CN115672263B - Preparation method of halloysite nanotube composite material and application of halloysite nanotube composite material in uranium pollution treatment - Google Patents
Preparation method of halloysite nanotube composite material and application of halloysite nanotube composite material in uranium pollution treatment Download PDFInfo
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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 56
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 56
- 239000002071 nanotube Substances 0.000 title claims abstract description 54
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 50
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000003463 adsorbent Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- -1 uranyl ions Chemical class 0.000 description 12
- 238000004065 wastewater treatment Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical compound O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of halloysite nanotube composite material, which comprises the following steps: s1, stirring and dissolving 4,4' -dihydroxydiphenyl sulfone and a catalyst in a solvent, and adding halloysite nanotubes for ultrasonic dispersion to obtain a mixture A; s2, stirring and dissolving hexachlorocyclotriphosphazene in a solvent, slowly adding the hexachlorocyclotriphosphazene into the mixture A, and stirring and dispersing the hexachlorocyclotriphosphazene to obtain a mixture B; s3, continuously stirring the mixture B at 60 ℃, and collecting a HNT@PZS crude product through centrifugation; s4, centrifugally washing the HNT@PZS crude product cooled to room temperature by using absolute ethyl alcohol and deionized water, and placing the product into an oven to heat up to 60 ℃ for vacuum drying to obtain an HNT@PZS composite material; according to the invention, hexachlorocyclotriphosphazene and 4,4' -dihydroxydiphenyl sulfone are used as raw materials, halloysite nanotubes are used as substrates, and a phosphate group and a sulfuric acid group are introduced by calcining after polycondensation reaction; exhibits super strong adsorption capacity and extremely high selectivity when uranium-containing wastewater is adsorbed.
Description
Technical Field
The invention belongs to the technical field of adsorbents, and particularly relates to a preparation method of a halloysite nanotube composite material and application of the halloysite nanotube composite material in uranium pollution treatment.
Background
Uranium is a radioactive metal element and can be used as a fuel for nuclear reactions. Nuclear energy is considered one of the best alternatives to fossil energy, and can provide large-scale electricity without releasing greenhouse gases. With the rapid development of the nuclear industry, the demand for uranium as a nuclear fuel has also increased dramatically. While the exploitation of uranium ores by humans produces a large amount of uranium-containing wastewater, the pollution range of the uranium-containing wastewater is dramatically increased along with the flushing of rainwater and the flowing of groundwater. Uranium is a very radioactive heavy metal, usually present in the form of uranyl ions in water, which poses a serious threat to the surrounding ecological environment due to its very long half-life (t1/2=4.5x109 a) and high solubility in water. Furthermore, the damage of uranyl ions to human bodies is more fatal, and can cause damage to human kidney organs and some cancerations. Therefore, the uranium acyl ions in the water body are effectively removed, and the problem to be solved is still needed.
In recent years, various methods for effectively removing uranyl ions from water have been developed, including precipitation, ion exchange, solution extraction, membrane separation, adsorption, and the like. However, the method has the limitations of poor low concentration removal capability, high price, easy secondary pollution generation, difficult treatment of residual medicament, high energy consumption, limited ion exchange capacity, low adsorption efficiency, easy membrane pollution and the like, so that the design of a preparation method of halloysite nanotube composite material and application of the halloysite nanotube composite material in uranium pollution treatment are needed to solve the problems.
Disclosure of Invention
The invention aims to provide a preparation method of a halloysite nanotube composite material and application of the halloysite nanotube composite material in uranium pollution treatment so as to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the halloysite nanotube composite material comprises the following steps:
s1, stirring and dissolving 4,4' -dihydroxydiphenyl sulfone and a catalyst in a solvent, and adding halloysite nanotubes for ultrasonic dispersion to obtain a mixture A;
s2, stirring and dissolving hexachlorocyclotriphosphazene in a solvent, slowly adding the hexachlorocyclotriphosphazene into the mixture A, and stirring and dispersing the hexachlorocyclotriphosphazene to obtain a mixture B;
s3, continuously stirring the mixture B at 60 ℃, and collecting a HNT@PZS crude product through centrifugation;
s4, centrifugally washing the HNT@PZS crude product cooled to room temperature by using absolute ethyl alcohol and deionized water, and placing the product into an oven to heat up to 60 ℃ for vacuum drying to obtain an HNT@PZS composite material;
s5, placing the dried HNT@PZS into a tubular furnace, and calcining at high temperature for a period of time in an air atmosphere to obtain the product halloysite nanotube composite material HNT@PZS-500.
Preferably, the mass ratio of hexachlorocyclotriphosphazene to halloysite nanotubes and 4,4' -dihydroxydiphenyl sulfone in the S2 is 6.655:1:8.6.
preferably, the solvent in S1 and S3 is acetonitrile solution, and the catalyst is triethylamine solution.
Preferably, the ultrasonic time in the step S1 is 15-30 min.
Preferably, the stirring time in S3 is 4 h and the centrifugation speed is 9000 rad/min.
Preferably, the drying time in S4 is 12 h.
Preferably, the calcination time in S5 is 2 h and the calcination temperature is 500 ℃.
An application of halloysite nanotube composite material in uranium pollution treatment comprises the following application methods:
adjusting the volume of uranium-containing wastewater to be treated and the mass ratio of the halloysite nanotube composite HNT@PZS-500 adsorbent to be 50 mL:0.010 g, adjusting the pH value to 3-9, the adsorption temperature to 25-45 ℃, the adsorption time to 5-180 min and the oscillation speed to 300 rad/min.
Preferably, the adsorption time is 60 min, the pH value is adjusted to 5.0, and the adsorption temperature is 25 ℃.
Preferably, the pH value is adjusted by 0.5 mol/L hydrochloric acid solution and 1 mol/L sodium hydroxide solution.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, hexachlorocyclotriphosphazene and 4,4' -dihydroxydiphenyl sulfone are used as raw materials, halloysite nanotubes are used as substrates, and a phosphate group and a sulfuric acid group are introduced by calcining after polycondensation reaction; exhibits super strong adsorption capacity and extremely high selectivity when uranium-containing wastewater is adsorbed.
2. The preparation method of the adsorbent has the advantages of low cost, environmental friendliness, high adsorption capacity, strong selectivity and high adsorption rate, and can realize the aim of effectively separating and enriching uranium ions from water.
3. The halloysite nanotube composite material disclosed by the invention is wide in application range, is used for extracting uranium while treating uranium-containing wastewater, has the advantages of high adsorption capacity, high adsorption rate, strong selectivity and the like in the uranium-containing wastewater treatment process, and can overcome the interference of various salt ions and other types of heavy metals in a water body, and uranium ions can be selectively extracted from the water body.
4. The halloysite nanotube composite material has the advantages of simple preparation process, short preparation period, wide raw material sources, low cost and the like.
Drawings
FIG. 1 is an infrared spectrum of a halloysite nanotube composite adsorbent of the present invention.
Fig. 2 is a scanning electron microscope image of a halloysite nanotube composite and a halloysite nanotube, a is a halloysite nanotube composite, and b is a halloysite nanotube.
FIG. 3 is a graph showing the adsorption capacity of the halloysite nanotube composite material according to the present invention as a function of time.
FIG. 4 is a graph comparing the removal rates of various metals adsorbed from actual wastewater by the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
referring to fig. 1 to 4, the present invention provides a technical solution: 4,4' -dihydroxydiphenyl sulfone 1.72g and 8 ml triethylamine were dissolved in 100 mL acetonitrile. Into the solution, 0.2g HNT was dispersed under ultrasound, and the mixture A was obtained by ultrasound for 15-30 min. Then 1.331 g hexachlorocyclotriphosphazene was dissolved in 100 mL acetonitrile with stirring, and then an acetonitrile solution of hexachlorocyclotriphosphazene was slowly added to the above mixture a with stirring to obtain a mixture B. Mixture B was stirred continuously at 60 ℃ for 4 hours. The crude product of hnt@pzs was collected by centrifugation at 9000 rad/min, washed two to three times with deionized water and ethanol, and dried under vacuum at 60 ℃ 12 h to give hnt@pzs. And (3) placing the dried HNT@PZS into a tubular furnace, and calcining for 2 hours in the air at 500 ℃ (5 ℃/min) to obtain the HNT@PZS-500 material.
The infrared spectrum of the HNT@PZS-500 material prepared in the embodiment is shown in figure 1, in which 3428 cm -1 The broad absorption peak at this location is attributed to the stretching vibration of-OH in the phosphate group, 1631 cm -1 The absorption peak at this point is a characteristic peak of c=c, 1284 cm -1 And 1158 cm -1 Is a characteristic peak of p=o, 1104 cm -1 The peak at which is ascribed to a phosphate group, 986 cm -1 The absorption peak at this point is a characteristic peak of P-O, 810 and 810 cm -1 The absorption peak at this point is a characteristic peak of S-O. The occurrence of the absorption peak shows that the halloysite nanotube composite material coated by the compact layer is successfully prepared.
Scanning electron microscope images (figure 2) and element distribution tables (table 1) of the compact layer coated halloysite nanotube composite materials and halloysite nanotubes prepared under the conditions of the example. As can be clearly seen from fig. 2 and table 1, the structure of the material still maintains the halloysite tubular structure, the ratio of silicon element to aluminum element is close to 1:1, and the ratio of silicon dioxide to aluminum oxide is also close to 1:1, which indicates that the halloysite nanotube is only dehydroxylated after being calcined at 500 ℃ and is not greatly affected. The dense layer is wrapped on the periphery of the tube shape, and the element analysis table shows that the content of phosphorus element is 72.991%, the content of sulfur element is 8.759%, the content of phosphoric anhydride is 73.157%, and the content of sulfuric anhydride is 7.394%, which means that the dense layer wrapped on the surface of the halloysite nanotube wraps a large amount of phosphoric anhydride and sulfuric anhydride on the surface of the halloysite.
Table 1: element distribution table
From the above description, the present invention has the following advantageous effects: the hexachlorocyclotriphosphazene and 4,4' -dihydroxydiphenyl sulfone are used as raw materials, halloysite nanotubes are used as substrates, and a phosphate group and a sulfuric acid group are introduced by calcining after polycondensation reaction; the method has the advantages that the ultra-strong adsorption capacity and the extremely high selectivity are shown when uranium-containing wastewater is adsorbed; the preparation method of the adsorbent has the advantages of low cost, environmental friendliness, high adsorption capacity, strong selectivity and high adsorption rate, and can realize the aim of effectively separating and enriching uranium ions from water.
In view of the operating cost, removal efficiency and process difficulty, the development of a high-efficiency and low-cost uranium adsorbent is a key to solving this environmental problem. The adsorption of uranium by using the adsorbent is the most effective method for uranium utilization at present, and has the characteristics of high efficiency, low cost, easy operation and sufficient selectivity and adsorption capacity. At present, different types of uranyl ion adsorbents comprise inorganic materials (metal-organic frameworks, phosphates and the like), carbon materials (carbon nanotubes, graphene oxide and the like), polymers (cellulose, chitosan and the like), porous framework materials (COF, MOF and the like), and the embodiment adopts halloysite nanotube composite materials for uranium-containing wastewater treatment and simultaneously extracting uranium, and has the advantages of high adsorption capacity, high adsorption rate, strong selectivity and the like in the uranium-containing wastewater treatment process, so that the interference of various salt ions and other types of heavy metals in a water body can be overcome, and the uranium ions can be selectively extracted from the water body
Examples
Referring to fig. 1 to fig. 4, on the basis of the first embodiment, the present invention provides a technical solution: the halloysite nanotube composite material with high-efficiency selective adsorption is used for uranium-containing wastewater treatment, and the specific method comprises the following steps:
firstly, 50 ml uranium is concentrated to 115 mg.L -1 The pH value of the uranium-containing wastewater is adjusted to 5, and then 5 mg of HNT@PZS-500 composite material is put into the solution for vibration absorption for 30 min.
As shown in FIG. 3, the HNT@PZS-500 composite material can effectively remove 92.93% of uranium in wastewater, and the adsorption capacity reaches 1074.2 mg g -1 . The adsorption capacity is calculated as shown in equation one below:
(1)
Q e : adsorption capacity; c (C) 0 : an initial concentration; c (C) t : equilibrium concentration; v: the volume of the solution; m: the mass of the adsorbent.
By adopting the technical scheme for extracting uranium while treating uranium-containing wastewater, the method has the advantages of high adsorption capacity, high adsorption rate, strong selectivity and the like in the uranium-containing wastewater treatment process.
Examples
Referring to fig. 1 to fig. 4, on the basis of the second embodiment, the present invention provides a technical solution: the halloysite nanotube composite material is used for extracting uranium from actual uranium-containing wastewater, and the concrete method comprises the following steps:
5 mg HNT@PZS-500 composite material is added into uranium-containing wastewater of 1L, and the stirring speed is 500 rpm/min, and the adsorption temperature is 25 ℃.
As shown in FIG. 4, after 1 day, the HNT@PZS-500 composite material can reduce the uranium concentration of uranium-containing wastewater to 48.72 mug.L -1 The removal rate reaches 97.48%, and reaches the first water taking point limit value of the radionuclide concentration limit value in (GB 23727-2009) uranium mining metallurgy radiation protection and environmental protection regulations.
The uranium-containing wastewater treatment method has the advantages of high adsorption capacity, high adsorption rate, strong selectivity and the like in the uranium-containing wastewater treatment technical scheme process, and can overcome the interference of various salt ions and other heavy metals in the water body, and uranium ions can be selectively extracted from the water body.
The adsorption of radionuclides by clay minerals is very important for radioactive waste because clay minerals have a high adsorption capacity and selectivity for various radionuclides. Halloysite Nanotubes (HNTs) are natural layered tubular aluminosilicate clay minerals, are composed of silicon dioxide tetrahedral sheets and alumina octahedral sheets with equal ratio, are of hollow nanotube structures, are developed in surface, have the advantages of being large in specific surface area by a plurality of times than that of kaolinite, and are low in economic cost, high in mechanical strength and thermal stability, but are low in adsorption capacity for radioactive elements due to the fact that active sites on the halloysite are fewer. In addition to the better structural properties, HNTs have surfaces rich in-OH groups, which enable chemical linking of functional groups. Diffusion of both agents hexachlorocyclophosphazene and 4,4 '-dihydroxydiphenyl sulfone is favored in the synthesis of highly crosslinked poly (cyclotriphosphazene-co-4, 4' -sulfonyldiphenol) (abbreviated PZS). Thus, the possibility of crosslinking between PZS and HNTs was estimated. And the compact layer can be generated on the surface of the halloysite nanotube by calcination, so that the loss of micromolecular substances is prevented, and phosphoric anhydride and sulfuric anhydride are generated between the compact layer and the halloysite nanotube, and can generate phosphoric acid and sulfuric acid in water, and the phosphoric acid group and the sulfuric acid group have strong complexing capability with uranium atoms.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is merely illustrative of the present invention and not restrictive, and other modifications and equivalents thereof may occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (9)
1. The preparation method of the halloysite nanotube composite material is characterized by comprising the following steps of:
s1, stirring and dissolving 4,4' -dihydroxydiphenyl sulfone and a catalyst in a solvent, and adding halloysite nanotubes for ultrasonic dispersion to obtain a mixture A;
s2, stirring and dissolving hexachlorocyclotriphosphazene in a solvent, slowly adding the hexachlorocyclotriphosphazene into the mixture A, and stirring and dispersing the hexachlorocyclotriphosphazene to obtain a mixture B;
s3, continuously stirring the mixture B at 60 ℃, and collecting a HNT@PZS crude product through centrifugation;
s4, centrifugally washing the HNT@PZS crude product cooled to room temperature by using absolute ethyl alcohol and deionized water, and placing the product into an oven to heat up to 60 ℃ for vacuum drying to obtain an HNT@PZS composite material;
s5, placing the dried HNT@PZS into a tubular furnace, and calcining at a high temperature of 500 ℃ for 2 h in an air atmosphere to obtain the product halloysite nanotube composite material HNT@PZS-500.
2. The method for preparing halloysite nanotube composite material according to claim 1, wherein the method comprises the following steps: the mass ratio of hexachlorocyclotriphosphazene to halloysite nanotubes and 4,4' -dihydroxydiphenyl sulfone in the S2 is 6.655:1:8.6.
3. the method for preparing halloysite nanotube composite material according to claim 1, wherein the method comprises the following steps: the solvent in S1 and S3 is acetonitrile solution, and the catalyst is triethylamine solution.
4. The method for preparing halloysite nanotube composite material according to claim 1, wherein the method comprises the following steps: the ultrasonic time in the step S1 is 15-30 min.
5. The method for preparing halloysite nanotube composite material according to claim 1, wherein the method comprises the following steps: the stirring time in S3 was 4 h and the centrifugation rate was 9000 rad/min.
6. The method for preparing halloysite nanotube composite material according to claim 1, wherein the method comprises the following steps: the drying time in S4 is 12 h.
7. Use of the halloysite nanotube composite material obtained by the preparation method according to claim 1 in uranium pollution treatment, comprising the following application methods:
adjusting the volume of uranium-containing wastewater to be treated and the mass ratio of the halloysite nanotube composite HNT@PZS-500 adsorbent to be 50 mL:0.010 g, adjusting the pH value to 3-9, the adsorption temperature to 25-45 ℃, the adsorption time to 5-180 min and the oscillation speed to 300 rad/min.
8. The use of a halloysite nanotube composite material in uranium pollution treatment according to claim 7, wherein: the adsorption time is 60 min, the pH value is regulated to 5.0, and the adsorption temperature is 25 ℃.
9. The use of a halloysite nanotube composite material in uranium pollution treatment according to claim 7, wherein: the pH value is regulated by 0.5 mol/L hydrochloric acid solution and 1 mol/L sodium hydroxide solution.
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