CN112169727A - Preparation method of halloysite-based micro-nano reactor for advanced catalytic oxidation - Google Patents
Preparation method of halloysite-based micro-nano reactor for advanced catalytic oxidation Download PDFInfo
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Abstract
The invention relates to a preparation method of a halloysite-based micro-nano reactor for advanced catalytic oxidation, belonging to the technical field of inorganic non-metallic materials. The method comprises the following specific steps: 1) placing natural halloysite powder in a mixed acid solution, performing ultrasonic dispersion for 5-8 hours, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃; 2) putting the product obtained in the step 1) into a modifier solution, stirring for 12-24 h at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃; 3) placing the product obtained in the step 2) in deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, then adding mixed alkali liquor,crystallizing at 80-95 ℃ for 2-5 h, centrifugally separating, and drying; 4) putting the product obtained in the step 3) into an organic pollutant solution, adding an oxidant, and completely degrading the organic pollutants after reacting for a plurality of times.
Description
Technical Field
The invention provides natural halloysite nano-tube in-situ growth of nano-Fe3O4The preparation method develops a novel micro-nano reactor for advanced catalytic oxidation to obtain a novel composite material with high catalytic activity, and belongs to inorganic non-goldBelongs to the technical field of materials.
Background
The organic pollution of water body is increasingly worsened in the global scope, the social and environmental problems caused by the organic pollution cause high attention of governments of all countries, and the demand of novel high-efficiency organic pollutant purification technology is more urgent. The biologically-nondegradable organic polluted wastewater has various types, high toxicity and stable structure, and is difficult to effectively treat by adopting the traditional physical chemistry or biodegradation method, thereby becoming a hotspot and a difficulty which are concerned in the environmental field. In recent years, advanced catalytic oxidation (advanced catalytic oxidation) is widely applied to the treatment of refractory organic polluted wastewater. The advanced catalytic oxidation technology takes transition metal ions as a catalyst to catalyze hydrogen peroxide or persulfate to generate hydroxyl radicals or sulfuric acid radicals with high oxidation activity, and the hydroxyl radicals or the sulfuric acid radicals can be used for indiscriminately oxidizing and degrading stubborn organic pollutants which are difficult to treat by other technologies in water. Although highly effective, advanced catalytic oxidation technology has a number of disadvantages in practical applications: the reaction pH value range is narrow, the utilization rate of hydrogen peroxide or persulfate is low, and transition metal ions are difficult to recover, so that secondary pollution is formed. To overcome these disadvantages, heterogeneous catalysts have received a great deal of attention, in which transition metal ions are immobilized in the structure of a solid catalyst.
In recent years, advanced catalytic oxidation techniques using different iron (hydroxy) oxides as catalysts have been extensively studied, such as Fe3O4、Fe2O3alpha-FeOOH, beta-FeOOH, etc., in which Fe has an inverse spinel structure3O4The catalytic activity is highest. Fe3O4The octahedral sites of the structure can accommodate both divalent fe (ii) and trivalent fe (iii), where the iron ions can be reversibly oxidized and reduced without changing the crystal structure. Further, Fe3O4Can be recycled by simple magnetic separation, has low solubility in water and good catalytic stability, and is considered to be a heterogeneous catalyst with great potential. However, nano Fe3O4The particles are easy to agglomerate in water body, the specific surface area and reactive site are reduced, and the reactive activity is reduced, the immobilization isSolving the aggregation problem and improving the dispersity.
The micro-nano reactor shows excellent chemical reaction activity due to the special confinement effect and the selective effect, and has generally attracted attention in the fields of chemistry, biology, medicine, materials and the like in recent years. At present, the micro-nano reactor is mostly artificially synthesized, and comprises a core-shell structure, a yolk-eggshell structure and the like, and commonly used materials mainly comprise a molecular sieve, mesoporous silica, a mesoporous carbon material, a layered silicate, a carbon nano tube and the like, so that the cost of the micro-nano reactor is undoubtedly increased. The natural Halloysite Nanotubes (HNTs) also have a typical hollow tubular structure, belong to clay minerals, and are rich in resources, cheap and easy to obtain. The halloysite nanotube has the advantages of high porosity, large specific surface area, adjustable surface chemical property, excellent thermal stability and the like, is widely applied and is an ideal choice for constructing a micro-nano reactor.
Mixing nano Fe3O4The particles grow in situ in the natural halloysite nanotube and are used as a micro-nano reactor for advanced catalytic oxidation. Nano Fe3O4The reactions of hydrogen peroxide or persulfate, free radicals with high oxidation activity and organic pollutants are catalyzed in the halloysite nanotube, and the limited domain effect and the selective effect of the microenvironment in the nanotube are utilized to enhance the catalytic oxidation reaction activity and improve the degradation efficiency of the organic pollutants. Moreover, China has rich halloysite resources and wide distribution, and is a big halloysite resource country. The implementation of the patent has important theoretical significance for the development of advanced catalytic oxidation technology and the promotion of comprehensive crossing and organic fusion of multiple disciplines. Meanwhile, the additional value of halloysite development and utilization in China can be improved, the structure adjustment of the traditional industry is promoted, the application research and development of halloysite in the environmental protection field are enhanced and deepened, and the resource advantages and characteristics in China are fully exerted.
Disclosure of Invention
The invention realizes the nanometer Fe by utilizing the natural halloysite nanotube structure3O4The in-situ growth of the particles in the tube develops a high-efficiency micro-nano reactor for advanced catalytic oxidation technology.
The invention providesThe basic idea is to combine the characteristics of components in the halloysite nano-tube and adopt a modifier to realize the expansion of the inner diameter of the tube and graft the inner diameter of the tube with a polymer group. The grafting group and the electrostatic adsorption of ferrous ions are utilized to make the ferrous ions adhere to the inner wall of the tube, and then the control of experimental conditions is utilized to realize the nano Fe3O4In situ growth of particles within the tube. Thereby obtaining the halloysite-based micro-nano reactor for advanced catalytic oxidation.
The invention provides a preparation method of a halloysite-based micro-nano reactor for advanced catalytic oxidation, which has the following main technical scheme:
1) acidifying and purifying the natural halloysite nanotube: placing natural halloysite powder in a mixed acid solution, performing ultrasonic dispersion for 5-8 hours, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃ for later use;
2) modifying in the halloysite nanotube: placing the purified halloysite in a modifier solution with a certain concentration, stirring for 12-24 h at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃ for later use;
3) nano Fe3O4In-situ growth in the tube: placing the modified halloysite nanotube into deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2And O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, adding mixed alkali liquor, crystallizing for 2-5 h at the temperature of 80-95 ℃, performing centrifugal separation, and drying to obtain the in-situ grown nano Fe in the tube3O4The halloysite-based micro-nano reactor;
4) advanced catalytic oxidation applications: growing nano Fe in situ in the tube3O4The halloysite nanotube is placed in an organic pollutant solution with a certain concentration, an oxidant is added, advanced catalytic oxidation is carried out in a halloysite-based micro-nano reactor, and the organic pollutants are efficiently degraded.
In the above technical solution of the present invention, the mixed acid used in step 1) is two of concentrated sulfuric acid, concentrated phosphoric acid, concentrated hydrochloric acid, and concentrated nitric acid.
In the technical scheme of the invention, the modifier used in the step 2) is one or a combination of several of sulfamic acid, sodium dodecyl benzene sulfonate, oxalic acid, acetic acid, vinyl acetate, citric acid, sodium citrate, ethylenediamine tetraacetic acid, benzoic acid, ammonium persulfate, toluene, xylene, propyl methyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, methyl ethyl ketoxime, azobisisobutyronitrile, dibenzoyl peroxide and methyl methacrylate.
In the above technical scheme of the invention, the mixed alkali liquor used in the step 3) is NaOH, KOH or Na2CO3、K2CO3、NaHCO3、KHCO3、NaNO3、KNO3One or a combination of several of them.
In the technical scheme of the invention, the oxidant used in the step 4) is hydrogen peroxide or persulfate.
In the technical scheme of the invention, the purity of the used chemical reagent is not lower than that of analytical purity.
The invention provides a preparation method of a halloysite-based micro-nano reactor for advanced catalytic oxidation, and Fe obtained by the preparation method3O4The particle size is 5 to 10 nm. The method provided by the invention is simple to operate, easy to control, low in synthesis temperature, low in energy consumption, low in preparation cost, green and environment-friendly in used reagent, non-toxic, non-corrosive and capable of realizing batch production.
Drawings
FIG. 1 is an XRD pattern of a representative sample;
FIG. 2 is a TEM photograph of a representative sample;
fig. 3 is an evaluation of catalytic oxidation performance of representative samples.
Detailed Description
Example 1
1) Placing natural halloysite powder in a mixed solution of concentrated sulfuric acid and concentrated phosphoric acid (volume ratio is 1:1), performing ultrasonic dispersion for 5-8 hours, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃ for later use;
2) placing the product obtained in the step 1) in a mixed solution of sulfamic acid and ethylene diamine tetraacetic acid, stirring for 12-24 h at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃ for later use;
3) placing the product obtained in the step 2) in deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2And O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, and then adding NaOH and Na2CO3Crystallizing the mixed solution at 80-95 ℃ for 2-5 h, performing centrifugal separation, and drying to obtain a product;
4) putting the product obtained in the step 3) into an organic pollutant solution, adding hydrogen peroxide, and completely degrading the organic pollutants after a certain time.
Example 2
1) Placing natural halloysite powder in a mixed solution of concentrated sulfuric acid and concentrated hydrochloric acid (volume ratio is 2:1), performing ultrasonic dispersion for 5-8 hours, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃ for later use;
2) putting the product obtained in the step 1) into an N-aminoethyl-3-aminopropylmethyldimethoxysilane solution, stirring for 12-24 h at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃ for later use;
3) placing the product obtained in the step 2) in deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2And O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, and then adding NaOH and KHCO3Crystallizing the mixed solution at 80-95 ℃ for 2-5 h, performing centrifugal separation, and drying to obtain a product;
4) putting the product obtained in the step 3) into an organic pollutant solution, adding persulfate, and completely degrading the organic pollutants after a plurality of times.
Example 3
1) Placing natural halloysite powder in a mixed solution of concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3:1), performing ultrasonic dispersion for 5-8 hours, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃ for later use;
2) putting the product obtained in the step 1) into an acetic acid solution, stirring for 12-24 h at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃ for later use;
3) placing the product obtained in the step 2) in deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2And O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, and then adding NaOH and NaNO3Crystallizing the mixed solution at 80-95 ℃ for 2-5 h, performing centrifugal separation, and drying to obtain a product;
4) putting the product obtained in the step 3) into an organic pollutant solution, adding hydrogen peroxide, and completely degrading the organic pollutants after a certain time.
Example 4
1) Placing natural halloysite powder in a mixed solution of concentrated phosphoric acid and concentrated nitric acid (volume ratio is 4:1), performing ultrasonic dispersion for 5-8 hours, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃ for later use;
2) placing the product obtained in the step 1) in a citric acid solution, stirring for 12-24 h at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃ for later use;
3) placing the product obtained in the step 2) in deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, and then adding NaHCO3And NaNO3Crystallizing the mixed solution at 80-95 ℃ for 2-5 h, performing centrifugal separation, and drying to obtain a product;
4) putting the product obtained in the step 3) into an organic pollutant solution, adding persulfate, and completely degrading the organic pollutants after a plurality of times.
Example 5
1) Placing natural halloysite powder in a mixed solution of concentrated phosphoric acid and concentrated hydrochloric acid (volume ratio is 5:1), performing ultrasonic dispersion for 5-8 hours, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃ for later use;
2) placing the product obtained in the step 1) in a mixed solution of azodiisobutyronitrile and dibenzoyl peroxide, stirring for 12-24 h at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃ for later use;
3) placing the product obtained in the step 2) in deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2And O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, and then adding NaOH and NaHCO3Crystallizing the mixed solution at 80-95 ℃ for 2-5 h, performing centrifugal separation, and drying to obtain a product;
4) putting the product obtained in the step 3) into an organic pollutant solution, adding hydrogen peroxide, and completely degrading the organic pollutants after a certain time.
Example 6
1) Placing natural halloysite powder in a mixed solution of concentrated nitric acid and concentrated hydrochloric acid (volume ratio is 6:1), performing ultrasonic dispersion for 5-8 hours, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃ for later use;
2) placing the product obtained in the step 1) in a mixed solution of toluene and propyl methyl dimethoxy silane, stirring for 12-24 h at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃ for later use;
3) placing the product obtained in the step 2) in deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, adding a mixed solution of NaOH and KOH, crystallizing for 2-5 h at the temperature of 80-95 ℃, performing centrifugal separation, and drying to obtain a product;
4) putting the product obtained in the step 3) into an organic pollutant solution, adding persulfate, and completely degrading the organic pollutants after a plurality of times.
Example 7
1) Placing natural halloysite powder in a mixed solution of concentrated nitric acid and concentrated phosphoric acid (volume ratio is 6:1), performing ultrasonic dispersion for 5-8 h, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃ for later use;
2) putting the product obtained in the step 1) into a mixed solution of sodium citrate and benzoic acid, stirring for 12-24 h at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃ for later use;
3) placing the product obtained in the step 2) in deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2And O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, and adding KOH and KHCO3Crystallizing the mixed solution at 80-95 ℃ for 2-5 h, performing centrifugal separation, and drying to obtain a product;
4) putting the product obtained in the step 3) into an organic pollutant solution, adding hydrogen peroxide, and completely degrading the organic pollutants after a certain time.
Example 8
1) Placing natural halloysite powder in a mixed solution of concentrated hydrochloric acid and concentrated phosphoric acid (volume ratio is 7:1), performing ultrasonic dispersion for 5-8 hours, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃ for later use;
2) placing the product obtained in the step 1) in a mixed solution of sodium dodecyl benzene sulfonate and oxalic acid, stirring for 12-24 hours at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃ for later use;
3) placing the product obtained in the step 2) in deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2And O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, and then adding KOH and KNO3Crystallizing the mixed solution at 80-95 ℃ for 2-5 h, performing centrifugal separation, and drying to obtain a product;
4) putting the product obtained in the step 3) into an organic pollutant solution, adding persulfate, and completely degrading the organic pollutants after a plurality of times.
Claims (5)
1. The invention grows nanometer Fe in situ in the natural halloysite nanotube3O4Developing a novel micro-nano reactor for advanced catalytic oxidation to obtain a new composite material with high catalytic activity, which is characterized by comprising the following process steps:
1) acidifying and purifying the natural halloysite nanotube: placing natural halloysite powder in a mixed acid solution, performing ultrasonic dispersion for 5-8 hours, performing centrifugal separation, alternately washing deionized water and absolute ethyl alcohol until filtrate is neutral, and drying at 60 ℃ for later use;
2) modifying in the halloysite nanotube: placing the purified halloysite in a modifier solution with a certain concentration, stirring for 12-24 h at 50-80 ℃, performing centrifugal separation, washing with deionized water until the filtrate is neutral, and drying at 60 ℃ for later use;
3) nano Fe3O4In-situ growth in the tube: placing the modified halloysite nanotube into deionized water, performing ultrasonic dispersion for 10-30 min, and adding FeSO4·7H2And O, performing ultrasonic dispersion for 10-30 min, placing the obtained suspension in a vacuum bottle, vacuumizing and standing for 1-3 h, performing ultrasonic dispersion again, vacuumizing and standing again, repeating the steps for 3-5 times, adding mixed alkali liquor, crystallizing for 2-5 h at the temperature of 80-95 ℃, performing centrifugal separation, and drying to obtain the in-situ grown nano Fe in the tube3O4The halloysite-based micro-nano reactor;
4) advanced catalytic oxidation applications: growing nano Fe in situ in the tube3O4The halloysite nanotube is placed in an organic pollutant solution with a certain concentration, an oxidant is added, advanced catalytic oxidation is carried out in a halloysite-based micro-nano reactor, and the organic pollutants are efficiently degraded.
2. The method for preparing the halloysite-based micro-nano reactor for advanced catalytic oxidation according to claim 1, wherein the mixed acid used in the step 1) is two of concentrated sulfuric acid, concentrated phosphoric acid, concentrated hydrochloric acid and concentrated nitric acid.
3. The method for preparing the halloysite-based micro-nano reactor for advanced catalytic oxidation according to claim 1, wherein the modifier used in the step 2) is one or a combination of several of sulfamic acid, sodium dodecyl benzene sulfonate, oxalic acid, acetic acid, vinyl acetate, citric acid, sodium citrate, ethylene diamine tetraacetic acid, benzoic acid, ammonium persulfate, toluene, xylene, propyl methyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, methyl ethyl ketoxime, azobisisobutyronitrile, dibenzoyl peroxide and methyl methacrylate.
4. The preparation method of the halloysite-based micro-nano reactor for advanced catalytic oxidation according to claim 1, wherein the mixed alkali solution used in the step 3) is NaOH, KOH or Na2CO3、K2CO3、NaHCO3、KHCO3、NaNO3、KNO3One or a combination of several of them.
5. The preparation method of the halloysite-based micro-nano reactor for advanced catalytic oxidation according to claim 1, wherein the oxidant used in the step 4) is hydrogen peroxide or persulfate.
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| CN114797876B (en) * | 2022-06-30 | 2022-09-23 | 广东工业大学 | Preparation method and application of photo-Fenton catalyst |
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