CN109382092A - Ozone oxidation catalyst and preparation method thereof based on the balloon borne body of active gama-alumina - Google Patents
Ozone oxidation catalyst and preparation method thereof based on the balloon borne body of active gama-alumina Download PDFInfo
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- CN109382092A CN109382092A CN201710668026.7A CN201710668026A CN109382092A CN 109382092 A CN109382092 A CN 109382092A CN 201710668026 A CN201710668026 A CN 201710668026A CN 109382092 A CN109382092 A CN 109382092A
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- 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 137
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 230000003647 oxidation Effects 0.000 title claims abstract description 94
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 36
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 36
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 7
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 74
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 14
- 239000012702 metal oxide precursor Substances 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006385 ozonation reaction Methods 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 239000008399 tap water Substances 0.000 description 31
- 235000020679 tap water Nutrition 0.000 description 31
- 239000000243 solution Substances 0.000 description 30
- 230000003197 catalytic effect Effects 0.000 description 22
- 239000010865 sewage Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 18
- 238000005406 washing Methods 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical group O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004069 wastewater sedimentation Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/72—Copper
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- C02F1/725—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
- 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
The present invention provides a kind of ozone oxidation catalysts based on the balloon borne body of active gama-alumina, the ozone oxidation catalyst based on the balloon borne body of active gama-alumina is the metal oxide of active gamma oxidation aluminium ball load, wherein, the metal oxide is at least one of ferriferous oxide, Cu oxide, ru oxide, cerium oxide, cobalt/cobalt oxide, Mn oxide, nickel oxide.
Description
Technical Field
The invention belongs to the technical field of catalytic oxidation of ozone, and particularly relates to an ozone oxidation catalyst based on an active gamma-alumina sphere carrier and a preparation method thereof.
Background
Along with the development of industry, more and more industrial wastewater enters a sewage pipe network, and meanwhile, more and more urban sewage treatment plants and sewage treatment plants in industrial parks mainly based on the industrial wastewater. Along with the more and more severe environment-friendly situation, the requirement on the effluent quality of the urban sewage treatment plant is more and more strict. In the secondary treatment of the conventional sewage treatment plant, most of biochemically degradable COD is removed by biochemical treatment, the rest is mainly soluble non-degradable organic matters (nbsCOD), and with the comprehensive implementation of the primary A standard, even part of economically developed areas are gradually implementing the similar surface four standard, and the COD requirement is not higher than 30 mg/L. The standard of effluent COD is higher and higher, and the difficulty that the effluent reached standard is more and more big is given to nbsCOD, is having more and more sewage treatment plant to this and increases the advanced treatment unit, and how the advanced treatment unit realizes that nbsCOD economy and stable getting rid of becomes a problem that needs to solve urgently.
The advanced oxidation technology is absolutely necessary as one of key processes for deeply treating nbsCOD in sewage, and the conventional advanced oxidation technology mainly comprises ozone oxidation, Fenton reaction, wet catalytic oxidation and the like. The existing Fenton method and wet catalytic oxidation technology can improve the sewage treatment effect to a certain extent, but have the defects of large dosage, high operation cost, secondary pollution, troublesome operation and the like. In addition, the fenton reaction has the defects of high labor intensity, high treatment cost, more sludge, high corrosivity and the like, the treatment effect on low-concentration COD (COD in effluent is difficult to reach below 50 mg/L), and high-strength advanced oxidation technology cannot be realized under the requirement of low cost, such as fenton, wet catalytic oxidation, supercritical technology and the like. Especially, when the concentration of nbsCOD in water is too high, advanced oxidation technologies such as Fenton method and dosing method are difficult to realize the COD index below 30 mg/L.
Ozone oxidation is favored by water pollution researchers due to its advantages of simple operation, no addition of chemicals, no secondary pollution, no sludge generation, etc., and its market needs to be vigorous. The ozone oxidation method is used as an effective advanced treatment technology, can further remove organic matters and meets increasingly strict effluent discharge standards. But also face some problems. Firstly, the solubility of ozone in water is low, so that how to effectively dissolve ozone in water and improve the utilization efficiency of ozone become the hot point of the technical research; secondly, the combined use of ozone and other technologies is researched, and a catalyst with good catalytic effect, long service life and high repeated utilization rate can be developed; thirdly, because the ozone generating efficiency is low and the energy consumption is large, the research of the ozone generating device with high efficiency and low energy consumption also becomes one of the key problems to be solved at present. Therefore, more and more sewage plants are additionally provided with advanced treatment units, how the advanced treatment units realize the economic and stable removal of nbsCOD becomes a problem to be solved urgently, and the advanced oxidation technology is absolutely necessary as one of key processes of advanced treatment and is a research and development trend in the technical field at present.
Disclosure of Invention
The invention aims to provide an ozone oxidation catalyst based on an active gamma-alumina sphere carrier and a preparation method thereof, and aims to solve the problems that the existing ozone oxidation catalyst based on the active gamma-alumina sphere carrier is difficult to carry out catalytic oxidation on nbsCOD, and further difficult to efficiently realize COD lower than 30mg/L in a sewage treatment process.
The invention is realized by the ozone oxidation catalyst based on the active gamma-alumina ball carrier, which is a metal oxide loaded on the active gamma-alumina ball, wherein the metal oxide is at least one of iron oxide, copper oxide, ruthenium oxide, cerium oxide, cobalt oxide, manganese oxide and nickel oxide.
And, a method for preparing an ozone oxidation catalyst based on an active γ -alumina sphere carrier, comprising the steps of:
providing an active gamma-alumina ball, cleaning, drying, and testing the water absorption rate of the dried active gamma-alumina ball;
placing the active gamma-alumina balls in a container, adding a precursor solution of a metal oxide by an isometric impregnation method, adsorbing the precursor of the metal oxide, and drying;
and (3) putting the active gamma-alumina ball adsorbed with the metal oxide precursor into a heating device, carrying out heat preservation and calcination for 2-8 hours at the temperature of 250-600 ℃, and carrying out aging treatment to obtain the ozone oxidation catalyst based on the active gamma-alumina ball carrier.
The ozone oxidation catalyst based on the active gamma-alumina ball carrier adopts active gamma-alumina balls to load at least one of iron oxide, copper oxide, ruthenium oxide, cerium oxide, cobalt oxide, manganese oxide and nickel oxide. When the catalyst is used for ozone catalytic oxidation of industrial sewage, nbsCOD in the sewage can be removed efficiently, the ozone catalytic oxidation lasts for 60min, the removal rate of the nbsCOD can reach 75%, and is more than 30% higher than that of ozone contact oxidation. In addition, under the condition of the same catalytic efficiency, the price of the ozone oxidation catalyst based on the active gamma-alumina ball carrier provided by the invention is lower than the average price of the catalyst of mainstream manufacturers in the current market by more than 50%; the ozone oxidation catalyst is adopted in ozone advanced oxidation equipment, so that the ozone input amount can be reduced under the condition of the same removal efficiency, and the operation cost is reduced by more than 10%.
The preparation method of the ozone oxidation catalyst based on the active gamma-alumina sphere carrier is simple and easy to control, the obtained ozone oxidation catalyst is good in catalytic effect, and the removal rate of nbsCOD can reach 75%.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides an ozone oxidation catalyst based on an active gamma-alumina ball carrier, which is a metal oxide loaded on an active gamma-alumina ball, wherein the metal oxide is at least one of iron oxide, copper oxide, ruthenium oxide, cerium oxide, cobalt oxide, manganese oxide and nickel oxide.
In the embodiment of the invention, the active gamma-alumina ball is used as a catalyst carrier for loading metal oxide which plays a catalytic role, and has the advantages of being porous, large in specific surface area, large in mechanical strength, strong in hygroscopicity, free of swelling and cracking after water absorption and capable of keeping the original state. Preferably, the diameter of the active gamma-alumina ball is 4-6mm, and the specific surface area is 200-300m2(ii) in terms of/g. The optimized active gamma-alumina balls have proper diameters and specific surface areas, so that the proper loading capacity of metal oxides can be provided on the premise of ensuring the particle strength, the stable and uniform removal of nbsCOD in sewage by the ozone oxidation catalyst is facilitated, and the removal rate of COD is improved; meanwhile, the metal oxide is uniformly dispersed on the surfaces of the gaps of the active gamma-alumina spheres, so that the use amount of the catalyst can be reduced, and the cost is further reduced. In addition, the preferred activated gamma-alumina spheres can be recycled after use.
In the embodiment of the invention, the loading capacity of the metal oxide has certain influence on removal of nbsCOD in the sewage. Preferably, the loading amount of the metal oxide is 1-10% based on 100% of the mass of the ozone oxidation catalyst based on the active gamma-alumina sphere carrier, and the obtained ozone oxidation catalyst has better removal effect on nbsCOD. If the loading capacity of the metal oxide is too low, the relative content of the catalyst is low, the effect of removing nbsCOD is relatively poor, and the removal rate of COD is reduced; if the loading capacity of the metal oxide is too high, metal sintering and pore channel blockage are easily caused, so that the catalytic activity is reduced, and the removal of nbsCOD is influenced.
In the ozone oxidation catalyst provided by the embodiment of the invention, the metal oxide capable of removing nbsCOD comprises metal oxide loaded on active gamma-alumina balls, wherein the metal oxide is at least one of iron oxide, copper oxide, ruthenium oxide, cerium oxide, cobalt oxide, manganese oxide and nickel oxide. Specifically, the iron oxide is preferably ferric oxide, and the manganese oxide is preferably manganese dioxide.
As a specific preferred embodiment, the ozone oxidation catalyst based on an active γ -alumina sphere support is iron sesquioxide supported on active γ -alumina spheres, and the supported amount of the iron sesquioxide is 3% based on 100% by mass of the ozone oxidation catalyst based on an active γ -alumina sphere support. The optimized ozone oxidation catalyst can efficiently remove nbsCOD in sewage, the ozone catalytic oxidation is carried out for 60min, the removal rate of the nbsCOD is over 80 percent, and the removal rate is improved by 35 percent compared with that of a blank control under a parallel condition.
As another specific preferred example, the active γ -alumina ball support-based ozonation catalyst is active γ -alumina ball supported manganese dioxide, and the loading amount of the manganese dioxide is 5% based on 100% by mass of the active γ -alumina ball support-based ozonation catalyst. The optimized ozone oxidation catalyst can efficiently remove nbsCOD in sewage, the ozone catalytic oxidation is carried out for 60min, the removal rate of the nbsCOD is over 78 percent, and the removal rate is improved by 30 percent compared with that of a blank control under a parallel condition.
The ozone oxidation catalyst based on the active gamma-alumina ball carrier provided by the embodiment of the invention adopts active gamma-alumina balls to load at least one of iron oxide, copper oxide, ruthenium oxide, cerium oxide, cobalt oxide, manganese oxide and nickel oxide. When the catalyst is used for ozone catalytic oxidation of industrial sewage, nbsCOD in the sewage can be removed efficiently, the ozone catalytic oxidation lasts for 60min, the removal rate of the nbsCOD can reach 75%, and is more than 30% higher than that of ozone contact oxidation. In addition, under the condition of the same catalytic efficiency, the price of the ozone oxidation catalyst based on the active gamma-alumina ball carrier provided by the embodiment of the invention is lower than the average price of the catalyst of mainstream manufacturers in the current market by more than 50%; the ozone oxidation catalyst is adopted in ozone advanced oxidation equipment, so that the ozone input amount can be reduced under the condition of the same removal efficiency, and the operation cost is reduced by more than 10%.
The ozone oxidation catalyst based on the active gamma-alumina sphere carrier provided by the embodiment of the invention can be prepared by the following method.
The embodiment of the invention also provides a preparation method of the ozone oxidation catalyst based on the active gamma-alumina sphere carrier, which comprises the following steps:
s01, providing an active gamma-alumina ball, cleaning, drying, and testing the water absorption rate of the dried active gamma-alumina ball;
s02, placing the active gamma-alumina balls in a container, adding a precursor solution of a metal oxide by adopting an isometric impregnation method, adsorbing the precursor of the metal oxide, and then drying;
s03, placing the active gamma-alumina ball adsorbed with the metal oxide precursor into a heating device, carrying out heat preservation and calcination for 2-8 hours at the temperature of 250-600 ℃, and carrying out aging treatment to obtain the ozone oxidation catalyst based on the active gamma-alumina ball carrier.
Specifically, in step S01, it is preferable thatThe diameter of the active gamma-alumina ball is 4-6mm, the specific surface area is 200-300m2(ii) in terms of/g. The active gamma-alumina balls are cleaned, so that surface micro powder can be removed, and the effective loading capacity and the catalytic effect are improved. Specifically, the surface fine powder can be removed by washing with tap water several times. Furthermore, the active gamma-alumina balls are dried so as to thoroughly remove the moisture in the carrier, thereby being beneficial to fully and uniformly dipping in the subsequent process. The drying treatment is preferably oven drying, and particularly preferably drying at 120 ℃ for 48 hours.
In the embodiment of the invention, in order to control the loading amount of the active component, an isometric impregnation method is adopted for loading. For this purpose, the water absorption of the alumina pellets needs to be measured in advance. Specifically, the following methods can be referred to for the method of measuring water absorption: 50g of alumina pellets are weighed into a 250ml beaker, 100ml of water is added to ensure that the alumina pellets fully absorb water for 12 hours, and then the filtrate is poured into a measuring cylinder to measure the volume and calculate the water absorption (ml/g).
In the step S02, the activated γ -alumina spheres are placed in a container, and a precursor solution of a metal oxide is added by an isometric impregnation method. Specifically, the concentration of the precursor solution of the metal nitrate oxide and the volume of the solution required for immersion are calculated from the water absorption obtained in step S01. Preferably, in order to achieve sufficient adsorption and improve adsorption efficiency, stirring is preferably used to promote adsorption during the impregnation process. In the embodiment of the invention, the precursor solution of the metal oxide is a metal salt solution with strong water solubility, and comprises a nitrate solution, a chloride solution and an acetate solution. The precursor solution of the metal oxide is selected according to the requirement that the precursor solution of the metal oxide can be decomposed at the subsequent calcining temperature to generate the oxide catalyst, and the precursor solution of the metal oxide with the decomposition temperature higher than 600 ℃ is not in the scope of the embodiment of the invention, such as sulfate solution, because the catalyst carrier is influenced and the catalytic activity is reduced when the calcining temperature is exceeded. And drying after adsorbing the metal oxide precursor to prevent the carrier from cracking caused by residual moisture in gaps after being heated violently in the subsequent calcining process. Specifically, the drying can be carried out at 120 ℃ for 48 hours.
In the step S03, the active γ -alumina spheres adsorbed with the metal oxide precursor are placed in a heating device, and are calcined at a temperature of 250-. In the embodiment of the invention, the calcination temperature is not suitable to be too high or too low, and if the temperature is too low or the heat preservation time is too short, the catalyst conversion is not complete; if the temperature is too high or the holding time is too long, not only time and energy are wasted, but also the specific surface area of the carrier is reduced, and the activity of the catalyst is reduced. More preferably, the active gamma-alumina ball absorbed with the metal oxide precursor is placed into a heating device and is calcined for 4 to 8 hours under the condition of 400-600 ℃ for heat preservation, so as to obtain the ozone oxidation catalyst with better catalytic performance.
Preferably, the activated gamma-alumina ball adsorbed with the metal oxide precursor is heated to 250-600 ℃ at a speed of 2-10 ℃/min after being placed in a heating device, so that the metal oxide precursor is gradually and fully converted into the metal oxide, and when the temperature is increased too fast, the metal oxide precursor on the outer surface is completely converted and covers the surface of the metal oxide precursor on the inner layer, which is not beneficial to full conversion.
Furthermore, the calcined ozone oxidation catalyst is aged, so that the service performance is improved. The aging time is preferably 24 hours or more. Furthermore, the micro powder on the surface of the ozone oxidation catalyst can be removed by cleaning, and the ozone oxidation catalyst is further dried for standby.
As a specific preferred embodiment, the preparation method of the ozone oxidation catalyst based on the active gamma-alumina sphere carrier comprises the following steps:
providing a diameter of 4-6mm and a specific surface area of 200-300m2Cleaning and drying the active gamma-alumina balls per gram, and testing the water absorption rate of the dried active gamma-alumina balls;
placing the active gamma-alumina balls in a container, adding a precursor solution of a metal oxide by an isometric immersion method, stirring for 12 hours, adsorbing the precursor of the metal oxide, and drying;
and (3) putting the active gamma-alumina balls adsorbed with the metal oxide precursor into a heating device, heating to 400 ℃ at the speed of 5 ℃/min, carrying out heat preservation and calcination for 6 hours, and aging for 24 hours to obtain the ozone oxidation catalyst based on the active gamma-alumina ball carrier.
The preparation method of the ozone oxidation catalyst based on the active gamma-alumina sphere carrier provided by the embodiment of the invention is simple and easy to control, the obtained ozone oxidation catalyst has a good catalytic effect, and the removal rate of nbsCOD can reach 75%.
The following description will be given with reference to specific examples.
Example 1
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 120 ℃. Putting the weighed active alumina balls into 900 ml of 0.128mol/L manganese nitrate solution for equal-volume impregnation treatment, and stirring for 3 hours. And (3) putting the activated alumina balls adsorbing the manganese nitrate into a drying oven to dry for 10 hours at 40 ℃. And putting the dried sample into a resistance furnace, heating to 250 ℃ at the heating rate of 2 ℃/min, calcining, and keeping the temperature for 2 h. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 120 ℃ for 10 hours to obtain the ozone oxidation catalyst with the load of 1%.
Example 2
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 150 ℃. And putting the weighed activated alumina balls into 900 ml of 0.703mol/L manganese nitrate solution for equal volume dipping treatment, and stirring for 7.5 h. And (3) putting the active alumina balls adsorbing the manganese nitrate into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 425 ℃ at the heating rate of 6 ℃/min, calcining, and keeping the temperature for 5 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 29 hours to obtain the 5.5% supported ozone oxidation catalyst.
Example 3
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 180 ℃. And putting the weighed activated alumina balls into 900 ml of 1.28mol/L manganese nitrate solution for isovolumetric immersion treatment, and stirring for 12 hours. And (3) putting the activated alumina balls adsorbing the manganese nitrate into a drying oven to dry for 48 hours at 100 ℃. And putting the dried sample into a resistance furnace, heating to 600 ℃ at a heating rate of 10 ℃/min, calcining, and keeping the temperature for 8 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 180 ℃ for 48 hours to obtain the ozone oxidation catalyst with the load of 10%.
Example 4
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 150 ℃. And (3) putting the weighed activated alumina balls into 900 ml of 0.128mol/L ferric chloride solution for soaking treatment in a medium volume, and stirring for 7.5 h. And (3) putting the activated alumina balls adsorbing the ferric chloride into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 425 ℃ at the heating rate of 6 ℃/min, calcining, and keeping the temperature for 5 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 29 hours to obtain the ozone oxidation catalyst with the load of 1%.
Example 5
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 150 ℃. And putting the weighed activated alumina balls into 900 ml of 1.28mol/L ferric chloride solution for soaking treatment in a medium volume, and stirring for 7.5 h. And (3) putting the activated alumina balls adsorbing the ferric chloride into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 425 ℃ at the heating rate of 6 ℃/min, calcining, and keeping the temperature for 5 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 29 hours to obtain the ozone oxidation catalyst with the load of 10%.
Example 6
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 150 ℃. And putting the weighed activated alumina balls into 900 ml of 0.703mol/L ferric chloride solution for soaking treatment in a medium volume, and stirring for 7.5 h. And (3) putting the activated alumina balls adsorbing the ferric chloride into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 250 ℃ at the heating rate of 6 ℃/min, calcining, and keeping the temperature for 5 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 29 hours to obtain the ozone oxidation catalyst with the load of 5.5%.
Example 7
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 150 ℃. And putting the weighed activated alumina balls into 900 ml of 0.703mol/L nickel nitrate solution for equal volume immersion treatment, and stirring for 7.5 h. And putting the active alumina balls adsorbing the nickel nitrate into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 600 ℃ at the heating rate of 6 ℃/min, calcining, and preserving heat for 5 h. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 29 hours to obtain the ozone oxidation catalyst with the load of 5.5%.
Example 8
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 150 ℃. And putting the weighed activated alumina balls into 900 ml of 0.238mol/L nickel nitrate solution for equal volume immersion treatment, and stirring for 7.5 h. And putting the active alumina balls adsorbing the nickel nitrate into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 525 ℃ at the heating rate of 9 ℃/min, calcining, and preserving heat for 2 h. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 29 hours to obtain the ozone oxidation catalyst with the load of 1.9%.
Example 9
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 150 ℃. And putting the weighed activated alumina balls into 900 ml of 0.895mol/L nickel nitrate solution for equal volume immersion treatment, and stirring for 7.5 h. And putting the active alumina balls adsorbing the nickel nitrate into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 425 ℃ at the heating rate of 8 ℃/min, calcining, and keeping the temperature for 8 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 29 hours to obtain the ozone oxidation catalyst with the load of 7%.
Example 10
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 150 ℃. And putting the weighed activated alumina balls into 900 ml of 0.703mol/L cobalt nitrate solution for equal volume dipping treatment, and stirring for 7.5 h. And (3) putting the active alumina balls adsorbing the cobalt nitrate into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 425 ℃ at the heating rate of 8 ℃/min, calcining, and keeping the temperature for 8 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 29 hours to obtain the ozone oxidation catalyst with the load of 5.5%.
Example 11
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 120 ℃. And putting the weighed activated alumina balls into 900 ml of 0.383mol/L cobalt nitrate solution for equal volume dipping treatment, and stirring for 7.5 h. And (3) putting the active alumina balls adsorbing the cobalt nitrate into a drying oven to dry for 30h at 60 ℃. And putting the dried sample into a resistance furnace, heating to 580 ℃ at the heating rate of 7 ℃/min, calcining, and keeping the temperature for 4 h. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 120 ℃ for 28 hours to obtain the ozone oxidation catalyst with the load of 3%.
Example 12
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 180 ℃. And putting the weighed activated alumina balls into 900 ml of 1.048mol/L cobalt nitrate solution for equal volume dipping treatment, and stirring for 7.5 h. And (3) putting the active alumina balls adsorbing the cobalt nitrate into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 455 ℃ at the heating rate of 6 ℃/min, calcining, and preserving heat for 8 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 24 hours to obtain the ozone oxidation catalyst with the load of 8.2%.
Example 13
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 180 ℃. And putting the weighed activated alumina balls into 900 ml of 0.703mol/L copper nitrate solution for equal-volume impregnation treatment, and stirring for 6 hours. And (3) putting the activated alumina ball adsorbing the copper nitrate into a drying oven to be dried for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 505 ℃ at a heating rate of 6 ℃/min, calcining, and keeping the temperature for 8 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 24 hours to obtain the ozone oxidation catalyst with the load of 5.5%.
Example 14
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 180 ℃. And (3) putting the weighed activated alumina balls into 900 ml of 0.758mol/L ruthenium nitrate solution for equal volume immersion treatment, and stirring for 8 hours. And putting the active alumina ball adsorbing the ruthenium nitrate into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 455 ℃ at the heating rate of 5 ℃/min, calcining, and preserving heat for 8 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 24 hours to obtain the ozone oxidation catalyst with the load of 5.5%.
Example 15
1000 g of activated alumina balls are washed by tap water for 3 times and then put into a drying oven to be dried at 180 ℃. And putting the weighed activated alumina balls into 900 ml of 0.912mol/L cerium nitrate solution for equal volume dipping treatment, and stirring for 7.5 h. And (3) putting the activated alumina ball adsorbing the cerium nitrate into a drying oven to dry for 29h at 70 ℃. And putting the dried sample into a resistance furnace, heating to 600 ℃ at the heating rate of 4 ℃/min, calcining, and keeping the temperature for 8 hours. And finally, washing the calcined sample by using tap water, removing surface micro powder, and drying the sample in a drying oven at 150 ℃ for 24 hours to obtain the ozone oxidation catalyst with the load of 5.5%.
The ozone oxidation catalyst prepared in the embodiments 1 to 15 of the present invention is used for the effluent of the sewage secondary sedimentation tank respectively added with aniline and phenol targets, and the COD removal rate and the decolorization rate are measured.
Specifically, under the conditions that the ozone concentration is 4-5 mg/L, the gas flow is 0.5L/min, the catalyst filling amount is 3L, the test water amount is about 4.5L, and the total test volume is about 6.5L, the COD removal rate is measured when the catalytic reaction is carried out for 60min, and the decolorization rate is calculated. Wherein,
the color was determined by dilution factor method. The decolorization ratio is calculated as follows:
decolorization ratio (%) (chroma O)3-colour scaleCatalyst and process for preparing same) Color number O3×100％；
The COD determination method adopts a rapid closed catalytic digestion method (potassium dichromate titration), and the COD removal rate calculation method comprises the following steps:
COD removal rate (%) - (COD)Inflow water-CODDischarging water)/CODInflow water×100％。
The test results of the effluent of the secondary wastewater sedimentation tank with the aniline standard added are shown in the following table 1. Wherein, the blank control group is directly oxidized by ozone contact without adding an ozone oxidation catalyst under the same condition.
TABLE 1
As can be seen from table 1 above, the COD removal rate is increased by at least 30% or more, and even by 45% after the ozone oxidation catalyst of the embodiment of the present invention is added, compared to the blank control group without the ozone oxidation catalyst of the embodiment of the present invention. After the ozone oxidation catalyst is added, the chroma removing effect is obviously better.
The test results of the effluent from the secondary sewage sedimentation tank with the phenol standard added are shown in table 2 below. Wherein, the blank control group is directly oxidized by ozone contact without adding an ozone oxidation catalyst under the same condition.
TABLE 2
As can be seen from table 2 above, the COD removal rate is increased by at least 30% or more, and even by 45% after the ozone oxidation catalyst of the embodiment of the present invention is added, compared to the blank control group without the ozone oxidation catalyst of the embodiment of the present invention. After the ozone oxidation catalyst is added, the chroma removing effect is obviously better.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. An ozone oxidation catalyst based on an active gamma-alumina ball carrier, which is characterized in that the ozone oxidation catalyst based on the active gamma-alumina ball carrier is a metal oxide loaded on an active gamma-alumina ball, wherein the metal oxide is at least one of iron oxide, copper oxide, ruthenium oxide, cerium oxide, cobalt oxide, manganese oxide and nickel oxide.
2. Ozone based on activated gamma-alumina sphere supports as claimed in claim 1The catalyst is characterized in that the diameter of the active gamma-alumina ball is 4-6mm, and the specific surface area is 200-300m2/g。
3. The active γ -alumina sphere support-based ozonation catalyst of claim 1, wherein a loading amount of the metal oxide is 1 to 10% based on 100% by mass of the active γ -alumina sphere support-based ozonation catalyst.
4. The active γ -alumina sphere support-based ozonation catalyst according to any one of claims 1 to 3, wherein the active γ -alumina sphere support-based ozonation catalyst is active γ -alumina sphere supported ferric oxide, and the supported amount of the ferric oxide is 3% based on 100% by mass of the active γ -alumina sphere support-based ozonation catalyst.
5. The active γ -alumina ball support-based ozonation catalyst of any one of claims 1 to 3, wherein the active γ -alumina ball support-based ozonation catalyst is active γ -alumina ball supported manganese dioxide, and a loading amount of the manganese dioxide is 5% based on 100% by mass of the active γ -alumina ball support-based ozonation catalyst.
6. A preparation method of an ozone oxidation catalyst based on an active gamma-alumina sphere carrier is characterized by comprising the following steps:
providing an active gamma-alumina ball, cleaning, drying, and testing the water absorption rate of the dried active gamma-alumina ball;
placing the active gamma-alumina balls in a container, adding a precursor solution of a metal oxide by an isometric impregnation method, adsorbing the precursor of the metal oxide, and drying;
and (3) putting the active gamma-alumina ball adsorbed with the metal oxide precursor into a heating device, carrying out heat preservation and calcination for 2-8 hours at the temperature of 250-600 ℃, and carrying out aging treatment to obtain the ozone oxidation catalyst based on the active gamma-alumina ball carrier.
7. The method for preparing the ozone oxidation catalyst based on the active gamma-alumina sphere carrier as claimed in claim 6, wherein the diameter of the active gamma-alumina sphere is 4-6mm, the specific surface area is 200-300m2/g。
8. The method of claim 6, wherein the temperature of the activated γ -alumina spheres adsorbed with the metal oxide precursor is raised to 250-600 ℃ at a rate of 2-10 ℃/min.
9. The method of preparing an ozone oxidation catalyst based on an active γ -alumina sphere support according to any one of claims 6 to 8, wherein the precursor solution of the metal oxide comprises a nitrate solution, a chloride solution, an acetate solution.
10. The method for preparing an ozone oxidation catalyst based on an active γ -alumina sphere support according to any one of claims 6 to 8, comprising the steps of:
providing a diameter of 4-6mm and a specific surface area of 200-300m2Cleaning and drying the active gamma-alumina balls per gram, and testing the water absorption rate of the dried active gamma-alumina balls;
placing the active gamma-alumina balls in a container, adding a precursor solution of a metal oxide by an isometric immersion method, stirring for 12 hours, adsorbing the precursor of the metal oxide, and drying;
and (3) putting the active gamma-alumina balls adsorbed with the metal oxide precursor into a heating device, heating to 400 ℃ at the speed of 5 ℃/min, carrying out heat preservation and calcination for 6 hours, and aging for 24 hours to obtain the ozone oxidation catalyst based on the active gamma-alumina ball carrier.
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