CN110773160A - Ozone oxidation catalyst and preparation method and application thereof - Google Patents
Ozone oxidation catalyst and preparation method and application thereof Download PDFInfo
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- CN110773160A CN110773160A CN201911085115.4A CN201911085115A CN110773160A CN 110773160 A CN110773160 A CN 110773160A CN 201911085115 A CN201911085115 A CN 201911085115A CN 110773160 A CN110773160 A CN 110773160A
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- ozone oxidation
- oxidation catalyst
- catalyst
- magnesium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 230000003647 oxidation Effects 0.000 title claims abstract description 88
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 56
- 239000002351 wastewater Substances 0.000 claims abstract description 43
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000032683 aging Effects 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 238000000975 co-precipitation Methods 0.000 claims abstract description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 51
- 229910018871 CoO 2 Inorganic materials 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- 239000000725 suspension Substances 0.000 claims description 28
- 239000000292 calcium oxide Substances 0.000 claims description 27
- 159000000003 magnesium salts Chemical class 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 239000012266 salt solution Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 21
- 239000012018 catalyst precursor Substances 0.000 claims description 20
- 239000012670 alkaline solution Substances 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000003929 acidic solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 238000006385 ozonation reaction Methods 0.000 claims description 7
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 5
- 239000011654 magnesium acetate Substances 0.000 claims description 5
- 235000011285 magnesium acetate Nutrition 0.000 claims description 5
- 229940069446 magnesium acetate Drugs 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 4
- 238000005070 sampling Methods 0.000 description 38
- 229910052760 oxygen Inorganic materials 0.000 description 33
- 239000000126 substance Substances 0.000 description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 26
- 239000001301 oxygen Substances 0.000 description 26
- 238000005303 weighing Methods 0.000 description 23
- 239000007787 solid Substances 0.000 description 21
- 239000000706 filtrate Substances 0.000 description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 239000007800 oxidant agent Substances 0.000 description 13
- 230000001590 oxidative effect Effects 0.000 description 13
- 239000012528 membrane Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000010842 industrial wastewater Substances 0.000 description 7
- 230000033558 biomineral tissue development Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
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- 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
- B01J23/38—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
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- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- 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
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- B01J35/615—
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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
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Abstract
The invention belongs to the field of catalyst preparation and application, and discloses an ozone oxidation catalyst which is prepared by taking magnesium oxide as a carrier and loading at least one metal oxide, wherein the molar ratio of the metal oxide to the magnesium oxide is 1: 10-100, solving the problem of low catalytic efficiency of the ozone oxidation catalyst; the invention also discloses a preparation method of the ozone oxidation catalyst, which comprises the steps of coprecipitation, aging, washing, drying and roasting in sequence; the invention also discloses application of the ozone oxidation catalyst in removing organic matters in wastewater. The ozone oxidation catalyst provided by the invention is used for removing organic matters in wastewater, and MgO is used as a main carrier, and various metal oxides are added as loads, so that the surface area of the catalyst is increased, the surface of the catalyst has more active sites, the removal rate of the organic matters in the wastewater is improved, and the removal rate of COD is up to more than 80.1%.
Description
Technical Field
The invention belongs to the field of catalyst preparation and application, and relates to an ozone oxidation catalyst for wastewater treatment, in particular to an ozone oxidation catalyst, and a preparation method and application thereof.
Background
Nowadays, with the acceleration of industrial production and the pace of life of people, the discharge amount of wastewater is also increased day by day. The development of modern science and technology leads to the increase of organic substances in wastewater, so that the treatment of the organic substances in the wastewater is a technical problem which is urgently needed to be solved by modern society.
In particular, industrial wastewater discharged by the pharmaceutical industry contains a large amount of polycyclic aromatic hydrocarbons, sulfur-containing compounds and nitrogen-containing compounds, and the compounds have strong toxicity, high concentration, difficult degradation and serious environmental pollution. The industrial wastewater discharged by the pharmaceutical industry not only seriously pollutes the water environment, but also increases the amount of the industrial wastewater discharged by the pharmaceutical industry along with the development of the pharmaceutical industry in China.
In recent years, the ozone advanced oxidation technology is generally adopted for treating industrial wastewater, and particularly, the industrial wastewater discharged by the pharmaceutical industry is treated. Ozone advanced oxidation technology is taken as a high-efficiency water treatment technology. The strong oxidizing property of ozone can generate a large amount of hydroxyl radicals in the reaction process, and the hydroxyl radicals can be combined with organic matters in industrial wastewater, so that the aim of removing the organic matters in the wastewater is fulfilled. The existing ozone advanced oxidation technology generally adopts three types of catalysts.
The most commonly used catalyst is prepared by alumina supported metal, and is used for removing organic matters in wastewater, and the catalyst has low removal efficiency of the organic matters in the wastewater due to small specific surface area.
The second catalyst is the potassium sulfate which is disclosed in the Chinese invention patent application with the application number of 201810884242.X and catalyzes the ozone oxidation to treat the wastewater in a synergic manner, the wastewater treatment time is reduced by adding the potassium sulfate, but the efficiency of removing organic matters in the wastewater is not improved, and the maximum removal rate of COD is 45.13%.
The latest catalyst is prepared by MgO/HC solid base catalyst disclosed in the Chinese patent application with application number 201710076937.0, so that the maximum removal rate of COD can reach 78.3%, and magnesium oxide is loaded on honeycomb ceramic, so that the specific surface area is further increased by increasing the geometric area, the active sites are increased, and the catalytic efficiency is improved. But the catalytic efficiency is still not ideal, and the removal rate of organic matters in the wastewater needs to be improved; and the service life of the catalyst is shortened due to serious damage of industrial wastewater to the catalyst.
In conclusion, the existing catalysts have the defects of small specific surface area, few active sites, low catalytic efficiency, short catalytic life and the like.
Disclosure of Invention
The invention aims to provide an ozone oxidation catalyst to solve the problem of low catalytic efficiency of the ozone oxidation catalyst;
another object of the present invention is to provide a method for preparing the above ozone oxidation catalyst;
it is a further object of the present invention to provide the use of the above ozone oxidation catalyst.
In order to achieve the purpose, the invention adopts the technical scheme that:
an ozone oxidation catalyst is prepared by taking magnesium oxide as a carrier and loading at least one metal oxide, wherein the molar ratio of the metal oxide to the magnesium oxide is 1: 10-100.
In one embodiment of the present invention, the metal oxide is at least one of a transition metal oxide, a rare earth oxide, and calcium oxide or sodium oxide.
As a further limitation of the invention, the transition metal oxide is RuO
x、MnO
2、CoO
x、Ag
2O、FeO
xAnd NiO.
As a further limitation of the invention, the rare earth oxide is Ce
2O
3Or/and La
2O
3。
The invention also provides a preparation method of the ozone oxidation catalyst, which comprises the following steps of:
step 1) coprecipitation and aging: taking the magnesium salt solution A and a solution B of at least one metal salt to be miscible, wherein the molar ratio of the metal salt in the solution B to the magnesium salt in the magnesium salt solution A is 1: 10-100, adding an alkaline solution C or an acidic solution D, mixing to obtain a suspension E, and aging to obtain a suspension F;
step 2), washing and drying: sequentially filtering, washing, drying and grinding the suspension F to obtain a catalyst precursor G;
step 3) roasting: and roasting the catalyst precursor G to prepare the catalyst which takes magnesium oxide as a carrier and is loaded with at least one metal oxide, namely the ozone oxidation catalyst.
As a limitation of the invention, the preparation process of the magnesium salt solution A comprises the following steps: dissolving at least one of magnesium nitrate, magnesium chloride, magnesium sulfate and magnesium acetate in deionized water to prepare a magnesium salt solution A;
preparation process of solution B: taking at least one RuCl
3、C
6H
9O
6Ru、Mn(NO
3)
2、KMnO
4、Mn(SO
4)
2、Co(NO
3)
2、C
2H
3CoO
2、AgNO
3、AgCl、Ag
2SO
4、Fe(NO
3)
3、KNO
3、Sr(NO
3)
2、Ce(NO
3)
2、Ni(NO
3)
2、La(NO
3)
2Dissolving in deionized water to prepare solution B;
the preparation process of the alkaline solution C comprises the following steps: dissolving at least one of sodium hydroxide, sodium carbonate and ammonia water in deionized water to prepare an alkaline solution C;
preparation process of the acidic solution D: dissolving oxalic acid in deionized water to prepare an acid solution D.
As a further limitation of the present invention, in step 1), the molar ratio of the cations in the basic solution C or the acidic solution D to the magnesium salt in the magnesium salt solution a is 1: 1-100.
As a limitation of the invention, in the step 1), the aging temperature is 20-30 ℃, and the aging time is 3-24 h; the stirring time after the magnesium salt solution A and the solution B are mixed is 15-30 min; adding the alkaline solution C or the acidic solution D, and stirring for 45-120 min;
in the step 2), washing is deionized water washing; the drying temperature is 90-120 ℃; the drying time is 4-8 h; the particle size of the catalyst precursor G is 10-30 nm;
in the step 3), the roasting temperature is 300-800 ℃, and the roasting time is 4-8 h.
The invention also provides an application of the ozone oxidation catalyst, and the ozone oxidation catalyst is used for removing organic matters in wastewater.
Compared with the prior art, the invention has the following progress: the ozone oxidation catalyst provided by the invention takes MgO as a main carrier, various metal oxides are added as a load, magnesium oxide with smaller molecular nucleus is selected, metal oxide with larger molecular weight is loaded, the geometric area of the metal oxide is increased to improve the specific surface, and the pore volume and the pore diameter of the metal oxide are simultaneously enlarged, so that the surface of the catalyst has more active sites, the removal rate of organic matters in wastewater is improved, and the removal rate of COD is more than 80.1-85%.
Drawings
FIG. 1 is an SEM photograph of the ozonation catalyst obtained in example 2 under a condition of being enlarged to 2 μm;
FIG. 2 is an SEM photograph of the ozonation catalyst obtained in example 2 under a condition of being enlarged to 10 μm;
FIG. 3 is a TEM image of the ozonation catalyst obtained in example 2 under an enlarged condition of 2 μm;
FIG. 4 is a TEM image of the ozonation catalyst obtained in example 2 under an enlarged condition of 2 μm.
Detailed Description
The present invention is further illustrated in detail by the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
In the present invention, it is to be noted that, unless otherwise stated, the MgO and Ru
2O
3、MnO
2、CoO
2、Ag
2O、Fe
2O
3、NiO、Ce
2O
3、La
2O
3、RuCl
3、C
6H
9O
6Ru、Mn(NO
3)
2、KMnO
4、Mn(SO
4)
2、Co(NO
3)
2、C
2H
3CoO
2、AgNO
3、AgCl、Ag
2SO
4、Fe(NO
3)
3、KNO
3、Sr(NO
3)
2、Ce(NO
3)
2、Ni(NO
3)
2、La(NO
3)
2All represent corresponding compounds.
Example 1 ozone Oxidation catalyst
An ozone oxidation catalyst is prepared from magnesium oxide as carrier, CaO and Ru
2O
3、La
2O
3The carrier is a carrier, wherein the molar ratio of the carrier to the magnesium oxide is 1: 15.
the above-mentioned loading substance may be any one of the following, but is not limited to the following, and specific loading substances are as follows:
Ru
2O
3；MnO
2；CoO
2；Ag
2O；Fe
2O
3；NiO；Ce
2O
3；La
2O
3；CaO；NaO；Ru
2O
3and MnO
2；Ru
2O
3And CoO
2；Ru
2O
3And Ag
2O；Ru
2O
3And Fe
2O
3；Ru
2O
3And NiO; ru
2O
3And Ce
2O
3；Ru
2O
3And La
2O
3；Ru
2O
3And CaO; and NaO; MnO
2And CoO
2；MnO
2And Ag
2O；MnO
2And Fe
2O
3；MnO
2And NiO; MnO
2And Ce
2O
3；MnO
2And La
2O
3；MnO
2And CaO; MnO
2And NaO; CoO
2And Ag
2O；CoO
2And Fe
2O
3；CoO
2And NiO; CoO
2And Ce
2O
3；CoO
2And La
2O
3；CoO
2And CaO; CoO
2And NaO; ag
2O and Fe
2O
3；Ag
2O and NiO; ag
2O and Ce
2O
3；Ag
2O and La
2O
3；Ag
2O and CaO; ag
2O and NaO; fe
2O
3And NiO; fe
2O
3And Ce
2O
3；Fe
2O
3And La
2O
3；Fe
2O
3And CaO; fe
2O
3And NaO; NiO and Ce
2O
3(ii) a NiO and La
2O
3(ii) a NiO and CaO; NiO and NaO; ce
2O
3And La
2O
3；Ce
2O
3And CaO; ce
2O
3And NaO; la
2O
3And CaO; la
2O
3And NaO; CaO and NaO; ru
2O
3、MnO
2And CoO
2；Ru
2O
3、MnO
2And Ag
2O；Ru
2O
3、MnO
2And Fe
2O
3；Ru
2O
3、MnO
2And NiO; ru
2O
3、MnO
2And Ce
2O
3；Ru
2O
3、MnO
2And La
2O
3；Ru
2O
3、MnO
2And CaO; ru
2O
3、MnO
2And NaO; ru
2O
3、CoO
2And Ag
2O；Ru
2O
3、CoO
2And Fe
2O
3；Ru
2O
3、CoO
2And NiO; ru
2O
3、CoO
2And Ce
2O
3；Ru
2O
3、CoO
2And La
2O
3；Ru
2O
3、CoO
2And CaO; ru
2O
3、CoO
2And NaO; ru
2O
3、Ag
2O and Fe
2O
3；Ru
2O
3、Ag
2O and NiO; ru
2O
3、Ag
2O and Ce
2O
3；Ru
2O
3、Ag
2O and La
2O
3；Ru
2O
3、Ag
2O and CaO; ru
2O
3、Ag
2O and NaO; ru
2O
3、Fe
2O
3And NiO; ru
2O
3、Fe
2O
3And Ce
2O
3；Ru
2O
3、Fe
2O
3And La
2O
3；Ru
2O
3、Fe
2O
3And CaO; ru
2O
3、Fe
2O
3And NaO; ru
2O
3、MnO
2、CoO
2And Ag
2O；Fe
2O
3、NiO、Ce
2O
3And La
2O
3；CaO、NaO、MnO
2And CoO
2；Ag
2O、Fe
2O
3NiO and Ce
2O
3；Ru
2O
3、MnO
2、CoO
2NiO and Ce
2O
3；CoO
2、La
2O
3、CaO、Ag
2O and Fe
2O
3；CoO
2、Ag
2O、Fe
2O
3NiO and Ce
2O
3；La
2O
3、CaO、NaO、Ru
2O
3、MnO
2And Fe
2O
3；Ru
2O
3、MnO
2、CoO
2、Ag
2O、Fe
2O
3And NiO; ru
2O
3、MnO
2、CoO
2、Ag
2O、Fe
2O
3NiO and Ce
2O
3；CoO
2、Ag
2O、Fe
2O
3、NiO、Ce
2O
3、La
2O
3And CaO; MnO
2、CoO
2、Ag
2O、Fe
2O
3、NiO、Ce
2O
3、La
2O
3And CaO; ru
2O
3、MnO
2、CoO
2、Ag
2O、Fe
2O
3、NiO、Ce
2O
3And La
2O
3；Ru
2O
3、MnO
2、CoO
2、Ag
2O、Fe
2O
3、NiO、Ce
2O
3、La
2O
3And CaO; MnO
2、CoO
2、Ag
2O、Fe
2O
3、NiO、Ce
2O
3、La
2O
3CaO and NaO; ru
2O
3、MnO
2、CoO
2、Ag
2O、Fe
2O
3、NiO、Ce
2O
3、La
2O
3、CaO、NaO；
The molar ratio of the load to the magnesium oxide is 1: 10-100.
The support in the present invention may also be any one or more metal oxides other than those enumerated above, in a molar ratio of metal oxide to magnesium oxide of still 1: 10-100, which will not be described in detail herein.
The ozone oxidation catalyst provided by the invention takes MgO as a main carrier, and various metal oxides are added as a load, so that the surface area of the catalyst is increased, and the surface of the catalyst has more active sites, thereby improving the removal rate of organic matters in wastewater and being applied to removing the organic matters in wastewater. The ozone oxidation catalyst can ensure that the removal rate of COD is more than 80.1 percent.
Example 2 preparation method and application of ozone oxidation catalyst
1) Coprecipitation; aging:
23.5906 kg of Mg (NO) were weighed out
3)
2Dissolving in 100L deionized water, and stirring to obtain magnesium salt solution A;
9.9769kg of Co (NO) were weighed out
3)
2Dissolving in 1m
3Preparing solution B in deionized water;
weighing 9.7511kgNa
2CO
3Dissolving in 100L deionized water to obtain alkaline solution C;
measuring 52L of solution B, adding the solution B into 100L of magnesium salt solution A, and stirring for 15min to obtain a mixed solution;
adding 100L of alkaline solution C into the mixed solution, and stirring for 45min to obtain suspension E;
aging the suspension E in a reactor at 25 ℃ for 3h to obtain suspension F;
2) washing and drying: filtering the suspension F to obtain a solid filtrate, washing the solid filtrate for 3 times by using 50L of deionized water, drying the solid filtrate at 90 ℃ for 4 hours, and grinding the solid filtrate into particles with the particle size of 10nm to obtain a catalyst precursor G;
3) roasting: precursor of catalystPlacing the body G in a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, roasting the catalyst precursor G at 500 ℃ for 4h to obtain the ozone oxidation catalyst, wherein the prepared ozone oxidation catalyst takes magnesium oxide as a carrier, CoO
2As a load, CoO
2The molar ratio of MgO to MgO is 1: 56; SEM picture under the condition in which the ozone oxidation catalyst is enlarged to 2 μm is shown in fig. 1; SEM image of the ozone oxidation catalyst at 10 μm magnification is shown in fig. 2; a TEM image under 2 μm magnification of the ozone oxidation catalyst is shown in fig. 3; a TEM image under 2 μm magnification of the ozone oxidation catalyst is shown in fig. 4.
4) The application comprises the following steps: pouring 300L of prepared simulated phenol wastewater at 210g/m into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the next hour, filtering with a filter membrane at 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value with the chemical oxygen demand determinator, and determining the result: the COD removal rate is 85 percent.
Wherein, the COD removal rate calculation method comprises
Example 3 preparation method and application of ozone oxidation catalyst
1) Coprecipitation; aging:
20kg of MgCl were weighed
2Dissolving in 100L deionized water, and stirring to obtain magnesium salt solution A;
9.9769kg of Fe (NO) were weighed out
3)
3Dissolving in 100L deionized water to obtain solution B;
weighing 8.4kg of NaOH and dissolving in 100L of deionized water to prepare an alkaline solution C;
measuring 25.5L of the solution B, adding the solution B into 50L of the magnesium salt solution A, and stirring for 30min to obtain a mixed solution;
adding 50L of alkaline solution C into the mixed solution, and stirring for 50min to obtain suspension E;
aging the suspension E in a reactor at 20 ℃ for 24h to obtain suspension F;
2) washing and drying: filtering the suspension F to obtain a solid filtrate, washing the solid filtrate for 2 times by using 60L of deionized water, drying the solid filtrate at 120 ℃ for 5 hours, and grinding the solid filtrate into particles with the particle size of 30nm to obtain a catalyst precursor G;
3) roasting: putting the catalyst precursor G into a muffle furnace, heating to 800 ℃ at the speed of 5 ℃/min, and roasting the catalyst precursor G at 800 ℃ for 5 hours to obtain the ozone oxidation catalyst, wherein the prepared ozone oxidation catalyst takes magnesium oxide as a carrier and Fe
2O
3As a support, Fe
2O
3The molar ratio of MgO to MgO is 1: 10.
4) the application comprises the following steps: pouring 300L of prepared simulated phenol wastewater at 210g/m into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the next hour, filtering with a filter membrane at 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value with the chemical oxygen demand determinator, and determining the result: the COD removal rate is 81.2 percent.
Example 4 preparation method and application of ozone oxidation catalyst
1) Coprecipitation; aging:
20kg of MgSO were weighed
4Dissolving in 100L deionized water, and stirring to obtain magnesium salt solution A;
9.9769kg of Ce (NO) were weighed out
3）
2Dissolving in deionized water for ethanol cultivation at 1m to obtain solution B;
weighing 233mL of NH
3·H
2O (25 wt%) is alkaline solution C;
measuring 54.4L of the solution B, adding the solution B into 100L of the magnesium salt solution A, and stirring for 20min to obtain a mixed solution;
adding 233mL of alkaline solution C into the mixed solution, and stirring for 120min to obtain suspension E;
aging the suspension E in a reactor at 30 ℃ for 5 hours to obtain suspension F;
2) washing and drying: filtering the suspension F to obtain a solid filtrate, washing the solid filtrate for 4 times by using 40L of deionized water, finally drying the solid filtrate at 100 ℃ for 8 hours, and grinding the solid filtrate into particles with the particle size of 20nm to obtain a catalyst precursor G;
3) roasting: putting the catalyst precursor G into a muffle furnace, heating to 700 ℃ at the speed of 5 ℃/min, and roasting the catalyst precursor G at 700 ℃ for 6h to obtain the ozone oxidation catalyst, wherein the prepared ozone oxidation catalyst takes magnesium oxide as a carrier, Ce is
2O
3As a support, Ce
2O
3The molar ratio of MgO to MgO is 1: 100.
4) the application comprises the following steps: pouring 300L of prepared 210kg/m simulated phenol wastewater into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the next hour, filtering with a filter membrane of 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value with the chemical oxygen demand determinator, and determining the result: the COD removal rate is 82.3 percent.
Example 5 preparation method and application of ozone oxidation catalyst
1) Coprecipitation; aging:
weighing 20kg of magnesium acetate, dissolving in 100L of deionized water, and uniformly stirring to obtain a magnesium salt solution A;
9.9769kg of Mn (NO) were weighed out
3)
2Dissolving in deionized water for ethanol cultivation at 1m to obtain solution B;
weighing 20L oxalic acid (25 wt%) as an acidic solution C;
adding 33L of the solution B into 100L of the magnesium salt solution A, and stirring for 25min to obtain a mixed solution;
adding 671mL of the acidic solution C into the mixed solution, and stirring for 100min to obtain a suspension E;
aging the suspension E in a reactor at 23 ℃ for 20h to obtain suspension F;
2) washing and drying: filtering the suspension F to obtain a solid filtrate, washing the solid filtrate for 5 times by using 2L of deionized water, drying the solid filtrate at 110 ℃ for 7 hours, and grinding the solid filtrate into particles with the particle size of 18nm to obtain a catalyst precursor G;
3) roasting: putting the catalyst precursor G into a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and roasting the catalyst precursor G at 300 ℃ for 8h to obtain the ozone oxidation catalyst, wherein the prepared ozone oxidation catalyst takes magnesium oxide as a carrier and MnO
2As a load, MnO
2The molar ratio of MgO to MgO is 1: 51.
4) the application comprises the following steps: pouring 300L of prepared simulated phenol wastewater at 210g/m into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the next hour, filtering with a filter membrane at 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value with the chemical oxygen demand determinator, and determining the result: the COD removal rate is 80.6 percent.
Example 6 preparation method and application of ozone oxidation catalyst
1) Coprecipitation; aging:
separately weighing 10kg Mg (NO)
3)
2And 10kg MgSO
4Dissolving in 100L deionized water, and stirring to obtain magnesium salt solution A;
9.9769kg of RuCl were weighed out separately
3And 9.9769kg of C
6H
9O
6Dissolving Ru in deionized water for ethanol cultivation at 1m to obtain solution B;
weighing 20L NH
3·H
2O (25 wt%) is alkaline solution C;
measuring 37L of solution B, adding into 100L of magnesium salt solution A, and stirring for 18min to obtain a mixed solution;
adding 1L of alkaline solution C into the mixed solution, and stirring for 70min to obtain suspension E;
aging the suspension E in a reactor at 28 ℃ for 12h to obtain suspension F;
2) washing and drying: filtering the suspension F to obtain a solid filtrate, washing the solid filtrate for 3 times by using 50L of deionized water, drying the solid filtrate at 95 ℃ for 6 hours, and grinding the solid filtrate into particles with the particle size of 25nm to obtain a catalyst precursor G;
3) roasting: putting the catalyst precursor G into a muffle furnace, heating to 400 ℃ at the speed of 5 ℃/min, and roasting the catalyst precursor G at 700 ℃ for 7h to obtain the ozone oxidation catalyst, wherein the prepared ozone oxidation catalyst takes magnesium oxide as a carrier and Ru as the carrier
2O
3As a load, Ru
2O
3The molar ratio of MgO to MgO is 1: 55.5.
4) the application comprises the following steps: pouring 300L of prepared 210g/m simulated phenol wastewater into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method, putting the ozone oxidation catalyst into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the later hour, filtering with a filter membrane of 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value by using the chemical oxygen demand determinator, and determining the result: the COD removal rate is 81.5 percent.
EXAMPLES 7 to 14A method for preparing an ozone oxidation catalyst and use thereof
Examples 7 to 14 are a method for preparing an ozone oxidation catalyst, and the preparation steps are the same as those in any one of examples 2 to 6, except that the raw material components and the ratios used in the preparation process are different, and the specific components and ratios are as follows:
TABLE 1 raw material molar ratio List
Example 7 ozone Oxidation catalyst on magnesium oxide, MnO
2As a load, MnO
2The mol ratio of MgO to MgO is 1: 15, the application thereof is as follows: pouring 300L of prepared 210g/m simulated phenol wastewater into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method, putting the ozone oxidation catalyst into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the later hour, filtering with a filter membrane of 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value by using the chemical oxygen demand determinator, and determining the result: the COD removal rate is 82 percent.
Example 8 ozone Oxidation catalyst on magnesium oxide, MnO
2As a load, MnO
2The mol ratio of MgO to MgO is 1: 10, the application of which is as follows: pouring 300L of prepared 210g/m simulated phenol wastewater into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method, putting the ozone oxidation catalyst into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the later hour, filtering with a filter membrane of 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value by using the chemical oxygen demand determinator, and determining the result: the COD removal rate is 80.7 percent.
The ozone oxidation catalyst prepared in example 9 uses magnesium oxide as carrier, CaO and Ce
2O
3、NiO、La
2O
3The molar ratio of the load to MgO is 1: 100, the application of which is as follows: pouring 300L of prepared simulated phenol wastewater at 210g/m into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method, putting the ozone oxidation catalyst into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the next hour, filtering with a 0.22 mu m filter membrane after sampling, and using a special oxidant to useDigesting by a chemical oxygen demand tester, measuring the COD value by the chemical oxygen demand tester, and measuring the result: the COD removal rate is 83.8 percent.
Example 10 ozone oxidation catalyst with magnesium oxide as support, Ag
2O, NaO and CaO are used as load, and the molar ratio of the load to MgO is 1: 50, the application thereof is as follows: pouring 300L of prepared 210g/m simulated phenol wastewater into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method, putting the ozone oxidation catalyst into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the later hour, filtering with a filter membrane of 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value by using the chemical oxygen demand determinator, and determining the result: the COD removal rate is 81.6 percent.
Example 11 ozone oxidation catalyst with magnesium oxide as support, Ag
2O as a support, Ag
2The molar ratio of O to MgO is 1: 40, the application thereof is as follows: pouring 300L of prepared 210g/m simulated phenol wastewater into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method, putting the ozone oxidation catalyst into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the later hour, filtering with a filter membrane of 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value by using the chemical oxygen demand determinator, and determining the result: the COD removal rate is 83.4 percent.
Example 12 ozone oxidation catalyst with magnesium oxide as support, CoO
2As a load, CoO
2The mol ratio of MgO to MgO is 1: 30, the application of which is as follows: pouring 300L of simulated phenol wastewater prepared at 210g/m into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method, putting the ozone oxidation catalyst into the wastewater in the reactor, introducing mixed gas of ozone and air at a flow rate of 1.5 m/min, reacting for two hours, sampling every 10min for the first hour, and sampling every 20min for the next hourThe sample was filtered through a 0.22 μm filter, digested with a special oxidizing agent using a chemical oxygen demand meter, and measured for its COD value using the chemical oxygen demand meter, and the results were determined as follows: the COD removal rate is 82.1 percent.
Example 13 ozone oxidation catalyst with magnesium oxide as support, Ru
2O
3The molar ratio of the load to MgO is 1: 90, the applications are as follows: pouring 300L of prepared 210g/m simulated phenol wastewater into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method, putting the ozone oxidation catalyst into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the later hour, filtering with a filter membrane of 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value by using the chemical oxygen demand determinator, and determining the result: the COD removal rate is 81.7 percent.
Example 14 ozone oxidation catalyst with magnesium oxide as carrier, La
2O
3As a load, La
2O
3The mol ratio of MgO to MgO is 1: 20, the application thereof is as follows: pouring 300L of prepared 210g/m simulated phenol wastewater into a reactor, weighing 0.5kg of ozone oxidation catalyst prepared by the preparation method, putting the ozone oxidation catalyst into the wastewater in the reactor, introducing mixed gas of ozone and air at the flow rate of 1.5 m/min, reacting for two hours, sampling every 10min in the previous hour, sampling every 20min in the later hour, filtering with a filter membrane of 0.22 mu m after sampling, digesting with a chemical oxygen demand determinator by using a special oxidant, determining the COD value by using the chemical oxygen demand determinator, and determining the result: the COD removal rate is 80.1 percent.
EXAMPLE 15 Performance testing and comparison of an ozone Oxidation catalyst
The mineralization rate and various performance parameters of the catalyst prepared by the invention are compared by 4 groups of comparative catalysts, and the preparation method of the 4 groups of comparative catalysts is as follows:
catalyst 1 group: commercially available MgO was calcined at 500 ℃ for 4 hours in an air atmosphere, and the mineralization rate was measured by the method described in example 2, whereby the COD removal rate was 59%.
Catalyst 2 group: 20kg of MgCl were weighed
2Dissolving in deionized water for 15m, adding 0.2kg of polyvinyl alcohol, stirring at 200rpm for 1h at room temperature, dropping 30ml of NaOH with the concentration of 10mol/L slowly into the solution, aging for 24h, washing with water and ethanol in sequence, drying the washed precipitate at 120 ℃ for 12h, and roasting at 500 ℃ for 2h in air atmosphere to obtain MgO prepared by homogeneous precipitation, wherein the mineralization rate detection method is as in example 2, and the COD removal rate is 64.34%.
Catalyst 3 group: 5.89765kg of Mg (NO) were weighed out
3)
2Dissolving the mixture in 25L of deionized water, and uniformly stirring to prepare a solution A; 8.6279kg of Al were weighed out
2O
3Stirring uniformly in 25L of deionized water to prepare a solution B; and pouring the B into the solution A, continuously stirring for 45min to obtain suspension C, filtering to obtain 3 groups of catalysts, and performing mineralization rate detection by the method in example 2 to obtain a COD removal rate of 56.29%.
Catalyst 4 group: weighing 8.5834kg of magnesium acetate, dissolving the magnesium acetate in 50L of deionized water, and uniformly stirring to obtain a solution A; weighing 14.65kgNaSiO
3Pouring into the solution A, and continuously stirring for 15min to obtain a mixed solution B; weighing 7.5642kg of oxalic acid and dissolving in 100L of water to prepare a solution C; adding the solution C into the mixed solution B, continuing stirring for 45min to obtain a suspension D, filtering to obtain 4 groups of catalysts, and obtaining the COD removal rate of 58.55% by the mineralization rate detection method as in example 2.
TABLE 2 mineralization rates of phenols as catalysts prepared by different preparation methods
TABLE 3 specific surface area of catalyst
Claims (9)
1. An ozone oxidation catalyst is characterized in that the main component for preparing the ozone oxidation catalyst is magnesium oxide as a carrier, at least one metal oxide is loaded, and the molar ratio of the metal oxide to the magnesium oxide is 1: 10-100.
2. The ozonation catalyst of claim 1, wherein the metal oxide is at least one of a transition metal oxide, a rare earth oxide, and calcium oxide or sodium oxide.
3. The ozonation catalyst of claim 2, wherein the transition metal oxide is RuO
x、MnO
2、CoO
x、Ag
2O、FeO
xAnd NiO.
4. The ozonation catalyst of claim 2 or 3, wherein the rare earth oxide is Ce
2O
3Or/and La
2O
3。
5. The method for preparing an ozone oxidation catalyst according to any one of claims 1 to 4, characterized in that the step of preparing it comprises the following steps carried out in order:
step 1) coprecipitation and aging: taking the magnesium salt solution A and a solution B of at least one metal salt to be miscible, wherein the molar ratio of the metal salt in the solution B to the magnesium salt in the magnesium salt solution A is 1: 10-100, adding an alkaline solution C or an acidic solution D, mixing to obtain a suspension E, and aging to obtain a suspension F;
step 2), washing and drying: sequentially filtering, washing, drying and grinding the suspension F to obtain a catalyst precursor G;
step 3) roasting: and roasting the catalyst precursor G to prepare the catalyst which takes magnesium oxide as a carrier and is loaded with at least one metal oxide, namely the ozone oxidation catalyst.
6. The method of producing an ozone oxidation catalyst according to claim 5,
the preparation process of the magnesium salt solution A comprises the following steps: dissolving at least one of magnesium nitrate, magnesium chloride, magnesium sulfate and magnesium acetate in deionized water to prepare a magnesium salt solution A;
preparation process of solution B: taking at least one RuCl
3、C
6H
9O
6Ru、Mn(NO
3)
2、KMnO
4、Mn(SO
4)
2、Co(NO
3)
2、C
2H
3CoO
2、AgNO
3、AgCl、Ag
2SO
4、Fe(NO
3)
3、KNO
3、Sr(NO
3)
2、Ce(NO
3)
2、Ni(NO
3)
2、La(NO
3)
2Dissolving in deionized water to prepare solution B;
the preparation process of the alkaline solution C comprises the following steps: dissolving at least one of sodium hydroxide, sodium carbonate and ammonia water in deionized water to prepare an alkaline solution C;
preparation process of the acidic solution D: dissolving oxalic acid in deionized water to prepare an acid solution D.
7. The method of producing an ozone oxidation catalyst according to claim 6,
in the step 1), the molar ratio of cations in the alkaline solution C or the acidic solution D to magnesium salts in the magnesium salt solution A is 1: 1-100.
8. The method of producing an ozone oxidation catalyst according to claim 5,
in the step 1), the aging temperature is 20-30 ℃, and the aging time is 3-24 h; the stirring time after the magnesium salt solution A and the solution B are mixed is 15-30 min; adding the alkaline solution C or the acidic solution D, and stirring for 45-120 min;
in the step 2), washing is deionized water washing; the drying temperature is 90-120 ℃; the drying time is 4-8 h; the particle size of the catalyst precursor G is 10-30 nm;
in the step 3), the roasting temperature is 300-800 ℃, and the roasting time is 4-8 h.
9. Use of the ozone oxidation catalyst according to any one of claims 1 to 4, wherein the ozone oxidation catalyst is used for removing organic matter from wastewater.
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