CN107585852B - Method and device for carrying out heterogeneous catalytic oxidation on COD (chemical oxygen demand) in wastewater by using ozone - Google Patents
Method and device for carrying out heterogeneous catalytic oxidation on COD (chemical oxygen demand) in wastewater by using ozone Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 58
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 239000000126 substance Substances 0.000 title abstract description 5
- 239000011949 solid catalyst Substances 0.000 claims abstract description 62
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
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- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 230000014759 maintenance of location Effects 0.000 claims abstract description 6
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 2
- 238000009827 uniform distribution Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a method and a device for carrying out heterogeneous catalytic oxidation on COD (chemical oxygen demand) in wastewater by ozone. The method decomposes ozone into hydroxyl free radicals with stronger oxidability by using a solid catalyst, and then the hydroxyl free radicals and organic matters in the wastewater generate oxidation reaction to convert the organic matters into carbon dioxide and water, thereby achieving the purpose of reducing COD in the wastewater. In the method, the mass ratio of ozone to COD in the wastewater is 0.5-1: 1, the using amount of the solid catalyst is 0.2-2 g/L, and the retention time is 0.1-2 h. The catalytic oxidation tower for realizing the method is designed, the upper part of the tower is a wastewater and hydrogen peroxide mixed liquid distribution area, the middle part of the tower is a catalyst area, and the lower part of the tower is an oxygen and ozone mixed gas distribution area. The invention has the advantages of solving the problems of low utilization rate and low oxidation rate of ozone in catalytic oxidation of ozone.
Description
Technical Field
The invention belongs to the field of wastewater treatment, relates to a method and a device for carrying out heterogeneous catalytic oxidation on COD (chemical oxygen demand) in wastewater by ozone, and particularly relates to a method and a device for treating COD in wastewater by catalyzing ozonolysis to hydroxyl radicals by using a solid catalyst.
Background
In the production and living process of human beings, a large amount of industrial waste water and town waste water are generated, and the waste water contains a large amount of benzene series, organic nitrile and phenols. The pollutants belong to the pollution indexes strictly controlled by China, and commonly used removal methods comprise an air floatation method, a precipitation method, an adsorption method, a filtration method and a biological method. These methods have limited ability to remove COD and cannot be used for advanced treatment. Later, oxidation methods have been proposed, in which the oxidizing agent is ozone, which has the advantages of strong oxidizing property, oxygen generation after reduction, and no environmental pollution, but has the disadvantages of low utilization rate, high operating cost, and selectivity to organic substances.
CN202924812 proposes a processing apparatus of organic waste water ozone catalytic oxidation, the device includes catalytic oxidation tower, porous regular ceramic catalysis, tank and play pond etc.. After the wastewater is treated by the device, the COD of the effluent is 0-100 mg/L. But has the disadvantages of high ozone utilization rate and high operating cost.
CN205616628 reports an ozone catalytic oxidation reaction apparatus, which comprises a plurality of oxidation towers, ozone generators, a water inlet main pipe, a water outlet main pipe and a water drainage main pipe connected in parallel. However, the report only suggests the implementation of the device, and does not suggest an example of the application of the device in wastewater for COD reduction.
Disclosure of Invention
The purpose of the invention is: in order to solve the problems of low ozone utilization rate and high operating cost in the ozone catalytic oxidation wastewater COD, a method for treating the COD in the wastewater by using a novel solid catalyst to catalyze the ozone oxidation and greatly reducing the ozone consumption and a realization device are provided.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a device for carrying out heterogeneous catalytic oxidation on COD in wastewater by ozone is a wastewater oxidation tower, wherein a water distribution device, a solid catalyst layer and a gas distribution device are sequentially arranged in a tower body from top to bottom;
the tower top is provided with a mixed liquid inlet which is connected with a wastewater inlet pipe and a hydrogen peroxide inlet pipe;
the tower bottom is provided with a mixed gas inlet of ozone and oxygen;
an oxygen outlet is arranged on the outer side of the tower wall of the water distribution equipment, and a water production outlet is arranged on the outer side of the tower wall of the solid catalyst layer.
Further, the solid catalyst layer comprises a catalyst fixed layer 1, a catalyst layer and a catalyst fixed layer 2 from top to bottom in sequence.
A method for heterogeneous catalytic oxidation of COD in wastewater by ozone comprises the following steps:
(1) mixing the wastewater and hydrogen peroxide, then feeding the mixture into the upper part of an oxidation tower from the tower top, and uniformly distributing the mixed solution through a water distribution device and then feeding the mixed solution into a solid catalyst layer; the mixed gas of ozone and oxygen enters the lower part of the oxidation tower from the bottom of the tower, is uniformly distributed by a gas distribution device and then enters a solid catalyst layer; wherein, the active component of the solid catalyst is aluminum and one of iron, manganese and cerium;
(2) ozone reacts with hydrogen peroxide on the surface of the solid catalyst to be decomposed into hydroxyl radicals, the hydroxyl radicals oxidize COD in the mixed liquid flowing into the solid catalyst layer into carbon dioxide and water, and the oxidized wastewater is discharged from a water production outlet.
Further, in the step (1), the molar concentration ratio of the hydrogen peroxide in the wastewater to the molar concentration of the ozone entering the lower part of the oxidation tower is 1:1 to 1.5.
Further, in the step (1), the mass ratio of the ozone to the COD in the wastewater is 0.5:1 to 1.5;
further, in the step (1), the concentration by mass of hydrogen peroxide in hydrogen peroxide is not limited, but is preferably 27.5%.
Further, in the step (1), the solid catalyst is prepared by taking a titanium silicalite TS-1 as a carrier, the mass fraction of the loaded aluminum is 15%, and the mass fraction of the loaded iron, manganese or cerium is 12%.
Further, in the step (1), the preparation method of the solid catalyst comprises the following steps:
1) preparing titanium silicalite TS-1 into small balls with the diameter of 5-10 mm by taking silica gel as an adhesive, drying at 70-120 ℃, and roasting at 500 ℃ for 1h to obtain a carrier;
2) dissolving aluminum salt and one of ferric salt, manganese salt and cerium salt serving as precursors of active ingredients in deionized water to obtain an impregnation solution, wherein the mass percentage of aluminum is 15%; the mass percentage of the iron, the manganese or the cerium is 12 percent.
3) And transferring the carrier into an impregnation liquid, impregnating the active component by adopting an impregnation method, drying at 70-120 ℃ after impregnating for 1-4 h, and roasting at 500 ℃ for 6h to obtain the solid catalyst.
Preferably, in step 2), the aluminum salt is aluminum nitrate or aluminum acetate, the iron salt is ferric nitrate or ferric acetate, the manganese salt is manganese nitrate or manganese acetate, and the cerium salt is cerium nitrate or cerium acetate.
Further, in the step (2), the retention time of the mixed solution flowing through the solid catalyst layer is 0.1-2 h;
further, in the step (2), the using amount of the solid catalyst in the tower body is 0.2-2 g/L.
The principle that the solid catalyst decomposes ozone and hydrogen peroxide into hydroxyl radicals is as follows:
O3 +OH- → HO2 - + O2
H2O2 + H2O → HO2 - + H3O
O3 + HO2 - → OH• + O2 - +O2
O3 + OH• → HO2• + O2
O3 + O2 - → O3 - + O2
O3 - + H2O→ OH• + OH- + O2
compared with the prior art, the invention has the following advantages and beneficial effects:
1. the novel solid catalyst is adopted, so that the utilization efficiency of the catalyst is improved, the ozone consumption is reduced, and the operation cost is reduced.
2. Compared with the existing catalyst, under the condition that various indexes of inlet water are the same with the added catalyst amount, the device and the method can improve the overall COD removal rate by 10-50% and reduce the ozone consumption by 10-30%.
Drawings
FIG. 1 is a schematic view showing the construction of an ozone heterogeneous catalytic oxidation wastewater treatment apparatus according to example 1;
in the figure: 1. the device comprises a wastewater inlet pipe, 2, a hydrogen peroxide inlet pipe, 3, a mixed liquid inlet, 4, a water distribution device, 5, catalyst fixing layers 1 and 6, a catalyst layer, 7, catalyst fixing layers 2 and 8, a gas distribution device, 9, an ozone and oxygen mixed gas inlet, 10, an oxygen outlet, 11 and a water production outlet.
Detailed Description
The principles and features of the present invention are described below in conjunction with the following drawings, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Device for carrying out heterogeneous catalytic oxidation on COD in wastewater by ozone
Example 1
A device for carrying out heterogeneous catalytic oxidation on COD in wastewater by ozone (as shown in figure 1) is specifically a wastewater oxidation tower, wherein a water distribution device 4, a solid catalyst layer and a gas distribution device 8 are arranged in the tower body from top to bottom in sequence; a mixed liquid inlet 3 is arranged at the top of the tower, and the mixed liquid inlet 3 is connected with a wastewater inlet pipe 1 and a hydrogen peroxide inlet pipe 2; the tower bottom is provided with a mixed gas inlet 9 of ozone and oxygen; an oxygen outlet 10 is arranged on the outer side of the tower wall of the water distribution device 4, and a water production outlet 11 is arranged on the outer side of the tower wall of the solid catalyst layer.
The solid catalyst layer is composed of a catalyst fixed layer 15, a catalyst layer 6 and a catalyst fixed layer 27 in this order from top to bottom.
The catalyst fixing layer 1 and the catalyst fixing layer 2 adopt cobblestones with the particle size of 2-15 mm to fix the solid catalyst; wherein the catalyst fixed layer 1 adopts 8-15 mm cobblestones, and the catalyst fixed layer 2 adopts 2-6 mm cobblestones.
Second, method for heterogeneous catalytic oxidation of COD in wastewater by ozone
In the following examples, the solid catalyst used was prepared by the following method:
1) preparing a titanium silicalite TS-1 into small balls with the diameter of 5-10 mm, drying at 70-120 ℃, and roasting at 500 ℃ for 1h to obtain a carrier;
2) dissolving aluminum salt and one of ferric salt, manganese salt and cerium salt which are used as precursors of active ingredients (all nitrate or acetate) in deionized water to obtain an impregnation solution, wherein the mass percentage of aluminum is 15%; the mass percentage of the iron, the manganese or the cerium is 12 percent.
3) And transferring the carrier into an impregnation liquid, impregnating the active component by adopting an impregnation method, drying at 70-120 ℃ after the impregnation is completed for 4h, and roasting at 500 ℃ for 6h to obtain the solid catalyst.
Example 2
A method for carrying out heterogeneous catalytic oxidation on COD in wastewater by ozone (adopting the device in the embodiment 1) comprises the following steps:
(1) respectively enabling the wastewater with the COD concentration of 100 mg/L to pass through a wastewater inlet pipe 1, enabling hydrogen peroxide with the hydrogen peroxide mass concentration of 27.5% to pass through a water inlet pipe 2, mixing, and then enabling the mixed solution to enter a water distribution device 4 for uniform distribution; the mixed gas of ozone and oxygen enters the lower part of the oxidation tower from the ozone and oxygen mixed gas inlet 9 at the bottom of the tower, and enters the solid catalyst layer (the catalyst fixed layer 15, the catalyst layer 6 and the catalyst fixed layer 27) after being uniformly distributed by the gas distribution device 8; wherein, the active components of the solid catalyst comprise 15 mass percent of aluminum and 12 mass percent of iron; controlling the molar ratio of ozone to hydrogen peroxide to be 1:1, the mass ratio of ozone to COD in the wastewater is 0.5: 1;
(2) in the solid catalyst layer, ozone reacts with hydrogen peroxide on the surface of the solid catalyst layer to be decomposed into hydroxyl radicals, the hydroxyl radicals oxidize COD in the mixed liquid flowing into the solid catalyst layer into carbon dioxide and water, and the wastewater after oxidation treatment is discharged from an overflow port at the upper part of the solid catalyst layer. The retention time of the mixed solution flowing through the solid catalyst layer is 0.5 h; the amount of the solid catalyst used was 0.2 g/L of wastewater.
The COD of the wastewater is reduced from 100 mg/L to 40 mg/L.
Example 3
A method for carrying out heterogeneous catalytic oxidation on COD in wastewater by ozone (adopting the device in the embodiment 1) comprises the following steps:
(1) respectively enabling the wastewater with the COD concentration of 200 mg/L to pass through a wastewater inlet pipe 1, enabling hydrogen peroxide with the hydrogen peroxide mass concentration of 27.5% to pass through a water inlet pipe 2, mixing, and then enabling the mixed solution to enter a water distribution device 4 for uniform distribution; the mixed gas of ozone and oxygen enters the lower part of the oxidation tower from the ozone and oxygen mixed gas inlet 9 at the bottom of the tower, and enters the solid catalyst layer (the catalyst fixed layer 15, the catalyst layer 6 and the catalyst fixed layer 27) after being uniformly distributed by the gas distribution device 8; wherein, the active components of the solid catalyst comprise 15 mass percent of aluminum and 12 mass percent of manganese; controlling the molar ratio of ozone to hydrogen peroxide to be 1:1, the mass ratio of ozone to COD in the wastewater is 0.8: 1;
(2) in the solid catalyst layer, ozone reacts with hydrogen peroxide on the surface of the solid catalyst layer to be decomposed into hydroxyl radicals, the hydroxyl radicals oxidize COD in the mixed liquid flowing into the solid catalyst layer into carbon dioxide and water, and the wastewater after oxidation treatment is discharged from an overflow port at the upper part of the solid catalyst layer. The retention time of the mixed solution flowing through the solid catalyst layer is 0.7 h; the amount of the solid catalyst used was 0.6 g/L of wastewater.
The COD of the wastewater is reduced from 100 mg/L to 30 mg/L.
Example 4
A method for carrying out heterogeneous catalytic oxidation on COD in wastewater by ozone (adopting the device in the embodiment 1) comprises the following steps:
(1) respectively enabling wastewater with the COD concentration of 300 mg/L to pass through a wastewater inlet pipe 1, enabling hydrogen peroxide with the hydrogen peroxide mass concentration of 27.5% to pass through a water inlet pipe 2, mixing, and then enabling the mixed solution to enter a water distribution device 4 for uniform distribution; the mixed gas of ozone and oxygen enters the lower part of the oxidation tower from the ozone and oxygen mixed gas inlet 9 at the bottom of the tower, and enters the solid catalyst layer (the catalyst fixed layer 15, the catalyst layer 6 and the catalyst fixed layer 27) after being uniformly distributed by the gas distribution device 8; wherein, the active components of the solid catalyst comprise 15 mass percent of aluminum and 12 mass percent of cerium; controlling the molar ratio of ozone to hydrogen peroxide to be 1:1, the mass ratio of ozone to COD in the wastewater is 1: 1;
(2) in the solid catalyst layer, ozone reacts with hydrogen peroxide on the surface of the solid catalyst layer to be decomposed into hydroxyl radicals, the hydroxyl radicals oxidize COD in the mixed liquid flowing into the solid catalyst layer into carbon dioxide and water, and the wastewater after oxidation treatment is discharged from an overflow port at the upper part of the solid catalyst layer. The retention time of the mixed solution flowing through the solid catalyst layer is 0.9 h; the amount of the solid catalyst used was 1.2 g/L of wastewater.
The COD of the wastewater is reduced from 100 mg/L to 20 mg/L.
Claims (9)
1. The utility model provides a device of COD in ozone heterogeneous catalytic oxidation waste water which characterized in that: in particular to a wastewater oxidation tower, wherein a water distribution device, a solid catalyst layer and a gas distribution device are arranged in a tower body from top to bottom in sequence;
the tower top is provided with a mixed liquid inlet which is connected with a wastewater inlet pipe and a hydrogen peroxide inlet pipe;
the tower bottom is provided with a mixed gas inlet of ozone and oxygen;
an oxygen outlet is arranged on the outer side of the tower wall of the water distribution equipment, and a water production outlet is arranged on the outer side of the tower wall of the solid catalyst layer;
wherein, the active component of the solid catalyst is aluminum and one of iron, manganese and cerium;
the preparation method of the solid catalyst comprises the following steps:
1) preparing a titanium silicalite TS-1 into small balls with the diameter of 5-10 mm, drying at 70-120 ℃, and roasting at 500 ℃ for 1h to obtain a carrier;
2) dissolving aluminum salt and one of ferric salt, manganese salt and cerium salt serving as precursors of active ingredients in deionized water to obtain an impregnation solution, wherein the mass percentage of aluminum is 15%; the mass percentage of the iron, the manganese or the cerium is 12 percent;
3) and transferring the carrier into an impregnation liquid, impregnating the active component by adopting an impregnation method, drying at 70-120 ℃ after impregnating for 1-4 h, and roasting at 500 ℃ for 6h to obtain the solid catalyst.
2. The apparatus of claim 1, wherein: the solid catalyst layer comprises a catalyst fixed layer 1, a catalyst layer and a catalyst fixed layer 2 from top to bottom in sequence.
3. The apparatus of claim 1, wherein: in the step (1), the solid catalyst takes a titanium silicalite TS-1 as a carrier, the mass fraction of the loaded aluminum is 15%, and the mass fraction of the loaded iron, manganese or cerium is 12%.
4. The apparatus of claim 3, wherein: in the step 2), the aluminum salt is aluminum nitrate or aluminum acetate, the ferric salt is ferric nitrate or ferric acetate, the manganese salt is manganese nitrate or manganese acetate, and the cerium salt is cerium nitrate or cerium acetate.
5. A method for heterogeneous catalytic oxidation of COD in wastewater by ozone according to the device of any of claims 1 to 4, characterized in that the steps comprise:
(1) mixing the wastewater and hydrogen peroxide, then feeding the mixture into the upper part of an oxidation tower from the tower top, and uniformly distributing the mixed solution through a water distribution device and then feeding the mixed solution into a solid catalyst layer; the mixed gas of ozone and oxygen enters the lower part of the oxidation tower from the bottom of the tower, is uniformly distributed by a gas distribution device and then enters a solid catalyst layer;
(2) ozone reacts with hydrogen peroxide on the surface of the solid catalyst to be decomposed into hydroxyl radicals, the hydroxyl radicals oxidize COD in the mixed liquid flowing into the solid catalyst layer into carbon dioxide and water, and the oxidized wastewater is discharged from a water production outlet.
6. The method of claim 5, wherein: in the step (1), the molar concentration ratio of the hydrogen peroxide in the wastewater to the ozone entering the lower part of the oxidation tower is 1:1 to 1.5; the mass concentration of hydrogen peroxide in hydrogen peroxide is 27.5%.
7. The method of claim 5, wherein: in the step (1), the mass ratio of ozone to COD in the wastewater is 0.5:1 to 1.5.
8. The method of claim 5, wherein: in the step (2), the retention time of the mixed solution flowing through the solid catalyst layer is 0.1-2 h.
9. The method of claim 5, wherein: in the step (2), the using amount of the solid catalyst in the tower body is 0.2-2 g/L.
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| TWI381883B (en) * | 2006-03-10 | 2013-01-11 | Nippon Catalytic Chem Ind | Catalyst for wastewater treatment and method for wastewater treatment using said catalyst |
| CN202924812U (en) * | 2012-11-14 | 2013-05-08 | 北京赛科康仑环保科技有限公司 | Organic wastewater ozone catalytic oxidation treatment device |
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| CN101327985A (en) * | 2008-07-31 | 2008-12-24 | 哈尔滨工业大学 | Method for removing organic pollutant in water by catalysis ozonation |
| CN106582808A (en) * | 2016-12-01 | 2017-04-26 | 济南大学 | Catalyst for catalysis of production of hydroxyl free radical from ozone and gasified hydrogen peroxide/water, and use thereof |
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Effective date of registration: 20240109 Address after: Room 351, Zhengfeng building, building 8, environmental protection science and Technology Park, 554 Zhengfeng Road, high tech Zone, Jinan City, Shandong Province Patentee after: SHANDONG BEIGUO DEVELOPMENT GROUP CO.,LTD. Address before: 250022 No. 336, South Xin Zhuang West Road, Shizhong District, Ji'nan, Shandong Patentee before: University of Jinan |