloride solution.
Porous prilled nanometer hydroxyapatite particle diameter distribution manufactured in the present embodiment is uniform, and grain size is 90~160nm, than
Surface area is 21~23m2/g。
Embodiment 5
A kind of porous prilled nanometer hydroxyapatite and preparation method thereof.The specific step of preparation method described in the present embodiment
Suddenly it is：
Step 1: according to Ca: the amount ratio of the substance of P is 1.67: 1, and calcium salt soln and phosphate solution are mixed to get preceding
Drive body I.
Step 2: the ammonium hydroxide of a concentration of 4.0~5.0wt% is added in flotation device mixing bunker, rotating speed be 1700~
Under conditions of 2000r/min, then it is 10.50~11.00 that the presoma I to pH value, which is added, into flotation device mixing bunker, then
1.2~1.5h is mixed to get presoma II.
Step 3: the presoma II is placed in closed container, it is aged 20~23h under the conditions of 25~28 DEG C, filters,
Up to presoma III.
Step 4: the presoma III is refrigerated to solid-state, then it is placed in freeze drier, is freezed under the conditions of -40 DEG C
Dry 32~36h is to get presoma IV.
Step 5: the presoma IV is roasted 2~3h under the conditions of 720~750 DEG C, porous prilled nanometer hydroxyl is made
Base apatite.
The calcium salt soln is calcium nitrate solution.
The phosphate solution is ammonium hydrogen phosphate solution.
Porous prilled nanometer hydroxyapatite particle diameter distribution manufactured in the present embodiment is uniform, and grain size is 60~140nm, than
Surface area is 22~25m2/g。
Embodiment 6
A kind of porous prilled nanometer hydroxyapatite and preparation method thereof.In addition to calcium salt soln, remaining is the same as embodiment 1：
The calcium salt soln is calcium chloride solution.
Porous prilled nanometer hydroxyapatite particle diameter distribution manufactured in the present embodiment is uniform, and grain size is 70~140nm, than
Surface area is 23~25m2/g。
The advantageous effect of present embodiment compared with prior art is：
Present embodiment uses the preparation flow of air Aerated stirring-ageing-drying-roasting, simple for process.It prepares
Reactant contact is abundant in the process, and the reaction was complete, and preparation process only has hydroxyapatite and the waste liquid containing ammonium nitrate, miscellaneous without other
Matter is interfered, and product purity is high.The ammonium nitrate that present embodiment generates does not influence present embodiment preparation process,
And ammonium nitrate can not only recycle, also as the raw material for preparing chemical fertilizer.Therefore entire specific implementation mode preparation process is green
Colour circle is protected, raw material availability is high low with production cost.
Present embodiment is stirred using inflatable and is combined with sol-gel chemistries preparation, by using flotation device height
The Aerated stirring of speed is stirred instead of tradition machinery so that preparation process reaction is abundant.Fig. 1 is that one kind prepared by embodiment 4 is porous
The SEM of graininess nanometer hydroxyapatite schemes, it will be seen from figure 1 that prepared porous prilled nanometer hydroxyapatite grain
Diameter is evenly distributed；It is calculated by particle diameter distribution and BET detections, the grain size of prepared porous prilled nanometer hydroxyapatite is
60~180nm, specific surface area are 20~25m2/g.In addition, present embodiment uses Freeze Drying Technique, for porous
The porous structure of graininess nanometer hydroxyapatite has protective effect.
In conclusion present embodiment has simple for process, of low cost, environmentally protective and raw material availability high
Feature, prepared porous prilled nanometer hydroxyapatite purity height, the uniform large specific surface area of particle diameter distribution.
Claims (4)
1. a kind of preparation method of porous prilled nanometer hydroxyapatite, it is characterised in that the step of preparation method is：
Step 1: according to Ca: the amount ratio of the substance of P is 1.67: 1, and calcium salt soln and phosphate solution are mixed to get presoma
Ⅰ；
It is 1000~2000r/ in rotating speed Step 2: the ammonium hydroxide of a concentration of 4.0~5.0wt% is added in flotation device mixing bunker
Under conditions of min, then it is 9.50~11.00 that the presoma I to pH value, which is added, into flotation device mixing bunker, is then mixed
0.5~1.5h is to get presoma II；
Step 3: by the presoma II be placed in closed container in, under the conditions of 18~28 DEG C be aged 20~25h, filtering to get
Presoma III；
Step 4: the presoma III is refrigerated to solid-state, then it is placed in freeze drier, is freeze-dried under the conditions of -40 DEG C
24~36h is to get presoma IV；
Step 5: the presoma IV is roasted 2~3h under the conditions of 650~750 DEG C, porous prilled nano hydroxyapatite is made
Lime stone.
2. the preparation method of porous prilled nanometer hydroxyapatite according to claim 1, it is characterised in that the calcium
Salting liquid is calcium nitrate solution or is calcium chloride solution.
3. the preparation method of porous prilled nanometer hydroxyapatite according to claim 1, it is characterised in that the phosphorus
Acid salt solution is one kind in ammonium dihydrogen phosphate, ammonium phosphate solution and ammonium hydrogen phosphate solution.
4. a kind of porous prilled nanometer hydroxyapatite, it is characterised in that the porous prilled nanometer hydroxyapatite is root
Porous prepared by preparation method according to any one of the claims 1 to 3 item porous prilled nanometer hydroxyapatite
Granular nanometer hydroxyapatite.
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| CN201810864165.1A CN108584899A (en) | 2018-08-01 | 2018-08-01 | A kind of porous prilled nanometer hydroxyapatite and preparation method thereof |
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| CN201810864165.1A CN108584899A (en) | 2018-08-01 | 2018-08-01 | A kind of porous prilled nanometer hydroxyapatite and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020181574A1 (en) * | 2019-03-13 | 2020-09-17 | 东北大学 | Method for purifying fluorapatite and method for preparing fluorohydroxyapatite bioceramic thereof |
| CN113814003A (en) * | 2021-09-29 | 2021-12-21 | 广东森格安环保新材料科技有限公司 | Air purifying agent made of nano materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6426114B1 (en) * | 2000-05-02 | 2002-07-30 | The University Of British Columbia | Sol-gel calcium phosphate ceramic coatings and method of making same |
| CN101519196A (en) * | 2009-04-10 | 2009-09-02 | 武汉工程大学 | Method for controlling aperture of porous carbonated hydroxyapatite prepared by bubble template method |
| CN201823495U (en) * | 2010-09-17 | 2011-05-11 | 中钢集团马鞍山矿山研究院有限公司 | Gas-filling stirring device |
| CN103112837A (en) * | 2013-03-18 | 2013-05-22 | 厦门大学 | Preparation method of nano-hydroxyapatite |
| CN106927443A (en) * | 2017-04-26 | 2017-07-07 | 武汉科技大学 | A kind of three-dimensional porous nano hydroxyapatite and preparation method thereof |
-
2018
- 2018-08-01 CN CN201810864165.1A patent/CN108584899A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6426114B1 (en) * | 2000-05-02 | 2002-07-30 | The University Of British Columbia | Sol-gel calcium phosphate ceramic coatings and method of making same |
| CN101519196A (en) * | 2009-04-10 | 2009-09-02 | 武汉工程大学 | Method for controlling aperture of porous carbonated hydroxyapatite prepared by bubble template method |
| CN201823495U (en) * | 2010-09-17 | 2011-05-11 | 中钢集团马鞍山矿山研究院有限公司 | Gas-filling stirring device |
| CN103112837A (en) * | 2013-03-18 | 2013-05-22 | 厦门大学 | Preparation method of nano-hydroxyapatite |
| CN106927443A (en) * | 2017-04-26 | 2017-07-07 | 武汉科技大学 | A kind of three-dimensional porous nano hydroxyapatite and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020181574A1 (en) * | 2019-03-13 | 2020-09-17 | 东北大学 | Method for purifying fluorapatite and method for preparing fluorohydroxyapatite bioceramic thereof |
| CN113814003A (en) * | 2021-09-29 | 2021-12-21 | 广东森格安环保新材料科技有限公司 | Air purifying agent made of nano materials |
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Application publication date: 20180928 |