CN105293462A - Method of preparing hydroxyapatite by mechanochemical method - Google Patents
Method of preparing hydroxyapatite by mechanochemical method Download PDFInfo
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- CN105293462A CN105293462A CN201510867889.8A CN201510867889A CN105293462A CN 105293462 A CN105293462 A CN 105293462A CN 201510867889 A CN201510867889 A CN 201510867889A CN 105293462 A CN105293462 A CN 105293462A
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 32
- 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 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract 8
- 239000007789 gas Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 241000237536 Mytilus edulis Species 0.000 claims description 6
- 235000020638 mussel Nutrition 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 5
- 238000001238 wet grinding Methods 0.000 claims description 5
- 102000002322 Egg Proteins Human genes 0.000 claims description 4
- 108010000912 Egg Proteins Proteins 0.000 claims description 4
- 241000237502 Ostreidae Species 0.000 claims description 4
- 229940036811 bone meal Drugs 0.000 claims description 4
- 239000002374 bone meal Substances 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 210000003278 egg shell Anatomy 0.000 claims description 4
- 235000020636 oyster Nutrition 0.000 claims description 4
- 229910021532 Calcite Inorganic materials 0.000 claims description 3
- 241000237509 Patinopecten sp. Species 0.000 claims description 3
- 235000020637 scallop Nutrition 0.000 claims description 3
- 241000238424 Crustacea Species 0.000 claims description 2
- 238000009837 dry grinding Methods 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims 3
- 239000004575 stone Substances 0.000 claims 2
- 235000014653 Carica parviflora Nutrition 0.000 claims 1
- 241000243321 Cnidaria Species 0.000 claims 1
- 235000019738 Limestone Nutrition 0.000 claims 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims 1
- -1 diamine hydrogen phosphate Chemical class 0.000 claims 1
- 239000006028 limestone Substances 0.000 claims 1
- 235000019837 monoammonium phosphate Nutrition 0.000 claims 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims 1
- 235000019796 monopotassium phosphate Nutrition 0.000 claims 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims 1
- 235000019799 monosodium phosphate Nutrition 0.000 claims 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000004137 mechanical activation Methods 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 39
- 230000035484 reaction time Effects 0.000 description 19
- 239000011575 calcium Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 4
- 235000019838 diammonium phosphate Nutrition 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a method of preparing hydroxyapatite by a mechanochemical method. The method comprises the steps that according to a mole ratio that Ca/P is equal to 1 to 2, adding a calcareous material and microcosmic salt into a ball miller, and ball-milling to obtain a mixture; then mixing the mixture with water, introducing CO2 gas, and reacting for 20 to 120min; or transferring the mixture and the water into a reaction kettle, and reacting for 5 to 30h under the temperature of 50 to 150 DEG C; after the reaction is ended, filtering and drying to obtain hydroxyapatite powder. The calcareous material is pretreated by means of a mechanical activation technology, so that a defected is generated on a structure, reaction activation energy is reduced, reactivity is enhanced, and reaction with the microcosmic salt is promoted; the mixture after the reaction is ended reacts with CO2 or is subjected to heat reaction with water for further edulcoration and crystallization, the crystallinity and the purity of the hydroxyapatite are improved, the technological process is simple, the reaction conditions are mild, and large-scale industrial production is easy.
Description
Technical field
The invention belongs to Inorganic synthese field, particularly a kind of mechanochemical method prepares the method for hydroxyapatite.
Background technology
Hydroxyapatite (HAP) is a kind of Inorganic biomatetials of high added value, has good biocompatibility and biological activity, very extensive at the research and apply in hard tissue repair or the field of replacement.In addition, HAP also has that higher surfactivity and selective adsorption, pore structure are unique, chemical stability high, have broad application prospects in fields such as sewage disposal, pharmaceutical carrier, separation and purification, Industrial Catalysis, there is research and development and utility value greatly.
The preparation method of current HAP mainly contains chemical precipitation method, sol-gel method, hydrothermal synthesis method, microemulsion method, solid reaction process and template etc.Dry method normally with tricalcium phosphate, secondary calcium phosphate, calcium carbonate or calcium hydroxide for raw material at high temperature (>1000 DEG C) pass into water vapor, obtained hydroxyapatite.This method temperature of reaction is relatively high, heat treatment time is relatively long, and after sintering, performance is relatively poor simultaneously, is not suitable for suitability for industrialized production.The preparation temperature of wet method is low than dry method, but also has the shortcoming that some cannot overcome.Prices are rather stiff for the chemical process relative complex of sol-gel method, alkoxide raw material, the toxicity of organic solvent large, easily pollutes environment.In the morphology control of hydroxy apatite powder, the nanometer hydroxyapatite of various structure (Nano microsphere, nanofiber, nano-pillar) is synthesized out, but in building-up process, need to add template or tensio-active agent, these additives are easy to pollute final product, affect the purity of hydroxyapatite.In sum, the preparation of current hydroxyapatite is confined to adopt industrial chemicals and organic formwork agent more, and synthesis temperature is higher, complex process, and will obtain the hydroxy apatite powder of specific morphology and structure, need to add foreign matter, purity is impacted.How developing low-cost, simple to operate, eco-friendly HAP controlled synthesis technology are problem demanding prompt solutions.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of mechanochemical method is provided to prepare the method for hydroxyapatite, the method has the advantages such as technical process is simple, reaction conditions is gentle, raw material sources are extensive, preparation cost is low, is easy to large-scale industrial production.
A kind of mechanochemical method of the present invention prepares the method for hydroxyapatite, and concrete technology step is:
Step (1), by the mol ratio of Ca/P=1 ~ 2, calcareous material and microcosmic salt are added ball mill and carry out ball milling, obtain compound; Wherein the rotating speed of ball mill is 100 ~ 600r/min, and Ball-milling Time is 6 ~ 30h;
After step (2), reaction terminate, the compound that step (1) obtains is mixed with water, passes into high-purity CO
2gas, reaction 20 ~ 120min; Or the compound obtain step (1) and water proceed in reactor, at 50 ~ 150 DEG C of temperature, react 5 ~ 30h; After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
The mass ratio of the compound that step (1) obtains and water is 1:5 ~ 30.
Described calcareous material includes but not limited to the shell of shell, eggshell, crustaceans, bone meal, Stalactitum, corallite, calcite or Wingdale; Wherein shell includes but not limited to oyster shells, mussel shell, scallop shell, pearl shell, freshwater mussel shell, CONCHA MERETRICID SEU CYCLINAE, abalone shells or raw oyster shell;
Described microcosmic salt includes but not limited to Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, diammonium hydrogen phosphate, primary ammonium phosphate, dipotassium hydrogen phosphate or potassium primary phosphate;
Described ball milling is dry grinding or wet-milling, and wet milling assistant includes but not limited to as water, ethanol or acetone;
Existing various hydroxyapatite preparation method exists that complex process, temperature of reaction are high, long reaction time, expensive raw material price, need to add the shortcomings such as template, and also there is a big difference for distance suitability for industrialized production.The present invention carries out pre-treatment by mechanical activation technology to calcareous raw material, makes its particle size reduction, and structure produces defect, reduces reaction activity, and intensified response is active, promotes, with the reaction of microcosmic salt, to reduce the reaction times, reduce temperature of reaction.Reaction terminate after compound by with CO
2reaction or the further removal of impurities crystallization of hydro-thermal reaction, improve the degree of crystallinity of hydroxyapatite and purity, thus reach that technical process is simple, reaction conditions is gentle, is easy to large-scale industrial production.Thus, the method has good application prospect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope of the hydroxyapatite that embodiment 1 prepares;
Fig. 2 is the scanning electron microscope of the hydroxyapatite that embodiment 2 prepares;
Fig. 3 is the scanning electron microscope of the hydroxyapatite that embodiment 3 prepares;
Fig. 4 is the scanning electron microscope of the hydroxyapatite that embodiment 4 prepares.
Embodiment
Below in conjunction with specific embodiment, the present invention is further analyzed.
Embodiment 1
1) by the mol ratio of Ca/P=1,100g scallop shell and 124.2g disodium hydrogen phosphate,anhydrous are put into planetary ball mill, setting drum's speed of rotation 100r/min, Ball-milling Time 30h.2), after reaction terminates, 200g compound is mixed with 6000g water, passes into high-purity CO
2gas, reaction 120min; Or 200g compound and 6000g water are proceeded in reactor, setting temperature of reaction 50 DEG C, reaction times 30h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.The scanning electron microscope of hydroxyapatite as shown in Figure 1.
Embodiment 2
1) by the mol ratio of Ca/P=1.5,100g oyster shells and 71.9g AMSP are put into stirring ball mill, setting drum's speed of rotation 600r/min, Ball-milling Time 6h.2), after reaction terminates, 150g compound is mixed with 750g water, passes into high-purity CO
2gas, reaction 20min; Or 150g compound and 750g water are proceeded in reactor, setting temperature of reaction 150 DEG C, reaction times 5h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.The scanning electron microscope of hydroxyapatite as shown in Figure 2.
Embodiment 3
1) by the mol ratio of Ca/P=2,100g mussel shell and 61.1g diammonium hydrogen phosphate are put into stirring ball mill, setting drum's speed of rotation 200r/min, Ball-milling Time 25h.2), after reaction terminates, 150g compound is mixed with 1500g water, passes into high-purity CO
2gas, reaction 30min; Or 150g compound and 1500g water are proceeded in reactor, setting temperature of reaction 60 DEG C, reaction times 26h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.The scanning electron microscope of hydroxyapatite as shown in Figure 3.
Embodiment 4
1) by the mol ratio of Ca/P=1.2,100g pearl shell and 91.1g primary ammonium phosphate are put into tumbling ball mill, setting drum's speed of rotation 300r/min, Ball-milling Time 20h.2), after reaction terminates, 150g compound is mixed with 3000g water, passes into high-purity CO
2gas, reaction 40min; Or 150g compound and 3000g water are proceeded in reactor, setting temperature of reaction 70 DEG C, reaction times 24h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.The scanning electron microscope of hydroxyapatite as shown in Figure 4.
Embodiment 5
1) by the mol ratio of Ca/P=1.3,100g freshwater mussel shell and 117.2g anhydrous di-potassium hydrogen phosphate are put into planetary ball mill, setting drum's speed of rotation 400r/min, Ball-milling Time 14h.2), after reaction terminates, 200g compound is mixed with 1200g water, passes into high-purity CO
2gas, reaction 50min; Or 200g compound and 1200g water are proceeded in reactor, setting temperature of reaction 80 DEG C, reaction times 22h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 6
1) by the mol ratio of Ca/P=1.4,100g CONCHA MERETRICID SEU CYCLINAE and 87.5g potassium primary phosphate are put into planetary ball mill, setting drum's speed of rotation 500r/min, Ball-milling Time 9h.2), after reaction terminates, 150g compound is mixed with 1200g water, passes into high-purity CO
2gas, reaction 60min; Or 150g compound and 1200g water are proceeded in reactor, setting temperature of reaction 90 DEG C, reaction times 20h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 7
1) by the mol ratio of Ca/P=1.5,100g abalone shells and 85.2g disodium hydrogen phosphate,anhydrous are put into planetary ball mill, setting drum's speed of rotation 100r/min, Ball-milling Time 30h.2), after reaction terminates, 150g compound is mixed with 4500g water, passes into high-purity CO
2gas, reaction 80min; Or 150g compound and 4500g water are proceeded in reactor, setting temperature of reaction 100 DEG C, reaction times 16h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 8
1) by the mol ratio of Ca/P=1.6, raw for 100g oyster shell and 69.4g AMSP are put into stirring ball mill, setting drum's speed of rotation 600r/min, Ball-milling Time 6h.2), after reaction terminates, 150g compound is mixed with 750g water, passes into high-purity CO
2gas, reaction 100min; Or 150g compound and 750g water are proceeded in reactor, setting temperature of reaction 120 DEG C, reaction times 13h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 9
1) by the mol ratio of Ca/P=1.7,100g eggshell and 67.9g diammonium hydrogen phosphate are put into stirring ball mill, setting drum's speed of rotation 200r/min, Ball-milling Time 25h.2), after reaction terminates, 150g compound is mixed with 1500g water, passes into high-purity CO
2gas, reaction 120min; Or 150g compound and 1500g water are proceeded in reactor, setting temperature of reaction 140 DEG C, reaction times 28h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 10
1) by the mol ratio of Ca/P=1.8,100g bone meal and 52.7g primary ammonium phosphate are put into tumbling ball mill, setting drum's speed of rotation 300r/min, Ball-milling Time 20h.2), after reaction terminates, 150g compound is mixed with 3000g water, passes into high-purity CO
2gas, reaction 20min; Or 150g compound and 3000g water are proceeded in reactor, setting temperature of reaction 150 DEG C, reaction times 5h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 11
1) by the mol ratio of Ca/P=1.9,100g Stalactitum and 82.7g anhydrous di-potassium hydrogen phosphate are put into planetary ball mill, setting drum's speed of rotation 400r/min, Ball-milling Time 14h.2), after reaction terminates, 150g compound is mixed with 900g water, passes into high-purity CO
2gas, reaction 50min; Or 150g compound and 900g water are proceeded in reactor, setting temperature of reaction 80 DEG C, reaction times 22h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 12
1) by the mol ratio of Ca/P=1.4,100g corallite and 80.2g potassium primary phosphate are put into planetary ball mill, setting drum's speed of rotation 500r/min, Ball-milling Time 9h.2), after reaction terminates, 150g compound is mixed with 1200g water, passes into high-purity CO
2gas, reaction 60min; Or 150g compound and 1200g water are proceeded in reactor, setting temperature of reaction 90 DEG C, reaction times 20h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 13
1) by the mol ratio of Ca/P=1.4,100g calcite and 94.8g potassium primary phosphate are put into planetary ball mill, setting drum's speed of rotation 500r/min, Ball-milling Time 9h.2), after reaction terminates, 150g compound is mixed with 1200g water, passes into high-purity CO
2gas, reaction 60min; Or 150g compound and 1200g water are proceeded in reactor, setting temperature of reaction 90 DEG C, reaction times 20h.Reaction terminates rear filtration, oven dry obtains hydroxy apatite powder.
Embodiment 13
1) by the mol ratio of Ca/P=1.5,100g Wingdale and 89.9g disodium hydrogen phosphate,anhydrous are put into planetary ball mill, setting drum's speed of rotation 100r/min, Ball-milling Time 30h.2), after reaction terminates, 150g compound is mixed with 4500g water, passes into high-purity CO
2gas, reaction 80min; Or 150g compound and 4500g water are proceeded in reactor, setting temperature of reaction 100 DEG C, reaction times 16h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 14
1) by the mol ratio of Ca/P=1.6, raw for 100g oyster shell, 69.4g AMSP and 2000ml water are put into stirring ball mill and carry out wet-milling, setting drum's speed of rotation 600r/min, Ball-milling Time 6h.2), after reaction terminates, 150g compound is mixed with 750g water, passes into high-purity CO
2gas, reaction 100min; Or 150g compound and 750g water are proceeded in reactor, setting temperature of reaction 120 DEG C, reaction times 13h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 15
1) by the mol ratio of Ca/P=1.7,100g eggshell, 67.9g diammonium hydrogen phosphate and 2500ml ethanol are put into stirring ball mill, setting drum's speed of rotation 200r/min, Ball-milling Time 25h.2), after reaction terminates, 150g compound is mixed with 900g water, passes into high-purity CO
2gas, reaction 120min; Or 150g compound and 900g water are proceeded in reactor, setting temperature of reaction 140 DEG C, reaction times 28h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
Embodiment 16
1) by the mol ratio of Ca/P=1.8,100g bone meal, 52.7g primary ammonium phosphate and 3000ml acetone are put into tumbling ball mill, setting drum's speed of rotation 300r/min, Ball-milling Time 20h.2), after reaction terminates, 150g compound is mixed with 900g water, passes into high-purity CO
2gas, reaction 20min; Or 150g compound and 900g water are proceeded in reactor, setting temperature of reaction 150 DEG C, reaction times 5h.After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equal replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105999276A (en) * | 2016-05-25 | 2016-10-12 | 湖北大学 | Novel composite material for drug carrier, as well as preparation method and application thereof |
| CN107500259A (en) * | 2017-10-18 | 2017-12-22 | 福州大学 | A kind of preparation method of different-shape abalone shells hydroxyapatite |
| CN108483417A (en) * | 2018-05-07 | 2018-09-04 | 南昌大学 | A kind of preparation method of carbonate hydroxyapatite |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1475279A (en) * | 2002-08-13 | 2004-02-18 | 中国科学院福建物质结构研究所 | A kind of preparation method of hydroxyapatite bone cement artificial bone |
| US20060260511A1 (en) * | 2000-10-16 | 2006-11-23 | University Of South Carolina | Biocompatible cement containing reactive calcium phosphate nanoparticles and methods for making and using such cement |
| CN1899957A (en) * | 2006-07-26 | 2007-01-24 | 中国科学院上海硅酸盐研究所 | Process for preparing modified hydroxy apatite powder |
| CN101343056A (en) * | 2008-07-30 | 2009-01-14 | 宁波大学 | A kind of preparation method of hydroxyapatite nanopowder |
| CN101486453A (en) * | 2009-02-16 | 2009-07-22 | 重庆大学 | Preparation of carbonate-containing hydroxylapatite powder |
| CN102167300A (en) * | 2011-03-10 | 2011-08-31 | 南京工业大学 | Preparation method of hexagonal columnar micro-powder hydroxyapatite material |
| CN102851664A (en) * | 2012-08-03 | 2013-01-02 | 华中科技大学 | Method for preparing hydroxy apatite biological ceramic coating containing fluorine |
| CN103086339A (en) * | 2013-02-18 | 2013-05-08 | 中国人民解放军南京军区南京总医院 | Porous hydroxyapatite flower-like microspheres and preparation method thereof |
| CN104512875A (en) * | 2013-10-08 | 2015-04-15 | 杜淑卿 | Method for preparing nano-hydroxyapatite through mechanochemical method |
| CN104528678A (en) * | 2014-12-31 | 2015-04-22 | 雅安美豪新材料科技有限公司 | Method for producing hydroxyapatite through waste phosphoric acid |
| CN105084336A (en) * | 2014-05-23 | 2015-11-25 | 中国科学院金属研究所 | Two-phase calcium phosphate material, preparation method thereof, and two-phase calcium phosphate artificial bone ceramic |
-
2015
- 2015-12-02 CN CN201510867889.8A patent/CN105293462A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060260511A1 (en) * | 2000-10-16 | 2006-11-23 | University Of South Carolina | Biocompatible cement containing reactive calcium phosphate nanoparticles and methods for making and using such cement |
| CN1475279A (en) * | 2002-08-13 | 2004-02-18 | 中国科学院福建物质结构研究所 | A kind of preparation method of hydroxyapatite bone cement artificial bone |
| CN1899957A (en) * | 2006-07-26 | 2007-01-24 | 中国科学院上海硅酸盐研究所 | Process for preparing modified hydroxy apatite powder |
| CN101343056A (en) * | 2008-07-30 | 2009-01-14 | 宁波大学 | A kind of preparation method of hydroxyapatite nanopowder |
| CN101486453A (en) * | 2009-02-16 | 2009-07-22 | 重庆大学 | Preparation of carbonate-containing hydroxylapatite powder |
| CN102167300A (en) * | 2011-03-10 | 2011-08-31 | 南京工业大学 | Preparation method of hexagonal columnar micro-powder hydroxyapatite material |
| CN102851664A (en) * | 2012-08-03 | 2013-01-02 | 华中科技大学 | Method for preparing hydroxy apatite biological ceramic coating containing fluorine |
| CN103086339A (en) * | 2013-02-18 | 2013-05-08 | 中国人民解放军南京军区南京总医院 | Porous hydroxyapatite flower-like microspheres and preparation method thereof |
| CN104512875A (en) * | 2013-10-08 | 2015-04-15 | 杜淑卿 | Method for preparing nano-hydroxyapatite through mechanochemical method |
| CN105084336A (en) * | 2014-05-23 | 2015-11-25 | 中国科学院金属研究所 | Two-phase calcium phosphate material, preparation method thereof, and two-phase calcium phosphate artificial bone ceramic |
| CN104528678A (en) * | 2014-12-31 | 2015-04-22 | 雅安美豪新材料科技有限公司 | Method for producing hydroxyapatite through waste phosphoric acid |
Non-Patent Citations (3)
| Title |
|---|
| CAI SHU等: "Synthesis of Crystalline Hydroxyapatite from CaCO3 and CaHPO4·2H2O by Mechanochemical Method", 《TRANSACTIONS OF TIANJIN UNIVERSITY》 * |
| 沈雁: "沉淀-球磨法制备羟基磷灰石粉体", 《科技通报》 * |
| 肖丽华, 吴建青: "在湿CO2气氛中热处理生成碳酸羟基磷灰石的探讨", 《硅酸盐学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105999276A (en) * | 2016-05-25 | 2016-10-12 | 湖北大学 | Novel composite material for drug carrier, as well as preparation method and application thereof |
| CN105999276B (en) * | 2016-05-25 | 2019-05-31 | 湖北大学 | A kind of advanced composite material (ACM) and its preparation method and application for pharmaceutical carrier |
| CN107500259A (en) * | 2017-10-18 | 2017-12-22 | 福州大学 | A kind of preparation method of different-shape abalone shells hydroxyapatite |
| CN108483417A (en) * | 2018-05-07 | 2018-09-04 | 南昌大学 | A kind of preparation method of carbonate hydroxyapatite |
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