CN114904565A - 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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- CN114904565A CN114904565A CN202110184523.6A CN202110184523A CN114904565A CN 114904565 A CN114904565 A CN 114904565A CN 202110184523 A CN202110184523 A CN 202110184523A CN 114904565 A CN114904565 A CN 114904565A
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- oxide
- molecular sieve
- metal
- manganese
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 239000011572 manganese Substances 0.000 title claims abstract description 97
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000003546 flue gas Substances 0.000 title claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 132
- 238000000576 coating method Methods 0.000 claims abstract description 132
- 239000002808 molecular sieve Substances 0.000 claims abstract description 82
- 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 82
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 41
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 33
- 238000011068 loading method Methods 0.000 claims abstract description 30
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 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
- 239000000919 ceramic Substances 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 14
- 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
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- 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
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 229910000476 molybdenum 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
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- 150000001875 compounds Chemical class 0.000 claims description 49
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- 238000001035 drying Methods 0.000 claims description 41
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 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
- 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 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
- 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
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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
- 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
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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
- 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
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- 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
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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, relative to the carrier, the loading capacity of the active coating is 3.5-60 wt%, the loading capacity of the modified coating is 0.5-15 wt%, 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 selected from molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, and the second metal oxide oxidizesThe substance is selected from 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 molecular sieve and/or porous SiO 2 . The catalyst provided by the invention has better SO resistance 2 Sex, anti-H 2 O-property and denitration activity.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a manganese-based denitration catalyst, a preparation method thereof and a flue gas denitration method.
Background
The non-electric industry including coking, steel, cement, garbage incineration and the like is NO x One of the main emission sources of (1), NO in non-electric industry of China x The emission adopts the strictest emission limit in the world, and the best technical approach for meeting the standard is ammonia selective catalytic reduction (NH) 3 SCR), the core of which is a denitration catalyst. In addition, the flue gas temperature in the non-electric industry is generally lower (140-. At present, hot spots of the low-temperature denitration catalyst are mainly Mn-based oxide catalyst, Mn is used as a multivalent element, can form a plurality of stable oxides, has high activity and high stability at low temperature, but is easily subjected to H at low temperature 2 Inhibition of O and generation of SO 2 Poisoning. For example in the absence of H 2 O and 10 v% H 2 Under the smoke condition of O, the performance of the manganese-based catalyst can be reduced by 50 percent, and particularly when the operating temperature of the catalyst is lower than 200 ℃, the water resistance of the catalyst is more important; at a concentration of 200mg/Nm 3 SO 2 Under the condition of flue gas, the performance of the manganese-based catalyst is slowly reduced by 20 percent after the operation for 200 hours. Therefore, the water resistance and sulfur resistance of the manganese-based low-temperature catalyst have been one of the bottlenecks of research.
CN111659364A discloses a sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and a preparation method thereof, the catalyst comprises a sulfur-resistant auxiliary agent, an active component and a hydrophobic substance, and the carrier of the catalyst is dioxygen synthesized by a hydrothermal method by taking a waste SCR catalyst as a raw materialThe titanium dioxide nanotube comprises manganese as active component, one or two of molybdenum disulfide and tungsten disulfide as sulfur-resistant auxiliary agent, and at least one of fluorocarbon resin, polytetrafluoroethylene emulsion and organosiloxane as hydrophobic substance at 1000mg/Nm 3 SO 2 And 10 v% H 2 O, the surface speed Av is 5m/h, and the denitration efficiency exceeds 90 percent at the temperature of 120-200 ℃.
CN109529948A discloses a method for improving water resistance and sulfur resistance of a manganese-based low-temperature SCR denitration catalyst, which is characterized in that hydrophobic polytetrafluoroethylene is used as a coating or doping agent, and the manganese-based low-temperature SCR denitration catalyst with excellent water resistance and sulfur resistance can be prepared by mixing, stirring, filtering, drying and calcining the manganese-based low-temperature SCR denitration catalyst. The catalyst was at 20 v% H 2 O、50ppm SO 2 Under the condition of (1), the denitration efficiency can be stabilized to be more than 80% at the temperature of 140 ℃ and 200 ℃.
However, the catalyst can only meet the use requirement at the temperature of 120-200 ℃, has poor adaptability to high temperature and is subjected to H in flue gas 2 O and SO 2 The performance of the cable is reduced quickly due to the influence of the magnetic field on the cable, and the service life of the cable is short. In addition, the hydrophobic substances used in the catalysts are all organic polymer materials, and are relatively expensive. Therefore, the development of a new manganese-based denitration catalyst is of 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 affected by H in flue gas 2 O and SO 2 The influence performance is reduced quickly, the service life is short, and the price of the used hydrophobic substance is high, SO that the manganese-based denitration catalyst and the preparation method thereof and the flue gas denitration method are provided, and the catalyst has better denitration activity and SO resistance 2 Sex and H resistance 2 And (4) performance of O.
In order to achieve the above object, a first aspect of the present invention provides a manganese-based denitration catalyst, which comprises a honeycomb ceramic support, and an active coating layer and a modified coating layer sequentially coated on the support, wherein relative to the support, a loading amount of the active coating layer is 3.5-60 wt%, a loading amount of the modified coating layer is 0.5-15 wt%, and a thickness of the active coating layer is 8%0-140 μm, the thickness of the modified coating is 10-40 μm; the active coating comprises manganese oxide, first metal oxide and second metal oxide, wherein the first metal oxide is selected from at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, the second metal oxide is selected from 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 molecular sieve and/or porous SiO 2 。
The second aspect of the present invention provides a method for preparing a manganese-based denitration catalyst, comprising:
(1) carrying out first coating on the 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; relative to the carrier, the loading amount of the active coating is 3.5-60 wt%, and the thickness of the active coating is 80-140 mu m;
(2) by using a catalyst containing molecular sieves and/or porous SiO 2 The intermediate is subjected to secondary coating by the slurry, and then secondary drying is carried out to obtain a catalyst precursor coated with an active coating layer and a modified coating layer simultaneously; the loading amount of the modified coating is 0.5-15 wt% relative to the carrier, and the thickness of the modified coating is 10-40 μm; then, carrying out first roasting on the catalyst precursor to obtain a manganese-based denitration catalyst;
the active component powder comprises manganese oxide, first metal oxide and second metal oxide, wherein the first metal oxide is selected from at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, and the second metal oxide is selected from 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 of the second aspect.
The fourth aspect of the present invention provides a flue gas denitration method, which comprises: the flue gas is contacted with the manganese-based denitration catalyst of the first aspect or the third aspect of the invention for reaction.
By the technical scheme, the invention sequentially coats the active coating and the modified coating (the molecular sieve and/or the porous SiO) on the carrier 2 ) And 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 at a wide temperature window of 140 ℃ and 300 DEG C 2 Sex, anti-H 2 O-nature 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 the temperature range of 140-300 ℃, the decrement of the denitration efficiency of the catalyst provided by the invention is less than 6 percent, while the decrement of the denitration efficiency of the catalyst which is not coated with the modified coating in the comparative example 1 reaches 24.2 percent; SO relative to catalysts prepared in comparative examples 2 and 4 at the same time 2 /SO 3 In terms of the conversion rates of 1.38% and 1.46%, the SO of the manganese-based denitration catalyst provided by the invention is 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 of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
In the prior art, the manganese-based catalyst has denitration effect at the temperature of 120- 2 O and SO 2 The denitration efficiency of the catalyst is reduced quickly, so that the service life of the catalyst is short, and most of hydrophobic substances on the existing manganese-based catalyst are organic high polymer materials and are expensive. In order to solve the above technical problems, the inventors of the present invention have found in their studies that an active coating layer and a modified coating layer (molecular sieve and/or porous SiO) having a specific thickness are sequentially coated on a honeycomb ceramic support 2 ) The prepared catalyst can be kept at 140-300 DEG CHas better SO resistance under a wide temperature window 2 Sex, anti-H 2 O-nature 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 within the specific range of 100-120 μm and the thickness of the modified coating layer within the specific range of 20-30 μm 2 Sex, anti-H 2 O and denitration activity.
As described above, the first aspect of the present invention provides a manganese-based denitration catalyst, which comprises a honeycomb ceramic support, and an active coating layer and a modified coating layer sequentially coated on the support, wherein, relative to the support, the loading amount of the active coating layer is 3.5 to 60 wt%, the loading amount of the modified coating layer is 0.5 to 15 wt%, 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 selected from at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, the second metal oxide is selected from 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 。
According to the invention, the active coating has a strong NH content 3 The activation and NO adsorption capacity has strong denitration efficiency at the temperature of 140 ℃ and 300 ℃, but the over-high oxidation can cause SO 2 The oxidation of (2) is enhanced. Therefore, by controlling the thickness of the active coating layer within the specific range of 80-140 μm, SO can be made to have the maximum denitration efficiency while ensuring the denitration efficiency 2 The oxidation rate of (2) becomes low. On the contrary, when the thickness of the active coating is less than 80 μm, a defect of insufficient denitration efficiency may occur; when the thickness of the active coating is greater than 140 μm, SO may occur 2 /SO 3 Too high conversion rate. In the invention, the thickness of the active coating layer is determined by the formula:
and calculating to obtain the result, wherein,ρ 1 shows the density (g/cm) of the honeycomb ceramic support 3 )，ρ 2 Shows the density (g/cm) of the active component powder 3 )，α 1 Represents the loading amount (wt%) of the active coating layer, W represents the width (square section, generally 150mm) of the honeycomb ceramic support, n represents the number of cells (generally 10 to 120 cells) of the honeycomb ceramic support in the width direction of the section, L represents 1 Indicating the side length of the hole, i.e. the diameter of the hole.
The modified coating has good hydrophobicity, inhibits the condensation of water molecules in the 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 operation condition of low temperature (140-300 ℃) by controlling the thickness of the modified coating within the specific range of 10-40 mu m. On the contrary, when the thickness of the modified coating is less than 10 μm, a defect of insufficient water resistance may occur; when the thickness of the modified coating layer is more than 40 μm, a defect of inhibiting the denitration reaction process may occur. In addition, compared with the expensive organic polymer material in the prior art, the invention adopts molecular sieve and/or porous SiO 2 The modified coating not only can save cost, but also can be efficiently combined and dispersed with the active coating through chemical bonds, thereby being beneficial to the stable coating of the modified coating. In the invention, the thickness of the modified coating is determined by the formula:
is calculated, wherein rho 1 Shows the density (g/cm) of the honeycomb ceramic support 3 )，ρ 3 Denotes molecular sieves and/or porous SiO 2 Density (g/cm) 3 )，α 2 Represents the amount of the modified coating layer (wt%), W represents the width of the honeycomb ceramic support (square cross section, generally 150mm), n represents the number of cells of the honeycomb ceramic support in the cross-sectional width direction (generally 10 to 120 cells), L 2 Indicating the side length of the hole, i.e. the diameter of the hole. In the present invention, the pore size is generally reduced relative to the previous one due to the application of the active coating layer, so L 2 Ratio L 1 It is small.
According to a preferred embodiment of the invention, the loading of the active coating is between 4.5 and 50% by weight and the loading of the modified coating is between 1 and 11% by weight with respect to the support; the thickness of the active coating is 100-120 mu m, and the thickness of the modified coating is 20-30 mu m. In such a preferred case, the catalyst is more favorable to obtain the effects of denitration, sulfur resistance and water resistance.
In some embodiments of the present invention, preferably, the first metal oxide is niobium oxide and/or antimony oxide, which is more advantageous to improve denitration stability.
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 the stability of denitration.
In some embodiments of the present invention, preferably, the molecular sieve is a molecular sieve containing a high silica to alumina molar ratio, and preferably, the molecular sieve has a silica to alumina molar ratio of 80 to 200: 1.
the selection range of the molecular sieve is wider, preferably, 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, and more preferably, the molecular sieve is selected from ZSM-5 type molecular sieve and/or BETA type molecular sieve. In this preferable case, it is more advantageous to improve the water resistance of the catalyst.
In some embodiments of the invention, preferably, the porous SiO 2 Is less than 2 nm. 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, is preferably a honeycomb ceramic carrier with 10-120 pores, is further preferably selected from one of cordierite, mullite, silicon carbide, alumina, silica, titania and zirconia, and is more preferably a cordierite honeycomb carrier.
The second aspect of the present invention provides a method for preparing a manganese-based denitration catalyst, comprising:
(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; relative to the carrier, the loading amount of the active coating is 3.5-60 wt%, and the thickness of the active coating is 80-140 mu m;
(2) by using a catalyst containing molecular sieves and/or porous SiO 2 The intermediate is subjected to secondary coating by the slurry, and then secondary drying is carried out to obtain a catalyst precursor coated with an active coating layer and a modified coating layer simultaneously; the loading amount of the modified coating is 0.5-15 wt% relative to the carrier, and the thickness of the modified coating is 10-40 μm; then, carrying out first roasting on the catalyst precursor to obtain a manganese-based denitration catalyst;
the active component powder comprises manganese oxide, first metal oxide and second metal oxide, wherein the first metal oxide is selected from at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, and the second metal oxide is selected from 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 component powder is used in an amount such that the loading amount of the active coating layer in the obtained intermediate coated with the active coating layer is 4.5-50 wt% relative to the vehicle, and the thickness of the active coating layer is 100-120 μm. In such a preferable 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 present invention, in the step (2), the silica gel contains a molecular sieve and/or porous SiO 2 The amount of the slurry of (a) is such that the amount of the modified coating layer supported relative to the support in the resulting catalyst precursor simultaneously coated with the active coating layer and the modified coating layer is from 1 to 11% by weight and the thickness of the modified coating layer is from 20 to 30 μm. In this preferable case, the water resistance and the denitration activity of the catalyst can be further improved, and the denitration stability of the catalyst can be improved.
In some embodiments of the present invention, preferably, in step (1), the method for preparing the slurry containing the active component 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, then 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 and pulping the active component powder with a binder, a second dispersing agent and water to obtain slurry containing the active component powder.
The solution containing the manganese source, the compound containing the first metal, and the compound containing the second metal obtained by mixing the manganese source, the compound containing the first metal, and the compound containing the second metal with water in step (a) is not particularly limited as long as a uniform and stable solution can be obtained. The mixing according to the invention can be carried out under stirring.
In some embodiments of the present invention, it is preferable that 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 in the range of 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 preferable case, the denitration effect of the catalyst can be further improved.
In step (a) of the present invention, preferably, the molar ratio of the manganese source calculated as Mn element to the total amount of 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: 1.5-2.5, more preferably 1.8-2.2. Under the preferable condition, the complete complexation of all metal ions is more favorably ensured, and a cross-linked structure of a space network is formed, so that the H resistance of the catalyst is further improved 2 O, anti-SO 2 And denitration stability.
In step (a) of the present invention, the first dispersing agent is preferably used in an amount of 5 to 20 wt%, more preferably 8 to 12 wt%, based on the mass of the organic complexing agent. In such a preferred case, it is more advantageousThe metal ions in the cross-linked body are dispersed uniformly, which is beneficial to the subsequent roasting to form a more uniform and fine-particle composite metal oxide catalyst, thereby further improving the H resistance of the catalyst 2 O, anti-SO 2 And denitration stability.
The organic complexing agent is not particularly limited in the present invention, and an organic acid having a complexing action may be used, and preferably, the organic acid is at least one selected from the group consisting of citric acid, oxalic acid and tartaric acid, and more preferably citric acid.
The first dispersant is selected from a wide range, and is preferably at least one selected from the group consisting of polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, carboxymethyl cellulose, polyacrylic acid, and polymethacrylic acid, and more preferably polyethylene glycol.
In the present invention, the evaporation conditions in step (a) are not particularly limited as long as the water content of the mixed solution can be evaporated to obtain a porous sol, and the evaporation temperature is preferably 70 to 90 ℃. The evaporation 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 12-24 h. The equipment for carrying out the drying in step (a) is not particularly limited in the present invention, and may be a conventional choice in the art, including, for example, 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 250-350 ℃ at the speed of 0.5-5 ℃/min, and keeping the temperature for 2-5 h; then raising the temperature to 450-550 ℃ at the speed of 0.5-5 ℃/min, and keeping the temperature for 3-8 h. The apparatus for carrying out the calcination in step (a) is not particularly limited in the present invention, and may be a conventional one in the art, including, but not limited to, calcination using a muffle furnace, for example.
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 10-50: 5-20: 0.01-1: 29-84.9, more preferably 15-25: 10-15: 0.5-1: 59-74.5, which is more favorable for obtaining slurry with proper viscosity, thereby further improving the sulfur resistance, water resistance and denitration activity of the catalyst.
The binder of step (b) is not particularly limited in the present invention, 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 better in the pore channels, the active component powder is mixed with a binder-containing solution, and the concentration of the binder-containing solution is preferably 5 to 10 wt%.
The present invention has a wide selection range of the soluble zirconium salt, 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 selection range of the soluble aluminum salt is wide, and preferably, the soluble aluminum salt is selected from at least one of aluminum trichloride, aluminum nitrate, aluminum sulfate and aluminum ammonium sulfate.
The selection range of the soluble titanium salt is wide, and preferably, the soluble titanium salt is selected from at least one of titanium trichloride, titanium sulfate and titanyl sulfate.
The silica sol, the aluminum sol and the zirconium sol are not particularly limited in the present invention, and the aluminum sol, the zirconium sol and the silica sol having a pH of 6 to 7 are preferable.
The second dispersant in step (b) is selected from a wide range, and is preferably 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, hydroxymethyl hydroxyethyl cellulose, and gelatin.
The beating conditions in the step (b) of the present invention are not particularly limited as long as the resulting slurry containing the active ingredient powder has a viscosity of 50 to 500 mPas, preferably 90 to 200 mPas, at 25 ℃. In such an optimal case, the denitration effect of the catalyst can be 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 30-100 min.
In some embodiments of the present invention, in order 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 includes: grinding the active component powder obtained in the step (a) to obtain powder with the particle size D50 being less than 2.5 mu m and D90 being less than 5 mu m, and then mixing the powder with a binder, a second dispersing agent and water. The grinding mode is not particularly limited in the present invention, and may be a conventional one in the art, and for example, includes, but is not limited to, grinding using a ball mill.
In the present invention, the first metal-containing compound is preferably a soluble compound containing the first metal. In the present invention, the term "soluble" means that it can be directly dissolved in a solvent (preferably water, more preferably deionized water). Specifically, for example, the first metal-containing compound is at least one of a nitrate, an acetate, a sulfide, a hydroxycarbonate, a sulfate, an oxalate, and a chloride of the first metal.
In the present invention, the second metal-containing compound is preferably a soluble second metal-containing compound. In the present invention, the term "soluble" means that it can be directly dissolved in a solvent (preferably water, more preferably deionized water). Specifically, for example, the second metal-containing compound is at least one of a nitrate, an acetate, a sulfide, a hydroxycarbonate, a sulfate, an oxalate and a chloride 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, an Fe-containing compound, a Co-containing compound, a Ni-containing compound, a Pr-containing compound, a Nd-containing compound, a La-containing compound, a Eu-containing compound, and a Sm-containing compound.
The invention has no particular limitation on the coating time and the number of coating and drying in the step (1), as long as the loading amount of the active coating layer in the obtained intermediate coated with the active coating layer is 3.5-60 wt% relative to the support, and the thickness of the active coating layer is 80-140 μm, and the skilled person can carry out coating and drying for many times according to the actual situation.
In some embodiments of the present invention, preferably, in step (1), the conditions of the first drying include: the temperature is 80-100 deg.C, and the time is 20-60 min. The drying equipment can be selected by the person skilled in the art according to the actual circumstances.
In some embodiments of the present invention, preferably, in the step (2), the silica gel contains a molecular sieve and/or porous SiO 2 The method for preparing the slurry of (1) comprises: mixing molecular sieve and/or porous SiO 2 Mixing with adhesive, second dispersant and water, and pulping to obtain the product containing molecular sieve and/or porous SiO 2 The slurry of (1).
Preferably, in step (2), the molecular sieve and/or porous SiO 2 The weight ratio of the adhesive to the second dispersant to 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 favorable for obtaining slurry with proper viscosity, thereby further improving the sulfur resistance, water resistance and denitration activity of the catalyst.
The conditions for the beating in the step (2) are not particularly limited in the present invention as long as they enable the resulting slurry containing a molecular sieve and/or porous SiO 2 The viscosity of the slurry of (2) at 25 ℃ is from 50 to 500 mPas, preferably from 90 to 200 mPas.
Preferably, the beating conditions include: the beating speed is 300-1000r/min, and the beating time is 30-100 min.
The present invention has no particular limitation on the coating time and the number of coating and drying in the step (2), as long as the catalyst precursor coated with the active coating layer and the modified coating layer simultaneously can be obtained, the loading amount of the modified coating layer relative to the support is 0.5-15 wt%, and the thickness of the modified coating layer is 10-40 μm, and the coating and drying can be performed several times by one skilled in the art according to actual situations.
In some embodiments of the present invention, preferably, in step (2), the second drying conditions include: the temperature is 80-100 deg.C, and the time is 20-60 min. The drying equipment can be selected by the person skilled in the art according to the actual circumstances.
In some embodiments of the present invention, preferably, in the step (2), the conditions of the first roasting include: the temperature is 400-500 ℃, and the time is 1-5 h. The skilled person can select the roasting equipment according to the actual situation.
In the present invention, for better making molecular sieve and/or porous SiO 2 Mixing with binder, second dispersant and water to obtain the product containing molecular sieve and/or porous SiO 2 The method further comprising: mixing molecular sieve and/or porous SiO 2 Grinding to obtain D90 with particle size of D50 less than 2.5 μm<5 μm powder, then mixed with a binder, a second dispersant, and water. The grinding mode is not particularly limited in the present invention, and may be a conventional one in the art, and for example, includes, but is not limited to, 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 subjected to primary drying or secondary drying. In the invention, the coating product is purged by high-pressure air, so that the pore passages of the carrier 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 the binder and the second dispersant are as described above, and will not be described herein.
In order to clearly describe the preparation method of the manganese-based denitration catalyst of the present invention, a preferred embodiment is provided as follows:
(I) preparation of slurry containing active ingredient powder:
(a) mixing a manganese source calculated by Mn element, a compound containing a first metal calculated by the first metal, a compound containing a second metal calculated by the second metal according to a ratio of 0.3-0.4: 0.1-0.2: mixing and stirring the mixture with deionized water at a molar ratio of 0.4-0.6 to obtain a solution containing a manganese source, a compound containing a first metal and a compound containing a second metal, and then mixing the solution with citric acid and polyethylene glycol, wherein the molar ratio of the total usage of the manganese source calculated as Mn element, the compound containing the first metal calculated as the first metal and the compound containing the second metal calculated as the second metal to the citric acid is 1: 1.8-2.2, wherein the dosage of the polyethylene glycol is 8-12 wt% of the mass of the citric acid, stirring and evaporating at 70-90 ℃ to obtain porous sol, drying at 90-120 ℃ for 12-24h, heating to 250-350 ℃ at 0.5-5 ℃/min, keeping the temperature for 2-5h, heating to 450-550 ℃ at 0.5-5 ℃/min, keeping the temperature for 3-8h to obtain active component powder, and grinding the active component powder into powder with the particle size D50 being less than 2.5 mu m and D90 being 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, and pulping for 30-100min under the condition that the pulping speed is 300-1000r/min to obtain the slurry containing the active component powder with the viscosity of 90-200mPa & s at 25 ℃;
(II) containing molecular sieves and/or porous SiO 2 Preparation of the slurry of
Firstly, molecular sieve and/or porous SiO 2 Grinding (average pore diameter less than 2nm) to obtain particle diameter D50 < 2.5 μm, D90<5 μm powder, then mixed with a solution containing a binder, a second dispersant, water in a ratio of 15-25: 10-15: 0.5-1: 59-74.5, and beating at 300-1000r/min for 30-100min to obtain molecular sieve and/or porous SiO with viscosity of 90-200 mPa.s at 25 deg.C 2 The slurry of (a);
(III) preparation of manganese-based denitration catalyst
(1) Firstly coating 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 an active coating in the obtained intermediate coated with the active coating is 4.5-50 wt% relative to the carrier, and the thickness of the active coating is 100-120 mu m;
(2) by using a catalyst containing molecular sieves and/or porous SiO 2 The slurry is used for carrying out second coating on the intermediate, the coated product is swept by high-pressure air, then second drying is carried out for 20-60min at the temperature of 80-100 ℃, so that the loading amount of the modified coating is 1-11 wt% relative to the carrier and the thickness of the modified coating is 20-30 mu m in the obtained catalyst precursor simultaneously coated with the active coating and the modified coating; and then, carrying out first roasting on the catalyst precursor at the temperature of 400-500 ℃ for 1-5h to obtain the manganese-based denitration catalyst.
In a third aspect, the invention provides a manganese-based denitration catalyst prepared by the method. The manganese-based denitration catalyst prepared by the preparation method provided by the invention has better and more stable denitration efficiency and SO resistance under the wide temperature window of 140-300 DEG C 2 And anti-H 2 And (4) O capacity.
The fourth aspect of the invention provides a method for denitration of flue gas, which comprises the following steps: the flue gas is contacted with the manganese-based denitration catalyst for reaction.
Preferably, the process is carried out at a temperature of 140 ℃ and 300 ℃.
Preferably, the volume space velocity of the flue gas is 2000- -1 And the surface speed of the flue gas is 5-50 m/h.
Preferably, SO is contained in the flue gas 2 The concentration of (A) is 50-500mg/Nm 3 ，NO x The concentration of (a) is 100-2000mg/Nm 3 ，NH 3 The concentration of (A) is 75-750mg/Nm 3 ，O 2 In an amount of 3-15 v%, H 2 The content of O is 8-40 v%.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
Example 1
(I) Preparation of slurry containing active ingredient powder
(a) Manganese acetate calculated by Mn element, niobium oxalate calculated by Nb element, and ferric nitrate calculated by Fe element were mixed in a ratio of 0.4: 0.2: 0.4 and deionized water, and mixing and stirring 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 usage of the manganese acetate, the niobium oxalate and the ferric nitrate to the citric acid is 1: 2, the using amount of polyethylene glycol is 10 wt% of the mass of citric acid, stirring the mixture at 80 ℃ and slowly evaporating the mixture to dryness to obtain porous sol, drying the sol at 110 ℃ for 12 hours, heating the sol to 300 ℃ at 5 ℃/min, keeping the temperature for 3 hours, heating the sol to 500 ℃ at 5 ℃/min, keeping the temperature for 5 hours to obtain active component powder, and grinding the active component powder into powder with the particle size D50 being less than 2.5 mu m and D90 being less than 5 mu m;
(b) mixing the powder with an aluminum sol solution (with the concentration of 10 wt%), polyethylene oxide and water according to the weight ratio of 15: 10: 0.5: 74.5, and pulping for 30min under the condition that the pulping speed is 300r/min to obtain pulp containing active component powder with the viscosity of 150mPa & s at 25 ℃;
(II) containing molecular sieves and/or porous SiO 2 Preparation of the slurry of
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 2nm) into powder with the particle sizes of D50 being less than 2.5 mu m and D90 being less than 5 mu m, and then mixing the powder with an aluminum sol solution (the concentration is 10 weight percent), polyoxyethylene and water according to the weight ratio of 15: 10: 0.5: mixing according to the weight ratio of 74.5, and pulping for 30min under the condition that the pulping speed is 300r/min to obtain slurry containing the ZSM-5 type molecular sieve with the viscosity of 150mPa & s at 25 ℃;
(III) preparation of manganese-based denitration catalyst
(1) Carrying out first coating on a 40-pore cordierite honeycomb carrier (with the sectional area of 150mm multiplied by 150mm and the height of 150mm) by using slurry containing active component powder for 5min, blowing the coated product by using high-pressure air, then carrying out first drying for 30min at 90 ℃, and repeating the steps for multiple times, so that the intermediate coated with the active coating is obtained, wherein the loading amount of the active coating is 20 wt% relative to the cordierite honeycomb carrier, the width W of the cordierite honeycomb carrier is 150mm, and the pore diameter L of the cordierite honeycomb carrier is 150mm 1 3.0mm, cordierite Honeycomb Carrier rho 1 Is 2.6g/cm 3 Density of active ingredient powder rho 2 Is 2.7g/cm 3 Then, the thickness of the active coating is 108 μm according to the formula;
(2) secondly coating the intermediate body for 5min by adopting slurry containing ZSM-5 type molecular sieve, blowing the coating product by adopting high-pressure air, secondly drying for 30min at 90 ℃, and repeating the steps for multiple times to ensure that the loading amount of the modified coating is 2.5 wt% relative to the cordierite honeycomb carrier in the obtained catalyst precursor simultaneously coated with the active coating and the modified coating, the width W of the cordierite honeycomb carrier is 150mm, and the pore diameter L is 150mm 2 2.8mm, cordierite honeycomb Carrier rho 1 Is 2.6g/cm 3 Density rho of ZSM-5 type molecular sieve 3 Is 2.1g/cm 3 Then, the thickness of the modified coating is 25 μm according to the formula, and the catalyst precursor is calcined at 450 ℃ for 3 hours to obtain the manganese-based denitration catalyst.
Example 2
(I) Preparation of slurry containing active ingredient powder
(a) Manganese acetate calculated as Mn element, antimony acetate calculated as Sb element, ferric nitrate calculated as Fe element were mixed in a ratio of 0.3: 0.2: 0.5 and deionized water are mixed and stirred to obtain a solution containing manganese acetate, antimony acetate and ferric nitrate, and then the solution is mixed with citric acid and polyethylene glycol, wherein the molar ratio of the total usage of the manganese acetate counted by Mn element, the antimony acetate counted by Sb element and the ferric nitrate counted by Fe element to the citric acid is 1: 1.8, stirring the mixture at 80 ℃ to slowly evaporate water to obtain porous sol, drying the sol at 110 ℃ for 12 hours, heating the sol to 300 ℃ at 5 ℃/min, keeping the temperature for 3 hours, heating the sol to 500 ℃ at 5 ℃/min, keeping the temperature for 5 hours to obtain active component powder, and grinding the active component powder into powder with the particle size D50 being less than 2.5 mu m and D90 being less than 5 mu m;
(b) mixing the powder with an aluminum sol solution (with the concentration of 10 wt%), polyethylene oxide and water according to the weight ratio of 20: 13: 0.8: 66.2, and pulping for 30min under the condition that the pulping speed is 300r/min to obtain slurry containing active component powder with the viscosity of 200mPa & s at 25 ℃;
(II) containing molecular sieves and/or porous SiO 2 Preparation of the slurry of
Firstly, grinding a BETA-type molecular sieve (the molar ratio of silicon to aluminum is 150, and the average pore diameter is less than 2nm) into powder with the particle sizes of D50 being less than 2.5 mu m and D90 being less than 5 mu m, and then mixing the powder with a silica sol solution (the concentration is 10wt percent), polyoxyethylene and water according to a ratio of 20: 13: 0.8: 66.2, pulping at 300r/min for 30min to obtain slurry containing BETA-type molecular sieve with viscosity of 200 mPas at 25 deg.C;
(III) preparation of manganese-based denitration catalyst
(1) Carrying out first coating on a 50-hole cordierite honeycomb carrier (with the sectional area of 150mm multiplied by 150mm and the height of 150mm) by adopting slurry containing active component powder for 5min, blowing the coated product by adopting high-pressure air, then carrying out first drying for 30min at 90 ℃, and repeating the steps for multiple times, so that the loading amount of an active coating relative to the cordierite honeycomb carrier in the obtained intermediate coated with the active coating is 25 wt%, the width W of the cordierite honeycomb carrier is 150mm, and the pore diameter L of the cordierite honeycomb carrier is 1 2.45mm, cordierite honeycomb Carrier rho 1 Is 2.6g/cm 3 Density of active ingredient powder rho 2 Is 2.75g/cm 3 Then, the thickness of the active coating is calculated to be 118 μm according to a formula;
(2) coating the intermediate with a slurry containing a BETA-type molecular sieve for 5min, blowing the coated product with high-pressure air, drying at 90 deg.C for 30min, repeating the above steps several times to obtain a catalyst precursor coated with an active coating and a modified coating at the same time, wherein the supported amount of the modified coating is 3 wt% relative to the cordierite honeycomb carrier, the width W of the cordierite honeycomb carrier is 150mm, and the pore diameter L is the same as that of the cordierite honeycomb carrier 2 2.2mm, cordierite honeycomb Carrier rho 1 Is 2.6g/cm 3 Density of BETA type molecular sieve rho 3 Is 2.2g/cm 3 Then, the thickness of the modified coating is calculated to be 30 μm according to a formula, and then the catalyst precursor is calcined at 450 ℃ for 3 hours to obtain the manganese-based denitration catalyst.
Example 3
(I) Preparation of slurry containing active ingredient powder
(a) Manganese acetate calculated by Mn element, niobium oxalate calculated by Nb element and cerium nitrate calculated by Ce element are mixed according to the weight ratio of 0.35: 0.1: mixing and stirring the mixture with deionized water in a molar ratio of 0.55 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 molar ratio of the total dosage of the manganese acetate, the niobium oxalate and the cerium nitrate to the citric acid is 1: 2.2, the using amount of polyethylene glycol is 8 wt% of the mass of citric acid, stirring at 80 ℃ and slowly evaporating to dryness to obtain porous sol, drying at 110 ℃ for 12 hours, heating to 300 ℃ at 5 ℃/min, keeping the temperature for 3 hours, heating to 500 ℃ at 5 ℃/min, keeping the temperature for 5 hours to obtain active component powder, and grinding the active component powder into powder with the particle size D50 being less than 2.5 mu m and D90 being less than 5 mu m;
(b) the powder was mixed with a zirconium sol solution (10 wt% concentration), polyethylene oxide, water in a 25: 15: 1: 59, and pulping for 30min at the pulping speed of 300r/min to obtain slurry containing active component powder with the viscosity of 90mPa & s at 25 ℃;
(II) containing molecular sieves and/or porous SiO 2 Preparation of the slurry of
Firstly, SiO is added 2 Grinding aerogel (average pore diameter less than 2nm) to obtain powder with particle size D50 less than 2.5 μm and D90<5 μm powder, then mixed with a silica sol solution (10% by weight concentration), polyethylene oxide, water in a weight ratio of 25: 15: 1: 59, and pulping for 30min at a pulping speed of 300r/min to obtain SiO-containing material with viscosity of 90 mPa.s at 25 DEG C 2 A slurry of aerogel;
(III) preparation of manganese-based denitration catalyst
(1) Carrying out first coating on an 80-pore cordierite honeycomb carrier (with the sectional area of 150mm multiplied by 150mm and the height of 150mm) by adopting slurry containing active component powder for 5min, blowing the coating product by adopting high-pressure air, then carrying out first drying for 30min at 90 ℃, and repeating the steps for multiple times, so that the loading capacity of the active coating relative to the cordierite honeycomb carrier in the obtained intermediate coated with the active coating is31 wt%, and a width W of 150mm and a pore diameter L in a cordierite honeycomb carrier 1 1.6mm, cordierite honeycomb Carrier rho 1 Is 2.6g/cm 3 Density of active ingredient powder rho 2 Is 3.0g/cm 3 Then, the thickness of the active coating is calculated to be 100 μm according to a formula;
(2) by using a gas containing SiO 2 Secondly coating the intermediate body with aerogel slurry for 5min, blowing the coated product with high-pressure air, secondly drying at 90 ℃ for 30min, and repeating the steps for multiple times, so that the load of the modified coating is 2.5 wt% relative to the cordierite honeycomb carrier in the obtained catalyst precursor simultaneously coated with the active coating and the modified coating, the width W of the cordierite honeycomb carrier is 150mm, and the pore diameter L of the cordierite honeycomb carrier is 150mm 2 1.4mm, cordierite honeycomb Carrier rho 1 Is 2.6g/cm 3 ，SiO 2 Density of aerogel ρ 3 Is 2.6g/cm 3 Then, the thickness of the modified coating is calculated to be 20 μm according to a formula, and then the catalyst precursor is calcined at 450 ℃ for 3 hours to obtain the manganese-based denitration catalyst.
Example 4
According to the method of example 1, except that (III) in the step (1) of preparing the manganese-based denitration catalyst, the amount of the slurry containing the active component powder is controlled so that the amount of the active coating supported on the cordierite honeycomb carrier is 15 wt% and the thickness of the active coating is 81 μm in the obtained intermediate coated with the active coating;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Example 5
The method of example 1 was followed except that in the step (2) of (III) the preparation of the manganese-based denitration catalyst, molecular sieves and/or porous SiO were contained by regulation 2 The amount of the slurry of (a) was such that the amount of the modified coating loaded was 1.5 wt% relative to the cordierite honeycomb carrier and the thickness of the modified coating was 15 μm in the catalyst precursor coated with both the active coating and the modified coating;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Example 6
The procedure of example 1 was followed except that (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
The procedure of example 1 was followed except that in the step (a) of preparing the slurry containing the active component powder (I), the molar ratio of the total amount 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 the step (a) of (I) preparation of the slurry containing the active ingredient powder, 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
The procedure of example 1 was followed except that in (I) the step (b) of preparing a slurry containing an active component powder, the weight ratio of the powder to an aluminum sol solution (concentration of 10% by weight), polyethylene oxide, and water was changed to 20: 20: 0.3: 59.7, the viscosity of the obtained slurry containing the active component powder is 400 mPas at 25 ℃;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Example 10
The process of example 1 is followed except that (II) contains molecular sieves and/or porous SiO 2 In the preparation of the slurry of (1), the weight ratio of the ZSM-5 type molecular sieve powder, the alumina sol solution (concentration of 10 wt%), polyethylene oxide, and water was changed to 10: 5: 0.3: 84.7 bringing the resulting ZSM-5 type molecular sieve-containing slurry to a viscosity at 25 ℃ of50mPa·s；
The other steps are the same as the embodiment, and the manganese-based denitration catalyst is obtained.
Comparative example 1
The process of example 1 is followed except that no step (II) contains molecular sieves and/or porous SiO 2 The preparation of the slurry and the step (2) in the step (III) of preparing the manganese-based denitration catalyst specifically include:
preparation of slurry containing active ingredient powder:
(a) manganese acetate calculated as Mn element, niobium oxalate calculated as Nb element, and ferric nitrate calculated as Fe element were mixed in a ratio of 0.4: 0.2: mixing the solution with citric acid and polyethylene glycol, wherein the molar ratio of the total usage of manganese acetate, niobium oxalate and iron nitrate in terms of Mn element, Nb element and Fe element to the citric acid is 1: 2, the using amount of polyethylene glycol is 10 wt% of the mass of citric acid, stirring the mixture at 80 ℃ and slowly evaporating the mixture to dryness to obtain porous sol, drying the sol at 110 ℃ for 12 hours, heating the sol to 300 ℃ at 5 ℃/min, keeping the temperature for 3 hours, heating the sol to 500 ℃ at 5 ℃/min, keeping the temperature for 5 hours to obtain active component powder, and grinding the active component powder into powder with the particle size D50 being less than 2.5 mu m and D90 being less than 5 mu m;
(b) mixing the powder with an aluminum sol solution (with the concentration of 10 wt%), polyethylene oxide and water according to the weight ratio of 15: 10: 0.5: mixing according to the weight ratio of 74.5, and pulping for 30min under the condition that the pulping speed is 300r/min to obtain the slurry containing the active component powder and having the viscosity of 150mPa & s at 25 ℃;
preparation of manganese-based denitration catalyst
Carrying out first coating on a 40-pore cordierite honeycomb carrier (with the sectional area of 150mm multiplied by 150mm and the height of 150mm) by adopting slurry containing active component powder for 5min, blowing the coated product by adopting high-pressure air, then carrying out first drying for 30min at 90 ℃, and repeating the steps for multiple times, so that the catalyst precursor coated with the active coating is obtained, the loading amount of the active coating is 20 wt% relative to the cordierite honeycomb carrier, and the catalyst precursor coated with the active coating is prepared from the cordierite honeycomb carrierThe width W of the pit carrier is 150mm, and the aperture L 1 3.0mm, cordierite honeycomb Carrier rho 1 Is 2.6g/cm 3 Density of active ingredient powder rho 2 Is 2.7g/cm 3 Then, the thickness of the active coating is 108 μm according to the formula; and then roasting the catalyst precursor for 3 hours at the temperature of 450 ℃ to obtain the manganese-based denitration catalyst.
Comparative example 2
According to the method of example 1, except that (III) in the step (1) of preparing the manganese-based denitration catalyst, the amount of slurry containing the active component powder is controlled so that the amount of the active coating supported on the obtained intermediate coated with the active coating is 33 wt% and the thickness of the active coating is 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
The method of example 1 was followed except that in the step (2) of (III) the preparation of the manganese-based denitration catalyst, molecular sieves and/or porous SiO were contained by regulation 2 The amount of the slurry of (a) was such that the supported amount of the modified coating layer relative to the cordierite honeycomb carrier in the resulting catalyst precursor simultaneously coated with the active coating layer and the modified coating layer was 7 wt%, and the thickness of the modified coating layer was 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 the step (1) of (III) preparation of the manganese-based denitration catalyst, the amount of the slurry containing the active component powder is adjusted so that the amount of the active coating supported is 33 wt% and the thickness of the active coating is 180 μm with respect to the cordierite honeycomb carrier in the obtained intermediate coated with the active coating; in the step (2), the content of molecular sieve and/or porous SiO is regulated and controlled 2 The amount of the slurry of (a) was such that the amount of the modified coating loaded was 0.3 wt% relative to the cordierite honeycomb carrier and the thickness of the modified coating was 3 μm in the catalyst precursor coated with both the active coating and the modified coating;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Comparative example 5
The procedure of example 1 was followed, except that (III) in the step (2) of preparation of the manganese-based denitration catalyst, a slurry containing a ZSM-5 type molecular sieve was coated by replacing it with a slurry containing hydrophobic polytetrafluoroethylene;
the other steps were the same as in example 1 to obtain a manganese-based denitration catalyst.
Test example
The manganese-based denitration catalyst prepared in the above examples and comparative examples was cut into test pieces of 20mm × 20mm × 150mm, and then placed in a stainless steel fixed bed reactor to perform denitration performance and SO resistance of the catalyst under simulated flue gas conditions in a laboratory 2 And (6) evaluating the performance. Simulating the test conditions of the flue gas: SO 2 ＝500mg/Nm 3 ，NO x ＝NH 3 ＝600mg/Nm 3 ，O 2 ＝7v％，H 2 O＝30v％，N 2 In order to balance the gas, the space velocity of the simulated smoke is 12000h -1 And the surface speed Av of the simulated smoke is 30 m/h.
Evaluation of denitration performance of the catalyst: the test temperature is respectively 140 ℃ and 300 ℃, the initial denitration efficiency of each test block and the denitration efficiency after 168 hours of operation are respectively tested, and the NO at the inlet and the outlet of the reactor is measured by adopting a American MKS flue gas analyzer x And is calculated according to the following formula:
wherein eta represents the denitration efficiency, and the unit is%;
anti-SO 2 Evaluation of the Properties: the testing temperature is 300 ℃, and the specific testing method comprises the following steps: sampling at the inlet of an SCR reactor, adopting hydrogen peroxide as absorption liquid, simultaneously measuring the flow and time of sampled flue gas, analyzing the sampling liquid by using an ion chromatograph, and analyzing SO in the sampling liquid 4 2- Ion concentration, determination of inlet SO by calculation 2 The content of (d) is recorded as S1 in mg. At the outlet of the SCR reactor, a condensing bottle is placed in a water bath at 65 ℃ to collect SO at the flue gas outlet 3 Simultaneously measuring the flow and time of the sampled smoke, and dissolving SO in the condensation bottle by using deionized water 3 And recording the amount of the sample liquid, and analyzing and measuring SO in the solution by using an ion chromatograph 4 2- Content, determining SO at the outlet by calculation 3 The content of (d) is recorded as S2 in mg. SO of the catalyst was calculated according to the following formula 2 /SO 3 Conversion rate α:
the average of three tests α was taken and the evaluation results are shown in table 1.
TABLE 1
As can be seen from the results in Table 1, compared with the prior art, the manganese-based denitration catalyst provided by the invention has the advantage that the decrement of the denitration efficiency after the operation for 168 hours at 140 ℃ and 300 ℃ is less than 6%, thereby indicating that the manganese-based denitration catalyst provided by the invention has good H resistance 2 O property, and shows excellent and stable denitration activity in a wide temperature window of 140-300 ℃, and the service life of the catalyst is longer.
Meanwhile, the SO of the manganese-based denitration catalyst provided by the invention 2 /SO 3 Conversion rateAre both between 0.66 and 0.72 percent and are reduced by more than 47 percent compared with comparative examples 2 and 4, SO the manganese-based denitration catalyst provided by the invention has better SO resistance 2 The ability to fail.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (15)
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 relative to the carrier, the loading capacity of the active coating is 3.5-60 wt%, the loading capacity of the modified coating is 0.5-15 wt%, 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, first metal oxide and second metal oxide, wherein the first metal oxide is selected from at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, the second metal oxide is selected from 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 molecular sieve and/or porous SiO 2 。
2. The catalyst as claimed in claim 1, wherein the loading amount of the active coating layer is 4.5-50 wt%, the loading amount of the modified coating layer is 1-11 wt%, the thickness of the active coating layer is 100-120 μm, and the thickness of the modified coating layer is 20-30 μm, relative to the support;
preferably, the first metal oxide is niobium oxide and/or antimony oxide;
preferably, the second metal oxide is selected from at least one of iron oxide, cerium oxide and lanthanum oxide.
3. The catalyst of claim 1 or 2, wherein the molecular sieve has a silica to alumina molar ratio of 80-200: 1;
preferably, 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, and more preferably is ZSM-5 type molecular sieve and/or BETA type molecular sieve;
preferably, the porous SiO 2 Is less than 2 nm;
preferably, the porous SiO 2 Is white carbon black and/or SiO 2 An aerogel.
4. A preparation method of a manganese-based denitration catalyst is characterized by comprising the following steps:
(1) carrying out first coating on the 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; relative to the carrier, the loading amount of the active coating is 3.5-60 wt%, and the thickness of the active coating is 80-140 μm;
(2) by using a catalyst containing molecular sieves and/or porous SiO 2 The intermediate is subjected to secondary coating by the slurry, and then secondary drying is carried out to obtain a catalyst precursor coated with an active coating layer and a modified coating layer simultaneously; the loading amount of the modified coating is 0.5-15 wt% relative to the carrier, and the thickness of the modified coating is 10-40 μm; then, carrying out first roasting on the catalyst precursor to obtain a manganese-based denitration catalyst;
the active component powder comprises manganese oxide, first metal oxide and second metal oxide, wherein the first metal oxide is selected from at least one of molybdenum oxide, niobium oxide, tantalum oxide, tungsten oxide and antimony oxide, and the second metal oxide is selected from 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.
5. The method as claimed in claim 4, wherein, in the step (1), the slurry containing the active component powder is used in an amount such that the loading amount of the active coating layer in the intermediate coated with the active coating layer obtained is 4.5-50 wt% relative to the carrier, and the thickness of the active coating layer is 100-120 μm;
preferably, in step (2), the silica-containing porous material contains a molecular sieve and/or porous SiO 2 The amount of the slurry of (a) is such that the amount of the modified coating layer supported relative to the support in the resulting catalyst precursor simultaneously coated with the active coating layer and the modified coating layer is from 1 to 11% by weight and the thickness of the modified coating layer is from 20 to 30 μm.
6. The method according to claim 4 or 5, wherein in the step (1), the preparation method of the slurry containing the active component powder comprises the following steps:
(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, then 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 and pulping the active component powder, a binder, a second dispersing agent and water to obtain slurry containing the active component powder.
7. The method according to claim 6, wherein 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 from 0.05 to 0.5: 0.05-0.3: 0.2 to 0.9, preferably 0.3 to 0.4: 0.1-0.2: 0.4-0.6;
preferably, the molar ratio of the manganese source calculated as the Mn element to the total amount of 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: 1.5-2.5, more preferably 1: 1.8-2.2;
preferably, the first dispersing agent is used in an amount of 5 to 20 wt%, more preferably 8 to 12 wt%, based on the mass of the organic complexing agent;
preferably, the organic complexing agent is selected from at least one of citric acid, oxalic acid and tartaric acid, more preferably citric acid;
preferably, the first dispersant is at least one selected from the group consisting of polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, carboxymethyl cellulose, polyacrylic acid, and polymethacrylic acid, and more preferably polyethylene glycol.
8. The method of claim 6 or 7, wherein in step (a), the drying conditions comprise: the temperature is 90-120 ℃, and the time is 12-24 h;
preferably, in step (a), the roasting conditions include: heating to 250-350 ℃ at the speed of 0.5-5 ℃/min, and keeping the temperature for 2-5 h; then raising the temperature to 450-550 ℃ at the speed of 0.5-5 ℃/min, and keeping the temperature for 3-8 h.
9. The method according to any one of claims 6 to 8, wherein in the step (b), the weight ratio of the active component powder to the binder, the second dispersant and the water is 10-50: 5-20: 0.01-1: 29-84.9, preferably 15-25: 10-15: 0.5-1: 59-74.5;
preferably, the binder is selected from at least one of titanium sol, silica sol, aluminum sol, zirconium sol, soluble zirconium salt, soluble aluminum salt, and soluble titanium salt;
preferably, the second dispersant is 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.
10. The process according to any one of claims 6 to 9, wherein in step (b), the beating is carried out under conditions such that the resulting slurry containing the active ingredient powder has a viscosity of 50 to 500 mPa-s, preferably 90 to 200 mPa-s, at 25 ℃;
preferably, in step (b), the beating conditions comprise: the beating speed is 300-1000r/min, and the beating time is 30-100 min.
11. The method according to claim 4, wherein in the step (2), the silica-containing particles contain a molecular sieve and/or porous SiO 2 The method for preparing the slurry of (1) comprises: mixing molecular sieve and/or porous SiO 2 Mixing with adhesive, second dispersant and water, and pulping to obtain the product containing molecular sieve and/or porous SiO 2 The slurry of (1);
preferably, the molecular sieve and/or porous SiO 2 The weight ratio of the adhesive to the second dispersant to 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;
preferably, the beating conditions are such that the resulting slurry contains molecular sieve and/or porous SiO 2 The viscosity of the slurry of (a) is 50 to 500 mPas, preferably 90 to 200 mPas, at 25 ℃;
preferably, the beating conditions include: the beating speed is 300-1000r/min, and the beating time is 30-100 min.
12. The method according to any one of claims 4 to 11, wherein in step (1), the conditions of the first drying comprise: the temperature is 80-100 deg.C, and the time is 20-60 min;
preferably, in the step (2), the second drying conditions include: the temperature is 80-100 deg.C, and the time is 20-60 min;
preferably, in the step (2), the conditions of the first firing include: the temperature is 400 ℃ and 500 ℃, and the time is 1-5 h.
13. The manganese-based denitration catalyst prepared by the method of any one of claims 4 to 12.
14. A method for denitration of flue gas, which is characterized by comprising the following steps: the flue gas is contacted with the manganese-based denitration catalyst according to any one of claims 1 to 3 and 13 to react.
15. The method as claimed in claim 14, wherein the method is carried out at a temperature of 140-300 ℃;
preferably, the volume space velocity of the flue gas is 2000- -1 The surface speed of the flue gas is 5-50 m/h;
preferably, SO is contained in the flue gas 2 The concentration of (A) is 50-500mg/Nm 3 ，NO x The concentration of (a) is 100-2000mg/Nm 3 ，NH 3 The concentration of (A) is 75-750mg/Nm 3 ，O 2 In an amount of 3-15 v%, H 2 The content of O is 8-40 v%.
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