CN112473682A - High-performance medium-low temperature NH3-SCR catalyst, preparation method and application thereof - Google Patents
High-performance medium-low temperature NH3-SCR catalyst, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010955 niobium Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003546 flue gas Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 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 abstract description 3
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims abstract description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 7
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 4
- 230000027455 binding Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 20
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- -1 coking Substances 0.000 description 14
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- JMAHHHVEVBOCPE-UHFFFAOYSA-N [Fe].[Nb] Chemical compound [Fe].[Nb] JMAHHHVEVBOCPE-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- PUUPYXQOFNNGRK-UHFFFAOYSA-N cerium niobium Chemical compound [Nb].[Ce] PUUPYXQOFNNGRK-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/002—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses high-performance medium-low temperature NH3An SCR catalyst, a preparation method and an application thereof, belonging to the technical field of catalysts. Dissolving cerous nitrate hexahydrate, ferric nitrate nonahydrate and niobium oxalate in distilled water by adopting a coprecipitation method, uniformly stirring at room temperature, dropwise adding ammonia water into the mixed solution to ensure that the mixed solution is completely precipitated, and finally aging, filtering, washing, drying and roasting in air atmosphere to prepare high-performance medium-low temperature NH3-an SCR catalyst. The application comprehensively utilizes the strong oxidation reduction capability of Ce, Fe and SO2Specific binding ability of (3) and acidity of Nb, NH of the non-electric industry3The SCR flue gas denitration reaction provides a catalyst with good catalytic performance, wide application range, low price, small environmental pollution and high N2 selectivityAnd a catalyst with a wide working temperature window, at medium and low NH temperatures3The SCR catalytic denitration field has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to NH3A SCR catalyst and a preparation method thereof, in particular to high-performance medium-low temperature NH3-SCR catalyst and its preparation method and use.
Background
In recent years, with the rapid development of economy, the industry has come from Nitrogen Oxides (NO) produced by incomplete combustion of fossil fuelsx) The pollution to the atmospheric environment is increasingly serious, and the pollution can not only cause photochemical smog, acid rain and ozone layer damage, but also cause harm to human bodies. NH (NH)3Selective catalytic reduction of NOx(NH3SCR) technology, which is commonly used as one of the most effective and widely used methods for industrial flue gas denitration, is V2O5-WO3(MoO3)/TiO2The catalyst has better chemical stability and sulfur resistance, and shows higher NO conversion rate between 300 ℃ and 400 ℃. It still possesses many disadvantages, such as: (1) v in the catalyst2O5Hazards to the environment and human body; (2) NH (NH)3Narrow working window of SCR reaction (300-; (3) high temperature N2Poor selectivity and easy formation of N2O; (4) the low temperature activity of the catalyst is not good. Therefore, the catalyst is mainly used for denitration of coal-fired power plants with high flue gas temperature, and is not suitable for non-electric industries with the flue gas temperature lower than 300 ℃, such as steel, glass, cement, coking, garbage incineration and other non-electric power industries. At present, the flue gas denitration treatment in the electric power industry of China is close to the end sound, and the non-electric industry is the key point for prevention and control in a long period of time in the future. Therefore, the development of an environment-friendly non-vanadium-based catalyst with high medium-low temperature denitration activity, which is suitable for flue gas denitration in the non-electric industry, is urgent.
CeO2The catalyst is widely used in flue gas denitration catalysts due to abundant reserves and excellent oxidation-reduction performance. But due to CeO2The substrate is less acidic, so that it acts as NH alone3The activity is not high in the case of SCR catalysts.
Disclosure of Invention
In view of the above problems in the prior art, a first technical problem to be solved by the present invention is to provide a high performance medium and low temperature NH3-a process for the preparation of an SCR catalyst; the second technical problem to be solved by the invention is to provide high-performance medium-low temperature NH prepared by the method3-an SCR catalyst; the third technical problem to be solved by the present invention is to provide high performance medium and low temperature NH3Application of SCR catalyst in flue gas denitration in non-electric industry.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
high-performance medium-low temperature NH3-a process for the preparation of an SCR catalyst comprising the steps of: dissolving cerous nitrate hexahydrate, ferric nitrate nonahydrate and niobium oxalate in distilled water by adopting a coprecipitation method, uniformly stirring at room temperature, dropwise adding ammonia water into the mixed solution to ensure that the mixed solution is completely precipitated, and finally aging, filtering, washing, drying and roasting in air atmosphere to prepare high-performance medium-low temperature NH3-an SCR catalyst.
Furthermore, the mol ratio of the niobium, the iron and the cerium is 1-5: 5-10: 10.
Furthermore, the mol ratio of the niobium, the iron and the cerium is 1-4: 6-9: 10.
Further, the molar ratio of the elements niobium, iron and cerium is 1: 9: 10.
Further, the mixture was uniformly stirred at room temperature for 30 min.
Further, dropwise adding ammonia water into the mixed solution to ensure that the pH value of the solution is more than or equal to 10.0, then carrying out magnetic stirring for 3 hours at room temperature to completely precipitate the mixed solution, finally carrying out aging for 3 hours, filtering, washing with deionized water for 3 times, drying in an oven at 100 ℃ for 12 hours, uniformly grinding, and roasting at 400 ℃ for 4 hours in a muffle furnace under the air atmosphere.
Further, the mass fraction of the ammonia water is 25% wt.
The high-performance medium-low temperature NH prepared by the method3-an SCR catalyst.
High-performance medium-low temperature NH prepared3Application of SCR catalyst in flue gas denitration in non-electric industry.
The application aims at the problems existing in the existing flue gas denitration technology, and comprehensively utilizes the strong oxidation reduction capability of Ce, Fe and SO2Specific binding capacity of (A), and acidity of Nb, by optimizing preparation conditions, design of synthetic Nb2O5-Fe2O3-CeO2The multifunctional catalyst is NH in non-electric industry3The SCR flue gas denitration reaction provides a catalyst with good catalytic performance, wide application range, low price, small environmental pollution, higher medium and low temperature denitration activity and high N2The catalyst with selectivity and wider working temperature window can be applied to industrial production and can be used for medium-low temperature NH3The SCR catalytic denitration field has wide application prospect.
Has the advantages that: compared with the prior art, the invention has the advantages that:
1) the prepared catalyst has better medium-low temperature catalytic activity and higher N2Selectivity;
2) the used raw materials are cheap and easily available, and the resources are rich;
3) the preparation method has low energy consumption, little pollution, environmental protection, simplicity, convenience and rapidness, and can be used for large-scale production.
Drawings
FIG. 1 is a XRD result chart of a niobium-iron-cerium composite oxide catalyst and an iron-cerium composite oxide catalyst;
FIG. 2 shows NH of a ferrocolumbium-cerium composite oxide catalyst3-a graph of results for TPD;
FIG. 3 shows the Nb-Fe-Ce composite oxide catalyst and H of pure Fe-Ce composite oxide2-a graph of TPR results;
FIG. 4 shows NH of a ferrocolumbium-cerium composite oxide catalyst and a simple iron-cerium composite oxide3-SCR reaction result graph, wherein (a) is NO conversion, (b) isb) Is N2And (4) selectivity.
Detailed Description
The invention is further described with reference to specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Comparative example
Accurately measuring 0.01mol CeNO3·6H2O and 0.01mol Fe2(NO3)3·9H2Dissolving O in 50mL of distilled water, magnetically stirring for 0.5h at room temperature, dropwise adding 25% wt of ammonia water into the solution to ensure that the pH of the solution is more than or equal to 10.0, magnetically stirring for 3h at room temperature to completely precipitate, aging for 3h, filtering, washing for 3 times with deionized water, drying in an oven at 100 ℃ for 12h, uniformly grinding, and roasting at 400 ℃ for 4h in an air atmosphere in a muffle furnace to obtain the iron and cerium sample. Its XRD and NH3TPD and H2TPR results are shown in FIGS. 1-3.
Example 1
Accurately measuring 0.01mol CeNO3·6H2O、0.001mol C10H5NbO20And 0.009mol Fe2(NO3)3·9H2O, respectively dissolving in 50mL of distilled water, magnetically stirring for 0.5h at room temperature, dropwise adding 25% wt of ammonia water into the solution to ensure that the pH of the solution is more than or equal to 10.0, magnetically stirring for 3h at room temperature to completely precipitate, aging for 3h, filtering, washing for 3 times with deionized water, drying in an oven at 100 ℃ for 12h, uniformly grinding, and roasting at 400 ℃ for 4h in a muffle furnace under the air atmosphere to obtain a niobium-iron-cerium composite oxide catalyst sample Nb0.1Fe0.9Ce。
Example 2
Accurately measuring 0.01mol CeNO3·6H2O、0.002mol C10H5NbO20And 0.008mol Fe2(NO3)3·9H2O, respectively dissolving in 50mL of distilled water, magnetically stirring at room temperature for 0.5h, dropwise adding 25 wt% ammonia water into the solution to ensure that the pH of the solution is more than or equal to 10.0, magnetically stirring at room temperature for 3h to completely precipitate, and agingFiltering for 3h, washing with deionized water for 3 times, drying in an oven at 100 ℃ for 12h, grinding uniformly, and roasting in a muffle furnace at 400 ℃ for 4h in air atmosphere to obtain a niobium-iron-cerium composite oxide catalyst sample Nb0.2Fe0.8Ce。
Example 3
Accurately measuring 0.01mol CeNO3·6H2O、0.004mol C10H5NbO20And 0.006mol Fe2(NO3)3·9H2O, respectively dissolving in 50mL of distilled water, magnetically stirring for 0.5h at room temperature, dropwise adding 25% wt of ammonia water into the solution to ensure that the pH of the solution is more than or equal to 10.0, magnetically stirring for 3h at room temperature to completely precipitate, aging for 3h, filtering, washing for 3 times with deionized water, drying in an oven at 100 ℃ for 12h, uniformly grinding, and roasting at 400 ℃ for 4h in a muffle furnace under the air atmosphere to obtain a niobium-iron-cerium composite oxide catalyst sample Nb0.4Fe0.6Ce。
Example 4
Applying the prepared niobium-iron-cerium composite oxide catalyst to NH3-SCR reaction, specific reaction conditions are as follows: the catalytic reaction tests were carried out in a fixed bed continuous flow quartz reactor. The catalyst has a particle size of 40-60 meshes and the dosage of 200 mg. The reaction gas composition is: 500ppm NO, 500ppm NH3，5％O2，N2As balance gas, the space velocity of gas in the reaction is 60000 mL-mg-1·h-1. Before reaction, high-purity N is used as catalyst2Purge at 200 ℃ for 20 min. The catalytic reaction is carried out at 100 ℃ and 400 ℃, and activity data are collected after the reaction reaches equilibrium. The product was analyzed by Thermofisiher IS10FTIR detection, NO conversion and N2The selectivity is calculated by the following formula:
the prepared niobium-iron-cerium composite oxide catalyst respectively passes through an X-ray diffraction (XRD) and an ammonia temperature programmed desorption curve (NH)3TPD), temperature programmed reduction (H)2TPR) and catalytic Performance test (NH)3-SCR reaction) and other characterization means to evaluate the bulk structure, surface acid sites, reduction properties and catalytic performance, and the results are shown in figures 1-4. XRD results show that the Nb element and the Fe element mentioned in the invention can be well doped with CeO2The crystal lattice of the cerium-iron-niobium composite oxide forms uniform niobium-iron composite oxide, and well maintains CeO2A crystalline form of (a). NH (NH)3The TPD results show that the addition of Nb increases Fe in the medium and low temperature range2O3-CeO2Catalyst acid sites. H2TPR results indicate that the addition of Nb improves Fe2O3-CeO2The redox performance of the catalyst improves its ability to selectively oxidize upon a rise in temperature. As can be seen from FIG. 3, the iron-cerium-niobium composite oxide catalyst has the best reduction performance when the molar ratio of iron to cerium niobium is 1: 9: 10. Meanwhile, the niobium-iron-cerium composite oxide catalyst is applied to NH3SCR reaction, showing very good catalytic performances (NO conversion and N)2Selectivity), NH of the niobium iron cerium composite oxide catalyst when the molar ratio of niobium iron cerium in the niobium iron cerium composite oxide is 1: 9: 103The adsorption was greatest, probably because a small amount of Nb increased the acidic sites of the catalyst, enhancing the adsorption of NH to the catalyst3Capacity, in favor of NH3-the performance of the SCR reaction. As the content of Nb increases, the cluster state of Nb begins to increase, and the exposed acid sites decrease, thereby decreasing the acidity of the catalyst and being not favorable for improving the reaction activity. Fe2O3As a common transition metal oxide, the metal oxide has the advantages of low price, no toxicity and large storage capacity. The Fe-based catalyst has high thermal stability, excellent medium-high temperature activity and N2Selectivity, while Fe, when used as a bulk dopant, is also effective in improving the sulfur resistance of the catalyst. NH (NH)3The SCR reaction result shows that the catalytic performance of the niobium-iron-cerium composite oxide catalyst is obviously superior to that of pure iron-cerium composite oxygenA compound catalyst, which mainly and comprehensively utilizes the strong oxidation reduction capability of Ce, Fe and SO2The specific binding ability of the Nb element, and the improved acid sites and excellent redox performance after the Nb element is added are related.
Claims (9)
1. High-performance medium-low temperature NH3-a process for the preparation of an SCR catalyst, characterized in that it comprises the following steps: dissolving cerous nitrate hexahydrate, ferric nitrate nonahydrate and niobium oxalate in distilled water by adopting a coprecipitation method, uniformly stirring at room temperature, dropwise adding ammonia water into the mixed solution to ensure that the mixed solution is completely precipitated, and finally aging, filtering, washing, drying and roasting in air atmosphere to prepare high-performance medium-low temperature NH3-an SCR catalyst.
2. The high performance medium and low temperature NH according to claim 13-a process for the preparation of an SCR catalyst, characterized in that the molar ratio of the elements niobium, iron and cerium is between 1 and 5: 5 and 10: 10.
3. The high performance medium and low temperature NH according to claim 23-a process for the preparation of an SCR catalyst, characterized in that the molar ratio of the elements niobium, iron and cerium is between 1 and 4: 6 and 9: 10.
4. The high performance medium and low temperature NH according to claim 33-a process for the preparation of an SCR catalyst, characterized in that the molar ratio of the elements niobium, iron and cerium is 1: 9: 10.
5. The high performance medium and low temperature NH according to claim 13-a process for the preparation of SCR catalysts, characterized in that it is stirred homogeneously for 30min at room temperature.
6. The high performance medium and low temperature NH according to claim 13The preparation method of the SCR catalyst is characterized in that ammonia water is dropwise added into the mixed solution to ensure that the pH of the solution is more than or equal to 10.0, the mixed solution is magnetically stirred for 3 hours at room temperature to completely precipitate, and finally the mixed solution is agedDissolving for 3h, filtering, washing with deionized water for 3 times, drying in an oven at 100 ℃ for 12h, grinding uniformly, and roasting in a muffle furnace at 400 ℃ for 4h under the air atmosphere.
7. The high performance medium and low temperature NH according to claim 63-a process for the preparation of an SCR catalyst, characterized in that the mass fraction of ammonia is 25% wt.
8. High performance medium and low temperature NH prepared by the method of any one of claims 1 to 73-an SCR catalyst.
9. The high performance medium low temperature NH of claim 83Application of SCR catalyst in flue gas denitration in non-electric industry.
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| CN113318746A (en) * | 2021-05-31 | 2021-08-31 | 南京大学 | Improve NH3Pretreatment method for SCR catalyst activity |
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