CN113751001B - Valence-controllable metal oxide catalyst and preparation method and application thereof - Google Patents
Valence-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 57
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 230000015556 catabolic process Effects 0.000 claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 claims abstract description 18
- 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 18
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 16
- 239000012855 volatile organic compound Substances 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 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
- 238000000034 method Methods 0.000 description 6
- 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
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 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
- 239000007789 gas Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006467 substitution reaction 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
Classifications
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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
-
- 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
-
- 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
-
- 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 metal oxide catalyst with controllable valence state. 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 hours; the metal nitrate is any two or more of ferric nitrate, manganese nitrate and cupric 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 metal oxide catalyst with controllable valence state can efficiently degrade ethyl acetate and/or toluene, and the degradation rate of the catalyst to ethyl acetate and/or toluene and the like is 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, a preparation method and application thereof.
Background
Due to the good catalytic performance of the polyvalent metal oxide catalyst, the catalyst plays an increasingly important role in the field of purification of volatile organic compounds. Among the reported patents related to the polyvalent metal oxide catalyst, patent CN111364006A regulates and controls the chemical potential of oxygen on the growth surface of the oxide by utilizing a vacuum or vapor deposition method, thereby realizing the control of the valence and phase of metal elements in the oxide, but the deposition method of the polyvalent metal oxide catalyst provided by the patent is magnetron sputtering or molecular beam epitaxy, requires a special target material, has strict requirements on vacuum degree, has a special inert gas as working gas, has harsh synthesis conditions and is unfavorable for mass preparation; the patent CN108329954a adopts mechanical force combined with a reducing agent to chemically reduce the metal oxide ore into the multivalent metal oxide, but the working environment also needs inert gas protection, and meanwhile, the physical ball milling method may cause the problems of uneven valence and content distribution of the multivalent metal oxide, impure product and the like. 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 polyvalent metal oxide. Therefore, the development of a rapid, simple and convenient preparation method of the metal oxide catalyst with controllable valence state is of great significance for realizing the mass preparation of the metal oxide catalyst with high efficiency and the application and popularization thereof.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, a controllable valence metal oxide catalyst is provided. When the catalyst is subjected to mixed heat treatment of different metal nitrates, the chemical valence state regulation and control of the multi-metal oxide catalyst are realized by different composite ratios and taking the generated low-valence metal ions as a reducing agent.
It is another object of the present invention to provide a method for preparing the above-mentioned controllable valence metal oxide catalyst.
It is a further object of the present invention to provide the use of the above-described controllable valence metal oxide catalyst.
The aim of the invention is achieved by the following technical scheme:
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.
Preferably, when the metal nitrate is two, the mass ratio of the two metal nitrates is 1: (1-9); when the metal nitrate is three, the mass ratio of the three metal nitrates is 1: (1-9): (1-9).
Preferably, the catalyst is Fe 2 O 3 -Mn 2 O 3 -MnO 2 、Cu 2 O-CuO-Fe 2 O 3 、CuO-Cu 2 O-MnO 2 、Cu 2 O-CuO-Mn 2 O 3 -MnO 2 、Fe 2 O 3 -CuO-Mn 2 O 3 -MnO 2 、Fe 2 O 3 -CuO-Cu 2 O-MnO 2 -Mn 2 O 3 。
Preferably, the mass ratio of the metal nitrate to the deionized water is 1: (0.1-50).
Preferably, the power of the ultrasonic wave is 100-300W, and the time of the ultrasonic wave is 1-30 min; the stirring speed is 10-100 r/min, and the stirring time is 1-30 min.
The application of the metal oxide catalyst with controllable valence state in purifying volatile organic compounds.
Preferably, the volatile organic compounds include ethyl acetate and/or toluene; the concentration of the volatile organic compound is 1-100 ppm.
In order to better realize the invention, the metal oxide catalyst with controllable valence is placed in a fluidized bed reactor (CN 208372820U), air containing ethyl acetate and/or toluene is introduced into the reactor at a speed of 10-100 mL/min, a xenon lamp is started, and the ethyl acetate and/or toluene are eliminated under the synergistic effect 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 meanwhile, high-valence metal ions are reduced by low-valence metal ions, in the process of the cooperative existence of 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 polyvalent metal oxide also forms an amorphous state due to the reduced crystallinity, so that abundant oxygen vacancies are introduced, and the catalytic performance of the synthetic material is improved.
2. The invention realizes the synthesis of the catalyst only under normal pressure and non-airtight working environment, and has low requirements on reaction equipment, simple synthesis steps, low energy consumption and easy large-scale preparation.
3. The invention realizes the efficient degradation of volatile organic compounds by using the metal oxide with controllable valence state, 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 kinetics of photocatalytic degradation 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 present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
Ferric nitrate, manganese nitrate and deionized water are mixed according to the mass ratio of 1:1:50, and performing ultrasonic treatment at ultrasonic power of 300W for 30min, stirring at stirring speed of 100r/min for 30min, and heat treating at 200deg.C for 48 hr to obtain Fe 2 O 3 -MnO 2 -Mn 2 O 3 A catalyst.
Air (70% relative humidity, 100% oxygen content, 30 ℃ C.) containing 70ppm ethyl acetate was introduced into a fluidized bed reactor (CN 208372820U, catalyst was Fe prepared in example 1) at a rate of 100mL/min 2 O 3 -MnO 2 -Mn 2 O 3 ) After the xenon lamp is started to irradiate for 120min, the concentration of ethyl acetate at the outlet of the reactor is 1.6ppm, and the degradation rate of the ethyl acetate reaches 97.7%.
Example 2
Ferric nitrate, copper nitrate and deionized water are mixed according to the mass ratio of 1:9:25, ultrasonic treating at 150W for 10min, stirring at 80r/min for 20min, and heat treating at 150deg.C for 12 hr to obtain Cu 2 O-CuO-Fe 2 O 3 A catalyst.
Air (relative humidity 50%, oxygen content 20%, temperature 25 ℃) containing 70ppm toluene was introduced into a fluidized bed reactor (CN 208372820U, catalyst Cu prepared in example 2) at a rate of 60mL/min 2 O-CuO-Fe 2 O 3 ) 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 toluene reaches 97.1 percent.
FIG. 1 is a graph showing the kinetics of photocatalytic degradation 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 can be seen from FIG. 1, fe of example 1 2 O 3 -MnO 2 -Mn 2 O 3 And Cu of example 2 2 O-CuO-Fe 2 O 3 The degradation rates of the catalyst to ethyl acetate and toluene respectively reach more than 97%, which shows that the metal oxide with controllable valence has high removal efficiency to volatile organic compounds.
Example 3
Copper nitrate, manganese nitrate and deionized water are mixed according to the mass ratio of 1:16:64, ultrasonic treating at ultrasonic power of 150W for 10min, stirring at stirring speed of 80r/min for 20min, and heat treating at 140deg.C for 12 hr to obtain CuO-MnO 2 -Mn 2 O 3 A catalyst. The degradation rate of the catalyst to ethyl acetate is 97.2%.
Example 4
Ferric nitrate, copper nitrate and deionized water are mixed according to the mass ratio of 1:16:64, ultrasonic treating at ultrasonic power of 300W for 10min, stirring at stirring speed of 80r/min for 20min, and heat treating at 180deg.C for 24 hr to obtain Cu 2 O-CuO-MnO 2 -Mn 2 O 3 A catalyst. The degradation rate of the catalyst to toluene is 97.3%.
Example 5
Ferric nitrate, copper nitrate and deionized water are mixed according to the mass ratio of 1:1:50, ultrasonic treating at ultrasonic power of 300W for 10min, stirring at stirring speed of 80r/min for 20min, and heat treating at 140deg.C for 12 hr to obtain Fe 2 O 3 -CuO-MnO 2 -Mn 2 O 3 A catalyst. The degradation rate of the catalyst to ethyl acetate is 97.5%.
Example 6
Ferric nitrate, copper nitrate and deionized water are mixed according to the mass ratio of 1:1:50, and ultrasound at an ultrasound power of 300W10min, stirring at stirring speed of 80r/min for 20min, and heat treating at 180deg.C for 24 hr to obtain Fe 2 O 3 -Cu 2 O-CuO-MnO 2 -Mn 2 O 3 A catalyst. The degradation rate of the catalyst to toluene is 97.7%.
Comparative example 1
After 2.5g of copper nitrate was directly heat-treated at 140℃for 10 hours, a CuO catalyst was prepared. The degradation rate of the catalyst to ethyl acetate is 50.5%.
Comparative example 2
Copper nitrate and deionized water are mixed according to the mass ratio of 1:0.1, and carrying out ultrasonic treatment for 1min under the ultrasonic power of 100W, then stirring for 10min under the stirring speed of 10r/min, and carrying out heat treatment at 140 ℃ for 10h to obtain the CuO catalyst. The degradation rate of the catalyst to ethyl acetate is 52.4%.
Comparative example 3
Ferric nitrate and deionized water are mixed according to the mass ratio of 1:10, and performing ultrasonic treatment at ultrasonic power of 100W for 1min, stirring at stirring speed of 10r/min for 10min, and heat treating at 180deg.C for 10 hr to obtain Fe 2 O 3 A catalyst. The degradation rate of the catalyst to toluene is 51.9%.
Comparative example 4
Manganese nitrate and deionized water are mixed according to the mass ratio of 1:50, and performing ultrasonic treatment at ultrasonic power of 100W for 1min, stirring at stirring speed of 10r/min for 10min, and heat treating at 200deg.C for 10 hr to obtain MnO 2 A catalyst. The degradation rate of the catalyst to toluene is 60.7%.
The invention realizes the efficient degradation of volatile organic compounds by using the metal oxide with controllable valence state, and the degradation rate of the volatile organic compounds on ethyl acetate and/or toluene reaches more than 97 percent.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (4)
1. Use of a metal oxide catalyst of controllable valence state for purifying volatile organic compounds, characterized in that the volatile organic compounds comprise ethyl acetate and/or toluene; the metal oxide catalyst with controllable valence state is prepared by mixing metal nitrate with deionized water, performing ultrasonic treatment and stirring, and performing heat treatment at 100-200 ℃ for 2-48 hours; the metal nitrate is any two or three of ferric nitrate, manganese nitrate and copper nitrate; placing a metal oxide catalyst with controllable valence state into a fluidized bed reactor, introducing air containing ethyl acetate and/or toluene into the reactor at a speed of 10-100 mL/min, and starting a xenon lamp, wherein the ethyl acetate and/or toluene are eliminated under the synergistic effect 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 ℃; the catalyst is Fe 2 O 3 -Mn 2 O 3 -MnO 2 、CuO-MnO 2 -Mn 2 O 3 、Cu 2 O-CuO-Mn 2 O 3 -MnO 2 、Fe 2 O 3 -CuO-Mn 2 O 3 -MnO 2 、Fe 2 O 3 -CuO-Cu 2 O-MnO 2 -Mn 2 O 3 、Cu 2 O-CuO-Fe 2 O 3 。
2. The application of the metal oxide catalyst with controllable valence in purifying volatile organic compounds according to claim 1, wherein the mass ratio of the metal nitrate to the deionized water is 1 (0.1-50).
3. The application of the metal oxide catalyst with controllable valence in purifying volatile organic compounds according to claim 1, wherein the power of the ultrasonic wave is 100-300W, and the time of the ultrasonic wave is 1-30 min; the stirring speed is 10-100 r/min, and the stirring time is 1-30 min.
4. The use of a metal oxide catalyst of controllable valence according to claim 1 for purifying volatile organic compounds, wherein 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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