CN114797759B - Hydroxyapatite/halloysite nanotube composite adsorption material, and preparation method and application thereof - Google Patents
Hydroxyapatite/halloysite nanotube composite adsorption material, and preparation method and application thereof Download PDFInfo
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- CN114797759B CN114797759B CN202210324324.5A CN202210324324A CN114797759B CN 114797759 B CN114797759 B CN 114797759B CN 202210324324 A CN202210324324 A CN 202210324324A CN 114797759 B CN114797759 B CN 114797759B
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 127
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 93
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 79
- 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 79
- 239000002071 nanotube Substances 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011737 fluorine Substances 0.000 claims abstract description 39
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims description 58
- -1 fluoride ions Chemical class 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims 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 description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000009388 chemical precipitation Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 25
- 239000002244 precipitate Substances 0.000 description 22
- 239000003463 adsorbent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000006115 defluorination reaction Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000003651 drinking water Substances 0.000 description 5
- 235000020188 drinking water Nutrition 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 208000004042 dental fluorosis Diseases 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010061481 Renal injury Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 208000037806 kidney injury Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (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 invention relates to a hydroxyapatite/halloysite nanotube composite adsorption material, and a preparation method and application thereof, wherein the composite adsorption material comprises halloysite nanotubes and hydroxyapatite, and the mass ratio of the halloysite nanotubes to the hydroxyapatite is (10-30) g: (12-150 g); the preparation method comprises the following steps: the preparation method comprises the steps of taking halloysite nanotubes as templates, taking water-soluble calcium salt and phosphate as raw materials to generate hydroxyapatite, chemically precipitating the hydroxyapatite on the surface of halloysite, and carrying out post-treatment to obtain a composite adsorption material; wherein, the mass mol ratio of the halloysite nanotube to the water-soluble calcium salt is (10-30) g: (18-180) mmol. The hydroxyapatite and halloysite in the invention have good ecological environment harmony and compatibility, and cannot produce secondary pollution; the adsorption capacity is large in the fluorine-containing water treatment, the process flow is simple and convenient, and the method has no strict requirements on equipment and process conditions.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a hydroxyapatite/halloysite nanotube composite adsorption material, and a preparation method and application thereof.
Background
The fluorine pollution in the underground water becomes a worldwide environmental problem, seriously threatens the ecological environment and the life health of human beings, and influences the development and progress of society. The World Health Organization (WHO) prescribes that the concentration of fluoride ions in drinking water should not exceed a maximum of 1.5mg/L. The drinking of the high-fluorine drinking water with the fluorine ion concentration of more than 1.5mg/L for a long time can lead to fluorosis, and causes diseases such as dental fluorosis, thyroid injury, kidney injury and the like.
The existing defluorination technology mainly comprises a coagulating sedimentation method, an adsorption method, a membrane separation method, an ion exchange method, an electrocoagulation method, an electrodialysis method and the like. Among these methods, the coagulation sedimentation method is suitable for treating contaminated water having a high concentration of fluorine ions, but cannot treat low concentration of fluorine ion water; the adsorption capacity of the ion exchange method is limited, biological propagation pollution exists on the surface, and organic matters in the ion exchange method are easy to dissolve and cannot be regenerated; the electrodialysis method has serious energy consumption, and the highly sensitive membrane is easy to be polluted; in the membrane separation method, the cost of the reverse osmosis membrane is high, the device is complex, and the influence of the water quality condition is great. Therefore, in the technical analysis, the fluoride ion treatment technology is still immature, and is difficult to widely popularize in the practical fluoride ion removal technology, and only the adsorption method is commonly used at present. The adsorption method defluorination technology adopts defluorination adsorption material to fill the filter column for filtering and purifying the drinking water polluted by high fluorine, and has the advantages of convenience, high efficiency, easy operation, simple process design, economy, environmental protection and the like, and is most applied and relatively mature compared with other defluorination technologies. The key point of the technology for treating fluoride ions by an adsorption method in drinking water is how to prepare an adsorbent material with excellent performance. The fluoride ion adsorbent filter materials commonly used in the world at present comprise active alumina, activated zeolite, hydroxyapatite, carbonyl apatite and the like, but the limitation of the fluoride ion adsorbent filter materials prevents the practical popularization of the adsorption method defluorination technology, such as easy secondary pollution generation, smaller specific surface area, lower adsorption capacity, complex preparation process or high equipment requirement and the like. Therefore, how to research and develop a high-performance defluorination adsorbent material for solving the problem of local high-fluorine drinking water has strong challenges, but has remarkable social significance.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a hydroxyapatite/halloysite nanotube composite adsorption material, a preparation method and application thereof, and solves the technical problems that a fluoride ion adsorbent in the prior art is easy to produce secondary pollution, small in specific surface area and low in adsorption capacity.
In order to achieve the technical purpose, the technical scheme of the composite adsorption material is as follows:
the components of the composite adsorption material comprise halloysite nanotubes and hydroxyapatite, wherein the mass ratio of the halloysite nanotubes to the hydroxyapatite is (10-30) g: (12-150 g).
Further, the halloysite nanotube is obtained by centrifugal classification and purification of halloysite raw ore.
The preparation method of the invention has the technical scheme that the preparation method comprises the following steps: the preparation method comprises the steps of taking halloysite nanotubes as templates, taking water-soluble calcium salt and phosphate as raw materials to generate hydroxyapatite, chemically precipitating the hydroxyapatite on the surface of halloysite, and carrying out post-treatment to obtain a composite adsorption material; wherein, the mass mol ratio of the halloysite nanotube to the water-soluble calcium salt is (10-30) g: (18-180) mmol.
Further, the preparation steps of the halloysite nanotube comprise: preparing halloysite raw ore into a halloysite suspension with the mass concentration of 4-6%, and carrying out centrifugal purification on the halloysite suspension in a plurality of stages to obtain the halloysite nanotube.
Further, the Ca/P molar ratio of the water-soluble calcium salt and the phosphate is the stoichiometric ratio of Ca/P in the hydroxyapatite.
Further, the chemical precipitation specifically comprises the following steps:
(a) Preparing halloysite nanotubes into halloysite nanotube suspension;
(b) Adding water-soluble calcium salt solution into halloysite nanotube suspension, stirring uniformly, adding water-soluble phosphate solution, adjusting pH value to be alkaline, reacting at 50-90 ℃ until precipitation is not increased, and completing chemical precipitation of hydroxyapatite.
Further, the concentration of the halloysite nanotube suspension is 3-10wt%; the concentration of the water-soluble calcium salt solution is 0.2-0.8 mol/L; the water-soluble calcium salt adopts calcium chloride, calcium nitrate or calcium acetate; the concentration of the water-soluble phosphate solution is 0.1-0.5 mol/L; the water-soluble phosphate adopts one of sodium/potassium phosphate, sodium/potassium/ammonium monobasic phosphate and sodium/potassium ammonium monobasic phosphate.
Further, ammonia water is adopted to adjust the pH value to 10-11 in the step (b).
Further, the reaction time in the step (b) is 2 to 6 hours.
The application of the hydroxyapatite/halloysite nanotube composite adsorbing material in removing fluoride ions in fluorine-containing water is described above.
Compared with the prior art, the invention has the beneficial effects that:
1. hydroxyapatite and halloysite are natural mineral materials widely existing in nature, have good ecological environment harmony and compatibility, and cannot produce secondary pollution.
2. The hydroxyapatite/halloysite nanocomposite adsorption material provided by the invention has the characteristics of large specific surface area and more active adsorption sites, and meanwhile, has high adsorption speed and large adsorption capacity (the maximum adsorption capacity can reach 50.56 mg/g), and has wide application prospects in the field of fluorine-containing water treatment.
3. The invention takes natural tubular nano material halloysite as a template, and obtains the efficient hydroxyapatite/halloysite nano composite adsorption material through simple chemical reaction. The process flow is simple and convenient, has no strict requirements on equipment and process conditions, has strong practicability, and is suitable for mass production and industrial application.
Drawings
FIG. 1 is a scanning electron microscope image of the hydroxyapatite/halloysite nanotube composite adsorbing material prepared by the invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The adsorption material of the invention is a tubular hydroxyapatite/halloysite nano composite adsorption material, and the components of the adsorption material comprise halloysite nanotubes and hydroxyapatite.
The preparation method of the hydroxyapatite/halloysite nanotube composite adsorbing material with the capability of adsorbing fluoride ions uses halloysite nanotubes (obtained by centrifugally classifying and purifying halloysite raw ores) as templates, uses water-soluble calcium salt and phosphate as raw materials, and chemically precipitates the hydroxyapatite on the surface of the halloysite to prepare the hydroxyapatite/halloysite composite adsorbing material. The method specifically comprises the following steps:
1) Preparing a suspension with the mass concentration of 4-6wt% from halloysite raw ore, stirring for 1-4 hours under the condition of 100-300 r/min by a magnetic stirrer, centrifuging for 2-5 minutes under the condition of 150-500 r/min, taking an upper suspension, regulating the pH value to 7.5-9.5, stirring for 1-4 hours under the action of 100-300 r/min rotating speed by the magnetic stirrer, centrifuging for 2-5 minutes under the condition of 150-500 r/min, discarding a lower sediment substance, taking the upper suspension, centrifuging for 5-15 minutes under the condition of 8000-12000 r/min, and drying the sediment to obtain the halloysite nanotube with high purity;
2) And (3) carrying out strong stirring on the halloysite nanotube suspension with the concentration of 3-10wt% for 1h to form the halloysite suspension with the concentration of a certain mass. Adding 0.2-0.8 mol/L water-soluble calcium salt solution, stirring for 10min, maintaining the system temperature at 50-90 ℃, adding 0.1-0.5 mol/L water-soluble phosphate solution dropwise to enable the final Ca/P ratio to reach 1.67, using 3-6 mol/L ammonia water to maintain the pH value at 10-11, and stirring for 2-6 h. The mass molar ratio of the halloysite nanotube to the water-soluble calcium salt is (10-30) g: (18-180) mmol.
3) And (3) carrying out post-treatment on the suspension obtained in the step (2), wherein the post-treatment is carried out by firstly standing for 8-24 h at room temperature, and then separating, washing and drying. The method comprises the steps of adopting a centrifugal method to carry out solid-liquid separation, washing the obtained precipitate to be neutral by distilled water, and carrying out vacuum drying on the obtained material to obtain the hydroxyapatite/halloysite nanotube composite material, wherein the mass ratio of the purified halloysite nanotube to the hydroxyapatite is (10-30) g: (12-150 g).
The nano hydroxyapatite/halloysite nanotube composite adsorption material is used as an adsorbent for removing fluorine in water.
The adsorption condition is that the pH=4-8, and the adsorption time is 10-100 min.
The invention provides a fluoride ion adsorbent with simple preparation process, low cost, high efficiency and environmental protection and a preparation method thereof.
Because of the special crystal chemical structure, the hydroxyapatite has excellent performance in adsorbing fluorine ions in water. The hydroxyl on the surface of the hydroxyapatite can adsorb fluorine ions in water through ion exchange, so as to achieve the purpose of reducing the concentration of the fluorine ions in the water. Nanomaterials exhibit quantum size effects, surface effects, macroscopic quantum tunneling, etc., and these unique properties make them also of great potential for water treatment applications. The nano material has extremely high surface area, small size and good mass transfer efficiency, and can provide excellent adsorption capacity for adsorbing toxic ions from aqueous solution. Therefore, the particle size of the hydroxyapatite is reduced, the nano-scale hydroxyapatite is prepared, and the nano-scale hydroxyapatite is an effective measure for improving the adsorption capacity of the hydroxyapatite to fluoride ions. Halloysite is a natural aluminosilicate nanotube-like material formed by combining a silicon oxygen tetrahedral layer outside a tube and an aluminum oxygen octahedral layer inside the tube in a ratio of 1:1. The high specific surface area and abundant surface hydroxyl groups enable the catalyst to have larger ion exchange capacity and strong adsorption capacity. Therefore, the tubular hydroxyapatite/halloysite nanocomposite adsorbing material can be prepared by taking the halloysite nanotube as a template, carrying out surface modification on the halloysite nanotube by calcium ions, and then adding phosphate for chemical reaction.
The invention is further illustrated by the following specific examples.
Example 1
Preparation and application of hydroxyapatite/halloysite nanotube composite adsorption material:
1) Adding halloysite into water at a proportion of 5wt%, stirring for 2 hours at a speed of 250r/min by using a magnetic stirrer to obtain a halloysite suspension (1), centrifuging the obtained suspension at a speed of 200r/min for 2 minutes, removing precipitates to obtain a suspension (2), regulating the pH value of the obtained suspension (2) to 9.0, stirring for 2 hours at a speed of 250r/min by using the magnetic stirrer, centrifuging at a speed of 200r/min for 2 minutes, removing precipitates to obtain a suspension (3), centrifuging the suspension (3) at a speed of 12000r/min for 10 minutes, taking the precipitates, and freeze-drying to obtain purified halloysite nanotubes.
2) Adding the halloysite nanotubes obtained in the step 1) into water to form a suspension with the weight percentage of 4%, and then adding a calcium nitrate solution with the weight percentage of 0.40mol/L into the suspension, wherein the mass molar ratio of the halloysite nanotubes to the calcium nitrate is 20g:100mmol; stirred for 1h, 0.16mol/L (NH) 4 ) 2 HPO 4 The final Ca/P molar ratio was brought to 1.67 (i.e., stoichiometric Ca/P ratio in hydroxyapatite 5:3), pH was adjusted to 10 with 5mol/L ammonia, vigorously stirred for 3 hours, allowed to stand at room temperature for 24 hours, centrifuged to obtain a precipitate, and washed with distilled water until the pH of the wash solution was neutral. And (3) carrying out vacuum drying on the precipitate to obtain the hydroxyapatite/halloysite composite adsorbing material (the mass ratio of the halloysite nanotubes to the hydroxyapatite is 20g:78 g).
3) Weighing 0.05g of the composite material, putting the composite material into a 50mL conical flask containing 10mg/L of fluoride ion water (calculated as fluorine element), regulating the pH value to 7, putting the conical flask into a 25 ℃ oscillator for oscillation, centrifuging the suspension after 50min of absorption, taking the supernatant to measure the concentration of fluoride ions in the solution, and calculating to obtain the removal rate of the fluoride ions in the fluoride ion water to be 96.2%.
The hydroxyapatite/halloysite composite adsorption material prepared by the embodiment has large specific surface area and more active adsorption sites.The specific surface area can reach 275.65m 2 And/g, the adsorption quantity of the fluorine ions is 43.53mg/g, and the fluorine ion adsorption and removal capacity is good. The removal rate and adsorption capacity of fluoride ions were calculated according to the following formula.
η is the removal rate; q e Mg/g for equilibrium adsorption capacity; c (C) 0 mg/L for initial concentration of fluoride ion before adsorption; c (C) e mg/L for equilibrium concentration after adsorption; v is the volume of the fluoride ion solution; m is the mass of the adsorption material, g. The specific surface area test method comprises the following steps: the composite adsorption material sample is placed in a vacuum drying oven to be dried for 5 hours at 50 ℃, and then the specific surface area of the composite adsorption material sample is measured by adopting a BET specific surface area test method.
Example 2
Preparation and application of hydroxyapatite/halloysite nanotube composite adsorption material:
1) Adding halloysite into water at a proportion of 5wt% and stirring for 3 hours under the condition of 200r/min by using a magnetic stirrer to obtain a halloysite suspension (1), centrifuging the obtained suspension under the condition of 350r/min for 3 minutes, removing precipitates to obtain a suspension (2), regulating the pH value of the obtained suspension (2) to 9.5, stirring for 3 hours under the condition of 200r/min under the action of the magnetic stirrer, centrifuging for 3 minutes under the condition of 350r/min, removing precipitates to obtain a suspension (3), centrifuging the suspension (3) under the condition of 10000r/min for 12 minutes, taking the precipitates, and freeze-drying to obtain the purified halloysite rice tube.
2) Adding the halloysite nanotubes obtained in the step 1) into water to form a 5wt% suspension, and then adding a 0.50mol/L calcium nitrate solution into the suspension, wherein the mass molar ratio of the halloysite nanotubes to the calcium nitrate is 20g:80mmol; stirred for 1h, 0.20mol/L (NH) 4 ) 2 HPO 4 So that the final Ca/P molar ratio reaches 1.67,the pH was adjusted to 10.5 with 4.5mol/L ammonia, stirred vigorously for 5 hours, allowed to stand at room temperature for 18 hours, centrifuged to give a precipitate, and washed with distilled water until the pH of the washing solution was neutral. And (3) carrying out vacuum drying on the precipitate to obtain the hydroxyapatite/halloysite composite adsorbing material (the mass ratio of the halloysite nanotubes to the hydroxyapatite is 20g:62 g).
3) Weighing 0.05g of the composite material, putting the composite material into a 100mL conical flask containing 10mg/L of fluoride ion water, regulating the pH value to 6.5, putting the conical flask into a 25 ℃ oscillator for oscillation, centrifuging the suspension after 80min of absorption at the oscillation speed of 200r/min, taking the supernatant to measure the concentration of fluoride ions in the solution, and calculating to obtain the fluoride ion removal rate of 94.7% in the fluoride-containing water.
The hydroxyapatite/halloysite composite adsorption material prepared by the embodiment has large specific surface area and more active adsorption sites. The specific surface area can reach 251.37m 2 And/g, the adsorption quantity of the fluorine ions is 41.25mg/g, and the fluorine ion adsorption and removal capacity is good.
Example 3
Preparation and application of hydroxyapatite/halloysite nanotube composite adsorption material:
1) Adding halloysite into water at a proportion of 5wt%, stirring for 2.5h at 300r/min by using a magnetic stirrer to obtain a halloysite suspension (1), centrifuging the obtained suspension at 400r/min for 4min, removing precipitates to obtain a suspension (2), regulating the pH of the obtained suspension (2) to 8.7, stirring for 2.5h at 300r/min by using the magnetic stirrer, centrifuging for 4min at 400r/min, removing precipitates to obtain a suspension (3), centrifuging the suspension (3) at 11000r/min for 11min, and freeze-drying the precipitates to obtain the purified halloysite nanotubes.
2) Adding the halloysite nanotubes obtained in the step 1) into water to form a suspension with the concentration of 6 weight percent, and adding 0.5mol/L CaCl into the suspension 2 Solution, halloysite nanotubes and CaCl 2 The mass molar ratio of (2) is 20g:150mmol; stirred for 1h, 0.20mol/L (NH) 4 )H 2 PO 4 So that the final Ca/P ratio reaches 1.67, 5mol/L ammonia water is usedThe pH was adjusted to 11, stirred vigorously for 3h, allowed to stand at room temperature for 22 hours, centrifuged to give a precipitate and washed with distilled water until the pH of the wash was neutral. And (3) carrying out vacuum drying on the precipitate to obtain the hydroxyapatite/halloysite composite adsorbing material (the mass ratio of the halloysite nanotubes to the hydroxyapatite is 20g:96 g).
3) Weighing 0.05g of the composite material obtained in the step 2), putting the composite material into a 50mL conical flask containing 10mg/L of fluoride ion water, regulating the pH value to 4.5 by adopting 0.1mol/L of HCl, putting the conical flask into a 30 ℃ oscillator for oscillation, centrifuging the suspension after adsorbing for 65min at the oscillation speed of 200r/min, taking the supernatant to measure the concentration of fluoride ion in the solution, and calculating to obtain the removal rate of the fluoride ion in the fluoride ion water of 96.43%.
The hydroxyapatite/halloysite composite adsorption material prepared by the embodiment has large specific surface area and more active adsorption sites. The specific surface area can reach 278.36m 2 And/g, the adsorption quantity of the fluorine ions is 48.73mg/g, and the fluorine ion adsorption and removal capacity is good.
Example 4
Preparation and application of hydroxyapatite/halloysite nanotube composite adsorption material:
1) Adding halloysite into water at a proportion of 5wt%, stirring for 2 hours at a speed of 250r/min by using a magnetic stirrer to obtain a halloysite suspension (1), centrifuging the obtained suspension at a speed of 200r/min for 2 minutes, removing precipitates to obtain a suspension (2), regulating the pH value of the obtained suspension (2) to 8.2, stirring for 2 hours at a speed of 250r/min by using the magnetic stirrer, centrifuging at a speed of 200r/min for 2 minutes, removing precipitates to obtain a suspension (3), centrifuging the suspension (3) at a speed of 12000r/min for 10 minutes, taking the precipitates, and freeze-drying to obtain purified halloysite nanotubes.
2) Adding the halloysite nanotubes obtained in the step 1) into water to form a suspension with the weight percentage of 4%, and then adding a calcium nitrate solution with the weight percentage of 0.40mol/L into the suspension, wherein the mass molar ratio of the halloysite nanotubes to the calcium nitrate is 20g:120mmol; stirred for 1h, 0.16mol/L (NH) 4 ) 2 HPO 4 So that the final Ca/P molar ratio reaches 1.67, 5mol/L of ammonia is usedThe pH was adjusted to 10 with water, stirred vigorously for 3 hours, allowed to stand at room temperature for 24 hours, centrifuged to give a precipitate, and washed with distilled water until the pH of the washing solution was neutral. And (3) carrying out vacuum drying on the precipitate to obtain the hydroxyapatite/halloysite composite adsorbing material (the mass ratio of the halloysite nanotubes to the hydroxyapatite is 20g:88 g).
3) Weighing 0.05g of the composite material, putting the composite material into a 50mL conical flask containing 10mg/L of fluoride ion water, regulating the pH value to 8, putting the conical flask into a vibrator at 25 ℃ for vibrating, adsorbing for 55min at the vibrating speed of 150r/min, centrifuging the suspension, taking supernatant to measure the concentration of fluoride ions in the solution, and calculating to obtain the removal rate of the fluoride ions in the fluoride ion water of 98.1%.
As shown in FIG. 1, the hydroxyapatite/halloysite composite adsorption material prepared in the embodiment has large specific surface area and more active adsorption sites. The specific surface area can reach 293.65m 2 And/g, the adsorption quantity of the fluorine ions is 50.56mg/g, and the fluorine ion adsorption and removal capacity is good.
Comparative example 1
Directly adding hydroxyapatite prepared by a chemical precipitation method into the halloysite nanotube suspension of the step 2), regulating the pH to 10 by using 5mol/L ammonia water, preparing a hydroxyapatite/halloysite mixed adsorption material by adopting other steps and conditions as in the example 4, adsorbing fluorine ions in fluorine-containing water by adopting the same conditions as in the example 4, calculating to obtain the removal rate of the fluorine ions in the fluorine-containing water to be 60.2%, the adsorption quantity of the fluorine ions to be 23.62mg/g, and the specific surface area of the adsorption material to be 163.61m 2 /g。
Comparative example 2
The hydroxyapatite prepared by adopting a chemical precipitation method is used for replacing the hydroxyapatite/halloysite composite adsorption material of the embodiment 4, the fluoride ions in the fluorine-containing water are adsorbed under the same condition, the removal rate of the fluoride ions in the fluorine-containing water is calculated to be 42.7%, the adsorption quantity of the fluoride ions is 18.51mg/g, and the specific surface area of the adsorption material is 153.22m 2 /g。
Comparative example 3
The hydroxyapatite/halloysite composite adsorption material of example 4 is replaced by halloysite raw ore, and fluoride ions in fluorine-containing water are removed under the same conditionsThe ions are adsorbed, the removal rate of fluorine ions in the fluorine-containing water is calculated to be 38.9 percent, the adsorption quantity of the fluorine ions is 16.72mg/g, and the specific surface area of the adsorption material is 177.97m 2 /g。
Comparative example 4
Removing step 1), namely directly preparing suspension by adopting halloysite raw ore, adding a calcium nitrate solution into the suspension, wherein other preparation methods are the same as those of example 4, and the prepared hydroxyapatite/halloysite composite adsorption material is used for removing fluorine ions in fluorine-containing water, and the other parameter conditions and the steps are the same as those of example 4, so that the removal rate of the fluorine ions in the fluorine-containing water is 73.8%, the adsorption capacity of the fluorine ions is 16.72mg/g, and the specific surface area of the adsorption material is 177.97m 2 /g。
As is clear from comparative example 1, the hydroxyapatite is directly used as a raw material, and cannot be precipitated on the surface of the halloysite nanotube, and the hydroxyapatite and the halloysite nanotube are physically mixed, so that the active adsorption sites cannot be effectively improved, and the adsorption amount of fluoride ions is low.
As is clear from comparative examples 2 to 3, the adsorption of the fluorine ions by hydroxyapatite and halloysite alone is not ideal, and the adsorption amount is low; as is clear from comparative example 4, the halloysite raw ore, without purification, has a larger particle size and contains a part of waste halloysite minerals, thus being unfavorable for the generation of a hydroxyapatite/halloysite composite material with a large specific surface area; as can be seen from the combination of example 4, the present invention effectively combines hydroxyapatite and halloysite, and can increase the active adsorption site and the specific surface area, thereby synergistically increasing the removal rate of fluoride ions.
In conclusion, the nano hydroxyapatite/halloysite nanotube composite adsorption material has the efficiency of removing fluoride ions in fluorine-containing water with the pH value of 4-8 and 0.1-10 mg/L of more than 98 percent, and the maximum adsorption capacity of 50.56mg/g (41.25-50.56 mg/g).
The invention removes fluorine from fluorine-containing water by adsorption method, and the obtained nano hydroxyapatite/halloysite nanotube composite adsorption material has large specific surface area (251.37-293.65 m) 2 And/g), the surface has the advantages of more adsorption active sites, large adsorption capacity and the like, and has strong adsorption capacity on fluorine ions. The composite adsorption materialThe preparation process of (2) is as follows: dispersing halloysite in water, repeatedly centrifuging and purifying to obtain halloysite nanotubes, adding water-soluble calcium salt into a halloysite nanotube suspension for modification, adding water-soluble phosphate dropwise, regulating the pH to 10-11 by ammonia water, reacting for 2-6 h at 50-90 ℃, standing the obtained suspension at room temperature, centrifuging and drying to obtain the nano hydroxyapatite/halloysite nanotube composite adsorbing material. The invention uses natural nano tubular material halloysite as a template, and the hydroxyapatite with strong adsorption capacity to fluoride ions is chemically deposited on the surface of the halloysite, so that the hydroxyapatite/halloysite nanotube composite adsorption material with large specific surface area and strong adsorption capacity is obtained.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (6)
1. The application of the hydroxyapatite/halloysite nanotube composite adsorbing material in removing fluoride ions in fluorine-containing water is characterized in that the components of the composite adsorbing material comprise halloysite nanotubes and hydroxyapatite, and the mass ratio of the halloysite nanotubes to the hydroxyapatite is 20g: (62-96) g; the specific surface area of the hydroxyapatite/halloysite nanotube composite adsorption material is 251.37-293.65 m 2 /g；
The preparation method of the halloysite nanotube comprises the following steps: preparing halloysite raw ore into a halloysite suspension with the mass concentration of 4-6%, stirring 1-4 h under the condition of 100-300 r/min by a magnetic stirrer, centrifuging for 2-5 min under the condition of 150-500 r/min, regulating the pH value of the suspension at the upper layer to 7.5-9.5, stirring 1-4 h under the action of the rotating speed of 100-300 r/min by the magnetic stirrer, centrifuging for 2-5 min under the condition of 150-500 r/min, discarding the sediment at the lower layer, taking the suspension at the upper layer, centrifuging for 5-15 min under the condition of 8000-12000 r/min, and drying the sediment to obtain the halloysite nanotube with high purity;
the preparation method of the hydroxyapatite/halloysite nanotube composite adsorption material comprises the following steps: the preparation method comprises the steps of taking halloysite nanotubes as templates, taking water-soluble calcium salt and water-soluble phosphate as raw materials to generate hydroxyapatite, chemically precipitating the hydroxyapatite on the surface of halloysite, and carrying out aftertreatment to obtain a composite adsorption material; wherein, the mass mol ratio of the halloysite nanotube to the water-soluble calcium salt is 20g: (80-150) mmol.
2. Use according to claim 1, characterized in that the Ca/P molar ratio of the water-soluble calcium salt and the water-soluble phosphate is the stoichiometric ratio of Ca/P in the hydroxyapatite.
3. Use according to claim 1, characterized in that said chemical precipitation comprises in particular the following steps:
(a) Preparing halloysite nanotubes into halloysite nanotube suspension;
(b) Adding water-soluble calcium salt solution into halloysite nanotube suspension, stirring uniformly, adding water-soluble phosphate solution, adjusting pH value to be alkaline, reacting at 50-90 ℃ until precipitation is not increased, and completing chemical precipitation of hydroxyapatite.
4. Use according to claim 3, characterized in that the halloysite nanotube suspension has a concentration of 3-10 wt%; the concentration of the water-soluble calcium salt solution is 0.2-0.8 mol/L; the water-soluble calcium salt adopts calcium chloride, calcium nitrate or calcium acetate; the concentration of the water-soluble phosphate solution is 0.1-0.5 mol/L.
5. The method according to claim 3, wherein in step (b) the pH is adjusted to 10-11 with ammonia.
6. The method according to claim 3, wherein the reaction time in step (b) is 2 to 6. 6h.
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