CN116037102A - Three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst and preparation and application thereof - Google Patents
Three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst and preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 17
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 239000011363 dried mixture Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 8
- 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 8
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003546 flue gas Substances 0.000 abstract description 9
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract description 2
- 239000004568 cement Substances 0.000 abstract description 2
- -1 nonferrous Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 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
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/63—Pore volume
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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Abstract
The invention relates to a three-dimensional ordered macroporous ultra-low Wen Tuoxiao water-resistant catalyst, and preparation and application thereof, wherein the preparation method comprises the following steps: preparing a titanium dioxide carrier with a three-dimensional ordered macroporous structure, adding the titanium dioxide carrier and precursors of active components cerium and manganese into deionized water according to a certain molar ratio, and stirring at normal temperature until the titanium dioxide carrier and the precursors of active components cerium and manganese are completely dissolved to obtain a mixed solution; heating and stirring the mixed solution in an oil bath at 100-120 ℃ and slowly evaporating redundant aqueous solution to obtain a semi-dried mixture; drying, calcining, grinding and sieving the semi-dried mixtureThe three-dimensional ordered macroporous ultra-low Wen Tuoxiao water-resistant catalyst is obtained. The prepared catalyst has the advantages of low activation temperature, high low-temperature activity, wide active temperature window and the like. Can be used for NO in flue gas of non-electric industries such as steel, nonferrous, chemical industry, cement and the like x Is a purification treatment of (a).
Description
Technical Field
The invention relates to the technical field of ammonia selective catalytic reduction catalysts, in particular to a three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst, and preparation and application thereof.
Background
Ammonia selective catalytic reduction (NH 3 SCR) technology has the advantages of high denitration efficiency, simple process and the like, and solves the problem of NO x One of the most effective technical means of emission. The catalyst being NH 3 The core of SCR technology. The traditional V-W-Ti catalyst can achieve better denitration effect at 350-400 ℃. However, unlike the thermal power industry, the flue gas outlet temperature in the non-electric industry is lower, usually<200 ℃ and a large amount of water vapor (15 vol%) is contained in the flue gas, so that the traditional V-based catalyst in the power industry is difficult to directly apply to the non-electric industry. In summary, the existing catalysts at present have the following disadvantages: the denitration activity is poor at low temperature; catalyst performance is susceptible to moisture in the flue gas, resulting in poisoning deactivation. Therefore, NH with water resistance and low-temperature high efficiency is developed 3 SCR catalyst is for controlling NO in non-electric industry x The key of ultra-low emission.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst and preparation and application thereof, and solves the technical problems of poor low-temperature activity and weak water resistance of the existing catalyst.
The technical scheme adopted by the invention is as follows:
the first aspect of the application provides a preparation method of a three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst, which comprises the following steps:
preparing a titanium dioxide carrier with a three-dimensional ordered macroporous structure, adding the titanium dioxide carrier and precursors of active components cerium and manganese into deionized water according to a certain molar ratio, and stirring at normal temperature until the titanium dioxide carrier and the precursors of active components cerium and manganese are completely dissolved to obtain a mixed solution;
heating and stirring the mixed solution in an oil bath at 100-120 ℃ and slowly evaporating redundant aqueous solution to obtain a semi-dried mixture;
and drying, calcining, grinding and sieving the semi-dried mixture to obtain the three-dimensional ordered macroporous ultra-low Wen Tuoxiao water-resistant catalyst.
The further technical scheme is as follows:
the preparation method of the titanium dioxide carrier with the three-dimensional ordered macroporous structure comprises the following steps:
adding tetrabutyl titanate solution into absolute ethyl alcohol under stirring to obtain a mixed solution A;
mixing a certain amount of water with absolute ethyl alcohol, slowly dropwise adding a nitric acid solution under stirring, and regulating the pH to 2-3 to obtain a mixed solution B;
slowly dripping the mixed solution B into the mixed solution A, and stirring until the solution A is clear and transparent to obtain a mixed solution C;
adding polymethyl methacrylate microsphere templates into the mixed solution C, soaking, and then carrying out suction filtration and repeating for a plurality of times to obtain a mixture;
and drying, calcining and grinding the mixture to obtain the three-dimensional ordered macroporous titanium dioxide carrier.
The polymethyl methacrylate microsphere template is formed by polymerizing methyl methacrylate, and the particle size range is 260-320 nm.
The drying is carried out for 10 to 15 hours at the temperature of 105 to 120 ℃, and the calcining procedure is as follows: under the air atmosphere, the temperature is firstly increased to 300 ℃ from normal temperature, the heat is preserved for 2 hours, then the calcination is carried out for 5 hours at 500-600 ℃, and the heating rate is 1 ℃/min.
The molar ratio of each component is as follows: 10 parts of titanium dioxide, 1-3 parts of metal cerium and 0.5-2 parts of metal manganese.
The precursors of the active components cerium and manganese are cerium nitrate hexahydrate and manganese nitrate respectively.
The drying is carried out for 10-15 h at 105-120 ℃, and the calcining is carried out for 4-6 h at 500-600 ℃ in air atmosphere.
The second aspect of the application provides a catalyst prepared by the preparation method of the three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst, wherein titanium dioxide with a three-dimensional ordered macroporous structure prepared by tetrabutyl titanate hydrolysis is used as a carrier, and rare earth cerium and transition manganese are used as active components.
In a third aspect, the application provides an application of the catalyst in an ammonia selective catalytic reduction denitration process.
The beneficial effects of the invention are as follows:
according to the preparation method of the catalyst, the polymethyl methacrylate template method is used for assisting in forming the titanium dioxide carrier with the three-dimensional ordered macroporous structure, the specific surface area and pore volume and pore diameter of the catalyst are increased based on the titanium dioxide carrier structure with the three-dimensional ordered macropores, so that active components are uniformly dispersed on the surface of the carrier, blocking is reduced, more importantly, the existence of the macroporous structure reduces the condensation phenomenon of water vapor in flue gas in the catalyst, and the water resistance of the catalyst is effectively improved.
The preparation method of the catalyst of the invention is based on the formula regulation and control of the active component Ce+Mn, and promotes the acid sites on the surface of the catalyst, thereby greatly promoting the low-temperature catalytic reduction of NO by the catalyst x Performance. T (T) 90 The minimum (temperature at which the conversion reaches 90%) can be as low as 75 ℃ and the denitration efficiency is kept to be nearly 100% in the low temperature range of 100 ℃ to 250 ℃. Has the advantages of low activation temperature, high low-temperature activity, wide active temperature window and the like. Can be used for NO in flue gas of non-electric industries such as steel, nonferrous, chemical industry, cement and the like x Is a purification treatment of (a).
The preparation raw material of the invention is vanadium-free rare earth-based metal oxide, and is green and pollution-free.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the catalysts prepared in examples 1-2 and comparative examples 1-2 of the present invention.
FIG. 2 is a scanning electron microscope image of the catalyst prepared in example 2 and comparative example 2 of the present invention.
FIG. 3 shows the NO removal rate of the catalysts prepared in examples 1-2 and comparative examples 1-2 according to the present invention in the denitration performance test.
FIG. 4 shows the NO removal rate of the catalysts prepared in example 1 and comparative example 1 according to the present invention in the water poisoning resistance test.
Detailed Description
The following describes specific embodiments of the present invention with reference to the drawings.
The application provides a preparation method of a three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst, which comprises the following steps:
preparing a titanium dioxide carrier with a three-dimensional ordered macroporous structure, adding the titanium dioxide carrier and precursors of active components cerium and manganese into deionized water according to a certain molar ratio, and stirring at normal temperature until the precursors are completely dissolved to obtain a mixed solution, wherein the molar ratio of each component is as follows: 10 parts of titanium dioxide, 1-3 parts of metal cerium and 0.5-2 parts of metal manganese, namely the molar ratio of the metal elements is as follows: cerium: manganese: titanium= (0.1 to 0.3): (0.05-0.2): 1, a step of;
heating and stirring the mixed solution in an oil bath at 100-120 ℃ and slowly evaporating redundant aqueous solution to obtain a semi-dried mixture;
and drying, calcining, grinding and sieving the semi-dried mixture to obtain the three-dimensional ordered macroporous ultra-low Wen Tuoxiao water-resistant catalyst. Specifically, the drying is carried out at 105-120 ℃ for 10-15 h, and the calcining is carried out at 500-600 ℃ for 4-6 h in air atmosphere.
Preferably, the precursors of the active components cerium and manganese are cerium nitrate hexahydrate and manganese nitrate respectively.
The preparation method of the titanium dioxide carrier with the three-dimensional ordered macroporous structure comprises the following steps:
adding tetrabutyl titanate solution into absolute ethyl alcohol under stirring to obtain a mixed solution A;
mixing a certain amount of water with absolute ethyl alcohol, slowly dropwise adding a nitric acid solution under stirring, and regulating the pH to 2-3 to obtain a mixed solution B;
slowly dripping the mixed solution B into the mixed solution A, and stirring until the solution A is clear and transparent to obtain a mixed solution C;
adding polymethyl methacrylate microsphere templates into the mixed solution C, soaking, and then carrying out suction filtration and repeating for a plurality of times to obtain a mixture;
and drying, calcining and grinding the mixture to obtain the three-dimensional ordered macroporous titanium dioxide carrier. Specifically, the drying is carried out for 10-15 hours at 105-120 ℃, and the calcining procedure is as follows: under the air atmosphere, the temperature is firstly increased to 300 ℃ from normal temperature, the heat is preserved for 2 hours, then the calcination is carried out for 5 hours at 500-600 ℃, and the heating rate is 1 ℃/min.
The polymethyl methacrylate microsphere template is formed by polymerizing methyl methacrylate, and the particle size range is 260-320 nm.
The preparation method of the three-dimensional ordered macroporous ultra-low Wen Tuoxiao water-resistant catalyst is further described in the following specific examples.
Example 1
8.6844g of cerium nitrate hexahydrate and 3.5790g of manganese nitrate are dissolved in deionized water, and 7.9866g of titanium dioxide carrier 3DOM-TiO with a three-dimensional ordered macroporous structure is added after stirring and dissolution 2 And stirred at room temperature for 2 hours to mix thoroughly. Subsequently, the mixture was heated and stirred in an oil bath at 105 ℃ to remove moisture. Drying the rest solid in an oven at 105deg.C for 12h, calcining at 500deg.C in air atmosphere for 5h, grinding and sieving the obtained solid to obtain sample Ce 0.2 Mn 0.2 /3DOM-TiO 2 The catalyst is denoted as catalyst A.
Example 2
8.6844g of cerium nitrate hexahydrate and 1.7895g of manganese nitrate are dissolved in deionized water, and 7.9866g of titanium dioxide carrier 3DOM-TiO with a three-dimensional ordered macroporous structure is added after stirring and dissolution 2 And stirred at room temperature for 2h to mix thoroughly. Subsequently, the mixture was heated and stirred in an oil bath at 105 ℃ to remove moisture. Drying the rest solid in an oven at 105deg.C for 12h, calcining at 500deg.C in air atmosphere for 5h, grinding and sieving the obtained solid to obtain sample Ce 0.2 Mn 0.1 /3DOM-TiO 2 The catalyst is denoted as catalyst B.
Comparative example 1
8.6844g of cerium nitrate hexahydrate and 3.5790g of manganese nitrate are dissolved in deionized water, and 7 g of manganese nitrate are added after stirring and dissolution9866g of nano titanium dioxide with non-macroporous structure, and stirring for 2h at room temperature, and mixing well. Subsequently, the mixture was heated and stirred in an oil bath at 105 ℃ to remove moisture. Drying the rest solid in an oven at 105deg.C for 12h, calcining at 500deg.C in air atmosphere for 5h, grinding and sieving the obtained solid to obtain sample Ce 0.2 Mn 0.2 /TiO 2 The catalyst, designated catalyst C.
Comparative example 2
8.6844g of cerium nitrate hexahydrate and 1.7895g of manganese nitrate are dissolved in deionized water, 7.9866g of nano titanium dioxide with a non-macroporous structure is added after stirring and dissolution, and stirring is carried out at room temperature for 2 hours for fully mixing. Subsequently, the mixture was heated and stirred in an oil bath at 105 ℃ to remove moisture. Drying the rest solid in an oven at 105deg.C for 12h, calcining at 500deg.C in air atmosphere for 5h, grinding and sieving the obtained solid to obtain sample Ce 0.2 Mn 0.1 /TiO 2 The catalyst is denoted as catalyst D.
FIG. 1 is an X-ray powder diffraction pattern of the catalysts prepared in examples 1-2 and comparative examples 1-2. As can be seen from FIG. 1, anatase TiO can be detected in the XRD patterns of all samples 2 Diffraction peaks of the carrier indicate that structural modification does not affect TiO 2 A crystalline form of the carrier. The diffraction peak at 28.6, 56.4 in the figure corresponds to CeO 2 Is a diffraction peak of (2). As can be seen from the XRD patterns of the comparative examples and comparative examples, the modification of the support structure does not affect TiO 2 The crystal form of the carrier, and the modified three-dimensional ordered macroporous structure is more beneficial to the dispersion of active components on the surface of the carrier.
FIG. 2 is a scanning electron microscope image of the catalyst prepared in example 2 and comparative example 2. The catalyst prepared in comparative example 2 had an agglomerated disordered structure, while the catalyst prepared in example 2 had a three-dimensionally ordered macroporous structure.
Denitration performance tests were conducted on the catalyst A, the catalyst B, the catalyst C and the catalyst D prepared in examples 1-2 and comparative examples 1-2, respectively, and the activity of the catalyst was expressed as NO conversion rate, and the concentration of NO was measured by using a Testo350 infrared flue gas analyzer. The specific test conditions are as follows:
the activity test of NO catalytic reduction is carried out in a fixed bed quartz tube reactor, the loading of the catalyst is 0.3mL, the granularity is 40-60 meshes, the reaction temperature is 75-300 ℃, the reaction temperature interval is 25 ℃, and the concentration at each temperature is based on the final stable indication of a flue gas analyzer. The concentration of NO in the raw material gas is 500ppm, and the reducing gas is NH 3 Is 500ppm of O 2 The volume concentration is 5%, N 2 For balancing the gas, the total mixed gas amount is 100mL/min; the reactor is a quartz tube with an inner diameter of 5mm, and a vertical tube type heating furnace with a temperature control system provides a reaction temperature environment. The test results are shown in FIG. 3.
As can be seen from FIG. 3, the NO removal rate of the catalyst in example 1-2 was maintained at about 80% in the test temperature range of 75℃to 300℃and was nearly 100% in the low temperature range of 100℃to 250 ℃.
The catalyst A prepared in example 1 and the catalyst C prepared in comparative example 1 were respectively tested for their water poisoning resistance, and the activity of the catalyst was expressed as NO conversion when water was introduced. The specific test conditions are as follows:
the activity test of NO catalytic reduction is carried out in a fixed bed quartz tube reactor, the catalyst loading amount is 0.3mL, the granularity is 40-60 meshes, and the reaction temperature is 150 ℃. The concentration of NO in the raw material gas is 500ppm, and the reducing gas is NH 3 Is 500ppm of O 2 The volume concentration is 5%, the volume concentration of water is 15%, N 2 For balancing the gas, the total mixed flue gas flow is 100mL/min; the reactor is a quartz tube with an inner diameter of 5mm, and a vertical tube type heating furnace with a temperature control system provides a reaction temperature environment. The test results are shown in fig. 4.
As can be seen from fig. 4, the catalyst of example 1 can still maintain 100% NO removal rate in the presence of 15% water, and the denitration activity is hardly affected by water, while the denitration activity of the sample of comparative example 1 is reduced under the same conditions.
The application also provides a catalyst prepared according to the preparation method of the three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst, wherein the catalyst takes titanium dioxide with a three-dimensional ordered macroporous structure synthesized by tetrabutyl titanate hydrolysis as a carrier and takes rare earth cerium and mixed transition manganese as active components.
The application also provides an application of the catalyst in an ammonia selective catalytic reduction denitration process.
Those of ordinary skill in the art will appreciate that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst is characterized by comprising the following steps of:
preparing a titanium dioxide carrier with a three-dimensional ordered macroporous structure, adding the titanium dioxide carrier and precursors of active components cerium and manganese into deionized water according to a certain molar ratio, and stirring at normal temperature until the titanium dioxide carrier and the precursors of active components cerium and manganese are completely dissolved to obtain a mixed solution;
heating and stirring the mixed solution in an oil bath at 100-120 ℃ and slowly evaporating redundant aqueous solution to obtain a semi-dried mixture;
and drying, calcining, grinding and sieving the semi-dried mixture to obtain the three-dimensional ordered macroporous ultra-low Wen Tuoxiao water-resistant catalyst.
2. The method for preparing the three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst according to claim 1, wherein the preparation of the titanium dioxide carrier with the three-dimensional ordered macroporous structure comprises the following steps:
adding tetrabutyl titanate solution into absolute ethyl alcohol under stirring to obtain a mixed solution A;
mixing a certain amount of water with absolute ethyl alcohol, slowly dropwise adding a nitric acid solution under stirring, and regulating the pH to 2-3 to obtain a mixed solution B;
slowly dripping the mixed solution B into the mixed solution A, and stirring until the solution A is clear and transparent to obtain a mixed solution C;
adding polymethyl methacrylate microsphere templates into the mixed solution C, soaking, and then carrying out suction filtration and repeating for a plurality of times to obtain a mixture;
and drying, calcining and grinding the mixture to obtain the three-dimensional ordered macroporous titanium dioxide carrier.
3. The method for preparing the three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst according to claim 2, wherein the polymethyl methacrylate microsphere template is formed by polymerizing methyl methacrylate, and the particle size range is 260-320 nm.
4. The method for preparing the three-dimensional ordered macroporous ultra-low Wen Tuoxiao water-resistant catalyst according to claim 2, wherein the drying is performed at 105-120 ℃ for 10-15 hours, and the calcining procedure is as follows: under the air atmosphere, the temperature is firstly increased to 300 ℃ from normal temperature, the heat is preserved for 2 hours, then the calcination is carried out for 5 hours at 500-600 ℃, and the heating rate is 1 ℃/min.
5. The method for preparing the three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst according to claim 1, wherein the molar ratio of the components is as follows: 10 parts of titanium dioxide, 1-3 parts of metal cerium and 0.5-2 parts of metal manganese.
6. The method for preparing the three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst according to claim 1, wherein the precursors of the active components cerium and manganese are cerium nitrate hexahydrate and manganese nitrate respectively.
7. The method for preparing the three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst according to claim 1, wherein the drying is carried out at 105-120 ℃ for 10-15 h, and the calcining is carried out at 500-600 ℃ for 4-6 h in an air atmosphere.
8. A catalyst prepared by the preparation method of the three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst according to any one of claims 1-7, wherein the catalyst takes titanium dioxide with a three-dimensional ordered macroporous structure prepared by tetrabutyl titanate hydrolysis as a carrier and takes rare earth cerium and transition manganese as active components.
9. Use of the catalyst of claim 8 in an ammonia selective catalytic reduction denitration process.
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