CN115041187A - Catalyst for catalyzing ozone oxidation and preparation method thereof - Google Patents
Catalyst for catalyzing ozone oxidation and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000003647 oxidation Effects 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 112
- 238000005187 foaming Methods 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000004113 Sepiolite Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 10
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000010459 dolomite Substances 0.000 claims abstract description 8
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 8
- 239000004579 marble Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 56
- 238000000227 grinding Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 12
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 10
- 230000007480 spreading Effects 0.000 claims description 9
- 238000003892 spreading Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000006260 foam Substances 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000004575 stone Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 15
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 grinding Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to an improvement of water treatment technology, in particular to a catalyst for catalyzing ozone oxidation and a preparation method thereof, wherein a silicon oxide material, a metal oxide active substance and an auxiliary agent are mixed, the auxiliary agent is decomposed to generate carbon dioxide when being heated at high temperature, the silicon oxide is foamed into a foam porous substance, and the metal oxide active substance is uniformly distributed in a foaming body; the catalyst prepared by the method can be used as a catalytic reaction site on the surface and inside, so that the reaction area is enlarged, and the ozone reaction time is prolonged; comprises a matrix, an active component and an auxiliary agent; the matrix is sepiolite or montmorilloniteOne or more of stone and glass powder, the active component is one or more of Cu, Mn, Co, Ce and Fe oxides, and the auxiliary agent is CaCO 3 、Na 2 CO 3 One or more of dolomite powder and marble powder; the weight percentage of each component is as follows: 65-85 parts; 5-15% of active component; auxiliary agent: 5 to 30.
Description
Technical Field
The invention relates to an improvement of a water treatment technology, in particular to a catalyst for catalyzing ozone oxidation and a preparation method thereof.
Background
In the wastewater treatment process, compared with other advanced oxidation technologies such as Fenton and the like, the direct oxidation capacity of ozone is not outstanding, but the advantages of no selectivity, strong oxidation property, no generation of solid wastes and simple operation are outstanding after the ozone is converted into hydroxyl radicals through the action of a catalyst.
The existing ozone oxidation catalyst is prepared by a porous adsorption medium (such as Al) 2 O 3 Activated carbon, etc.) as a carrier, loading metal salt on the carrier by an impregnation method, a precipitation method, etc., and then roasting to obtain a catalyst loaded with metal oxide; the other method is to directly mix the porous medium and the powder of the metal oxide, then mix with other additives and granulate to obtain the catalyst. The preparation method of ozone catalyst as disclosed in CN112791732, using Al 2 O 3 The carrier is used, and the metal oxide is combined with the carrier through impregnation, coprecipitation and calcination to form a catalyst; the method disclosed in patent application No. CN105381804 uses manganese sand filter material or pyrolusite as raw material, adds adhesive, peptizing agent and pore-enlarging agent, and finally forms the ozone oxidation catalyst through a series of processes such as grinding, mixing, kneading, extrusion forming, drying and roasting.
However, the density of the catalyst obtained by the preparation method of the catalyst is more than 1, the catalyst is in a stacking state in a reactor, and the problems of surface area reduction, catalytic efficiency reduction and the like of the catalyst are caused by hardening and micropore structure blockage in the long-time ozone catalytic oxidation process, so that the application and popularization of the catalyst in actual sewage treatment engineering are adversely affected.
Disclosure of Invention
Aiming at the problems mentioned in the background technology, the invention provides a catalyst for catalyzing ozone oxidation and a preparation method thereof, wherein a silicon oxide material, a metal oxide active substance and an auxiliary agent are mixed, the auxiliary agent is decomposed to generate carbon dioxide when being heated at high temperature, the silicon oxide is foamed into a foam porous substance, and the metal oxide active substance is uniformly distributed in a foaming body; the catalyst prepared by the method can be used as a catalyst reaction site on the surface and inside, so that the reaction area is enlarged, and the ozone reaction time is prolonged.
The technical purpose of the invention is realized by the following technical scheme: catalysisThe catalyst for ozone oxidation comprises a matrix, an active component and an auxiliary agent; the matrix is one or more of sepiolite, montmorillonite and glass powder, the active component is one or more of Cu, Mn, Co, Ce and Fe oxides, and the auxiliary agent is CaCO 3 、Na 2 CO 3 One or more of dolomite powder and marble powder; the weight percentage of each component is
Matrix: 65-85 parts;
5-15% of active component;
auxiliary agent: 5 to 30.
Preferably, the active component can adopt a mixture of Cu, Mn, Co, Ce and Fe oxides, wherein the weight ratio of the Cu oxide to the Mn oxide is 3: 1-1: 2, the contents of the Co oxide, the Ce oxide and the Fe oxide are respectively 0-15% of the sum of the weights of the Cu oxide and the Mn oxide, and the sum of the weights of all the active components is 5-15% of the weight of the catalyst.
The technical purpose of the invention is realized by the following technical scheme: a preparation method of a catalyst for catalyzing ozone oxidation comprises the following steps:
(1) selecting one or more of sepiolite, montmorillonite and glass powder to grind, wherein 90% of the powder can pass through a 200-mesh sieve;
(2) grinding various metal oxides to ensure that 90 percent of the powder can pass through a 400-mesh sieve;
(3) selection of CaCO 3 、Na 2 CO 3 One or more of dolomite powder and marble powder, grinding, wherein 90% of the powder can pass through a 400-mesh sieve;
(4) the three materials are prepared according to the following steps: 65-85 parts; 5-15% of active component; auxiliary agent: 5-30, spreading the mixture into a powder layer with the thickness of 20cm, and sending the powder layer into a heating furnace; preheating, primary heating, sintering and heating, secondary heating and foaming and heating by a heating furnace for 5 stages to prepare a foaming type catalyst, taking out the foaming type catalyst, and naturally cooling to room temperature to obtain a catalyst finished product; wherein the preheating temperature is 300-400 ℃, and the duration is 15-20 minutes; the primary heating temperature is 550-600 ℃, and the duration time is 10-30 minutes; the sintering heating temperature is 700-750 ℃, and the duration is 5-15 minutes; the secondary heating temperature is 780-800 ℃, and the duration is 5-20 minutes; the foaming heating temperature is 900-950 ℃, and the duration time is 4-10 minutes; then, the temperature is reduced to 550 ℃ within 30 minutes, and finally the temperature is naturally cooled to room temperature for 24 hours;
(5) and taking out the catalyst, and crushing to obtain particles with the particle size of 5-10 mm.
Preferably, the catalyst has a particle size of 5-10mm and a density of 0.55-0.85 g/cm 3 The porosity is more than 80%, the average pore diameter is 2mm, and the compressive strength is more than 3.5 MPa.
In conclusion, the invention has the following beneficial effects:
(1) according to the invention, under the action of the auxiliary agent, in the sintering and foaming stages, the carbon dioxide generated by decomposition of the auxiliary agent enables the catalyst to be in a foaming type, the density of the catalyst is less than 1, and the catalyst is in a suspension state in wastewater treatment, while the density of the existing various catalysts for ozone catalytic oxidation is more than 1, and the catalyst is in a stacking state in a reactor for a long time and is easy to harden and the like;
(2) the heating temperature of the invention is obviously higher than the preparation temperature of the conventional catalyst, the ionic valence state of the transition metal in the catalyst is richer, and the foaming effect of the auxiliary agent avoids the problems of agglomeration of the transition metal oxide on the surface of the carrier, blockage of a microporous structure, reduction of the surface area of the catalyst and the like caused by high temperature, thereby being beneficial to the catalytic effect of the catalyst on ozone.
(3) The catalyst prepared by the invention has the porosity of more than or equal to 80 percent and the average pore diameter of 2mm, and in the reaction process, wastewater and micron-sized ozone bubbles can enter the inner cavity of the catalyst for reaction, so that the reaction area is enlarged, and the reaction time is prolonged.
Drawings
FIG. 1 is a graph showing the efficiency of the product obtained in the example of the invention in catalyzing ozone to treat wastewater and degrade COD.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In specific practice, the present invention provides the following examples;
example 1
(1) Selecting 350g of sepiolite powder and montmorillonite powder respectively, mixing, grinding, and finishing grinding when 90% of powder can pass through a 200-mesh sieve;
(2) selecting 60g of CuO powder and MnO 2 Powder 30g, CeO 2 Powder 5g, Co 3 O 4 Powder 3g, Fe 2 O 3 2g of powder, and grinding the powder respectively, wherein when 90% of the powder can pass through a 400-mesh sieve, the grinding is finished;
(3) selection of CaCO 3 Mixing the powder and dolomite powder 100g, grinding, and finishing grinding when 90% of the powder can pass through a 400-mesh sieve;
(4) mixing the above three materials, spreading into powder layer with thickness of 20cm, feeding into heating furnace, and heating. Wherein the preheating temperature is 350 ℃ and the duration time is 15 minutes; the primary temperature rise is 550 ℃ and the duration is 15 minutes; the sintering heating temperature is 700 ℃, and the duration time is 15 minutes; the secondary heating temperature is 780 ℃ and the duration time is 20 minutes; the foaming heating temperature was 900 ℃ and the duration was 4 minutes. Then, the temperature is reduced to 550 ℃ within 30 minutes, and finally, the temperature is naturally cooled to room temperature for 24 hours.
(5) The catalyst was taken out and pulverized to a particle size of 5 mm.
Example 2
(1) Selecting 800g of waste glass, grinding, and finishing grinding when 90% of powder of the waste glass can pass through a 200-mesh sieve;
(2) selecting 33g of CuO powder and MnO 2 Powder 33g, CeO 2 Powder 7g, Co 3 O 4 Powder 5g, Fe 2 O 3 2g of powder, minGrinding, and finishing grinding when 90% of powder can pass through a 400-mesh sieve;
(3) selection of Na 2 CO 3 60g of powder and 60g of marble powder are mixed and ground, and when 90% of the powder can pass through a 400-mesh sieve, the grinding is finished;
(4) mixing the three materials uniformly, spreading the mixture into a powder layer with the thickness of 20cm, and feeding the powder layer into a heating furnace; heating was started. Wherein the preheating temperature is 300 ℃ and the duration time is 20 minutes; the primary temperature rise is 600 ℃, and the duration time is 10 minutes; the sintering heating temperature is 750 ℃, and the duration is 8 minutes; the secondary heating temperature is 800 ℃, and the duration time is 6 minutes; the foaming heating temperature was 950 ℃ for 4 minutes. Then, the temperature is reduced to 550 ℃ within 30 minutes, and finally, the temperature is naturally cooled to room temperature for 24 hours.
(5) The catalyst was taken out and pulverized to a particle size of 10 mm.
Example 3
(1) 350g of montmorillonite powder and 300g of waste glass are selected and ground respectively, and when 90% of powder can pass through a 200-mesh sieve, the grinding is finished;
(2) selecting 42g of CuO powder and MnO 2 84g of powder, CeO 2 Powder 12g, Co 3 O 4 12g of powder, and grinding the powder respectively when 90 percent of the powder can pass through a 400-mesh sieve;
(3) selection of Na 2 CO 3 60g of powder and 60g of marble powder are mixed and ground, and when 90% of the powder can pass through a 400-mesh sieve, the grinding is finished;
(4) mixing the above three materials, spreading into powder layer with thickness of 20cm, and feeding into heating furnace. Heating was started. Wherein the preheating temperature is 300 ℃ and the duration time is 20 minutes; the primary temperature rise is 600 ℃, and the duration time is 10 minutes; the sintering heating temperature is 750 ℃, and the duration is 8 minutes; the secondary heating temperature is 800 ℃, and the duration time is 6 minutes; the foaming heating temperature is 950 ℃, and the duration time is 4 minutes; then, the temperature is reduced to 550 ℃ within 30 minutes, and finally, the temperature is naturally cooled to room temperature for 24 hours.
(5) The catalyst was taken out and pulverized to a particle size of 8 mm.
Example 4
(1) Selecting 220g of montmorillonite powder, 220g of sepiolite powder and 220g of waste glass, and grinding respectively, wherein when 90% of powder can pass through a 200-mesh sieve, the grinding is finished;
(2) selecting 99g of CuO powder and MnO 2 Powder 33g, CeO 2 Powder 10g, Fe 2 O 3 8g of powder, grinding respectively, and finishing grinding when 90% of the powder can pass through a 400-mesh sieve;
(3) selection of CaCO 3 Powder 70g, Na 2 CO 3 60g of powder and 60g of marble powder are mixed and ground, and when 90% of the powder can pass through a 400-mesh sieve, the grinding is finished;
(4) mixing the above three materials, spreading into powder layer with thickness of 20cm, and feeding into heating furnace. Heating was started. Wherein the preheating temperature is 400 ℃ and the duration time is 20 minutes; the primary temperature rise is 550 ℃ and the duration is 22 minutes; the sintering heating temperature is 720 ℃, and the duration time is 10 minutes; the secondary heating temperature is 780 ℃ and the duration time is 10 minutes; the foaming heating temperature was 920 ℃ and the duration was 10 minutes. Then, the temperature is reduced to 550 ℃ within 30 minutes, and finally, the temperature is naturally cooled to room temperature for 24 hours.
(5) The catalyst was taken out and pulverized to a particle size of 6 mm.
Comparative example 1
(1) Selecting 450g of sepiolite powder and montmorillonite powder respectively, mixing, grinding, and finishing grinding when 90% of powder can pass through a 200-mesh sieve;
(2) selecting 60g of CuO powder and MnO 2 Powder 30g, CeO 2 Powder 5g, Co 3 O 4 Powder 3g, Fe 2 O 3 2g of powder, and grinding the powder respectively, wherein when 90% of the powder can pass through a 400-mesh sieve, the grinding is finished;
(3) mixing the above two materials, spreading into powder layer with thickness of 20cm, and feeding into heating furnace. Heating was started. Wherein the preheating temperature is 350 ℃ and the duration time is 15 minutes; the primary temperature rise is 550 ℃, and the duration is 15 minutes; the sintering heating temperature is 700 ℃, and the duration time is 15 minutes; the secondary heating temperature is 780 ℃ and the duration time is 20 minutes; the foaming heating temperature was 900 ℃ and the duration was 4 minutes. Then, the temperature is reduced to 550 ℃ within 30 minutes, and finally, the temperature is naturally cooled to room temperature for 24 hours.
(5) The catalyst was taken out and pulverized to a particle size of 5 mm.
Comparative example 2
(1) Selecting 355g of sepiolite powder and montmorillonite powder, mixing, grinding, and finishing grinding when 90% of powder can pass through a 200-mesh sieve;
(2) selecting 60g of CuO powder and MnO 2 30g of powder, and grinding the powder respectively when 90% of the powder can pass through a 400-mesh sieve;
(3) selection of CaCO 3 Mixing the powder and dolomite powder 100g, grinding, and finishing grinding when 90% of the powder can pass through a 400-mesh sieve;
(4) mixing the above three materials, spreading into powder layer with thickness of 20cm, and feeding into heating furnace. Heating was started. Wherein the preheating temperature is 350 ℃ and the duration time is 15 minutes; the primary temperature rise is 550 ℃ and the duration is 15 minutes; the sintering heating temperature is 700 ℃, and the duration time is 15 minutes; the secondary heating temperature is 780 ℃ and the duration time is 20 minutes; the foaming heating temperature was 900 ℃ and the duration was 4 minutes. Then, the temperature is reduced to 550 ℃ within 30 minutes, and finally, the temperature is naturally cooled to room temperature for 24 hours.
(5) The catalyst was taken out and pulverized to a particle size of 5 mm.
Comparative example 3
(1) Selecting 360g of sepiolite powder and montmorillonite powder respectively, mixing, grinding, and finishing grinding when 90% of powder can pass through a 200-mesh sieve;
(2) selecting 60g of CuO powder and MnO 2 Powder 10g, CeO 2 Powder 5g, Co 3 O 4 Powder 3g, Fe 2 O 3 2g of powder, and grinding the powder respectively, wherein when 90% of the powder can pass through a 400-mesh sieve, the grinding is finished;
(3) selection of CaCO 3 Mixing the powder and dolomite powder 100g, grinding, and finishing grinding when 90% of the powder can pass through a 400-mesh sieve;
(4) mixing the above three materials, spreading into powder layer with thickness of 20cm, and heating in a heating furnace. Wherein the preheating temperature is 350 ℃ and the duration time is 15 minutes; the primary temperature rise is 550 ℃ and the duration is 15 minutes; the sintering heating temperature is 700 ℃, and the duration time is 15 minutes; the secondary heating temperature is 780 ℃ and the duration time is 20 minutes; the foaming heating temperature was 900 ℃ and the duration was 4 minutes. Then, the temperature is reduced to 550 ℃ within 30 minutes, and finally, the temperature is naturally cooled to room temperature for 24 hours.
(5) The catalyst was taken out and pulverized to a particle size of 5 mm.
And (3) testing the activity of the catalyst:
evaluation experiments were conducted by adding only ozone to the catalysts of examples 1 to 4 of the present invention, the catalysts of comparative examples 1 to 3, commercial ozone catalysts purchased commercially, and the catalysts. The catalyst is filled in the column type ozone reactor, the dosage of the catalyst is 100g, 1000mL of effluent of a sewage treatment station of a pesticide production enterprise, the COD is 132mg/L, the adding amount of ozone is 60mg/L, the treatment condition is normal temperature and normal pressure, samples are taken when the wastewater is treated for 20min and 40min respectively to measure the COD, the removal rate of the COD is calculated, and the result is shown in figure 1. The removal rate of the catalyst 40minCOD prepared in the examples 1-4 of the invention is higher than 37%, while the removal rate of the catalyst 40minCOD prepared in the comparative examples 1-3 is about 30%, and the removal rate of the commercial ozone catalyst 40minCOD in the market is only 24%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. The catalyst for catalyzing ozone oxidation is characterized by comprising a matrix, an active component and an auxiliary agent; the matrix is one or more of sepiolite, montmorillonite and glass powder, the active component is one or more of Cu, Mn, Co, Ce and Fe oxides, and the auxiliary agent is CaCO 3 、Na 2 CO 3 One or more of dolomite powder and marble powderA plurality of types; the weight percentage of each component is
Matrix: 65-85 parts;
5-15% of active component;
auxiliary agent: 5 to 30.
2. The catalyst for catalyzing ozone oxidation according to claim 1, wherein the active component can be a mixture of oxides of Cu, Mn, Co, Ce and Fe, the weight ratio of the Cu oxide to the Mn oxide is 3: 1-1: 2, the content of the Co oxide, the Ce oxide and the Fe oxide is 0-15% of the total weight of the Cu oxide and the Mn oxide respectively, and the total weight of all the active components is 5-15% of the weight of the catalyst.
3. A preparation method of a catalyst for catalyzing ozone oxidation is characterized by comprising the following steps:
(1) selecting one or more of sepiolite, montmorillonite and glass powder to grind, wherein 90% of the powder can pass through a 200-mesh sieve;
(2) grinding various metal oxides to ensure that 90 percent of the powder can pass through a 400-mesh sieve;
(3) selection of CaCO 3 、Na 2 CO 3 Grinding one or more of dolomite powder and marble powder, wherein 90% of the powder can pass through a 400-mesh sieve;
(4) the three materials are prepared according to the following steps: 65-85 parts; 5-15% of active component; auxiliary agent: 5-30, spreading the mixture into a powder layer with the thickness of 20cm, and sending the powder layer into a heating furnace; preheating, primary heating, sintering and heating, secondary heating and foaming and heating by a heating furnace for 5 stages to prepare a foaming type catalyst, taking out the foaming type catalyst, and naturally cooling to room temperature to obtain a catalyst finished product; wherein the preheating temperature is 300-400 ℃, and the duration is 15-20 minutes; the primary heating temperature is 550-600 ℃, and the duration time is 10-30 minutes; the sintering heating temperature is 700-750 ℃, and the duration is 5-15 minutes; the secondary heating temperature is 780-800 ℃, and the duration is 5-20 minutes; the foaming heating temperature is 900-950 ℃, and the duration time is 4-10 minutes; then, the temperature is reduced to 550 ℃ within 30 minutes, and finally the temperature is naturally cooled to room temperature for 24 hours;
(5) and taking out the catalyst, and crushing to obtain particles with the particle size of 5-10 mm.
4. The method of claim 3, wherein the catalyst has a particle size of 5-10mm and a density of 0.55-0.85 g/cm 3 The porosity is more than 80%, the average pore diameter is 2mm, and the compressive strength is more than 3.5 MPa.
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