CN113559849A - Preparation method of amorphous manganese oxide catalyst applied to catalytic decomposition of ozone - Google Patents
Preparation method of amorphous manganese oxide catalyst applied to catalytic decomposition of ozone Download PDFInfo
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- CN113559849A CN113559849A CN202110912475.8A CN202110912475A CN113559849A CN 113559849 A CN113559849 A CN 113559849A CN 202110912475 A CN202110912475 A CN 202110912475A CN 113559849 A CN113559849 A CN 113559849A
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- ozone
- manganese oxide
- manganese
- oxide catalyst
- catalytic decomposition
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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 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000003421 catalytic decomposition reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 46
- 239000011572 manganese Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052748 manganese Inorganic materials 0.000 claims description 26
- 239000012286 potassium permanganate Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 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
- 238000001514 detection method Methods 0.000 claims description 2
- 229910002096 lithium permanganate Inorganic materials 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 28
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000004887 air purification Methods 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 33
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 30
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 30
- 239000000047 product Substances 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 11
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000002860 competitive effect Effects 0.000 description 4
- 230000036541 health Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005949 ozonolysis reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 210000001508 eye Anatomy 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910003144 α-MnO2 Inorganic materials 0.000 description 1
- 229910006648 β-MnO2 Inorganic materials 0.000 description 1
- 229910006287 γ-MnO2 Inorganic materials 0.000 description 1
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- 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
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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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—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
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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Abstract
The invention relates to a preparation method of an amorphous manganese oxide catalyst applied to catalytic decomposition of ozone, belonging to the technical field of air purification. The method comprises the following steps: adding permanganate solid into a manganous salt solution at room temperature to prepare a mixed solution, carrying out hydrothermal reaction at a specific temperature, and washing and drying a product to obtain the amorphous manganese oxide catalyst. The catalyst prepared by the invention has high activity, high moisture resistance and stability, and the ozone removal rate is close to 100% after 8 hours when the ozone inlet concentration is 20ppm, the airspeed is 600L/g/h and the relative humidity is 60%; when the relative humidity is 80%, the removal rate is kept above 85% after 8 h. The catalyst has excellent performance of catalyzing and decomposing ozone under the condition of wide relative humidity, overcomes the defect that the traditional catalyst is easy to inactivate under the condition of high relative humidity, has simple preparation method, short time consumption and low energy consumption, and is suitable for large-scale application and ozone removal.
Description
The technical field is as follows:
the invention belongs to the technical field of air purification, and particularly relates to a preparation method of an amorphous manganese oxide catalyst applied to catalytic decomposition of ozone.
Background art:
ozone near the surface is an important gaseous pollutant, which can cause serious harm to human health, such as causing diseases related to respiratory tract, brain, eye and the like. Ozone has strong oxidizing property, is often used in aspects such as sewage treatment, medical health, and the like, a large amount of residual ozone can aggravate air ozone pollution in the use process, and indoor equipment such as printers, air purifiers and the like can also generate non-negligible ozone. The world health organization set the limit for indoor ozone to an average level of 50ppb for 8 hours per day. Therefore, studies for removing ozone gas pollution are necessary.
The catalytic ozonolysis method mainly comprises a thermal decomposition method, an activated carbon adsorption method, an electromagnetic wave radiation method and a catalytic decomposition method. Compared with other methods, the catalytic decomposition method has the advantages of high efficiency, economy and safety, and is an ideal ozonolysis method at present. The catalyst for catalytically decomposing ozone comprises noble metals and transition metal oxides, the noble metals have high catalytic efficiency, but the preparation cost is high, and the catalyst is not suitable for large-scale industrial production; the transition metal oxide has relatively low cost and high catalytic activity, so the method has great practical significance for the research of the transition metal oxide. The manganese oxide has high activity, simple preparation and low price, and thus becomes a research hotspot. At present, the manganese oxide catalyst for catalyzing and decomposing ozone is researched by using crystalline MnO2Predominantly, e.g. alpha-MnO2、β-MnO2、γ-MnO2Iso, crystalline MnO2Has certain activity for catalyzing and decomposing ozone, but has MnO crystal2Has poor moisture resistance and is easily deactivated under conditions of high relative humidity.
Amorphous oxides of manganese, unlike crystalline oxides of manganese, are short-range ordered in structure, contain a large number of coordinately unsaturated atoms, generally have a larger specific surface area and more surface active sites, and thus have higher catalytic activity. Amorphous manganese oxides have proven to be very effective in electrocatalytic and thermocatalytic oxidation of CO, which is related to the mobility of lattice oxygen and excess surface oxygen. In addition, the preparation conditions of the amorphous manganese oxide are mild, and the cost for preparing the catalyst can be effectively reduced. Patent CN109603817A discloses an amorphous manganese oxide catalyst for catalytic decomposition of ozone, which is prepared by a simple and easy preparation method, and achieves the purpose of regulating and controlling the manganese valence state through micro-oxidation-reduction, so that the catalyst can keep higher ozone removal efficiency under the condition of 50% relative humidity for a long time.
The invention aims to provide a novel amorphous manganese oxide catalyst for catalytic decomposition of ozone, which is prepared by a hydrothermal method, and the manganese oxide catalyst with high catalytic activity and moisture resistance is prepared by a short-time hydrothermal reaction; the preparation method is simple, the required reaction time is short, the time and energy consumption for preparing the catalyst are greatly reduced, and the preparation method has obvious significance for actual industrial production.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provides a preparation method of an amorphous manganese oxide catalyst applied to catalytic decomposition of ozone, wherein the amorphous manganese oxide has special structural properties, so that the amorphous manganese oxide has high catalytic activity and high stability in a wide relative humidity range; the preparation method disclosed by the invention is simple, short in reaction time and low in energy consumption, remarkably reduces the cost for preparing the catalyst, and has great significance for actual industrial production.
The mechanism of the manganese oxide catalyst for decomposing ozone is as follows: unsaturated Mn element, i.e. Mn3+Forming an oxygen vacancy, the ozone being combined with the oxygen vacancy, the oxygen vacancy transferring two electrons to one O atom of the ozone, thereby forming one O on the oxygen vacancy2-And one oxygen molecule, which is released into the air. Then another ozone molecule with O2-Reacting to form an oxygen molecule and an O2 2-. Finally, O2 2-Desorb from the oxygen vacancy and convert to oxygen molecules.
Thus, trivalent manganese represents oxygen vacancies at the surface of the manganese oxide, and the amount of trivalent manganese determines the activity of the manganese oxide catalyst. The invention changes the concentration and the molar ratio of the precursor and the time of hydrothermal reaction,The temperature is used to control the properties of the final oxides of manganese product so that the catalyst activity remains high. Moisture resistance is an important indicator of catalyst performance, since competitive adsorption of water molecules under humid environmental conditions can deactivate the catalyst. The invention can keep high ozone removing rate for a long time under the condition of high relative humidity, which shows that the invention has strong moisture resistance. Preferably, the manganese oxide surface Mn3+The proportion of (A) is 62-66%.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the amorphous manganese oxide catalyst applied to catalytic decomposition of ozone comprises the following steps:
(1) preparing a bivalent manganese aqueous solution;
(2) adding the permanganate solid into a divalent manganese solution, and uniformly stirring to obtain a mixed solution;
(3) transferring the mixed solution into a reaction kettle, and placing the reaction kettle in an oven for hydrothermal reaction to obtain a hydrothermal reaction product, wherein the hydrothermal reaction temperature is 90-160 ℃, and the hydrothermal reaction time is 1-5 hours;
(4) washing and drying the hydrothermal reaction product to obtain the amorphous manganese oxide catalyst applied to catalytic decomposition of ozone.
In the step (1), the divalent manganese is one or more of manganese acetate, manganese sulfate, manganese nitrate or manganese chloride, and when a plurality of manganese are mixed, the mixing ratio is any ratio.
In the step (1), the concentration of the divalent manganese aqueous solution is 0.05-0.34 mol/L.
In the step (1), the concentration of the divalent manganese aqueous solution is preferably 0.06-0.17 mol/L.
In the step (2), the permanganate is one or more of potassium permanganate, sodium permanganate and lithium permanganate, and when a plurality of permanganate are mixed, the mixing ratio is any ratio.
In the step (2), the molar ratio of the permanganate to the divalent manganese salt is 1 (0.5-3).
In the step (2), the molar ratio of the permanganate to the divalent manganese salt is preferably 1 (0.75-1.75), and when the molar ratio is lower than 1:0.75, the permanganate is relatively excessive and is insufficient to form a complete amorphous structure, so that the activity is reduced; when the molar ratio is higher than 1:1.75, the product is converted into crystalline manganese dioxide, and the activity of the product is also lowered.
In the step (2), the stirring time is 5-60 min, and the stirring temperature is 20-70 ℃.
In the step (2), preferably, the stirring time is 5-30 min, and the stirring temperature is 20-30 ℃.
In the step (3), the hydrothermal reaction kettle consists of a stainless steel outer sleeve and a polytetrafluoroethylene inner liner, has good tightness and corrosion resistance, and enables reactants to fully react under the special environmental conditions of higher temperature and pressure.
In the step (3), the hydrothermal temperature is preferably 100-140 ℃ and the time is 1-4 hours, and when the hydrothermal temperature is too high or the reaction time is too long, the product is converted into the crystalline manganese dioxide, so that the activity of the product is reduced.
In the step (4), the washing mode is deionized water washing, and the washing times are 2-6 times; and drying in an oven at the temperature of 70-100 ℃ for 6-20 h.
In the step (4), preferably, the washing times are 3-4 times, the drying temperature is 80-90 ℃, and the time is 10-15 hours.
In the step (4), the amorphous manganese oxide catalyst applied to catalytic decomposition of ozone is a nano-structured catalyst containing mesopores, and the specific surface area is 209.3-269.1 m2Per g, pore volume of 0.44-0.73 cm3The pore diameter is 4.5-10 nm.
In the step (4), through detection, when the relative humidity of the amorphous manganese oxide catalyst applied to catalytic decomposition of ozone is 60%, the ozone removal rate reaches 98-100% in 3 hours and 97-100% in 8 hours; when the relative humidity is 80%, the ozone removal rate reaches 85-93% after 8 hours.
The invention controls the hydrothermal parameters to ensure that the manganese oxide catalyst has high activity and moisture resistance, and the surface Mn3+The content is 62-66 percent according to the catalytic decompositionMechanism of ozone, Mn3+The higher the content, the greater the number of surface oxygen vacancies and the higher the catalytic activity. The prepared amorphous manganese oxide has larger specific surface area, is of a mesoporous structure, and the size of the specific surface area and the type of the pore diameter determine MnOxA key factor in activity, the increased specific surface area may expose more active sites on the surface. The moisture resistance is an important performance index because water molecules and ozone have competitive adsorption and occupy the surface active sites of the catalyst, so that the catalyst is deactivated. The enhanced porous structure mitigates deactivation due to competitive adsorption of water over a range of relative humidities. According to the Kelvin equation, capillary condensation of water vapor in ideal cylindrical pores of 2nm and 20nm, respectively, typically occurs at relative humidities of 59% and 95%, indicating that the corresponding MnO is present in a certain humidity rangexThe increased porosity helps to inhibit competitive adsorption of water molecules. The aperture of the catalyst prepared by the method is 4.5-10 nm, so that the hydrophobicity is enhanced. MnO of the present invention at a relative humidity of less than 60%xThe method shows the characteristic of almost no inactivation, and the removal rate can still be kept above 85% within 8h when the relative humidity is increased to 80%.
The invention has the beneficial effects that:
the manganese oxide catalyst provided by the invention is applied to catalytic ozone decomposition reaction, the reaction space velocity is 600L/g/h, the ozone inlet concentration is 20ppm, and the removal rate of the catalyst to ozone is close to 100% within 8h under the conditions of normal temperature and relative humidity lower than 60%; the removal rate of the ozone can be kept above 85% within 8h under the conditions of normal temperature and relative humidity of 80%.
Secondly, the catalyst has simple preparation method, short time, low energy consumption and low cost.
In conclusion, the manganese oxide catalyst prepared by the invention has higher removal efficiency under the condition of wide relative humidity, overcomes the defect that the traditional catalyst is easy to inactivate under the humid condition, and has the advantages of simple preparation method, low cost, low energy consumption, short used time and extremely high application value.
Description of the drawings:
FIG. 1 is an XRD pattern of manganese oxide catalysts prepared in examples 1-2 of the present invention and comparative example 1;
FIG. 2 is an XPS plot of a manganese oxide catalyst prepared in example 1 of the present invention;
FIG. 3 is an XPS plot of a manganese oxide catalyst prepared according to comparative example 1 of the present invention;
FIG. 4 is an XPS plot of a manganese oxide catalyst prepared in example 2 of the present invention.
The specific implementation mode is as follows:
the present invention is further explained by the following embodiments, which are only part of examples of the present invention and do not limit the present invention in any way, i.e. the present invention is not limited to the following steps, and equivalent replacement of the raw materials of the present invention or change of the quality of the raw materials, etc. are within the protection scope of the present invention.
The ozone inlet concentration of the activity test in the following examples and comparative examples was 20ppm and the space velocity was 600L/g/h.
Example 1
A method for preparing an amorphous manganese oxide, comprising the steps of:
the method comprises the following steps: dissolving manganese acetate tetrahydrate in deionized water, uniformly stirring, wherein the concentration of the manganese acetate tetrahydrate is 0.11mol/L, and marking as A solution; adding potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to manganese acetate tetrahydrate is 1:1, and stirring at room temperature for 20min to obtain a solution B;
step two: transferring the solution B into a reaction kettle, and placing the reaction kettle into an oven to perform hydrothermal reaction at the reaction temperature of 120 ℃ for 2 hours;
step three: washing the obtained product with deionized water for 3 times, and finally drying in an oven at 85 ℃ overnight to obtain the manganese oxide catalyst which is marked as MnOx-1. XRD analysis is shown in figure 1, XPS test result is shown in figure 2, and Mn in the catalyst is calculated3+In an amount of 62.4%, Mn4+The proportion of (A) is 37.6%, and other valence manganese is not contained. The catalyst is tabletted and sieved to prepare 40-60-mesh particles, 0.1g of the catalyst is placed in a quartz tube reactor to test the activity, and part of parameters and performance data are shown in table 1.
Comparative example 1
A preparation method of crystalline manganese dioxide comprises the following steps:
the method comprises the following steps: dissolving manganese acetate tetrahydrate in deionized water, uniformly stirring, wherein the concentration of the manganese acetate tetrahydrate is 0.23mol/L, and marking as A solution; adding potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to divalent manganese salt is 1:2, and stirring at room temperature for 20min to obtain a solution B;
step two: transferring the solution B into a reaction kettle, and placing the reaction kettle into an oven to perform hydrothermal reaction at the reaction temperature of 120 ℃ for 2 hours;
step three: washing the obtained product with deionized water for 3 times, and finally drying in an oven at 85 ℃ overnight to obtain the manganese oxide catalyst which is marked as MnOx-A. XRD analysis is shown in FIG. 1, XPS test result is shown in FIG. 3, and Mn in the catalyst is calculated3+In a ratio of 45.4%, Mn4+The proportion of (A) is 54.6%, and other valence manganese is not contained. The catalyst is tabletted and sieved to prepare 40-60-mesh particles, 0.1g of the catalyst is placed in a quartz tube reactor to test the activity, and part of parameters and performance data are shown in table 1.
Example 2
A method for preparing an amorphous manganese oxide, comprising the steps of:
the method comprises the following steps: dissolving manganese acetate tetrahydrate in deionized water, uniformly stirring, wherein the concentration of the manganese acetate tetrahydrate is 0.17mol/L, and marking as A solution; adding potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to manganese acetate tetrahydrate is 1:1.5, and stirring at room temperature for 20min to obtain a solution B;
step two: transferring the solution B into a reaction kettle, and placing the reaction kettle into an oven to perform hydrothermal reaction at the reaction temperature of 120 ℃ for 2 hours;
step three: washing the obtained product with deionized water for 3 times, and finally drying in an oven at 85 ℃ overnight to obtain the manganese oxide catalyst which is marked as MnOx-2. XRD analysis is shown in FIG. 1, XPS test result is shown in FIG. 4, and Mn in the catalyst is calculated3+In an amount of 65.8%, Mn4+The proportion of (A) is 34.2%, and other valence state manganese is not contained. Tabletting and sieving the catalyst to prepare 40-60-mesh granules, and adding 0.1g of the catalystThe catalyst was placed in a quartz tube reactor and tested for activity, with some of the parameters and performance data shown in table 1. The relative humidity was calculated to be 60% and the catalyst reactivity was calculated to be 428(μ g/g)catMin); the relative humidity was 80% and the catalyst reactivity was 398(μ g/g)cat·min)。
In summary, fig. 1 shows the results of XRD tests performed on the present invention, examples 1-2 only have a distinct peak near 37 ° 2 θ, and comparative example 1 corresponds to α -MnO2Indicating that the catalyst is transformed from amorphous to crystalline when the content of divalent manganese is too high. As can be seen from the data in Table 1, the catalysts of examples 1-2, which are amorphous, have larger specific surface areas than comparative example 1, and particularly under the condition of 80% relative humidity, the ozone removal rate of examples 1-2 reaches more than 90% within 8 h. The catalytic activity of the examples 1-2 is significantly higher than that of the comparative example 1, and the activity of the example 2 is relatively higher, which indicates that the amorphous manganese oxide with a larger specific surface area can expose more active sites, and further shows higher catalytic activity. And based on the catalyst activity examination, example 2 also has excellent stability and moisture resistance. Under high relative humidity conditions, humidity affects the activity of the catalyst as competing adsorption of water molecules with ozone molecules deactivates the catalyst. Example 2 under the condition of relative humidity of 80%, the ozone removal efficiency still reaches 93% after 8h, which shows that the catalyst prepared by the invention has good humidity resistance. FIGS. 2 to 4 show XPS test results of catalysts prepared in example 1, comparative example 1 and example 2, respectively, and Mn of example 13+Mn content of 62.4% in example 23+The content of 65.8 percent is obviously higher than that of the comparative example 1, which shows that the surface oxygen vacancy content of the examples 1 and 2 is high, the catalytic decomposition effect on ozone is strong, and the results are consistent with the specific surface area and activity test results.
Comparative example 2
The difference from example 2 is that potassium permanganate was prepared as a 50ml solution at a concentration of 0.046mol/L, manganese acetate tetrahydrate as a 50ml solution at a concentration of 0.069mol/L, and the potassium permanganate solution was slowly added dropwise to the solutionVigorously stirring the manganese acetate solution at room temperature for 12h, washing, drying and standing overnight to obtain a manganese oxide catalyst which is marked as MnOx-B. Detected and calculated by XPS, wherein Mn is contained2+(17％)、Mn3+(57.3％)、Mn4+(25.7%). The activity was tested under the same conditions, and when the relative humidity was 60%, the removal rate was only 84% for 3h, and when the relative humidity was 80%, the removal rate was 50% for 8 h. The main reason is Mn3+Low content of Mn and partial surface Mn2+Mn due to incomplete reaction2+Remain so that Mn is present3+The (oxygen vacancy) ratio decreases and thus the activity is poor.
Example 3
A method for preparing an amorphous manganese oxide, comprising the steps of:
the method comprises the following steps: dissolving manganese acetate tetrahydrate in deionized water, uniformly stirring, wherein the concentration of the manganese acetate tetrahydrate is 0.07mol/L, and marking as solution A; adding potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to manganese acetate tetrahydrate is 1:1, and stirring for 10min to obtain a solution B;
step two: transferring the solution B into a reaction kettle, and placing the reaction kettle into an oven to perform hydrothermal reaction at the reaction temperature of 120 ℃ for 2 hours;
step three: washing the obtained product with deionized water for 3 times, and finally drying in an oven at 85 ℃ overnight to obtain the manganese oxide catalyst which is marked as MnOx-3. Calculated Mn in the catalyst3+In an amount of 62.8%, Mn4+The proportion of (A) is 37.2%, and other valence manganese is not contained. The catalyst is tabletted and sieved to prepare 40-60-mesh particles, 0.1g of the catalyst is placed in a quartz tube reactor to test the activity, and part of parameters and performance data are shown in table 1.
Comparative example 3
A method for preparing an amorphous manganese oxide, comprising the steps of:
the method comprises the following steps: dissolving manganese acetate tetrahydrate in deionized water, uniformly stirring, wherein the concentration of the manganese acetate tetrahydrate is 0.05mol/L, and marking as A solution; adding potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to manganese acetate tetrahydrate is 1:0.5, and stirring for 20min to obtain a solution B;
step two: transferring the solution B into a reaction kettle, and placing the reaction kettle into an oven to perform hydrothermal reaction at the reaction temperature of 120 ℃ for 2 hours;
step three: washing the obtained product with deionized water for 3 times, and finally drying in an oven at 85 ℃ overnight to obtain the manganese oxide catalyst which is marked as MnOx-C. The catalyst is tabletted and sieved to prepare 40-60-mesh particles, 0.1g of the catalyst is placed in a quartz tube reactor to test the activity, and part of parameters and performance data are shown in table 1.
Example 4
A method for preparing an amorphous manganese oxide, comprising the steps of:
the method comprises the following steps: dissolving manganese acetate tetrahydrate in deionized water, uniformly stirring, wherein the concentration of the manganese acetate tetrahydrate is 0.09mol/L and is marked as A solution; adding potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to manganese acetate tetrahydrate is 1:1, and stirring for 15min to obtain a solution B;
step two: transferring the solution B into a reaction kettle, and placing the reaction kettle into an oven to perform hydrothermal reaction at the reaction temperature of 120 ℃ for 2 hours;
step three: washing the obtained product with deionized water for 3 times, and finally drying in an oven at 85 ℃ overnight to obtain the manganese oxide catalyst which is marked as MnOx-4. Calculated Mn in the catalyst3+In a ratio of 63.4%, Mn4+The proportion of (A) is 36.6%, and other valence manganese is not contained. The catalyst is tabletted and sieved to prepare 40-60-mesh particles, 0.1g of the catalyst is placed in a quartz tube reactor to test the activity, and part of parameters and performance data are shown in table 1.
Comparative example 4
The difference from example 4 is that the hydrothermal parameters in step two were adjusted to 160 ℃ for 1 hour. Detected, the manganese oxide catalyst MnO finally preparedxD is crystalline manganese dioxide, and part of the parameters and performance data are shown in Table 1.
Example 5
A method for preparing an amorphous manganese oxide, comprising the steps of:
the method comprises the following steps: dissolving manganese acetate tetrahydrate in deionized water, uniformly stirring, wherein the concentration of the manganese acetate tetrahydrate is 0.13mol/L, and marking as A solution; adding potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to manganese acetate tetrahydrate is 1:1.2, and stirring for 20min to obtain a solution B;
step two: transferring the solution B into a reaction kettle, and placing the reaction kettle into an oven to perform hydrothermal reaction at the temperature of 130 ℃ for 1 h;
step three: washing the obtained product with deionized water for 3 times, and finally drying in an oven at 85 ℃ overnight to obtain the manganese oxide catalyst which is marked as MnOx-5. Calculated Mn in the catalyst3+In a ratio of 63.9%, Mn4+The proportion is 36.1%, and other valence state manganese is not contained. The catalyst is tabletted and sieved to prepare 40-60-mesh particles, 0.1g of the catalyst is placed in a quartz tube reactor to test the activity, and part of parameters and performance data are shown in table 1.
Example 6
A method for preparing an amorphous manganese oxide, comprising the steps of:
the method comprises the following steps: dissolving manganese acetate tetrahydrate in deionized water, uniformly stirring, wherein the concentration of the manganese acetate tetrahydrate is 0.11mol/L, and marking as A solution; adding potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to manganese acetate tetrahydrate is 1:1, and stirring at room temperature for 20min to obtain a solution B;
step two: transferring the solution B into a reaction kettle, and placing the reaction kettle into an oven to perform hydrothermal reaction at the reaction temperature of 110 ℃ for 3 hours;
step three: washing the obtained product with deionized water for 3 times, and finally drying in an oven at 85 ℃ overnight to obtain the manganese oxide catalyst which is marked as MnOx-6. Calculated Mn in the catalyst3+In an amount of 62.5%, Mn4+The proportion is 37.5%, and other valence state manganese is not contained. The catalyst is tabletted and sieved to prepare 40-60-mesh particles, 0.1g of the catalyst is placed in a quartz tube reactor to test the activity, and part of parameters and performance data are shown in table 1.
Example 7
A method for preparing an amorphous manganese oxide, comprising the steps of:
the method comprises the following steps: dissolving manganese acetate tetrahydrate in deionized water, uniformly stirring, wherein the concentration of the manganese acetate tetrahydrate is 0.08mol/L and is marked as solution A; adding potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to manganese acetate tetrahydrate is 1:0.75, and stirring at room temperature for 20min to obtain a solution B;
step two: transferring the solution B into a reaction kettle, and placing the reaction kettle into an oven to perform hydrothermal reaction at the reaction temperature of 120 ℃ for 2 hours;
step three: washing the obtained product with deionized water for 3 times, and finally drying in an oven at 85 ℃ overnight to obtain the manganese oxide catalyst which is marked as MnOx-7. Calculated Mn in the catalyst3+In an amount of 64.1%, Mn4+The proportion is 35.9 percent, and the manganese in other valence states is not contained. The catalyst is tabletted and sieved to prepare 40-60-mesh particles, 0.1g of the catalyst is placed in a quartz tube reactor to test the activity, and part of parameters and performance data are shown in table 1.
Example 8
A method for preparing an amorphous manganese oxide, comprising the steps of:
the method comprises the following steps: dissolving manganese acetate tetrahydrate in deionized water, uniformly stirring, wherein the concentration of the manganese acetate tetrahydrate is 0.11mol/L, and marking as A solution; adding potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to manganese acetate tetrahydrate is 1:1, and stirring at room temperature for 20min to obtain a solution B;
step two: transferring the solution B into a reaction kettle, and placing the reaction kettle into an oven to perform hydrothermal reaction at the reaction temperature of 100 ℃ for 4 hours;
step three: washing the obtained product with deionized water for 3 times, and finally drying in an oven at 85 ℃ overnight to obtain the manganese oxide catalyst which is marked as MnOx-8. Calculated Mn in the catalyst3+In an amount of 62.2%, Mn4+The proportion is 37.8 percent, and the manganese in other valence states is not contained. The catalyst is tabletted and sieved to prepare 40-60-mesh particles, 0.1g of the catalyst is placed in a quartz tube reactor to test the activity, and part of parameters and performance data are shown in table 1.
TABLE 1
Claims (10)
1. The preparation method of the amorphous manganese oxide catalyst applied to catalytic decomposition of ozone is characterized by comprising the following steps:
(1) preparing a bivalent manganese aqueous solution;
(2) adding the permanganate solid into a divalent manganese solution, and uniformly stirring to obtain a mixed solution;
(3) carrying out hydrothermal reaction on the mixed solution to obtain a hydrothermal reaction product, wherein the hydrothermal reaction temperature is 90-160 ℃, and the hydrothermal reaction time is 1-5 h;
(4) washing and drying the hydrothermal reaction product to obtain the amorphous manganese oxide catalyst applied to catalytic decomposition of ozone.
2. The method of claim 1, wherein in the step (1), the divalent manganese is one or more of manganese acetate, manganese sulfate, manganese nitrate and manganese chloride, and when the divalent manganese is mixed, the mixing ratio is any ratio, and the concentration of the divalent manganese aqueous solution is 0.05-0.34 mol/L.
3. The method for preparing the amorphous manganese oxide catalyst used for catalytic decomposition of ozone according to claim 2, wherein in the step (1), the concentration of the aqueous solution of divalent manganese is 0.06-0.17 mol/L.
4. The method for preparing the amorphous manganese oxide catalyst used for catalytic decomposition of ozone according to claim 1, wherein in the step (2), the permanganate is one or more of potassium permanganate, sodium permanganate and lithium permanganate, and when a plurality of permanganate and sodium permanganate are mixed, the mixing ratio is any ratio, and the molar ratio of the permanganate to the divalent manganese salt is 1 (0.5-3).
5. The method for preparing the amorphous manganese oxide catalyst used for catalytic decomposition of ozone according to claim 4, wherein in the step (2), the molar ratio of the permanganate to the manganous salt is 1 (0.75-1.75).
6. The method for preparing the amorphous manganese oxide catalyst for catalytic decomposition of ozone according to claim 1, wherein in the step (2), the stirring time is 5-60 min, and the stirring temperature is 20-70 ℃.
7. The method for preparing the amorphous manganese oxide catalyst used for catalytic decomposition of ozone according to claim 1, wherein in the step (3), the hydrothermal temperature is 100-140 ℃ and the hydrothermal time is 1-4 h.
8. The method for preparing the amorphous manganese oxide catalyst for catalytic decomposition of ozone according to claim 1, wherein in the step (4), the washing mode is deionized water washing, and the washing times are 2-6 times; and drying in an oven at the temperature of 70-100 ℃ for 6-20 h.
9. The method for preparing the amorphous manganese oxide catalyst for catalytic decomposition of ozone according to claim 1, wherein the amorphous manganese oxide catalyst for catalytic decomposition of ozone in the step (4) is a nano-structured catalyst containing mesopores and has a specific surface area of 209.3-269.1 m2Per g, pore volume of 0.44-0.73 cm3The pore diameter is 4.5-10 nm.
10. The preparation method of the amorphous manganese oxide catalyst for catalytic decomposition of ozone according to claim 1, wherein in the step (4), the detection shows that the ozone removal rate of 3h reaches 98-100% and the ozone removal rate of 8h reaches 97-100% when the relative humidity of the amorphous manganese oxide catalyst for catalytic decomposition of ozone is 60%; when the relative humidity is 80%, the ozone removal rate reaches 85-93% after 8 hours.
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