CN114904565B - Manganese-based denitration catalyst, preparation method thereof and flue gas denitration method - Google Patents
Manganese-based denitration catalyst, preparation method thereof and flue gas denitration method Download PDFInfo
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- CN114904565B CN114904565B CN202110184523.6A CN202110184523A CN114904565B CN 114904565 B CN114904565 B CN 114904565B CN 202110184523 A CN202110184523 A CN 202110184523A CN 114904565 B CN114904565 B CN 114904565B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 239000011572 manganese Substances 0.000 title claims abstract description 103
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 68
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003546 flue gas Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 113
- 238000000576 coating method Methods 0.000 claims abstract description 113
- 239000002808 molecular sieve Substances 0.000 claims abstract description 81
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000011068 loading method Methods 0.000 claims abstract description 39
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 35
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 35
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 16
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 9
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 9
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 8
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005751 Copper oxide Substances 0.000 claims abstract description 7
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 7
- 229910001940 europium oxide Inorganic materials 0.000 claims abstract description 7
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 7
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- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 7
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- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 7
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 63
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
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- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
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- 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 description 33
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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
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- 239000002071 nanotube Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to the technical field of catalysts, and discloses a manganese-based denitration catalyst, a preparation method thereof and a flue gas denitration method, wherein the catalyst comprises a honeycomb ceramic carrier, and an active coating and a modified coating which are sequentially coated on the carrier, wherein the loading amount of the active coating is 3.5-60wt% and the loading amount of the modified coating is 0.5-15wt% relative to the carrier, the thickness of the active coating is 80-140 mu m, and the thickness of the modified coating is 10-40 mu m; the active coating comprises manganese oxide, a first metal oxide and a second metal oxide, wherein the first metal oxide is at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, the second metal oxide is at least one of copper oxide, cerium oxide, iron oxide, cobalt oxide, nickel oxide, praseodymium oxide, neodymium oxide, lanthanum oxide, europium oxide and samarium oxide, and the modified coating comprises a molecular sieve and/or porous SiO 2 . The catalyst provided by the invention has better SO resistance 2 Resistance to H 2 O-character and denitrification activity.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a manganese-based denitration catalyst, a preparation method thereof and a flue gas denitration method.
Background
The non-electric industry comprises coking, steel, cement, garbage incineration and the like and is NO x Is one of the main emission sources of the non-electric industry NO in China x The emission adopts the world-wide emission limit value, and the best technical approach meeting the standard is ammonia selective catalytic reduction (NH 3 SCR), the core of the technology is a denitration catalyst. Moreover, the flue gas temperature in the non-electric industry is generally low (140-300 ℃), which is far lowerIn the active temperature window of the traditional vanadium-titanium catalyst, the development of the low-temperature denitration catalyst becomes a current research hot spot. The hot spot of the existing low-temperature denitration catalyst is mainly Mn-based oxide catalyst, mn is taken as a polyvalent element, and can form several stable oxides, and the catalyst has high activity and high stability at low temperature, but is easy to receive H at low temperature 2 Inhibition of O and generation of SO 2 Poisoning. For example in the absence of H 2 O and 10v% H 2 Under the flue gas condition of O, the performance of the manganese-based catalyst can be reduced by 50 percent, and particularly, when the running temperature of the catalyst is lower than 200 ℃, the water resistance is more important; at a concentration of 200mg/Nm 3 SO 2 The performance of the manganese-based catalyst slowly decreases by 20% after 200 hours of operation under the flue gas condition. Therefore, the water resistance and sulfur resistance of manganese-based low temperature catalysts have been one of the bottlenecks of research.
CN111659364a discloses a sulfur-resistant water-resistant manganese-based low-temperature denitration catalyst and a preparation method thereof, the catalyst comprises sulfur-resistant auxiliary agent, active component and hydrophobic substance, the carrier of the catalyst is titanium dioxide nanotube synthesized by using waste SCR catalyst as raw material through hydrothermal method, the active component is manganese, the sulfur-resistant auxiliary agent is one or two of molybdenum disulfide and tungsten disulfide, the hydrophobic substance is at least one of fluorocarbon resin, polytetrafluoroethylene emulsion and organosiloxane, and the concentration of the hydrophobic substance is 1000mg/Nm 3 SO 2 And 10v% H 2 Under the condition of O and surface speed Av=5m/h, the denitration efficiency exceeds 90 percent at 120-200 ℃.
CN109529948A discloses a method for improving water-resistant and sulfur-resistant properties of a manganese-based low-temperature SCR denitration catalyst, which adopts hydrophobic polytetrafluoroethylene as a coating or doping material, and the manganese-based catalyst is subjected to mixing, stirring, filtering, drying and calcining to prepare the manganese-based low-temperature SCR denitration catalyst with excellent water-resistant and sulfur-resistant properties. The catalyst was in 20v% H 2 O、50ppm SO 2 Under the condition of 140-200 ℃, the denitration efficiency can be stabilized to be more than 80 percent.
However, the catalyst can only be used at 120-200 ℃, has poor adaptability to high temperature and is subjected to H in flue gas 2 O and SO 2 Is of (1) affects its performanceThe drop is faster and the service life is short. In addition, the hydrophobic substances used by the catalyst are all organic polymer materials, and the price is relatively high. Therefore, the development of a new manganese-based denitration catalyst has great significance.
Disclosure of Invention
The invention aims to solve the problems that the existing manganese-based denitration catalyst has poor adaptability to high temperature and is subjected to H in flue gas 2 O and SO 2 The catalyst has the advantages of quick performance reduction, short service life and high price of the used hydrophobic substance, and the catalyst has better denitration activity and SO resistance 2 Resistance and H resistance 2 O-property.
In order to achieve the above object, a first aspect of the present invention provides a manganese-based denitration catalyst comprising a honeycomb ceramic support, and an active coating layer and a modified coating layer sequentially coated on the support, wherein the loading amount of the active coating layer is 3.5 to 60wt% and the loading amount of the modified coating layer is 0.5 to 15wt% relative to the support, the thickness of the active coating layer is 80 to 140 μm, and the thickness of the modified coating layer is 10 to 40 μm; the active coating comprises manganese oxide, a first metal oxide and a second metal oxide, wherein the first metal oxide is at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, the second metal oxide is at least one of copper oxide, cerium oxide, iron oxide, cobalt oxide, nickel oxide, praseodymium oxide, neodymium oxide, lanthanum oxide, europium oxide and samarium oxide, and the modified coating comprises a molecular sieve and/or porous SiO 2 。
The second aspect of the invention provides a method for preparing a manganese-based denitration catalyst, which comprises the following steps:
(1) The method comprises the steps of (1) carrying out first coating on a honeycomb ceramic carrier by adopting slurry containing active component powder, and then carrying out first drying to obtain an intermediate coated with an active coating; the active coating has a loading of 3.5 to 60wt% relative to the support, and a thickness of 80 to 140 μm;
(2) By using molecular sieves and/or porous SiO-containing materials 2 Is a slurry of (2)Performing second coating on the intermediate by using liquid, and then performing second drying to obtain a catalyst precursor coated with an active coating and a modified coating simultaneously; the loading amount of the modified coating is 0.5-15wt% relative to the carrier, and the thickness of the modified coating is 10-40 mu m; then, the catalyst precursor is subjected to first roasting to obtain a manganese-based denitration catalyst;
the active component powder comprises manganese oxide, a first metal oxide and a second metal oxide, wherein the first metal oxide is at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, and the second metal oxide is at least one of copper oxide, cerium oxide, iron oxide, cobalt oxide, nickel oxide, praseodymium oxide, neodymium oxide, lanthanum oxide, europium oxide and samarium oxide.
In a third aspect, the present invention provides a manganese-based denitration catalyst prepared by the method according to the second aspect of the present invention.
In a fourth aspect, the present invention provides a method for denitrating flue gas, the method comprising: the flue gas is contacted with the manganese-based denitration catalyst according to the first aspect or the third aspect of the present invention to react.
By adopting the technical scheme, the invention sequentially coats the active coating and the modified coating (molecular sieve and/or porous SiO) on the carrier 2 ) The thicknesses of the active coating and the modified coating are controlled within a specific range, SO that the prepared catalyst has better SO resistance under a wide temperature window of 140-300 DEG C 2 Resistance to H 2 O-character and better, more stable denitration activity. When the catalyst provided by the invention is applied to flue gas denitration reaction, after the catalyst is operated for 168 hours in a temperature range of 140-300 ℃, the attenuation of the denitration efficiency of the catalyst provided by the invention is less than 6%, and the attenuation of the denitration efficiency of the catalyst without the modified coating in comparative example 1 reaches 24.2%; SO with respect to the catalysts prepared in comparative examples 2 and 4 at the same time 2 /SO 3 The conversion rate is 1.38 percent and 1.46 percent, and the SO of the manganese-based denitration catalyst provided by the invention 2 /SO 3 The conversion rate is reduced to 0.66-0.72%, and the reduction range is more than 47%.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the prior art, the manganese-based catalyst has denitration effect at 120-200 ℃ but is subjected to H in flue gas 2 O and SO 2 The denitration efficiency of the catalyst is reduced rapidly, the service life of the catalyst is short, and most of hydrophobic substances on the existing manganese-based catalyst are organic polymer materials, so that the catalyst is expensive. In order to solve the above technical problems, the present inventors have found in studies that, by sequentially coating an active coating layer and a modified coating layer (molecular sieve and/or porous SiO) having specific thicknesses on a honeycomb ceramic support 2 ) The prepared catalyst has better SO resistance at a wide temperature window of 140-300 DEG C 2 Resistance to H 2 O-character and better, more stable denitration activity. Further, the inventors of the present invention have found that the SO resistance of the catalyst can be further improved by controlling the thickness of the active coating layer to be within a specific range of 100 to 120. Mu.m, and controlling the thickness of the modified coating layer to be within a specific range of 20 to 30. Mu.m 2 Resistance to H 2 O and denitration activity.
As described above, the first aspect of the present invention provides a manganese-based denitration catalyst comprising a honeycomb ceramic carrier, and an active coating layer and a modified coating layer sequentially coated on the carrier, wherein the active coating layer has a loading amount of 3.5 to 60wt% and the modified coating layer has a loading amount of 0.5 to 15wt% relative to the carrier, the active coating layer has a thickness of 80 to 140 μm, and the modified coating layer has a thickness of 10 to 40 μm; the active coating comprises manganese oxide, a first metal oxide and a second metal oxide, wherein the first metal oxide is at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxideThe second metal oxide is at least one selected from copper oxide, cerium oxide, iron oxide, cobalt oxide, nickel oxide, praseodymium oxide, neodymium oxide, lanthanum oxide, europium oxide and samarium oxide, and the modified coating comprises a molecular sieve and/or porous SiO 2 。
According to the invention, the active coating has very strong NH 3 The activation and NO adsorption capacities have strong denitration efficiency at 140-300 ℃, but the excessive oxidizing property can lead to SO 2 Is enhanced by oxidation. Therefore, by controlling the thickness of the active coating layer within a specific range of 80-140 μm, SO can be made while ensuring maximum denitration efficiency 2 The oxidation rate of (2) becomes low. In contrast, when the thickness of the active coating is less than 80 μm, a defect of insufficient denitration efficiency occurs; when the thickness of the active coating is greater than 140. Mu.m, SO may occur 2 /SO 3 And the conversion rate is too high. In the present invention, the thickness of the active coating is calculated by the formula:calculated, where ρ 1 Represents the density (g/cm) of the honeycomb ceramic support 3 )，ρ 2 Represents the density (g/cm) of the active ingredient powder 3 )，α 1 Represents the loading (wt%) of the active coating, W represents the width (square cross section, typically 150 mm) of the honeycomb ceramic support, n represents the number of pores (typically 10-120 pores) of the honeycomb ceramic support in the cross section width direction, L 1 Indicating the side length of the hole, i.e. the pore diameter.
The modified coating has good hydrophobicity, inhibits condensation of water molecules in capillary holes of the catalyst, improves the water resistance of the catalyst, and can ensure that the catalyst has better denitration activity and water resistance under the low-temperature (140-300 ℃) operation condition by controlling the thickness of the modified coating to be within a specific range of 10-40 mu m. In contrast, when the thickness of the modified coating layer is less than 10 μm, a defect of insufficient water resistance occurs; when the thickness of the modified coating layer is more than 40 μm, defects in inhibiting the denitration reaction process may occur. In addition, compared with the expensive organic polymer material in the prior art, the invention adopts the following steps Sub-sieves and/or porous SiO 2 As the modified coating, the cost can be saved, and the modified coating can be efficiently combined and dispersed with the active coating through chemical bonds, so that the stable coating of the modified coating is facilitated. In the invention, the thickness of the modified coating is calculated by the formula:calculated, where ρ 1 Represents the density (g/cm) of the honeycomb ceramic support 3 )，ρ 3 Representing molecular sieves and/or porous SiO 2 Density (g/cm) 3 )，α 2 Represents the loading (wt%) of the modified coating, W represents the width (square cross section, typically 150 mm) of the honeycomb ceramic support, n represents the number of pores (typically 10-120 pores) of the honeycomb ceramic support in the cross-sectional width direction, L 2 Indicating the side length of the hole, i.e. the pore diameter. In the present invention, since the pore diameter becomes smaller than before due to the application of the active coating, L is generally 2 Ratio L 1 Is small.
According to a preferred embodiment of the present invention, the active coating is supported in an amount of 4.5 to 50wt% with respect to the support, and the modified coating is supported in an amount of 1 to 11wt%; the thickness of the active coating is 100-120 mu m, and the thickness of the modified coating is 20-30 mu m. In this preferred case, the catalyst is more advantageous in achieving denitration, sulfur-and water-repellent effects.
In some embodiments of the present invention, preferably, the first metal oxide is niobium oxide and/or antimony oxide, which is more advantageous for improving the stability of denitration.
In some embodiments of the present invention, preferably, the second metal oxide is selected from at least one of iron oxide, cerium oxide, and lanthanum oxide, which is more advantageous in improving stability of denitration.
In some embodiments of the invention, the molecular sieve is preferably a molecular sieve having a high molar ratio of silicon to aluminum, preferably a molar ratio of silicon to aluminum of from 80 to 200:1.
the molecular sieve is selected from at least one of ZSM-5 type molecular sieve, BETA type molecular sieve, SBA-15 type molecular sieve, SBA-16 type molecular sieve, SBA-2 type molecular sieve, MCM-41 type molecular sieve, MCM-48 type molecular sieve, SSZ-13 type molecular sieve, SSZ-39 type molecular sieve and SAPO-34 type molecular sieve, more preferably ZSM-5 type molecular sieve and/or BETA type molecular sieve. In this preferred case, it is more advantageous to improve the water resistance of the catalyst.
In some embodiments of the invention, preferably, the porous SiO 2 The average pore size of (2) is smaller than 2nm. Further preferably, the porous SiO 2 Is white carbon black and/or SiO 2 An aerogel.
The honeycomb ceramic carrier has a wide selection range, preferably a honeycomb ceramic carrier with 10-120 holes, further preferably the honeycomb ceramic carrier is selected from one of cordierite, mullite, silicon carbide, alumina, silicon oxide, titanium oxide and zirconium oxide, and more preferably the cordierite honeycomb carrier.
The second aspect of the invention provides a method for preparing a manganese-based denitration catalyst, which comprises the following steps:
(1) The method comprises the steps of (1) carrying out first coating on a honeycomb ceramic carrier by adopting slurry containing active component powder, and then carrying out first drying to obtain an intermediate coated with an active coating; the active coating has a loading of 3.5 to 60wt% relative to the support, and a thickness of 80 to 140 μm;
(2) By using molecular sieves and/or porous SiO-containing materials 2 Second coating the intermediate, and then second drying to obtain a catalyst precursor coated with both an active coating and a modified coating; the loading amount of the modified coating is 0.5-15wt% relative to the carrier, and the thickness of the modified coating is 10-40 mu m; then, the catalyst precursor is subjected to first roasting to obtain a manganese-based denitration catalyst;
the active component powder comprises manganese oxide, a first metal oxide and a second metal oxide, wherein the first metal oxide is at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, and the second metal oxide is at least one of copper oxide, cerium oxide, iron oxide, cobalt oxide, nickel oxide, praseodymium oxide, neodymium oxide, lanthanum oxide, europium oxide and samarium oxide.
According to a preferred embodiment of the present invention, in step (1), the slurry containing the active ingredient powder is used in such an amount that the resulting intermediate coated with the active coating layer has a loading amount of 4.5 to 50wt% with respect to the support and a thickness of 100 to 120 μm. In this preferred case, the sulfur resistance and the denitration activity of the catalyst can be further improved, and the denitration stability of the catalyst can be improved.
According to a preferred embodiment of the invention, in step (2), the catalyst comprises molecular sieves and/or porous SiO 2 The amount of the slurry of (c) is such that, in the resulting catalyst precursor coated with both the active coating layer and the modified coating layer, the loading amount of the modified coating layer is 1 to 11wt% with respect to the support, and the thickness of the modified coating layer is 20 to 30 μm. In this preferred case, it is possible to further improve the water resistance and the denitration activity of the catalyst, and improve the denitration stability of the catalyst.
In some embodiments of the present invention, preferably, in step (1), the preparation method of the slurry containing the active ingredient powder includes:
(a) Mixing a manganese source, a compound containing a first metal and a compound containing a second metal with water to obtain a solution containing the manganese source, the compound containing the first metal and the compound containing the second metal, mixing the solution with an organic complexing agent and a first dispersing agent, and then sequentially evaporating, drying and roasting to obtain active component powder;
(b) And mixing the active component powder with a binder, a second dispersing agent and water, and pulping to obtain slurry containing the active component powder.
The solution containing the manganese source, the first metal-containing compound and the second metal-containing compound obtained by mixing the manganese source, the first metal-containing compound and the second metal-containing compound with water in the step (a) is not particularly limited as long as a uniform and stable solution can be obtained. The mixing according to the invention may be carried out under stirring.
In some embodiments of the present invention, preferably, in the step (a), the molar ratio of the manganese source calculated as Mn element to the first metal-containing compound calculated as the first metal and the second metal-containing compound calculated as the second metal is 0.05 to 0.5:0.05-0.3:0.2 to 0.9, more preferably 0.3 to 0.4:0.1-0.2:0.4-0.6. In this preferred case, the denitration effect of the catalyst can be further improved.
In step (a) of the present invention, preferably, the molar ratio of the total amount of the manganese source calculated as Mn element to the first metal-containing compound calculated as the first metal and the second metal-containing compound calculated as the second metal to the organic complexing agent is 1:1.5 to 2.5, more preferably 1.8 to 2.2. In the preferred case, it is more advantageous to ensure complete complexation of all metal ions to form a cross-linked structure of the space network, thereby further improving the H resistance of the catalyst 2 O, SO-resistant 2 And stability to denitrification.
In step (a) of the present invention, the first dispersant is preferably used in an amount of 5 to 20wt%, more preferably 8 to 12wt% based on the mass of the organic complexing agent. Under the preferable condition, the method is more favorable for uniformly dispersing metal ions in the crosslinked body and is favorable for forming a more uniform and fine-particle composite metal oxide catalyst by subsequent roasting, thereby further improving the H resistance of the catalyst 2 O, SO-resistant 2 And stability to denitrification.
The organic complexing agent is not particularly limited, and any organic acid having a complexing effect may be used, and preferably, the organic acid is at least one selected from citric acid, oxalic acid and tartaric acid, and more preferably, citric acid.
The first dispersant is selected from polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, carboxymethyl cellulose, polyacrylic acid and polymethacrylic acid, and more preferably polyethylene glycol.
The evaporation conditions in the step (a) are not particularly limited as long as the water content of the mixed solution can be evaporated to dryness to obtain a porous sol, and the evaporation temperature is preferably 70 to 90 ℃. The evaporation according to the invention is carried out under stirring.
In some embodiments of the present invention, preferably, in step (a), the drying conditions include: the temperature is 90-120 ℃ and the time is 12-24h. The apparatus for performing the drying of step (a) is not particularly limited in the present invention and may be selected as is conventional in the art, including, but not limited to, drying using an oven.
In some embodiments of the present invention, preferably, in step (a), the roasting conditions include: heating to 250-350deg.C at 0.5-5deg.C/min, and keeping constant temperature for 2-5h; then heating to 450-550 ℃ at 0.5-5 ℃/min, and keeping the temperature for 3-8h. The apparatus for carrying out the calcination of step (a) is not particularly limited in the present invention, and may be selected conventionally in the art, for example, including but not limited to, calcination using a muffle furnace.
In some embodiments of the present invention, preferably, in the step (b), the weight ratio of the active component powder to the binder, the second dispersant, and the water is 10 to 50:5-20:0.01-1:29-84.9, more preferably 15-25:10-15:0.5-1:59-74.5, which is more advantageous in obtaining a slurry of suitable viscosity, thereby further improving the sulfur resistance, water resistance and denitration activity of the catalyst.
The binder of step (b) is not particularly limited, and preferably the binder is at least one selected from the group consisting of titanium sol, silica sol, aluminum sol, zirconium sol, soluble zirconium salt, soluble aluminum salt and soluble titanium salt. In the present invention, in order to make the slurry flow in the pore channels better, the active component powder is mixed with a binder-containing solution, the concentration of which is preferably 5 to 10wt%.
The soluble zirconium salt is selected from a wide range of the present invention, and preferably the soluble zirconium salt is at least one selected from the group consisting of zirconium acetate, zirconium nitrate, zirconium sulfate, zirconium chloride and zirconium silicate.
The soluble aluminum salt is widely selected, and preferably, the soluble aluminum salt is at least one selected from aluminum trichloride, aluminum nitrate, aluminum sulfate and aluminum ammonium sulfate.
The soluble titanium salt is selected from at least one of titanium trichloride, titanium sulfate and titanyl sulfate.
The silica sol, the alumina sol and the zirconia sol are not particularly limited, but are preferably those having a pH of 6 to 7.
The second dispersant in step (b) is preferably selected from at least one of polyacrylamide, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxymethyl hydroxyethyl cellulose and gelatin.
The beating conditions in the step (b) are not particularly limited in the present invention, as long as the slurry containing the active ingredient powder obtained has a viscosity of 50 to 500 mPas, preferably 90 to 200 mPas, at 25 ℃. In this preferred case, the denitration effect of the catalyst is more favorably improved.
In some embodiments of the present invention, preferably, in step (b), the beating conditions include: the beating speed is 300-1000r/min, and the beating time is 30-100min.
In some embodiments of the invention, to better mix the active ingredient powder with the binder, the second dispersant, and water to obtain a slurry containing the active ingredient powder, the method further comprises: grinding the active component powder obtained in the step (a) to obtain powder with the particle size D50 smaller than 2.5 mu m and the particle size D90 smaller than 5 mu m, and then mixing the powder with a binder, a second dispersing agent and water. The manner of the grinding is not particularly limited in the present invention, and may be a conventional choice in the art, including, for example, grinding using a ball mill.
In the present invention, the first metal-containing compound is preferably a first metal-containing soluble compound. In the present invention, the term "soluble" means directly soluble in a solvent (preferably water, more preferably deionized water). Specifically, for example, the first metal-containing compound is at least one of a nitrate, acetate, sulfide, basic carbonate, sulfate, oxalate, and chloride salt containing the first metal.
In the present invention, the second metal-containing compound is preferably a second metal-containing soluble compound. In the present invention, the term "soluble" means directly soluble in a solvent (preferably water, more preferably deionized water). Specifically, for example, the second metal-containing compound is at least one of a nitrate, acetate, sulfide, basic carbonate, sulfate, oxalate, and chloride salt of the second metal.
According to the present invention, the first metal-containing compound is preferably at least one of a Mo-containing compound, a Nb-containing compound, a Ta-containing compound, a W-containing compound, and an Sb-containing compound.
According to the present invention, the second metal-containing compound is preferably at least one of a Cu-containing compound, a Ce-containing compound, a Fe-containing compound, a Co-containing compound, a Ni-containing compound, a Pr-containing compound, an Nd-containing compound, a La-containing compound, a Eu-containing compound, and a Sm-containing compound.
The time of the coating and the number of times of coating and drying in the step (1) are not particularly limited in the present invention, so long as the resulting intermediate coated with the active coating layer has a loading amount of 3.5 to 60wt% with respect to the support and a thickness of 80 to 140 μm, and those skilled in the art can perform the coating and drying for a plurality of times according to practical situations.
In some embodiments of the present invention, preferably, in step (1), the first drying condition includes: the temperature is 80-100deg.C, and the time is 20-60min. The person skilled in the art can choose the drying apparatus according to the actual circumstances.
In some embodiments of the present invention, preferably, in step (2), the catalyst comprises a molecular sieve and/or porous SiO 2 The preparation method of the slurry comprises the following steps: molecular sieves and/or porous SiO 2 Mixing with binder, second dispersant and water, and pulping to obtain a mixture containing molecular sieve and/or porous SiO 2 Is a slurry of (a) and (b).
PreferablyIn step (2), the molecular sieve and/or porous SiO 2 The weight ratio of the adhesive, the second dispersant and the water is 10-50:5-20:0.01-1:29-84.9, more preferably 15-25:10-15:0.5-1:59-74.5, which is more advantageous in obtaining a slurry of suitable viscosity, thereby further improving the sulfur resistance, water resistance and denitration activity of the catalyst.
The beating conditions in the step (2) are not particularly limited as long as the beating conditions can be such that the obtained slurry contains molecular sieves and/or porous SiO 2 The viscosity of the slurry at 25℃is 50 to 500 mPas, preferably 90 to 200 mPas.
Preferably, the beating conditions include: the beating speed is 300-1000r/min, and the beating time is 30-100min.
The time of the coating and the number of times of coating and drying in the step (2) are not particularly limited in the present invention, so long as it is possible to obtain a catalyst precursor coated with both the active coating layer and the modified coating layer, the modified coating layer having a loading amount of 0.5 to 15wt% with respect to the support and a thickness of 10 to 40 μm, and those skilled in the art can apply and dry a plurality of times according to practical circumstances.
In some embodiments of the present invention, preferably, in step (2), the second drying condition includes: the temperature is 80-100deg.C, and the time is 20-60min. The person skilled in the art can choose the drying apparatus according to the actual circumstances.
In some embodiments of the present invention, preferably, in step (2), the conditions of the first firing include: the temperature is 400-500 ℃ and the time is 1-5h. The person skilled in the art can choose the roasting equipment according to the actual situation.
In the present invention, in order to better make molecular sieve and/or porous SiO 2 Mixing with binder, second dispersant and water to obtain a mixture containing molecular sieve and/or porous SiO 2 The method further comprising: molecular sieves and/or porous SiO 2 Grinding to obtain particles with a diameter D50 less than 2.5 μm and D90 <5 μm powder, then mixed with binder, second dispersant, water. The polishing method of the present invention is not particularly limited, and may be conventional in the artThe selection includes, for example, grinding using a ball mill.
In the present invention, before the first drying in step (1) or before the second drying in step (2), the method further comprises: the coated product is purged with high pressure air and then either first or second dried. In the invention, the high-pressure air is used for blowing the coating product, so that the carrier pore channels can be prevented from being blocked, and better coating is facilitated.
In the invention, the molecular sieve and the porous SiO 2 The types of binder and second dispersant are as described above and will not be described in detail herein.
In order to clearly describe the preparation method of the manganese-based denitration catalyst according to the present invention, a preferred embodiment is provided below for illustration:
(I) Preparation of slurry containing active component powder:
(a) Mixing a manganese source calculated as Mn element with a first metal-containing compound calculated as a first metal and a second metal-containing compound calculated as a second metal in a ratio of 0.3 to 0.4:0.1-0.2: mixing and stirring the manganese source, the compound containing the first metal and the compound containing the second metal with deionized water in a molar ratio of 0.4-0.6 to obtain a solution containing a manganese source, the compound containing the first metal and the compound containing the second metal, and then mixing the solution with citric acid and polyethylene glycol, wherein the molar ratio of the total amount of the manganese source and the compound containing the first metal and the compound containing the second metal to the citric acid calculated by the Mn element is 1:1.8-2.2 weight percent of polyethylene glycol accounting for 8-12 weight percent of the mass of citric acid, stirring and evaporating at 70-90 ℃ to obtain porous sol, drying at 90-120 ℃ for 12-24 hours, heating to 250-350 ℃ at 0.5-5 ℃/min, keeping the temperature for 2-5 hours, heating to 450-550 ℃ at 0.5-5 ℃/min, keeping the temperature for 3-8 hours to obtain active component powder, and grinding the active component powder into powder with the particle size D50 less than 2.5 mu m and the particle size D90 less than 5 mu m;
(b) Mixing the powder with a solution containing a binder, a second dispersant and water according to a ratio of 15-25:10-15:0.5-1:59-74.5, pulping for 30-100min at a pulping speed of 300-1000r/min to obtain slurry containing active component powder with viscosity of 90-200mPa.s at 25deg.C;
(II) molecular sieves and/or porous SiO-containing materials 2 Is prepared from the slurry of (a) and (b)
Molecular sieves and/or porous SiO are first added 2 (average pore diameter less than 2 nm) grinding to particle diameter D50 < 2.5 μm, D90<5 μm powder, then mixed with a binder-containing solution, a second dispersant, water according to 15-25:10-15:0.5-1:59-74.5, pulping at a pulping speed of 300-1000r/min for 30-100min to obtain a mixture containing molecular sieve and/or porous SiO with viscosity of 90-200mPa.s at 25deg.C 2 Is a slurry of (a) and (b);
(III) preparation of manganese-based denitration catalyst
(1) The preparation method comprises the steps of (1) carrying out first coating on a honeycomb ceramic carrier by adopting slurry containing active component powder, blowing a coating product by adopting high-pressure air, and then carrying out first drying at 80-100 ℃ for 20-60min, so that the loading amount of the active coating is 4.5-50wt% relative to the carrier in the obtained intermediate coated with the active coating, and the thickness of the active coating is 100-120 mu m;
(2) By using molecular sieves and/or porous SiO-containing materials 2 The intermediate is subjected to second coating, the coating product is purged by adopting high-pressure air, and then the second drying is carried out for 20-60min at the temperature of 80-100 ℃, so that the loading amount of the modified coating is 1-11wt% relative to the carrier and the thickness of the modified coating is 20-30 mu m in the obtained catalyst precursor coated with the active coating and the modified coating simultaneously; and then the catalyst precursor is subjected to first roasting for 1-5 hours at 400-500 ℃ to obtain the manganese-based denitration catalyst.
In a third aspect, the present invention provides a manganese-based denitration catalyst prepared by the method described above. The manganese-based denitration catalyst prepared by the preparation method provided by the invention has better and more stable denitration efficiency and SO resistance at a wide temperature window of 140-300 DEG C 2 And H resistance 2 O capability.
In a fourth aspect, the present invention provides a method for denitrating flue gas, the method comprising: the flue gas is contacted with the manganese-based denitration catalyst of the present invention as described above to react.
Preferably, the process is carried out at a temperature of 140-300 ℃.
Preferably, the volume airspeed of the flue gas is 2000-20000h -1 The surface speed of the flue gas is 5-50m/h.
Preferably, in the flue gas, SO 2 Is 50-500mg/Nm 3 ，NO x Is 100-2000mg/Nm 3 ，NH 3 Is 75-750mg/Nm 3 ，O 2 The content of (3-15 v%, H) 2 The content of O is 8-40v%.
The invention will be described in detail below by way of examples. In the examples below, various raw materials used were available from commercial sources without particular explanation.
Example 1
(I) Preparation of slurries containing active component powders
(a) Manganese acetate as Mn element, niobium oxalate as Nb element, and ferric nitrate as Fe element were mixed in the following ratio of 0.4:0.2: mixing and stirring 0.4 molar ratio with deionized water to obtain a solution containing manganese acetate, niobium oxalate and ferric nitrate, and then mixing the solution with citric acid and polyethylene glycol, wherein the molar ratio of the total amount of manganese acetate calculated by Mn element to niobium oxalate calculated by Nb element to ferric nitrate calculated by Fe element to citric acid is 1:2, the dosage of polyethylene glycol is 10wt% of the mass of citric acid, then the mixture is stirred at 80 ℃ and slowly evaporated to dryness to obtain porous sol, the porous sol is dried at 110 ℃ for 12 hours, the temperature is raised to 300 ℃ at 5 ℃/min, the temperature is kept constant for 3 hours, then the temperature is raised to 500 ℃ at 5 ℃/min, the temperature is kept constant for 5 hours, active component powder is obtained, and the active component powder is ground into powder with the particle size D50 of less than 2.5 mu m and the particle size D90 of less than 5 mu m;
(b) The powder was mixed with an alumina sol solution (concentration 10 wt%), polyethylene oxide, water according to 15:10:0.5:74.5, and pulping for 30min at a pulping speed of 300r/min to obtain slurry containing active component powder with a viscosity of 150 mPa.s at 25 ℃;
(II) molecular sieves and/or porous SiO-containing materials 2 Is prepared from the slurry of (a) and (b)
Firstly, grinding a ZSM-5 type molecular sieve (the molar ratio of silicon to aluminum is 120 and the average pore diameter is less than 2 nm) into powder with the particle diameter D50 less than 2.5 mu m and the particle diameter D90 less than 5 mu m, and then mixing the powder with an aluminum sol solution (the concentration is 10 wt%), polyethylene oxide and water according to the proportion of 15:10:0.5:74.5, and pulping for 30min at a pulping speed of 300r/min to obtain slurry containing ZSM-5 molecular sieve with viscosity of 150 mPa.s at 25 ℃;
(III) preparation of manganese-based denitration catalyst
(1) The 40-pore cordierite honeycomb carrier (150 mm in cross-sectional area. Times.150 mm in height: 150 mm) was first coated with the slurry containing the active component powder for 5 minutes, the coated product was purged with high-pressure air, and then first dried at 90℃for 30 minutes, and the above steps were repeated a plurality of times, so that the active coating-coated intermediate was obtained in which the loading amount of the active coating was 20% by weight relative to the cordierite honeycomb carrier, and the width W in the cordierite honeycomb carrier was 150mm, the pore diameter L 1 Cordierite honeycomb carrier ρ of 3.0mm 1 2.6g/cm 3 Density ρ of active component powder 2 2.7g/cm 3 Calculating according to a formula to obtain the thickness of the active coating which is 108 mu m;
(2) Second coating the intermediate with slurry containing ZSM-5 type molecular sieve for 5min, purging the coated product with high pressure air, second drying at 90deg.C for 30min, and repeating the above steps for several times to obtain catalyst precursor coated with active coating and modified coating at the same time, wherein the loading amount of the modified coating is 2.5wt% relative to cordierite honeycomb carrier, and the width W of the cordierite honeycomb carrier is 150mm, and the pore diameter L 2 Cordierite honeycomb carrier ρ of 2.8mm 1 2.6g/cm 3 Density ρ of ZSM-5 molecular sieve 3 2.1g/cm 3 And (3) calculating according to a formula to obtain the thickness of the modified coating layer of 25 mu m, and roasting the catalyst precursor at 450 ℃ for 3 hours to obtain the manganese-based denitration catalyst.
Example 2
(I) Preparation of slurries containing active component powders
(a) Manganese acetate as Mn element, antimony acetate as Sb element, and ferric nitrate as Fe element were mixed in the following ratio of 0.3:0.2: mixing and stirring 0.5 molar ratio with deionized water to obtain solution containing manganese acetate, antimony acetate and ferric nitrate, and then mixing the solution with citric acid and polyethylene glycol, wherein the molar ratio of the total amount of manganese acetate calculated by Mn element to antimony acetate calculated by Sb element to ferric nitrate calculated by Fe element to citric acid is 1:1.8, the dosage of polyethylene glycol is 12wt% of the mass of citric acid, then the mixture is stirred at 80 ℃ and slowly evaporated to dryness to obtain porous sol, the porous sol is dried at 110 ℃ for 12 hours, the temperature is raised to 300 ℃ at 5 ℃/min, the temperature is kept constant for 3 hours, the temperature is raised to 500 ℃ at 5 ℃/min, the temperature is kept constant for 5 hours, active component powder is obtained, and the active component powder is ground into powder with the particle size D50 of less than 2.5 mu m and the particle size D90 of less than 5 mu m;
(b) The powder was mixed with an alumina sol solution (concentration 10 wt%), polyethylene oxide, water according to 20:13:0.8:66.2, and pulping for 30min at a pulping speed of 300r/min to obtain slurry containing active component powder with a viscosity of 200 mPa.s at 25 ℃;
(II) molecular sieves and/or porous SiO-containing materials 2 Is prepared from the slurry of (a) and (b)
Firstly grinding BETA type molecular sieve (silicon-aluminum mole ratio is 150, average pore diameter is less than 2 nm) into powder with particle diameter D50 less than 2.5 μm and D90 less than 5 μm, then mixing with silica sol solution (concentration is 10wt%), polyethylene oxide and water according to 20:13:0.8:66.2, pulping for 30min at a pulping speed of 300r/min to obtain slurry containing BETA-type molecular sieve with viscosity of 200mPa.s at 25deg.C;
(III) preparation of manganese-based denitration catalyst
(1) The 50-pore cordierite honeycomb carrier (150 mm. Times.150 mm in cross-sectional area and 150mm in height) was first coated with slurry containing an active component powder for 5 minutes, the coated product was purged with high-pressure air, and then first dried at 90℃for 30 minutes, and the above steps were repeated a plurality of times, so that the active coating-coated intermediate was obtained with a loading amount of 25% by weight of the active coating layer relative to the cordierite honeycomb carrier, and a width W of the cordierite honeycomb carrier was 150mm, pore diameter L 1 Cordierite honeycomb carrier ρ of 2.45mm 1 2.6g/cm 3 Density ρ of active component powder 2 2.75g/cm 3 The thickness of the active coating is 118 mu m according to the formula;
(2) Second coating the intermediate with slurry containing BETA-type molecular sieve for 5min, purging the coated product with high pressure air, second drying at 90deg.C for 30min, and repeating the above steps for several times to obtain catalyst precursor coated with active coating and modified coating at the same time, wherein the loading amount of the modified coating is 3wt% relative to cordierite honeycomb carrier, and the width W of the cordierite honeycomb carrier is 150mm, and the pore diameter L 2 Cordierite honeycomb carrier ρ of 2.2mm 1 2.6g/cm 3 Density ρ of BETA-type molecular sieve 3 Is 2.2g/cm 3 And (3) calculating according to a formula to obtain the thickness of the modified coating layer of 30 mu m, and roasting the catalyst precursor at 450 ℃ for 3 hours to obtain the manganese-based denitration catalyst.
Example 3
(I) Preparation of slurries containing active component powders
(a) Manganese acetate as Mn element, niobium oxalate as Nb element, cerium nitrate as Ce element were mixed in the following ratio of 0.35:0.1: mixing and stirring 0.55 mol ratio with deionized water to obtain a solution containing manganese acetate, niobium oxalate and cerium nitrate, and then mixing the solution with citric acid and polyethylene glycol, wherein the mol ratio of the total consumption of the manganese acetate and the niobium oxalate calculated by Mn element and the cerium nitrate calculated by Ce element to the citric acid is 1:2.2, the dosage of polyethylene glycol is 8wt% of the mass of citric acid, then the mixture is stirred at 80 ℃ and slowly evaporated to dryness to obtain porous sol, the porous sol is dried at 110 ℃ for 12 hours, the temperature is raised to 300 ℃ at 5 ℃/min, the temperature is kept constant for 3 hours, the temperature is raised to 500 ℃ at 5 ℃/min, the temperature is kept constant for 5 hours, active component powder is obtained, and the active component powder is ground into powder with the particle size D50 of less than 2.5 mu m and the particle size D90 of less than 5 mu m;
(b) The powder was mixed with a zirconium sol solution (concentration 10 wt%), polyethylene oxide, water according to 25:15:1:59, and pulping for 30min at a pulping speed of 300r/min to obtain slurry containing active component powder with a viscosity of 90 mPa.s at 25 ℃;
(II) molecular sieves and/or porous SiO-containing materials 2 Is prepared from the slurry of (a) and (b)
SiO is firstly put into 2 Grinding aerogel (average pore diameter less than 2 nm) to obtain particle diameter D50 < 2.5 μm, D90<5 μm powder, then mixed with a silica sol solution (concentration 10 wt%), polyethylene oxide, water according to 25:15:1:59 by weight, and pulping for 30min at a pulping speed of 300r/min to obtain a SiO-containing material with a viscosity of 90 mPa.s at 25deg.C 2 A slurry of aerogel;
(III) preparation of manganese-based denitration catalyst
(1) The 80-pore cordierite honeycomb carrier (150 mm in cross-sectional area, 150mm in height, 150 mm) was first coated with slurry containing the active component powder for 5 minutes, the coated product was purged with high-pressure air, and then first dried at 90 ℃ for 30 minutes, and the above steps were repeated a plurality of times, so that the active coating-coated intermediate was obtained with a loading of 31wt% of the active coating relative to the cordierite honeycomb carrier, and a width W of 150mm in the cordierite honeycomb carrier, and a pore diameter L 1 1.6mm, cordierite honeycomb carrier ρ 1 2.6g/cm 3 Density ρ of active component powder 2 3.0g/cm 3 Calculating according to a formula to obtain the thickness of the active coating as 100 mu m;
(2) By using a material containing SiO 2 The intermediate is subjected to second coating for 5min by using slurry of aerogel, the coated product is purged by adopting high-pressure air, the second drying is carried out for 30min at 90 ℃, and the steps are repeated for a plurality of times, so that the obtained catalyst precursor coated with the active coating and the modified coating simultaneously has the loading capacity of 2.5wt% relative to the cordierite honeycomb carrier, the width W of the cordierite honeycomb carrier is 150mm, and the pore diameter L 2 1.4mm, cordierite honeycomb carrier ρ 1 2.6g/cm 3 ，SiO 2 Density ρ of aerogel 3 2.6g/cm 3 The thickness of the modified coating is calculated to be 20 mu m according to a formula, and then the catalyst precursor is roasted for 3 hours at 450 ℃ to obtain the manganese-based denitration catalystAnd (3) an agent.
Example 4
According to the method of example 1, except that in step (1) of the preparation of (III) the manganese-based denitration catalyst, the amount of the slurry containing the active ingredient powder was controlled so that the active coating-coated intermediate obtained had a loading amount of 15% by weight with respect to the cordierite honeycomb carrier and a thickness of the active coating layer was 81. Mu.m;
The other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Example 5
According to the method of example 1, except that in the step (2) of the preparation of the (III) manganese-based denitration catalyst, the catalyst is prepared by controlling the catalyst containing a molecular sieve and/or porous SiO 2 The amount of the slurry of (c) is such that the loading amount of the modified coating layer with respect to the cordierite honeycomb carrier is 1.5wt% and the thickness of the modified coating layer is 15 μm in the resulting catalyst precursor coated with both the active coating layer and the modified coating layer;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Example 6
According to the method of example 1, except that in step (a) of preparing the slurry containing the active ingredient powder, (I) the molar ratio of manganese acetate in terms of Mn element, niobium oxalate in terms of Nb element, and iron nitrate in terms of Fe element was changed to 0.2:0.3:0.5;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Example 7
According to the method of example 1, except that in step (a) of preparing (I) the slurry containing the active ingredient powder, the molar ratio of manganese acetate in terms of Mn element to niobium oxalate in terms of Nb element and iron nitrate in terms of Fe element to citric acid was changed to 1:1.5;
The other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Example 8
The procedure of example 1 was followed except that in step (a) of preparing a slurry containing an active ingredient powder, (I) the amount of polyethylene glycol was changed to 5% by weight based on the mass of citric acid;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Example 9
According to the method of example 1, except that in step (b) of preparing slurry containing active ingredient powder, (I) the weight ratio of the powder to aluminum sol solution (concentration 10 wt%), polyethylene oxide, water was changed to 20:20:0.3:59.7, wherein the slurry containing the active ingredient powder obtained had a viscosity of 400 mPas at 25 ℃;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Example 10
According to the method of example 1, except that (II) contains molecular sieves and/or porous SiO 2 In the preparation of the slurry of (a), ZSM-5 type molecular sieve powder, alumina sol solution (concentration of 10 wt%), polyethylene oxide and water were changed to 10:5:0.3:84.7, the viscosity of the slurry containing ZSM-5 type molecular sieve obtained was 50 mPas at 25 ℃;
other steps were the same as in example to obtain a manganese-based denitration catalyst.
Comparative example 1
The procedure of example 1 is followed, except that no step (II) contains molecular sieves and/or porous SiO 2 Specifically, the step (2) in the preparation of the manganese-based denitration catalyst in the step (III) is as follows:
preparation of slurry containing active component powder:
(a) Manganese acetate as Mn element, niobium oxalate as Nb element, and ferric nitrate as Fe element were mixed in the following ratio of 0.4:0.2: mixing 0.4 molar ratio with deionized water to obtain a solution containing manganese acetate, niobium oxalate and ferric nitrate, and mixing the solution with citric acid and polyethylene glycol, wherein the molar ratio of the total amount of manganese acetate calculated by Mn element to niobium oxalate calculated by Nb element to ferric nitrate calculated by Fe element to citric acid is 1:2, the dosage of polyethylene glycol is 10wt% of the mass of citric acid, then the mixture is stirred at 80 ℃ and slowly evaporated to dryness to obtain porous sol, the porous sol is dried at 110 ℃ for 12 hours, the temperature is raised to 300 ℃ at 5 ℃/min, the temperature is kept constant for 3 hours, then the temperature is raised to 500 ℃ at 5 ℃/min, the temperature is kept constant for 5 hours, active component powder is obtained, and the active component powder is ground into powder with the particle size D50 of less than 2.5 mu m and the particle size D90 of less than 5 mu m;
(b) The powder was mixed with an alumina sol solution (concentration 10 wt%), polyethylene oxide, water according to 15:10:0.5:74.5, and pulping for 30min at a pulping speed of 300r/min to obtain slurry containing active component powder with a viscosity of 150 mPa.s at 25 ℃;
Preparation of manganese-based denitration catalyst
The 40-pore cordierite honeycomb carrier (150 mm in cross-sectional area. Times.150 mm in height: 150 mm) was first coated with the slurry containing the active component powder for 5 minutes, the coated product was purged with high-pressure air, and then first dried at 90℃for 30 minutes, and the above steps were repeated a plurality of times, so that the active coating-coated catalyst precursor was obtained in which the loading amount of the active coating layer was 20% by weight relative to the cordierite honeycomb carrier, and the width W in the cordierite honeycomb carrier was 150mm, the pore diameter L 1 Cordierite honeycomb carrier ρ of 3.0mm 1 2.6g/cm 3 Density ρ of active component powder 2 2.7g/cm 3 Calculating according to a formula to obtain the thickness of the active coating which is 108 mu m; and then roasting the catalyst precursor for 3 hours at 450 ℃ to obtain the manganese-based denitration catalyst.
Comparative example 2
According to the method of example 1, except that in step (1) of the preparation of (III) the manganese-based denitration catalyst, the amount of the slurry containing the active ingredient powder was controlled so that the active coating-coated intermediate obtained had a loading amount of 33% by weight and a thickness of the active coating layer of 180 μm with respect to the cordierite honeycomb carrier;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Comparative example 3
According to the method of example 1, except that in the step (2) of the preparation of the (III) manganese-based denitration catalystOverregulating and controlling molecular sieve and/or porous SiO-containing material 2 The amount of the slurry of (c) is such that the loading amount of the modified coating layer is 7wt% with respect to the cordierite honeycomb carrier in the resulting catalyst precursor coated with both the active coating layer and the modified coating layer, and the thickness of the modified coating layer is 70 μm;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Comparative example 4
According to the method of example 1, except that in step (1) of the preparation of (III) the manganese-based denitration catalyst, the amount of the slurry containing the active ingredient powder was controlled so that the active coating-coated intermediate obtained had a loading amount of 33% by weight and a thickness of the active coating layer of 180 μm with respect to the cordierite honeycomb carrier; in the step (2), the molecular sieve and/or porous SiO is/are contained by regulating and controlling 2 The amount of the slurry of (c) is such that the loading amount of the modified coating layer is 0.3wt% with respect to the cordierite honeycomb carrier in the resulting catalyst precursor coated with both the active coating layer and the modified coating layer, and the thickness of the modified coating layer is 3 μm;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Comparative example 5
According to the method of example 1, except that in the step (2) of preparing the (III) manganese-based denitration catalyst, the slurry containing the ZSM-5 type molecular sieve is replaced with the slurry containing hydrophobic polytetrafluoroethylene to be coated;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Test case
The test example was used to cut the manganese-based denitration catalyst prepared in the above examples and comparative examples into test pieces of 20mm×20mm×150mm, and then put into a stainless steel fixed bed reactor, and the denitration performance and SO resistance of the catalyst were respectively carried out under the condition of simulating flue gas in a laboratory 2 Evaluation of the Performance. Simulating the testing conditions of the flue gas: SO (SO) 2 ＝500mg/Nm 3 ，NO x ＝NH 3 ＝600mg/Nm 3 ，O 2 ＝7v％，H 2 O＝30v％，N 2 To balance the gas, the airspeed of the simulated flue gas = 12000h -1 The face velocity av=30m/h of the simulated flue gas.
Evaluation of catalyst denitration performance: testing the initial denitration efficiency and the denitration efficiency after 168 hours of operation of each test block at 140 ℃ and 300 ℃ respectively, and measuring NO at the inlet and the outlet of the reactor by using an MKS flue gas analyzer in the United states x And calculated according to the following formula:
wherein eta represents denitration efficiency, and the unit is;
for inlet NO of reactor x Concentration in mg/Nm 3 ；
For outlet NO of reactor x Concentration in mg/Nm 3 The evaluation results are shown in Table 1.
SO resistance 2 Evaluation of Performance: the test temperature is 300 ℃, and the specific test method is as follows: sampling at the inlet of the SCR reactor, taking hydrogen peroxide as absorption liquid, simultaneously measuring and sampling flue gas flow and time, analyzing the sampling liquid by using an ion chromatograph, and analyzing SO in the sampling liquid 4 2- Ion concentration, SO at inlet was determined by calculation 2 The content of (2) is denoted as S1 and is expressed in mg. At the outlet of the SCR reactor, placing the condensation bottle in a water bath at 65 ℃ to collect SO at the flue gas outlet 3 Simultaneously measuring the flow and time of sampling flue gas, and dissolving SO in a condensation bottle by deionized water 3 And the amount of sample liquid was recorded, and the SO in the solution was measured by analysis using an ion chromatograph 4 2- Content of SO at outlet by calculation 3 The content of (2) is expressed as S2 in mg. The SO of the catalyst was calculated according to the following formula 2 /SO 3 Conversion α:
the results of the evaluation are shown in Table 1, taking the average of three tests α.
TABLE 1
As can be seen from the results in Table 1, compared with the prior art, the Mn-based denitration catalyst provided by the invention has the advantages that the attenuation of the denitration efficiency is less than 6% after the Mn-based denitration catalyst is operated for 168 hours at 140 ℃ and 300 ℃, thereby showing that the Mn-based denitration catalyst provided by the invention has good H resistance 2 O property, excellent and stable denitration activity at a wide temperature window of 140-300 ℃, and longer service life of the catalyst.
Meanwhile, the invention provides SO of the manganese-based denitration catalyst 2 /SO 3 The conversion rate is 0.66-0.72%, and the reduction amplitude is more than 47% relative to comparative examples 2 and 4, SO the manganese-based denitration catalyst provided by the invention has better SO resistance 2 Failure capability.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (39)
1. The manganese-based denitration catalyst is characterized by comprising a honeycomb ceramic carrier, and an active coating and a modified coating which are sequentially coated on the carrier, wherein the loading amount of the active coating is 3.5-60wt% and the loading amount of the modified coating is 0.5-15wt% relative to the carrier, the thickness of the active coating is 80-140 mu m, and the thickness of the modified coating is 10-40 mu m; The active coating comprises manganese oxide, a first metal oxide and a second metal oxide, wherein the first metal oxide is at least one of niobium oxide, tantalum oxide and antimony oxide, the second metal oxide is at least one of copper oxide, cerium oxide, iron oxide, cobalt oxide, nickel oxide, praseodymium oxide, neodymium oxide, lanthanum oxide, europium oxide and samarium oxide, and the modified coating comprises a molecular sieve and/or porous SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of manganese oxide calculated as Mn element to first metal oxide calculated as first metal and second metal oxide calculated as second metal is 0.05-0.5:0.05-0.3:0.2-0.9.
2. The catalyst according to claim 1, wherein the loading of the active coating layer is 4.5 to 50wt%, the loading of the modified coating layer is 1 to 11wt%, the thickness of the active coating layer is 100 to 120 μm, and the thickness of the modified coating layer is 20 to 30 μm, relative to the support.
3. The catalyst of claim 1, wherein the first metal oxide is niobium oxide and/or antimony oxide.
4. The catalyst of claim 1, wherein the second metal oxide is selected from at least one of iron oxide, cerium oxide, and lanthanum oxide.
5. The catalyst of any one of claims 1-4, wherein the molecular sieve has a molar ratio of silicon to aluminum of 80-200:1.
6. the catalyst of any one of claims 1-4, wherein the porous SiO 2 The average pore size of (2) is smaller than 2nm.
7. The catalyst of any one of claims 1-4, wherein the porous SiO 2 Is white carbon black and/or SiO 2 An aerogel.
8. The catalyst of any one of claims 1-4, wherein the molecular sieve is selected from at least one of a ZSM-5 type molecular sieve, a BETA type molecular sieve, a SBA-15 type molecular sieve, a SBA-16 type molecular sieve, a SBA-2 type molecular sieve, a MCM-41 type molecular sieve, a MCM-48 type molecular sieve, a SSZ-13 type molecular sieve, a SSZ-39 type molecular sieve, and a SAPO-34 type molecular sieve.
9. The catalyst of claim 8, wherein the molecular sieve is a ZSM-5 type molecular sieve and/or a BETA type molecular sieve.
10. A method for preparing a manganese-based denitration catalyst, which is characterized by comprising the following steps:
(1) The method comprises the steps of (1) carrying out first coating on a honeycomb ceramic carrier by adopting slurry containing active component powder, and then carrying out first drying to obtain an intermediate coated with an active coating; the active coating has a loading of 3.5 to 60wt% relative to the support, and a thickness of 80 to 140 μm;
(2) By using molecular sieves and/or porous SiO-containing materials 2 Second coating the intermediate, and then second drying to obtain a catalyst precursor coated with both an active coating and a modified coating; the loading amount of the modified coating is 0.5-15wt% relative to the carrier, and the thickness of the modified coating is 10-40 mu m; then, the catalyst precursor is subjected to first roasting to obtain a manganese-based denitration catalyst;
the active component powder comprises manganese oxide, a first metal oxide and a second metal oxide, wherein the first metal oxide is at least one of niobium oxide, tantalum oxide and antimony oxide, and the second metal oxide is at least one of copper oxide, cerium oxide, iron oxide, cobalt oxide, nickel oxide, praseodymium oxide, neodymium oxide, lanthanum oxide, europium oxide and samarium oxide;
wherein the molar ratio of the manganese source calculated as Mn element to the compound containing the first metal calculated as the first metal and the compound containing the second metal calculated as the second metal is 0.05-0.5:0.05-0.3:0.2-0.9.
11. The method according to claim 10, wherein in the step (1), the slurry containing the active component powder is used in such an amount that the resulting intermediate coated with the active coating layer has a loading amount of 4.5 to 50wt% with respect to the support and a thickness of 100 to 120 μm;
In step (2), the catalyst comprises molecular sieve and/or porous SiO 2 The amount of the slurry of (c) is such that, in the resulting catalyst precursor coated with both the active coating layer and the modified coating layer, the loading amount of the modified coating layer is 1 to 11wt% with respect to the support, and the thickness of the modified coating layer is 20 to 30 μm.
12. The method according to claim 10 or 11, wherein in the step (1), the slurry containing the active ingredient powder is prepared by a method comprising:
(a) Mixing a manganese source, a compound containing a first metal and a compound containing a second metal with water to obtain a solution containing the manganese source, the compound containing the first metal and the compound containing the second metal, mixing the solution with an organic complexing agent and a first dispersing agent, and then sequentially evaporating, drying and roasting to obtain active component powder;
(b) And mixing the active component powder with a binder, a second dispersing agent and water, and pulping to obtain slurry containing the active component powder.
13. The method according to claim 12, wherein in the step (a), a molar ratio of the manganese source in terms of Mn element to the first metal-containing compound in terms of the first metal and the second metal-containing compound in terms of the second metal is 0.3 to 0.4:0.1-0.2:0.4-0.6.
14. The method according to claim 12, wherein in the step (a), a molar ratio of the manganese source in terms of Mn element to the total amount of the first metal-containing compound in terms of the first metal and the second metal-containing compound in terms of the second metal to the organic complexing agent is 1:1.5-2.5.
15. The method of claim 14, wherein in step (a), the molar ratio of the manganese source in terms of Mn element to the total amount of the first metal-containing compound in terms of the first metal and the second metal-containing compound in terms of the second metal to the organic complexing agent is 1:1.8-2.2.
16. The method of claim 12, wherein in step (a), the first dispersant is used in an amount of 5-20wt% of the mass of the organic complexing agent.
17. The method of claim 16, wherein in step (a), the first dispersant is used in an amount of 8-12wt% of the mass of the organic complexing agent.
18. The method of claim 12, wherein in step (a), the organic complexing agent is selected from at least one of citric acid, oxalic acid, and tartaric acid.
19. The method of claim 18, wherein in step (a), the organic complexing agent is citric acid.
20. The method of claim 12, wherein in step (a), the first dispersant is selected from at least one of polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, carboxymethyl cellulose, polyacrylic acid, and polymethacrylic acid.
21. The method of claim 20, wherein in step (a), the first dispersant is polyethylene glycol.
22. The method of claim 12, wherein in step (a), the drying conditions comprise: the temperature is 90-120 ℃ and the time is 12-24 hours;
in step (a), the roasting conditions include: heating to 250-350deg.C at 0.5-5deg.C/min, and keeping constant temperature for 2-5h; then heating to 450-550 ℃ at 0.5-5 ℃/min, and keeping the temperature for 3-8h.
23. The method of claim 12, wherein in step (b), the weight ratio of the active component powder to the binder, the second dispersant, and water is 10-50:5-20:0.01-1:29-84.9.
24. The method of claim 23, wherein in step (b), the weight ratio of the active component powder to the binder, the second dispersant, and water is 15-25:10-15:0.5-1:59-74.5.
25. The method of claim 12, wherein in step (b), the binder is selected from at least one of a titanium sol, a silica sol, an aluminum sol, a zirconium sol, a soluble zirconium salt, a soluble aluminum salt, and a soluble titanium salt;
The second dispersant is at least one selected from polyacrylamide, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose and gelatin.
26. The method according to claim 12, wherein in the step (b), the beating is performed under such conditions that the resulting slurry containing the active ingredient powder has a viscosity of 50 to 500 mPa-s at 25 ℃.
27. The method according to claim 26, wherein in the step (b), the beating is performed under such conditions that the resulting slurry containing the active ingredient powder has a viscosity of 90 to 200 mPa-s at 25 ℃.
28. The method of claim 12, wherein in step (b), the beating conditions include: the beating speed is 300-1000r/min, and the beating time is 30-100min.
29. The method of claim 10, wherein in step (2), the catalyst comprises molecular sieve and/or porous SiO 2 The preparation method of the slurry comprises the following steps: molecular sieves and/or porous SiO 2 Mixing with binder, second dispersant and water, and pulping to obtain a mixture containing molecular sieve and/or porous SiO 2 Is a slurry of (a) and (b).
30. The method of claim 29, wherein in step (2), the molecular sieve and/or porous SiO 2 The weight ratio of the adhesive, the second dispersant and the water is 10-50:5-20:0.01-1:29-84.9.
31. The method of claim 30, wherein in step (2), the molecular sieve and/or porous SiO 2 The weight ratio of the adhesive, the second dispersant and the water is 15-25:10-15:0.5-1:59-74.5.
32. The process of claim 29, wherein in step (2), the beating conditions are such that the resulting slurry contains molecular sieves and/or porous SiO 2 The viscosity of the slurry at 25 ℃ is 50-500 mPas.
33. The process of claim 32, wherein in step (2), the beating conditions are such that the resulting slurry contains molecular sieves and/or porous SiO 2 The viscosity of the slurry at 25 ℃ is 90-200 mPas.
34. The method of claim 29, wherein in step (2), the beating conditions include: the beating speed is 300-1000r/min, and the beating time is 30-100min.
35. The method according to claim 10 or 11, wherein in step (1), the first drying conditions include: the temperature is 80-100deg.C, and the time is 20-60min;
In step (2), the second drying conditions include: the temperature is 80-100deg.C, and the time is 20-60min;
in step (2), the first firing conditions include: the temperature is 400-500 ℃ and the time is 1-5h.
36. A manganese-based denitration catalyst produced by the method of any one of claims 10 to 35.
37. A method for flue gas denitrification, the method comprising: contacting the flue gas with the manganese-based denitration catalyst as claimed in any one of claims 1 to 9 and 36 to effect a reaction.
38. The method of claim 37, wherein the method is performed at a temperature of 140-300 ℃.
39. The method of claim 38, wherein the flue gas has a volumetric space velocity of 2000-20000h -1 The surface speed of the flue gas is 5-50m/h;
in the flue gas, SO 2 Is 50-500mg/Nm 3 ，NO x Is 100-2000mg/Nm 3 ，NH 3 Is 75-750mg/Nm 3 ，O 2 The content of (3-15 v%, H) 2 The content of O is 8-40v%.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407154A (en) * | 2011-09-29 | 2012-04-11 | 浙江师范大学 | Molecular sieve coating load manganese based composite oxide integrated catalyst and preparation method thereof |
| CN104415780A (en) * | 2013-08-22 | 2015-03-18 | 中国石油化工股份有限公司 | Denitration catalyst and preparation method thereof |
| CN104998680A (en) * | 2015-07-13 | 2015-10-28 | 煤炭工业济南设计研究院有限公司 | Low temperature denitration catalyst for anti-SO2 and H2O poisoning and preparation method of same |
| CN105126827A (en) * | 2015-09-10 | 2015-12-09 | 西南化工研究设计院有限公司 | Coated low-temperature flue gas denitration catalyst, and preparation method and application thereof |
| WO2018113004A1 (en) * | 2016-12-23 | 2018-06-28 | 中节能万润股份有限公司 | Method for preparing molecular sieve-multielement oxide composite integrally extruded denitration catalyst |
| CN110605122A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Low-temperature flue gas denitration catalyst and preparation method and application thereof |
| CN112275314A (en) * | 2020-09-14 | 2021-01-29 | 无锡威孚环保催化剂有限公司 | Manganese-cerium-based molecular sieve SCR denitration catalyst and preparation method thereof |
-
2021
- 2021-02-08 CN CN202110184523.6A patent/CN114904565B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407154A (en) * | 2011-09-29 | 2012-04-11 | 浙江师范大学 | Molecular sieve coating load manganese based composite oxide integrated catalyst and preparation method thereof |
| CN104415780A (en) * | 2013-08-22 | 2015-03-18 | 中国石油化工股份有限公司 | Denitration catalyst and preparation method thereof |
| CN104998680A (en) * | 2015-07-13 | 2015-10-28 | 煤炭工业济南设计研究院有限公司 | Low temperature denitration catalyst for anti-SO2 and H2O poisoning and preparation method of same |
| CN105126827A (en) * | 2015-09-10 | 2015-12-09 | 西南化工研究设计院有限公司 | Coated low-temperature flue gas denitration catalyst, and preparation method and application thereof |
| WO2018113004A1 (en) * | 2016-12-23 | 2018-06-28 | 中节能万润股份有限公司 | Method for preparing molecular sieve-multielement oxide composite integrally extruded denitration catalyst |
| CN110605122A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Low-temperature flue gas denitration catalyst and preparation method and application thereof |
| CN112275314A (en) * | 2020-09-14 | 2021-01-29 | 无锡威孚环保催化剂有限公司 | Manganese-cerium-based molecular sieve SCR denitration catalyst and preparation method thereof |
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