CN110280264B - Denitration catalyst and preparation method and application thereof - Google Patents
Denitration catalyst and preparation method and application thereof Download PDFInfo
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- CN110280264B CN110280264B CN201910620841.5A CN201910620841A CN110280264B CN 110280264 B CN110280264 B CN 110280264B CN 201910620841 A CN201910620841 A CN 201910620841A CN 110280264 B CN110280264 B CN 110280264B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 184
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 57
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 24
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 24
- 230000005855 radiation Effects 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims description 74
- 239000010949 copper Substances 0.000 claims description 52
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 26
- 239000003546 flue gas Substances 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 229910052748 manganese Inorganic materials 0.000 claims description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 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 12
- 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 12
- 239000012691 Cu precursor Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- -1 ammonium ions Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 19
- 239000011593 sulfur Substances 0.000 abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 9
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- 229910021641 deionized water Inorganic materials 0.000 description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000000635 electron micrograph Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
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- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- 231100000956 nontoxicity Toxicity 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
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- 239000005751 Copper oxide Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
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- 239000012717 electrostatic precipitator Substances 0.000 description 1
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- 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
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention provides a denitration catalyst and a preparation method and application thereof. The denitration catalyst comprises Mn doped with a Cu compound3O4Wherein the molar ratio of Cu atoms to Mn atoms is 1: 1-50; the average particle size of the denitration catalyst is less than 75 nm; an X-ray diffraction pattern of the denitration catalyst has a characteristic peak at a position of 36.1 ± 0.2 in 2 θ (°) when analyzed using a powder X-ray diffraction method using CuK α radiation experimental conditions; or when analyzed by a powder X-ray diffraction method under CuK alpha radiation experimental conditions, the denitration catalyst has an X-ray diffraction pattern having a characteristic peak at a position of 35.3 + -0.2 in terms of 2 theta (°). The denitration catalyst disclosed by the invention has excellent denitration efficiency at low temperature, is low in price, is environment-friendly and has no obvious toxicity. The denitration catalyst provided by the invention has stronger sulfur resistance, and can reduce irreversible inactivation of the denitration catalyst in the using process.
Description
Technical Field
The invention provides a denitration catalyst, a preparation method and application thereof, and belongs to the field of catalysts.
Background
With the rapid reduction of the emission of coal-fired power plants, the building material industry has become a main source of atmospheric pollutants, and the emission control and system solution of flue gas pollutants in the building material industry become the key to improve the current air quality. However, the current method for efficiently controlling the emission of smoke pollutants in the building material industry still has great difficulty.
Nitrogen Oxides (NO)x) Is one of the main byproducts of the combustion of fossil fuel and can conductCausing severe environmental problems such as haze, photochemical smog, acid rain, and the like. Foreign cement industry for NOxThe main denitration technologies include low-nitrogen combustion, staged combustion, selective non-catalytic reduction (SNCR) denitration, high-temperature Selective Catalytic Reduction (SCR) denitration systems and the like. However, with a high-temperature Selective Catalytic Reduction (SCR) denitration system, denitration after dust removal requires heating to a temperature of 250 ℃ or higher, which results in energy loss. The high-temperature selective catalytic reduction technology is also applied to denitration in some glass industries, but denitration at a lower temperature is still difficult after waste heat utilization.
In the prior art, the conventional selective catalytic reduction catalyst is V2O5-WO3(MoO3)/TiO2System (wherein, TiO)2As main carrier, V2O5As the main active component) such a conventional selective catalytic reduction catalyst must be installed upstream of the electrostatic precipitator in order to satisfy its operating temperature (300-. Therefore, the traditional SCR denitration device often faces the problems of alkali metal poisoning, dust erosion and the like, and is difficult to be applied to the complex smoke conditions of high dust and high alkali metal concentration in the building material industry.
Citation document [1] discloses a catalyst for low-temperature flue gas denitration, which relates to the technical field of environmental protection and flue gas purification, and mainly comprises a carrier and an active component, wherein the carrier accounts for 85-91 wt%, and the active component accounts for 9-12 wt%; the carrier is nitric acid modified shell activated carbon, and the active component is manganese oxide and/or copper oxide. However, the manganese oxide in the cited document is one or more of manganese oxide, manganese dioxide and manganese sesquioxide, and the preparation method of the catalyst is complex and cannot solve the problem of sulfur poisoning.
Reference document [2]]Discloses a low-temperature SCR catalyst taking carbon spheres as a template and a preparation method thereof, belonging to the technical field of low-temperature SCR catalysts. The method comprises the steps of taking glucose as a carbon source, dissolving, stirring, carrying out hydrothermal treatment, carrying out suction filtration and drying to obtain a colloidal carbon sphere template, adding an ethanol solution of the carbon sphere template into an aqueous solution of a transition metal and a nitrogen source, and refluxing to obtain the CSs @ MOX core-shell microspheresAnd finally, dissolving the CSs @ MOX core-shell microspheres in a Mn solution, heating, filtering, drying in vacuum, and roasting at high temperature to obtain the Mn-based low-temperature SCR catalyst. The Mn-based low-temperature SCR catalyst has good SO resistance2But the preparation steps are multiple, the method is complex, and the NO is treated at the temperature of less than 150 DEG CxThe removal rate of (A) is low.
The cited document [3] discloses a limited-domain molecular sieve catalyst and a preparation method thereof, the catalyst takes a molecular sieve as a carrier, a metal oxide as an active component, the active component of the metal oxide is limited in the pore canal of the molecular sieve by a coprecipitation method, and the active component of the metal oxide accounts for 5-60% of the weight of the catalyst. However, according to the examples of the cited document, the conversion of nitrogen oxides is low at low temperatures.
Therefore, there is a need to develop a catalyst for catalytic removal of NO at low temperaturexThe catalyst of (1). However, low temperature catalysts tend to be exposed to Sulfur (SO)2) The trouble of poisoning and a small amount of SO in the flue gas2This can lead to irreversible deactivation of the catalyst.
Cited document [1 ]: CN109092325A
Cited document [2 ]: CN108906074A
Cited document [3 ]: CN109433254A
Disclosure of Invention
Problems to be solved by the invention
In view of the current situation that the research degree of the denitration catalyst is not sufficient in the prior art, the technical problem to be solved by the present invention is to provide a denitration catalyst by using Mn doped with Cu compound3O4Therefore, the denitration catalyst disclosed by the invention has excellent denitration efficiency at low temperature. And the denitration catalyst solves the problem of Sulfur (SO)2) Poisoning and does not result in irreversible deactivation of the catalyst.
Furthermore, the invention also provides a preparation method of the denitration catalyst, and the preparation method has the advantages of easily obtained raw materials, simple process and no toxicity.
Means for solving the problems
[1]A denitration catalyst comprising Mn doped with a Cu compound3O4Wherein, in the step (A),
the molar ratio of Cu atoms to Mn atoms is 1: 1-50;
an X-ray diffraction pattern of the denitration catalyst has a characteristic peak at a position of 36.1 ± 0.2 in 2 θ (°) when analyzed using a powder X-ray diffraction method using CuK α radiation experimental conditions; or
When analyzed by a powder X-ray diffraction method under CuK α radiation experimental conditions, the X-ray diffraction pattern of the denitration catalyst has a characteristic peak at a position of 35.3 ± 0.2 in 2 θ (°).
[2] The denitration catalyst according to [1], wherein the denitration catalyst is represented by:
(CuxMn3–x)1–O4
wherein x is the molar amount of Cu and 0< x < 1;
is the vacancy content.
[3] The denitration catalyst according to [1], wherein the denitration catalyst further has characteristic peaks in the positions of 28.9 ± 0.2, 32.3 ± 0.2, and 59.8 ± 0.2 in terms of 2 θ (°) when analyzed by using a powder X-ray diffraction method under CuK α radiation experimental conditions; or
The denitration catalyst further has an X-ray diffraction pattern having characteristic peaks at positions of 30.0 ± 0.2, 43.0 ± 0.2, 56.8 ± 0.2, 62.4 ± 0.2, 89.3 ± 0.2 in 2 θ (°) when analyzed using a powder X-ray diffraction method using CuK α radiation experimental conditions.
[4]According to the above [1]-[3]Any one of the denitration catalysts, wherein the specific surface area of the denitration catalyst is 20-100 m2g–1(ii) a And/or
The denitration catalyst has an average particle diameter of 75nm or less.
[5] The preparation method of the denitration catalyst comprises the steps of preparing the denitration catalyst by using a coprecipitation method; wherein the denitration catalyst comprises:
the molar ratio of Cu atoms to Mn atoms is 1: 1-50;
an X-ray diffraction pattern of the denitration catalyst has a characteristic peak at a position of 36.1 ± 0.2 in 2 θ (°) when analyzed using a powder X-ray diffraction method using CuK α radiation experimental conditions; or
When analyzed by a powder X-ray diffraction method under CuK α radiation experimental conditions, the X-ray diffraction pattern of the denitration catalyst has a characteristic peak at a position of 35.3 ± 0.2 in 2 θ (°).
[6] The denitration catalyst according to the above [5], comprising the steps of:
dissolving and mixing a copper precursor and a manganese precursor to obtain a precursor solution;
putting the precursor solution into an alkali solution for aging to generate crystals;
and calcining the crystal to obtain the denitration catalyst.
[7] The production method according to the above [6], wherein the copper precursor comprises one or a combination of two or more of copper nitrate, copper sulfate, copper chloride and copper acetate; and/or
The manganese precursor comprises one or the combination of more than two of manganese nitrate, manganese sulfate, manganese chloride and manganese acetate; and/or
The alkali solution is an ammonia water solution, preferably, the ammonia water solution is a mixture of 25-28% ammonia water and water, wherein the volume ratio of the 25-28% ammonia water to the water is 3: 1-1: 3.
[8] The preparation method according to the above [6] or [7], wherein the content of ammonium ions in the aqueous ammonia solution used for generating 1mol of the denitration catalyst is 8 to 20 mol; and/or
The aging time is 1-10 h; and/or
The calcining time is 2-12 h, and the calcining temperature is 300-500 ℃.
[9] The production process according to any one of the above [6] to [8], wherein the calcination further comprises a washing and/or drying step; preferably, the first and second electrodes are formed of a metal,
the washing times are 2-10 times;
the drying temperature is 80-120 ℃, and the drying time is 4-24 h.
[10] The application of the denitration catalyst prepared according to any one of the items [1] to [4] or the preparation method of any one of the items [5] to [9] in catalytic removal of nitrogen oxides in flue gas.
ADVANTAGEOUS EFFECTS OF INVENTION
The denitration catalyst disclosed by the invention has excellent denitration efficiency at low temperature, is low in price, is environment-friendly and has no obvious toxicity. The denitration catalyst provided by the invention has stronger sulfur resistance, and can reduce irreversible inactivation of the denitration catalyst in the using process.
Furthermore, the preparation method of the denitration catalyst has the advantages of easily available raw materials, simple operation of the technological process, no toxicity, no harm and low cost, and is suitable for mass production.
Drawings
Fig. 1 shows an electron micrograph of a denitration catalyst according to example 1 of the present invention;
fig. 2 shows an electron micrograph of a denitration catalyst according to example 2 of the present invention;
FIG. 3 shows an electron micrograph of a denitration catalyst according to example 3 of the present invention;
FIG. 4 shows Mn3O4Electron micrographs of (A);
FIG. 5 shows denitration catalysts and Mn according to examples 1 to 3 of the present invention3O4X-ray diffraction patterns of (a);
FIG. 6 shows denitration catalysts and Mn according to examples 1 to 3 of the present invention3O4NO in aqueous but sulfur-free conditionsxA plot of conversion versus reaction temperature;
FIG. 7 shows denitration catalysts and Mn according to examples 1 to 3 of the present invention3O4NO under aqueous sulfur-containing conditionsxConversion versus reaction temperature.
Detailed Description
Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
All units used in the present invention are international standard units unless otherwise stated, and numerical values and numerical ranges appearing in the present invention should be understood to include errors allowed in industrial production.
As used herein, "water" includes any feasible water such as tap water, deionized water, distilled water, double distilled water, purified water, ion-exchanged water, and the like.
If "about", "substantially", "approximately" or the like is used herein, the error may be 5%.
First embodiment
A first embodiment of the present invention provides a denitration catalyst including Mn doped with a Cu compound3O4。
As shown in FIG. 5, in the present invention, CuK is used when powder X-ray diffraction method is usedαAn X-ray diffraction pattern of the denitration catalyst has a characteristic peak at a position of 36.1 + -0.2 in 2 theta (°) when analyzed under irradiation experiment conditions, or
When analyzed by a powder X-ray diffraction method under CuK α radiation experimental conditions, the X-ray diffraction pattern of the denitration catalyst has a characteristic peak at a position of 35.3 ± 0.2 in 2 θ (°).
It was confirmed by the powder X-ray diffraction method that Mn can be contained in the denitration catalyst of the present invention3O4And for different catalysts, Mn thereof3O4May exist in a crystalline formDifferent.
The inventor of the invention unexpectedly finds that the denitration catalyst has excellent denitration efficiency at low temperature, is low in price, is environment-friendly and has no obvious toxicity. The denitration catalyst provided by the invention has stronger sulfur resistance, and can reduce irreversible inactivation of the denitration catalyst in the using process.
Specifically, as shown in FIG. 5, CuK is adopted when powder X-ray diffraction method is usedαWhen analyzed under the radiation experiment conditions, the X-ray diffraction pattern of the denitration catalyst can also have characteristic peaks at the positions with 2 theta (DEG) of 28.9 +/-0.2, 32.3 +/-0.2 and 59.8 +/-0.2; preferably, the denitration catalyst may further have an X-ray diffraction pattern having characteristic peaks at 31.0. + -. 0.2, 36.4. + -. 0.2, 38.0. + -. 0.2, 44.4. + -. 0.2, 50.7. + -. 0.2, 58.5. + -. 0.2 and 64.7. + -. 0.2 in 2. theta. (°). In this case, Mn in the denitration catalyst obtained3O4Belongs to the tetragonal system (tetragonal system).
Specifically, as shown in FIG. 5, CuK is adopted when powder X-ray diffraction method is usedαWhen the denitration catalyst is analyzed under the radiation experiment condition, the X-ray diffraction pattern of the denitration catalyst can also have characteristic peaks at the positions with 2 theta (DEG) of 30.0 +/-0.2, 43.0 +/-0.2, 56.8 +/-0.2, 62.4 +/-0.2 and 89.3 +/-0.2; preferably, the denitration catalyst may further have characteristic peaks at positions of 53.3. + -. 0.2 and 73.7. + -. 0.2 in terms of 2. theta. (. degree.) in an X-ray diffraction pattern. In this case, Mn in the denitration catalyst obtained3O4Belonging to the cubic crystal system (cubic crystal system).
The tetragonal system of the invention belongs to the middle-grade crystal group, and the characteristic symmetric element is a quadruple axis. The crystal with quadruple axis or quadruple reverse axis characteristic symmetric elements in the direction of the only c-axis main axis with higher minor axis belongs to a tetragonal system. And the cubic system means a crystal having 4 cubic diagonal direction triad axis characteristic symmetric elements.
In the present invention, in order to more effectively exhibit the effect of the denitration catalyst, the molar ratio of the Cu atoms to the Mn atoms is 1:1 to 50, preferably 1:1.2 to 45, more preferably 1:3 to 1:40, further preferably 1:1.5 to 35, and further preferably 1:1.8 to 30. For example: the molar ratio of Cu atoms to Mn atoms may be 1:5, 1:8, 1:10, 1:15, 1:20, 1:25, etc.
Typically, the denitration catalyst of the present invention has an average particle size of 75nm or less, for example: the particle diameter may be 70nm or less, 60nm or less, 50nm or less, 45nm or less, 40nm or less, or the like. The denitration catalyst provided by the invention has smaller particle size, can have more excellent denitration efficiency at low temperature, and has stronger sulfur resistance and water resistance, and in addition, the catalyst cannot be irreversibly inactivated in the using process.
In the present invention, the Cu compound may be a Cu oxide such as: may be CuO.
Specifically, the denitration catalyst of the present invention can be represented as:
(CuxMn3–x)1–O4
wherein x is the molar amount of Cu and 0< x < 1;
is the vacancy content.
Specifically, x may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, etc.
Preferably, the specific surface area of the denitration catalyst is 20-100 m2g–1For example: the denitration catalyst may have a specific surface area of 30m2g–1、40m2g–1、50m2g–1、60m2g–1、70m2g–1、80m2g–1And the like.
Further, it is preferable that the denitration catalyst of the present invention does not contain a support component other than the specific composition of the denitration catalyst of the present invention. For example, a substance which does not contain a molecular sieve or the like as a carrier. The denitration catalyst of the present invention has a higher activity when it does not contain other carrier components.
The denitration catalyst is suitable for catalytic removal of Nitrogen Oxide (NO) in flue gasx). Flue gas is a mixture of gas and smoke dust and is the main cause of atmospheric pollution. The composition of the flue gas is complex, and although the definition varies internationally in each country or international organization, such gas usually contains water vapor and SO2、N2、O2、CO、CO2Hydrocarbon and nitrogen oxide compounds, and the like. Therefore, the pollution of the smoke to the environment is the compound pollution of various toxic gases.
In the prior art, although various denitration catalysts are provided for the catalytic removal of nitrogen oxides in flue gases, the removal is usually accompanied by high temperatures, while at low temperatures, due to SO2In the presence of Sulfur (SO)2) Poisoning and a small amount of SO in the flue gas2The irreversible inactivation of the catalyst can be caused, so that the denitration efficiency is reduced.
Specifically, in the present invention, the low temperature may be 250 ℃ or lower, preferably 220 ℃ or lower, more preferably 200 ℃ or lower, and further preferably 180 ℃ or lower, for example: 80-220 ℃.
Second embodiment
In a second embodiment of the present invention, there is provided a method of preparing the denitration catalyst of the first embodiment, that is, the denitration catalyst is prepared by using a co-precipitation method.
< coprecipitation method >
The coprecipitation method is a method in which two or more cations are contained in a solution and exist in the solution in a homogeneous phase, a precipitant is added, and a precipitation reaction is performed to obtain uniform precipitates of various components, and is an important method for preparing composite oxide ultrafine powder containing two or more metal elements.
The invention uses coprecipitation method to directly obtain powder material through chemical reaction in solution. Specifically, during the co-precipitation, the process conditions that can be controlled include: chemical proportion, solution concentration, solution temperature, the type and quantity of dispersing agents, mixing mode, stirring speed, pH value, washing mode, drying temperature and mode, calcining temperature and mode and the like. By controlling the process conditions, the powder material with uniform chemical components and small particle size and uniform distribution is obtained.
Specifically, in the prepared denitration catalyst, the molar ratio of the Cu atoms to the Mn atoms is 1:1 to 50, preferably 1:1.2 to 45, more preferably 1:1.5 to 1:40, further preferably 1:1.8 to 35, further preferably 1:2 to 30, for example: the molar ratio of Cu atoms to Mn atoms may be 1:5, 1:8, 1:10, 1:15, 1:20, 1:25, etc.
The denitration catalyst obtained by a coprecipitation method has an average particle size of 75nm or less. For example, the denitration catalyst may have an average particle diameter of 70nm or less, 65nm or less, 60nm or less, 55nm or less, 50nm or less, 45nm or less, or the like.
And, for the denitration catalyst thus prepared, when analyzed by a powder X-ray diffraction method under CuK α radiation experimental conditions, the X-ray diffraction pattern of the denitration catalyst has a characteristic peak at a position of 36.1 ± 0.2 in 2 θ (°); or
When analyzed by a powder X-ray diffraction method under CuK α radiation experimental conditions, the X-ray diffraction pattern of the denitration catalyst has a characteristic peak at a position of 35.3 ± 0.2 in 2 θ (°).
Specifically, the preparation method comprises the following steps:
dissolving and mixing a copper precursor and a manganese precursor to obtain a precursor solution;
putting the precursor solution into an alkali solution for aging to generate crystals;
and calcining the crystal to obtain the denitration catalyst.
< precursor solution >
In the precursor solution of the present invention, a copper precursor and a manganese precursor are contained, that is, a mixed solution of the copper precursor and the manganese precursor. In particular, the precursor solution may be formulated using water. For example: the copper precursor and the manganese precursor can be weighed and dissolved in water, and the mixture is stirred until the copper precursor and the manganese precursor are completely dissolved to obtain a precursor solution.
Specifically, the copper precursor may be a water-soluble salt containing copper, for example, the copper precursor includes one or a combination of two or more of copper nitrate, copper sulfate, copper chloride, and copper acetate. The manganese precursor can be a water-soluble salt containing manganese, and the manganese precursor comprises one or a combination of more than two of manganese nitrate, manganese sulfate, manganese chloride and manganese acetate.
< aging >
The invention puts the precursor solution into alkali solution to age, thereby generating crystal. The precursor solution can be quickly placed in an alkali solution to be stirred and aged, so that crystals are precipitated and grow. Preferably, the aging time is 1-10 h.
In the aging process, other conditions for the aging treatment are not particularly limited, and the aging treatment may be performed under air conditions, for example.
< alkali solution >
The alkaline solution of the present invention can be all feasible alkaline solutions capable of generating crystals, such as alkaline solutions of urea, NaOH, KOH, etc.
Specifically, the aqueous alkali of the present invention preferably uses an aqueous ammonia solution, which has the advantages of rapid precipitation, less residue, etc. as a precipitant. Preferably, the ammonia water solution is a mixture of 25-28% ammonia water and water, wherein the volume ratio of the 25-28% ammonia water to the water is 3: 1-1: 3. For example: the volume ratio of the ammonia water with the concentration of 25-28% to the water is 2.5:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:2 and 1: 2.5.
In the preparation process, the content of ammonium ions in the ammonia water solution used for generating 1mol of the denitration catalyst is 8-20 mol, for example: the content of ammonium ions in the aqueous ammonia solution to be used may be 10mol, 12mol, 14mol, 16mol, 18mol, or the like.
< calcination >
The denitration catalyst is obtained by calcining the generated crystals. Specifically, the calcining time is 2-12 h, and the calcining temperature is 300-500 ℃.
The apparatus for calcination is not particularly limited, and, for example, a tube furnace, a muffle furnace, or the like can be used.
Other conditions for the calcination in the present invention are not particularly limited, and examples thereof include: the reaction can be carried out under vacuum, inert gas protection or air condition, and the inert gas can be nitrogen and the like. Preferably, it can be carried out directly under air conditions.
< washing and drying >
The method also comprises a step of washing and/or drying before the calcination.
Specifically, after washing, the solid-liquid separation may be performed by filtration, centrifugation, or the like, and then drying may be performed. In order to obtain a catalyst having excellent performance, washing and solid-liquid separation may be performed a plurality of times. Generally, the number of washing and the number of solid-liquid separation are the same. For example: the number of washing and solid-liquid separation may be 2 to 10.
In the invention, the drying temperature can be 80-120 ℃, and the drying time is 4-24 h.
Third embodiment
A third embodiment of the present invention provides a use of a denitration catalyst in catalytic removal of nitrogen oxides from flue gas, wherein the denitration catalyst comprises the denitration catalyst according to the first embodiment or the denitration catalyst prepared by the preparation method according to the second embodiment.
When used to remove nitrogen oxides, it may be a denitration catalyst composition. The denitration catalyst composition may include other various known denitration catalysts in the art. In a preferred embodiment of the present invention, the denitration catalyst composition includes at least 60 mass% or more of the denitration catalyst of the present invention, preferably 80 mass% or more, and more preferably 90 mass% or more, based on the total mass of the denitration catalyst composition.
The denitration catalyst can be used for catalytically removing nitrogen oxides in all flue gas, and specifically, the flue gas can comprise flue gas of a coal-fired power plant, flue gas of a cement plant, flue gas of a glass furnace, flue gas of a ceramic furnace, flue gas of a brick and tile plant and/or flue gas generated in a steel metallurgy process.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(Cu0.3Mn2.7)1–O4Preparation of the catalyst:
the method comprises the following steps: weighing 1.88g of precursor copper nitrate and 32.21g of manganese nitrate solution with the mass fraction of 50% by taking copper and manganese according to the molar ratio of 0.3: 2.7;
step two: adding the copper nitrate and the manganese nitrate weighed in the step one into 100ml of deionized water, and uniformly stirring until the copper nitrate and the manganese nitrate are completely dissolved;
step three: weighing 100ml of concentrated ammonia water (the concentration is 25-28%) and 100ml of deionized water, and uniformly stirring after mixing;
step four: quickly pouring the solution obtained in the step two into the ammonia water solution obtained in the step three, stirring and aging for 3 hours to precipitate and grow the obtained crystal;
step five: washing and centrifugally separating the crystal obtained in the step four by using deionized water, and repeating the washing and centrifuging steps for 5 times;
step six: and (3) drying the filter cake obtained in the fifth step at 100 ℃ for 12h, and calcining the filter cake at 450 ℃ for 3h under the air condition to obtain the denitration catalyst I, wherein an electron micrograph is shown as figure 2, and the average particle size of the denitration catalyst II is below 75nm and is recorded as: (Cu)0.3Mn2.7)1–O4。
Example 2
(Cu0.7Mn2.3)1–O4Preparation of the catalyst:
the method comprises the following steps: weighing 4.39g of precursor copper nitrate and 27.44g of manganese nitrate solution with the mass fraction of 50% according to the molar ratio of 0.7:2.3 of copper and manganese;
step two: adding the copper nitrate and the manganese nitrate weighed in the step one into 100ml of deionized water, and uniformly stirring until the copper nitrate and the manganese nitrate are completely dissolved;
step three: weighing 100ml of concentrated ammonia water (the concentration is 25-28%) and 100ml of deionized water, and uniformly stirring after mixing;
step four: quickly pouring the solution obtained in the step two into the ammonia water solution obtained in the step three, stirring and aging for 3 hours to precipitate and grow the obtained crystal;
step five: washing and centrifugally separating the crystal obtained in the step four by using deionized water, and repeating the washing and centrifuging steps for 5 times;
step six: and (3) drying the filter cake obtained in the fifth step at 100 ℃ for 12h, and calcining the filter cake at 450 ℃ for 3h under the air condition to obtain the denitration catalyst II, wherein an electron microscopic picture is shown in figure 2, and the average particle size of the denitration catalyst II is below 75nm and is recorded as: (Cu)0.7Mn2.3)1–O4。
Example 3
(Cu1.0Mn2.0)1–O4Preparation of the catalyst:
the method comprises the following steps: weighing 6.27g of precursor copper nitrate and 23.86g of 50% manganese nitrate solution according to the molar ratio of 1.0:2.0 of copper to manganese;
step two: adding the copper nitrate and the manganese nitrate weighed in the step one into 100ml of deionized water, and uniformly stirring until the copper nitrate and the manganese nitrate are completely dissolved;
step three: weighing 100ml of concentrated ammonia water (the concentration is 25-28%) and 100ml of deionized water, and uniformly stirring after mixing;
step four: quickly pouring the solution obtained in the step two into the ammonia water solution obtained in the step three, stirring and aging for 3 hours to precipitate and grow the obtained crystal;
step five: washing the substance obtained in the step four with deionized water, performing centrifugal separation, and repeating the washing and centrifugal steps for 5 times;
step six: and (3) drying the filter cake obtained in the fifth step at 100 ℃ for 12h, and calcining the filter cake at 450 ℃ for 3h under the air condition to obtain the denitration catalyst III, wherein an electron microscopic picture is shown in figure 3, and the average particle size of the denitration catalyst II is below 75nm and is recorded as: (Cu)1.0Mn2.0)1–O4。
Performance testing
1. Denitration activity test under water-containing and sulfur-free conditions
And (3) testing conditions are as follows: tabletting, crushing and screening the catalyst powder, selecting 40-60 meshes of catalyst particles for denitration activity evaluation, wherein 0.1g of catalyst has the total flow of flue gas of 100ml/min and the gas space velocity GHSV of 60,000h-1(Standard conditions), the flue gas concentration is NO 500ppm, NH3 500ppm，O2 5vol.％，H2O5 vol.%; the specific test results are shown in fig. 6.
As can be seen from FIG. 6, (Cu) of examples 1 to 30.3Mn2.7)1–O4Catalyst, (Cu)0.7Mn2.3)1–O4Catalyst, (Cu)1.0Mn2.0)1–O4The activity of the catalyst increases significantly with increasing temperature below 150 ℃ and decreases slightly above 200 ℃.
(Cu) of example 10.3Mn2.7)1–O4The activity of the catalyst is slightly lower than that of a reference catalyst Mn3O4. (Cu) of examples 2 to 30.7Mn2.3)1–O4Catalyst, (Cu)1.0Mn2.0)1–O4The activity of the catalyst is slightly superior to that of a reference catalyst Mn3O4。
2. Denitration activity test under conditions of containing water and sulfur
And (3) testing conditions are as follows: tabletting, crushing and screening catalyst powder, selecting 40-60 meshes of catalyst particles for denitration activity evaluation, wherein 0.1g of catalyst has the total flow of flue gas of 100ml/min and the gas space velocity GHSV of 60,000h-1(Standard conditions), the flue gas concentration is NO 500ppm, NH3 500ppm，O2 5vol.％，H2O 5vol.％，SO250 ppm; the specific test results are shown in fig. 7.
As can be seen from FIG. 7, (Cu) of examples 1 to 30.3Mn2.7)1–O4Catalyst, (Cu)0.7Mn2.3)1–O4Catalyst, (Cu)1.0Mn2.0)1–O4The activity of the catalyst increases significantly with increasing temperature below 150 ℃ and decreases slightly above 200 ℃.
(Cu) of examples 1 to 30.3Mn2.7)1–O4Catalyst, (Cu)0.7Mn2.3)1–O4Catalyst, (Cu)1.0Mn2.0)1–O4Catalyst under aqueous sulfur-containing conditions (Cu)1.0Mn2.0)1–O4The activity of the catalyst is obviously superior to that of a reference catalyst Mn3O4。
The combination of the above test results shows that: the denitration catalyst disclosed by the invention has no obvious influence on the denitration activity of the catalyst under the conditions of water content and no sulfur, but the denitration performance of the catalyst under the conditions of water content and sulfur content can be obviously improved by adding a small amount of copper. Wherein (Cu)1.0Mn2.0)1–O4The catalyst shows the most excellent denitration performance and water and sulfur resistance, and the optimal denitration efficiency can reach 90% at 150 ℃ under the condition of containing water and sulfur, which shows that the catalyst can reach the excellent denitration performance and sulfur poisoning resistance under the condition of low temperature, and has the advantages of no toxicity, simple preparation process and the like, thereby being an environment-friendly low-temperature denitration catalyst.
3. Powder X-ray diffraction method test
Taking (Cu) of example 10.3Mn2.7)1–O4Catalyst, when using powder X-ray diffraction method employing CuKα2 theta (°) sum of diffraction peaks when analyzed under radiation experimental conditions
The intensities of the diffraction peaks have the values shown in table 1 below:
TABLE 1
As can be seen from Table 1, when usedPowder X-ray diffraction method using CuKαWhen analyzed under the radiation test conditions, the X-ray diffraction pattern thereof has characteristic peaks at positions of 28.9 + -0.2, 31.0 + -0.2, 32.3 + -0.2, 36.1 + -0.2, 36.4 + -0.2, 38.0 + -0.2, 44.4 + -0.2, 50.7 + -0.2, 58.5 + -0.2, 59.8 + -0.2 and 64.6 + -0.2 in 2 theta (°), and the obtained (Cu)0.3Mn2.7)1–O4Mn in the catalyst3O4Belongs to the tetragonal system.
(Cu) of example 31.0Mn2.0)1–O4Catalyst, when using powder X-ray diffraction method employing CuKα2 theta (°) sum of diffraction peaks when analyzed under radiation experimental conditions
The intensities of the diffraction peaks have the values shown in table 2 below:
TABLE 2
As can be seen from Table 2, CuK was used when powder X-ray diffraction method was usedα(Cu) having characteristic peaks at positions of 30.0 + -0.2, 35.3 + -0.2, 43.0 + -0.2, 56.8 + -0.2, 62.4 + -0.2 and 89.3 + -0.2 in the X-ray diffraction pattern under the analysis of the radiation experimental conditions1.0Mn2.0)1–O4Mn in the catalyst3O4Belongs to the cubic crystal system.
Further, as can be seen from FIG. 5, (Cu) of example 2 of the present invention0.7Mn2.3)1–O4Mn in the catalyst3O4Peak appearance of (1) and (Cu) of example 10.3Mn2.7)1–O4The catalysts are similar and therefore belong to the tetragonal system.
Industrial applicability
The denitration catalyst can be industrially prepared and applied as a denitration catalyst for catalytically removing nitrogen oxides in flue gas.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (12)
1. A denitration catalyst is characterized by comprising Mn doped with Cu oxide3O4Wherein, in the step (A),
the molar ratio of Cu atoms to Mn atoms is 1: 1-15, and the average particle size of the denitration catalyst is less than 75 nm;
an X-ray diffraction pattern of the denitration catalyst having characteristic peaks at positions of 28.9 + -0.2, 32.3 + -0.2, 36.1 + -0.2, 59.8 + -0.2 in 2 theta DEG when analyzed using a powder X-ray diffraction method using CuK alpha radiation experimental conditions, the Mn in the denitration catalyst3O4Belongs to the tetragonal system; or
An X-ray diffraction pattern of a denitration catalyst having characteristic peaks at positions of 30.0 + -0.2, 35.3 + -0.2, 62.4 + -0.2 in 2 theta DEG when analyzed using a powder X-ray diffraction method using CuK alpha radiation experimental conditions, Mn in the denitration catalyst3O4Belongs to the cubic crystal system.
2. The denitration catalyst according to claim 1, wherein the denitration catalyst is represented by:
(CuxMn3–x)1–O4
wherein x is the molar amount of Cu and 0< x < 1;
is the vacancy content.
3. The denitration catalyst according to claim 1,
when using powder X-ray diffraction methodWhen analyzed under CuK alpha radiation experimental conditions, the X-ray diffraction pattern of the denitration catalyst also has characteristic peaks at positions with 2 theta degrees of 43.0 +/-0.2, 56.8 +/-0.2 and 89.3 +/-0.2, and Mn in the denitration catalyst3O4Belongs to the cubic crystal system.
4. The denitration catalyst according to any one of claims 1 to 3, wherein the denitration catalyst has a specific surface area of 20 to 100m2 g–1。
5. A preparation method of a denitration catalyst is characterized by comprising the steps of preparing the denitration catalyst by a coprecipitation method; wherein the denitration catalyst comprises Mn doped with Cu oxide3O4Wherein
The molar ratio of Cu atoms to Mn atoms is 1: 1-15, and the average particle size of the denitration catalyst is less than 75 nm;
an X-ray diffraction pattern of the denitration catalyst having characteristic peaks at positions of 28.9 + -0.2, 32.3 + -0.2, 36.1 + -0.2, 59.8 + -0.2 in 2 theta DEG when analyzed using a powder X-ray diffraction method using CuK alpha radiation experimental conditions, the Mn in the denitration catalyst3O4Belongs to the tetragonal system; or
An X-ray diffraction pattern of a denitration catalyst having characteristic peaks at positions of 30.0 + -0.2, 35.3 + -0.2, 62.4 + -0.2 in 2 theta DEG when analyzed using a powder X-ray diffraction method using CuK alpha radiation experimental conditions, Mn in the denitration catalyst3O4Belongs to the cubic crystal system.
6. The method of claim 5, comprising the steps of:
dissolving and mixing a copper precursor and a manganese precursor to obtain a precursor solution;
putting the precursor solution into an alkali solution for aging to generate crystals;
and calcining the crystal to obtain the denitration catalyst.
7. The production method according to claim 6, wherein the copper precursor includes one or a combination of two or more of copper nitrate, copper sulfate, copper chloride, and copper acetate; and/or
The manganese precursor comprises one or the combination of more than two of manganese nitrate, manganese sulfate, manganese chloride and manganese acetate; and/or
The alkali solution is an ammonia solution.
8. The method according to claim 7, wherein the aqueous ammonia solution is a mixture of 25-28% aqueous ammonia and water, and the volume ratio of the 25-28% aqueous ammonia to the water is 3: 1-1: 3.
9. The method according to any one of claims 6 to 8, wherein the content of ammonium ions in the aqueous ammonia solution used for producing 1mol of the denitration catalyst is 8 to 20 mol; and/or
The aging time is 1-10 h; and/or
The calcining time is 2-12 h, and the calcining temperature is 300-500 ℃.
10. The method according to any one of claims 6 to 8, wherein the calcination further comprises a washing and/or drying step.
11. The method according to claim 10, wherein the number of washing is 2 to 10; the drying temperature is 80-120 ℃, and the drying time is 4-24 h.
12. Use of the denitration catalyst according to any one of claims 1 to 4 or the denitration catalyst prepared by the preparation method according to any one of claims 5 to 11 for catalytic removal of nitrogen oxides from flue gas.
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