CN115672263A - 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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- CN115672263A CN115672263A CN202211533058.3A CN202211533058A CN115672263A CN 115672263 A CN115672263 A CN 115672263A CN 202211533058 A CN202211533058 A CN 202211533058A CN 115672263 A CN115672263 A CN 115672263A
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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 51
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 51
- 239000002071 nanotube Substances 0.000 title claims abstract description 49
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 48
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 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
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 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
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000001132 ultrasonic dispersion 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
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims 2
- 239000000463 material Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- -1 uranyl ions Chemical class 0.000 description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 5
- 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
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- 230000002285 radioactive effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- 229920001661 Chitosan Polymers 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
- 208000027418 Wounds and injury Diseases 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method 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
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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
- 238000001000 micrograph Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 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
- 239000002901 radioactive waste Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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Abstract
The invention discloses a preparation method of a halloysite nanotube composite material, which comprises the following steps: s1, stirring and dissolving 4,4' -dihydroxy diphenyl sulfone and a catalyst in a solvent, and adding a halloysite nanotube for ultrasonic dispersion to obtain a mixture A; s2, stirring and dissolving hexachlorocyclotriphosphazene in a solvent, slowly adding the solution into the mixture A, and stirring and dispersing 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 under the conditions of absolute ethyl alcohol and deionized water, putting the product into an oven, heating to 60 ℃, and drying in vacuum to obtain the HNT @ PZS composite material; according to the invention, hexachlorocyclotriphosphazene and 4,4' -dihydroxy diphenyl sulfone are used as raw materials, a halloysite nanotube is used as a substrate, and after polycondensation reaction, a phosphate group and a sulfate group are introduced by calcination; the adsorption material shows super strong adsorption capacity and extremely high selectivity when adsorbing uranium-containing wastewater.
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 to be one of the best alternatives to fossil energy sources, providing large-scale electricity without the release of greenhouse gases. With the rapid development of the nuclear power industry, the demand of uranium as a nuclear fuel is also sharply increased. Human beings produce a large amount of uranium-bearing waste water to the exploitation of uranium ore, along with the washing of rainwater and the flow of groundwater, the pollution scope of uranium-bearing waste water sharply increases. Uranium is a heavy metal with extremely high radioactivity, is usually present in water in the form of uranyl ions, and poses a serious threat to the surrounding ecological environment due to its extremely long half-life (T1/2 =4.5 × 109 a) and high solubility in water. Moreover, the uranyl ions are fatal to human bodies, and can cause kidney organ injury and some canceration of the human bodies. Therefore, the effective removal of uranyl ions in water still remains a problem to be solved urgently.
In recent years, various effective methods for 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 generation of secondary pollution, difficult treatment of residual medicament, high energy consumption, limited ion exchange capacity, low adsorption efficiency, easy pollution of membranes and the like, so that a preparation method of the halloysite nanotube composite material and application of the halloysite nanotube composite material in uranium pollution treatment are needed to be designed 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 art.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a halloysite nanotube composite material comprises the following steps:
s1, stirring and dissolving 4,4' -dihydroxy diphenyl sulfone and a catalyst in a solvent, and adding a halloysite nanotube for ultrasonic dispersion to obtain a mixture A;
s2, stirring and dissolving hexachlorocyclotriphosphazene in a solvent, slowly adding the solution into the mixture A, and stirring and dispersing 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 under the conditions of absolute ethyl alcohol and deionized water, putting the product into an oven, heating to 60 ℃, and drying in vacuum to obtain the HNT @ PZS composite material;
and S5, putting 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 HNT @ PZS-500 of the halloysite nanotube composite material.
Preferably, the mass ratio of hexachlorocyclotriphosphazene to halloysite nanotubes and 4,4' -dihydroxydiphenylsulfone in the S2 is 6.655: 8.6.
preferably, the solvent in S1 and S3 is acetonitrile solution, and the catalyst is triethylamine solution.
Preferably, the ultrasonic time in S1 is 15-30min.
Preferably, the stirring time in S3 is 4h, and the centrifugation speed is 9000rad/min.
Preferably, the drying time in S4 is 12h.
Preferably, the calcination time in S5 is 2h, and the calcination temperature is 500 ℃.
An application of a halloysite nanotube composite material in uranium pollution treatment comprises the following application methods:
adjusting the volume of the uranium-containing wastewater to be treated and the mass ratio of the halloysite nanotube composite material HNT @ PZS-500 adsorbent to be 50mL:0.010g, adjusting the pH value to 3-9, the adsorption temperature to 25-45 ℃, the adsorption time to 5-180min and the oscillation speed to 300rad/min.
Preferably, the adsorption time is 60min, the pH value is adjusted to 5.0, and the adsorption temperature is 25 ℃.
Preferably, the pH value is adjusted by 0.5mol/L hydrochloric acid solution and 1mol/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' -dihydroxy diphenyl sulfone are taken as raw materials, halloysite nanotube is taken as a substrate, and after polycondensation reaction, phosphate groups and sulfate groups are introduced by calcination; the adsorption material shows super strong adsorption capacity and extremely high selectivity when adsorbing uranium-containing wastewater.
2. The preparation method of the adsorbent prepared by the invention 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 a water body.
3. The halloysite nanotube composite material disclosed by the invention is wide in application range, can be 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, can overcome the interference of various salt ions and other heavy metals in water, and can selectively extract uranium ions from the water.
4. The preparation process of the halloysite nanotube composite material has the advantages of simple process, short preparation period, wide raw material source, low cost and the like.
Drawings
FIG. 1 is an infrared spectrum of a halloysite nanotube composite adsorbent of the invention;
FIG. 2 is a scanning electron microscope image of a halloysite nanotube composite material and halloysite nanotubes, wherein a is a halloysite nanotube composite material and b is a halloysite nanotube;
FIG. 3 is a graph of the adsorption capacity of a halloysite nanotube composite of the invention as a function of time;
FIG. 4 is a graph comparing the removal rates of various metals adsorbed from actual wastewater according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
referring to fig. 1 to 4, the present invention provides a technical solution: 4,4' -dihydroxydiphenyl sulfone 1.72g and 8 mL of triethylamine were dissolved in 100mL of acetonitrile. To this solution, 0.2g of HNT was dispersed under sonication for 15-30min to give mixture A. 1.331g of hexachlorocyclotriphosphazene was then dissolved in 100mL of acetonitrile with stirring, and then a solution of hexachlorocyclotriphosphazene in acetonitrile was slowly added to the above mixture A with stirring to give mixture B. The mixture B was stirred continuously at 60 ℃ for 4 hours. The crude product of HNT @ PZS was collected by centrifugation at 9000rad/min, washed two to three times with deionized water and ethanol, and vacuum dried at 60 ℃ for 12h to yield HNT @ PZS. And (3) putting the dried HNT @ PZS into a tubular furnace, and calcining the HNT @ PZS in the air at 500 ℃ (5 ℃/min) for 2 hours to obtain the HNT @ PZS-500 material.
The infrared spectrum of the HNT @ PZS-500 material obtained in this example is shown in FIG. 1, wherein 3428cm -1 The broad absorption peak at (A) is attributed to the stretching vibration of-OH in the phosphate group, 1631cm -1 The absorption peak at (A) is a characteristic peak of C = C, 1284cm -1 And 1158cm -1 Is a characteristic peak of P = O, 1104cm -1 Peaks at 986cm, attributable to phosphate groups -1 The absorption peak is the characteristic peak of P-O, 810cm -1 The absorption peak at (A) is a characteristic peak of S-O. The appearance of the absorption peak indicates that the halloysite nanotube composite material coated by the compact layer is successfully prepared.
Scanning electron micrographs (fig. 2) of the dense layer-coated halloysite nanotube composite material prepared under the conditions of this example and halloysite nanotubes and an element distribution table (table 1) analyzed by X-ray fluorescence spectroscopy. As is clear from fig. 2 and table 1, the structure of the material still maintains the tubular structure of the halloysite, the ratio of silicon element to aluminum element is close to 1. The dense layer is wrapped on the periphery of the tubular body, and the element analysis table shows that the content of phosphorus element accounts for 72.991%, the content of sulfur element accounts for 8.759%, the content of phosphoric anhydride accounts for 73.157%, and the content of sulfuric anhydride accounts for 7.394%, which indicates 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 halloysite.
Table 1: element distribution table
As apparent from the above description, the present invention has the following advantageous effects: the preparation method comprises the steps of taking hexachlorocyclotriphosphazene and 4,4' -dihydroxy diphenyl sulfone as raw materials, taking halloysite nanotubes as a substrate, and calcining after polycondensation reaction to introduce phosphate groups and sulfate groups; the adsorption capacity is super strong and the selectivity is extremely high when the uranium-bearing wastewater is adsorbed; the preparation method of the adsorbent prepared by the invention 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 a water body.
In consideration of the operation cost, the removal efficiency and the process difficulty, the development of a uranium adsorbent with high efficiency and low cost is the key to solve the 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, there are different types of uranyl ion adsorbents, including inorganic materials (metal-organic framework, phosphate, etc.), carbon materials (carbon nanotube, graphene oxide, etc.), polymers (cellulose, chitosan, etc.), porous framework materials (COF, MOF, etc.), in this embodiment, the halloysite nanotube composite material is used for extraction of uranium while being used for treatment of uranium-containing wastewater, in the uranium-containing wastewater treatment process, advantages of high adsorption capacity, fast adsorption rate, strong selectivity, etc. are shown, interference of various salt ions and other heavy metals in a water body can be overcome, uranium ions are selectively extracted from the water body
Example two:
referring to fig. 1 to 4, on the basis of the first embodiment, the present invention provides a technical solution: the method for treating uranium-containing wastewater by using the halloysite nanotube composite material capable of being efficiently and selectively adsorbed comprises the following steps:
first 50ml of uranium having a concentration of 115 mg.L -1 The pH value of the uranium-containing wastewater is adjusted to 5, and then 5mg of HNT @ PZS-500 composite material is put into the solution for vibration adsorption for 30min.
As shown in figure 3, the HNT @ PZS-500 composite material can effectively remove 92.93% of uranium in wastewater, and the adsorption capacity reaches 1074.2mg g -1 . The calculation formula of the adsorption capacity is shown in the following equation one:
Q e ＝((C 0 -C t )V)/m (1)
Q e : adsorption capacity; c 0 : an initial concentration; c t : equilibrium concentration; v: volume of solution; m: mass of adsorbent.
Adopt above-mentioned a technical scheme to extracting of uranium when being used for uranium-bearing waste water's processing, in uranium-bearing waste water treatment process, show advantages such as high adsorption capacity, fast adsorption rate and strong selectivity.
Example three:
referring to fig. 1 to 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 uranium-containing waste water, and the specific method comprises the following steps:
adding a 5mg HNT @ PZS-500 composite material into 1L uranium-containing wastewater, and stirring at 500rpm/min, wherein the adsorption temperature is 25 ℃.
As shown in figure 4, after 1 day, the HNT @ PZS-500 composite material can reduce the uranium concentration of the uranium-containing wastewater to 48.72 mu g.L -1 The removal rate reaches 97.48 percent and reaches (GB)23727-2009 radionuclides concentration limits in uranium mining & metallurgy regulations and environmental protection regulations.
By adopting the technical scheme, the uranium-bearing wastewater treatment method has the advantages of high adsorption capacity, high adsorption rate, strong selectivity and the like, can overcome the interference of various salt ions and other heavy metals in the water body, and selectively extracts uranium ions from the water body.
The adsorption of radionuclides by clay minerals is very important for radioactive wastes because clay minerals have high adsorption capacity and selectivity for various radionuclides. Halloysite Nanotubes (HNTs) are natural layered tubular aluminosilicate clay minerals, consist of silicon dioxide tetrahedral sheets and alumina octahedral sheets with equal ratio, wherein the silicon dioxide tetrahedral sheets and the alumina octahedral sheets alternate from outside to inside, have a hollow nanotube structure, have developed surfaces, have the advantages of low economic cost, high mechanical strength and thermal stability, and have low adsorption capacity on radioactive elements due to fewer active sites on halloysite, and the specific surface area of halloysite is far more than that of kaolinite. Besides good structural properties, HNTs nanotubes have surfaces rich in-OH groups, which makes chemical connection of functional groups possible. Diffusion of both hexachlorocyclophosphazene and 4,4 '-dihydroxydiphenylsulfone reagents is favored in the synthesis of highly crosslinked poly (cyclotriphosphazene-co-4, 4' -sulfonyldiphenol) (PZS for short). The possibility of cross-linking PZS with HNTs was thus presumed. And a compact layer can be generated on the surface of the halloysite nanotube through calcination, so that loss of small molecular substances is prevented, phosphoric anhydride and sulfuric anhydride are generated between the compact layer and the halloysite nanotube, phosphoric acid and sulfuric acid can be generated from the phosphoric anhydride and the sulfuric anhydride in water, and the phosphoric acid group and the sulfuric acid group have strong complexing ability with uranium atoms.
It is noted that, herein, relational terms such as first and second, and the like may be 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. Also, 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 phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a halloysite nanotube composite material is characterized by comprising the following steps:
s1, stirring and dissolving 4,4' -dihydroxy diphenyl sulfone and a catalyst in a solvent, and adding a halloysite nanotube for ultrasonic dispersion to obtain a mixture A;
s2, stirring and dissolving hexachlorocyclotriphosphazene in a solvent, slowly adding the solution into the mixture A, and stirring and dispersing 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 under the conditions of absolute ethyl alcohol and deionized water, putting the product into an oven, heating to 60 ℃, and drying in vacuum to obtain the HNT @ PZS composite material;
and S5, putting 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 HNT @ PZS-500 of the halloysite nanotube composite material.
2. The method of claim 1, wherein the method comprises the steps of: the mass ratio of hexachlorocyclotriphosphazene to halloysite nanotubes and 4,4' -dihydroxydiphenylsulfone in S2 is 6.655: 8.6.
3. the method of claim 1, wherein the method comprises the steps of: and the solvent in the S1 and the S3 is acetonitrile solution, and the catalyst is triethylamine solution.
4. The method of claim 1, wherein the method comprises the steps of: and the ultrasonic time in the S1 is 15-30min.
5. The method of claim 1, wherein the method comprises the steps of: the stirring time in the S3 is 4h, and the centrifugal speed is 9000rad/min.
6. The method of claim 1, wherein the method comprises the steps of: and the drying time in the S4 is 12h.
7. The method of claim 1, wherein the method comprises the steps of: the calcination time in S5 is 2h, and the calcination temperature is 500 ℃.
8. The application of the halloysite nanotube composite material in uranium pollution treatment is characterized by comprising the following application methods:
adjusting the volume of the uranium-containing wastewater to be treated and the mass ratio of the halloysite nanotube composite material HNT @ PZS-500 adsorbent to be 50mL:0.010g, adjusting the pH value to 3-9, the adsorption temperature to 25-45 ℃, the adsorption time to 5-180min and the oscillation speed to 300rad/min.
9. The use of a halloysite nanotube composite material according to claim 8 in uranium contamination treatment, wherein: the adsorption time is 60min, the pH value is adjusted to 5.0, and the adsorption temperature is 25 ℃.
10. The use of a halloysite nanotube composite material according to claim 8 in uranium contamination treatment, wherein: the pH value is adjusted by 0.5mol/L hydrochloric acid solution and 1mol/L sodium hydroxide solution.
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