CN111167437A - Honeycomb low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition and preparation method thereof - Google Patents
Honeycomb low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition and preparation method thereof Download PDFInfo
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- CN111167437A CN111167437A CN202010021602.0A CN202010021602A CN111167437A CN 111167437 A CN111167437 A CN 111167437A CN 202010021602 A CN202010021602 A CN 202010021602A CN 111167437 A CN111167437 A CN 111167437A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 31
- 230000001737 promoting effect Effects 0.000 title claims abstract description 29
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 8
- 229920000742 Cotton Polymers 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 6
- 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
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 3
- 230000001413 cellular effect Effects 0.000 claims description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- 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 description 3
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 2
- FUECGUJHEQQIFK-UHFFFAOYSA-N [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] FUECGUJHEQQIFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 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
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- LEDZTLLWGZWUMH-UHFFFAOYSA-H cerium(3+) lanthanum(3+) trisulfate Chemical compound S(=O)(=O)([O-])[O-].[Ce+3].[La+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] LEDZTLLWGZWUMH-UHFFFAOYSA-H 0.000 claims description 2
- AMKLQLYNAGNCJE-UHFFFAOYSA-N cerium(3+);lanthanum(3+);hexanitrate Chemical compound [La+3].[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AMKLQLYNAGNCJE-UHFFFAOYSA-N 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000005287 vanadyl group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 229910052758 niobium Inorganic materials 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 21
- 239000003546 flue gas Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
-
- B01J35/56—
-
- 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 discloses a honeycomb-shaped low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition and a preparation method thereof, and vanadium oxide V is used2O5As the active component, at least one of Ce, Mo or Nb is used as the component for promoting ABS decomposition. The preparation process of the honeycomb catalyst comprises the steps of mixing, ageing and extruding an active component, an auxiliary agent, an ABS decomposition promoting component, a carrier and a forming auxiliary agent to obtain a honeycomb green body; and drying and calcining the honeycomb green body to obtain the honeycomb low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition. The ABS decomposition promoting component can enhance the electron transfer capability in the catalyst and can effectively improve the catalytic activity of the vanadium-based catalyst at low temperature; and, promote ABS decompositionThe components can effectively reduce the decomposition temperature of ABS on the catalyst, effectively make up for the defect that the traditional SCR catalyst is easy to activate due to ABS deposition at low temperature, improve the low-temperature stability of the catalyst, and reduce the energy consumption and the cost for catalyst regeneration.
Description
Technical Field
The invention belongs to the technical field of catalytic purification of industrial flue gas, and particularly relates to a honeycomb-shaped low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition and a preparation method thereof.
Background
Nitrogen Oxides (NO)x) Is one of the main atmospheric pollutants, and the emission into the atmosphere causes environmental problems such as acid rain, photochemical smog, haze and the like. In recent years, with our country moving source NOxImprovement of emission control standards and implementation of ultra-low emissions, NO, from coal-fired power plants in stationary sourcesxThe amount of discharge of (c) is controlled. But NO emitted from industrial sources in industries such as steel, coking, cement, glass, building materials, etcxIs not effectively controlled, so that NO in China is causedxThe total amount of emissions remains high. Thus, NO for industrial sourcesxThe control of emission reduction is imperative.
In the existing NOxAmong emission control technologies, Selective Catalytic Reduction (SCR) denitration technology is the most widely used and technically mature removal technology in the world at present. Conventional commercial V2O5-WO3(MO3)/TiO2The denitration catalyst is mature in application in the coal-fired power industry (the smoke temperature is generally more than 300 ℃). However, for other industrial flue gases, the actual flue temperature is generally < 300 ℃ and generally contains a certain amount of SO2. This results in a conventional V2O5-WO3(MO3)/TiO2The denitration catalyst is easily deactivated. The main reason is because of SO in the flue gas2Or from SO2SO generated by catalytic oxidation3And NH3And H2The O reacts to form Ammonium Bisulfate (ABS), and the Temperature of industrial flue gas is generally lower than the Dew Point (T) of ABSDew320 ℃) is adopted, so ABS generated under the condition of industrial smoke is liquid with strong viscosity and is easy to coverThe catalyst surface causes its deactivation. At present, the common ABS poisoning resistance method for industrial flue gas denitration utilizes extra energy to heat the catalyst to a temperature above the dew point temperature of ABS, but the energy consumption of the method is quite high.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a honeycomb-shaped low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition.
The invention also aims to provide a preparation method of the low-temperature vanadium-titanium-based SCR denitration catalyst.
The technical scheme of the invention is as follows:
a cellular low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition uses titanium dioxide TiO2Is a carrier, active components, additives and cellular ABS decomposition promoting components are loaded on the carrier, and the carrier also comprises inactive components; wherein the content of the first and second substances,
the active component is V2O5，
The auxiliary agent is WO3，
The component for promoting ABS decomposition is Nb2O5、CeO2And MoO3At least one of (a) and (b),
the inactive components are prepared by fully mixing water, ammonia water, stearic acid, lactic acid, silicon dioxide, glass fiber, wood cotton pulp, carboxymethyl cellulose and polyoxyethylene and then calcining.
In a preferred embodiment of the present invention, said V2O5In an amount of 1 to 5 wt.%, WO31-10 wt%, ABS decomposition promoting component 1-15 wt%, carrier 70-90 wt%, and inactive component for the rest.
In a preferred embodiment of the present invention: the inactive components are prepared by fully mixing and calcining water, ammonia water, stearic acid, lactic acid, silicon dioxide, glass fiber, wood cotton pulp, carboxymethyl cellulose and polyoxyethylene according to the mass ratio of 43-53: 5-12: 0.1-4: 0.5-2.5: 1-4: 5-12: 0.1-3: 0.5-1.5.
The preparation method of the honeycomb-shaped low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition is characterized by comprising the following steps of: the method comprises the following steps:
(1) mixing the active component precursor, the auxiliary agent precursor, the precursor for promoting ABS decomposition component, the carrier and the inactive component to obtain pug with water content of 26-30 wt% and pH of 7.5-9, and ageing and extruding to obtain honeycomb green body;
(2) and drying and calcining the honeycomb-shaped green body to obtain the low-temperature vanadium-titanium-based SCR denitration catalyst.
In a preferred embodiment of the present invention, the active component precursor is at least one of sodium metavanadate, ammonium metavanadate and potassium metavanadate.
In a preferred embodiment of the present invention, the auxiliary agent precursor is at least one of ammonium metatungstate, ammonium paratungstate, ammonium tungstate, and tungsten nitrate.
In a preferred embodiment of the present invention, the ABS decomposition-promoting component Nb2O5The precursor of (a) is niobium oxalate or niobium pentoxide; the component CeO for promoting ABS decomposition2The precursor of (a) is at least one of cerium nitrate, ammonium cerium nitrate, cerium sulfate, lanthanum cerium nitrate and lanthanum cerium sulfate, or cerium oxide; the component MoO for promoting ABS decomposition3The precursor of (a) is at least one of ammonium orthomolybdate, ammonium paramolybdate, ammonium dimolybdate, ammonium tetramolybdate, molybdenum nitrate and molybdenum sulfate.
In a preferred embodiment of the invention, the temperature of the ageing is 20-40 ℃ and the time is 8-24 h; the drying temperature is 60-90 ℃ and the drying time is 6-12 d; the calcining temperature is 400-620 ℃, and the calcining time is 5-30 h.
The invention has the beneficial effects that:
1. the invention uses vanadium oxide V2O5As an active component, at least one of Ce, Mo or Nb is used as a component for promoting the decomposition of ABS, so that the electron transfer capability in the catalyst can be enhanced, and the catalytic activity of the vanadium-based catalyst at low temperature can be effectively improved; moreover, the ABS decomposition promoting component can effectively reduce the decomposition temperature of ABS on the catalyst, effectively make up for the defect that the traditional SCR catalyst is easy to activate due to ABS deposition at low temperature, and improve the catalystThe low-temperature stability of the catalyst reduces the energy consumption and the cost of catalyst regeneration.
2. The invention can contain 0-3000mg/m at 150-300 deg.C3SO of (A)2And 0-25% of steam, the denitration efficiency of the catalyst can be stabilized to be more than 80%, and the catalyst is suitable for NO in industrial source flue gas such as steel sintering, coking, cement and the likexThe emission control of (1).
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
(1) Ammonium metavanadate, ammonium metatungstate, ammonium heptamolybdate, ammonium cerium nitrate and titanium dioxide TiO2Mixing the components with the inactive components to obtain pug with the water content of 28 wt% and the pH value of 8.2, and ageing at 25 ℃ for 12 hours and extruding to obtain a honeycomb green body;
the inactive components comprise the following components in parts by weight: 45 parts of ammonia water: 8 parts, stearic acid: 1.2 parts, lactic acid: 1.5 parts, silica: 3 parts, glass fiber: 6 parts of wood pulp cotton: 0.3 part, carboxymethyl cellulose: 0.8 part, polyoxyethylene: 0.9 part;
(2) drying the honeycomb-shaped green body at 60 ℃ for 10 days, and calcining at 550 ℃ for 22 hours to obtain the low-temperature vanadium-titanium-based SCR denitration catalyst (V)2O5In an amount of 3 wt%, WO3Is 4 wt%, MoO3Is 5 wt% CeO2Content of 3 wt%, titanium dioxide TiO2The content of (b) is 77 wt%, and the content of inactive components is 8 wt%).
The prepared low-temperature vanadium titanium-based SCR denitration catalyst is cut into 3 multiplied by 3 holes, the length of the catalyst is 40cm, and denitration activity and other various detections are carried out.
Example 2:
(1) mixing ammonium metavanadate, ammonium metatungstate, cerium dioxide and titanium dioxide TiO2Mixing the components with the inactive components to obtain pug with the water content of 27 wt% and the pH value of 7.8, and ageing at 30 ℃ for 14h and extruding to obtain a honeycomb green body;
the inactive components comprise the following components in parts by weight: 43 parts of ammonia water: 5 parts, stearic acid: 1 part, lactic acid: 0.7 part, silica: 1.9 parts, glass fiber: 5 parts of wood pulp cotton: 0.9 part, carboxymethyl cellulose: 0.7 part, polyoxyethylene: 1.0 part;
(2) drying the honeycomb-shaped green body at 60 ℃ for 8 days, and calcining at 500 ℃ for 28 hours to obtain the low-temperature vanadium-titanium-based SCR denitration catalyst (V)2O5In an amount of 4 wt%, WO3Is 5 wt% CeO2Content of (2) 7 wt%, titanium dioxide TiO2Is 78 wt% and the content of inactive components is 6 wt%).
The prepared low-temperature vanadium titanium-based SCR denitration catalyst is cut into 3 multiplied by 3 holes, the length of the catalyst is 40cm, and denitration activity and other various detections are carried out.
Example 3:
(1) ammonium metavanadate, ammonium metatungstate, ammonium heptamolybdate, niobium oxalate and titanium dioxide TiO2Mixing the components with the inactive components to obtain pug with the water content of 29 wt% and the pH value of 8.5, and ageing at 30 ℃ for 10 hours and extruding to obtain a honeycomb green body;
the inactive components comprise the following components in parts by weight: 49 parts, ammonia water: 10 parts, stearic acid: 2 parts, lactic acid: 0.9 part, silica: 2 parts, glass fiber: 7 parts of wood pulp cotton: 1.2 parts, carboxymethyl cellulose: 1.0 part, polyoxyethylene: 1.2 parts;
(2) drying the honeycomb-shaped green body at 70 ℃ for 6 days, and calcining at 550 ℃ for 18 hours to obtain the low-temperature vanadium-titanium-based SCR denitration catalyst (V)2O5In an amount of 5 wt%, WO3Is 5 wt%, Nb2O5Is 5 wt%, MoO32 wt% of titanium dioxide TiO2The content of (b) is 77 wt%, and the content of inactive components is 6 wt%).
The prepared low-temperature vanadium titanium-based SCR denitration catalyst is cut into 3 multiplied by 3 holes, the length of the catalyst is 40cm, and denitration activity and other various detections are carried out.
Example 4:
(1) mixing ammonium metavanadate, ammonium metatungstate, niobium pentoxide and cerium dioxideTitanium white TiO powder2Mixing the components with the inactive components to obtain pug with the water content of 28 wt% and the pH value of 8.0, and ageing for 16h at 25 ℃ and extruding to obtain a honeycomb green body;
the inactive components comprise the following components in parts by weight: 50 parts of ammonia water: 6 parts, stearic acid: 1.2 parts, lactic acid: 2 parts, silica: 2.2 parts, glass fiber: 8.8 parts of wood pulp cotton: 0.3 part, carboxymethyl cellulose: 0.7 part, polyoxyethylene: 1 part;
(2) drying the honeycomb-shaped green body at 60 ℃ for 10 days, and calcining at 480 ℃ for 18 hours to obtain the low-temperature vanadium-titanium-based SCR denitration catalyst (V)2O5In an amount of 2.2 wt.%, WO3Is 4 wt%, Nb2O5Is 5 wt% CeO22 wt% of titanium dioxide TiO2Is 80 wt%, and the content of inactive components is 6.8 wt%).
The prepared low-temperature vanadium titanium-based SCR denitration catalyst is cut into 3 multiplied by 3 holes, the length of the catalyst is 40cm, and denitration activity and other various detections are carried out.
Comparative example 1
This comparative example uses commercial V2O5-WO3/TiO2A denitration catalyst.
To better illustrate the characteristics of the low-temperature SCR denitration catalyst provided by the embodiment of the present invention, the low-temperature vanadium-titanium-based SCR denitration catalysts of examples 1 to 4 and the commercial V of comparative example 1 are described below2O5-WO3/TiO2The denitration performance of the denitration catalyst is detected, and the detection result is shown in the following table.
The smoke conditions are as follows: 300ppm NO, 300ppm NH3，100ppm SO2，6％O2，10％H2O，N2As carrier gas, space velocity (GHSV) is 5000h-1。NOxThe instrument used for inlet and outlet readings was a Testo-350 smoke analyzer.
As is apparent from the above table, the low-temperature SCR denitration catalysts provided in embodiments 1 to 4 of the present invention have denitration efficiency of 80 to 96% in a wide temperature range of 180 to 300 ℃ under the condition of moisture-containing and sulfur-containing flue gas, and have excellent water resistance and sulfur resistance.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (8)
1. A honeycomb-shaped low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition is characterized in that: titanium dioxide TiO2Is a carrier, active components, additives and cellular ABS decomposition promoting components are loaded on the carrier, and the carrier also comprises inactive components; wherein the content of the first and second substances,
the active component is V2O5The auxiliary agent is WO3The component for promoting ABS decomposition is Nb2O5、CeO2And MoO3At least one of the inactive components is prepared by fully mixing and calcining water, ammonia water, stearic acid, lactic acid, silicon dioxide, glass fiber, wood cotton pulp, carboxymethyl cellulose and polyoxyethylene.
2. The honeycomb-shaped low-temperature vanadium-titanium-based SCR denitration catalyst for promoting ABS decomposition of claim 1, wherein the low-temperature vanadium-titanium-based SCR denitration catalyst comprises the following components in percentage by weight: the V is2O5In an amount of 1 to 5 wt.%, WO31-10 wt%, ABS decomposition promoting component 1-15 wt%, carrier 70-90 wt%, and inactive component for the rest.
3. The low temperature vanadyl SCR denitration catalyst of claim 1, wherein: the inactive components are prepared by fully mixing and calcining water, ammonia water, stearic acid, lactic acid, silicon dioxide, glass fiber, wood cotton pulp, carboxymethyl cellulose and polyoxyethylene according to the mass ratio of 43-53: 5-12: 0.1-4: 0.5-2.5: 1-4: 5-12: 0.1-3: 0.5-1.5.
4. The preparation method of the honeycomb-shaped low-temperature vanadium-titanium-based SCR denitration catalyst for promoting ABS decomposition as claimed in any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) mixing the active component precursor, the auxiliary agent precursor, the precursor for promoting ABS decomposition component, the carrier and the inactive component to obtain pug with water content of 26-30 wt% and pH of 7.5-9, and ageing and extruding to obtain honeycomb green body;
(2) and drying and calcining the honeycomb-shaped green body to obtain the low-temperature vanadium-titanium-based SCR denitration catalyst.
5. The method of claim 4, wherein: the active component precursor is at least one of sodium metavanadate, ammonium metavanadate and potassium metavanadate.
6. The method of claim 4, wherein: the auxiliary agent precursor is at least one of ammonium metatungstate, ammonium paratungstate, ammonium tungstate and tungsten nitrate.
7. The method of claim 4, wherein: the component Nb for promoting ABS decomposition2O5The precursor of (a) is niobium oxalate or niobium pentoxide; the component CeO for promoting ABS decomposition2The precursor of (a) is at least one of cerium nitrate, ammonium cerium nitrate, cerium sulfate, lanthanum cerium nitrate and lanthanum cerium sulfate, or cerium oxide; the component MoO for promoting ABS decomposition3The precursor of (a) is at least one of ammonium orthomolybdate, ammonium paramolybdate, ammonium dimolybdate, ammonium tetramolybdate, molybdenum nitrate and molybdenum sulfate.
8. The production method according to any one of claims 4 to 7, characterized in that: the temperature of the ageing is 20-40 ℃, and the time is 8-24 h; the drying temperature is 60-90 ℃ and the drying time is 6-12 d; the calcining temperature is 400-620 ℃, and the calcining time is 5-30 h.
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| CN113457665A (en) * | 2021-06-22 | 2021-10-01 | 苏州西热节能环保技术有限公司 | Efficient low-temperature honeycomb type SCR denitration catalyst and preparation method thereof |
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