CN116371350A - Preparation method of hydroxyapatite-loaded defluorination adsorbent and defluorination adsorbent - Google Patents
Preparation method of hydroxyapatite-loaded defluorination adsorbent and defluorination adsorbent Download PDFInfo
- Publication number
- CN116371350A CN116371350A CN202310272688.8A CN202310272688A CN116371350A CN 116371350 A CN116371350 A CN 116371350A CN 202310272688 A CN202310272688 A CN 202310272688A CN 116371350 A CN116371350 A CN 116371350A
- Authority
- CN
- China
- Prior art keywords
- hydroxyapatite
- solution
- mixed
- adsorbent
- defluorination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 64
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 62
- 239000003463 adsorbent Substances 0.000 title claims abstract description 47
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011259 mixed solution Substances 0.000 claims abstract description 52
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000008247 solid mixture Substances 0.000 claims abstract description 32
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 25
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 24
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 24
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 24
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 24
- 229960004853 betadex Drugs 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 21
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 19
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 19
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims description 39
- 229910052731 fluorine Inorganic materials 0.000 claims description 39
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 30
- -1 amine bicarbonate Chemical class 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000002351 wastewater Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 229960004887 ferric hydroxide Drugs 0.000 description 8
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The application relates to a preparation method of a hydroxyapatite-loaded defluorination adsorbent and the defluorination adsorbent, and the method comprises the following steps: s100, proportionally obtaining beta-cyclodextrin and high polymer polyethylene glycol, and mixing to prepare a first mixed solution; s200, after the calcium nitrate and the manganese nitrate are obtained in proportion, prefabricating a mixed aqueous solution of the calcium nitrate and the manganese nitrate, and mixing the mixed aqueous solution with the first mixed solution according to a preset proportion; s300, obtaining ammonium bicarbonate solution, and dropwise adding the ammonium bicarbonate solution into the mixed solution obtained in the step S200 to prepare a solid mixture; s400, drying and calcining the solid mixture to obtain the hydroxyapatite-loaded defluorination adsorbent. The supported hydroxyapatite defluorination adsorbent prepared by the preparation method is in a thorn sphere shape, has a thorn sphere hollow structure formed by nano short rod clusters, namely has a larger specific surface area, and the defluorination efficiency and the adsorption capacity are both obviously improved.
Description
Technical Field
The application relates to the field of defluorination adsorbents, in particular to a preparation method of a hydroxyapatite-loaded defluorination adsorbent and the defluorination adsorbent.
Background
Fluorine is one of the microelements necessary for human body, and the optimal concentration in drinking water is 0.5-1mg/L. When the intake of fluorine ions in a human body is small for a long period of time, caries is liable to occur, but if the intake of fluorine ions is excessive for a long period of time, the human body health is impaired, for example, long-term intake of water with a high fluorine ion content causes chronic diseases of the whole body represented by dental fluorosis, fluorimatosis and the like, and even damages to the brain nervous system of the human body.
The discharge of fluorine-containing wastewater in China has strict regulations, wherein the wastewater discharge standard regulated in GB8978-1996 integrated wastewater discharge standard clearly requires that the fluoride mass concentration is lower than 10mg/L, and the discharge standard of inorganic chemical enterprises is more strict, and particularly requires that the fluoride mass concentration in discharged wastewater is lower than 6mg/L, so that the efficient and simple fluorine removal process is always the research focus in the fields of domestic and foreign environmental protection and sanitation.
At present, various adsorbents for adsorbing and removing fluorine are available, such as natural zeolite, bone charcoal, resin, activated alumina, hydroxyapatite and the like, wherein the hydroxyapatite is used as a novel fluorine removing filter material, has the advantages of no toxicity, no pollution, reusability and the like, and is widely applied to the field of wastewater fluorine removal, in particular to the field of drinking water fluorine removal. The method is characterized in that aluminum or magnesium loaded hydroxyapatite is generally adopted to prepare a defluorination filter material, the defluorination capacity of the hydroxyapatite is pre-improved, fluoride ions in water are removed, but the effluent of the activated alumina adsorbent can remain aluminum ions, secondary pollution is easy to cause, the method is particularly unsuitable for defluorination of drinking water, and the magnesium doped hydroxyapatite is not essentially improved in structure although the adsorption capacity of the hydroxyapatite is improved.
Disclosure of Invention
In view of this, the present application proposes a method for preparing a hydroxyapatite-loaded defluorinated adsorbent, comprising the steps of:
s100, proportionally obtaining beta-cyclodextrin and high polymer polyethylene glycol, and mixing to prepare a first mixed solution;
s200, after the calcium nitrate and the manganese nitrate are obtained in proportion, prefabricating a mixed aqueous solution of the calcium nitrate and the manganese nitrate, and mixing the prepared mixed aqueous solution with the first mixed solution according to a preset proportion;
s300, obtaining ammonium bicarbonate solution, and dropwise adding the ammonium bicarbonate solution into the mixed solution obtained in the step S200 to obtain a solid mixture;
s400, drying and calcining the solid mixture to obtain the hydroxyapatite-loaded defluorinated adsorbent.
In one possible implementation manner, in step S100, the β -cyclodextrin and the high molecular polyethylene glycol are obtained in proportion and then mixed to prepare a first mixed solution, which includes:
s110, according to the mole ratio of 1:1, obtaining beta-cyclodextrin and high molecular polyethylene glycol according to the proportion;
s120, mixing the beta-cyclodextrin and the high polymer polyethylene glycol, and stirring for 0.5h at the constant temperature of 37 ℃;
and S130, adjusting the pH value of the mixed solution of the beta-cyclodextrin and the high polymer polyethylene glycol obtained in the step 120 by using an ammonia water solution to obtain a first mixed solution.
In one possible implementation manner, in step S200, after the calcium nitrate and the manganese nitrate are obtained in proportion, a mixed aqueous solution of the calcium nitrate and the manganese nitrate is prepared and mixed with the first mixed solution according to a preset proportion, including:
s210, calcium nitrate and manganese nitrate are obtained, wherein the mass ratio of the calcium to the manganese is 1: (0.1-0.3);
s220, preparing a mixture of calcium nitrate and manganese nitrate obtained in the step S210 into a mixed aqueous solution, and mixing the mixed aqueous solution with the first mixed solution according to a volume ratio of 1: (2-5) uniformly stirring and mixing at a preset temperature.
In a possible implementation manner, in step S300, an ammonium bicarbonate solution is obtained, and the ammonium bicarbonate is added dropwise to the mixed solution obtained in step S200 according to a preset ratio, so as to obtain a solid mixture, which includes:
s310, obtaining an amine bicarbonate solution;
s320, dropwise adding the ammonium bicarbonate solution into the mixed solution obtained in the step S200, wherein the molar ratio of calcium to phosphorus is 1.67;
s330, continuously stirring for 2-5 hours after the dripping is completed, so as to obtain a solid mixture.
In one possible implementation, in step S400, drying and calcining the solid mixture to obtain the hydroxyapatite-loaded defluorinated adsorbent comprises:
s410, drying the solid mixture under a preset drying condition to obtain a dried material;
and S420, calcining the dried material under a preset calcining condition, and calcining to obtain the hydroxyapatite-loaded defluorinated adsorbent.
In one possible implementation manner, in step S410, the preset drying condition is:
the drying temperature is 50 ℃;
the drying time was 2h.
In one possible implementation manner, in step S420, the preset calcining conditions are:
the calcination temperature is 200-600 ℃;
the calcination time is 1-5h.
In one possible implementation, in step S130, the ammonia solution is an ammonia solution (1+2).
According to another aspect of the application, a hydroxyapatite-loaded defluorination adsorbent is provided, and the hydroxyapatite-loaded defluorination adsorbent is prepared by adopting the preparation method of any one of the hydroxyapatite-loaded defluorination adsorbents.
The beneficial effects of this application:
the hydroxyapatite prepared by the preparation method is in a thorn sphere shape, has a thorn sphere hollow structure formed by nano short rod clusters, namely has larger specific surface area, and the defluorination efficiency and the adsorption capacity are both obviously improved. Specifically, beta-cyclodextrin and high molecular polyethylene glycol are mixed to prepare a first mixed solution, calcium nitrate and manganese nitrate are mixed to prepare a mixed aqueous solution, and then the mixed aqueous solution and the first mixed solution are mixed according to the method, and manganese is doped to distort the structure of hydroxyapatite, so that the crystal defect is increased, the crystallinity is reduced, the specific surface area is increased, and the adsorption capacity are improved. Furthermore, on one hand, as the hydroxyapatite is loaded with manganese, iron ions in the water body can be removed while removing fluorine, ferric hydroxide precipitates are formed with the iron ions, and the ferric hydroxide can further enhance the removal of fluorine ions, so that the fluorine removal effect is better. On the other hand, the loaded hydroxyapatite prepared by the method is not an aluminum material, is nontoxic and pollution-free, and cannot cause the phenomenon that the content of aluminum ions in water exceeds the standard so as to cause secondary pollution of water.
Other features and aspects of the present application will become apparent from the following detailed description of exemplary embodiments, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate exemplary embodiments, features and aspects of the present application and together with the description, serve to explain the principles of the present application.
FIG. 1 shows a flow chart of a preparation method of a supported hydroxyapatite fluorine removal agent according to an embodiment of the application;
fig. 2 shows SEM images of the loaded hydroxyapatite of the examples of the present application.
Detailed Description
Various exemplary embodiments, features and aspects of the present application will be described in detail below with reference to the accompanying drawings. In the drawings, like reference numbers indicate identical or functionally similar elements. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
It should be understood, however, that the terms "center," "longitudinal," "transverse," "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counter-clockwise," "axial," "radial," "circumferential," and the like indicate or are based on the orientation or positional relationship shown in the drawings, and are merely for convenience of description or to simplify the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be configured and operated in a particular orientation, and therefore should not be construed as limiting the present application.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
In addition, numerous specific details are set forth in the following detailed description in order to provide a better understanding of the present application. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In some instances, methods, means, elements, and circuits have not been described in detail as not to unnecessarily obscure the present application.
As shown in fig. 1, the preparation method of the hydroxyapatite-loaded defluorination adsorbent comprises the following steps:
s100, proportionally obtaining beta-cyclodextrin and high polymer polyethylene glycol, and mixing to prepare a first mixed solution;
s200, after the calcium nitrate and the manganese nitrate are obtained in proportion, prefabricating a mixed aqueous solution of the calcium nitrate and the manganese nitrate, and mixing the prepared mixed aqueous solution with the first mixed solution according to a preset proportion;
s300, obtaining ammonium bicarbonate solution, and dropwise adding the ammonium bicarbonate solution into the mixed solution obtained in the step S200 to obtain a solid mixture;
s400, drying and calcining the solid mixture to obtain the hydroxyapatite-loaded defluorinated adsorbent.
In the embodiment, the hydroxyapatite prepared by the preparation method is in a thorn sphere shape as shown in fig. 2, has a thorn sphere hollow structure formed by clustering nano short rods, namely has larger specific surface area, obviously improves the fluorine removal efficiency and the adsorption capacity, can adsorb more fluorine ions in the process of contacting fluorine-containing wastewater, and achieves the purpose of removing fluorine ions in water. Specifically, beta-cyclodextrin and high polymer polyethylene glycol are mixed to prepare a first mixed solution, calcium nitrate and manganese nitrate are mixed to prepare a mixed aqueous solution, and then the mixed aqueous solution and the first mixed solution are mixed according to a preset proportion, wherein the preset proportion of the first mixed solution and the mixed aqueous solution is that the volume ratio is 1: (2-5) the structure of the hydroxyapatite is distorted by doping manganese, the crystal defect is increased, the crystallinity is reduced, the specific surface area is increased, more fluoride ions are adsorbed, and meanwhile, the defluorination time is shorter, namely, the adsorption capacity and the adsorption capacity are effectively improved. Furthermore, as the hydroxyapatite is loaded with manganese, iron ions in the water body can be removed while removing fluorine, ferric hydroxide precipitates are formed with the iron ions, the removal of fluorine ions can be further enhanced by the ferric hydroxide, the fluorine removal effect is better, and the higher fluorine removal amount is maintained. The method has the advantages that the loaded hydroxyapatite defluorination adsorbent prepared by the preparation method does not contain aluminum, secondary pollution to the water body in the defluorination process is avoided, and the phenomenon that residues exist in the water body after defluorination by using activated alumina is prevented.
In one possible implementation manner, in step S100, the β -cyclodextrin and the high molecular polyethylene glycol are obtained in proportion and then mixed to prepare a first mixed solution, which includes:
s110, according to the mole ratio of 1:1, obtaining beta-cyclodextrin and high molecular polyethylene glycol according to the proportion;
s120, mixing the beta-cyclodextrin and the high polymer polyethylene glycol, and stirring for 0.5h at the constant temperature of 37 ℃;
and S130, adjusting the pH value of the mixed solution of the beta-cyclodextrin and the high polymer polyethylene glycol obtained in the step 120 by using an ammonia water solution to obtain a first mixed solution.
In this example, the molar ratio is 1:1, adding water after the beta-cyclodextrin and the high polymer polyethylene glycol are obtained, stirring for 0.5h through a constant temperature water bath, wherein the specific constant temperature water bath temperature is 37 ℃, and stirring through the constant temperature water bath to ensure that the beta-cyclodextrin and the high polymer polyethylene glycol can be fully and uniformly mixed. The pH value of the mixed beta-cyclodextrin and high polymer polyethylene glycol is adjusted to 9-11 by adopting ammonia water to prepare a first mixed solution, and the first mixed solution is prepared by adopting 1+2 ammonia water for adjusting the pH value, namely an ammonia water solution obtained by uniformly mixing one part of concentrated ammonia water with two parts of distilled water.
In one possible implementation manner, in step S200, after the calcium nitrate and the manganese nitrate are obtained in proportion, a mixed aqueous solution of the calcium nitrate and the manganese nitrate is prepared and mixed with the first mixed solution according to a preset proportion, including:
s210, calcium nitrate and manganese nitrate are obtained, wherein the mass ratio of the calcium to the manganese is 1: (0.1-0.3);
s220, preparing a mixture of calcium nitrate and manganese nitrate obtained in the step S210 into a mixed aqueous solution, and mixing the mixed aqueous solution with the first mixed solution according to a volume ratio of 1: (2-5) uniformly stirring and mixing at a preset temperature.
In the embodiment, calcium nitrate and manganese nitrate are obtained according to a specific proportion, wherein in a mixed aqueous solution of the calcium nitrate and the manganese nitrate, the mass ratio of the calcium to the manganese is 1:0.1-0.3, the prepared mixed aqueous solution is mixed with the first mixed solution, and the volume ratio of the first mixed solution to the mixed aqueous solution is 1:2-5, and simultaneously stirring rapidly at 50-90 ℃ to ensure that the first mixed solution and the mixed aqueous solution can be fully mixed. It is specially stated that the calcium nitrate and the manganese nitrate are selected to prepare the mixed aqueous solution in the preparation process, so that on one hand, raw materials are convenient to obtain, and on the other hand, the manganese is doped to distort the structure of the hydroxyapatite, so that the lattice defect is increased, the specific surface area is increased, more fluorine ions can be adsorbed in the same time, and the fluorine removal effect and fluorine removal efficiency are essentially improved. It should be noted that manganese can remove iron ions in the water body additionally while removing fluorine, so as to form ferric hydroxide precipitate, and the removal of fluorine ions is further enhanced through ferric hydroxide.
In a possible implementation manner, in step S300, an ammonium bicarbonate solution is obtained, and the ammonium bicarbonate is added dropwise to the mixed solution obtained in step S200 according to a preset ratio, so as to obtain a solid mixture, which includes:
s310, obtaining an amine bicarbonate solution;
s320, dropwise adding the ammonium bicarbonate solution into the mixed solution obtained in the step S200, wherein the molar ratio of calcium to phosphorus is 1.67;
s330, continuously stirring for 2-5 hours after the dripping is completed, so as to obtain a solid mixture.
Further, in one possible implementation, in step S400, drying and calcining the solid mixture to obtain the hydroxyapatite-loaded defluorinated adsorbent includes:
s410, drying the solid mixture under a preset drying condition to obtain a dried material;
and S420, calcining the dried material under a preset calcining condition, and calcining to obtain the hydroxyapatite-loaded defluorinated adsorbent.
Further, in step S410, the preset drying conditions are:
the drying temperature is 50 ℃;
the drying time was 2h.
Further, in step S420, the preset calcining conditions are:
the calcination temperature is 200-600 ℃;
the calcination time is 1-5h.
In this embodiment, the ammonium bicarbonate solution is added dropwise to the mixture of the first mixture and the mixed aqueous solution, and it should be noted that the specific amount of the added ammonium bicarbonate solution needs to ensure that the molar ratio of calcium to phosphorus in the mixture is 1.67:1, continuing stirring for 2-5h after the completion of the dripping, and obtaining a solid mixture. And (3) carrying out forced air drying on the solid mixture in an oven, specifically setting the temperature of the oven to be 50 ℃, drying for 2 hours, then placing the dried solid mixture in a muffle furnace for calcining at the temperature of 200-600 ℃ for 1-5 hours, and obtaining the hydroxyapatite-loaded defluorination adsorbent after calcining.
In one possible implementation, in step S130, the ammonia solution is an ammonia solution (1+2).
In summary, by using the preparation method of the supported hydroxyapatite defluorination adsorbent, the prepared supported hydroxyapatite defluorination adsorbent is not an aluminum material, is nontoxic and pollution-free, and cannot cause the phenomenon that the aluminum ion content in water exceeds the standard to cause secondary pollution of water. Meanwhile, the hydroxyapatite prepared by the bionic method is in a thorn spherical hollow structure, the structure of the hydroxyapatite is distorted by doping manganese, the lattice defects are increased, the cleanliness is reduced, the hydroxyapatite has larger specific surface area, the adsorption capacity and the adsorption capacity are improved, and the defluorination effect is better. The hydroxyapatite is loaded with manganese, iron ions in the water body can be removed in the defluorination process, ferric hydroxide precipitates are generated, and the ferric hydroxide further enhances the removal of the fluorine ions. The preparation method is simple in process, raw materials are easy to obtain, and industrial production is convenient to carry out.
Further description will be provided below with reference to specific examples.
Example 1
(1) The molar ratio is 1:1, adding water to mix after beta-cyclodextrin and high polymer polyethylene glycol are obtained in proportion, stirring for 0.5h through a constant temperature water bath at 37 ℃, and adjusting the pH value to 11 through 1+2 ammonia water to prepare a first mixed solution;
(2) According to m Ca :m Mn Preparing a mixed aqueous solution of calcium nitrate and manganese nitrate in a ratio of=1:0.2;
(3) Mixing the first mixed solution and the mixed aqueous solution according to the volume ratio of 1:3, rapidly stirring at 90 ℃, and simultaneously dropwise adding a certain amount of ammonium hydrogen phosphate solution to ensure that the molar ratio of calcium to phosphorus in the mixed solution is 1.67:1, continuing stirring for 2 hours after the dripping is completed to obtain a solid mixture;
(4) And (3) drying the obtained solid mixture in a 50 ℃ oven for 2 hours in a blowing way, and then placing the dried solid mixture in a 600 ℃ muffle furnace for roasting for 5 hours to obtain the hydroxyapatite-loaded defluorinated adsorbent.
The fluorine-containing wastewater after the ferric salt precipitation treatment was removed by using the hydroxyapatite-loaded defluorination adsorbent prepared in example 1. The concentration of the fluoride ions of the effluent after being adsorbed by the adsorbent in the embodiment 1 meets the national emission standard, and meanwhile, the residual iron ions in the primary treatment can be removed, and compared with the adsorption of active alumina, the effluent is clear and has no yellowing problem.
Example 2
(1) The molar ratio is 1:1, adding water to mix after beta-cyclodextrin and high polymer polyethylene glycol are obtained in proportion, stirring for 0.5h through a constant temperature water bath at 37 ℃, and adjusting the pH value to 10 through 1+2 ammonia water to prepare a first mixed solution;
(2) According to m Ca :m Mn Preparing a mixed aqueous solution of calcium nitrate and manganese nitrate in a ratio of=1:0.3;
(3) Mixing the first mixed solution and the mixed aqueous solution according to the volume ratio of 1:2, rapidly stirring at 70 ℃, and simultaneously dropwise adding a certain amount of ammonium hydrogen phosphate solution to ensure that the molar ratio of calcium to phosphorus in the mixed solution is 1.67:1, continuously stirring for 4 hours after the dripping is completed to obtain a solid mixture;
(4) And (3) drying the obtained solid mixture in a 50 ℃ oven for 2 hours in a blowing way, and then placing the dried solid mixture in a 400 ℃ muffle furnace for roasting for 5 hours to obtain the hydroxyapatite-loaded defluorinated adsorbent.
Compared with the method of removing fluoride ions in wastewater by adopting coagulating sedimentation, resin adsorption defluorination, bipolar membrane and electrodialysis, the method of removing fluoride ions in wastewater by using the supported hydroxyapatite defluorination adsorbent prepared in the embodiment 2 effectively solves the problems that aluminum ions of defluorination resin fall off, aluminum hydroxide generated when sodium hydroxide is encountered in the acid-base preparation stage of the bipolar membrane after electrodialysis concentration, so that the effluent of the alkali solution end of the bipolar membrane is turbid, the defluorination of wastewater by using the defluorination agent in the embodiment 2 has no aluminum ion residue, and the process is normal.
Example 3
(1) The molar ratio is 1:1, adding water to mix after beta-cyclodextrin and high polymer polyethylene glycol are obtained in proportion, stirring for 0.5h through a constant temperature water bath at 37 ℃, and adjusting the pH value to 11 through 1+2 ammonia water to prepare a first mixed solution;
(2) According to m Ca :m Mn Preparing a mixed aqueous solution of calcium nitrate and manganese nitrate in a ratio of=1:0.3;
(3) Mixing the first mixed solution and the mixed aqueous solution according to the volume ratio of 1:4, rapidly stirring at 80 ℃, and simultaneously dropwise adding a certain amount of ammonium hydrogen phosphate solution to ensure that the molar ratio of calcium to phosphorus in the mixed solution is 1.67:1, continuing stirring for 2 hours after the dripping is completed to obtain a solid mixture;
(4) And (3) drying the obtained solid mixture in a 50 ℃ oven for 2 hours in a blowing way, and then placing the dried solid mixture in a 200 ℃ muffle furnace for roasting for 5 hours to obtain the hydroxyapatite-loaded defluorinated adsorbent.
Compared with activated alumina, the supported hydroxyapatite defluorinating agent prepared in the embodiment 3 is used for defluorinating, the defluorinating agent in the embodiment 3 is used for adsorbing and defluorinating, the fluorine content of the effluent meets the recycling standard, the defluorinating efficiency is greatly improved, and the regeneration interval of the filter material is prolonged by more than five times.
The performance comparison of the modified load bionic hydroxyapatite with the existing hydroxyapatite, activated alumina, natural zeolite, bone charcoal and other defluorination filter materials is shown in Table 1
As shown in Table 1, the fluorine removal capacity of the supported hydroxyapatite fluorine removal adsorbent prepared by the preparation method is 9.0-20mg/L, the fluorine removal time is 5-10min, the fluorine content of the treated effluent meets the standard, namely, the fluorine removal time is shorter under the condition of ensuring better fluorine removal capacity, the stability and the safety are good, on one hand, the water outlet efficiency is high, on the other hand, the operation cost is low, the production cost can be effectively saved, and the supported hydroxyapatite fluorine removal adsorbent is put into industrial operation. Compared with the prior unmodified hydroxyapatite, the method has the advantages of shorter defluorination time, better defluorination capacity, namely substantially improved defluorination efficiency and adsorption capacity, and higher water outlet efficiency, and the defluorination effect and efficiency are far superior to those of the prior unmodified hydroxyapatite.
The application provides a defluorination adsorbent prepared by the preparation method of the loaded hydroxyapatite defluorination agent.
The embodiments of the present application have been described above, the foregoing description is exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the improvement of technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (9)
1. The preparation method of the hydroxyapatite-loaded defluorination adsorbent is characterized by comprising the following steps of:
s100, proportionally obtaining beta-cyclodextrin and high polymer polyethylene glycol, and mixing to prepare a first mixed solution;
s200, after the calcium nitrate and the manganese nitrate are obtained in proportion, prefabricating a mixed aqueous solution of the calcium nitrate and the manganese nitrate, and mixing the prepared mixed aqueous solution with the first mixed solution according to a preset proportion;
s300, obtaining ammonium bicarbonate solution, and dropwise adding the ammonium bicarbonate solution into the mixed solution obtained in the step S200 to obtain a solid mixture;
s400, drying and calcining the solid mixture to obtain the hydroxyapatite-loaded defluorinated adsorbent.
2. The method for preparing the hydroxyapatite-supported defluorinated adsorbent according to claim 1, wherein in step S100, the β -cyclodextrin and the high molecular polyethylene glycol are obtained in proportion and then mixed to prepare a first mixed solution, comprising:
s110, according to the mole ratio of 1:1, obtaining beta-cyclodextrin and high molecular polyethylene glycol according to the proportion;
s120, mixing the beta-cyclodextrin and the high polymer polyethylene glycol, and stirring for 0.5h at the constant temperature of 37 ℃;
and S130, adjusting the pH value of the mixed solution of the beta-cyclodextrin and the high polymer polyethylene glycol obtained in the step 120 by using an ammonia water solution to obtain a first mixed solution.
3. The method for preparing the hydroxyapatite-supported defluorinated adsorbent according to claim 1, wherein in step S200, after obtaining the calcium nitrate and the manganese nitrate in proportion, a mixed aqueous solution of the calcium nitrate and the manganese nitrate is prepared and mixed with the first mixed solution in a preset proportion, comprising:
s210, calcium nitrate and manganese nitrate are obtained, wherein the mass ratio of the calcium to the manganese is 1: (0.1-0.3);
s220, preparing a mixture of calcium nitrate and manganese nitrate obtained in the step S210 into a mixed aqueous solution, and mixing the mixed aqueous solution with the first mixed solution according to a volume ratio of 1: (2-5) uniformly stirring and mixing at a preset temperature.
4. The method for preparing the hydroxyapatite-supported defluorinated adsorbent according to claim 1, wherein in step S300, an ammonium bicarbonate solution is obtained, and the ammonium bicarbonate is added dropwise to the mixed solution obtained in step S200 according to a predetermined ratio, to prepare a solid mixture, comprising:
s310, obtaining an amine bicarbonate solution;
s320, dropwise adding the ammonium bicarbonate solution into the mixed solution obtained in the step S200, wherein the molar ratio of calcium to phosphorus is 1.67;
s330, continuously stirring for 2-5 hours after the dripping is completed, so as to obtain a solid mixture.
5. The method for producing a supported hydroxyapatite defluorinated adsorbent according to claim 1, wherein in step S400, the solid mixture is dried and then calcined to obtain a supported hydroxyapatite defluorinated adsorbent, comprising:
s410, drying the solid mixture under a preset drying condition to obtain a dried material;
and S420, calcining the dried material under a preset calcining condition, and calcining to obtain the hydroxyapatite-loaded defluorinated adsorbent.
6. The method of preparing a supported hydroxyapatite fluorine scavenger according to claim 5, wherein in step S410, the preset drying conditions are:
the drying temperature is 50 ℃;
the drying time was 2h.
7. The method of preparing a supported hydroxyapatite fluorine scavenger according to claim 5 wherein in step S420, said predetermined calcination conditions are:
the calcination temperature is 200-600 ℃;
the calcination time is 1-5h.
8. The method of preparing a supported hydroxyapatite fluorine scavenger according to claim 2 wherein in step S130 said aqueous ammonia solution is aqueous ammonia solution (1+2).
9. A hydroxyapatite-loaded defluorination adsorbent, characterized in that the hydroxyapatite-loaded defluorination adsorbent is prepared by the preparation method of any one of claims 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310272688.8A CN116371350A (en) | 2023-03-20 | 2023-03-20 | Preparation method of hydroxyapatite-loaded defluorination adsorbent and defluorination adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310272688.8A CN116371350A (en) | 2023-03-20 | 2023-03-20 | Preparation method of hydroxyapatite-loaded defluorination adsorbent and defluorination adsorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116371350A true CN116371350A (en) | 2023-07-04 |
Family
ID=86968596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310272688.8A Pending CN116371350A (en) | 2023-03-20 | 2023-03-20 | Preparation method of hydroxyapatite-loaded defluorination adsorbent and defluorination adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116371350A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268614A (en) * | 2016-10-18 | 2017-01-04 | 南京信息工程大学 | A kind of preparation method of magnesium hydroxyapatite adsorbent |
| CN106745628A (en) * | 2016-12-19 | 2017-05-31 | 中国矿业大学 | A kind of production method of carbon doping hydroxyapatite defluoridation filter material |
| US20200385270A1 (en) * | 2017-11-30 | 2020-12-10 | Solvay Sa | Hydroxyapatite composite for use in removal of contaminants from effluents and methods of making |
| CN113952919A (en) * | 2021-11-19 | 2022-01-21 | 西北师范大学 | Preparation method of manganese oxide coated hydroxyapatite nanowire |
| CN114057173A (en) * | 2021-09-13 | 2022-02-18 | 曲阜师范大学 | Method for synthesizing hydroxyapatite with large specific surface area by using seed crystal |
| CN114870792A (en) * | 2022-05-17 | 2022-08-09 | 华南理工大学 | Manganese-doped hydroxyapatite material and preparation method and application thereof |
| CN115708893A (en) * | 2022-09-08 | 2023-02-24 | 上海交通大学医学院附属第九人民医院 | Manganese-doped hydroxyapatite nanowire bioceramic, preparation method and application |
-
2023
- 2023-03-20 CN CN202310272688.8A patent/CN116371350A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268614A (en) * | 2016-10-18 | 2017-01-04 | 南京信息工程大学 | A kind of preparation method of magnesium hydroxyapatite adsorbent |
| CN106745628A (en) * | 2016-12-19 | 2017-05-31 | 中国矿业大学 | A kind of production method of carbon doping hydroxyapatite defluoridation filter material |
| US20200385270A1 (en) * | 2017-11-30 | 2020-12-10 | Solvay Sa | Hydroxyapatite composite for use in removal of contaminants from effluents and methods of making |
| CN114057173A (en) * | 2021-09-13 | 2022-02-18 | 曲阜师范大学 | Method for synthesizing hydroxyapatite with large specific surface area by using seed crystal |
| CN113952919A (en) * | 2021-11-19 | 2022-01-21 | 西北师范大学 | Preparation method of manganese oxide coated hydroxyapatite nanowire |
| CN114870792A (en) * | 2022-05-17 | 2022-08-09 | 华南理工大学 | Manganese-doped hydroxyapatite material and preparation method and application thereof |
| CN115708893A (en) * | 2022-09-08 | 2023-02-24 | 上海交通大学医学院附属第九人民医院 | Manganese-doped hydroxyapatite nanowire bioceramic, preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| 朱丹琛;肖秀峰;刘榕芳;傅涵萍;徐佳;王梅芳;: "以环糊精为模板水热合成羟基磷灰石", 人工晶体学报, no. 01, 15 February 2010 (2010-02-15), pages 223 - 229 * |
| 朱丹琛等: ""羟基磷灰石微球的仿生合成及除氟性能"", 《化学研究与应用》, 30 March 2019 (2019-03-30), pages 570 - 575 * |
| 窦妍;李东旭;曹丰;李延报;: "羟基磷灰石微球制备方法的研究进展", 材料导报, no. 2, 30 November 2010 (2010-11-30), pages 417 - 419 * |
| 肖东琴;匙峰;姚宁;张成栋;段可;翁杰;: "模板法制备羟基磷灰石纳米结构微球及其机制探讨", 生物化学与生物物理进展, no. 10, 4 December 2013 (2013-12-04), pages 50 - 62 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101007261B (en) | Zeolite adsorbent and its preparation method | |
| Rao et al. | Colour removal from a dyestuff industry effluent using activated carbon | |
| CN110372075B (en) | Efficient defluorination medicament and application thereof | |
| CN103212364A (en) | Ferro-manganese composite oxide as well as preparation method and application thereof in removing arsenic in water | |
| CN110193342A (en) | A kind of modified attapulgite earth adsorbing and preparation method thereof | |
| CN107096498B (en) | A kind of modified zeolite ball preparation method and application | |
| CN101306345A (en) | Impregnated activated carbon and its preparation method | |
| CN104138750A (en) | Method for deep dephosphorization by using embedded lanthanum oxide composite resin | |
| CN112093844A (en) | Nitrogen-removing water purifying agent and preparation method thereof | |
| CN111170400A (en) | Water quality substrate modifying agent, preparation method thereof and water quality substrate modifying method | |
| CN107970885A (en) | Compound ammonia nitrogen adsorbent prepared by a kind of microwave radiation method and preparation method thereof | |
| CN109231842A (en) | A kind of foamed glass material and preparation method thereof reducing water quality total phosphorus index | |
| US20030089665A1 (en) | Arsenic removal media | |
| CN108714412A (en) | A kind of preparation method of fluorine ion absorber | |
| CN109650545A (en) | A kind of compounded mix and its application for artificial swamp | |
| CN111450805A (en) | Chitosan-based lead ion imprinted adsorbent and preparation method thereof | |
| CN116371350A (en) | Preparation method of hydroxyapatite-loaded defluorination adsorbent and defluorination adsorbent | |
| CN115041152A (en) | Resin-based neodymium-loaded nanocomposite, preparation method thereof and application thereof in deep removal of phosphate radical in water | |
| CN101862644A (en) | Preparation method of Al-doped hydroxyapatite high-efficiency defluorinating adsorbent | |
| CN116102142B (en) | Efficient defluorinating agent and preparation method thereof | |
| CN1724362A (en) | Process for preparing fluorine reducing ion sieve of aquatic body | |
| JP4631425B2 (en) | Method and apparatus for treating fluorine-containing wastewater containing phosphoric acid | |
| CN108940225B (en) | Preparation method and application of sodium alginate/amino mesoporous silica gel spheres for low-concentration uranium-containing wastewater treatment | |
| CN106977034A (en) | A kind of method that hydrogen fluoride is reclaimed from high-concentration fluorine-containing waste water | |
| CN113332953B (en) | Novel phosphorus removing agent and preparation method and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |