CN113694933A - High-entropy co-doped low-temperature SCR denitration catalyst and preparation method and application thereof - Google Patents
High-entropy co-doped low-temperature SCR denitration catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005751 Copper oxide Substances 0.000 claims abstract description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 16
- 230000010355 oscillation Effects 0.000 claims description 14
- 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 12
- 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 description 12
- 239000002245 particle Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 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 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims 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 description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003546 flue gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 21
- 229910005855 NiOx Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910001960 metal nitrate Inorganic materials 0.000 description 8
- 229910003320 CeOx Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
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- 238000002791 soaking Methods 0.000 description 4
- 229910016978 MnOx Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910016553 CuOx Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000006698 induction Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 229910001930 tungsten oxide 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
- B01J23/002—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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J23/8892—Manganese
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
Abstract
The invention discloses a high-entropy co-doped low-temperature SCR denitration catalyst and a preparation method and application thereof, the catalyst is prepared by adopting an impregnation method, biochar or anatase type nano titanium dioxide is used as a carrier, high-entropy co-doped nano particles are loaded on the surface of the biochar or anatase type nano titanium dioxide and are used as active components, the high-entropy co-doped nano particles are prepared by mixing iron oxide, manganese oxide, cerium oxide, copper oxide and nickel oxide in equal molar ratio, and the loading capacity of the high-entropy co-doped nano particles is 5% -30%. According to the invention, the denitration activity of the catalyst is improved through the interaction between the high-entropy oxide nanoparticles and the carrier; the SCR activity of the catalyst is over 90 percent when ammonia is used as a reducing agent and the temperature is 120-180 ℃.
Description
Technical Field
The invention relates to the technical field of environmental protection and environmental catalysis, in particular to a high-entropy co-doped low-temperature SCR denitration catalyst and a preparation method and application thereof.
Background
With the acceleration of industrialized pace in China, atmospheric pollution has become an important problem facing the current environment. Among the numerous atmospheric pollutants, Nitric Oxide (NO), which can produce acid rain, cause ozone layer destruction and bring about bad weather such as photochemical smog and hazex) The method becomes an important factor influencing ecological environment and sustainable development of economic society, and is widely concerned by society in recent years.
Selective Catalytic Reduction (SCR) technology is currently controlling Nitrogen Oxides (NO)x) The most effective and widely applied industrialized denitration technology is provided. Aiming at the characteristics of low flue gas temperature in non-electric power industries such as steel sintering/pelletizing flue gas temperature of 120-.
Disclosure of Invention
The first purpose of the invention is to provide a high-entropy co-doped low-temperature SCR denitration catalyst.
The second purpose of the invention is to provide a preparation method of the high-entropy co-doped low-temperature SCR denitration catalyst.
The third purpose of the invention is to provide the application of the high-entropy co-doped low-temperature SCR denitration catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a high-entropy co-doped low-temperature SCR denitration catalyst, which takes biochar or anatase type nano titanium dioxide as a carrier, and high-entropy co-doped nano particles loaded on the surface of the biochar or anatase type nano titanium dioxide as an active component, wherein the high-entropy co-doped nano particles are prepared by mixing iron oxide, manganese oxide, cerium oxide, copper oxide and nickel oxide in equal molar ratio, and the loading amount of the high-entropy co-doped nano particles is 5% -30%.
In a second aspect, the invention also provides a preparation method of the high-entropy co-doped low-temperature SCR denitration catalyst.
(1) Respectively weighing equal molar amounts of ferric nitrate, manganese nitrate, cerium nitrate, copper nitrate and nickel nitrate, adding into a certain amount of absolute ethyl alcohol together, and performing ultrasonic oscillation to completely dissolve the materials to obtain a precursor solution;
(2) weighing a certain amount of carrier biochar or anatase type nano titanium dioxide, adding the carrier biochar or anatase type nano titanium dioxide into the precursor solution for dipping, then performing vacuum rotary evaporation, and drying;
(3) and (3) carrying out high-temperature heat treatment on the blocky solid obtained in the step (2) in an air atmosphere to obtain the high-entropy co-doped low-temperature SCR denitration catalyst.
Preferably, in the step (1), the power of the ultrasonic oscillation is 200-600W, and the oscillation time is 10-40 min.
Preferably, in the step (2), the impregnation time is 4-12 h.
Preferably, in the step (2), the temperature of the vacuum rotary evaporation is 35-45 ℃ and the time is 1-2 h.
Preferably, in the step (2), the drying temperature is 80-120 ℃ and the time is 10-14 h.
Preferably, in the step (2), the particle size of the biochar is 40-60 meshes; the particle size of the anatase type nano titanium dioxide is less than 50 nm.
Preferably, in the step (3), the high-temperature heat treatment temperature is 300-.
In a third aspect, the invention also provides application of the high-entropy co-doped low-temperature SCR denitration catalyst in a low-temperature SCR flue gas denitration system.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, high-entropy co-doped nanoparticles (iron oxide, manganese oxide, cerium oxide, tungsten oxide and cobalt oxide) are used as active components, so that the individual catalytic performance (such as low-temperature activity, anti-poisoning performance and the like) of each element can be fully exerted, and the synergistic effect among multiple elements can be displayed.
2. According to the invention, the biochar is taken as a carrier, so that the excellent adsorption performance of the biochar is exerted, the particle size grade of 40-60 meshes is realized, the specific surface area of the carrier is increased, and the catalytic effect is further improved.
3. The invention takes anatase type nano titanium dioxide as a carrier, and not only exerts TiO2Has excellent active component dispersibility and SO resistance2And the particle size grade of less than 50nm increases the specific surface area of the carrier, thereby improving the catalytic effect.
4. The method has the advantages of simple required equipment, simple and convenient operation, no secondary pollution, no need of introducing protective gas or reducing agent during calcination and low cost.
Drawings
Fig. 1 is a scanning electron microscope (20000 times) of a high-entropy co-doped low-temperature SCR denitration catalyst prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope (5000 times) of the high-entropy co-doped low-temperature SCR denitration catalyst prepared in example 1 of the present invention.
Fig. 3 is a scanning electron microscope (10000 times) of a high-entropy co-doped low-temperature SCR denitration catalyst prepared in example 3 of the present invention.
FIG. 4 is a scanning electron microscope (25000 times) of a high-entropy co-doped low-temperature SCR denitration catalyst prepared in example 3 of the present invention.
Fig. 5 is an XRD pattern of the high-entropy co-doped low-temperature SCR denitration catalyst prepared in example 3 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
Preparing 20 percent FeO by adopting an impregnation methodx-MnOx-CeOx-CuOx-NiOxThe supported amount of the/BC catalyst is 20 percent. The specific implementation steps are as follows:
weighing a metal nitrate precursor: 1.0576g of ferric nitrate, 0.3286g of manganese nitrate, 0.5684g of cerium nitrate, 0.3162g of copper nitrate and 0.3806g of nickel nitrate, adding 50mL of absolute ethyl alcohol, and carrying out ultrasonic oscillation for 30min, wherein the ultrasonic oscillation power is 500W, and completely dissolving the materials to prepare a precursor solution;
weighing 3g of biochar with the particle size of 40 meshes, soaking the biochar in the precursor solution for 6h, then completely transferring the biochar into a rotary evaporator, carrying out vacuum rotary evaporation for 1h at 40 ℃ to remove absolute ethyl alcohol, and then drying the biochar at 100 ℃ for 12 h;
finally calcining the mixture for 5 hours at 550 ℃ in a tubular furnace to decompose and oxidize the metal nitrate at high temperature to obtain 20 percent FeOx-MnOx-CeOx-CuOx-NiOxthe/AC high-entropy co-doped low-temperature SCR denitration catalyst.
Fig. 1 and 2 are scanning electron micrographs of a high-entropy co-doped low-temperature SCR denitration catalyst prepared in example 1 of the present invention; shows that the co-doped high-entropy oxide with uniform components and agglomerated particles is formed on the surface of the porous BC of the carrier, and the components of different components are shown in Table 1.
Example 2
The 10 percent FeO is prepared by adopting an impregnation methodx-MnOx-CeOx-CuOx-NiOxThe supported amount of the/BC catalyst is 10 percent. The specific implementation steps are as follows:
weighing a metal nitrate precursor: 0.4701g of ferric nitrate, 0.1460g of manganese nitrate, 0.2526g of cerium nitrate, 0.1406g of copper nitrate and 0.1692g of nickel nitrate, adding 50mL of absolute ethyl alcohol, and carrying out ultrasonic oscillation for 30min, wherein the ultrasonic oscillation power is 500W, and completely dissolving the materials to prepare a precursor solution;
weighing 3g of biochar with the particle size of 40 meshes, soaking the biochar in the precursor solution for 5h, then completely transferring the biochar into a rotary evaporator, carrying out vacuum rotary evaporation for 1h at 40 ℃ to remove absolute ethyl alcohol, and then drying the biochar at 100 ℃ for 12 h;
finally calcining the mixture in a tube furnace at 550 ℃ for 5 hours to ensure thatThe metal nitrate is decomposed and oxidized at high temperature to obtain 10 percent FeOx-MnOx-CeOx-CuOx-NiOxthe/BC high-entropy co-doped low-temperature SCR denitration catalyst.
Example 3
Preparing 20 percent FeO by adopting an impregnation methodx-MnOx-CeOx-CuOx-NiOx/TiO2Catalyst, loading was 20%. The specific implementation steps are as follows:
weighing a metal nitrate precursor: 1.0576g of ferric nitrate, 0.3286g of manganese nitrate, 0.5684g of cerium nitrate, 0.3162g of copper nitrate and 0.3806g of nickel nitrate, adding 50mL of absolute ethyl alcohol, and carrying out ultrasonic oscillation for 30min, wherein the ultrasonic oscillation power is 500W, and completely dissolving the materials to prepare a precursor solution;
3g of anatase type nano TiO 2 with the particle size of 30nm2Soaking in the precursor solution for 6h, transferring to a rotary evaporator, vacuum rotary evaporating at 40 deg.C for 1h to remove anhydrous ethanol, and oven drying at 100 deg.C for 12 h;
finally calcining the mixture for 5 hours at 550 ℃ in a tubular furnace to decompose and oxidize the metal nitrate at high temperature to obtain 20 percent FeOx-MnOx-CeOx-CuOx-NiOx/TiO2High-entropy co-doped low-temperature SCR denitration catalyst.
Fig. 3 and 4 are scanning electron micrographs of a high-entropy co-doped low-temperature SCR denitration catalyst prepared in example 3 of the present invention; indicating FeO producedx-MnOx-CeOx-CuOx-NiOx/TiO2Dense holes are uniformly distributed on the surface of the catalyst, and the high-entropy oxide presents spherical particles with nanometer sizes.
Fig. 5 is an XRD pattern of the high-entropy co-doped low-temperature SCR denitration catalyst prepared in example 3 of the present invention. Is shown in TiO2Successfully load FeOx-MnOx-CeOx-CuOx-NiOxHigh entropy co-doped oxide.
Example 4
The 10 percent FeO is prepared by adopting an impregnation methodx-MnOx-CeOx-CuOx-NiOx/TiO2Catalyst, loading 10%. The specific implementation steps are as follows:
weighing a metal nitrate precursor: 0.4701g of ferric nitrate, 0.1460g of manganese nitrate, 0.2526g of cerium nitrate, 0.1406g of copper nitrate and 0.1692g of nickel nitrate, adding 50mL of absolute ethyl alcohol, and carrying out ultrasonic oscillation for 30min, wherein the ultrasonic oscillation power is 500W, and completely dissolving the materials to prepare a precursor solution;
3g of anatase type nano TiO 2 with the particle size of 30nm2Soaking in the precursor solution for 6h, transferring to a rotary evaporator, vacuum rotary evaporating at 40 deg.C for 1h to remove anhydrous ethanol, and oven drying at 100 deg.C for 12 h;
finally calcining the mixture for 5 hours at 550 ℃ in a tubular furnace to decompose and oxidize the metal nitrate at high temperature to obtain 10 percent FeOx-MnOx-CeOx-CuOx-NiOx/TiO2High-entropy co-doped low-temperature SCR denitration catalyst.
The element ICP-OES test results of the prepared (FeMnCeCuNi) Ox high-entropy co-doped low-temperature SCR denitration catalyst are shown in Table 1:
table 1 contents of respective elements in the high-entropy co-doped low-temperature SCR denitration catalysts prepared in examples 1 to 4
Comparative example 1
The impregnation method is adopted to prepare FeOx-MnOx-CeOxa/BC catalyst. The specific implementation steps are as follows:
the procedure of example 1 was exactly the same except that copper nitrate and nickel nitrate were not added, to obtain FeOx-MnOx-CeOxthe/BC high-entropy co-doped low-temperature SCR denitration catalyst.
Comparative example 2
The impregnation method is adopted to prepare FeOx-MnOx-CeOx/TiO2A catalyst. The specific implementation steps are as follows:
the procedure of example 4 was followed except that copper nitrate and nickel nitrate were not addedCompletely the same to obtain FeOx-MnOx-CeOx/TiO2High-entropy co-doped low-temperature SCR denitration catalyst.
The denitration catalyst prepared by the above examples and comparative examples is placed in a fixed bed quartz tube reactor for denitration performance test, the particle size of the catalyst is 40-60 meshes, the dosage is 0.5-1.0g, and the simulated flue gas is NO and NH3、O2、CO2、H2O、N2Composition, wherein NO is 500ppm, NH3500ppm, O25 vol% and CO28 vol%, H2O is 3 vol%, N2As equilibrium gas, the reaction space velocity is 10000h-1The total flow rate was 120 mL/min. And simultaneously detecting the concentration of NO in the reaction tail gas on line by adopting a gas chromatograph, wherein the detection precision is 0.5 ppm. Collecting data 30min after the SCR reaction reaches a stable state, wherein the temperature range of activity evaluation is 80-240 ℃, and the NOx conversion rate is calculated according to the following formula:
in the formula etaNOxFor NOx conversion, [ NOx]in and [ NOx ]]And out is the concentration of NOx at the inlet and the outlet of the reactor under the steady state respectively.
The results of the performance test on NO removal efficiency are shown in Table 2.
TABLE 2 denitration rates of examples and comparative examples at different temperatures
According to the test results, the (1) denitration catalyst taking the biochar as the carrier has the maximum NO conversion rate at 220 ℃, and the temperature of SCR denitration reaction is 220 ℃; the denitration catalyst taking anatase type nano titanium dioxide as a carrier has the maximum NO conversion rate at 160 ℃, and the temperature of SCR denitration reaction is 120-180 ℃; the catalyst in the embodiment has better low-temperature activity, wherein the catalytic effect of the catalyst taking anatase type nano titanium dioxide as a carrier is obviously better than that of the catalyst taking biological carbon as a carrier;
(2) example 2 and comparative example 1, example 3 and comparative example 2 were compared, with FeO alonex、MnOx、CeOxThe catalytic efficiency is low when three metal oxides are compounded, and FeO is usedx、MnOx、CeOx、CuOx、NiOxThe catalytic activity is obviously improved when the five metal oxides are compounded. This is due to the formation of a single solid solution by the high entropy induction of the five metals.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (9)
1. The high-entropy co-doped low-temperature SCR denitration catalyst is characterized in that biochar or anatase type nano titanium dioxide is used as a carrier, high-entropy co-doped nano particles are loaded on the surface of the carrier and are used as active components, the high-entropy co-doped nano particles are prepared by mixing iron oxide, manganese oxide, cerium oxide, copper oxide and nickel oxide in equal molar ratio, and the loading amount of the high-entropy co-doped nano particles is 5% -30%.
2. The preparation method of the high-entropy co-doped low-temperature SCR denitration catalyst of claim 1, which is characterized by comprising the following steps:
(1) respectively weighing equal molar amounts of ferric nitrate, manganese nitrate, cerium nitrate, copper nitrate and nickel nitrate, adding into a certain amount of absolute ethyl alcohol together, and performing ultrasonic oscillation to completely dissolve the materials to obtain a precursor solution;
(2) weighing a certain amount of carrier biochar or anatase type nano titanium dioxide, adding the carrier biochar or anatase type nano titanium dioxide into the precursor solution for dipping, then performing vacuum rotary evaporation, and drying;
(3) and (3) carrying out high-temperature heat treatment on the blocky solid obtained in the step (2) in an air atmosphere to obtain the high-entropy co-doped low-temperature SCR denitration catalyst.
3. The preparation method of the high-entropy co-doped low-temperature SCR denitration catalyst as claimed in claim 2, wherein in the step (1), the power of the ultrasonic oscillation is 200-600W, and the oscillation time is 10-40 min.
4. The preparation method of the high-entropy co-doped low-temperature SCR denitration catalyst according to claim 2, wherein in the step (2), the impregnation time is 4-12 h.
5. The preparation method of the high-entropy co-doped low-temperature SCR denitration catalyst according to claim 2, wherein in the step (2), the temperature of the vacuum rotary evaporation is 35-45 ℃ and the time is 1-2 h.
6. The preparation method of the high-entropy co-doped low-temperature SCR denitration catalyst according to claim 2, wherein in the step (2), the drying temperature is 80-120 ℃ and the drying time is 10-14 h.
7. The preparation method of the high-entropy co-doped low-temperature SCR denitration catalyst according to claim 2, wherein in the step (2), the biochar has a particle size of 40-60 meshes; the particle size of the anatase type nano titanium dioxide is less than 50 nm.
8. The preparation method of the high-entropy co-doped low-temperature SCR denitration catalyst as claimed in claim 2, wherein the high-temperature heat treatment temperature in step (3) is 300-600 ℃ and the time is 3-6 h.
9. The application of the high-entropy co-doped low-temperature SCR denitration catalyst in a low-temperature SCR flue gas denitration system according to claim 1.
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