CN115779856B - Hydroxyapatite/activated carbon composite defluorination material and preparation method thereof - Google Patents
Hydroxyapatite/activated carbon composite defluorination material and preparation method thereof Download PDFInfo
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- CN115779856B CN115779856B CN202211454756.4A CN202211454756A CN115779856B CN 115779856 B CN115779856 B CN 115779856B CN 202211454756 A CN202211454756 A CN 202211454756A CN 115779856 B CN115779856 B CN 115779856B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 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 118
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 117
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011737 fluorine Substances 0.000 claims abstract description 62
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 62
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 229960000892 attapulgite Drugs 0.000 claims abstract description 25
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 25
- 239000011265 semifinished product Substances 0.000 claims abstract description 19
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 104
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 52
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 239000001110 calcium chloride Substances 0.000 claims description 21
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 21
- BWTHZGPZSRARLU-UHFFFAOYSA-M [NH4+].[Cl-].[Ca+].OC([O-])=O Chemical compound [NH4+].[Cl-].[Ca+].OC([O-])=O BWTHZGPZSRARLU-UHFFFAOYSA-M 0.000 claims description 17
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 15
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 15
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 15
- 239000001099 ammonium carbonate Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 239000004927 clay Substances 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 239000011775 sodium fluoride Substances 0.000 description 5
- 235000013024 sodium fluoride Nutrition 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- 235000020188 drinking water Nutrition 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- -1 fluoride ions Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 208000020084 Bone disease Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
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- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002964 excitative effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
Classifications
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- 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
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a hydroxyapatite/activated carbon composite defluorination material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Adding activated carbon into the hydroxyapatite solution, stirring and mixing uniformly, adding attapulgite, continuously stirring at 60-90 ℃ for 30-60 min, extruding and forming, and drying to obtain a formed semi-finished product; wherein the mass ratio of the hydroxyapatite in the hydroxyapatite solution to the activated carbon is (0.2-5): 1, a step of; (2) Sintering the formed semi-finished product at 900-1000 ℃ for 120-180 min in inert atmosphere or nitrogen atmosphere to obtain the product. The composite fluorine removal material prepared by using the high fluorine adsorption capacity of the hydroxyapatite and the high pore structure of the activated carbon through adding the attapulgite with high adhesion and surface activity catalysis can produce synergistic fluorine removal effect, and the fluorine removal effect is good.
Description
Technical Field
The invention belongs to the technical field of defluorination materials, and particularly relates to a hydroxyapatite/activated carbon composite defluorination material and a preparation method thereof.
Background
Fluorine is one of the essential microelements in the human body, and a proper amount of fluorine is beneficial to the firmness of bones and teeth, reduces the incidence rate of dental caries, and has benefits on excitatory conduction of nervous system, parathyroid gland function, cellular enzyme system and reproduction process. However, excessive fluorine has carcinogenic and teratogenic effects, so that light people can cause fluorine spots on teeth, and heavy people can cause fluorine bone diseases, so that the health of human bodies is endangered. Thus, the World Health Organization (WHO) prescribes that the fluorine content in drinking water does not exceed 1.5mg/L, whereas according to China 'sanitary Standard for Drinking Water' (GB 5749-2006), it is prescribed that the fluoride concentration in drinking water should be less than 1.0mg/L. How to remove high concentrations of fluoride ions in drinking water has attracted considerable attention by researchers.
At present, the removal of fluoride ions mainly comprises chemical precipitation, electrolysis, ion exchange, adsorption removal and other methods. The chemical precipitation method has the defects that the process flow is complex, and more waste residues which are difficult to treat are generated; the electrolytic method has low selectivity and high energy consumption; the ion exchange method is simple to operate, the water consumption of regeneration is high, and the treatment difficulty of the regenerated waste liquid is high; the adsorption method is an important physicochemical method, and has been widely used in fluorine-containing water treatment due to simple operation and high efficiency, especially for removing low-concentration pollutants. The key point of the adsorption method for treating fluorine-containing water is to select proper adsorbents, and common adsorbents include metal oxide adsorbents, natural mineral adsorbents, biomass adsorbents, hydrotalcite-like adsorbents, ion exchange resin adsorbents, waste utilization adsorbents and the like.
Hydroxyapatite is a defluorinating agent which is researched more at present, has the advantages of convenience in synthesis, good defluorination effect and the like, and is widely applied to the adsorption treatment of fluorine-containing wastewater. However, when the single hydroxyapatite is used for the defluorination adsorbing material, the specific surface area is small, the contact with the polluted wastewater is insufficient, the defluorination effect is unfavorable, and the wide application is limited, so that the related art mainly uses the hydroxyapatite and modifies the hydroxyapatite to achieve the purpose of deep defluorination, but the cost of the material is still relatively high, the defluorination capacity is required to be further improved, the improvement of the defluorination capacity and the reduction of the cost are the perpetual subjects of the defluorination adsorbing material, and therefore, the development of the defluorination adsorbing material with better comprehensive performance is needed to be urgently developed.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a hydroxyapatite/activated carbon composite defluorination material and a preparation method thereof.
In one aspect, the embodiment of the invention provides a preparation method of a hydroxyapatite/activated carbon composite defluorination material, which comprises the following steps:
(1) Adding activated carbon into the hydroxyapatite solution, stirring and mixing uniformly, then adding attapulgite, continuously stirring at 60-90 ℃ for 30-60 min, extruding and forming, and drying to obtain a formed semi-finished product; wherein the mass ratio of the hydroxyapatite in the hydroxyapatite solution to the activated carbon is (0.2-5): 1, a step of;
(2) Sintering the molded semi-finished product at 900-1000 ℃ for 120-180 min in inert atmosphere or nitrogen atmosphere to obtain the hydroxyapatite/activated carbon composite defluorination material.
In the preparation method of the embodiment of the invention, the hydroxyapatite/activated carbon composite defluorination material is prepared by compositing the hydroxyapatite with activated carbon and adding attapulgite as a binder, wherein the hydroxyapatite has high fluorine adsorption capacity, the dispersity of the hydroxyapatite is greatly enhanced by the porous structure of the activated carbon, and the utilization rate of the hydroxyapatite is improved; the rare earth oxide in the attapulgite clay and the like can further enhance the fluorine removal capacity of the composite material, the three play a role in synergy, the prepared composite fluorine removal material has good fluorine removal effect and wide application range, the method has simple process, the used equipment is conventional equipment, the cost is low, and the method is easy for industrial production.
In some embodiments of the invention, the attapulgite clay is added in an amount of 10-30% of the sum of the mass of hydroxyapatite in the hydroxyapatite solution and the mass of activated carbon after activation;
further, the particle size of the attapulgite clay is 1-15 mu m.
In some embodiments of the present invention, the mass ratio of the hydroxyapatite in the hydroxyapatite solution and the activated carbon after activation is preferably (2 to 4): 1.
In some embodiments of the invention, the activated carbon has a particle size of 0.5 to 10 μm, preferably 0.5 to 2 μm; the pore diameter is2 to 10nm, preferably 2 to 5nm.
In some embodiments of the invention, the extrusion pressure is 0.3 to 0.5MPa, preferably 0.5MPa; the temperature is 30 to 60℃and preferably 50 ℃.
In some embodiments of the invention, the hydroxyapatite solution is prepared by a method comprising the steps of: s1, calcium chloride and phosphoric acid are adopted as raw materials, and the adding quality of the calcium chloride and the phosphoric acid is determined according to the molar ratio of the calcium to the phosphorus of (1.45-1.85) 1; s2, preparing a phosphoric acid solution according to the volume ratio of phosphoric acid to water being 1:3; s3, dissolving calcium chloride in water at 60-90 ℃ and keeping the water temperature to prepare 20-50 wt% of calcium chloride solution; dissolving ammonium bicarbonate into the prepared calcium chloride solution, and uniformly stirring to obtain a calcium chloride-ammonium bicarbonate solution; s4, dropwise adding the phosphoric acid solution into the calcium chloride-ammonium bicarbonate solution at the dropwise adding speed of 0.2L/h, continuously stirring, and then adding ammonia water to adjust the pH value of the reaction system to be kept in the range of 9-11 in real time; s5, continuously stirring for 30-90 min at normal temperature after the phosphoric acid solution is completely dripped, so as to obtain the hydroxyapatite solution;
in the step S4, the molar ratio of the ammonium bicarbonate in the calcium chloride-ammonium bicarbonate solution to the phosphoric acid in the phosphoric acid solution is (0.02-0.1): 1.
In some embodiments of the invention, the activated carbon is prepared by a process comprising the steps of: grinding and sieving commercial activated carbon serving as a raw material, roasting the commercial activated carbon in nitrogen atmosphere at 500-600 ℃ for 30-60 min, and cooling to obtain the activated carbon.
In some embodiments of the invention, the specific surface area of the commercial activated carbon is 1000-1800 m 2/g; the average pore diameter is 2-10 nm, preferably 2.5-5 nm; ash content is less than or equal to 2%, preferably less than or equal to 1.2%.
The embodiment of the invention also provides a hydroxyapatite/active carbon composite defluorination material, which is prepared by the preparation method of the hydroxyapatite/active carbon composite defluorination material.
The features and advantages described above for the preparation method of the hydroxyapatite/activated carbon composite defluorination material are also applicable to the hydroxyapatite/activated carbon composite defluorination material, and are not described herein.
The embodiment of the invention also provides an application of the hydroxyapatite/activated carbon composite defluorination material in the treatment of fluorine-containing wastewater.
The invention has the following advantages and beneficial effects: the embodiment of the invention utilizes the high fluorine adsorption capacity of the hydroxyapatite, and the prepared composite fluorine removal material can generate synergistic fluorine removal effect by adding attapulgite with high adhesion effect and surface activity catalysis effect by means of the high pore structure of activated carbon, so that the fluorine removal effect is better; the preparation method provided by the embodiment of the invention has the advantages of simple process, easiness in operation and low cost, and is beneficial to large-scale planning production and popularization and utilization.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without creative efforts, based on the described embodiments of the present invention belong to the protection scope of the present invention.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
In one aspect, the embodiment of the invention provides a preparation method of a hydroxyapatite/activated carbon composite defluorination material, which comprises the following steps:
(1) Adding activated carbon into the hydroxyapatite solution, stirring and mixing uniformly, then adding attapulgite, continuously stirring at 60-90 ℃ for 30-60 min, extruding and forming, and drying to obtain a formed semi-finished product; wherein the mass ratio of the hydroxyapatite in the hydroxyapatite solution to the activated carbon is (0.2-5): 1, a step of;
(2) Sintering the molded semi-finished product at 900-1000 ℃ for 120-180 min in inert atmosphere or nitrogen atmosphere to obtain the hydroxyapatite/activated carbon composite defluorination material.
In the preparation method of the embodiment of the invention, the hydroxyapatite/activated carbon composite defluorination material is prepared by compounding the hydroxyapatite with activated carbon and adding attapulgite as a binder and enhancing the wear resistance of the material by extrusion molding, wherein the hydroxyapatite has high fluorine adsorption capacity, the dispersity of the hydroxyapatite is greatly enhanced by the porous structure of the activated carbon, and the utilization rate of the hydroxyapatite is improved; the rare earth oxide in the attapulgite clay and the like can further enhance the fluorine removal capacity of the composite material, the three play a role in synergy, the prepared composite fluorine removal material has good fluorine removal effect and wide application range, the method has simple process, the used equipment is conventional equipment, the cost is low, and the method is easy for industrial production.
In some embodiments of the invention, the amount of attapulgite clay added is 10-30% (e.g., without limitation, 10%, 15%, 20%, 30%, etc.) of the sum of the mass of hydroxyapatite in the hydroxyapatite solution and the mass of activated carbon after activation;
Further, the particle size of the attapulgite clay is 1 to 15 μm (for example, but not limited to, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, etc.).
In some embodiments of the present invention, the mass ratio of the hydroxyapatite in the hydroxyapatite solution to the activated carbon after activation is preferably (2 to 4): 1 (for example, but not limited to, 2:1, 3:1, 4:1, etc.), the purpose is to fully distribute the hydroxyapatite in the pores of the activated carbon, enhance the contact with the fluoride ions in the water quality, and improve the utilization rate of the activated carbon.
In some embodiments of the invention, the activated carbon has a particle size of 0.5 to 10 μm (e.g., without limitation, 0.5 μm,2 μm, 5 μm, 8 μm, 10 μm, etc.), preferably 0.5 to 2 μm (e.g., without limitation, 0.5 μm, 1 μm,2 μm, etc.); the pore diameter is 2 to 10nm (for example, but not limited to, 2nm, 5nm, 8nm, 10nm, etc.), preferably 2 to 5nm (for example, but not limited to, 2nm, 3nm, 5nm, etc.).
In some embodiments of the invention, the extrusion pressure is 0.3 to 0.5MPa (e.g., without limitation, 0.3MPa, 0.4MPa, 0.5MPa, etc.), preferably 0.5MPa; the temperature is 30 to 60 ℃ (for example, but not limited to, 30 ℃, 45 ℃, 50 ℃, 60 ℃ and the like), preferably 50 ℃;
further, the particle size of the molded semi-finished product obtained after extrusion molding was 1mm.
In some embodiments of the invention, the hydroxyapatite solution is prepared by a method comprising the steps of: s1, calcium chloride and phosphoric acid are adopted as raw materials, and the adding quality of the calcium chloride and the phosphoric acid is determined according to the molar ratio of the calcium to the phosphorus of (1.45-1.85) 1; s2, preparing a phosphoric acid solution according to the volume ratio of phosphoric acid to water being 1:3; s3, dissolving calcium chloride in water at 60-90 ℃ and keeping the water temperature to prepare 20-50 wt% of calcium chloride solution; dissolving ammonium bicarbonate into the prepared calcium chloride solution, and uniformly stirring to obtain a calcium chloride-ammonium bicarbonate solution; s4, dropwise adding the phosphoric acid solution into the calcium chloride-ammonium bicarbonate solution at the dropwise adding speed of 0.2L/h, continuously stirring, and then adding ammonia water to adjust the pH value of the reaction system to be kept in the range of 9-11 in real time so as to ensure the purity and fluorine removal capacity of the product; s5, continuously stirring for 30-90 min at normal temperature after the phosphoric acid solution is added dropwise, and obtaining the hydroxyapatite solution.
In some embodiments of the invention, in the step S4, the molar ratio of the ammonium bicarbonate in the calcium chloride-ammonium bicarbonate solution to the phosphoric acid in the phosphoric acid solution is (0.02-0.1): 1; by adding a small amount of ammonium bicarbonate, the doping of CO 3 2- can lead to the distortion of crystal lattice of the hydroxyapatite, the vacancy concentration of the surface is correspondingly increased, and the structure becomes loose, so that the hydroxyapatite forms a state of vacancy, further the surface chemical activity of the hydroxyapatite is enhanced, and the fluorine removal capability of the hydroxyapatite is improved.
In some embodiments of the invention, activated carbon is prepared by a process comprising the steps of: commercial activated carbon is taken as a raw material, and is subjected to grinding and sieving, roasting for 30-60 min in nitrogen atmosphere at 500-600 ℃, and cooling to obtain activated carbon. The ash on the surface of the activated carbon and impurities adsorbed in the pores can be removed by roasting and activating the commercial activated carbon, so that unstable components in the activated carbon are removed, and the performance of the activated carbon can be fully exerted.
In some embodiments of the invention, the specific surface area of the commercial activated carbon is 1000-1800 m 2/g (e.g., without limitation, 1000m 2/g、1200m2/g、1500m2/g、1800m2/g, etc.); the average pore diameter is 2 to 10nm (for example, but not limited to, 2nm, 5nm, 8nm, 10nm, etc.), preferably 2.5 to 5nm (for example, but not limited to, 2.5nm, 3nm, 5nm, etc.); ash content is not more than 2% (for example, but not limited to, 0.5%, 1%, 1.2%, 2%, etc.), preferably not more than 1.2% (for example, but not limited to, 0.5%, 1%, 1.2%, etc.).
The embodiment of the invention also provides a hydroxyapatite/active carbon composite defluorination material, which is prepared by the preparation method of the hydroxyapatite/active carbon composite defluorination material.
The features and advantages described above for the preparation method of the hydroxyapatite/activated carbon composite defluorination material are also applicable to the hydroxyapatite/activated carbon composite defluorination material, and are not described herein.
The embodiment of the invention also provides an application of the hydroxyapatite/activated carbon composite defluorination material in the treatment of fluorine-containing wastewater.
The following non-limiting examples and comparative examples of the present invention are described: the solution of the comparative example is not prior art, but is provided for comparison with the solution of the examples only, and is not intended as a limitation of the invention; the raw materials referred to in examples and comparative examples, unless otherwise specified, were commercially available, wherein the commercial activated carbon in examples and comparative examples was coal crushed activated carbon, had a particle size of 4 to 8 mesh, an iodine value of 1500mg/g, and an abrasion resistance of 92%.
Example 1
A preparation method of a hydroxyapatite/activated carbon composite defluorination material comprises the following steps:
(1) Preparation of hydroxyapatite solution
S1, calcium chloride and phosphoric acid are adopted as raw materials, and the adding quality of the calcium chloride and the phosphoric acid is determined according to the molar ratio of the calcium to the phosphorus being 1.45:1;
S2, preparing a phosphoric acid solution according to the volume ratio of phosphoric acid to water being 1:3;
S3, dissolving 25g of calcium chloride in 100g of water at 90 ℃ and keeping the water temperature to prepare 20wt% of calcium chloride solution; then 0.28g of ammonium bicarbonate is dissolved into the prepared calcium chloride solution, and the mixture is stirred uniformly to obtain a calcium chloride-ammonium bicarbonate solution;
S4, dropwise adding 69mL of phosphoric acid solution into the calcium chloride-ammonium bicarbonate solution (wherein the molar ratio of the ammonium bicarbonate to the phosphoric acid is 0.02:1) at the dropwise adding speed of 0.2L/h, continuously stirring, and then adding ammonia water to adjust the pH value of the reaction system to be kept at 9.8 in real time;
S5, continuously stirring for 60min at normal temperature after the phosphoric acid solution is completely dripped, so as to obtain a hydroxyapatite solution;
(2) Preparation of activated carbon
Taking commercial activated carbon (the specific surface area is 1500m 2/g, the average pore diameter is 2.5nm, and the ash content is 1.2%) as a raw material, grinding, sieving activated carbon powder with the mesh size of below 200, roasting for 30min in nitrogen atmosphere at 600 ℃, and cooling to obtain activated carbon;
(3) Preparation of hydroxyapatite/activated carbon composite defluorination material
S1, adding 128g of activated carbon into a hydroxyapatite solution (wherein the mass ratio of the hydroxyapatite in the hydroxyapatite solution to the activated carbon is 0.2:1), stirring and mixing uniformly, then adding 15.4g of attapulgite clay with the thickness of 2 mu m (wherein the addition amount of attapulgite clay mineral is 10% of the sum of the mass of the hydroxyapatite in the hydroxyapatite solution and the mass of the activated carbon), continuously stirring at 90 ℃ for 30min, extruding and molding at 30 ℃ and 0.5MPa, and finally air-drying and drying at room temperature to obtain a molded semi-finished product;
S2, sintering the molded semi-finished product at 1000 ℃ for 120min under nitrogen atmosphere to obtain 169g of hydroxyapatite/activated carbon composite defluorination material.
The fluorine-containing wastewater with the fluorine concentration of 21.6mg/L is prepared by dissolving sodium fluoride in tap water, and the fluorine removal capacity of the composite fluorine removal material of the embodiment is measured, so that the result is 8.12mg/g, and the higher fluorine removal capacity is shown.
Example 2
A preparation method of a hydroxyapatite/activated carbon composite defluorination material comprises the following steps:
(1) Preparation of hydroxyapatite solution
S1, calcium chloride and phosphoric acid are adopted as raw materials, and the adding quality of the calcium chloride and the phosphoric acid is determined according to the molar ratio of the calcium to the phosphorus being 1.65:1;
S2, preparing a phosphoric acid solution according to the volume ratio of phosphoric acid to water being 1:3;
S3, dissolving 107g of calcium chloride in 75 ℃ water, and keeping the water temperature to prepare 35wt% of calcium chloride solution; then 2.63g of ammonium bicarbonate is dissolved into the prepared calcium chloride solution, and the mixture is stirred uniformly to obtain a calcium chloride-ammonium bicarbonate solution;
S4, dropwise adding 261mL of phosphoric acid solution into a calcium chloride-ammonium bicarbonate solution (wherein the molar ratio of the ammonium bicarbonate to the phosphoric acid is 0.05:1) at a dropwise adding rate of 0.2L/h, continuously stirring, and then adding ammonia water to adjust the pH value of a reaction system to be kept at 10.5 in real time;
s5, continuously stirring for 90min at normal temperature after the phosphoric acid solution is completely dripped, so as to obtain a hydroxyapatite solution;
(2) Preparation of activated carbon
Taking commercial activated carbon (the specific surface area is 1500m 2/g, the average pore diameter is 2.5nm, and the ash content is 1.2%) as a raw material, grinding, sieving activated carbon powder with the mesh size of below 200, roasting for 60min in nitrogen atmosphere at 600 ℃, and cooling to obtain activated carbon;
(3) Preparation of hydroxyapatite/activated carbon composite defluorination material
S1, adding 55.7g of activated carbon (wherein the mass ratio of the hydroxyapatite in the hydroxyapatite solution to the activated carbon is 2:1) into the hydroxyapatite solution, stirring and mixing uniformly, then adding 33g of attapulgite clay with the thickness of 15 mu m (wherein the addition amount of the attapulgite clay mineral is 20% of the sum of the mass of the hydroxyapatite in the hydroxyapatite solution and the mass of the activated carbon), continuously stirring at 75 ℃ for 30min, extruding and forming at 50 ℃ and 0.4MPa, and finally air-drying at room temperature to obtain a formed semi-finished product;
s2, sintering the molded semi-finished product at 1000 ℃ for 120min under nitrogen atmosphere to obtain 203g of hydroxyapatite/activated carbon composite defluorination material.
The fluorine-containing wastewater with the fluorine concentration of 21.6mg/L is prepared by dissolving sodium fluoride in tap water, and the fluorine removal capacity of the composite fluorine removal material of the embodiment is measured, so that the result is 9.86mg/g, and the higher fluorine removal capacity is shown.
Example 3
A preparation method of a hydroxyapatite/activated carbon composite defluorination material comprises the following steps:
(1) Preparation of hydroxyapatite solution
S1, calcium chloride and phosphoric acid are adopted as raw materials, and the adding quality of the calcium chloride and the phosphoric acid is determined according to the molar ratio of the calcium to the phosphorus being 1.85:1;
S2, preparing a phosphoric acid solution according to the volume ratio of phosphoric acid to water being 1:3;
S3, dissolving 150g of calcium chloride in water at 60 ℃, and keeping the water temperature to prepare a 50wt% calcium chloride solution; then 6.54g of ammonium bicarbonate is dissolved into the prepared calcium chloride solution, and the mixture is stirred uniformly to obtain a calcium chloride-ammonium bicarbonate solution;
S4, dropwise adding the phosphoric acid solution into the calcium chloride-ammonium bicarbonate solution (wherein the molar ratio of the ammonium bicarbonate to the phosphoric acid is 0.1:1) at the dropwise adding speed of 0.2L/h, continuously stirring, and then adding ammonia water to adjust the pH value of the reaction system to be kept at 10.1 in real time;
S5, continuously stirring for 60min at normal temperature after the phosphoric acid solution is completely dripped, so as to obtain a hydroxyapatite solution;
(2) Preparation of activated carbon
Taking commercial activated carbon (the specific surface area is 1500m 2/g, the average pore diameter is 2.5nm, and the ash content is 1.2%) as a raw material, grinding, sieving activated carbon powder with the mesh size of below 200, roasting for 30min in nitrogen atmosphere at 600 ℃, and cooling to obtain activated carbon;
(3) Preparation of hydroxyapatite/activated carbon composite defluorination material
S1, adding 27.7g of activated carbon (wherein the mass ratio of the hydroxyapatite in the hydroxyapatite solution to the activated carbon is 5:1) into the hydroxyapatite solution, stirring and mixing uniformly, then adding 49.8g of attapulgite clay with the thickness of 8 mu m (wherein the addition amount of the attapulgite clay mineral is 30% of the sum of the mass of the hydroxyapatite in the hydroxyapatite solution and the mass of the activated carbon), continuously stirring at 60 ℃ for 30min, extruding and molding at 60 ℃ and 0.3MPa, and finally air-drying and drying at room temperature to obtain a molded semi-finished product;
s2, sintering the molded semi-finished product at 1000 ℃ for 120min under nitrogen atmosphere to obtain 220g of hydroxyapatite/activated carbon composite defluorination material.
The fluorine-containing wastewater with the fluorine concentration of 21.6mg/L is prepared by dissolving sodium fluoride in tap water, and the fluorine removal capacity of the composite fluorine removal material of the embodiment is measured, so that the result is 9.28mg/g, and the higher fluorine removal capacity is shown.
Comparative example 1
A preparation method of a hydroxyapatite defluorination material comprises the following steps:
(1) Preparation of hydroxyapatite solution
S1, calcium chloride and phosphoric acid are adopted as raw materials, and the adding quality of the calcium chloride and the phosphoric acid is determined according to the molar ratio of the calcium to the phosphorus being 1.65:1;
S2, preparing a phosphoric acid solution according to the volume ratio of phosphoric acid to water being 1:3;
S3, dissolving 107g of calcium chloride in 75 ℃ water, and keeping the water temperature to prepare 35wt% of calcium chloride solution; then 2.63g of ammonium bicarbonate is dissolved into the prepared calcium chloride solution, and the mixture is stirred uniformly to obtain a calcium chloride-ammonium bicarbonate solution;
S4, dropwise adding 261mL of phosphoric acid solution into a calcium chloride-ammonium bicarbonate solution (wherein the molar ratio of the ammonium bicarbonate to the phosphoric acid is 0.05:1) at a dropwise adding rate of 0.2L/h, continuously stirring, and then adding ammonia water to adjust the pH value of a reaction system to be kept at 10.5 in real time;
s5, continuously stirring for 90min at normal temperature after the phosphoric acid solution is completely dripped, so as to obtain a hydroxyapatite solution;
(2) Preparation of hydroxyapatite defluorination material
S1, adding 33g of 15 mu m attapulgite into a hydroxyapatite solution, continuously stirring for 30min at 75 ℃, then extruding and forming at 50 ℃ and 0.4MPa, and finally air-drying and drying at room temperature to obtain a formed semi-finished product;
s2, sintering the molded semi-finished product at 1000 ℃ for 120min in nitrogen atmosphere to obtain the hydroxyapatite defluorination material.
The fluorine-containing wastewater with the fluorine concentration of 21.6mg/L was prepared by dissolving sodium fluoride in tap water, and the fluorine removal capacity of the hydroxyapatite fluorine removal material of the comparative example was measured, and as a result, the fluorine removal capacity was 6.57mg/g, and the fluorine removal capacity was general.
Comparative example 2
The preparation method of the active carbon defluorination material comprises the following steps:
(1) Preparation of activated carbon
Taking commercial activated carbon (the specific surface area is 1500m 2/g, the average pore diameter is 2.5nm, and the ash content is 1.2%) as a raw material, grinding, sieving activated carbon powder with the mesh size of below 200, roasting for 30min in nitrogen atmosphere at 600 ℃, and cooling to obtain activated carbon;
(2) Preparation of activated carbon defluorination material
S1, adding 33g of 15 mu m attapulgite into 100g of activated carbon, continuously stirring at 60 ℃ for 30min, extruding at 50 ℃ and 0.4MPa for molding, and finally air-drying at room temperature to obtain a molded semi-finished product;
S2, sintering the molded semi-finished product at 1000 ℃ for 120min in nitrogen atmosphere to obtain the active carbon defluorination material.
The fluorine-containing wastewater with the fluorine concentration of 21.6mg/L is prepared by dissolving sodium fluoride in tap water, and the fluorine removal capacity of the active carbon fluorine removal material of the comparative example is measured, so that the result is 1.41mg/g, and the lower fluorine removal capacity is shown.
As can be seen from the fluorine removal capacities of the fluorine removal materials in the examples and the comparative examples, the prepared composite fluorine removal material can generate synergistic fluorine removal effect by compounding the hydroxyapatite with activated carbon and adding attapulgite as a binder, and the fluorine removal capacity of the composite fluorine removal material can be improved by about 1.5 times compared with that of a single hydroxyapatite filter material and is improved by about 6 times compared with that of the activated carbon, so that the fluorine removal effect is better.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (6)
1. The preparation method of the hydroxyapatite/activated carbon composite defluorination material is characterized by comprising the following steps of:
(1) Adding activated carbon into the hydroxyapatite solution, stirring and mixing uniformly, then adding attapulgite, continuously stirring at 60-90 ℃ for 30-60 min, extruding and forming, and drying to obtain a formed semi-finished product; wherein the mass ratio of the hydroxyapatite in the hydroxyapatite solution to the activated carbon is (0.2-5): 1, a step of; the particle size of the attapulgite clay is 1-15 mu m; the extrusion molding pressure is 0.3-0.5 MPa, and the temperature is 30-60 ℃;
(2) Sintering the molded semi-finished product at 900-1000 ℃ for 120-180 min in inert atmosphere or nitrogen atmosphere to obtain the hydroxyapatite/activated carbon composite defluorination material;
Wherein, in the step (1), the activated carbon is prepared by a method comprising the following steps: grinding and sieving commercial activated carbon serving as a raw material, roasting the commercial activated carbon in an inert atmosphere at 500-600 ℃ for 30-60 min, and cooling to obtain activated carbon; the specific surface area of the commercial activated carbon is 1000-1800 m 2/g, the aperture is 2-10 nm, and the ash content is less than or equal to 2%; the particle size of the activated carbon is 0.5-10 mu m, and the average pore diameter is 2-10 nm.
2. The method for producing a hydroxyapatite/activated carbon composite defluorinated material according to claim 1, wherein the amount of the attapulgite to be added is 10 to 30% of the sum of the mass of the hydroxyapatite in the hydroxyapatite solution and the mass of the activated carbon after activation.
3. The method for producing a hydroxyapatite/activated carbon composite defluorinated material according to claim 1, wherein the mass ratio of the hydroxyapatite in the hydroxyapatite solution to the activated carbon is (2 to 4): 1.
4. The method for preparing the hydroxyapatite/activated carbon composite defluorination material according to claim 1, wherein the hydroxyapatite solution is prepared by a method comprising the following steps: s1, calcium chloride and phosphoric acid are adopted as raw materials, and the adding quality of the calcium chloride and the phosphoric acid is determined according to the molar ratio of the calcium to the phosphorus of (1.45-1.85) 1; s2, preparing a phosphoric acid solution according to the volume ratio of phosphoric acid to water being 1:3; s3, dissolving calcium chloride in water at 60-90 ℃ and keeping the water temperature to prepare 20-50 wt% of calcium chloride solution; dissolving ammonium bicarbonate into the prepared calcium chloride solution, and uniformly stirring to obtain a calcium chloride-ammonium bicarbonate solution; s4, dropwise adding the phosphoric acid solution into the calcium chloride-ammonium bicarbonate solution at the dropwise adding speed of 0.2L/h, continuously stirring, and then adding ammonia water to adjust the pH value of the reaction system to be kept in the range of 9-11 in real time; s5, continuously stirring for 30-90 min at normal temperature after the phosphoric acid solution is completely dripped, so as to obtain the hydroxyapatite solution;
in the step S4, the molar ratio of the ammonium bicarbonate in the calcium chloride-ammonium bicarbonate solution to the phosphoric acid in the phosphoric acid solution is (0.02-0.1): 1.
5. The hydroxyapatite/activated carbon composite defluorination material is characterized in that the hydroxyapatite/activated carbon composite defluorination material is prepared by the preparation method of the hydroxyapatite/activated carbon composite defluorination material according to any one of claims 1-4.
6. The use of the hydroxyapatite/activated carbon composite defluorination material of claim 5 in the treatment of fluorine-containing wastewater.
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