CN111659413A - Low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst and preparation method thereof - Google Patents
Low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 70
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011593 sulfur Substances 0.000 title claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 39
- 229910001868 water Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 45
- 239000011248 coating agent Substances 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000000919 ceramic Substances 0.000 claims abstract description 22
- 238000000975 co-precipitation Methods 0.000 claims abstract description 18
- -1 aluminum oxide-cerium oxide-manganese dioxide Chemical compound 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 16
- 229910052878 cordierite Inorganic materials 0.000 claims description 14
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 3
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000004568 cement Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 12
- 230000032683 aging Effects 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 230000006378 damage Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 229910018669 Mn—Co Inorganic materials 0.000 description 1
- 229910018651 Mn—Ni Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
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- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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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- 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
- B01J23/16—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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- 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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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst and a preparation method thereof. The low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises a porous ceramic carrier and a rare earth-based catalyst coating coated on the carrier, wherein the rare earth-based catalyst coating comprises an active component and an auxiliary agent, the active component comprises an alumina-ceria-manganese dioxide composite oxide, and the auxiliary agent comprises one or more of Fe, Co, Ni, W, Y and Cr. The invention also discloses a method for preparing the active component of the catalyst by coprecipitation. The rare earth-based denitration catalyst disclosed by the invention is prepared from the aluminum oxide-cerium oxide-manganese dioxide composite oxide by adopting a coprecipitation method, so that the low-temperature activity of the catalyst is higher, the active temperature window is widened, and in addition, the sulfur resistance and the water resistance of the rare earth-based catalyst are enhanced by introducing the auxiliary agent, so that the rare earth-based denitration catalyst can be widely applied to tail gas denitration treatment of thermal power plants and cement plants.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst and a preparation method thereof.
Background
NOx is not only a major contributor to acid rain, but also a prerequisite for near-formation atmospheric ozone pollution, photochemical smog, secondary fine particle pollution, and surface eutrophication, and the problems caused thereby have become the most prominent atmospheric environmental hot-spot problems together with ozone layer destruction, global climate change.
At present, Selective Catalytic Reduction (SCR) is considered as the best denitration technology in specific areasSelective reduction of NOx to N with ammonia or other reducing agents over a catalyst2The method of (1). Wherein, with NH3The SCR technology, which is a reducing agent, is widely used because of its high efficiency and no secondary pollution. The catalyst is the most central part of the system in the whole SCR process. SCR catalyst development has gone through mainly three stages, noble metal catalysts, molecular sieve catalysts and metal oxide catalysts. The noble metal catalyst usually uses Pt, Rh, Pd, etc. as active components, uses alumina or monolithic ceramic as a carrier, and has low activity temperature range of catalytic reaction, usually below 300 ℃, but has narrow temperature window and by-product N2O formation, alternatively to NH3Has a certain oxidation effect on SO in the flue gas2It is also sensitive and costly. The metal ion exchange molecular sieve catalyst mainly comprises Y type, ZSM series, luminous zeolite and the like, has higher effective active temperature range up to 600 ℃, but is mainly used under the conditions of higher temperature such as fuel gas emission control and the like. NH of metal oxide catalyst under oxygen-enriched condition3Better catalytic activity in SCR reactions, currently assembled in power plants as V2O5-WO3/TiO2The catalyst has a narrow active temperature window, the used V is toxic and can cause serious harm to the environment and human health, and the waste flue gas denitration catalyst (vanadium-titanium system) is definitely brought into dangerous waste management in the notice on strengthening the supervision work of the waste flue gas denitration catalyst issued by the environmental protection department of China. Therefore, the important significance is achieved in developing the rare earth-based denitration catalyst which is environment-friendly and has excellent performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst and a preparation method thereof aiming at the defects of the prior art. Compared with the traditional vanadium-based denitration catalyst, the aluminum oxide-cerium oxide-manganese dioxide composite oxide prepared by the coprecipitation method enables the catalyst to have higher low-temperature activity, widens the activity temperature window, and enhances the sulfur resistance and water resistance of the rare earth-based denitration catalyst by introducing the auxiliary agent.
In order to solve the technical problems, the invention adopts the following technical scheme: a low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises a porous ceramic carrier and a rare earth-based catalyst coating coated on the carrier, wherein the rare earth-based catalyst coating comprises an active component and an auxiliary agent, the active component comprises an aluminum oxide-cerium oxide-manganese dioxide composite oxide, and the auxiliary agent comprises one or more of Fe, Co, Ni, W, Y and Cr.
The rare earth-based sulfur-resistant water-resistant denitration catalyst comprises the following components in parts by weight: 10-40 parts of aluminum oxide, 20-80 parts of cerium oxide, 5-20 parts of manganese dioxide and 0.5-5 parts of an auxiliary agent.
The size of the porous ceramic carrier is 100-150 mm-50-400 mm, and the mesh number is 25-300 meshes.
The porous ceramic carrier is made of cordierite, mullite, aluminum titanate or silicon carbide.
The element composition of the auxiliary agent comprises one or more of Fe, Co, Ni, W and Cr.
The preparation method of the low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises the following steps:
(1) preparing an active component composite oxide by a coprecipitation method: mixing Al (NO)3)3、Ce(NO3)3With Mn (NO)3)2Mixing the mixture in a precipitator aqueous solution according to a certain proportion, stirring uniformly, regulating the pH value of the mixed solution to be within the range of 7.5-8.5, washing, filtering, drying, grinding and calcining the solid product to obtain an aluminum oxide-cerium oxide-manganese dioxide composite oxide;
(2) preparing catalyst slurry: uniformly mixing the aluminum oxide-cerium oxide-manganese dioxide composite oxide, an auxiliary agent and deionized water to prepare a mixed solution A, wherein the solid content of the mixed solution A is controlled to be 20-50 wt.%, and the solid content ratio of the auxiliary agent to the catalyst is controlled to be 0.5-5 wt.%;
(3) rare earth based catalyst coating: coating the mixed solution A in the step (2) on a porous ceramic carrier according to the coating amount of 50-200g/L to prepare a catalyst B, drying the catalyst B at 100-200 ℃ for 0.5-5 hours, and roasting in a roasting furnace for 0.5-5 hours to obtain the rare earth-based catalyst.
Further, in the step (1), the precipitant is sodium hydroxide and/or potassium hydroxide.
Further, in the step (2), the auxiliary agent is one or more of iron oxide, cobalt oxide, nickel oxide, tungsten oxide or chromium oxide.
Further, the coating method used for coating the mixed solution a on the porous carrier in the step (3) is one or more of a dipping method, a vacuum suction method, and a spraying method.
Further, the calcination temperature in the step (3) is 400-600 ℃.
Compared with the prior art, the invention has the following advantages:
the catalyst prepared by the invention is nontoxic and environment-friendly, and has higher denitration efficiency under the conditions of low temperature, water and sulfur. The invention adopts aluminum-cerium-manganese series catalyst, uses Mn with excellent low-temperature activity to replace vanadium with toxicity, and the introduction of transition metals Fe, Co, Ni, W and Cr can be preferentially mixed with SO2Combine to form a stable compound which sterically hinders SO2Further adsorption and accumulation on the catalyst surface. XRD results show that the MnOx catalyst prepared by the coprecipitation method shows an amorphous structure, which is beneficial to improving the sulfur-resistant and water-resistant performance of the catalyst.
Drawings
FIG. 1 is a graph of the SCR performance of fresh catalysts of examples 1-5 of the present invention and comparative example 1.
FIG. 2 is a graph showing the SCR performance of catalysts in high temperature hydrothermal aging state in examples 1 to 5 of the present invention and comparative example 1.
FIG. 3 is a graph of the SCR performance of sulfur-aged catalysts of examples 1-5 of the present invention and comparative example 1.
Detailed Description
The technical solution of the present invention is further explained below with reference to the specific embodiments and the accompanying drawings.
Example 1
A low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises a porous ceramic carrier and a rare earth-based catalyst coating coated on the carrier, wherein the rare earth-based catalyst comprises the following components in parts by weight: 20 parts of aluminum oxide, 50 parts of cerium oxide, 10 parts of manganese oxide and 2.5 parts of iron oxide, wherein the size of the porous ceramic carrier is 100mm x 50mm, and the mesh number is 25-300 meshes.
The preparation method of the low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises the following steps:
(1) preparing an active component composite oxide by a coprecipitation method: mixing Al (NO)3)3With Ce (NO)3)3With Mn (NO)3)2Mixing the above materials in sodium hydroxide aqueous solution, stirring, regulating pH of the mixed solution to 7.5, washing, filtering, drying, grinding, and calcining to obtain aluminum oxide-cerium oxide-manganese dioxide composite oxide;
(2) preparing catalyst slurry: uniformly mixing the alumina-cerium oxide-manganese dioxide composite oxide catalyst powder obtained by coprecipitation in the step (1), ferric oxide and deionized water to prepare a mixed solution A with the solid content of 30 wt%;
(3) rare earth based catalyst coating: and (3) coating the mixed solution A prepared in the step (2) on a porous cordierite carrier by adopting a spraying method, wherein the coating amount of a catalyst coating is 150g/L, drying the porous cordierite carrier coated with the mixed solution A at 120 ℃ for 3 hours, and then roasting at 500 ℃ for 2 hours in an air atmosphere to prepare the Al-Ce-Mn-Fe rare earth-based catalyst.
Example 2
A low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises a porous ceramic carrier and a rare earth-based catalyst coating coated on the carrier, wherein the rare earth-based catalyst comprises the following components in parts by weight: 20 parts of alumina, 50 parts of cerium oxide, 10 parts of manganese oxide and 2.5 parts of cobalt oxide, wherein the size of the porous ceramic carrier is 100mm x 50mm, and the mesh number is 25-300 meshes.
The preparation method of the low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises the following steps:
(1) preparation of active group by coprecipitation methodAnd (3) composite oxide: mixing Al (NO)3)3With Ce (NO)3)3With Mn (NO)3)2Mixing the above materials in sodium hydroxide aqueous solution, stirring, regulating pH of the mixed solution to 7.5, washing, filtering, drying, grinding, and calcining to obtain aluminum oxide-cerium oxide-manganese dioxide composite oxide;
(2) preparing catalyst slurry: uniformly mixing the alumina-cerium oxide-manganese dioxide composite oxide catalyst powder obtained by coprecipitation in the step (1), cobalt oxide and deionized water to prepare a mixed solution A with the solid content of 30 wt%;
(3) rare earth based catalyst coating: and (3) coating the mixed solution A prepared in the step (2) on a porous cordierite carrier by adopting a spraying method, wherein the coating amount of a catalyst coating is 150g/L, drying the porous cordierite carrier coated with the mixed solution A at 120 ℃ for 3 hours, and then roasting at 500 ℃ for 2 hours in an air atmosphere to prepare the Al-Ce-Mn-Co rare earth-based catalyst.
Example 3
A low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises a porous ceramic carrier and a rare earth-based catalyst coating coated on the carrier, wherein the rare earth-based catalyst comprises the following components in parts by weight: 20 parts of aluminum oxide, 50 parts of cerium oxide, 10 parts of manganese oxide and 2.5 parts of nickel oxide, wherein the size of the porous ceramic carrier is 100mm x 50mm, and the mesh number is 25-300 meshes.
The preparation method of the low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises the following steps:
(1) preparing an active component composite oxide by a coprecipitation method: mixing Al (NO)3)3With Ce (NO)3)3With Mn (NO)3)2Mixing the above materials in sodium hydroxide aqueous solution, stirring, regulating pH of the mixed solution to 8, washing, filtering, drying, grinding, and calcining the solid product to obtain aluminum oxide-cerium oxide-manganese dioxide composite oxide;
(2) preparing catalyst slurry: uniformly mixing the aluminum oxide-cerium oxide-manganese dioxide composite oxide catalyst powder obtained by coprecipitation in the step a, nickel oxide and deionized water to prepare a mixed solution A with the solid content of 30 wt.%;
(3) rare earth based catalyst coating: and (3) coating the mixed solution A prepared in the step (2) on a porous cordierite carrier by adopting a spraying method, wherein the coating amount of a catalyst coating is 150g/L, drying the porous cordierite carrier coated with the mixed solution A at 120 ℃ for 3 hours, and then roasting at 500 ℃ for 2 hours in an air atmosphere to prepare the Al-Ce-Mn-Ni rare earth-based catalyst.
Example 4
A low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises a porous ceramic carrier and a rare earth-based catalyst coating coated on the carrier, wherein the rare earth-based catalyst comprises the following components in parts by weight: 20 parts of alumina, 50 parts of cerium oxide, 10 parts of manganese oxide and 2.5 parts of tungsten oxide, wherein the size of the porous ceramic carrier is 100mm x 50mm, and the mesh number is 25-300 meshes.
The preparation method of the low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises the following steps:
(1) preparing an active component composite oxide by a coprecipitation method: mixing Al (NO)3)3With Ce (NO)3)3With Mn (NO)3)2Mixing the above materials in sodium hydroxide aqueous solution, stirring, regulating pH of the mixed solution to 8.5, washing, filtering, drying, grinding, and calcining to obtain aluminum oxide-cerium oxide-manganese dioxide composite oxide;
(2) preparing catalyst slurry: uniformly mixing the aluminum oxide-cerium oxide-manganese dioxide composite oxide catalyst powder obtained by coprecipitation in the step a, tungsten oxide and deionized water to prepare a mixed solution A with the solid content of 30 wt.%;
(3) rare earth based catalyst coating: and (3) coating the mixed solution A prepared in the step (2) on a porous cordierite carrier by adopting a spraying method, wherein the coating amount of a catalyst coating is 150g/L, drying the porous cordierite carrier coated with the mixed solution A at 120 ℃ for 3 hours, and then roasting at 500 ℃ for 2 hours in an air atmosphere to prepare the Al-Ce-Mn-W rare earth-based catalyst.
Example 5
A low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises a porous ceramic carrier and a rare earth-based catalyst coating coated on the carrier, wherein the rare earth-based catalyst comprises the following components in parts by weight: 20 parts of aluminum oxide, 50 parts of cerium oxide, 10 parts of manganese oxide and 2.5 parts of chromium oxide, wherein the size of the porous ceramic carrier is 100mm x 50mm, and the mesh number is 25-300 meshes.
The preparation method of the low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises the following steps:
(1) preparing an active component composite oxide by a coprecipitation method: mixing Al (NO)3)3With Ce (NO)3)3With Mn (NO)3)2Mixing the above materials in sodium hydroxide aqueous solution, stirring, regulating pH of the mixed solution to 8.5, washing, filtering, drying, grinding, and calcining to obtain aluminum oxide-cerium oxide-manganese dioxide composite oxide;
(2) preparing catalyst slurry: uniformly mixing the aluminum oxide-cerium oxide-manganese dioxide composite oxide catalyst powder obtained by coprecipitation in the step a, chromium oxide and deionized water to prepare a mixed solution A with the solid content of 30 wt.%;
(3) rare earth based catalyst coating: and (3) coating the mixed solution A prepared in the step (2) on a porous cordierite carrier by adopting a spraying method, wherein the coating amount of a catalyst coating is 150g/L, drying the porous cordierite carrier coated with the mixed solution A at 120 ℃ for 3 hours, and then roasting at 500 ℃ for 2 hours in an air atmosphere to prepare the Al-Ce-Mn-Cr rare earth-based catalyst.
Comparative example 1
A rare earth-based denitration catalyst with water resistance and sulfur resistance comprises a porous ceramic carrier and a rare earth-based catalyst coating coated on the carrier, wherein the rare earth-based catalyst comprises the following components in parts by weight: 20 parts of alumina, 50 parts of cerium oxide and 10 parts of manganese oxide, wherein the size of the porous ceramic carrier is 100mm x 50mm, and the mesh number is 25-300 meshes.
A preparation method of a rare earth-based SCR denitration catalyst with water resistance and sulfur resistance comprises the following steps:
a. mixing Al (NO)3)3With Ce (NO)3)3With Mn (NO)3)2Mixing the above materials in sodium hydroxide aqueous solution, stirring, regulating pH of the mixed solution to 8.5, washing, filtering, drying, grinding, and calcining to obtain aluminum oxide-cerium oxide-manganese dioxide composite oxide;
b. uniformly mixing the alumina-ceria-manganese dioxide composite oxide catalyst powder obtained by coprecipitation in the step a with deionized water to prepare a mixed solution A with the solid content of 30 wt.%, and coating the mixed solution A on a porous cordierite carrier by adopting a spraying method, wherein the coating amount of a catalyst coating is 150 g/L;
c. and c, drying the porous cordierite carrier coated with the mixed solution A in the step b at 120 ℃ for 3 hours, and then roasting at 500 ℃ for 2 hours in an air atmosphere to obtain the Al-Ce-Mn rare earth-based catalyst.
The catalysts prepared in examples 1 to 5 and comparative example 1 were subjected to NOx conversion tests in a fresh state, a high-temperature hydrothermal aging state, and a sulfur aging state, respectively, as shown in fig. 1 to 3, and catalyst evaluation conditions: 600ppm NH3，600ppm NO，10%O2，10%H2O，50ppm SO2，N2The space velocity is 50000h for balancing gas-1。
Wherein, the fresh state: catalysts prepared in examples 1-5 and comparative example 1.
High-temperature hydrothermal aging state: the catalysts prepared in the examples 1-5 and the comparative example 1 are aged for 30-60h under the conditions of 600-800 ℃ and 10% water vapor.
The state of sulfur aging: the catalysts prepared in examples 1-5 and comparative example 1 were aged at 150-200 deg.C for 15-30h in 100ppm sulfur dioxide atmosphere.
Among them, the fresh catalysts in FIGS. 1 to 3 are the catalysts obtained in examples 1 to 5 and comparative example 1. The high-temperature hydrothermal aged catalyst is the catalyst prepared by the catalyst prepared in the example 1-5 and the comparative example 1 and aged for 45 hours at the temperature of 700 ℃ under the condition of 10% water vapor. The sulfur-aged catalysts were those obtained in examples 1 to 5 and comparative example 1 after aging the catalysts at 200 ℃ for 20 hours in an atmosphere of 100ppm of sulfur dioxide.
As can be seen from the comparison of NOx conversion rates of the catalysts in different states in examples 1 to 5 and comparative example 1 in fig. 1 to 3, the catalyst T80 of the alumina-ceria-manganese dioxide prepared by the coprecipitation method of the present invention has a temperature of about 150 ℃, while the highest conversion rate of the catalyst is increased from 90% to about 99% by introducing one or more additives of Fe, Co, Ni, W and Cr, and the catalyst still maintains high activity in the hydrothermal aging and sulfur aging states due to the introduction of one or more additives of Fe, Co, Ni, W and Cr. Wherein the Ni-containing catalyst performs best.
Claims (10)
1. The low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst comprises a porous ceramic carrier and a rare earth-based catalyst coating coated on the carrier, and is characterized in that the rare earth-based catalyst coating comprises an active component and an auxiliary agent, the active component comprises an alumina-ceria-manganese dioxide composite oxide, and the auxiliary agent comprises one or more of Fe, Co, Ni, W, Y and Cr.
2. The low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst as claimed in claim 1, wherein the rare earth-based sulfur-resistant water-resistant denitration catalyst comprises the following components in parts by weight: 10-40 parts of aluminum oxide, 20-80 parts of cerium oxide, 5-20 parts of manganese dioxide and 0.5-5 parts of an auxiliary agent.
3. The low-temperature rare-earth-based sulfur-resistant, water-resistant and denitration catalyst as claimed in claim 1, wherein the porous ceramic carrier has a size of 100-150 mm-50-400 mm, and a mesh number of 25-300 meshes.
4. The low-temperature rare-earth-based sulfur-resistant water-resistant denitration catalyst as claimed in claim 1, wherein the porous ceramic carrier material is cordierite, mullite, aluminum titanate or silicon carbide.
5. The low-temperature rare-earth-based sulfur-resistant water-resistant denitration catalyst as claimed in claim 1, wherein the elemental composition of the auxiliary comprises one or more of Fe, Co, Ni, W and Cr.
6. The preparation method of the low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst as claimed in claim 1, characterized by comprising the steps of:
(1) preparing an active component composite oxide by a coprecipitation method: mixing Al (NO)3)3、Ce(NO3)3With Mn (NO)3)2Mixing the mixture in a precipitator aqueous solution according to a certain proportion, stirring uniformly, regulating the pH value of the mixed solution to be within the range of 7.5-8.5, washing, filtering, drying, grinding and calcining the solid product to obtain an aluminum oxide-cerium oxide-manganese dioxide composite oxide;
(2) preparing catalyst slurry: uniformly mixing the aluminum oxide-cerium oxide-manganese dioxide composite oxide, an auxiliary agent and deionized water to prepare a mixed solution A, wherein the solid content of the mixed solution A is controlled to be 20-50 wt.%, and the solid content ratio of the auxiliary agent to the catalyst is controlled to be 0.5-5 wt.%;
(3) rare earth based catalyst coating: coating the mixed solution A in the step (2) on a porous ceramic carrier according to the coating amount of 50-200g/L to prepare a catalyst B, drying the catalyst B at 100-200 ℃ for 0.5-5 hours, and roasting in a roasting furnace for 0.5-5 hours to obtain the rare earth-based catalyst.
7. The preparation method of the low-temperature rare-earth-based sulfur-resistant water-resistant denitration catalyst according to claim 6, wherein the precipitant in the step (1) is sodium hydroxide and/or potassium hydroxide.
8. The preparation method of the low-temperature rare-earth-based sulfur-resistant water-resistant denitration catalyst according to claim 6, wherein the auxiliary in the step (2) is one or more of iron oxide, cobalt oxide, nickel oxide, tungsten oxide or chromium oxide.
9. The preparation method of the low-temperature rare earth-based sulfur-resistant, water-resistant and denitration catalyst according to claim 6, wherein the coating method used for coating the mixed solution A on the porous carrier in the step (3) is one or more of a soaking method, a vacuum suction method and a spraying method.
10. The method for preparing the low-temperature rare-earth-based sulfur-resistant, water-resistant and denitration catalyst as claimed in claim 6, wherein the calcination temperature in the step (3) is 400-600 ℃.
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Cited By (6)
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| CN112473683A (en) * | 2020-11-18 | 2021-03-12 | 浙江工业大学 | Powder sintering filtering catalytic material based on gradient pore structure and preparation method thereof |
| CN113976102A (en) * | 2021-11-29 | 2022-01-28 | 中国科学院兰州化学物理研究所 | Low-temperature rare earth-based denitration catalyst powder and preparation method thereof |
| CN114192138A (en) * | 2021-12-31 | 2022-03-18 | 上海大学 | Low-temperature metal oxide catalyst resisting hydrothermal aging and preparation method thereof |
| CN115301283A (en) * | 2021-05-08 | 2022-11-08 | 国家能源投资集团有限责任公司 | Mn-Fe-based catalyst, preparation method thereof and method for removing NOx and dioxin in flue gas |
| CN115672312A (en) * | 2022-10-24 | 2023-02-03 | 南京工业大学 | Vanadium-free rare earth-based wide-temperature denitration catalyst with hollow structure and preparation method thereof |
| WO2023020579A1 (en) * | 2021-08-19 | 2023-02-23 | Basf Corporation | Metal oxide catalyst for selective catalytic reduction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112473683A (en) * | 2020-11-18 | 2021-03-12 | 浙江工业大学 | Powder sintering filtering catalytic material based on gradient pore structure and preparation method thereof |
| CN115301283A (en) * | 2021-05-08 | 2022-11-08 | 国家能源投资集团有限责任公司 | Mn-Fe-based catalyst, preparation method thereof and method for removing NOx and dioxin in flue gas |
| CN115301283B (en) * | 2021-05-08 | 2023-12-22 | 国家能源投资集团有限责任公司 | Mn-Fe-based catalyst, preparation method thereof and method for removing NOx and dioxin in flue gas |
| WO2023020579A1 (en) * | 2021-08-19 | 2023-02-23 | Basf Corporation | Metal oxide catalyst for selective catalytic reduction |
| CN113976102A (en) * | 2021-11-29 | 2022-01-28 | 中国科学院兰州化学物理研究所 | Low-temperature rare earth-based denitration catalyst powder and preparation method thereof |
| CN114192138A (en) * | 2021-12-31 | 2022-03-18 | 上海大学 | Low-temperature metal oxide catalyst resisting hydrothermal aging and preparation method thereof |
| CN115672312A (en) * | 2022-10-24 | 2023-02-03 | 南京工业大学 | Vanadium-free rare earth-based wide-temperature denitration catalyst with hollow structure and preparation method thereof |
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