CN113751001A - Valence-state-controllable metal oxide catalyst and preparation method and application thereof - Google Patents
Valence-state-controllable metal oxide catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 36
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 54
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 12
- 239000012855 volatile organic compound Substances 0.000 claims description 11
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 17
- 238000006731 degradation reaction Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01D53/864—Removing carbon monoxide or 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
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8894—Technetium
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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
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention belongs to the technical field of catalytic materials, and discloses a preparation method and application of a controllable valence metal oxide catalyst. The catalyst is prepared by mixing metal nitrate with deionized water, performing ultrasonic treatment and stirring, and performing heat treatment at 100-200 ℃ for 2-48 h; the metal nitrate is more than two of ferric nitrate, manganese nitrate and copper nitrate. The preparation method has the advantages of simple steps, low equipment requirement, low energy consumption, high yield and large-scale production, and the prepared controllable valence metal oxide catalyst can efficiently degrade ethyl acetate and/or toluene, and the degradation rate of the catalyst on ethyl acetate, toluene and the like reaches more than 97%.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a controllable valence metal oxide catalyst and a preparation method and application thereof.
Background
Due to the good catalytic performance of the multi-valence metal oxide catalyst, the catalyst plays an increasingly important role in the field of purification of volatile organic compounds. In the reported patents related to the multi-valence metal oxide catalyst, the patent CN111364006A utilizes a vacuum or vapor deposition method to regulate and control the chemical potential of oxygen on the growth surface of the oxide, thereby realizing the control of the valence and phase of the metal elements in the oxide, but the deposition method of the multi-valence metal oxide catalyst provided by the patent is magnetron sputtering or molecular beam epitaxy, requires a special target material, has strict requirements on the vacuum degree, uses a special inert gas as a working gas, has harsh synthesis conditions, and is not beneficial to macro preparation; patent CN108329954A uses mechanical force in combination with reducing agent to partially chemically reduce metal oxide ore into multi-valence metal oxide, but the working environment also needs inert gas protection, and the physical ball milling method may cause the problems of uneven distribution of valence and content of multi-valence metal oxide, impure product, etc. In addition, the above two patents require special equipment, such as a growth chamber, a radio frequency power supply, a ball mill, etc., for preparing the multi-valence metal oxide. Therefore, the development of a rapid and simple preparation method of the controllable valence metal oxide catalyst has a very important significance for realizing the high-efficiency macroscopic preparation and application and popularization of the metal oxide catalyst.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, a controllable valence metal oxide catalyst is provided. When different metal nitrates are subjected to mixed heat treatment, the chemical valence regulation of the multi-metal oxide catalyst is realized by different compounding proportions and by taking the generated low-valence metal ions as a reducing agent.
Another object of the present invention is to provide a method for preparing the above-mentioned metal oxide catalyst with controllable valence.
It is a further object of the present invention to provide the use of the above-mentioned metal oxide catalyst with a controllable valence state.
The purpose of the invention is realized by the following technical scheme:
a controllable valence metal oxide catalyst is prepared by mixing metal nitrate with deionized water, performing ultrasonic treatment and stirring, and performing heat treatment at 100-200 ℃ for 2-48 h; the metal nitrate is any two or three of ferric nitrate, manganese nitrate and copper nitrate.
Preferably, when the metal nitrates are two, the mass ratio of the two metal nitrates is 1: (1-9); when the metal nitrates are three, the mass ratio of the three metal nitrates is 1: (1-9): (1-9).
Preferably, the catalyst is Fe2O3-Mn2O3-MnO2、Cu2O-CuO-Fe2O3、CuO-Cu2O-MnO2、Cu2O-CuO-Mn2O3-MnO2、Fe2O3-CuO-Mn2O3-MnO2、Fe2O3-CuO-Cu2O-MnO2-Mn2O3。
Preferably, the mass ratio of the metal nitrate to the deionized water is 1: (0.1 to 50).
Preferably, the power of the ultrasound is 100-300W, and the time of the ultrasound is 1-30 min; the stirring speed is 10-100 r/min, and the stirring time is 1-30 min.
The controllable valence metal oxide catalyst is applied to purifying volatile organic compounds.
Preferably, the volatile organic comprises ethyl acetate and/or toluene; the concentration of the volatile organic compounds is 1-100 ppm.
In order to better realize the method, the metal oxide catalyst with the controllable valence state is placed into a fluidized bed reactor (CN208372820U), air containing ethyl acetate and/or toluene is introduced into the reactor at the speed of 10-100 mL/min, a xenon lamp is turned on, the ethyl acetate and/or toluene is eliminated under the synergistic action of light and the catalyst, and the degradation rate is more than 97%. The relative humidity of the air is 30-70%, the oxygen content of the air is 10-100%, and the temperature of the air is 5-30 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention takes metal nitrate as raw material, in the heat treatment process of the metal nitrate, the metal nitrate can be oxidized by oxygen, and simultaneously high valence metal ions are reduced by low valence metal ions, in the process of the synergistic existence of the oxidation and reduction, the synthesis of the controllable valence metal oxide is realized by regulating and controlling different heat treatment temperatures and times, dissolved oxygen content and the proportion among the metal nitrate. The formed multi-valence metal oxide forms an amorphous state due to the reduction of crystallinity, so that abundant oxygen vacancies are introduced, and the catalytic performance of the synthetic material is improved.
2. The method realizes the synthesis of the catalyst only under the working environment of normal pressure and no sealing, and has the advantages of low requirement on reaction equipment, simple synthesis steps, low energy consumption and easy large-scale preparation.
3. The invention realizes the high-efficiency degradation of volatile organic compounds by using the controllable valence metal oxide, and the degradation rate of the volatile organic compounds on ethyl acetate, toluene and the like reaches more than 97 percent.
Drawings
FIG. 1 is a graph showing the photocatalytic degradation kinetics of ethyl acetate by the controlled-valence metal oxide catalyst prepared in example 1 and toluene by the controlled-valence metal oxide catalyst prepared in example 2.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Mixing iron nitrate, manganese nitrate and deionized water in a mass ratio of 1: 1: 50, performing ultrasonic treatment at the ultrasonic power of 300W for 30min, then stirring at the stirring speed of 100r/min for 30min, and performing heat treatment at 200 ℃ for 48h to obtain Fe2O3-MnO2-Mn2O3A catalyst.
Air (70% relative humidity, oxygen content) containing 70ppm ethyl acetate100% at 30 ℃ and 100mL/min (CN208372820U, catalyst Fe from example 1)2O3-MnO2-Mn2O3) And after the xenon lamp is started for irradiation for 120min, the concentration of the ethyl acetate at the outlet of the reactor is 1.6ppm, and the degradation rate of the ethyl acetate reaches 97.7 percent.
Example 2
Mixing ferric nitrate, copper nitrate and deionized water in a mass ratio of 1: 9: 25, performing ultrasonic treatment at the ultrasonic power of 150W for 10min, then stirring at the stirring speed of 80r/min for 20min, and performing heat treatment at the temperature of 150 ℃ for 12h to prepare Cu2O-CuO-Fe2O3A catalyst.
Air (50% relative humidity, 20% oxygen content, 25 ℃ C.) containing 70ppm of toluene was fed into a fluidized bed reactor (CN208372820U, catalyst Cu obtained in example 2) at a rate of 60mL/min2O-CuO-Fe2O3) And after the xenon lamp is started to irradiate for 120min, the concentration of toluene at the outlet of the reactor is 2.0ppm, and the degradation rate of the toluene reaches 97.1 percent.
FIG. 1 is a graph showing the photocatalytic degradation kinetics of ethyl acetate by the controlled-valence metal oxide catalyst prepared in example 1 and toluene by the controlled-valence metal oxide catalyst prepared in example 2. As is clear from FIG. 1, Fe of example 12O3-MnO2-Mn2O3And Cu of example 22O-CuO-Fe2O3The degradation rates of the ethyl acetate and the toluene respectively reach more than 97 percent, which shows that the metal oxide with controllable valence has high removal efficiency on volatile organic compounds.
Example 3
Copper nitrate, manganese nitrate and deionized water are mixed according to a mass ratio of 1: 16: 64 mixing, performing ultrasonic treatment for 10min under the ultrasonic power of 150W, then stirring for 20min under the stirring speed of 80r/min, and performing heat treatment at 140 ℃ for 12h to obtain CuO-MnO2-Mn2O3A catalyst. The degradation rate of the catalyst to ethyl acetate is 97.2%.
Example 4
Iron nitrate, copper nitrate and deionizationWater is mixed according to the mass ratio of 1: 16: 64 mixing, performing ultrasonic treatment at the ultrasonic power of 300W for 10min, stirring at the stirring speed of 80r/min for 20min, and performing heat treatment at 180 ℃ for 24h to obtain Cu2O-CuO-MnO2-Mn2O3A catalyst. The catalyst has a degradation rate of 97.3% to toluene.
Example 5
Mixing ferric nitrate, copper nitrate and deionized water in a mass ratio of 1: 1: 50 mixing, performing ultrasonic treatment at ultrasonic power of 300W for 10min, stirring at stirring speed of 80r/min for 20min, and performing heat treatment at 140 deg.C for 12h to obtain Fe2O3-CuO-MnO2-Mn2O3A catalyst. The degradation rate of the catalyst to ethyl acetate is 97.5%.
Example 6
Mixing ferric nitrate, copper nitrate and deionized water in a mass ratio of 1: 1: 50 mixing, performing ultrasonic treatment at ultrasonic power of 300W for 10min, stirring at stirring speed of 80r/min for 20min, and performing heat treatment at 180 deg.C for 24h to obtain Fe2O3-Cu2O-CuO-MnO2-Mn2O3A catalyst. The catalyst has a degradation rate of 97.7% to toluene.
Comparative example 1
2.5g of copper nitrate is directly subjected to heat treatment at 140 ℃ for 10 hours to prepare the CuO catalyst. The degradation rate of the catalyst to ethyl acetate is 50.5%.
Comparative example 2
Copper nitrate and deionized water are mixed according to a mass ratio of 1: 0.1, performing ultrasonic treatment for 1min under the ultrasonic power of 100W, then stirring for 10min under the stirring speed of 10r/min, and performing heat treatment at 140 ℃ for 10h to prepare the CuO catalyst. The catalyst has a degradation rate of 52.4% to ethyl acetate.
Comparative example 3
Mixing ferric nitrate and deionized water in a mass ratio of 1: 10 mixing, performing ultrasonic treatment at the ultrasonic power of 100W for 1min, then stirring at the stirring speed of 10r/min for 10min, and performing heat treatment at 180 ℃ for 10h to obtain Fe2O3A catalyst. The catalyst has a toluene degradation rate of 51.9%.
Comparative example 4
Manganese nitrate and deionized water are mixed according to a mass ratio of 1: 50 mixing, performing ultrasonic treatment at the ultrasonic power of 100W for 1min, then stirring at the stirring speed of 10r/min for 10min, and performing heat treatment at 200 ℃ for 10h to obtain MnO2A catalyst. The catalyst has a toluene degradation rate of 60.7%.
The invention realizes the high-efficiency degradation of volatile organic compounds by using the controllable valence metal oxide, and the degradation rate of the volatile organic compounds on ethyl acetate and/or toluene reaches more than 97 percent.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A controllable valence metal oxide catalyst is characterized in that the catalyst is prepared by mixing metal nitrate with deionized water, performing ultrasonic treatment and stirring, and performing heat treatment at 100-200 ℃ for 2-48 h; the metal nitrate is any two or three of ferric nitrate, manganese nitrate and copper nitrate.
2. The controlled-valence metal oxide catalyst according to claim 1, wherein when the metal nitrate is two, the mass ratio of the two metal nitrates is 1: (1-9); when the metal nitrates are three, the mass ratio of the three metal nitrates is 1: (1-9): (1-9).
3. The controlled-valence metal oxide catalyst according to claim 1, wherein the catalyst is Fe2O3-Mn2O3-MnO2、CuO-MnO2-Mn2O3、Cu2O-CuO-Mn2O3-MnO2、Fe2O3-CuO-Mn2O3-MnO2、Fe2O3-CuO-Cu2O-MnO2-Mn2O3、Cu2O-CuO-Fe2O3。
4. The controllable valence state metal oxide catalyst according to claim 1, wherein the mass ratio of the metal nitrate to the deionized water is 1: (0.1 to 50).
5. The controllable valence state metal oxide catalyst according to claim 1, wherein the power of the ultrasound is 100-300W, and the time of the ultrasound is 1-30 min; the stirring speed is 10-100 r/min, and the stirring time is 1-30 min.
6. Use of a controlled valence metal oxide catalyst as claimed in any one of claims 1 to 5 for the purification of volatile organic compounds.
7. The use of a controlled-valence metal oxide catalyst according to claim 6, wherein the volatile organic compound comprises ethyl acetate and/or toluene; the concentration of the volatile organic compounds is 1-100 ppm.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012115732A (en) * | 2010-11-29 | 2012-06-21 | Daihatsu Motor Co Ltd | Catalyst for purifying exhaust gas |
| CN103212406A (en) * | 2013-04-19 | 2013-07-24 | 重庆工商大学 | MnOx catalyst for catalytically eliminating benzene series in air and preparation method of MnOx catalyst |
| CN108479762A (en) * | 2018-03-14 | 2018-09-04 | 中国科学院城市环境研究所 | A kind of manganese oxide catalyst and its preparation method and application |
| CN208372820U (en) * | 2018-03-22 | 2019-01-15 | 广东工业大学 | A kind of cleaning equipment of volatile organic matter |
| CN109894124A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院上海硅酸盐研究所 | A kind of copper mangenese spinel oxide and its preparation method and application |
| CN111036232A (en) * | 2019-12-20 | 2020-04-21 | 南京工业大学 | Composite metal oxide catalyst for catalytic combustion and preparation method thereof |
| CN111905714A (en) * | 2020-07-14 | 2020-11-10 | 南京工业大学 | Method for preparing spinel catalyst for VOCs catalytic combustion under assistance of low-temperature plasma |
| CN113145108A (en) * | 2021-04-26 | 2021-07-23 | 中国科学院城市环境研究所 | MnO capable of adjusting oxygen species distributionxCatalyst, preparation method and application thereof |
-
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012115732A (en) * | 2010-11-29 | 2012-06-21 | Daihatsu Motor Co Ltd | Catalyst for purifying exhaust gas |
| CN103212406A (en) * | 2013-04-19 | 2013-07-24 | 重庆工商大学 | MnOx catalyst for catalytically eliminating benzene series in air and preparation method of MnOx catalyst |
| CN109894124A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院上海硅酸盐研究所 | A kind of copper mangenese spinel oxide and its preparation method and application |
| CN108479762A (en) * | 2018-03-14 | 2018-09-04 | 中国科学院城市环境研究所 | A kind of manganese oxide catalyst and its preparation method and application |
| CN208372820U (en) * | 2018-03-22 | 2019-01-15 | 广东工业大学 | A kind of cleaning equipment of volatile organic matter |
| CN111036232A (en) * | 2019-12-20 | 2020-04-21 | 南京工业大学 | Composite metal oxide catalyst for catalytic combustion and preparation method thereof |
| CN111905714A (en) * | 2020-07-14 | 2020-11-10 | 南京工业大学 | Method for preparing spinel catalyst for VOCs catalytic combustion under assistance of low-temperature plasma |
| CN113145108A (en) * | 2021-04-26 | 2021-07-23 | 中国科学院城市环境研究所 | MnO capable of adjusting oxygen species distributionxCatalyst, preparation method and application thereof |
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