CN106976850B - 一种介孔羟基磷灰石规模化的制备方法 - Google Patents
一种介孔羟基磷灰石规模化的制备方法 Download PDFInfo
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 53
- 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 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 229940088594 vitamin Drugs 0.000 claims abstract description 13
- 229930003231 vitamin Natural products 0.000 claims abstract description 13
- 235000013343 vitamin Nutrition 0.000 claims abstract description 13
- 239000011782 vitamin Substances 0.000 claims abstract description 13
- 150000003722 vitamin derivatives Chemical class 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims abstract description 3
- 239000013049 sediment Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 9
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 7
- 229930003268 Vitamin C Natural products 0.000 claims description 7
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims description 7
- 235000019154 vitamin C Nutrition 0.000 claims description 7
- 239000011718 vitamin C Substances 0.000 claims description 7
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 claims description 3
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 3
- 229930003471 Vitamin B2 Natural products 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229960002477 riboflavin Drugs 0.000 claims description 3
- 235000019164 vitamin B2 Nutrition 0.000 claims description 3
- 239000011716 vitamin B2 Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- GHOKWGTUZJEAQD-UHFFFAOYSA-N Chick antidermatitis factor Natural products OCC(C)(C)C(O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-UHFFFAOYSA-N 0.000 claims description 2
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 claims description 2
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 2
- 229930003451 Vitamin B1 Natural products 0.000 claims description 2
- 229930003779 Vitamin B12 Natural products 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019152 folic acid Nutrition 0.000 claims description 2
- 239000011724 folic acid Substances 0.000 claims description 2
- 229960000304 folic acid Drugs 0.000 claims description 2
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 claims description 2
- 229960000367 inositol Drugs 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000001968 nicotinic acid Nutrition 0.000 claims description 2
- 239000011664 nicotinic acid Substances 0.000 claims description 2
- 229960003512 nicotinic acid Drugs 0.000 claims description 2
- 235000019161 pantothenic acid Nutrition 0.000 claims description 2
- 239000011713 pantothenic acid Substances 0.000 claims description 2
- 229940055726 pantothenic acid Drugs 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 claims description 2
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 229960003495 thiamine Drugs 0.000 claims description 2
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 claims description 2
- 235000010374 vitamin B1 Nutrition 0.000 claims description 2
- 239000011691 vitamin B1 Substances 0.000 claims description 2
- 235000019163 vitamin B12 Nutrition 0.000 claims description 2
- 239000011715 vitamin B12 Substances 0.000 claims description 2
- 235000019158 vitamin B6 Nutrition 0.000 claims description 2
- 239000011726 vitamin B6 Substances 0.000 claims description 2
- 229940011671 vitamin b6 Drugs 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims 1
- 235000019838 diammonium phosphate Nutrition 0.000 claims 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims 1
- 235000019832 sodium triphosphate Nutrition 0.000 claims 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 abstract description 9
- 229910052586 apatite Inorganic materials 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 5
- 210000000988 bone and bone Anatomy 0.000 abstract description 3
- 238000012377 drug delivery Methods 0.000 abstract description 3
- 230000035876 healing Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000011282 treatment Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- ABSPRNADVQNDOU-UHFFFAOYSA-N Menaquinone 1 Natural products C1=CC=C2C(=O)C(CC=C(C)C)=C(C)C(=O)C2=C1 ABSPRNADVQNDOU-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SHUZOJHMOBOZST-UHFFFAOYSA-N phylloquinone Natural products CC(C)CCCCC(C)CCC(C)CCCC(=CCC1=C(C)C(=O)c2ccccc2C1=O)C SHUZOJHMOBOZST-UHFFFAOYSA-N 0.000 description 2
- MBWXNTAXLNYFJB-NKFFZRIASA-N phylloquinone Chemical compound C1=CC=C2C(=O)C(C/C=C(C)/CCC[C@H](C)CCC[C@H](C)CCCC(C)C)=C(C)C(=O)C2=C1 MBWXNTAXLNYFJB-NKFFZRIASA-N 0.000 description 2
- 235000019175 phylloquinone Nutrition 0.000 description 2
- 239000011772 phylloquinone Substances 0.000 description 2
- 229960001898 phytomenadione Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 229910017251 AsO4 Inorganic materials 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012637 gene transfection Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000000278 osteoconductive effect Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000002351 wastewater Substances 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
- C01B25/322—Preparation by neutralisation of orthophosphoric acid
-
- 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
-
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明属于磷灰石制备领域，特别涉及一种介孔羟基磷灰石规模化的制备方法。使用可溶性钙盐作为钙源，磷酸或磷酸盐作为磷源，去离子水作为溶剂，将钙源、磷源和含有羟基或羧基的水溶性维生素按照钙元素、磷元素和水溶性维生素摩尔比为1～2：1：0.001～0.1加入到去离子水中混合均匀，记为溶液A；调节溶液A的pH值为6～12，60～200℃条件下在水热反应釜中水热反应1～24小时，过滤、水洗并在50～80℃空气氛围下干燥所得沉淀物，制得介孔羟基磷灰石。本发明制得的介孔羟基磷灰石具有高比表面积，在药物传输、组织工程、骨缺损修复、分离提纯和污水处理等领域得到了广泛地应用。
Description
技术领域
本发明属于磷灰石制备领域，特别涉及一种介孔羟基磷灰石规模化的制备方法。
背景技术
羟基磷灰石(Hydroxyapatite，简称HA)，化学式为Ca10(PO4)6(OH)2，是脊椎动物体内骨和齿的主要无机成分，具有良好的生物相容性、生物活性及骨传导性能。植入人体后，羟基磷灰石会逐渐被机体组织吸收，部分或全部被组织吸收和取代。故而羟基磷灰石是一类理想的生物材料，被广泛应用于组织工程、骨修复、药物输运、基因转染和血液净化等领域。此外由于羟基磷灰石中钙离子易于被Fe2+、Mn2+、Pb2+、Cd2+、Zn2+、Hg2+、Ba2+、Cr6+置换，磷酸根离子易于被AsO4 3-、VO4 3-、CrO4 2-等络阴离子基团取代，氢氧根离子可以被F-、Cl-等阴离子替代。这种广泛替换的特点使它在处理含有各类离子废水时具有广谱性和开放性、高效价廉、不易产生二次污染的优点，尤其在处理铅、铬、镉、汞等重金属离子方面效果显著。但是常见的羟基磷灰石的比表面积较低，缺少孔隙结构，吸附能力还有提高的空间。
介孔材料是一类孔径在2-50nm的材料，具有较大的比表面积和孔容，使其在催化、吸附和组织工程等领域具有广阔的应用潜力。而介孔羟基磷灰石具有高比表面积，从而获得了更为优秀的吸附能力。发展新的简单绿色经济的介孔羟基磷灰石的制备方法具有重要的研究和商业价值。目前国内外主要通过模板法制备介孔羟基磷灰石，但模板法所使用的模板具有一定的毒性，其残留会污染介孔羟基磷灰石的纯度，且在高温煅烧去除模板的过程中可能会导致颗粒团聚。这些都增加了工艺的复杂性和生产成本，并可能造成环境污染。除了模板法，也有通过反应构建新型的水热反应体系制备介孔羟基磷灰石的报道，但这些体系与常规的水热反应釜相比需要特殊的设备，无法进行简单的扩大化生产。目前有简易法大规模生产介孔羟基磷灰石，但制备的羟基磷灰石形貌不均一、颗粒较大。
发明内容
本发明的目的：针对介孔羟基磷灰石制备工艺复杂、成本较高而无法大规模生产，且简易法制备的介孔羟基磷灰石形貌不均一、颗粒较大等问题，本发明提供了一种介孔羟基磷灰石规模化的制备方法，具有简单绿色经济的特点。
本发明的技术方案：提供一种介孔羟基磷灰石规模化的制备方法，操作步骤具体包括：(1)使用可溶性钙盐作为钙源，磷酸或磷酸盐作为磷源，去离子水作为溶剂，将钙源、磷源和含有羟基或羧基的水溶性维生素按照钙元素、磷元素和水溶性维生素摩尔比为1～2：1：0.001～0.1加入到去离子水中混合均匀，记为溶液A；
(2)调节溶液A的pH值为6～12，60～200℃条件下在水热反应釜中水热反应1～24小时，过滤、水洗并在50～80℃空气氛围下干燥所得沉淀物，制得介孔羟基磷灰石。
作为优选，步骤(1)中可溶性钙盐为氯化钙和/或其水合物、硝酸钙和/或其水合物、乙酸钙和/或其水合物、氧化钙、氢氧化钙中的一种或一种以上；步骤(1)中磷酸盐为磷酸氢二铵、磷酸二氢铵、磷酸氢二钠、磷酸二氢钠、磷酸氢二钾、磷酸二氢钾、焦磷酸钠、三聚磷酸钠、六偏磷酸钠中的一种或一种以上；步骤(1)中水溶性维生素为维生素C、维生素B1、维生素B2、维生素B6、维生素B12、烟酸、泛酸、叶酸、肌醇中的一种或一种以上。
作为优选，步骤(1)中钙源摩尔浓度为0.01～1摩尔/升；步骤(1)中磷源摩尔浓度为0.01～1摩尔/升；步骤(1)中水溶性维生素质量浓度为0.001-0.01克/升。
作为优选，步骤(2)中调节溶液A的pH值为7-12，部分羟基磷灰石在酸性环境中会降解，对颗粒形貌及产率有一定影响，所以选择在中性及碱性环境下发生水热反应。
作为优选，步骤(2)中水热反应温度为100-160℃；步骤(2)中水热反应时间为2-8小时。
作为优选，步骤(2)中水热反应条件为微波和/或超声，微波、超声可调控介孔羟基磷灰石的形貌。
本发明的技术效果：本发明通过调节反应体系的pH、原料成分、反应时间、反应温度等条件可以制备一系列形貌各异的介孔羟基磷灰石。将含有羟基或羧基的水溶性维生素作为添加剂，在水热条件下参与羟基磷灰石的合成，羟基或羧基与钙离子结合，然后进入羟基磷灰石结构内，在水热反应过程中维生素高温一次性降解成小分子，小分子从磷灰石中脱落而形成孔隙。维生素大小均一，尺寸在介孔尺寸范围内，因此形成的孔洞同样大小均一，尺寸会落入到介孔尺寸范围内，这样就达到了调控羟基磷灰石微观结构的目的。水热反应在常规的水热反应釜中进行，可结合微波、超声等外在条件调控介孔羟基磷灰石的形貌。本发明工艺简单、无特殊设备要求、成本低廉、原料简单易得、适用于规模化生产。制得的介孔羟基磷灰石具有高比表面积，在药物传输、组织工程、骨缺损修复、分离提纯和污水处理等领域得到了广泛地应用。
附图说明
图1是实施例1制备的介孔羟基磷灰石XRD图，与羟基磷灰石标准峰对比发现，两者一致，表明本发明制备的产物含有羟基磷灰石成分。
图2是实施例1制备的介孔羟基磷灰石TEM图，图2表明实验获得了介孔羟基磷灰石。
图3是实施例2制备的介孔羟基磷灰石TEM图，图3表明实验获得了介孔羟基磷灰石。
图4是实施例3制备的梭形羟基磷灰石TEM图，由于六偏磷酸钠是逐步水解的，水解过程不容易控制，水解后形成的缺陷就无法控制，水溶性维生素调控形貌的作用在一定程度上弥补了多磷酸盐所造成的缺陷，但制备的介孔羟基磷灰石结构并不理想。
图5是对比实施例1制备的羟基磷灰石TEM图，图5表明不添加维生素无法得到介孔结构的羟基磷灰石。
图6是对比实施例2制备的羟基磷灰石TEM图，实施例2中添加的维生素不含羟基或羧基，图6表明获得的羟基磷灰石不含介孔结构。
具体实施方式
实施例1
将0.74g氢氧化钙、0.85g磷酸氢二钠和0.005克维生素C加到去离子水中形成500mL溶液A，搅拌5分钟。用1M NaOH调节溶液A的pH值为10，将溶液A置于水热反应釜中，水热加热温度为120℃，反应2小时。反应后过滤收集产物，水洗，60℃空气干燥后获得介孔羟基磷灰石。
实施例2
将0.74g氢氧化钙、0.85g磷酸氢二钠和0.05克维生素C加到去离子水中形成500mL溶液A，搅拌5分钟。用1M NaOH调节溶液A的pH值为10，将溶液A置于水热反应釜中，水热加热温度为120℃，反应2小时。反应后过滤收集产物，水洗，60℃空气干燥后获得介孔羟基磷灰石。
实施例3
将0.74g氢氧化钙、1.02g六偏磷酸钠和0.005克维生素C加到去离子水中形成500mL溶液A，搅拌5分钟。用1M NaOH调节溶液A的pH值为10，将溶液A置于水热反应釜中，水热加热温度为120℃，反应4小时。反应后过滤收集产物，水洗，60℃空气干燥后获得梭形羟基磷灰石。
实施例4
将0.74g氢氧化钙、0.85g磷酸氢二钠和0.005克维生素C加到去离子水中形成500mL溶液A，搅拌5分钟。用1M NaOH调节溶液A的pH值为10，将溶液A置于微波水热反应釜中，反应1小时。反应后过滤收集产物，水洗，60℃空气干燥后获得介孔羟基磷灰石。
实施例5
将0.74g氢氧化钙、0.85g磷酸氢二钠和0.005克维生素C加到去离子水中形成500mL溶液A，搅拌5分钟。用1M NaOH调节溶液A的pH值为10，将溶液A置于超声辅助水热反应釜中，反应2小时。反应后过滤收集产物，水洗，60℃空气干燥后获得介孔羟基磷灰石。
实施例6
将0.74g氢氧化钙、0.85g磷酸氢二钠和0.01克维生素B2加到去离子水中形成500mL溶液A，搅拌5分钟。用1M NaOH调节溶液A的pH值为10，将溶液A置于水热反应釜中，水热加热温度为120℃，反应2小时。反应后过滤收集产物，水洗，60℃空气干燥后获得介孔羟基磷灰石。
对比实施例1
将0.74g氢氧化钙、0.85g磷酸氢二钠加到去离子水中形成500mL溶液A，搅拌5分钟。用1M NaOH调节溶液A的pH值为10，将溶液A置于水热反应釜中，水热加热温度为120℃，反应2小时。反应后过滤收集产物，水洗，60℃空气干燥后获得实心棒状羟基磷灰石。
对比实施例2
将0.74g氢氧化钙、0.85g磷酸氢二钠和0.005g克维生素K1加到去离子水中形成500mL溶液A，搅拌5分钟。用1M NaOH调节溶液A的pH值为10，将溶液A置于水热反应釜中，水热加热温度为120℃，反应2小时。反应后过滤收集产物，水洗，60℃空气干燥后获得实心棒状羟基磷灰石。其中，维生素K1不含羟基或羧基。
Claims (6)
1.一种介孔羟基磷灰石规模化的制备方法，其特征在于，所述制备方法具体操作为：
(1)使用可溶性钙盐作为钙源，磷酸或磷酸盐作为磷源，去离子水作为溶剂，将钙源、磷源和含有羟基或羧基的水溶性维生素按照钙元素、磷元素和水溶性维生素摩尔比为1～2：1：0.001～0.1加入到去离子水中混合均匀，记为溶液A；
(2)调节溶液A的pH值为6～12，60～200℃条件下在水热反应釜中水热反应1～24小时，过滤、水洗并在50～80℃空气氛围下干燥所得沉淀物，制得介孔羟基磷灰石。
2.如权利要求1所述的介孔羟基磷灰石规模化的制备方法，其特征在于，步骤(1)中可溶性钙盐为氯化钙和/或其水合物、硝酸钙和/或其水合物、乙酸钙和/或其水合物、氧化钙、氢氧化钙中的一种或几种；步骤(1)中磷酸盐为磷酸氢二铵、磷酸二氢铵、磷酸氢二钠、磷酸二氢钠、磷酸氢二钾、磷酸二氢钾、焦磷酸钠、三聚磷酸钠、六偏磷酸钠中的一种或几种；步骤(1)中水溶性维生素为维生素C、维生素B1、维生素B2、维生素B6、维生素B12、烟酸、泛酸、叶酸、肌醇中的一种或几种。
3.如权利要求1所述的介孔羟基磷灰石规模化的制备方法，其特征在于，步骤(1)中钙源摩尔浓度为0.01～1摩尔/升；步骤(1)中磷源摩尔浓度为0.01～1摩尔/升；步骤(1)中水溶性维生素质量浓度为0.001-0.01克/升。
4.如权利要求1所述的介孔羟基磷灰石规模化的制备方法，其特征在于，步骤(2)中调节溶液A的pH值为7-12。
5.如权利要求1所述的介孔羟基磷灰石规模化的制备方法，其特征在于，步骤(2)中水热反应温度为100-160℃；步骤(2)中水热反应时间为2-8小时。
6.如权利要求1所述的介孔羟基磷灰石规模化的制备方法，其特征在于，步骤(2)中水热反应条件为微波和/或超声。
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