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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- 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 47
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 45
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000008367 deionised water Substances 0.000 claims abstract description 33
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 26
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- 230000007935 neutral effect Effects 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002071 nanotube Substances 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 35
- 230000000593 degrading effect Effects 0.000 abstract description 10
- 229910052603 melanterite Inorganic materials 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical class [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- WXBLLCUINBKULX-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 WXBLLCUINBKULX-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910006540 α-FeOOH Inorganic materials 0.000 description 1
- 229910003153 β-FeOOH Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
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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| CN114308134A (en) * | 2022-01-11 | 2022-04-12 | 北京科技大学 | Method for preparing metal oxide microreactor by using halloysite nanotubes and application of method |
| CN114950433A (en) * | 2022-06-24 | 2022-08-30 | 河北科技大学 | Fe 0 @Fe 3 O 4 Preparation method and application of volcanic catalyst |
| CN114797876A (en) * | 2022-06-30 | 2022-07-29 | 广东工业大学 | Preparation method and application of photo-Fenton catalyst |
| 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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