CN111001402A - Low-temperature SCR denitration catalyst and preparation method thereof - Google Patents
Low-temperature SCR denitration catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN111001402A CN111001402A CN201910987063.3A CN201910987063A CN111001402A CN 111001402 A CN111001402 A CN 111001402A CN 201910987063 A CN201910987063 A CN 201910987063A CN 111001402 A CN111001402 A CN 111001402A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- coating
- low
- catalyst coating
- scr denitration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 96
- 239000011248 coating agent Substances 0.000 claims abstract description 95
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 50
- 239000002243 precursor Substances 0.000 claims description 33
- 239000011268 mixed slurry Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 239000012695 Ce precursor Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000012692 Fe precursor Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- MSOUIOOSDCFNQJ-UHFFFAOYSA-N [Mo].[W].[Ti] Chemical compound [Mo].[W].[Ti] MSOUIOOSDCFNQJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- PYCBFXMWPVRTCC-UHFFFAOYSA-N ammonium metaphosphate Chemical compound N.OP(=O)=O PYCBFXMWPVRTCC-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 2
- 229960001759 cerium oxalate Drugs 0.000 claims description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003546 flue gas Substances 0.000 abstract description 5
- 229940031098 ethanolamine Drugs 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- -1 coking Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 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 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004056 waste incineration Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a low-temperature SCR denitration catalyst, wherein a first catalyst coating is coated on a honeycomb ceramic carrier, a second catalyst coating is coated on the first catalyst coating, the total coating amount of the catalyst coatings is 100-250 g/L, and the first catalyst coating contains MoO3、WO3、TiO2Containing MnO in the second catalyst coating layer2、Fe2O3、CeO2One or more of (a). The preparation method comprises the steps of side coating of the first catalyst coating layer, preparation of the second catalyst coating layer and coating of the second catalyst coating layer. The catalyst has the nitrogen oxide removal rate of 65-80% at the flue gas temperature of 100-120 ℃, and the nitrogen oxide removal rate of more than 85% at the temperature of 150-350 ℃.
Description
Technical Field
The invention relates to a low-temperature SCR denitration catalyst and a preparation method thereof, belonging to the technical field of catalysts for removing nitrogen oxides in industrial or motor vehicle tail gas pollutants by selective catalytic reduction and preparation methods thereof.
Background
In recent years, the problem of environmental pollution has been increasingThe haze problem especially stabbing the social nerves is a serious social problem related to the living health of people and the sustainable development of national economy. Dust, sulfur dioxide (SO)2) And Nitrogen Oxides (NO)x) Is a main pollutant for forming haze, generating photochemical smog and the like.
The smoke emission of coal-fired power plants and the tail gas emission of motor vehicles are one of the most important factors that the PM2.5 in the atmospheric environment exceeds the standard and the haze weather frequently occurs in China. At present, dust removal and desulfurization technologies are widely applied to thermal power generating units, and only the pollution of nitrogen oxides is not effectively controlled. Aiming at a coal-fired power plant, the activity temperature of the current commercial selective catalytic reduction denitration (SCR) catalyst is 300-420 ℃, the operation is stable, the impurity content in the flue gas is low, and the like. However, compared with coal-fired power stations, the flue gas discharged by industries such as glass, coking, cement, industrial kilns, waste incineration and chemical plants is low in temperature ranging from 150 ℃ to 300 ℃, and SO in tail gas2And H2The concentration of O is high, and the denitration catalyst widely applied at present is difficult to adapt to the working condition, so that the development of the catalyst which has high activity under the low temperature condition (100-350 ℃) and strong sulfur-resistant and water poisoning-resistant capability is necessary.
Disclosure of Invention
One of the purposes of the invention is to overcome the defects in the prior art and provide the low-temperature SCR denitration catalyst with high nitrogen oxide removal rate and higher water-resistant and sulfur-resistant performance.
The invention also aims to provide a preparation method of the low-temperature SCR denitration catalyst.
According to the technical scheme provided by the invention, the low-temperature SCR denitration catalyst is characterized in that a first catalyst coating is coated on a honeycomb ceramic carrier, a second catalyst coating is coated on the first catalyst coating, the total coating amount of the first catalyst coating and the second catalyst coating is 100-250 g/L, and MoO is contained in the first catalyst coating3、WO3、TiO2One or more of (a) a second catalystMnO is contained in the agent coating2、Fe2O3、CeO2The first catalyst coating layer and the second catalyst coating layer constitute a catalyst coating layer, and MnO is2、Fe2O3、CeO2、MoO3、WO3With TiO2The content of the catalyst coating is 10-30 wt%, 0-10 wt%, 10-20 wt%, 0-5 wt%, 5-10 wt% and 30-75 wt%, respectively.
The preparation method of the low-temperature SCR denitration catalyst comprises the following steps:
a. mixing a tungsten precursor solution and a molybdenum precursor solution, adding a surface dispersant, fully stirring to uniformly disperse the tungsten precursor solution and the molybdenum precursor solution, adding metatitanic acid into the solution, controlling the solid content of the mixed solution to be 40-55%, adjusting the pH value of the mixed solution to be 8-10 by using ethanolamine, aging for 5-24h under stirring, filtering to obtain a filter cake, drying the filter cake at 120 ℃ for 12-24h, and calcining at 400-550 ℃ for 2-5 h to obtain a required first catalyst coating;
b. preparing a manganese precursor solution, a cerium precursor solution, an iron precursor solution, titanium-tungsten-molybdenum powder and a binder into mixed slurry, adjusting the pH value to 3-5 by using nitric acid, grinding and uniformly mixing, controlling the solid content of the mixed slurry to be 30-45%, and stirring for later use;
c. b, coating the mixed slurry obtained in the step b on a first catalyst coating by using coating equipment, and drying at 120 ℃ for 12 hours; and (3) putting the dried carrier into a muffle furnace, roasting for 2h at 450 ℃, and cooling to room temperature after heat preservation is finished to obtain the low-temperature SCR denitration catalyst.
Preferably, the method comprises the following steps: the surface dispersing agent is one or more of ammonium citrate, ammonium oxalate, ammonium fluoride or ammonium metaphosphate.
Preferably, the method comprises the following steps: the binder is one or more of aluminum sol, silica sol and zirconium sol.
Preferably, the method comprises the following steps: the mass of the sol cured substance accounts for 1-5% of that of the catalyst cured substance.
Preferably, the method comprises the following steps: the manganese precursor is one or more of manganese nitrate, manganese acetate and manganese chloride.
Preferably, the method comprises the following steps: the cerium precursor may be one or more of cerium nitrate, cerium oxalate, and ammonium cerium nitrate.
Preferably, the method comprises the following steps: the iron precursor can be one or more of ferric nitrate, ferric sulfate, ferric chloride and ferric acetate.
Preferably, the method comprises the following steps: the molybdenum precursor may be one or more of ammonium molybdate, ammonium paramolybdate, and ammonium tetramolybdate.
Preferably, the method comprises the following steps: the tungsten precursor may be one or more of ammonium tungstate and ammonium metatungstate.
The catalyst has the advantages that the removal rate of nitrogen oxide can reach 65-80% at the flue gas temperature of 100-120 ℃, the removal rate of nitrogen oxide can reach more than 85% at the temperature of 150-350 ℃, and the catalyst has high water resistance and sulfur resistance.
The preparation method disclosed by the invention is simple, large in specific surface area and good in coating firmness, and can be suitable for tail gas/flue gas denitration treatment of mobile sources and fixed sources.
Detailed Description
The present invention will be further described with reference to the following specific examples.
In the following six examples, cylindrical cordierite honeycomb ceramics having a diameter of 101.6mm and a height of 123.3mm were used as a carrier, and the volume was 1L and the carrier weight was 324 g.
Example 1
The preparation method of the low-temperature SCR denitration catalyst comprises the following steps:
a. firstly, mixing a tungsten precursor solution and a molybdenum precursor solution, adding a surface dispersant, fully stirring to uniformly disperse, then adding metatitanic acid into the solution, wherein the solid content of the mixed solution is 40%, adjusting the pH value to 8.3 by using ethanol amine, aging for 15h under stirring, filtering, drying a filter cake at 120 ℃ for 12h, and calcining at 400 ℃ for 2h to obtain a required first catalyst coating;
b. then preparing a manganese precursor solution, a cerium precursor solution, an iron precursor solution, titanium-tungsten-molybdenum powder and a binder into mixed slurry, adjusting the pH value to 3.5 by using nitric acid, grinding and uniformly mixing, wherein the solid content of the mixed slurry is 30%, and stirring for later use;
c. b, coating the mixed slurry obtained in the step b on a first catalyst coating by using coating equipment, and drying at 120 ℃ for 12 hours; and (3) putting the dried carrier into a muffle furnace, roasting for 2h at 450 ℃, cooling to room temperature after heat preservation is finished, and forming a second catalyst coating on the first catalyst coating to obtain the low-temperature SCR denitration catalyst, wherein the first catalyst coating and the second catalyst coating form a catalyst coating.
Oxides MnO in the catalyst coating2、Fe2O3、CeO2、MoO3、WO3With TiO2The weight ratio is 10 wt%, 5 wt%, 20 wt%, 5 wt%, 10 wt% and 50 wt%, respectively.
Example 2
The preparation method of the low-temperature SCR denitration catalyst comprises the following steps:
a. firstly, mixing a tungsten precursor solution and a molybdenum precursor solution, adding a surface dispersant, fully stirring to uniformly disperse, then adding metatitanic acid into the solution, wherein the solid content of the mixed solution is 45%, adjusting the pH value to 9.0 by using ethanol amine, aging for 24 hours under stirring, filtering, drying a filter cake at 120 ℃ for 14 hours, and calcining at 450 ℃ for 3 hours to obtain a required first catalyst coating;
b. then preparing a manganese precursor solution, a cerium precursor solution, titanium-tungsten-molybdenum powder and a binder into mixed slurry, adjusting the pH value to 3.3 by using nitric acid, grinding and uniformly mixing, wherein the solid content of the mixed slurry is 35%, and stirring for later use;
c. b, coating the mixed slurry obtained in the step b on a first catalyst coating by using coating equipment, and drying at 120 ℃ for 12 hours; and (3) putting the dried carrier into a muffle furnace, roasting for 2h at 450 ℃, cooling to room temperature after heat preservation is finished, and forming a second catalyst coating on the first catalyst coating to obtain the low-temperature SCR denitration catalyst, wherein the first catalyst coating and the second catalyst coating form a catalyst coating.
Oxides MnO in the catalyst coating2、CeO2、MoO3、WO3、TiO2The weight ratio is 14 wt%, 10 wt%, 1 wt%, 5 wt% and 70 wt%, respectively.
Example 3
The preparation method of the low-temperature SCR denitration catalyst comprises the following steps:
a. firstly, adding a surface dispersant into a tungsten precursor solution, fully stirring to uniformly disperse, then adding metatitanic acid into the solution, wherein the solid content of the mixed solution is 48%, adjusting the pH value to 10 by using ethanolamine, aging for 17h under stirring, filtering, drying a filter cake at 120 ℃ for 18h, and calcining for 4h at 500 ℃ to obtain a required first catalyst coating;
(2) then preparing a manganese precursor solution, a cerium precursor solution, an iron precursor solution, titanium-tungsten-molybdenum powder and a binder into mixed slurry, adjusting the pH value to 4 by using nitric acid, grinding and uniformly mixing, wherein the solid content of the mixed slurry is 37%, and stirring for later use;
(3) coating the mixed slurry obtained in the step (2) on a first catalyst coating by using coating equipment, and drying at 120 ℃ for 12 h; and (3) putting the dried carrier into a muffle furnace, roasting for 2h at 450 ℃, cooling to room temperature after heat preservation is finished, and forming a second catalyst coating on the first catalyst coating to obtain the low-temperature SCR denitration catalyst, wherein the first catalyst coating and the second catalyst coating form a catalyst coating.
Oxides MnO in the catalyst coating2、Fe2O3、CeO2、WO3、TiO2The weight ratio is 18 wt%, 4 wt%, 12 wt%, 9 wt% and 57 wt%, respectively.
Example 4
The preparation method of the low-temperature SCR denitration catalyst comprises the following steps:
a. firstly, mixing a tungsten precursor solution and a molybdenum precursor solution with certain concentration, adding a proper amount of surface dispersant, fully stirring to uniformly disperse, then adding metatitanic acid into the solution, wherein the solid content of the mixed solution is 52%, adjusting the pH value to 9.10 by using ethanolamine, aging for 20h under stirring, filtering, drying a filter cake at 120 ℃ for 23h, and calcining at 550 ℃ for 2h to obtain a required first catalyst coating;
b. then preparing a manganese precursor solution, a cerium precursor solution, an iron precursor solution, titanium-tungsten-molybdenum powder and a binder into mixed slurry according to a certain proportion, adjusting the pH value to 3 by using nitric acid, grinding and uniformly mixing, wherein the solid content of the mixed slurry is 40%, and stirring for later use;
c. b, coating the mixed slurry obtained in the step b on a first catalyst coating by using coating equipment, and drying at 120 ℃ for 12 hours; and (3) putting the dried carrier into a muffle furnace, roasting for 2h at 450 ℃, cooling to room temperature after heat preservation is finished, and forming a second catalyst coating on the first catalyst coating to obtain the low-temperature SCR denitration catalyst, wherein the first catalyst coating and the second catalyst coating form a catalyst coating.
Oxides MnO in the catalyst coating2、Fe2O3、CeO2、MoO3、WO3、TiO2The weight ratios are 22 wt%, 6 wt%, 14 wt%, 3 wt%, 8 wt% and 47 wt%, respectively.
Example 5
The preparation method of the low-temperature SCR denitration catalyst comprises the following steps:
a. firstly, mixing a tungsten precursor solution and a molybdenum precursor solution, adding a surface dispersant, fully stirring to uniformly disperse, then adding metatitanic acid into the solution, adjusting the solid content of the mixed solution to 53%, using ethanol amine to adjust the pH value to 9.30, and aging for 12 hours under stirring. Filtering, drying the filter cake at 120 ℃ for 16h, and calcining at 510 ℃ for 3h to obtain the required first catalyst coating
b. Then preparing a manganese precursor solution, a cerium precursor solution, an iron precursor solution, titanium-tungsten-molybdenum powder and a binder into mixed slurry, adjusting the pH value to 4.3 by using nitric acid, grinding and uniformly mixing, wherein the solid content of the mixed slurry is 45%, and stirring for later use;
c. b, coating the mixed slurry obtained in the step b on a first catalyst coating by using coating equipment, and drying at 120 ℃ for 12 hours; and (3) putting the dried carrier into a muffle furnace, roasting for 2h at 450 ℃, cooling to room temperature after heat preservation is finished, and forming a second catalyst coating on the first catalyst coating to obtain the low-temperature SCR denitration catalyst, wherein the first catalyst coating and the second catalyst coating form a catalyst coating.
Oxides MnO in the catalyst coating2、Fe2O3、CeO2、MoO3、WO3、TiO2The weight ratio is 26 wt%, 4 wt%, 18 wt%, 4 wt%, 5 wt% and 53 wt%, respectively.
Example 6
The preparation method of the low-temperature SCR denitration catalyst comprises the following steps:
a. firstly, mixing a tungsten precursor solution and a molybdenum precursor solution with certain concentration, adding a proper amount of surface dispersant, fully stirring to uniformly disperse, then adding metatitanic acid into the solution, wherein the solid content of the mixed solution is 55%, adjusting the pH value to 8 by using ethanolamine, aging for 13h under stirring, filtering, drying a filter cake at 120 ℃ for 19h, and calcining at 480 ℃ for 4h to obtain the required first catalyst coating
b. Then preparing a manganese precursor solution, a cerium precursor solution, an iron precursor solution, titanium-tungsten-molybdenum powder and a binder into mixed slurry according to a certain proportion, adjusting the pH value to 3.6 by using nitric acid, grinding and uniformly mixing, wherein the solid content of the mixed slurry is 36%, and stirring for later use;
c. b, coating the mixed slurry obtained in the step b on a first catalyst coating by using coating equipment, and drying at 120 ℃ for 12 hours; and (3) putting the dried carrier into a muffle furnace, roasting for 2h at 450 ℃, cooling to room temperature after heat preservation is finished, and forming a second catalyst coating on the first catalyst coating to obtain the low-temperature SCR denitration catalyst, wherein the first catalyst coating and the second catalyst coating form a catalyst coating.
Oxides MnO in the catalyst coating2、Fe2O3、CeO2、MoO3、WO3、TiO2The weight ratio is 30wt%, 5 wt%, 15 wt%, 5 wt%, 8 wt% and 42 wt%, respectively.
Evaluation of catalyst Activity of examples 1 to 6
The activity experiment was carried out on a fixed bed reactor, with a catalyst volume of 0.5L. The initial gas concentrations were: NO and NH3Are all 1200ppm, O26% of SO2200ppm, H2O is 10% and the balance gas is N2. The reaction space velocity was 6000h-1, the reaction temperature was 100 ℃, 120 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃ and 350 ℃, and the test results are shown in Table 1.
TABLE 1
Claims (10)
1. A low-temperature SCR denitration catalyst is characterized in that: the method comprises the steps of coating a first catalyst coating on a honeycomb ceramic carrier, coating a second catalyst coating on the first catalyst coating, wherein the total coating amount of the first catalyst coating and the second catalyst coating is 100-250 g/L, and the first catalyst coating contains MoO3、WO3、TiO2Containing MnO in the second catalyst coating layer2、Fe2O3、CeO2The first catalyst coating layer and the second catalyst coating layer constitute a catalyst coating layer, and MnO is2、Fe2O3、CeO2、MoO3、WO3With TiO2The content of the catalyst coating is 10-30 wt%, 0-10 wt%, 10-20 wt%, 0-5 wt%, 5-10 wt% and 30-75 wt%, respectively.
2. The preparation method of the low-temperature SCR denitration catalyst comprises the following steps:
a. mixing a tungsten precursor solution and a molybdenum precursor solution, adding a surface dispersant, fully stirring to uniformly disperse the tungsten precursor solution and the molybdenum precursor solution, adding metatitanic acid into the solution, controlling the solid content of the mixed solution to be 40-55%, adjusting the pH value of the mixed solution to be 8-10 by using ethanolamine, aging for 5-24h under stirring, filtering to obtain a filter cake, drying the filter cake at 120 ℃ for 12-24h, and calcining at 400-550 ℃ for 2-5 h to obtain a required first catalyst coating;
b. preparing a manganese precursor solution, a cerium precursor solution, an iron precursor solution, titanium-tungsten-molybdenum powder and a binder into mixed slurry, adjusting the pH value to 3-5 by using nitric acid, grinding and uniformly mixing, controlling the solid content of the mixed slurry to be 30-45%, and stirring for later use;
c. coating the mixed slurry obtained in the step (2) on a first catalyst coating by using coating equipment, and drying at 120 ℃ for 12 h; and (3) placing the dried carrier into a muffle furnace, roasting for 2h at 450 ℃, and cooling to room temperature after heat preservation is finished to obtain the low-temperature SCR denitration catalyst.
3. The method for preparing a low-temperature SCR denitration catalyst according to claim 2, comprising the steps of: the surface dispersing agent is one or more of ammonium citrate, ammonium oxalate, ammonium fluoride or ammonium metaphosphate.
4. The method for preparing a low-temperature SCR denitration catalyst according to claim 2, comprising the steps of: the binder is one or more of aluminum sol, silica sol and zirconium sol.
5. The method for preparing a low-temperature SCR denitration catalyst according to claim 2, comprising the steps of: the mass of the sol cured substance accounts for 1-5% of that of the catalyst cured substance.
6. The method for preparing a low-temperature SCR denitration catalyst according to claim 2, comprising the steps of: the manganese precursor is one or more of manganese nitrate, manganese acetate and manganese chloride.
7. The method for preparing a low-temperature SCR denitration catalyst according to claim 2, comprising the steps of: the cerium precursor may be one or more of cerium nitrate, cerium oxalate, and ammonium cerium nitrate.
8. The method for preparing a low-temperature SCR denitration catalyst according to claim 2, comprising the steps of: the iron precursor can be one or more of ferric nitrate, ferric sulfate, ferric chloride and ferric acetate.
9. The method for preparing a low-temperature SCR denitration catalyst according to claim 2, comprising the steps of: the molybdenum precursor may be one or more of ammonium molybdate, ammonium paramolybdate, and ammonium tetramolybdate.
10. The method for preparing a low-temperature SCR denitration catalyst according to claim 2, comprising the steps of: the tungsten precursor may be one or more of ammonium tungstate and ammonium metatungstate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910987063.3A CN111001402A (en) | 2019-10-17 | 2019-10-17 | Low-temperature SCR denitration catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910987063.3A CN111001402A (en) | 2019-10-17 | 2019-10-17 | Low-temperature SCR denitration catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111001402A true CN111001402A (en) | 2020-04-14 |
Family
ID=70111818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910987063.3A Withdrawn CN111001402A (en) | 2019-10-17 | 2019-10-17 | Low-temperature SCR denitration catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111001402A (en) |
-
2019
- 2019-10-17 CN CN201910987063.3A patent/CN111001402A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20170007990A1 (en) | Honeycomb denitration catalyst for flue gas at 400°c-600°c and preparation method thereof | |
| CN104338545B (en) | A kind of efficient SCR catalyst that is applied to diesel engine vent gas purification of nitrogen oxides | |
| CN110605114B (en) | Application of mullite oxide supported catalyst in low-temperature selective catalytic reduction denitration | |
| CN109876856B (en) | Low-temperature flue gas denitration catalyst and preparation method thereof | |
| CN106000455B (en) | A kind of environmental-friendly SCR catalyst and preparation method thereof | |
| CN112657541B (en) | Preparation method of molecular sieve based low-temperature environment-friendly SCR denitration catalyst | |
| CN110052264B (en) | Preparation method of SCR denitration catalyst used under low temperature condition | |
| CN107649116A (en) | Cerium tin composite oxides denitrating catalyst and its preparation method and application | |
| CN103846083A (en) | Tungsten titanium composite oxide supported cerium oxide catalyst, preparation method as well as application of catalyst | |
| CN105833901A (en) | PrOx-MnOx/SAPO-34 low-temperature SCR smoke denitration catalyst and preparation method and application thereof | |
| CN111167487B (en) | Multifunctional catalyst, preparation method and application thereof | |
| CN112275314A (en) | Manganese-cerium-based molecular sieve SCR denitration catalyst and preparation method thereof | |
| CN111036229A (en) | Low-temperature V2O5-WO3/TiO2NH3Selective reduction catalytic NO catalyst and preparation method thereof | |
| CN103769083A (en) | Efficient denitration composite oxide catalyst as well as preparation method and application thereof | |
| CN103769240A (en) | Preparation method of catalyst for selective catalytic reduction denitration reactions | |
| CN105233814A (en) | Cerium oxide catalyst for catalyzing and purifying nitric oxides, preparation method and application | |
| CN107569984A (en) | A kind of method of denitrating flue gas | |
| CN112844374A (en) | Mn-Ce-Ti oxide aerogel denitration catalyst and preparation method and application thereof | |
| CN109745995B (en) | Wide-temperature-window SCR flue gas denitration catalyst and preparation method and application thereof | |
| CN104324728B (en) | Mesoporous composite oxide catalyst for purifying tail gases and preparation method thereof | |
| CN105879869A (en) | Catalyst used for hydrogen selective reduction of nitric oxide as well as preparation method and application thereof | |
| CN110694640B (en) | Water-resistant sulfur-resistant denitration catalyst and preparation method thereof | |
| CN112717967A (en) | Rare earth-based medium-low temperature SCR catalyst and preparation method thereof | |
| CN109046324B (en) | Medium-low temperature denitration catalyst with mesoporous cerium oxide as carrier and preparation method thereof | |
| CN103691425A (en) | Cerium tungsten titanium composite oxide denitrification catalyst preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200414 |