CN111559795A - Method for catalyzing ozone to oxidize antibiotics in water - Google Patents
Method for catalyzing ozone to oxidize antibiotics in water Download PDFInfo
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- CN111559795A CN111559795A CN202010688831.8A CN202010688831A CN111559795A CN 111559795 A CN111559795 A CN 111559795A CN 202010688831 A CN202010688831 A CN 202010688831A CN 111559795 A CN111559795 A CN 111559795A
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- Prior art keywords
- oxide
- aluminum
- magnesium
- ferroferric oxide
- ferroferric
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 43
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 23
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 94
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 82
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 claims abstract description 40
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000011068 loading method Methods 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- 239000006249 magnetic particle Substances 0.000 claims description 40
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 19
- 239000004202 carbamide Substances 0.000 claims description 19
- 235000013877 carbamide Nutrition 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 16
- 239000001099 ammonium carbonate Substances 0.000 claims description 16
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 12
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 12
- 230000003115 biocidal effect Effects 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 150000000703 Cerium Chemical class 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- AYIRNRDRBQJXIF-NXEZZACHSA-N (-)-Florfenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)C=C1 AYIRNRDRBQJXIF-NXEZZACHSA-N 0.000 claims description 5
- 229960003760 florfenicol Drugs 0.000 claims description 5
- 229960000282 metronidazole Drugs 0.000 claims description 5
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004098 Tetracycline Substances 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
- 229930101283 tetracycline Natural products 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000006385 ozonation reaction Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 24
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 12
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 12
- 239000011565 manganese chloride Substances 0.000 description 12
- 235000002867 manganese chloride Nutrition 0.000 description 12
- 229940099607 manganese chloride Drugs 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 2
- 229940009827 aluminum acetate Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for catalyzing and oxidizing antibiotics in water by ozone, wherein a manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide-catalyst is adopted in the catalytic ozonation process, the catalyst can be effectively separated due to the existence of magnetic ferroferric oxide, the magnesium-aluminum composite oxide grows on the surface of the aluminum oxide, the dispersity of active components is improved, the loading capacity of the active components is reduced, and meanwhile, the catalyst still has excellent catalytic performance, so that the antibiotics in the water can be well removed by the ozone oxidation under the condition of the existence of ozone, the removal rate can reach 99.4%, and the removal rate can still reach 98.1% after 5 times of circulation.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a method for catalyzing ozone to oxidize antibiotics in water.
Background
With the development of times, water pollution has seriously influenced daily life of people, particularly, waste water containing antibiotics has seriously influenced cultivation and human health, and how to effectively treat the waste water containing the antibiotics is a problem which is urgently needed to be solved at present. The antibiotic wastewater mainly comes from a crystal liquid, a waste liquid, washing wastewater and cooling water in the antibiotic production process, and has high pollution degree and high treatment difficulty.
At present, the main methods for treating antibiotic wastewater comprise a physical method, a biological treatment method and a chemical treatment method. The physical method includes an adsorption method, an air floatation method, a sand filtration method, etc., and the adsorption method is one of important methods for treating antibiotic wastewater, and the adsorption method can effectively treat antibiotics by using physical adsorption and chemical adsorption, but the adsorption method is influenced by the pH value, temperature, solubility, etc. of a water body, so that the cost is relatively high. The biological treatment method is an aerobic treatment method, an anaerobic treatment method, a facultative aerobic treatment method and an anaerobic treatment method, although the treatment is quick and the flow is simple, the water treatment capacity of high-concentration antibiotics is poor, the automation degree is poor, and the biological treatment method is not suitable for large-scale production. The chemical treatment method has the characteristics of high treatment efficiency, short period, large treatment capacity and the like, and is widely applied.
Wherein the advanced oxidation method utilizes the strong oxidizing capability of hydroxyl free radicals of strong oxidative active molecules to decompose and remove the antibiotics. The catalytic ozonation technology gradually occupies an important position in the treatment and application of antibiotic wastewater due to the characteristics of high reaction rate, strong oxidation capacity, easily controlled reaction process and the like. Yuchaoyun and the like research the advanced treatment process of the wastewater generated by certain antibiotics by adopting a catalytic oxidation process, explore the influence of pH, contact reaction time, oxidant species and catalyst dosage on CODCr and chromaticity removal rate, and the result shows that: the catalytic ozone oxidation method has obvious treatment effect on the antibiotic wastewater, the CODCr of the wastewater can be reduced to 44 mg/L from the original 300 mg/L, the removal rate reaches 85%, and the effluent quality reaches the discharge standard in the discharge Standard of Water pollutants for pharmaceutical industry of fermentation. The catalytic ozonation technology has stronger oxidizing capability than single ozonation, faster reaction rate and better treatment effect on pollutants. The Sunzhi and the like research the catalytic ozonization degradation of metronidazole by nano Mg (OH)2 with different morphologies, and the results show that in the single ozonization process, the degradation efficiency and the mineralization efficiency of the metronidazole are lower when the reaction is carried out for 10min and are respectively 51.9 percent and 17.4 percent, while Mg (OH)2-1 and Mg (OH)2-2 are respectively added into an ozonization system, the removal efficiency and the mineralization efficiency of the metronidazole are obviously improved, and the catalytic ozonization performance of Mg (OH)2-2 is superior to that of Mg (OH) 2-1. However, the above catalyst is not easily recovered, and the catalytic effect is not so high, and the amount of the catalyst used is also large. Therefore, there is an urgent need to develop a new catalyst which can efficiently catalyze and oxidize antibiotics and efficiently separate antibiotics while reducing the active components, and the problem still needs to be solved at present when the loading amount of the active components is relatively small.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for catalyzing ozone to oxidize antibiotics in water aiming at the defects in the prior art, wherein a manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide catalyst is adopted in the catalytic ozone oxidation process, the catalyst can be effectively separated due to the existence of magnetic ferroferric oxide in the catalyst, and the dispersibility of active components is improved and the loading capacity of the active components is reduced by adopting aluminum oxide to coat the ferroferric oxide and growing the magnesium-aluminum composite oxide on the surface of the aluminum oxide, so that the catalytic ozone has excellent catalytic performance. Under the condition of ozone, the catalyst can well remove antibiotics in water by catalyzing ozone oxidation, the removal rate can reach 99.4%, and the removal rate can still reach 98.1% after 5 times of circulation.
The invention adopts the following technical scheme:
the method for catalyzing the ozone to oxidize the antibiotics in the water comprises the following steps that the concentration of the antibiotics is 50-100 mg/L, the adding amount of a catalyst is 40-60 g, the ozone air input is 1-2L/min, the concentration of ozone is 3-12 mg/L, the catalyst is manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide, the ferroferric oxide is used as a core, the aluminum oxide is coated on the surface of the ferroferric oxide, the magnesium-aluminum oxide grows on the surface of the aluminum oxide, then an active component manganese-cerium composite oxide is loaded, the loading amount of the active component is 0.5-2 wt%, the molar ratio of manganese to cerium is 1: 3-3: 1.
preferably, the antibiotic comprises one or more of tetracycline, metronidazole and florfenicol.
Preferably, the preparation method of the catalyst comprises the following steps:
(1) preparing ferroferric oxide magnetic particles;
(2) preparing aluminum oxide coated ferroferric oxide:
mixing ferroferric oxide magnetic particles, an aluminum source and a precipitator in 40-60 mL of solvent water, refluxing at 80-100 ℃ under stirring for hydrolysis reaction for 1-3 h, centrifuging, washing and drying to obtain aluminum hydroxide coated ferroferric oxide particles, and calcining at 450-550 ℃ for 1-3 h to obtain aluminum oxide coated ferroferric oxide particles;
(3) preparation of magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Immersing the alumina-coated ferroferric oxide particles prepared in the step (2) in a magnesium salt solution, adding a certain amount of urea into the mixed aqueous solution, carrying out heat treatment at 70-90 ℃ for 12-24 hours, filtering, washing, drying at 90-140 ℃ for 2-6 hours, and roasting at 400-600 ℃ for 2-6 hours to obtain a magnesium-aluminum composite oxide @ alumina @ ferroferric oxide;
(4) preparation of manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Preparing an aqueous solution containing manganese salt and cerium salt, wherein the molar ratio of the manganese salt to the cerium salt is 1: 3-3: soaking the magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide in the step (3) into the solution for 2-4 h, drying at 100-140 ℃ for 2-6 h, and roasting at 400-600 ℃ for 2-6 h to obtain manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide, wherein the loading amount of the manganese-cerium composite oxide is 0.5-2 wt%.
Preferably, in the step (1), the preparation process of the ferroferric oxide magnetic particles is as follows: weighing a ferrous iron source and anhydrous sodium acetate, wherein the molar ratio of the ferrous iron source to the anhydrous sodium acetate is 1: 8-10, 100-140 mL of ethylene glycol is placed into a polytetrafluoroethylene high-pressure reaction kettle and stirred and dissolved completely, after stirring for 20-40 min, sealing and heating to 180-240 ℃, keeping the temperature for 3-6 h, after the reaction is finished, taking out and cooling to room temperature, washing the obtained black magnetic sample with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 40-60 ℃ for 10-14 h to obtain the ferroferric oxide magnetic particles.
Preferably, in the step (1), the ferrous source is one or more selected from ferrous chloride, ferrous sulfate and ferrous acetate.
Preferably, in the step (2), the aluminum source is at least one selected from chloride, sulfate, nitrate, acetate and alkoxide of aluminum element; the precipitant is selected from at least one of urea, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
Preferably, in the step (3), the magnesium salt is selected from one or more of magnesium sulfate, magnesium nitrate, magnesium acetate and magnesium chloride.
Preferably, in the step (4), the manganese salt or cerium salt is selected from at least one of chloride, sulfate, nitrate, and acetate.
Preferably, in the step (2), the mass ratio of the ferroferric oxide magnetic particles to the aluminum source to the precipitant is 1: 0.5-1: 5-10.
Preferably, in the step (3), the molar ratio of the urea to the magnesium salt is 2-10: 1; the molar ratio of the aluminum oxide to the magnesium salt is 3-20: 1.
The method for catalyzing the ozone to oxidize the antibiotics in the water has the following technical effects:
(1) the magnetic ferroferric oxide prepared by the hydrothermal method has uniform particles, is beneficial to coating of alumina, and can effectively separate the catalyst due to the existence of the magnetic ferroferric oxide, thereby improving the cyclic utilization of the catalyst and reducing the loss of the catalyst.
(2) By introducing magnesium salt into the aqueous solution containing urea, the water-soluble Mg can be used as an active component, and a network structure is formed on the surface of the alumina, the network structure is favorable for dispersing and anchoring the active component, and the network structure can be still maintained after the active component is loaded, so that the specific surface area of the carrier is improved, the loading capacity of the active component of the catalyst is reduced, the ozone catalyzing capability is improved, more hydroxyl radicals are generated, and the ozone oxidation of antibiotics is more favorable.
(3) The catalyst catalyzes ozone oxidation to remove antibiotics in water, the removal rate can reach 99.4%, 98.1% can be achieved after 5 times of circulation, and the treatment method is simple, easy to control and beneficial to industrial production.
In conclusion, the catalyst provided by the invention has excellent catalytic performance, good catalytic ozone oxidation capability on antibiotics in wastewater and strong recovery capability, and is an ideal material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally shown may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide catalyst comprises the following steps:
(1) preparing ferroferric oxide magnetic particles;
the preparation process of the ferroferric oxide magnetic particles comprises the following steps: weighing ferrous sulfate and anhydrous sodium acetate, wherein the molar ratio of a ferrous source to the anhydrous sodium acetate is 1mmol:9mmol, adding 100 mL of ethylene glycol into a polytetrafluoroethylene high-pressure reaction kettle, stirring and dissolving the ethylene glycol completely, stirring the mixture for 30min, sealing the mixture, heating the mixture to 200 ℃, keeping the temperature for 5h, taking out the mixture after the reaction is finished, cooling the mixture to room temperature, washing an obtained black magnetic sample with ethanol for 6 times, and finally drying the black magnetic sample in a vacuum drying oven at 55 ℃ for 12 h to obtain ferroferric oxide magnetic particles;
(2) preparing aluminum oxide coated ferroferric oxide:
mixing ferroferric oxide magnetic particles, aluminum chloride and ammonium carbonate in 50mL of solvent water, refluxing at 90 ℃ under stirring for hydrolysis reaction for 2h, centrifuging, washing, drying at 80 ℃ for 5h to obtain aluminum hydroxide coated ferroferric oxide particles, and calcining at 500 ℃ for 3h to obtain aluminum oxide coated ferroferric oxide particles; the mass ratio of the ferroferric oxide magnetic particles to the aluminum chloride to the ammonium carbonate is 0.2g:0.1g:1 g;
(3) preparation of magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Immersing the alumina-coated ferroferric oxide particles prepared in the step (2) in a magnesium nitrate solution and a mixed aqueous solution added with a certain amount of urea, carrying out heat treatment at 80 ℃ for 20 hours, filtering, washing, drying at 100 ℃ for 5 hours, and roasting at 550 ℃ for 5 hours to obtain a magnesium-aluminum composite oxide @ alumina @ ferroferric oxide; the molar ratio of the urea to the magnesium nitrate is 1.2mol:0.2 mol; the molar ratio of the aluminum oxide to the magnesium nitrate is 3mol:0.2 mol;
(4) preparation of manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Preparing an aqueous solution containing manganese chloride and cerium nitrate, wherein the molar ratio of manganese chloride to cerium nitrate is 1:1, soaking the magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide in the step (3) into the solution for 2 hours, drying at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain the manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide, wherein the loading amount of the manganese-cerium composite oxide is 1 wt%.
Example 2
A preparation method of a manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide catalyst comprises the following steps:
(1) preparing ferroferric oxide magnetic particles;
the preparation process of the ferroferric oxide magnetic particles comprises the following steps: weighing ferrous chloride and anhydrous sodium acetate, wherein the molar ratio of a ferrous iron source to the anhydrous sodium acetate is 1mmol:8.5mmol, adding 120 mL of ethylene glycol into a polytetrafluoroethylene high-pressure reaction kettle, stirring and dissolving the ethylene glycol completely, stirring the ethylene glycol for 40min, sealing the ethylene glycol, heating the ethylene glycol to 220 ℃, keeping the temperature for 4h, taking out the ethylene glycol after the reaction is finished, cooling the ethylene glycol to room temperature, washing the obtained black magnetic sample with ethanol for 6 times, and finally drying the black magnetic sample in a vacuum drying oven at 50 ℃ for 14h to obtain ferroferric oxide magnetic particles;
(2) preparing aluminum oxide coated ferroferric oxide:
mixing ferroferric oxide magnetic particles, aluminum nitrate and ammonium bicarbonate in 60mL of solvent water, refluxing at 80 ℃ under stirring for hydrolysis reaction for 3h, centrifuging, washing, drying at 80 ℃ for 5h to obtain aluminum hydroxide coated ferroferric oxide particles, and calcining at 550 ℃ for 1h to obtain aluminum oxide coated ferroferric oxide particles; the mass ratio of the ferroferric oxide magnetic particles to the aluminum nitrate to the ammonium bicarbonate is 0.2g:0.2g:2 g;
(3) preparation of magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Immersing the alumina-coated ferroferric oxide particles prepared in the step (2) in a magnesium chloride solution and a mixed aqueous solution added with a certain amount of urea, carrying out heat treatment at 90 ℃ for 12 hours, filtering, washing, drying at 140 ℃ for 2 hours, and roasting at 600 ℃ for 2 hours to obtain a magnesium-aluminum composite oxide @ alumina @ ferroferric oxide; the molar ratio of the urea to the magnesium nitrate is 2mol:0.2 mol; the molar ratio of the aluminum oxide to the magnesium nitrate is 4mol:0.2 mol;
(4) preparation of manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Preparing an aqueous solution containing manganese chloride and cerium nitrate, wherein the molar ratio of manganese chloride to cerium nitrate is 1:3, soaking the magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide in the step (3) into the solution for 4 hours, drying at 140 ℃ for 2 hours, and roasting at 600 ℃ for 2 hours to obtain the manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide, wherein the loading capacity of the manganese-cerium composite oxide is 2 wt%.
Example 3
A preparation method of a manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide catalyst comprises the following steps:
(1) preparing ferroferric oxide magnetic particles;
the preparation process of the ferroferric oxide magnetic particles comprises the following steps: weighing ferrous acetate and anhydrous sodium acetate, wherein the molar ratio of a ferrous iron source to the anhydrous sodium acetate is 1mmol:10mmol, 140mL of ethylene glycol is put into a polytetrafluoroethylene high-pressure reaction kettle and stirred and dissolved completely, after stirring for 20min, sealing and heating to 180 ℃, keeping the temperature for 6h, taking out after the reaction is finished, cooling to room temperature, washing the obtained black magnetic sample with ethanol for 3 times, and finally drying in a vacuum drying oven at 40 ℃ for 14h to obtain ferroferric oxide magnetic particles;
(2) preparing aluminum oxide coated ferroferric oxide:
mixing ferroferric oxide magnetic particles, aluminum acetate and diammonium phosphate in 40mL of solvent water, refluxing at 100 ℃ under stirring for hydrolysis reaction for 1h, centrifuging, washing, drying at 80 ℃ for 5h to obtain aluminum hydroxide coated ferroferric oxide particles, and calcining at 450 ℃ for 3h to obtain aluminum oxide coated ferroferric oxide particles; the mass ratio of the ferroferric oxide magnetic particles to the aluminum acetate to the diammonium hydrogen phosphate is 0.2g:0.1g:1 g;
(3) preparation of magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Immersing the alumina-coated ferroferric oxide particles prepared in the step (2) in a magnesium chloride solution, adding a certain amount of urea into a mixed aqueous solution, carrying out heat treatment at 70 ℃ for 24 hours, filtering, washing, drying at 90 ℃ for 6 hours, and roasting at 400 ℃ for 6 hours to obtain a magnesium-aluminum composite oxide @ alumina @ ferroferric oxide; the molar ratio of the urea to the magnesium nitrate is 0.4mol:0.2 mol; the molar ratio of the aluminum oxide to the magnesium nitrate is 0.6mol:0.2 mol;
(4) preparation of manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Preparing an aqueous solution containing manganese nitrate and cerium chloride, wherein the molar ratio of manganese nitrate to cerium chloride is 3:1, soaking the magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide in the step (3) into the solution for 4 hours, drying at 100 ℃ for 6 hours, and roasting at 400 ℃ for 6 hours to obtain the manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide, wherein the loading amount of the manganese-cerium composite oxide is 0.5 wt%.
Example 4
A preparation method of a manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide catalyst comprises the following steps:
(1) preparing ferroferric oxide magnetic particles;
the preparation process of the ferroferric oxide magnetic particles comprises the following steps: weighing ferrous sulfate and anhydrous sodium acetate, wherein the molar ratio of a ferrous source to the anhydrous sodium acetate is 1mmol:9mmol, adding 100 mL of ethylene glycol into a polytetrafluoroethylene high-pressure reaction kettle, stirring and dissolving the ethylene glycol completely, stirring the mixture for 30min, sealing the mixture, heating the mixture to 200 ℃, keeping the temperature for 5h, taking out the mixture after the reaction is finished, cooling the mixture to room temperature, washing an obtained black magnetic sample with ethanol for 6 times, and finally drying the black magnetic sample in a vacuum drying oven at 55 ℃ for 12 h to obtain ferroferric oxide magnetic particles;
(2) preparing aluminum oxide coated ferroferric oxide:
mixing ferroferric oxide magnetic particles, aluminum chloride and ammonium carbonate in 50mL of solvent water, refluxing at 90 ℃ under stirring for hydrolysis reaction for 2h, centrifuging, washing, drying at 80 ℃ for 5h to obtain aluminum hydroxide coated ferroferric oxide particles, and calcining at 500 ℃ for 3h to obtain aluminum oxide coated ferroferric oxide particles; the mass ratio of the ferroferric oxide magnetic particles to the aluminum chloride to the ammonium carbonate is 0.2g:0.1g:1 g;
(3) preparation of magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Immersing the alumina-coated ferroferric oxide particles prepared in the step (2) in a magnesium nitrate solution and a mixed aqueous solution added with a certain amount of urea, carrying out heat treatment at 80 ℃ for 20 hours, filtering, washing, drying at 100 ℃ for 5 hours, and roasting at 550 ℃ for 5 hours to obtain a magnesium-aluminum composite oxide @ alumina @ ferroferric oxide; the molar ratio of the urea to the magnesium nitrate is 1.2mol:0.2 mol; the molar ratio of the aluminum oxide to the magnesium nitrate is 3mol:0.2 mol;
(4) preparation of manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Preparing an aqueous solution containing manganese chloride and cerium nitrate, wherein the molar ratio of manganese chloride to cerium nitrate is 1:2, soaking the magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide in the step (3) into the solution for 2 hours, drying at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain the manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide, wherein the loading amount of the manganese-cerium composite oxide is 1 wt%.
Example 5
A preparation method of a manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide catalyst comprises the following steps:
(1) preparing ferroferric oxide magnetic particles;
the preparation process of the ferroferric oxide magnetic particles comprises the following steps: weighing ferrous sulfate and anhydrous sodium acetate, wherein the molar ratio of a ferrous source to the anhydrous sodium acetate is 1mmol:9mmol, adding 100 mL of ethylene glycol into a polytetrafluoroethylene high-pressure reaction kettle, stirring and dissolving the ethylene glycol completely, stirring the mixture for 30min, sealing the mixture, heating the mixture to 200 ℃, keeping the temperature for 5h, taking out the mixture after the reaction is finished, cooling the mixture to room temperature, washing an obtained black magnetic sample with ethanol for 6 times, and finally drying the black magnetic sample in a vacuum drying oven at 55 ℃ for 12 h to obtain ferroferric oxide magnetic particles;
(2) preparing aluminum oxide coated ferroferric oxide:
mixing ferroferric oxide magnetic particles, aluminum chloride and ammonium carbonate in 50mL of solvent water, refluxing at 90 ℃ under stirring for hydrolysis reaction for 2h, centrifuging, washing, drying at 80 ℃ for 5h to obtain aluminum hydroxide coated ferroferric oxide particles, and calcining at 500 ℃ for 3h to obtain aluminum oxide coated ferroferric oxide particles; the mass ratio of the ferroferric oxide magnetic particles to the aluminum chloride to the ammonium carbonate is 0.2g:0.1g:1 g;
(3) preparation of magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Immersing the alumina-coated ferroferric oxide particles prepared in the step (2) in a magnesium nitrate solution and a mixed aqueous solution added with a certain amount of urea, carrying out heat treatment at 80 ℃ for 20 hours, filtering, washing, drying at 100 ℃ for 5 hours, and roasting at 550 ℃ for 5 hours to obtain a magnesium-aluminum composite oxide @ alumina @ ferroferric oxide; the molar ratio of the urea to the magnesium nitrate is 1.2mol:0.2 mol; the molar ratio of the aluminum oxide to the magnesium nitrate is 3mol:0.2 mol;
(4) preparation of manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Preparing an aqueous solution containing manganese chloride and cerium nitrate, wherein the molar ratio of manganese chloride to cerium nitrate is 2:1, soaking the magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide in the step (3) into the solution for 2 hours, drying at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain the manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide, wherein the loading amount of the manganese-cerium composite oxide is 1 wt%.
Comparative example 1
A preparation method of a manganese-cerium composite oxide @ aluminum oxide @ ferroferric oxide catalyst comprises the following steps:
(1) preparing ferroferric oxide magnetic particles;
the preparation process of the ferroferric oxide magnetic particles comprises the following steps: weighing ferrous sulfate and anhydrous sodium acetate, wherein the molar ratio of a ferrous source to the anhydrous sodium acetate is 1mmol:9mmol, adding 100 mL of ethylene glycol into a polytetrafluoroethylene high-pressure reaction kettle, stirring and dissolving the ethylene glycol completely, stirring the mixture for 30min, sealing the mixture, heating the mixture to 200 ℃, keeping the temperature for 5h, taking out the mixture after the reaction is finished, cooling the mixture to room temperature, washing an obtained black magnetic sample with ethanol for 6 times, and finally drying the black magnetic sample in a vacuum drying oven at 55 ℃ for 12 h to obtain ferroferric oxide magnetic particles;
(2) preparing aluminum oxide coated ferroferric oxide:
mixing ferroferric oxide magnetic particles, aluminum chloride and ammonium carbonate in 50mL of solvent water, refluxing at 90 ℃ under stirring for hydrolysis reaction for 2h, centrifuging, washing, drying at 80 ℃ for 5h to obtain aluminum hydroxide coated ferroferric oxide particles, and calcining at 500 ℃ for 3h to obtain aluminum oxide coated ferroferric oxide particles; the mass ratio of the ferroferric oxide magnetic particles to the aluminum chloride to the ammonium carbonate is 0.2g:0.1g:1 g;
(3) preparation of manganese-cerium composite oxide @ aluminum oxide @ ferroferric oxide
Preparing an aqueous solution containing manganese chloride and cerium nitrate, wherein the molar ratio of manganese chloride to cerium nitrate is 1:1, soaking the magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide in the step (2) into the solution for 2 hours, drying at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain the manganese-cerium composite oxide @ aluminum oxide @ ferroferric oxide, wherein the loading amount of the manganese-cerium composite oxide is 1 wt%.
Comparative example 2
A preparation method of manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide comprises the following steps:
(1) preparation of alumina:
mixing aluminum chloride and ammonium carbonate in 50mL of solvent water, refluxing at 90 ℃ under stirring for hydrolysis reaction for 2h, centrifuging, washing, drying at 80 ℃ for 5h to obtain aluminum hydroxide particles, and calcining at 500 ℃ for 3h to obtain aluminum oxide particles; the mass ratio of the aluminum chloride to the ammonium carbonate is 0.1g to 1 g;
(3) preparation of magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide
Soaking the aluminum oxide particles prepared in the step (2) in a magnesium nitrate solution and a mixed aqueous solution added with a certain amount of urea, carrying out heat treatment at 80 ℃ for 20 hours, filtering, washing, drying at 100 ℃ for 5 hours, and roasting at 550 ℃ for 5 hours to obtain a magnesium-aluminum composite oxide @ aluminum oxide; the molar ratio of the urea to the magnesium nitrate is 1.2mol:0.2 mol; the molar ratio of the aluminum oxide to the magnesium nitrate is 3mol:0.2 mol;
(4) preparation of manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide
Preparing an aqueous solution containing manganese chloride and cerium nitrate, wherein the molar ratio of manganese chloride to cerium nitrate is 1:1, soaking the magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide in the step (3) into the solution for 2 hours, drying at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain the manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide, wherein the loading amount of the manganese-cerium composite oxide is 1 wt%.
The catalysts of examples 1-5 and comparative examples 1-2 were used to catalyze the ozonation of florfenicol. The specific experimental steps are as follows:
the concentration of florfenicol is 100mg/L, the adding amount of the catalyst is 50g, the air inflow of ozone is 2L/min, and the concentration of ozone is 8 mg/L. Florfenicol was analyzed by high performance liquid chromatography for removal at 4 min. And the removal rate at 4min was determined after 5 repetitions. Specific test results are shown in table 1:
TABLE 1 antibiotic degradation rates for examples 1-5 and comparative examples 1-2
Therefore, in the catalytic ozonation process, the antibiotics in the water can be well removed through ozonation, the removal rate can reach 99.4%, and the removal rate can still reach 98.1% after 5 times of circulation. The catalyst can be effectively separated due to the existence of the magnetic ferroferric oxide in the catalyst, and the aluminum oxide is adopted to cover the ferroferric oxide, and the magnesium-aluminum composite oxide grows on the surface of the aluminum oxide, so that the dispersity of the active component is improved, the loading capacity of the active component is reduced, and meanwhile, the catalyst still has excellent catalytic performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for catalyzing ozone to oxidize antibiotics in water is characterized by comprising the following steps: the concentration of the antibiotic is 50-100 mg/L, the adding amount of the catalyst is 40-60 g, the ozone air input is 1-2L/min, the concentration of the ozone is 3-12 mg/L, the catalyst is manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide, the ferroferric oxide is used as a core, the aluminum oxide is coated on the surface of the ferroferric oxide, the magnesium-aluminum oxide is grown on the surface of the aluminum oxide, then the active component manganese-cerium composite oxide is loaded, the loading amount of the active component is 0.5-2 wt%, and the molar ratio of manganese to cerium is 1: 3-3: 1.
2. the method of claim 1, wherein: the antibiotic comprises one or more of tetracycline, metronidazole and florfenicol.
3. The method of claim 1, wherein: the preparation method of the catalyst comprises the following steps:
(1) preparing ferroferric oxide magnetic particles;
(2) preparing aluminum oxide coated ferroferric oxide:
mixing ferroferric oxide magnetic particles, an aluminum source and a precipitator in 40-60 mL of solvent water, refluxing at 80-100 ℃ under stirring for hydrolysis reaction for 1-3 h, centrifuging, washing and drying to obtain aluminum hydroxide coated ferroferric oxide particles, and calcining at 450-550 ℃ for 1-3 h to obtain aluminum oxide coated ferroferric oxide particles;
(3) magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide is prepared by immersing aluminum oxide-coated ferroferric oxide particles prepared in the step (2) in a magnesium salt solution, adding a certain amount of urea into a mixed aqueous solution, carrying out heat treatment at 70-90 ℃ for 12-24 hours, filtering, washing, drying at 90-140 ℃ for 2-6 hours, and roasting at 400-600 ℃ for 2-6 hours to obtain magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide;
(4) the preparation method of the manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide comprises the steps of preparing an aqueous solution containing manganese salt and cerium salt, wherein the molar ratio of the manganese salt to the cerium salt is 1: 3-3: soaking the magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide in the step (3) into the solution for 2-4 h, drying at 100-140 ℃ for 2-6 h, and roasting at 400-600 ℃ for 2-6 h to obtain manganese-cerium composite oxide @ magnesium-aluminum composite oxide @ aluminum oxide @ ferroferric oxide, wherein the loading amount of the manganese-cerium composite oxide is 0.5-2 wt%.
4. The method of claim 3, wherein: in the step (1), the preparation process of the ferroferric oxide magnetic particles is as follows: weighing a ferrous iron source and anhydrous sodium acetate, wherein the molar ratio of the ferrous iron source to the anhydrous sodium acetate is 1: 8-10, 100-140 mL of ethylene glycol is placed into a polytetrafluoroethylene high-pressure reaction kettle and stirred and dissolved completely, after stirring for 20-40 min, sealing and heating to 180-240 ℃, keeping the temperature for 3-6 h, after the reaction is finished, taking out and cooling to room temperature, washing the obtained black magnetic sample with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 40-60 ℃ for 10-14 h to obtain the ferroferric oxide magnetic particles.
5. The method of claim 4, wherein: the ferrous source is one or more of ferrous chloride, ferrous sulfate and ferrous acetate.
6. The method of claim 3, wherein: in the step (2), the aluminum source is selected from at least one of chloride, sulfate, nitrate, acetate and alkoxide of aluminum element; the precipitant is selected from at least one of urea, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
7. The method of claim 3, wherein: in the step (3), the magnesium salt is selected from one or more of magnesium sulfate, magnesium nitrate, magnesium acetate and magnesium chloride.
8. The method of claim 3, wherein: in the step (4), the manganese salt or cerium salt is selected from at least one of chloride, sulfate, nitrate, and acetate.
9. The method of claim 3, wherein: in the step (2), the mass ratio of the ferroferric oxide magnetic particles to the aluminum source to the precipitator is 1: 0.5-1: 5-10.
10. The method of claim 3, wherein: in the step (3), the molar ratio of the urea to the magnesium salt is 2-10: 1; the molar ratio of the aluminum oxide to the magnesium salt is 3-20: 1.
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Application publication date: 20200821 |