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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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)
1. mechanochemical method prepares a method for hydroxyapatite, it is characterized in that the method comprises the following steps:
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;
Step (2), the compound that step (1) obtained are that 1:5 ~ 30 mix with water according to mass ratio, pass into CO
2gas, reaction 20 ~ 120min; After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
2. mechanochemical method prepares a method for hydroxyapatite, it is characterized in that the method comprises the following steps:
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;
Step (2), compound step (1) obtained and water are that 1:5 ~ 30 proceed in reactor according to mass ratio, at 50 ~ 150 DEG C of temperature, react 5 ~ 30h; After reaction terminates, filtration, oven dry obtain hydroxy apatite powder.
3. a kind of mechanochemical method as claimed in claim 1 or 2 prepares the method for hydroxyapatite, and the calcareous material that it is characterized in that described in step (1) 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, raw oyster shell.
4. a kind of mechanochemical method as claimed in claim 1 or 2 prepares the method for hydroxyapatite, it is characterized in that the microcosmic salt described in step (1) includes but not limited to Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, diammonium hydrogen phosphate, primary ammonium phosphate, dipotassium hydrogen phosphate, potassium primary phosphate.
5. a kind of mechanochemical method as claimed in claim 1 or 2 prepares the method for hydroxyapatite, and it is characterized in that the ball milling described in step (2) is dry grinding or wet-milling, wet milling assistant includes but not limited to as water, ethanol or acetone.
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| 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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