CN110841627B - Rare earth modified adsorption enrichment-catalytic oxidation bifunctional catalyst and preparation method and application thereof - Google Patents
Rare earth modified adsorption enrichment-catalytic oxidation bifunctional catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 38
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 120
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 15
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000012286 potassium permanganate Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 24
- 238000002791 soaking Methods 0.000 claims description 23
- 238000005303 weighing Methods 0.000 claims description 20
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- -1 ammonia modified activated carbon Chemical class 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 4
- CBRVNNFPYLQDQN-UHFFFAOYSA-N zirconium(4+) tetranitrate hexahydrate Chemical compound O.O.O.O.O.O.[N+](=O)([O-])[O-].[Zr+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] CBRVNNFPYLQDQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000000711 cancerogenic effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B01J35/394—
-
- B01J35/61—
Abstract
The invention relates to a rare earth modified adsorption enrichment-catalytic oxidation bifunctional catalyst and a preparation method and application thereof, wherein the catalyst mainly comprises a carrier and an active component, the active component is loaded on the carrier, and the carrier is rare earth element (Ce, Zr, La) modified active carbon; the active component is manganese oxide. Wherein, the loading capacity of the rare earth element is 0.5 to 1 percent and the loading capacity of the manganese is 2 to 5 percent based on the element mol. The catalyst prepared by the preparation method has high catalytic efficiency, simple preparation method and low production and application cost.
Description
Technical Field
The invention belongs to the technical field of catalytic environment protection, and particularly relates to a rare earth modified adsorption enrichment-catalytic oxidation bifunctional catalyst, and a preparation method and application thereof.
Background
Along with the increasingly prominent environmental problems, indoor environmental problems have led to the attention of more people. Formaldehyde is one of the most common and most toxic pollutants in interior decoration. Formaldehyde has been identified by the world health organization as a carcinogenic and teratogenic substance, is a well-recognized source of allergy, is also one of the potential strong mutagens, causes various diseases, and has strong carcinogenic and carcinogenic effects. According to the survey of the international organization, nearly 300 million people worldwide die directly or indirectly from formaldehyde pollution caused by decoration every year. Therefore, the problem of formaldehyde pollution in indoor air needs to be solved.
Since formaldehyde has high toxicity and dynamically changes in the air, the detection difficulty is huge, and the research work for removing low-concentration formaldehyde is difficult. At present, the formaldehyde is removed mainly by adopting an adsorption method, and although a single adsorption method has relatively good formaldehyde removal effect, the single adsorption method is easy to inactivate due to adsorption saturation and easily causes secondary pollution. The catalytic oxidation method can convert formaldehyde into carbon dioxide, but the effect of removing low-concentration pollution is not good, and the currently researched catalyst is mainly a noble metal catalyst, so that the cost of the catalyst is high, and the application effect is poor. Aiming at the problems of the existing formaldehyde purification material, the invention provides a purification material integrating adsorption enrichment and catalytic oxidation, active components grow in situ, the purification effect of the material on formaldehyde is greatly improved, and the catalyst is low in cost.
Disclosure of Invention
Aiming at the problems that formaldehyde treated by a single adsorption technology is easily saturated and easily causes secondary pollution, and formaldehyde with extremely low concentration is difficult to treat by single catalytic oxidation, the invention aims to provide a rare earth modified adsorption enrichment-catalytic oxidation dual-function catalyst.
Yet another object of the present invention is to: provides a preparation method of the rare earth modified adsorption enrichment-catalytic oxidation dual-function catalyst product.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: the rare earth modified adsorption enrichment-catalytic oxidation dual-function catalyst comprises a carrier and an active component, wherein the carrier is activated carbon modified by rare earth elements Ce, Zr and/or La, and the active component is manganese oxide, wherein the loading capacity of the rare earth elements is 0.5% -1% and the loading capacity of the manganese is 2% -5% in terms of element molar weight.
The invention also provides a preparation method of the rare earth modified adsorption enrichment-catalytic oxidation dual-function catalyst, which comprises the steps of preparing a rare earth element impregnation liquid, impregnating activated carbon into the prepared impregnation liquid to prepare a rare earth element modified carrier, adding a potassium permanganate solution into the rare earth element impregnated activated carbon carrier, synthesizing an activated carbon-supported manganese oxide catalyst in situ by using the redox reaction of the activated carbon and potassium permanganate, and further modifying the surface of the prepared catalyst by using ammonia water, and comprises the following steps:
(1) dissolving cerium nitrate, zirconium nitrate or lanthanum nitrate in water with a certain volume to prepare a rare earth element precursor solution, wherein the molar concentration of the rare earth element is 0.01 mol/L;
(2) taking a certain volume of the rare earth element precursor solution prepared in the step (1), soaking a certain mass of activated carbon in the obtained rare earth element precursor solution, and standing overnight;
(3) preparing a potassium permanganate solution with a certain volume of 0.1mol/L, adding the potassium permanganate solution with a certain volume into the carriers impregnated with different rare earth elements in the step 2 respectively, and stirring for 4-6h to obtain a precipitate;
(4) filtering and washing the obtained precipitate, and drying at 40-60 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (4) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4), soaking 10% diluted ammonia water in an equal volume, and drying at 40-60 ℃ to obtain the ammonia modified activated carbon supported manganese oxide catalyst.
The invention also provides application of the rare earth modified adsorption enrichment-catalytic oxidation dual-function catalyst, in order to be used for formaldehyde purification, the total flow of gas is 500ml/min, the reaction pressure is normal pressure and 1atm, the initial concentration of formaldehyde is 2ppm (V/V), and the sample dosage is 2 g.
The formaldehyde purification catalyst prepared by the method has a good effect on removing formaldehyde in air, the conversion rate can reach 80% -100% at room temperature, and the preparation method disclosed by the invention is simple, low in cost, and high in practical value due to one-step forming of the catalyst.
Compared with the existing formaldehyde purification material and the preparation method thereof, the formaldehyde purification material has the following characteristics: the purification efficiency of low-concentration formaldehyde pollutants is greatly improved by utilizing the synergistic action of adsorption and catalysis, and the removal efficiency of formaldehyde at normal temperature can reach 100%; the catalyst utilizes the in-situ oxidation-reduction reaction of the activated carbon and the potassium permanganate in the surface and the pore channel structure, and simultaneously generates active components in situ on the surface and the pore channel structure, thereby greatly improving the dispersion degree of the active components and further improving the catalytic activity. The catalyst prepared by the preparation method has high catalytic efficiency, simple preparation method and low production and application cost.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
A rare earth modified adsorption enrichment-catalytic oxidation dual-function catalyst comprises a carrier and an active component, wherein the carrier is rare earth element Ce, Zr and/or La modified active carbon, the active component is manganese oxide, the preparation comprises the steps of preparing rare earth element impregnation liquid, impregnating the active carbon in the prepared impregnation liquid to prepare the rare earth element modified carrier, adding a potassium permanganate solution into the rare earth element impregnated active carbon carrier, synthesizing an active carbon-loaded manganese oxide catalyst in situ by using the redox reaction of the active carbon and the potassium permanganate, and further modifying the surface of the prepared catalyst by using ammonia water, and the preparation method comprises the following steps:
(1) weighing 0.87g of cerous nitrate hexahydrate to be dissolved in 200ml of water to prepare a cerous nitrate solution with the concentration of 0.01 mol/L;
(2) weighing 20g of active carbon, soaking the active carbon in 71ml of cerium nitrate solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding 73ml of the potassium permanganate solution into the activated carbon impregnated with different rare earth elements Ce, and stirring for 4 hours to obtain a precipitate;
(4) filtering and washing the obtained precipitate, and drying at 60 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (3) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4) to be 1.2g of water/g of activated carbon, soaking 10% diluted ammonia water in an equal volume, and drying at 60 ℃ to obtain the ammonia modified activated carbon loaded manganese oxide catalyst, which is recorded as 2Mn-Ac-0.5 Ce.
Example 2
A rare earth modified adsorption enrichment-catalytic oxidation dual-function catalyst is prepared by the following method:
(1) weighing 0.87g of lanthanum nitrate hexahydrate, dissolving in 200ml of water, and preparing lanthanum nitrate with the concentration of 0.01 mol/L;
(2) weighing 20g of activated carbon, soaking the activated carbon in 142ml of lanthanum nitrate solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding 73ml of the potassium permanganate solution into the activated carbon impregnated with the rare earth elements in the step (2), and stirring for 4 to obtain a precipitate;
(4) filtering and washing the obtained precipitate, and drying at 40 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (3) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4) to be 1.2g of water/g of activated carbon, soaking 10% diluted ammonia water in an equal volume, and drying at 40 ℃ to obtain the ammonia modified activated carbon loaded manganese oxide catalyst, which is recorded as 2Mn-Ac-1 La.
Example 3
A rare earth modified adsorption enrichment-catalytic oxidation dual-function catalyst is prepared by the following method:
(1) weighing 0.87g of lanthanum nitrate hexahydrate, dissolving in 200ml of water, and preparing a lanthanum nitrate solution with the concentration of 0.01 mol/L;
(2) weighing 20g of activated carbon, soaking the activated carbon in 71ml of lanthanum nitrate solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding 182ml of 0.1mol/L potassium permanganate solution into the carrier soaked with the rare earth elements in the step (2), and stirring for 4 hours to obtain a precipitate;
(4) filtering and washing the obtained precipitate, and drying at 60 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (3) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4) to be 1.2g of water/g of activated carbon, soaking 10% diluted ammonia water in an equal volume, and drying at 60 ℃ to obtain the ammonia modified activated carbon loaded manganese oxide catalyst which is recorded as 5Mn-Ac-0.5 La.
Example 4
A preparation method of a rare earth modified adsorption enrichment-catalytic oxidation bifunctional catalyst comprises the following steps:
(1) weighing 0.86g of zirconium nitrate hexahydrate, dissolving in 200ml of water, and preparing a zirconium nitrate solution with the concentration of 0.01 mol/L;
(2) weighing 20g of active carbon, soaking the active carbon in 71ml of zirconium nitrate solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding 73ml of 0.1mol/L potassium permanganate solution into the carrier soaked with different rare earth elements in the step (2), and stirring for 4 hours to obtain a precipitate;
(4) filtering and washing the obtained precipitate, and drying at 40 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (3) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4) to be 1.2g of water/g of activated carbon, soaking 10% diluted ammonia water in an equal volume, and drying at 40 ℃ to obtain the ammonia modified activated carbon loaded manganese oxide catalyst, which is recorded as 2Mn-Ac-0.5 Zr.
Example 5
A preparation method of a rare earth modified adsorption enrichment-catalytic oxidation bifunctional catalyst comprises the following steps:
(1) weighing 0.86g of zirconium nitrate hexahydrate, dissolving in 200ml of water, and preparing a zirconium nitrate solution with the concentration of 0.01 mol/L;
(2) weighing 20g of activated carbon, soaking the activated carbon in 142ml of zirconium nitrate solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding 182ml of 0.1mol/L potassium permanganate solution into the carriers soaked with different rare earth elements in the step (2), and stirring for 4 hours to obtain precipitates;
(4) filtering and washing the obtained precipitate, and drying at 40 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (3) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4) to be 1.2g of water/g of activated carbon, soaking 10% diluted ammonia water in an equal volume, and drying at 40 ℃ to obtain the ammonia modified activated carbon loaded manganese oxide catalyst, which is recorded as 5Mn-Ac-1 Zr.
Evaluation of Formaldehyde catalyst Performance
The performance was tested in a continuous flow fixed bed unit. The total flow rate of gases was 500ml/min, the reaction pressure was 1atm at normal pressure, the initial concentration of formaldehyde was 2ppm (V/V), and the amount of the sample was 2 g. The results of the catalytic performance test are shown in table 1 below:
the results in table 1 show that the formaldehyde purification catalyst prepared by the method has a good effect on removing formaldehyde in air, the conversion rate can reach 80% -100% at room temperature, and the preparation method disclosed by the invention is simple, low in cost, and high in practical value due to one-step molding of the catalyst.
Claims (8)
1. The preparation method of the Ce, Zr or La modified adsorption enrichment-catalytic oxidation dual-function catalyst is characterized in that the catalyst comprises a carrier and an active component, wherein the carrier is Ce, Zr or La modified active carbon, and the active component is manganese oxide, wherein the loading amount of Ce, Zr or La is 0.5% -1% and the loading amount of manganese is 2% -5% in terms of element molar weight;
the preparation method comprises the steps of preparing Ce, Zr or La element impregnation liquid, impregnating active carbon in the prepared impregnation liquid to prepare a Ce, Zr or La element modified carrier, adding the carrier into potassium permanganate solution, synthesizing an active carbon-loaded manganese oxide catalyst in situ by using the redox reaction of the active carbon and potassium permanganate, and further modifying the surface of the prepared catalyst by using ammonia water, wherein the preparation method comprises the following steps:
(1) dissolving cerium nitrate, zirconium nitrate or lanthanum nitrate in water to prepare a Ce, Zr or La element precursor solution, wherein the molar concentration of the Ce, Zr or La element is 0.01 mol/L;
(2) taking the Ce, Zr or La element precursor solution prepared in the step (1), dipping activated carbon into the obtained Ce, Zr or La element precursor solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding the potassium permanganate solution into the carriers impregnated with different elements Ce, Zr or La in the step (2), and stirring for 4-6h to obtain precipitates;
(4) filtering and washing the obtained precipitate, and drying at 40-60 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (4) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4), soaking 10% diluted ammonia water in an equal volume, and drying at 40-60 ℃ to obtain the ammonia modified activated carbon supported manganese oxide catalyst.
2. The preparation method of the Ce, Zr or La modified adsorption enrichment-catalytic oxidation dual-function catalyst according to claim 1, is characterized by comprising the following steps:
(1) weighing 0.87g of cerous nitrate hexahydrate to be dissolved in 200ml of water to prepare a cerous nitrate solution with the concentration of 0.01 mol/L;
(2) weighing 20g of active carbon, soaking the active carbon in 71ml of cerium nitrate solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding 73ml of the potassium permanganate solution into the activated carbon impregnated with different rare earth elements Ce in the step (2), and stirring for 4 hours to obtain a precipitate;
(4) filtering and washing the obtained precipitate, and drying at 60 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (3) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4) to be 1.2g of water/g of activated carbon, soaking 10% diluted ammonia water in an equal volume, and drying at 60 ℃ to obtain the ammonia modified activated carbon loaded manganese oxide catalyst, which is recorded as 2Mn-Ac-0.5 Ce.
3. The preparation method of the Ce, Zr or La modified adsorption enrichment-catalytic oxidation dual-function catalyst according to claim 1, is characterized by comprising the following steps:
(1) weighing 0.87g of lanthanum nitrate hexahydrate, dissolving in 200ml of water, and preparing lanthanum nitrate with the concentration of 0.01 mol/L;
(2) weighing 20g of activated carbon, soaking the activated carbon in 142ml of lanthanum nitrate solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding 73ml of the potassium permanganate solution into the activated carbon impregnated with the rare earth elements in the step (2), and stirring for 4 hours to obtain a precipitate;
(4) filtering and washing the obtained precipitate, and drying at 40 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (3) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4) to be 1.2g of water/g of activated carbon, soaking 10% diluted ammonia water in an equal volume, and drying at 40 ℃ to obtain the ammonia modified activated carbon loaded manganese oxide catalyst, which is recorded as 2Mn-Ac-1 La.
4. The preparation method of the Ce, Zr or La modified adsorption enrichment-catalytic oxidation dual-function catalyst according to claim 1, is characterized by comprising the following steps:
(1) weighing 0.87g of lanthanum nitrate hexahydrate, dissolving in 200ml of water, and preparing a lanthanum nitrate solution with the concentration of 0.01 mol/L;
(2) weighing 20g of activated carbon, soaking the activated carbon in 71ml of lanthanum nitrate solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding 182ml of 0.1mol/L potassium permanganate solution into the carrier soaked with the rare earth elements in the step (2), and stirring for 4 hours to obtain a precipitate;
(4) filtering and washing the obtained precipitate, and drying at 60 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (3) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4) to be 1.2g of water/g of activated carbon, soaking 10% diluted ammonia water in an equal volume, and drying at 60 ℃ to obtain the ammonia modified activated carbon loaded manganese oxide catalyst which is recorded as 5Mn-Ac-0.5 La.
5. The preparation method of the Ce, Zr or La modified adsorption enrichment-catalytic oxidation dual-function catalyst according to claim 1, is characterized by comprising the following steps:
(1) weighing 0.86g of zirconium nitrate hexahydrate, dissolving in 200ml of water, and preparing a zirconium nitrate solution with the concentration of 0.01 mol/L;
(2) weighing 20g of active carbon, soaking the active carbon in 71ml of zirconium nitrate solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding 73ml of 0.1mol/L potassium permanganate solution into the carrier soaked with the Zr element in the step (2), and stirring for 4 hours to obtain a precipitate;
(4) filtering and washing the obtained precipitate, and drying at 40 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (3) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4) to be 1.2g of water/g of activated carbon, soaking 10% diluted ammonia water in an equal volume, and drying at 40 ℃ to obtain the ammonia modified activated carbon loaded manganese oxide catalyst, which is recorded as 2Mn-Ac-0.5 Zr.
6. The preparation method of the Ce, Zr or La modified adsorption enrichment-catalytic oxidation dual-function catalyst according to claim 1, is characterized by comprising the following steps:
(1) weighing 0.86g of zirconium nitrate hexahydrate, dissolving in 200ml of water, and preparing a zirconium nitrate solution with the concentration of 0.01 mol/L;
(2) weighing 20g of activated carbon, soaking the activated carbon in 142ml of zirconium nitrate solution, and standing overnight;
(3) preparing 0.1mol/L potassium permanganate solution, adding 182ml of 0.1mol/L potassium permanganate solution into the carrier soaked with the Zr element in the step (2), and stirring for 4 hours to obtain a precipitate;
(4) filtering and washing the obtained precipitate, and drying at 40 ℃ to obtain an active carbon catalyst loaded with an active component manganese;
(5) and (3) measuring the water absorption rate of the manganese oxide activated carbon catalyst obtained in the step (4) to be 1.2g of water/g of activated carbon, soaking 10% diluted ammonia water in an equal volume, and drying at 40 ℃ to obtain the ammonia modified activated carbon loaded manganese oxide catalyst, which is recorded as 5Mn-Ac-1 Zr.
7. A Ce, Zr or La modified adsorption enrichment-catalytic oxidation bifunctional catalyst, characterized in that it is obtained according to any one of the preparation methods of claims 1 to 6.
8. The use of the Ce, Zr or La modified adsorptive enrichment-catalytic oxidation bifunctional catalyst according to claim 7 for purifying formaldehyde, wherein the total gas flow is 500ml/min, the reaction pressure is 1atm at normal pressure, the initial concentration V/V of formaldehyde is 2ppm, and the sample amount is 2 g.
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