CN111215067A - Preparation method and application of lutecium gadolinium modified delta-manganese oxide compound supported platinum catalyst - Google Patents
Preparation method and application of lutecium gadolinium modified delta-manganese oxide compound supported platinum catalyst Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 title abstract description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 title abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 title description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 135
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229910006364 δ-MnO2 Inorganic materials 0.000 claims abstract description 41
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 18
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- APRNQTOXCXOSHO-UHFFFAOYSA-N lutetium(3+);trinitrate Chemical compound [Lu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O APRNQTOXCXOSHO-UHFFFAOYSA-N 0.000 claims abstract description 7
- OSGMVZPLTVJAFX-UHFFFAOYSA-N [Gd].[Lu] Chemical group [Gd].[Lu] OSGMVZPLTVJAFX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 88
- 238000003756 stirring Methods 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 229920002125 Sokalan® Polymers 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 21
- 239000012153 distilled water Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000004584 polyacrylic acid Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011268 mixed slurry Substances 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000003379 elimination reaction Methods 0.000 abstract description 10
- 230000008030 elimination Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000012286 potassium permanganate Substances 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 229940099596 manganese sulfate Drugs 0.000 abstract description 2
- 235000007079 manganese sulphate Nutrition 0.000 abstract description 2
- 239000011702 manganese sulphate Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052765 Lutetium Inorganic materials 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 22
- 238000007084 catalytic combustion reaction Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 11
- 229920002554 vinyl polymer Polymers 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 10
- 150000001555 benzenes Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 241000894007 species Species 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 5
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- 238000000643 oven drying Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920006221 acetate fiber Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 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
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B01J35/61—
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
- F23C13/08—Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- 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 discloses a preparation method and application of a platinum catalyst loaded by a lutetium-gadolinium exchange delta-manganese oxide compound. The preparation of the catalyst is that under the strong acid environment regulated by concentrated nitric acid, dispersant is added, manganese sulfate and potassium permanganate carry out reflux reaction to prepare delta-manganese oxide, then lutetium nitrate and gadolinium nitrate are used for dipping the delta-manganese oxide, and surfactant is added simultaneously to obtain Lu-Gd/delta-MnO exchanged with lutetium and gadolinium2Compounding, adding Pt (en)2Cl2The ligand is loaded on the catalyst, and the catalyst is subjected to high-temperature and hydrogen reduction treatment to prepare the catalyst with a high specific surface area (100-130 m)2(g) and high thermal stability>650 ℃ Pt/Lu-Gd-delta-MnO2A catalyst. Hair brushCatalyst pair prepared at high space velocity (60,000 h)‑1～100,000h‑1) And low concentration toluene and ethyl acetate (500 ppm-1000 ppm) have higher elimination efficiency. The catalyst prepared by the invention has the advantages of cheap raw materials, simple preparation process, strong practicability, low temperature for completely eliminating Volatile Organic Compounds (VOCs), high efficiency, no secondary pollution and the like.
Description
Technical Field
The invention relates to a lutetium-gadolinium exchange delta-manganese oxide loaded platinum Pt/Lu-Gd-delta-MnO for catalytic combustion elimination of Volatile Organic Compounds (VOCs)2The preparation of the catalyst and the application of the catalyst in low-temperature high-efficiency catalytic combustion for eliminating VOCs.
Background
Benzene series is one of the main components of Volatile Organic Compounds (VOCs). It typically comprises eight compounds, benzene, toluene, ethylbenzene, o-xylene, etc., of which the benzene series has been prioritized for control of pollutants by the United States Environmental Protection Agency (USEPA) for the list of toxic pollutants in the atmosphere. Benzene series in the air can enter human bodies through respiratory tracts, digestive tracts and skins, so that the human bodies are discomforted, diseases are induced, further cancer is generated, and the benzene series has great influence on the environment and the health of the human bodies. Ethyl acetate (C)4H8O2) Is a typical Volatile Organic Compound (VOCs), has excellent solubility and quick drying property, and is an organic chemical raw material and an industrial solvent with wide application. Is widely used in the production process of acetate fiber, ethyl fiber, chlorinated rubber, vinyl resin, acetate fiber resin, synthetic rubber, paint and the like. The VOCs treatment technology mainly comprises incineration, wherein two modes of direct combustion and catalytic combustion are adopted for incineration treatment, products generated by direct combustion easily cause secondary pollution, and the catalytic combustion is to decompose benzene series into carbon dioxide and water vapor by means of flameless combustion at a lower ignition temperature by means of a catalyst. As toluene is the most difficult species to be eliminated by catalytic combustion in benzene series, the toluene is used for representing the benzene series, and the toluene and ethyl acetate are used for representing VOCs gas. At present, the research on the catalytic combustion elimination of the benzene series is less at home and abroad, and the reaction temperature for completely catalyzing and eliminating the benzene series is higher. For example: "The effect of a magnetic resonance on The catalytic resonance of a benzene and methane over palladium catalysts", published by The research of The Korean Gon SeoO subject groupIn the paper of ported on porous materials (Catal. Total, 83(2003) 131-139), at an airspeed of 60,000h-1Benzene concentration of 10,000ppm (space velocity lower than 100,000h of the present invention)-1Benzene concentration is higher than 1000ppm of the invention), benzene is catalyzed and combusted by FAU zeolite, MCM-41 and KIT-1 loaded Pd catalyst, and the temperature for completely catalyzing, combusting and eliminating benzene is mostly above 300 ℃.
Manganese oxide (MnO) prepared by the method2) Support of delta-MnO2The molecular sieve has a porous structure, manganese ions with mixed valence states, mild acid-base property of the surface and excellent ion exchange performance, so that the molecular sieve becomes a new research hotspot after a zeolite-type tetrahedral molecular sieve. Its crystal structure is composed of octahedron [ MnO ] with common edges6]Chain formation, with octahedra [ MnO ] passing between chains6]The oxygen atoms at the top points are connected by common edges to form a one-dimensional structure. As a novel functional material, supported MnO has been reported2Has ideal catalytic activity in catalytic thermal decomposition and catalytic oxidation of organic matters, thereby having wide industrial application prospect.
The implementation of this project resulted in: national science foundation project (number: 21277008; 20777005); the subsidization of the national emphasis research and development plan (2I005011201702) is also the research content of the projects.
Disclosure of Invention
The invention aims to provide a method for preparing a lutetium-gadolinium exchange modified compound delta-manganese oxide (delta-MnO) with high specific surface area and high thermal stability by using cheap potassium permanganate and manganese sulfate as raw materials and using concentrated nitric acid and a dispersing agent for regulation and refluxing in a strong acid environment2) Load platinum Pt/Lu-Gd-delta-MnO2And the catalyst is used for eliminating Volatile Organic Compounds (VOCs) by low-temperature catalytic combustion.
The invention provides a preparation method of a catalyst for eliminating Volatile Organic Compounds (VOCs) by catalytic combustion.
(1) The preparation method of the catalyst provided by the invention comprises the following steps:
polyvinyl alcohol PVA (polyvinyl alcohol-vinyl polymer, molecule)Formula (C)2H4O)n) Adding 50-100mL of distilled water to form a solution (0.5-1 wt%), adding the solution into a three-neck flask, uniformly stirring at 65-75 ℃, and then adding K2MnO4Adding to the above solution, K2MnO4The final concentration is 0.15 mol/L-0.50 mol/L, wherein n [ K ]2MnO4]: polyvinyl alcohol PVA ═ (0.015 to 0.05) mol: 1g of the total weight of the composition. Then adding MnSO4Adding the solution (0.10-0.75 mol/L) into the mixed solution, and stirring for 6-10 h, wherein n [ KMnO ]4]：n[MnSO4](0.5 to 1.0) mol: 1mol, simultaneously dripping 15-20mL of concentrated nitric acid (5.0-6.0mol/L), keeping pH 2-3 strong acid environment, and adding 5-10W/cm2Performing ultrasonic treatment for 1-2 h, continuously stirring for 1-2 h, refluxing at 100-110 deg.C for 24-48h, vacuum filtering, washing with deionized water to neutrality, drying at 80-120 deg.C to obtain brown solid, and treating with pure oxygen (O)2) Roasting at the medium temperature of 300-400 ℃ for 1-4 h to obtain one-dimensional delta-MnO2。
20-50mL of lutetium nitrate Lu (NO)3)3·6H2O solution (0.001-0.005 mol/L) and gadolinium nitrate Gd (NO)3)3·6H2Stirring and mixing the O solution (0.001-0.005 mol/L) uniformly to form a mixed solution, wherein n [ Lu (NO)3)3]：n[Gd(NO3)3]1 mol: 1mol, and at a rate of 5-10W/cm2Carrying out intensity ultrasound for 1-2 h, then continuously stirring for 2-6 h, and standing for later use. In addition, F127(Pluronic, polyoxyethylene, HO (C) is added at 120-140 deg.C2H4O)m(C3H6O)nH, molecular weight 1000-7000) powder is dissolved in 20-50mL of distilled water and 20-50mL of ethanol to form a 0.5-2 wt% F127 solution, stirred until F127 is completely dissolved, then 1.0-1.5mL of HCl hydrochloride solution (36-38 wt%) is added, stirring is continued for 1-5H, and delta-MnO prepared above is added2To form a mixed slurry. Adding the rare earth mixed solution into delta-MnO2In the slurry, and at a rate of 5-10W/cm2The ultrasonic intensity is carried out for 1-2 h, then the mixture is continuously stirred for 2-6 h, the mixture is refluxed for 24h, and the solution is evaporated after rotary evaporation for 3-4 h. The obtained product is heated to 300-400 ℃ at the speed of 1-2 ℃/min in pure oxygen atmosphereRoasting for 2-4 hours to finally obtain Lu-Gd/delta-MnO2And (c) a complex.
Adding ethylenediamine (en) to 50-100mL of H2PtCl6Solution (5-10mmol L)-1) In which n is [ H ]2PtCl6]: n [ Ethylenediamine (en)]1 mol: 2-3mol, and uniformly mixing and stirring to obtain Pt (en)2Cl2And (3) precursor solution. In addition, Lu-Gd/delta-MnO was added2Adding 50-100mL of Polyacrylic acid PAA (Polyacrylic acid, molecular formula (C)3H4O2)n) In the solution (1-15 mg/L), wherein Lu-Gd/delta-MnO is contained2: polyacrylic acid PAA ═ 1 g: 10mL, thoroughly mixing and stirring to form a suspension, and stirring at 5-10W/cm2The intensity of the ultrasonic wave is kept for 1-2 h, and then the ultrasonic wave is continuously stirred for 2-6 h. Mixing Pt (en)2Cl2Adding the precursor solution into Lu-Gd-delta-MnO2In which n [ Pt (en) ]2Cl2]：Lu-Gd-δ-MnO2(0.005-0.01) mol: 1-2g, stirring for 4 hours, then carrying out rotary evaporation for 3-4 hours to evaporate the solution to obtain a solid, filtering, washing with distilled water, and finally drying at 60-80 ℃ for 12-24 hours to obtain a black solid. The solid obtained is reacted in H2(5-10％H2Ar) atmosphere in a tube furnace porcelain boat at 400-500 ℃ for 1-3h, and the heating rate is 5-10 ℃/min. After natural cooling to room temperature, the heat treated sample was washed in hydrochloric acid for 10-12 h. Finally, centrifugally separating the sample, washing the sample to be neutral by using deionized water, then washing the sample by using ethanol, and drying the sample at 80-100 ℃ to obtain the obtained product Pt/Lu-Gd-delta-MnO2。
(2) The invention also provides an application of the catalyst in eliminating VOCs gas by low-temperature catalytic combustion.
The catalytic combustion elimination reaction of VOCs gas represented by toluene and ethyl acetate is carried out in a fixed bed quartz tube reactor. A miniature quartz reaction tube. Introducing a mixed gas of toluene or ethyl acetate and air, wherein the concentration of the toluene and the ethyl acetate is 500 ppm-1000 ppm, and the air flow space velocity is 60,000h-1～100,000h-1. Gas chromatography TCD detection reaction tail gas CO2And CO, FID detects the content of other organic species such as toluene or ethyl acetate. Hair brushThe obvious effect is as follows: under the concentration and space velocity of the toluene or ethyl acetate, the catalyst prepared by the invention has higher low-temperature catalytic combustion elimination activity, and can completely convert the toluene into nontoxic CO at the temperature of 220-240 DEG C2And H2O, at the temperature, the elimination rate of the toluene is kept for 100 hours>90 percent, can completely convert the ethyl acetate into nontoxic CO at the temperature of 180-220 DEG C2And H2O, at the temperature, the elimination rate of ethyl acetate is kept within 100 hours>90 percent. The potassium permanganate used as the raw material for preparing the catalyst is low in price, the preparation process of the catalyst is simple, and other metals or noble metals are not loaded. The invention does not need to add any fuel and directly utilizes O in the air2Is an oxidant, and has the advantages of economical and practical raw materials, low energy consumption in the using process, simple and convenient operation, mild reaction conditions, capability of reducing secondary pollution, continuous work and the like.
Drawings
FIG. 1 is a Pt/Lu-Gd-delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention2XRD pattern of
FIG. 2 is a Pt/Lu-Gd-delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention2N of (A)2Adsorption/desorption curve diagram
FIG. 3 is a Pt/Lu-Gd-delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention2Catalytic combustion activity of toluene
FIG. 4 is a Pt/Lu-Gd-delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention2Catalytic combustion activity of ethyl acetate
FIG. 5 is a Pt/Lu-Gd-delta-MnO prepared in example 4 of the present invention2catalyst-I catalytic Combustion stability of catalyst to toluene
FIG. 6 is a Pt/Lu-Gd-delta-MnO prepared in example 4 of the present invention2-I catalyst stability to ethyl acetate catalytic combustion
Detailed Description
Example 1
(1) The preparation method of the catalyst provided by the invention comprises the following steps:
mixing polyvinyl alcohol PVA (polyvinyl alcohol-vinyl polymer, molecular formula (C)2H4O)n) Adding 50mL of distilled water to form a solution (0.5 wt%) and adding the solution into a three-neck flask, stirring the solution uniformly at 65 ℃, and then adding K2MnO4Adding to the above solution, K2MnO4The final concentration is 0.15mol/L, where n [ K ]2MnO4]: polyvinyl alcohol PVA 0.015 mol: 1g of the total weight of the composition. Then adding MnSO4Adding solution (0.10mol/L) into the above mixed solution, and stirring for 6 hr, wherein n [ KMnO ]4]：n[MnSO4]0.5 mol: 1mol, 15mL of concentrated nitric acid (5.0mol/L) is added dropwise at the same time, and a strong acid environment with pH 2 is kept at 5W/cm2Performing ultrasonic treatment for 1h, stirring for 1h, refluxing at 100 deg.C for 24h, vacuum filtering, washing with deionized water to neutrality, oven drying at 80 deg.C to obtain brown solid, and purifying with pure oxygen (O)2) Roasting at the medium temperature of 300 ℃ for 1h to obtain one-dimensional delta-MnO2。
20mL of lutetium nitrate Lu (NO)3)3·6H2O solution (0.001mol/L) and gadolinium nitrate Gd (NO)3)3·6H2Stirring and mixing the O solution (0.001mol/L) uniformly to form a mixed solution, wherein n [ Lu (NO)3)3]：n[Gd(NO3)3]1 mol: 1mol, and at 5W/cm2Carrying out intensity ultrasonic treatment for 1h, continuously stirring for 2h, and standing for later use. In addition, F127(Pluronic, polyoxyethylene, HO (C)) was reacted at 120 ℃2H4O)m(C3H6O)nH) Dissolving the powder in 20mL of distilled water and 20mL of ethanol to form a 0.5 wt% F127 solution, stirring until the F127 is completely dissolved, adding 1.0mL of HCl (36 wt%) solution, stirring for 1h, and adding the delta-MnO prepared above2To form a mixed slurry. Adding the rare earth mixed solution into delta-MnO2In the slurry, and at 5W/cm2The mixture was refluxed for 24 hours and the solution was evaporated off by rotary evaporation for 3 hours. Heating the obtained product to 300 ℃ at the speed of 1 ℃/min in pure oxygen atmosphere and roasting for 2 hours to finally obtain Lu-Gd/delta-MnO2And (c) a complex.
Ethylenediamine (en) was added to 50mL H of chloroplatinic acid2PtCl6Solution (5mmol L)-1) In which n is [ H ]2PtCl6]: n [ Ethylenediamine (en)]1 mol: 2mol, uniformly mixing and stirring to obtain Pt (en)2Cl2And (3) precursor solution. In addition, Lu-Gd/delta-MnO was added2To 50mL of Polyacrylic acid PAA (Polyacrylic acid, formula (C))3H4O2)n) In solution (1mg/L), wherein Lu-Gd/delta-MnO2: polyacrylic acid PAA ═ 1 g: 10mL, mixed well and stirred to homogeneity to form a suspension, and the concentration is 5W/cm2The intensity of (1) was sonicated for 1h and stirring was continued for 2 h. Mixing Pt (en)2Cl2Adding the precursor solution into Lu-Gd-delta-MnO2In which n [ Pt (en) ]2Cl2]：Lu-Gd-δ-MnO20.005 mol: 1g, stirred for 4 hours, then rotary evaporated for 3 hours to evaporate the solution to obtain a solid, filtered, washed with distilled water and finally dried at 60 ℃ for 12 hours to obtain a black solid. The solid obtained is reacted in H2(5％H2Ar) atmosphere in a tube furnace porcelain boat at 400 ℃ for 1h, and the heating rate is 5 ℃/min. After natural cooling to room temperature, the heat-treated sample was washed in HCl (37 wt%) for 10 h. Finally, centrifugally separating the sample, washing the sample to be neutral by using deionized water, then washing the sample by using ethanol, and drying the sample at 80 ℃ to obtain the obtained product Pt/Lu-Gd-delta-MnO2-I。
(2) And (4) evaluating the activity of the catalyst. The concentration of toluene or ethyl acetate is 500ppm, and the air flow space velocity is 60,000h-1. Gas chromatography TCD detection reaction tail gas CO2And CO, FID detects the content of toluene or ethyl acetate and other organic species. The temperature for eliminating the toluene (100 percent conversion of the toluene) by the catalyst prepared in the embodiment 1 of the invention through complete catalytic combustion is 220 ℃, the conversion rate of the toluene reaches 50 percent at 210 ℃, when the temperature is in the range of 190-220 ℃, the conversion rate of the toluene is linearly increased until reaching 100 percent, and the toluene is completely converted into CO in the catalytic combustion elimination reaction of the toluene2And H2O; the conversion rate of ethyl acetate reaches 50% when the reaction temperature is 150 ℃, the conversion rate of ethyl acetate reaches 100% when the reaction temperature is 180 ℃, and the reaction product only contains CO2And H2O。
Example 2
(1) The preparation method of the catalyst provided by the invention comprises the following steps:
mixing polyvinyl alcohol PVA (polyvinyl alcohol-vinyl polymer, molecular formula (C)2H4O)n) 70mL of distilled water was added to form a solution (0.7 wt%) which was added to a three-necked flask, stirred at 69 ℃ and then K was added thereto2MnO4Adding to the above solution, K2MnO4The final concentration is 0.30mol/L, where n [ K ]2MnO4]: polyvinyl alcohol PVA 0.03 mol: 1g of the total weight of the composition. Then adding MnSO4Adding solution (0.5mol/L) into the above mixed solution, and stirring for 7h, wherein n [ KMnO ]4]：n[MnSO4]17mL of concentrated nitric acid (5.3mol/L) was added dropwise thereto (0.7 mol: 1 mol), and the pH was maintained at 3 in a strongly acidic atmosphere at 7W/cm2Performing ultrasonic treatment for 1h, stirring for 1h, refluxing at 100 deg.C for 30h, vacuum filtering, washing with deionized water to neutrality, oven drying at 90 deg.C to obtain brown solid, and purifying with pure oxygen (O)2) Roasting at 350 ℃ for 2h to obtain one-dimensional delta-MnO2。
30mL of lutetium nitrate Lu (NO)3)3·6H2O solution (0.003mol/L) and gadolinium nitrate Gd (NO)3)3·6H2Stirring and mixing the O solution (0.003mol/L) uniformly to form a mixed solution, wherein n [ Lu (NO)3)3]：n[Gd(NO3)3]1 mol: 1mol, and at 7W/cm2Carrying out intensity ultrasonic treatment for 1h, continuously stirring for 4h, and standing for later use. In addition, F127(Pluronic, polyoxyethylene, HO (C)) was reacted at 130 deg.C2H4O)m(C3H6O)nH) Dissolving the powder in 30mL of distilled water and 30mL of ethanol to form a 1 wt% F127 solution, stirring until the F127 is completely dissolved, adding 1.0mL of HCl (36 wt%) solution, stirring for 3h, and adding the delta-MnO prepared above2To form a mixed slurry. Adding the rare earth mixed solution into delta-MnO2In the slurry, and at a rate of 7W/cm2The mixture was refluxed for 24 hours and the solution was evaporated off by rotary evaporation for 3 hours. Heating the obtained product to 300 ℃ at the speed of 1 ℃/min in pure oxygen atmosphere and roasting for 3 hours to finally obtain Lu-Gd/delta-MnO2Composite material。
Ethylenediamine (en) was added to 70mL H of chloroplatinic acid2PtCl6Solution (7mmol L)-1) In which n is [ H ]2PtCl6]: n [ Ethylenediamine (en)]1 mol: 2mol, uniformly mixing and stirring to obtain Pt (en)2Cl2And (3) precursor solution. In addition, Lu-Gd/delta-MnO was added2To 70mL of Polyacrylic acid PAA (Polyacrylic acid, formula (C))3H4O2)n) In solution (7mg/L) with Lu-Gd/delta-MnO2: polyacrylic acid PAA ═ 1 g: 10mL, mixed well and stirred to homogeneity to form a suspension, and the concentration is 7W/cm2The intensity of (1) was sonicated for 1h and stirring was continued for another 3 h. Mixing Pt (en)2Cl2Adding the precursor solution into Lu-Gd-delta-MnO2In which n [ Pt (en) ]2Cl2]：Lu-Gd-δ-MnO20.007 mol: 1g, stirred for 4 hours, then rotary evaporated for 3 hours to evaporate the solution to give a solid, filtered, washed with distilled water and finally dried at 70 ℃ for 12 hours to give a black solid. The solid obtained is reacted in H2(7％H2Ar) atmosphere in a tube furnace porcelain boat at 400 ℃ for 1h, and the heating rate is 7 ℃/min. After natural cooling to room temperature, the heat-treated sample was washed in HCl (37 wt%) for 10 h. Finally, centrifugally separating the sample, washing the sample to be neutral by using deionized water, then washing the sample by using ethanol, and drying the sample at 90 ℃ to obtain the obtained product Pt/Lu-Gd-delta-MnO2-II。
(2) And (4) evaluating the activity of the catalyst. The concentration of toluene or ethyl acetate is 500ppm, and the air flow space velocity is 60,000h-1. Gas chromatography TCD detection reaction tail gas CO2And CO, FID detects the content of toluene and other organic species. The temperature of the catalyst for completely catalyzing, burning and eliminating the toluene (100 percent conversion of the toluene) prepared in the embodiment 2 of the invention is 260 ℃, the conversion rate of the toluene reaches 50 percent at 235 ℃, when the temperature is in the range of 220-260 ℃, the conversion rate of the toluene is linearly increased until reaching 100 percent, and in the catalytic burning and eliminating reaction of the toluene, the toluene is completely converted into CO2And H2O; the conversion rate of the ethyl acetate reaches 50% when the reaction temperature is 180 ℃, the conversion rate of the ethyl acetate reaches 100% when the reaction temperature is 220 ℃, and only reaction products are obtainedCO2And H2O。
Example 3
(1) The preparation method of the catalyst provided by the invention comprises the following steps:
mixing polyvinyl alcohol PVA (polyvinyl alcohol-vinyl polymer, molecular formula (C)2H4O)n) Adding 90mL of distilled water to form a solution (1 wt%) and adding the solution into a three-neck flask, stirring the solution uniformly at 70 ℃, and then adding K2MnO4Adding to the above solution, K2MnO4The final concentration is 0.40mol/L, where n [ K ]2MnO4]: polyvinyl alcohol PVA 0.04 mol: 1g of the total weight of the composition. Then adding MnSO4Adding solution (0.5mol/L) into the above mixed solution, stirring for 9h, wherein n [ KMnO ]4]：n[MnSO4]0.9 mol: 1mol, and simultaneously dripping 20mL of concentrated nitric acid (6.0mol/L), maintaining a strong acid environment with pH value of 3 and controlling the pH value to be 9W/cm2Performing ultrasonic treatment for 2h, stirring for 2h, refluxing at 110 deg.C for 48h, vacuum filtering, washing with deionized water to neutrality, oven drying at 120 deg.C to obtain brown solid, and purifying with pure oxygen (O)2) Roasting at the medium temperature of 400 ℃ for 4h to obtain one-dimensional delta-MnO2。
50mL of lutetium nitrate Lu (NO)3)3·6H2O solution (0.004mol/L) and gadolinium nitrate Gd (NO)3)3·6H2Stirring and mixing the O solution (0.004mol/L) uniformly to form a mixed solution, wherein n [ Lu (NO)3)3]：n[Gd(NO3)3]1 mol: 1mol, and at 5W/cm2Carrying out intensity ultrasonic treatment for 2h, continuously stirring for 5h, and standing for later use. In addition, F127(Pluronic, polyoxyethylene, HO (C)) was reacted at 140 deg.C2H4O)m(C3H6O)nH) Dissolving the powder in 40mL of distilled water and 40mL of ethanol to form a 1.5 wt% F127 solution, stirring until the F127 is completely dissolved, adding 1.3mL of HCl (38 wt%) solution, stirring for 4h, and adding the delta-MnO prepared above2To form a mixed slurry. Adding the rare earth mixed solution into delta-MnO2In the slurry, and at 9W/cm22h, stirring for a further 5h, refluxing the mixture for 24h, and rotary evaporating for 4hThe solution was evaporated. Heating the obtained product to 400 ℃ at the speed of 2 ℃/min in pure oxygen atmosphere, and roasting for 4 hours to finally obtain Lu-Gd/delta-MnO2And (c) a complex.
Ethylenediamine (en) was added to chloroplatinic acid 90mL H2PtCl6Solution (9mmol L)-1) In which n is [ H ]2PtCl6]: n [ Ethylenediamine (en)]1 mol: 3mol, uniformly mixing and stirring to obtain Pt (en)2Cl2And (3) precursor solution. In addition, Lu-Gd/delta-MnO was added2To 90mL of Polyacrylic acid PAA (Polyacrylic acid, formula (C))3H4O2)n) In solution (13mg/L) with Lu-Gd/delta-MnO2: polyacrylic acid PAA ═ 1 g: 10mL, mixed well and stirred to form a suspension, and the concentration is 9W/cm2The intensity of (2) was sonicated for 2h and stirring was continued for another 6 h. Mixing Pt (en)2Cl2Adding the precursor solution into Lu-Gd-delta-MnO2In which n [ Pt (en) ]2Cl2]：Lu-Gd-δ-MnO20.009 mol: 2g, stirred for 4 hours, then rotary evaporated for 4 hours to evaporate the solution to give a solid, filtered, washed with distilled water and finally dried at 80 ℃ for 24 hours to give a black solid. The solid obtained is reacted in H2(9％H2Ar) atmosphere in a tube furnace porcelain boat at 500 ℃ for 3h, and the heating rate is 9 ℃/min. After natural cooling to room temperature, the heat-treated sample was washed in HCl (37 wt%) for 12 h. Finally, centrifugally separating the sample, washing the sample to be neutral by using deionized water, then washing the sample by using ethanol, and drying the sample at 90 ℃ to obtain the obtained product Pt/Lu-Gd-delta-MnO2-III。
(2) And (4) evaluating the activity of the catalyst. The concentration of benzene or ethyl acetate is 1000ppm, and the air flow space velocity is 100,000h-1. Gas chromatography TCD detection reaction tail gas CO2And CO, FID detects the content of toluene and other organic species. The temperature for eliminating the toluene (100 percent conversion of the toluene) by the catalyst prepared in the embodiment 3 of the invention through complete catalytic combustion is 240 ℃, the conversion rate of the toluene reaches 50 percent at 210 ℃, when the temperature is in the range of 200-240 ℃, the conversion rate of the toluene is linearly increased until reaching 100 percent, and the toluene is completely converted into CO in the catalytic combustion elimination reaction of the toluene2And H2O; the conversion rate of ethyl acetate reaches 50% at the reaction temperature of 160 ℃, the conversion rate of ethyl acetate reaches 100% at the reaction temperature of 200 ℃, and the reaction product only contains CO2And H2O。
Example 4
(1) The preparation method of the catalyst provided by the invention comprises the following steps:
mixing polyvinyl alcohol PVA (polyvinyl alcohol-vinyl polymer, molecular formula (C)2H4O)n) Adding 100mL of distilled water to form a solution (1 wt%) and adding the solution into a three-neck flask, stirring the solution uniformly at 75 ℃, and then adding K2MnO4Adding to the above solution, K2MnO4The final concentration is 0.50mol/L, where n [ K ]2MnO4]: polyvinyl alcohol PVA 0.05 mol: 1g of the total weight of the composition. Then adding MnSO4Adding the solution 0.75mol/L into the above mixed solution, and stirring for 10h, wherein n [ KMnO ]4]：n[MnSO4]1.0 mol: 1mol, simultaneously dripping 20mL of concentrated nitric acid 6.0mol/L, keeping a strong acid environment with pH value of 3, and adding 10W/cm2Performing ultrasonic treatment for 2h, stirring for 2h, refluxing at 110 deg.C for 48h, vacuum filtering, washing with deionized water to neutrality, oven drying at 120 deg.C to obtain brown solid, and purifying with pure oxygen (O)2) Roasting at the medium temperature of 400 ℃ for 4h to obtain one-dimensional delta-MnO2。
50mL of lutetium nitrate Lu (NO)3)3·6H2O solution (0.005mol/L) and gadolinium nitrate Gd (NO)3)3·6H2Stirring and mixing the O solution (00.005mol/L) uniformly to form a mixed solution, wherein n [ Lu (NO)3)3]：n[Gd(NO3)3]1 mol: 1mol, and at 10W/cm2Carrying out intensity ultrasonic treatment for 2h, continuously stirring for 6h, and standing for later use. In addition, F127(Pluronic, polyoxyethylene, HO (C)) was reacted at 140 deg.C2H4O)m(C3H6O)nH) Dissolving the powder in 50mL of distilled water and 50mL of ethanol to form a 2 wt% F127 solution, stirring until the F127 is completely dissolved, adding 1.5mL of HCl (38 wt%) solution, stirring for 5h, and adding the delta-MnO prepared above2To form a mixed slurry. Mixing the above rare earth solutionsAdding to delta-MnO2In the slurry, and at a rate of 10W/cm2The mixture was refluxed for 24 hours and the solution was evaporated by rotary evaporation for 4 hours. Heating the obtained product to 400 ℃ at the speed of 2 ℃/min in pure oxygen atmosphere, and roasting for 4 hours to finally obtain Lu-Gd/delta-MnO2And (c) a complex.
Ethylenediamine (en) was added to chloroplatinic acid 100mL H2PtCl6Solution (10mmol L)-1) In which n is [ H ]2PtCl6]: n [ Ethylenediamine (en)]1 mol: 3mol, uniformly mixing and stirring to obtain Pt (en)2Cl2And (3) precursor solution. In addition, Lu-Gd/delta-MnO was added2To 100mL of Polyacrylic acid PAA (Polyacrylic acid, formula (C))3H4O2)n) In solution (15mg/L), wherein Lu-Gd/delta-MnO2: polyacrylic acid PAA ═ 1 g: 10mL, thoroughly mixed and stirred to form a suspension, and the concentration is 10W/cm2The intensity of (2) was sonicated for 2h and stirring was continued for another 6 h. Mixing Pt (en)2Cl2Adding the precursor solution into Lu-Gd-delta-MnO2In which n [ Pt (en) ]2Cl2]：Lu-Gd-δ-MnO20.01 mol: 2g, stirred for 4 hours, then rotary evaporated for 4 hours to evaporate the solution to give a solid, filtered, washed with distilled water and finally dried at 80 ℃ for 24 hours to give a black solid. The solid obtained is reacted in H2(10％H2Ar) atmosphere in a tube furnace porcelain boat at 500 ℃ for 3h, and the heating rate is 10 ℃/min. After natural cooling to room temperature, the heat-treated sample was washed in HCl (37 wt%) for 12 h. Finally, centrifugally separating the sample, washing the sample to be neutral by using deionized water, then washing the sample by using ethanol, and drying the sample at 100 ℃ to obtain the obtained product Pt/Lu-Gd-delta-MnO2-IV。
(2) And (4) evaluating the activity of the catalyst. The concentration of benzene or ethyl acetate is 1000ppm, and the air flow space velocity is 100,000h-1. Gas chromatography TCD detection reaction tail gas CO2And CO, FID detects the content of toluene and other organic species. The temperature for eliminating toluene (100 percent conversion of toluene) by the complete catalytic combustion of the catalyst prepared in the embodiment 4 of the invention is 250 ℃, the conversion rate of toluene reaches 50 percent at 230 ℃, and when the temperature is inThe conversion rate of toluene is increased linearly to 100% in the range of 150-230 ℃, and toluene is completely converted into CO in the catalytic combustion elimination reaction of toluene2And H2O; the conversion rate of ethyl acetate reaches 50% at the reaction temperature of 170 ℃, the conversion rate of ethyl acetate reaches 100% at the reaction temperature of 210 ℃, and the reaction product only contains CO2And H2O。
Claims (3)
1. A preparation method of a platinum catalyst loaded by a lutetium-gadolinium modified delta-manganese oxide compound is characterized by comprising the following steps:
adding polyvinyl alcohol PVA into 50-100mL of distilled water to form 0.5-1 wt% solution, adding the solution into a three-neck flask, uniformly stirring at 65-75 ℃, and then adding K2MnO4Adding to the above solution, K2MnO4The final concentration is 0.15 mol/L-0.50 mol/L, wherein n [ K ]2MnO4]: polyvinyl alcohol PVA ═ (0.015 to 0.05) mol: 1g of a compound; then MnSO with the concentration of 0.10 mol/L-0.75 mol/L is added4Adding the solution into the mixed solution, and stirring for 6-10 h, wherein n [ KMnO ]4]：n[MnSO4](0.5 to 1.0) mol: 1mol, simultaneously dripping 15-20mL of concentrated nitric acid with the concentration of 5.0-6.0mol/L, keeping the pH value at 2-3 in strong acid environment, and keeping the pH value at 5-10W/cm2Performing ultrasonic treatment at the intensity for 1-2 h, continuously stirring for 1-2 h, refluxing for 24-48h at 100-110 ℃, performing suction filtration, washing to be neutral by using deionized water, drying at 80-120 ℃ to obtain brown solid, and roasting the brown solid in pure oxygen at the temperature of 300-400 ℃ for 1-4 h to obtain one-dimensional delta-MnO2；
20-50mL of lutetium nitrate Lu (NO) with the concentration of 0.001-0.005 mol/L3)3·6H2O solution and gadolinium nitrate Gd (NO) with the concentration of 0.001-0.005 mol/L3)3·6H2Stirring and mixing the O solution uniformly to form a mixed solution, wherein n [ Lu (NO)3)3]：n[Gd(NO3)3]1 mol: 1mol, and at a rate of 5-10W/cm2Carrying out intensity ultrasound for 1-2 h, then continuously stirring for 2-6 h, and standing for later use; dissolving polyoxyethylene F127 powder in 20-50mL distilled water and 20-50mL ethanol at 120-140 deg.C to obtain 0.5-2 wt% F127 solution, and stirring until F127 is completely dissolvedDissolving, adding 1.0-1.5ml of hydrochloric acid solution with the concentration of 36-38 wt%, continuously stirring for 1-5h, and adding the prepared delta-MnO2Forming a mixed slurry; adding the rare earth mixed solution into delta-MnO2In the slurry, and at a rate of 5-10W/cm2Carrying out ultrasonic treatment for 1-2 h, continuously stirring for 2-6 h, refluxing the mixture for 24h, and carrying out rotary evaporation for 3-4 h to evaporate the solution; the obtained product is heated to 300-400 ℃ at the speed of 1-2 ℃/min in pure oxygen atmosphere and is roasted for 2-4 hours to finally obtain Lu-Gd/delta-MnO2A complex;
adding ethylenediamine (en) to 50-100mL of H2PtCl6Solution of H2PtCl6The solution concentration is 5-10mmol L-1In which n [ H ]2PtCl6]: n [ Ethylenediamine (en)]1 mol: 2-3mol, and uniformly mixing and stirring to obtain Pt (en)2Cl2Precursor solution; in addition, Lu-Gd/delta-MnO was added2Adding the mixture into 50-100mL polyacrylic acid PAA solution with the concentration of 1-15 mg/L, wherein Lu-Gd/delta-MnO2: polyacrylic acid PAA ═ 1 g: 10mL, thoroughly mixing and stirring to form a suspension, and stirring at 5-10W/cm2Carrying out ultrasonic treatment for 1-2 h, and then continuously stirring for 2-6 h; mixing Pt (en)2Cl2Adding the precursor solution into Lu-Gd-delta-MnO2In which n [ Pt (en) ]2Cl2]：Lu-Gd-δ-MnO2(0.005-0.01) mol: 1-2g, stirring for 4 hours, then carrying out rotary evaporation for 3-4 hours to evaporate the solution to obtain a solid, filtering, washing with distilled water, and finally drying at 60-80 ℃ for 12-24 hours to obtain a black solid; the solid obtained is reacted in H2Treating in a tube furnace porcelain boat with an Ar mixed atmosphere at 400-500 ℃ for 1-3H2H in mixed Ar atmosphere25-10% of volume percentage; the heating rate is 5-10 ℃/min; naturally cooling to room temperature, and washing the heat-treated sample in a hydrochloric acid solution for 10-12 h; finally, centrifugally separating the sample, washing the sample to be neutral by using deionized water, then washing the sample by using ethanol, and drying the sample at 80-100 ℃ to obtain the obtained product Pt/Lu-Gd-delta-MnO2。
2. According to claim 1The application of the catalyst prepared by the preparation method in eliminating volatile organic compounds is characterized in that: putting the catalyst in a continuous flow fixed bed device, and introducing mixed gas of toluene or ethyl acetate and air to react; the reaction pressure is normal pressure-2 MPa, and the reaction space velocity is 60,000h-1～100,000h-1In the mixed gas of air and toluene or the mixed gas of air and ethyl acetate, the concentration of toluene or ethyl acetate is 500 ppm-1000 ppm, and the reaction temperature is 25-300 ℃.
3. Use according to claim 2, characterized in that: the air in the reaction mixed gas is prepared standard gas, N2：O2The volume ratio is 79: 21.
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| CN113648997A (en) * | 2021-08-11 | 2021-11-16 | 北京工业大学 | δ-MnO2Method and application of loaded graphene oxide Bi-Pd composite catalyst |
| CN115347198B (en) * | 2021-05-12 | 2024-05-17 | 昆明理工大学 | Method for preparing N-rGO supported MnO nano catalyst by using complexing agent |
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| CN115347198B (en) * | 2021-05-12 | 2024-05-17 | 昆明理工大学 | Method for preparing N-rGO supported MnO nano catalyst by using complexing agent |
| CN113648998A (en) * | 2021-08-11 | 2021-11-16 | 北京工业大学 | δ-MnO2Method and application of loaded graphene oxide and Ag-Gd composite catalyst |
| CN113648997A (en) * | 2021-08-11 | 2021-11-16 | 北京工业大学 | δ-MnO2Method and application of loaded graphene oxide Bi-Pd composite catalyst |
| CN113648998B (en) * | 2021-08-11 | 2023-10-20 | 北京工业大学 | δ-MnO 2 Method for loading graphene oxide and Ag-Gd composite catalyst and application |
| CN113648997B (en) * | 2021-08-11 | 2023-11-24 | 北京工业大学 | δ-MnO 2 Method for loading graphene oxide Bi-Pd composite catalyst and application |
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