CN110773151B - Porous bixbyite Mn loaded with diatomite2O3Catalyst, preparation method and application thereof - Google Patents
Porous bixbyite Mn loaded with diatomite2O3Catalyst, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 123
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000011572 manganese Substances 0.000 claims abstract description 39
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- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- -1 manganese alkoxide Chemical class 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 230000000593 degrading effect Effects 0.000 claims description 8
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- 238000005406 washing Methods 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 150000001555 benzenes Chemical class 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000003379 elimination reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000003905 indoor air pollution Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 208000005623 Carcinogenesis Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- 230000036952 cancer formation Effects 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/61—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
A porous bixbyite catalyst loaded by diatomite, a preparation method and application thereof, belonging to the technical field of inorganic functional materials. The invention takes divalent inorganic manganese salt and diatomite as raw materials, dissolves in a mixed solvent of glycerol and isopropanol, utilizes solvothermal reaction to uniformly load manganese alkoxide on the diatomite to prepare a manganese alkoxide/diatomite composite material, and obtains porous bixbyite Mn loaded with the diatomite after heating treatment2O3A catalyst. The surface of the diatomite has a plurality of silicon hydroxyl groups and hydrogen bonds, so that the diatomite is connected with Mn2O3Form strong binding energy. The composite material can prevent Mn2O3Agglomeration and reduction of Mn2O3The dosage, the diatomite has high specific surface area and strong adsorbability, realizes the targeted enrichment of benzene pollutants in the air, can rapidly catalyze and degrade benzene at lower temperature, and has high removal rate of benzene. The invention has the characteristics of simple preparation method, low production cost, no introduction of other pollutants and the like, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to a diatomite-loaded porous bixbyite catalyst, a preparation method and application thereof.
Background
After the pollution of the coal smoke type and the photochemical smog type, the indoor air pollution problem becomes a global problem which cannot be ignored when people get trapped in the indoor air pollution at present. The source of indoor air pollution is Volatile Organic Compounds (VOCs), in which benzene series (benzene, toluene, xylene, etc.) are the main gaseous pollutants in the room. Benzene series has three-cause harm to human body, such as mutation, teratogenesis and carcinogenesis, seriously threatens human health and environment, has attracted high attention of all countries in the world, and has been determined as a strong carcinogen by the international health organization. The residential design Specification (GB50096-2011) issued by China stipulates the concentration of indoor benzeneThe limit value of the degree is 0.09mg/m3. Therefore, the research on the method for improving the indoor air quality and efficiently removing the benzene series has become a hot research in the field of indoor air.
At present, a plurality of benzene series scavengers used in rooms and automobiles exist on the market, most of the scavengers mainly comprise activated carbon, and the benzene series scavengers can only reduce the concentration of the benzene series but cannot completely remove the benzene series scavengers by virtue of the adsorption effect of the activated carbon. In order to eliminate the harm of benzene series on human health and environment, a great deal of research is carried out by related researchers at home and abroad. Up to now, most of the catalysts for degrading benzene series have been reported to be supported noble metal catalysts (ACS Catalysis,2016,6, 3433-3441; Applied Catalysis A: General,2017,529, 60-67; Applied Catalysis B: Environmental,2018,220,462-470), which can oxidize benzene series into carbon dioxide and water at relatively low temperature. However, the price of noble metals limits their industrial large-scale use, and it is therefore important to develop a cheap and efficient catalyst.
In recent years, reports of benzene series elimination by transition metal oxide Catalysis are increasing, particularly manganese oxide shows better catalytic activity and stability (Journal of Industrial and Engineering Chemistry,2008,14, 779-; Applied catalysts B: Environmental,2017,209, 689- & gt 700), but the synthesis methods are complicated, mostly need template agents or organic surfactants, and the like, the steps are complicated, the cost is increased, meanwhile, the conversion rate of completely catalytic oxidation of benzene series is still not ideal, the reaction temperature is above 350 ℃, and the practical application is limited. Aiming at the problems, the stable Mn which has better catalytic activity to the benzene series is synthesized by one step by adopting a solvothermal method2O3The diatomite composite catalytic material.
Disclosure of Invention
The invention aims to provide a porous bixbyite Mn loaded by diatomite2O3Catalyst, preparation method and application thereof. The catalyst provided by the invention can be used for rapidly catalyzing and degrading benzene at a lower reaction temperature (less than or equal to 240 ℃) and obtaining 100% benzene removal. The catalyst has low production cost and high stability,the preparation process is simple, and the porous bixbyite Mn is prepared in one step on the premise of not adding a template agent and a surfactant2O3The diatomite is loaded in situ, and no other pollutants are generated. The prepared porous bixbyite Mn2O3The diameter of the rod is 200-600 nm, the length of the rod is 1-10 mu m, the rod is dispersed on the surface of a crown disk-shaped shell of the diatomite, the diameter of the diatomite shell is dozens of micrometers, and a plurality of radial and orderly arranged micropores exist.
In order to achieve the purpose, the invention provides porous bixbyite Mn loaded by diatomite2O3The preparation method of the catalyst comprises the following steps:
(1) adding 0.5-4.0 mmol of divalent inorganic manganese salt into the mixed solution of isopropanol and glycerol, adding 0.05-0.5 g of diatomite, and stirring at room temperature for 1-5 hours; the volume of the mixed solution of the isopropanol and the glycerol is 30-60 mL;
the volume ratio of the isopropanol to the glycerol is 2-6: 1;
the divalent inorganic manganese salt is one or more of manganese acetate, manganese nitrate and manganese chloride, and when several divalent inorganic manganese salts are selected, the divalent inorganic manganese salts are mixed according to any proportion;
the diatomite is diatomite in which the content of the diatom shells in percentage by mass is more than 65%.
(2) Transferring the mixed solution obtained in the step (1) into a polytetrafluoroethylene lining reaction kettle, and carrying out hydrothermal reaction for 3-7 h at the temperature of 150-220 ℃;
(3) naturally cooling the suspension obtained in the step (2) to room temperature, centrifuging and washing, and drying the obtained precipitate at 70-90 ℃ for 10-15 h to obtain manganese alkoxide/diatomite solid powder;
washing is to wash the centrifuged precipitate for 3-5 times by using absolute ethyl alcohol;
(4) heating the manganese alkoxide/diatomite solid powder obtained in the step (3) and cooling to room temperature to obtain the porous bixbyite Mn2O3A diatomite catalyst;
and the heating treatment is to place the manganese alkoxide/diatomite solid powder in a muffle furnace, heat the powder to 400-700 ℃ at the heating rate of 1-10 ℃/min, and calcine the powder at constant temperature for 2-4 h.
The invention also provides the diatomite-loaded porous bixbyite Mn obtained by the method2O3A catalyst.
The invention also provides the diatomite-loaded porous bixbyite Mn2O3The application of the catalyst in catalyzing and degrading benzene.
The invention has the following advantages:
1. the preparation process is simple, and the porous bixbyite Mn is prepared by a one-step method on the premise of not adding a template agent and a surfactant2O3The diatomite is loaded on the diatomite in situ, and other pollutants are not generated, so that the production cost is low, and the large-scale production is easy.
2. The surface of the diatomite has a plurality of silicon hydroxyl groups and hydrogen bonds, and the silicon hydroxyl groups and the hydrogen bonds can be matched with the bixbyite Mn2O3Form strong binding energy. The composite material can prevent the Mn of the bixbyite2O3Agglomeration and reduction of Mn in the manganese ore2O3The dosage, the targeted enrichment of benzene pollutants in the air is realized by utilizing high specific surface area and strong adsorbability, the catalytic degradation activity of benzene can be improved at a lower temperature, and the application prospect is good.
Drawings
FIG. 1: mn prepared in example 12O3X-ray diffraction (XRD) spectrum of diatomite catalyst;
FIG. 2: scanning Electron Microscope (SEM) spectrum of the raw material diatomaceous earth described in example 1;
FIG. 3: mn prepared in example 12O3Scanning Electron Microscope (SEM) spectra of/diatomaceous earth catalysts;
FIG. 4: mn prepared in examples 1, 2, 3 and 42O3The conversion of benzene over the kieselguhr catalyst curve.
Detailed Description
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to the following examples. It will be apparent to those skilled in the art that variations or modifications of the present invention can be made without departing from the spirit and scope of the invention, and these variations or modifications are also within the scope of the invention.
Example 1:
adding 1.1mmol of manganese acetate and 0.2g of kieselguhr (the mass percentage content of the kieselguhr shell is about 68%) in Jilin province Yangjiang city into 40mL of mixed solution of isopropanol and glycerol (the volume ratio is 3:1), stirring at room temperature for 3h, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, and putting the reaction kettle into a constant-temperature drying box to react for 6h at 180 ℃. Naturally cooling the obtained suspension to room temperature, centrifuging, washing with absolute ethanol, putting the obtained precipitate into a constant-temperature drying oven, and drying at 80 ℃ for 12h to obtain manganese alkoxide/diatomite solid powder. Placing the powder in a muffle furnace, heating to 500 ℃ at the heating rate of 3 ℃/min, and calcining at constant temperature for 3h to obtain the porous bixbyite Mn loaded with diatomite2O3(Mn2O3Kieselguhr-500).
Mn prepared by the above method2O3The phase structure and the morphology of the diatomite catalyst are characterized. Prepared Mn2O3The X-ray diffraction (XRD) pattern of the/diatomaceous earth catalyst is shown in FIG. 1, and from FIG. 1, the composite material shows not only bixbyite Mn2O3A series of characteristic diffraction peaks, and also shows diatomaceous earth (SiO)2) The characteristic diffraction peak shows that the prepared composite material is prepared from diatomite and bixbyite Mn2O3Composition, it was confirmed that Mn was obtained by the preparation2O3A diatomite catalyst. Diatomaceous earth raw material and Mn produced2O3The Scanning Electron Microscope (SEM) spectrograms of the diatomite catalyst are shown in figures 2 and 3, and figure 2 shows that the diatomite shell is in a shape of a crown disk, the diameter of the crown disk is about 30-40 mu m, and a plurality of radial and orderly arranged micropores exist; FIG. 3 shows Mn2O3/the diatomite surface of the diatomite composite material is accumulated with a rod-shaped bixbyite Mn2O3。
The catalyst prepared in example 1 was evaluated for catalytic activity. Weighing 100mg of catalyst, and loading into a microtubular fixed bed reactor for reactionIn the tube, the temperature was gradually raised, the initial concentration of benzene was 1000 ppm, and the space velocity was 24000mL g- 1h-1And detecting the content of the effluent benzene on line by gas chromatography. Prepared Mn2O3The conversion of benzene over the kieselguhr catalyst is shown in Mn in FIG. 42O3500 parts of diatomite. The temperature of the catalyst for completely catalyzing and degrading benzene (100 percent conversion of benzene) prepared in the embodiment 1 of the invention is 240 ℃, when the temperature is in the range of 180-240 ℃, the conversion rate of benzene is increased linearly until reaching 100 percent, and benzene is completely converted into CO in the catalytic degradation elimination reaction of benzene2And H2O。
Example 2:
adding 1.1mmol of manganese acetate and 0.2g of kieselguhr (the mass percentage content of the kieselguhr shell is about 68%) in Jilin province Yangjiang city into 40mL of mixed solution of isopropanol and glycerol (the volume ratio is 3:1), stirring at room temperature for 3h, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, and putting the reaction kettle into a constant-temperature drying box to react for 6h at 180 ℃. Naturally cooling the obtained suspension to room temperature, centrifuging, washing with absolute ethanol, putting the obtained precipitate into a constant-temperature drying oven, and drying at 80 ℃ for 12h to obtain manganese alkoxide/diatomite solid powder. Placing the powder in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min, and calcining at constant temperature for 3h to obtain the porous bixbyite Mn loaded with diatomite2O3(Mn2O3Kieselguhr-400).
The catalyst prepared in example 2 was evaluated for catalytic activity. Weighing 100mg of catalyst, loading the catalyst into a reaction tube of a miniature tubular fixed bed reactor, gradually heating, introducing benzene with the initial concentration of 1000 ppm and the space velocity of 24000mL g-1h-1And detecting the content of the effluent benzene on line by gas chromatography. Prepared Mn2O3The conversion of benzene over the kieselguhr catalyst is shown in Mn in FIG. 42O3400 parts of diatomite. The temperature of the catalyst for completely catalyzing and degrading benzene (100 percent conversion of benzene) prepared in the embodiment 2 of the invention is 244 ℃, when the temperature is in the range of 180-244 ℃, the conversion rate of benzene is increased linearly until reaching 100 percent, and benzene is completely degraded and eliminated in the catalytic degradation elimination reaction of benzeneConversion to CO2And H2O。
Example 3:
adding 1.1mmol of manganese acetate and 0.2g of kieselguhr (the mass percentage content of the kieselguhr shell is about 68%) in Jilin province Yangjiang city into 40mL of mixed solution of isopropanol and glycerol (the volume ratio is 3:1), stirring at room temperature for 3h, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, and putting the reaction kettle into a constant-temperature drying box to react for 6h at 180 ℃. Naturally cooling the obtained suspension to room temperature, centrifuging, washing with absolute ethanol, putting the obtained precipitate into a constant-temperature drying oven, and drying at 80 ℃ for 12h to obtain manganese alkoxide/diatomite solid powder. Placing the powder in a muffle furnace, heating to 600 ℃ at the heating rate of 3 ℃/min, and calcining at constant temperature for 3h to obtain the porous bixbyite Mn loaded with diatomite2O3(Mn2O3Kieselguhr-600).
The catalyst prepared in example 3 was evaluated for catalytic activity. Weighing 100mg of catalyst, loading the catalyst into a reaction tube of a miniature tubular fixed bed reactor, gradually heating, introducing benzene with the initial concentration of 1000 ppm and the space velocity of 24000mL g-1h-1And detecting the content of the effluent benzene on line by gas chromatography. Prepared Mn2O3The conversion of benzene over the kieselguhr catalyst is shown in Mn in FIG. 42O3Diatomite-600. The temperature of the catalyst for completely catalyzing and degrading benzene (100% conversion of benzene) prepared in the embodiment 3 of the invention is 260 ℃, when the temperature is in the range of 220-260 ℃, the conversion rate of benzene is increased linearly until reaching 100%, and benzene is completely converted into CO in the catalytic degradation elimination reaction of benzene2And H2O。
Example 4:
adding 1.1mmol of manganese acetate and 0.2g of kieselguhr (the mass percentage content of the kieselguhr shell is about 68%) in Jilin province Yangjiang city into 40mL of mixed solution of isopropanol and glycerol (the volume ratio is 3:1), stirring at room temperature for 3h, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, and putting the reaction kettle into a constant-temperature drying box to react for 6h at 180 ℃. Naturally cooling the obtained suspension to room temperature, centrifuging, washing with anhydrous ethanol, and adding the obtained precipitateAnd drying for 12h in a constant-temperature drying oven at 80 ℃ to obtain manganese alkoxide/kieselguhr solid powder. Placing the powder in a muffle furnace, heating to 700 ℃ at the heating rate of 3 ℃/min, and calcining at constant temperature for 3h to obtain the porous bixbyite Mn loaded with diatomite2O3(Mn2O3Kieselguhr-700).
The catalyst prepared in example 4 was evaluated for catalytic activity. Weighing 100mg of catalyst, loading the catalyst into a reaction tube of a miniature tubular fixed bed reactor, gradually heating, introducing benzene with the initial concentration of 1000 ppm and the space velocity of 24000mL g- 1h-1And detecting the content of the effluent benzene on line by gas chromatography. Prepared Mn2O3The conversion of benzene over the kieselguhr catalyst is shown in Mn in FIG. 42O3Diatomite-700. The temperature of the catalyst for completely catalyzing and degrading benzene (100% conversion of benzene) prepared in the embodiment 4 of the invention is 280 ℃, when the temperature is in the range of 220-280 ℃, the conversion rate of benzene is increased linearly until reaching 100%, and benzene is completely converted into CO in the catalytic degradation elimination reaction of benzene2And H2O。
Claims (5)
1. Porous bixbyite Mn loaded with diatomite2O3The preparation method of the catalyst comprises the following steps:
(1) adding 0.5-4.0 mmol of divalent inorganic manganese salt into the mixed solution of isopropanol and glycerol, adding 0.05-0.5 g of diatomite, and stirring at room temperature for 1-5 hours; the volume of the mixed solution of the isopropanol and the glycerol is 30-60 mL; the divalent inorganic manganese salt is one or more of manganese acetate, manganese nitrate or manganese chloride, and when several divalent inorganic manganese salts are selected, the divalent inorganic manganese salts are mixed according to any proportion; the volume ratio of the isopropanol to the glycerol is 2-6: 1;
(2) transferring the mixed solution obtained in the step (1) to a polytetrafluoroethylene lining reaction kettle at a temperature of 150-220 DEG CoC, carrying out hydrothermal reaction for 3-7 h;
(3) naturally cooling the suspension obtained in the step (2) to room temperature, centrifuging and washing, and then precipitating the obtained precipitate at 70-90 DEG CoDrying for 10-15 h under C to obtain manganese alkoxide/diatomiteA solid powder;
(4) heating the manganese alkoxide/diatomite solid powder obtained in the step (3) and cooling to room temperature to obtain the porous bixbyite Mn2O3A diatomite catalyst; the prepared porous bixbyite Mn2O3The diameter of the rod is 200-600 nm, the length of the rod is 1-10 mu m, the rod is dispersed on the surface of a crown disk-shaped shell of the diatomite, the diameter of the diatomite shell is dozens of micrometers, and a plurality of radial and orderly arranged micropores exist.
2. The diatomaceous earth-loaded porous bixbyite Mn of claim 12O3The preparation method of the catalyst is characterized by comprising the following steps: the diatomite in the step (1) is diatomite with the content of the diatom shells in the diatomite by mass percent being more than 65%.
3. The diatomaceous earth-loaded porous bixbyite Mn of claim 12O3The preparation method of the catalyst is characterized by comprising the following steps: the heating treatment in the step (4) is to place manganese alkoxide/diatomite solid powder in a muffle furnace for 1-10 timesoHeating to 400-700 ℃ at a temperature rise rate of C/minoAnd C, calcining for 2-4 h at constant temperature.
4. Porous bixbyite Mn loaded with diatomite2O3A catalyst, characterized by: is prepared by the method of any one of claims 1 to 3.
5. The diatomaceous earth-supported porous bixbyite Mn of claim 42O3The application of the catalyst in catalyzing and degrading benzene.
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