CN112844394A - CuO-CeO2Preparation method of supported catalyst and application of supported catalyst in tail gas NOxAnd application in anaerobic elimination of CO - Google Patents
CuO-CeO2Preparation method of supported catalyst and application of supported catalyst in tail gas NOxAnd application in anaerobic elimination of CO Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 230000008030 elimination Effects 0.000 title claims abstract description 6
- 238000003379 elimination reaction Methods 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000012716 precipitator Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 150000000703 Cerium Chemical class 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005234 chemical deposition Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 25
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000000746 purification Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019017 PtRh Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011937 reductive transformation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/70—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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/23—
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- B01J35/613—
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- B01J35/615—
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- B01J35/643—
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- B01J35/647—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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 discloses CuO-CeO2A preparation method of a supported catalyst and application thereof in the anaerobic elimination of NO and CO in tail gas. By using hydrothermal synthesis and chemical deposition methods, the uniform loading of 3-7 nm-sized nano particles is successfully realized, and the ultra-stable CuO-CeO is formed2Catalyst and process for preparing sameAnd then, a nano-load catalyst is utilized to perform reduction and conversion research of CO on NO under an anaerobic condition. Compared with the prior art, the catalyst has extremely high catalytic activity, strong thermal stability, high conversion rate of polluted gas, simple preparation method and easy operation, can be suitable for industrial production, can eliminate two main automobile tail gas pollutants simultaneously, and shows extremely strong industrial application prospect.
Description
Technical Field
The present invention belongs to CO and NO in tail gas of motor vehiclexIn particular to a nano CuO-CeO2Preparation method of supported catalyst and CO to NO under anaerobic conditionxThe use of the reductive transformation of (1).
Background
The combustion of fossil fuels meets the high-speed development of modern industry and simultaneously emits a large amount of nitrogen oxides, and the nitrogen oxides polluting air are mainly NO and NO2Presence, with NOxAnd (4) showing. Under high temperature combustion conditions, NOxMainly in the form of NO, initially emitted NOxThe medium NO accounts for about 95%. However, NO is very reactive with oxygen in the air to form NO2So NO in the atmospherexGenerally with NO2Exist in the form of (1). NO and NO in air2Equilibrium is reached by interconversion through photochemical reactions. In the presence of high temperature or cloud2Further reacting with water molecule to form nitric acid (HNO) as the second important acid in acid rain3). In the presence of a catalyst, in addition to suitable gas phase conditions, NO2The conversion to nitric acid is accelerated.
The motor vehicle exhaust gas comprises Hydrocarbon (HC), carbon monoxide (CO), and Nitrogen Oxide (NO)x) Sulfide (SO)2) Soot, aldehydes, carcinogens, and particulates, among others. Wherein HC, CO and NOxIs the main component of the tail gas pollutant of urban motor vehicles. These pollutants cause serious environmental problems such as acid rain, smog formation, global warming and ozone layer weakening, high PM2.5Appearance of haze weather of value. Pollution control of automobile exhaust becomes one of important means for improving air quality in cities, and air pollution is a worldwide problem to be solved urgently. Nitrogen oxides and carbon monoxide, which are major atmospheric pollutants and whose environmental and human harm is not negligible, are netThe chemical treatment has very important practical significance.
The automobile exhaust purification technology mainly comprises two aspects: on one hand, the generation of harmful substances, namely the internal purification, is reduced as much as possible, the fuel quality is improved, and the combustion condition of an engine is improved; another aspect is to eliminate the harmful gas generated, i.e. to purify the gas outside the machine. The internal purification mode can only reduce the generation amount of harmful gas to a certain extent, but cannot completely remove the generated harmful gas. Therefore, an external purification technique must be employed. The purification outside the engine is to convert harmful gas components into harmless gas by using a catalytic purifier before tail gas is discharged out of a cylinder and enters the atmosphere. Because the generation of harmful gas is inevitable in the combustion process of gasoline, the thermal reactor has limited conversion of CO and CH and can not convert NOxThe conversion is carried out, so the purification technology outside the machine is particularly important. The catalytic purification is one of the most fundamental and effective methods for solving the problem of tail gas pollution during the purification outside the machine.
CO elimination and NO conversion to NO under oxygen-rich conditions as mentioned in CN102423629A2The removal techniques of (2) still require the presence of oxygen.
CN102941088B proposes a method for preparing a catalyst for eliminating CO, CH, NOx and PM at the same time, but the catalyst composition is complicated and noble metals are used.
CN101384335A mentions a flue gas device for eliminating CO and NO, and focuses on the optimization of a reaction device.
CN101468295A mentions that with respect to a combined catalyst and a purification method capable of simultaneously eliminating four main pollutants in diesel engine exhaust, perovskite, molecular sieve, alumina and other aspects of supported catalysts are prepared, and oxygen is added in a reaction test.
CN1091650C proposes a catalyst for catalytic reduction of nitrogen monoxide by carbon monoxide, which consists of an active component, CoMMgAl, and a component, PtRh/CoMMgAl, where M ═ Cu, Cr, and Ni, and noble metals are used in the test reaction.
CN101474553A discloses a three-way catalyst for purifying and treating lean-burn engine exhaust and a preparation method thereof, wherein the catalyst contains oxides of zirconium, cerium and copper, and oxygen is added in the catalyst test. 300 ℃ and 350 ℃, NO conversion reaches more than 70 percent.
CN100391580C mentions a catalyst for simultaneously reducing nitrogen oxides and eliminating soot particles, the catalyst uses a mixture of activated carbon and cerium oxide as a carrier, and copper is used as an active component for loading. The reaction activity has 46.5 to 100 percent conversion change at 400 ℃ and 500 ℃.
CN102049257B mentions CO-reduction of SO2And NO, with TiO2-Al2O3The composite is used as a carrier, adopts transition metal as an active component to be loaded on the composite, and is used for treating SO at 320 DEG C2The conversion rate of NO and the reaction temperature is close to 100 percent, and the reaction temperature is higher.
In summary, the catalytic reduction of NO by CO is an important reaction in three-way catalytic purification. The dispersion degree of the CuO as an active component, the oxygen storage and release capacity of the carrier and the interaction between the active component and the carrier influence the final catalytic effect, and the catalyst is difficult to realize the dispersion degree, the oxygen storage and release capacity and the interaction between the active component and the carrier.
Disclosure of Invention
The invention aims to provide a nano CuO-CeO2Supported catalyst for CO to NO under oxygen-free conditionxReducing and converting, simultaneously eliminating CO and NOx of pollution gases, and generating nontoxic and harmless CO2And N2. The price of the raw materials for preparing the catalyst is relatively low, the preparation process is simple and easy to implement, and the catalyst has high conversion rate and strong stability.
The invention provides a nano CuO-CeO2The preparation method of the supported catalyst comprises the steps of adopting an oxide of rare earth metal cerium as a carrier and an oxide of non-noble metal copper as an activity regulation component, wherein nano particles of the copper oxide are highly dispersed on the surface of the carrier, and the content of the copper oxide is 1-500%;
the preparation method comprises the following steps;
(1)CeO2the preparation of (1): dissolving cerium salt and a precipitator in a solvent A according to a mass ratio of 1 (1-100) to form a mixed solution A, then placing the mixed solution A in a reaction kettle and transferring the mixed solution A into an oven, setting the temperature range of the oven as 100-300 ℃, after hydrothermal reaction for 4-20h, cooling the temperature to room temperature to obtain the cerium-doped cerium oxideThe white suspension was filtered, washed and dried to obtain white cerium oxide powder.
(2)CuO-CeO2The preparation of (1): subjecting the CeO to2Dispersing the white powder in the aqueous solution, and then adding copper salt to obtain a mixed solution B; placing the mixed solution B in water bath at 30-80 ℃, stirring at constant temperature for 1-3h, filtering, washing and drying to obtain CuO-CeO2；
(3)CuO-CeO2Calcining: mixing CuO-CeO2Calcining in a muffle furnace for 1-4 h; the calcination temperature is 200-700 ℃.
Based on the technical scheme, the preferable mass ratio of the cerium salt to the precipitator is 1: 1-100.
Based on the technical scheme, the cerium salt is preferably cerium sulfate, cerium nitrate and cerium trichloride.
Based on the technical scheme, preferably, the precipitating agent is urea, sodium carbonate, potassium carbonate, light sodium carbonate and sodium hydroxide.
Based on the technical scheme, preferably, the copper salt and the CeO2The mass ratio of the carrier is 1 (1-500).
Based on the technical scheme, the copper salt is preferably copper chloride, copper nitrate or copper sulfate.
The invention also provides the CuO-CeO prepared by the method2Supported catalyst, said CuO-CeO2The supported pore diameter is 1.5-3nm, and the surface area is 73-210m2And/g, the size of the CuO nano-particles is 3-7 nm.
Based on the above technical scheme, it is preferable that CuO nanoparticles are dispersed in CeO2The mass of CuO on the surface of the carrier is CeO21-500% of the mass.
The invention also provides the CuO-CeO2Application of supported catalyst, CuO-CeO2When the supported catalyst is applied to reduction elimination of CO and NO, the conversion rate of CO is over 85 percent, the conversion rate of NO is over 95 percent, and N of NO is2The selectivity is over 80 percent.
Advantageous effects
1. The change of the cerium oxide carrier prepared by the method has little influence on the catalytic performance, and the subsequent commercial production is easy to realize.
2. The invention disperses the CuO in the CeO in nanometer2A carrier surface.
3. In the catalyst obtained by the invention, a large amount of CuO is highly dispersed on cerium oxide, and the catalyst is not easy to sinter at high temperature and has good thermal stability.
4. The catalyst prepared by the method has high low-temperature activity, good selectivity and large reaction window.
5. The invention realizes the simultaneous conversion of various pollution gases into nontoxic and harmless CO2And N2。
Drawings
FIG. 1 is a view showing CuO-CeO prepared in example 12Catalyst and CeO2XRD pattern of the support.
FIG. 2 is a view showing CuO-CeO prepared in example 12Catalyst and CeO2H of the vector2-a TPR map.
Detailed Description
Example 1
(1) And (2) forming a mixed solution by 1g and 3g of cerium nitrate and sodium carbonate, then placing the mixed solution in a reaction kettle, transferring the mixed solution into an oven, setting the temperature interval of the oven at 120 ℃, keeping the temperature for 10 hours, and filtering, washing and drying the obtained white suspension when the temperature is reduced to room temperature to obtain white cerium oxide powder (carrier).
(2) The 1gCeO obtained in (1) is used2The white powder was dispersed in an aqueous solution, and then 0.1g of copper nitrate was added thereto. The precipitator is the same as the precipitator in the step (1), the mixed solution is placed in a water bath with the temperature of 70 ℃, the constant temperature stirring is carried out for 2 hours, then the mixed solution after the water bath is filtered, washed and dried, and 10 percent CuO to 90 percent CeO is obtained2。
(3) And (3) placing the material (2) in a muffle furnace to be calcined for 2 hours at the temperature of 200 ℃. Finally obtaining 10 percent of CuO to 90 percent of CeO2Designated as CuCe-1.
FIG. 1 is a view showing CuO-CeO prepared in example 12Catalyst and CeO2The XRD pattern of the support, where no peak of CuO is seen, indicates that CuO is highly dispersed and the particles are extremely small.
FIG. 2 is a view showing CuO-CeO prepared in example 12Catalyst and CeO2H of the vector2TPR diagram, after CuO is added, a reduction peak appears at a lower temperature, which shows that the redox capability is improved after CuO nano-particles are added, and the activity of the catalyst is enhanced.
Example 2
(1) And (2) forming a mixed solution by 1g and 3g of cerium nitrate and sodium bicarbonate, then placing the mixed solution in a reaction kettle, transferring the mixed solution into an oven, setting the temperature interval of the oven at 120 ℃, keeping the temperature for 10 hours, and filtering, washing and drying the obtained white suspension when the temperature is room temperature to obtain white cerium oxide powder (carrier).
(2) The 1gCeO obtained in (1) is used2The white powder was dispersed in an aqueous solution, and then 1g of copper nitrate was added thereto. The precipitator is the same as the precipitator in the step (1), the mixed solution is placed in a water bath with the temperature of 70 ℃, the constant temperature stirring is carried out for 2 hours, then the mixed solution after the water bath is filtered, washed and dried, and the 50 percent CuO to 50 percent CeO is obtained2。
And (3) placing the material (2) in a muffle furnace to be calcined for 2 hours, wherein the calcination temperature is 250 ℃. Finally obtaining 50 percent of CuO to 50 percent of CeO2Designated as CuCe-2.
Example 3
And (2) forming a mixed solution by 1g and 3g of cerium nitrate and potassium carbonate, then placing the mixed solution in a reaction kettle, transferring the mixed solution into an oven, setting the temperature interval of the oven at 120 ℃, keeping the temperature for 10 hours, and filtering, washing and drying the obtained white suspension when the temperature is room temperature to obtain white cerium oxide powder (carrier).
The 1gCeO obtained in (1) is used2The white powder was dispersed in an aqueous solution, and 4g of copper nitrate was then added thereto. The precipitator is the same as the precipitator in the step (1), the mixed solution is placed in a water bath with the temperature of 70 ℃, the constant temperature stirring is carried out for 2 hours, then the mixed solution after the water bath is filtered, washed and dried, and 80 percent CuO to 20 percent CeO is obtained2。
And (3) placing the material (2) in a muffle furnace to be calcined for 2 hours, wherein the calcination temperature is 300 ℃. Finally obtaining 80 percent CuO-20 percent CeO2It is designated as CuCe-3.
Example 4
The catalyst CuCe-1 of example 1 was filledFilling the mixture into a quartz tube type resistance furnace, introducing nitrogen for 10 minutes, and then beginning to introduce NO and NO2Mixed gas of CO (9% by volume of CO, 5% by volume of NO, NO)22% by volume, the remainder being nitrogen), then entering a reaction device, and detecting tail gas by gas chromatography. The catalytic activity of the catalyst at 100-300 ℃ is evaluated by adopting a temperature programming control technology in the reaction, the diameter of the tubular furnace is 3cm, and the gas flow rate is 40 mL/min. NO conversion rate reaches 100% at 210 ℃, NO2The conversion rate reaches 98 percent, the CO conversion rate reaches 98 percent, and NO is applied to N2Selectivity of (3) to 100%, NO2For N2The selectivity of (A) is up to 95%.
Example 5
The catalyst CuCe-2 in the example 2 is filled in a quartz tube type resistance furnace, nitrogen is firstly introduced for 10 minutes, and then NO and NO are introduced2Mixed gas of CO (9% by volume of CO, 5% by volume of NO, NO)22% by volume, the remainder being nitrogen), then entering a reaction device, and detecting tail gas by gas chromatography. The catalytic activity of the catalyst at 100-300 ℃ is evaluated by adopting a temperature programming control technology in the reaction, the diameter of the tubular furnace is 3cm, and the gas flow rate is 40 mL/min. NO conversion rate of 90% at 250 deg.C2The conversion rate reaches 95 percent, the CO conversion rate reaches 94 percent, and NO is applied to N2The selectivity of (A) is up to 95%, NO2For N2The selectivity of the catalyst reaches 92 percent.
Example 6
The catalyst CuCe-3 in the example 3 is filled in a quartz tube type resistance furnace, nitrogen is firstly introduced for 10 minutes, and then NO and NO are introduced2Mixed gas of CO (9% by volume of CO, 5% by volume of NO, NO)22% by volume, the remainder being nitrogen), then entering a reaction device, and detecting tail gas by gas chromatography. The catalytic activity of the catalyst at 100-300 ℃ is evaluated by adopting a temperature programming control technology in the reaction, the diameter of the tubular furnace is 3cm, and the gas flow rate is 40 mL/min. The NO conversion rate reaches 95 percent at 210 ℃, and NO2The conversion rate reaches 92 percent, the CO conversion rate reaches 93 percent, and NO is applied to N2Selectivity of (3) to 100%, NO2For N2The selectivity of (A) is up to 97%.
Claims (9)
1. Nano CuO-CeO2A preparation method of the supported catalyst, which is characterized in that;
the preparation method comprises the following steps;
(1)CeO2the preparation of (1): dissolving cerium salt and a precipitator in a solvent A to form a mixed solution A, carrying out hydrothermal reaction on the mixed solution A at the temperature of 100 ℃ and 300 ℃ for 4-20h, filtering, washing and drying to obtain cerium oxide powder;
(2)CuO-CeO2the preparation of (1): subjecting the CeO to2Dispersing the powder in an aqueous solution, and then adding copper salt to obtain a mixed solution B; stirring the mixed solution B at 30-80 ℃ for 1-3h, filtering, washing and drying to obtain CuO-CeO2；
(3)CuO-CeO2Calcining: mixing CuO-CeO2Calcining in a muffle furnace for 1-4 h; the calcination temperature is 200-700 ℃.
2. The method for preparing a supported catalyst according to claim 1, wherein the mass ratio of the cerium salt to the precipitant is 1:1 to 100.
3. The method of claim 1, wherein the cerium salt is selected from the group consisting of cerium sulfate, cerium nitrate, and cerium trichloride.
4. The method for preparing the supported catalyst according to claim 1, wherein the precipitant is urea, sodium carbonate, potassium carbonate, light sodium carbonate, or sodium hydroxide.
5. The method for preparing a supported catalyst according to claim 1, wherein the copper salt is mixed with CeO2The mass ratio of (A) to (B) is 1: 1-500.
6. The method of claim 1, wherein the copper salt is selected from the group consisting of copper chloride, copper nitrate, and copper sulfate.
7. CuO-CeO prepared by the method of any one of claims 1 to 62The supported catalyst is characterized in that the CuO-CeO2The supported pore diameter is 1.5-3nm, and the surface area is 73-210m2And/g, the size of the CuO nano-particles is 3-7 nm.
8. The CuO-CeO of claim 72The supported catalyst is characterized in that CuO nano-particles are dispersed in CeO2The mass of CuO on the surface of the carrier is CeO21-500% of the mass.
9. The CuO-CeO according to claim 7 or 82The application of the supported catalyst is characterized in that the supported catalyst is CuO-CeO2The supported catalyst is applied to reduction elimination of CO and NO, the conversion rate of CO is more than 85 percent, the conversion rate of NO is more than 95 percent, and N of NO is2The selectivity is over 80 percent.
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