CN115245833B - Preparation method, product and application of high-efficiency ozone catalyst hydrofluoric acid modified alumina - Google Patents
Preparation method, product and application of high-efficiency ozone catalyst hydrofluoric acid modified alumina Download PDFInfo
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 124
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 64
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 16
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004098 Tetracycline Substances 0.000 claims description 7
- 229960002180 tetracycline Drugs 0.000 claims description 7
- 229930101283 tetracycline Natural products 0.000 claims description 7
- 235000019364 tetracycline Nutrition 0.000 claims description 7
- 150000003522 tetracyclines Chemical class 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960001699 ofloxacin Drugs 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000033558 biomineral tissue development Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 238000006385 ozonation reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- -1 aluminum hydroxide fluoride Chemical compound 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of high-efficiency ozone catalyst hydrofluoric acid modified alumina, which comprises the following steps: mixing aluminum sec-butoxide with an alcohol reagent, adding hydrofluoric acid solution for reaction, forming gel, drying and calcining to obtain the high-efficiency ozone catalyst hydrofluoric acid modified alumina. According to the preparation method, fluorine is introduced in the preparation process of the alumina so as to prepare the high-efficiency ozone catalyst hydrofluoric acid modified alumina, so that the fluorine is uniformly distributed in the alumina, the content is easy to regulate and control, the electron cloud density on the alumina can be effectively reduced, the Lewis acidity of the alumina is enhanced, and the alumina and O are enhanced 3 Is to catalyze the interaction of O 3 And more hydroxyl radicals are generated by rapid decomposition, so that the oxidative degradation of organic pollutants in water is enhanced, and the mineralization degree of the organic pollutants is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of water pollution strengthening treatment, and particularly relates to a preparation method, a product and application of an efficient ozone catalyst hydrofluoric acid modified alumina.
Background
With the continuous development of industry, a great deal of water and energy are consumed in the production process, so that the discharge amount of wastewater is gradually increased. The industrial wastewater has complex sources, and the generated wastewater has multiple types, high chromaticity and large toxicity, and is especially used in textile printing and dyeing, papermaking chemical industry, food processing, biopharmaceuticals and other industries. The pollution problems of various industries are continuously accumulated, the development of low-carbon economy is hindered, and the problem of how to improve the industrial wastewater which is difficult to treat is urgent. The catalytic ozonation technology is an efficient and green advanced oxidation technology (AOPs) which can degrade organic pollutants with high efficiency and is widely applied to the water pollution treatment market.
The traditional homogeneous catalytic ozonation technology mainly uses transition metal ions to catalyze ozone to decompose active oxygen species, so as to oxidize and degrade organic pollutants into carbon dioxide and water, thereby thoroughly removing the organic pollutants. However, the homogeneous catalyst is not easy to recycle, the problem of subsequent removal exists in the introduction of metal ions, otherwise secondary pollution to the water body is easy to cause, and the application of the homogeneous catalytic ozonation technology in water treatment is limited. The heterogeneous catalytic ozonation technology adopts a solid catalyst which is more suitable for practical production, and is one of research hotspots at present.
Heterogeneous catalytic ozonation uses solid loaded with active components as a catalyst to form a catalytic oxidation system with three phases of gas, liquid and solid, so as to promote the generation of hydroxyl free radicals. The common solid catalyst mainly comprises three kinds of carbon materials, metal oxides and supported metal oxides. The metal oxide represented by alumina has wide sources and easy treatment, but has low catalytic activity and limited capability of catalyzing ozone to form hydroxyl radicals.
The catalytic activity of the alumina is related to Lewis acid sites on the surface of the metal oxide, and the more the surface hydroxyl groups are, the more the surface acid sites are, the stronger the adsorption and catalytic ozonolysis activities are. Doping/loading of the more catalytically active components into the metal oxide is thus currently the main direction for increasing the catalytic activity of heterogeneous catalysts. Fluorine is the element with the strongest electronegativity, and the fluorine atom doped metal oxide can further change the charge distribution of metal atoms around the doped site, so that ozone decomposition is promoted to generate active oxygen free radicals. Therefore, fluorine is doped into the alumina to enhance the catalytic ozone activity, improve the defect of low catalytic activity of metal oxide and promote the development of catalytic ozonation technology.
However, in the fluorine-doped alumina prepared in the prior art, fluorine elements are unevenly distributed in the alumina, the content of fluorine elements doped in the alumina is not easy to regulate and control, and the catalytic activity of the fluorine-doped alumina product is affected.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method, a product and application of an efficient ozone catalyst hydrofluoric acid modified alumina.
A preparation method of high-efficiency ozone catalyst hydrofluoric acid modified alumina comprises the following steps:
mixing aluminum sec-butoxide with an alcohol reagent, adding hydrofluoric acid solution for reaction, forming gel, drying and calcining to obtain the high-efficiency ozone catalyst hydrofluoric acid modified alumina.
According to the preparation method, aluminum sec-butoxide and an alcohol reagent are used as substrates, hydrofluoric acid is added to prepare amorphous aluminum hydroxide fluoride gel, and then the amorphous aluminum hydroxide fluoride gel is dried and calcined to obtain the gamma-type high-efficiency ozone catalyst hydrofluoric acid modified alumina with the best catalytic adsorption effect. Fluorine is introduced before aluminum hydroxide fluoride gel (precursor) is prepared, so that the fluorine is distributed in aluminum oxide (surface and inside) more uniformly, the Lewis acid position of the aluminum oxide surface is increased, and the Lewis acid of the aluminum oxide surface is enhanced; and the content of fluorine doped in the alumina is easier to regulate and control, so that the fluorine doping amount with optimal catalytic effect can be obtained, and the catalytic efficiency is improved.
Preferably, after the aluminum sec-butoxide is mixed with the alcohol reagent, hydrofluoric acid solution is added under constant temperature stirring, and stirring reaction is continued until gel is formed.
More preferably, the stirring time is 1 to 12 hours and the constant temperature is 20 to 30 ℃. More preferably 2 to 10 hours. More preferably 2 to 4 hours.
Preferably, the gel is formed and then equilibrated for 1 to 12 hours, followed by drying and calcination. More preferably 3 to 10 hours. More preferably 3 to 6 hours.
Alternatively, an appropriate amount of water is added simultaneously with the addition of the hydrofluoric acid solution.
Preferably, the molar volume ratio of the aluminum sec-butoxide to the alcohol reagent is 1 mol/(1 to 100) L.
Further preferably 1 mol/(1 to 50) L. Still more preferably 1 mol/(1 to 30) L. Further preferably 1 mol/(1 to 10) L.
Preferably, the alcohol reagent is one or more of methanol, ethanol, n-propanol and isopropanol. Further preferred is one or a mixture of isopropyl alcohol and n-propyl alcohol.
Preferably, the molar ratio of the hydrogen fluoride to the aluminum sec-butoxide in the hydrofluoric acid solution is 1: (0.1-20).
Further preferably 1: (0.5-10). Still more preferably 1: (0.5-5).
Preferably, the calcination temperature is 100 to 700 ℃. Further preferably 300 to 700 ℃. Still more preferably 500 to 700 ℃.
Preferably, the calcination time is 2 to 48 hours. More preferably 5 to 24 hours. More preferably 10 to 12 hours.
Preferably, after the calcination is finished, the obtained solid is washed by ethanol and deionized water and then dried, and the high-efficiency ozone catalyst hydrofluoric acid modified alumina is obtained.
Preferably, the calcination can be performed in a muffle furnace, and after the calcination is performed for a set time at a set temperature, the high-efficiency ozone catalyst hydrofluoric acid modified alumina is obtained by washing and drying.
The high-efficiency ozone catalyst prepared by the preparation method has a plurality of Lewis acid sites on the surface of the hydrofluoric acid modified alumina and extremely strong acidity, and can catalyze ozone (O) efficiently 3 ) The active oxygen species with stronger oxidizing ability are generated by decomposition, so that the degradation rate and mineralization rate of organic pollutants in the wastewater are greatly improved.
An efficient ozone catalyst hydrofluoric acid modified alumina, which is prepared by the preparation method of any one of the above. The high-efficiency ozone catalyst of the invention, hydrofluoric acid modified alumina, can improve ozone degradation reaction, catalyze ozone to be effectively decomposed into hydroxyl free radicals, improve efficiency of ozone reaction degradation and mineralization of organic pollutants in water, and can be applied to water pollution strengthening treatment.
The application of the high-efficiency ozone catalyst hydrofluoric acid modified alumina in degrading organic pollutants in wastewater.
Preferably, the organic contaminant is one or more of salicylic acid, p-nitrophenol, ofloxacin, tetracycline, or an analog of any of the above. P-nitrophenol or tetracycline is further preferred.
Preferably, the high-efficiency ozone catalyst hydrofluoric acid modified alumina is added into the wastewater containing the organic pollutants, ozone is introduced, and ozone catalytic oxidation is carried out.
Preferably, the organic contaminant concentration is 10 to 300ppm. Further preferably 10 to 200ppm. Still more preferably 10 to 100ppm.
Preferably, the fluorine-doped alumina catalyst is added in an amount of 0.1 to 20. 20g L -1 . Further preferably 0.1 to 10. 10g L -1 . More preferably 0.1 to 3. 3g L -1 。
Preferably, the concentration of ozone is 0.001 to 1. 1g L -1 The flow rate is 10-200 mL min -1 . More preferably, the concentration of ozone is 0.001 to 0.5. 0.5g L -1 The flow rate is 10-150 mL min -1 . More preferably, the concentration of ozone is 0.001 to 0.1. 0.1g L -1 The flow rate is 40-120 mL min -1 。
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method, fluorine is introduced in the preparation process of the alumina so as to prepare the high-efficiency ozone catalyst hydrofluoric acid modified alumina, so that the fluorine is uniformly distributed in the alumina, the content is easy to regulate and control, the electron cloud density on the alumina can be effectively reduced, the Lewis acidity of the alumina is enhanced, and the alumina and O are enhanced 3 Is to catalyze the interaction of O 3 And more hydroxyl radicals are generated by rapid decomposition, so that the oxidative degradation of organic pollutants in water is enhanced, and the mineralization degree of the organic pollutants is remarkably improved.
Drawings
FIG. 1 is an SEM morphology of the high efficiency ozone catalyst hydrofluoric acid modified alumina prepared in example 1;
FIG. 2 is a graph showing the residual rate of ozone oxidation of p-nitrophenol over time for hydrofluoric acid modified alumina catalysts with different F doping levels.
Detailed Description
The technical scheme of the present invention will be further described by the following examples.
Example 1
The preparation method of the high-efficiency ozone catalyst hydrofluoric acid modified alumina comprises the steps of mixing aluminum sec-butoxide, isopropanol and hydrofluoric acid solution to form gel, evaporating, drying and calcining to obtain the high-efficiency ozone catalyst hydrofluoric acid modified alumina.
A preparation method of high-efficiency ozone catalyst hydrofluoric acid modified alumina comprises the following steps:
(1) 0.02mol of aluminum sec-butoxide was added to 100mL of isopropanol with vigorous stirring, a hydrofluoric acid solution containing 0.01mol of hydrogen fluoride and 10 equivalents of deionized water were added, stirred at 25℃for 3 hours, the resulting gel was equilibrated for 4 hours, and the solvent was evaporated to give a precursor solid.
(2) And (3) placing the precursor solid into a crucible to react for 12 hours at 700 ℃ in a muffle furnace, washing and drying the obtained solid by ethanol and deionized water, and drying at a low temperature to obtain the high-efficiency ozone catalyst hydrofluoric acid modified alumina.
The hydrofluoric acid modified alumina of the high-efficiency ozone catalyst prepared above is mainly in a rod shape with two pointed ends (shown in figure 1), wherein the diameter is about 6 mu m.
Example 2
The preparation method of the high-efficiency ozone catalyst hydrofluoric acid modified alumina comprises the following steps:
(1) 0.02mol of aluminum sec-butoxide was added to 150mL of isopropanol with vigorous stirring, a hydrofluoric acid solution containing 0.02mol of hydrogen fluoride and 10 equivalents of deionized water were added, stirred at 25℃for 3 hours, the resulting gel was equilibrated for 4 hours, and the solvent was evaporated to give a precursor solid.
(2) And (3) placing the precursor solid into a crucible to react for 12 hours at 700 ℃ in a muffle furnace, washing and drying the obtained solid by ethanol and deionized water, and drying at a low temperature to obtain the high-efficiency ozone catalyst hydrofluoric acid modified alumina.
Example 3
The preparation method of the high-efficiency ozone catalyst hydrofluoric acid modified alumina comprises the following steps:
(1) 0.02mol of aluminum sec-butoxide was added to 50mL of isopropanol with vigorous stirring, a hydrofluoric acid solution containing 0.005mol of hydrogen fluoride and 10 equivalents of deionized water were added, stirred at 25℃for 3 hours, the resulting gel was equilibrated for 4 hours, and the solvent was evaporated to give a precursor solid.
(2) And (3) placing the precursor solid into a crucible to react for 12 hours at 700 ℃ in a muffle furnace, washing and drying the obtained solid by ethanol and deionized water, and drying at a low temperature to obtain the high-efficiency ozone catalyst hydrofluoric acid modified alumina.
Degradation Performance test
The degradation rates of the hydrofluoric acid-modified alumina p-nitrophenol obtained in examples 1 to 3 were respectively tested according to the following procedures, and were tested with no catalyst added as a control group:
300mL of 10mg L -1 Placing p-nitrophenol solution (water as solvent) in beaker, placing in heat collecting magnetic stirrer, regulating temperature of heat collecting magnetic stirrer to 25deg.C, and rotating at 200rpm for min -1 . Accurately weighing 120mg of the fluorine-doped alumina catalyst, adding the catalyst into the p-nitrophenol solution, and introducing O into the system 3 (concentration is 3mg L) -1 The flow rate is 120mL min -1 ) The ozonation reaction is triggered. 5mL (0 min, 5min, 10min, 15min, 20min, 25min, 30 min) was sampled every 5min, filtered through a 0.22 μm needle filter, and residual ozone and reactive oxygen species in the filtrate were rapidly quenched with 10. Mu.L t-butanol. Each set of experiments was repeated three times.
The concentration of p-nitrophenol is measured by adopting an Agilent 1260 type high performance liquid chromatograph, and the analysis conditions are as follows: agilent ZORBAX Eclipse XDB-C18 chromatographic column (3.5 μm,4.6 x 150 mm) is used as stationary phase, column temperature is 30deg.C, mobile phase is mixed solution of water and methanol (30/70), and flow rate and sample injection amount are respectively 0.8mL min -1 And 20. Mu.L. The retention time of p-nitrophenol is2.14min. The concentration C of the sample is sampled at the time points of 0min, 5min, 10min, 15min, 20min, 25min and 30min t With the initial concentration C of the p-nitrophenol solution 0 The ratio is plotted on the ordinate, the time point is plotted on the abscissa, and the result is shown in fig. 2.
As can be seen from FIG. 2, after 30 minutes of reaction, hydrofluoric acid modified aluminas prepared in examples 1 to 3 (F are shown in the figure respectively 0.5 -Al 2 O 3 +O 3 、F 1 -Al 2 O 3 +O 3 、F 0.25 -Al 2 O 3 +O 3 ) The degradation rates of the p-nitrophenol are 98.31%, 99.15% and 93.14% respectively. The degradation rate of the hydrofluoric acid modified aluminum oxide p-nitrophenol prepared in examples 1 to 3 gradually increases with the doping amount of fluorine, and the hydrofluoric acid modified aluminum oxide prepared in example 2 (the molar ratio of the hydrogen fluoride to the aluminum sec-butoxide is 1:1) can reach the maximum degradation rate in the shortest time, which is the best example.
Example 4
The preparation method of the high-efficiency ozone catalyst hydrofluoric acid modified alumina comprises the following steps:
(1) 0.02mol of aluminum sec-butoxide was added to 50mL of isopropanol with vigorous stirring, a hydrofluoric acid solution containing 0.01mol of hydrogen fluoride and 10 equivalents of deionized water were added, stirred at 25℃for 3 hours, the resulting gel was equilibrated for 4 hours, and the solvent was evaporated to give a precursor solid.
(2) And (3) placing the precursor solid into a crucible to react for 12 hours at 700 ℃ in a muffle furnace, washing and drying the obtained solid by ethanol and deionized water, and drying at a low temperature to obtain the high-efficiency ozone catalyst hydrofluoric acid modified alumina.
By adopting the degradation performance test method in the embodiment 1, the p-nitrophenol solution is replaced by the tetracycline solution, and after 30 minutes of reaction is obtained by test, the degradation rate of the high-efficiency ozone catalyst hydrofluoric acid modified alumina prepared in the embodiment to the tetracycline solution is 91.33%.
Example 5
The preparation method of the high-efficiency ozone catalyst hydrofluoric acid modified alumina comprises the following steps:
(1) 0.02mol of aluminum sec-butoxide was added to 100mL of n-propanol with vigorous stirring, a hydrofluoric acid solution containing 0.02mol of hydrogen fluoride and 10 equivalents of deionized water were added, stirred at 25℃for 3 hours, the resulting gel was equilibrated for 4 hours, and the solvent was evaporated to give a precursor solid.
(2) And (3) placing the precursor solid into a crucible to react for 12 hours at 700 ℃ in a muffle furnace, washing and drying the obtained solid by ethanol and deionized water, and drying at a low temperature to obtain the high-efficiency ozone catalyst hydrofluoric acid modified alumina.
By adopting the degradation performance test method in the embodiment 1, the p-nitrophenol solution is replaced by the tetracycline solution, and after the reaction is measured for 30min, the degradation rate of the high-efficiency ozone catalyst hydrofluoric acid modified alumina prepared in the embodiment on the tetracycline solution is 95.25%.
Claims (3)
1. An application of a high-efficiency ozone catalyst hydrofluoric acid modified alumina in degrading organic pollutants in wastewater is disclosed, wherein the high-efficiency ozone catalyst hydrofluoric acid modified alumina is added into the wastewater containing the organic pollutants, and ozone is introduced; wherein the concentration of the organic pollutants is 10-300 ppm; the input amount of the fluorine doped alumina catalyst is 0.1-20 g L -1 The method comprises the steps of carrying out a first treatment on the surface of the Ozone is introduced to a concentration of 0.001-1 g L -1 The flow rate is 10-200 mL min -1 ;
The preparation method of the high-efficiency ozone catalyst hydrofluoric acid modified alumina comprises the following steps:
mixing aluminum sec-butoxide with an alcohol reagent, adding hydrofluoric acid solution for reaction to form gel, and drying and calcining to obtain the high-efficiency ozone catalyst hydrofluoric acid modified alumina; adding proper amount of water while adding hydrofluoric acid solution;
the calcination temperature is 500-700 ℃, and the calcination time is 10-12 hours;
the molar volume ratio of the aluminum sec-butoxide to the alcohol reagent is 1 mol/(1-100) L;
the alcohol reagent is one or more of methanol, ethanol, n-propanol and isopropanol;
the molar ratio of the hydrogen fluoride to the aluminum sec-butoxide in the hydrofluoric acid solution is 1: (0.1 to 20).
2. The application of the high-efficiency ozone catalyst hydrofluoric acid modified alumina in degrading organic pollutants in wastewater, which is characterized in that after gel formation, the alumina is balanced for 1-12 hours and then dried and calcined.
3. The use of the high efficiency ozone catalyst hydrofluoric acid modified alumina of claim 1 for degrading organic contaminants in wastewater, wherein the organic contaminants are one or more of salicylic acid, p-nitrophenol, ofloxacin, tetracycline or analogues of any of the above.
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