CN110694612A - Rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst and preparation method thereof - Google Patents
Rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003546 flue gas Substances 0.000 title claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 24
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 24
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003365 glass fiber Substances 0.000 claims abstract description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 69
- 238000003756 stirring Methods 0.000 claims description 42
- 238000001354 calcination Methods 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 28
- 238000005303 weighing Methods 0.000 claims description 23
- 239000012752 auxiliary agent Substances 0.000 claims description 19
- 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 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 17
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 16
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 16
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 16
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 16
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- -1 polyoxyethylene Polymers 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 230000007613 environmental effect Effects 0.000 claims description 7
- 239000012700 ceramic precursor Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 239000012695 Ce precursor Substances 0.000 claims description 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- 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 claims description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 3
- 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 3
- 239000007767 bonding agent Substances 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- 206010027439 Metal poisoning Diseases 0.000 abstract description 2
- 229910052785 arsenic Inorganic materials 0.000 abstract description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 239000004310 lactic acid Substances 0.000 description 7
- 235000014655 lactic acid Nutrition 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 6
- 229910001863 barium hydroxide Inorganic materials 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 208000008316 Arsenic Poisoning Diseases 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 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
- 238000012797 qualification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/16—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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst, which is characterized by comprising the following components in percentage by weight: CeO (CeO)21‑5wt％、V2O50.01‑0.5wt％、WO30.01‑5wt％、MoO30.01-6 wt%, glass fiber 5-8 wt%, TiO263.0‑88.20wt％、Ba(OH)20.01-1 wt%. The invention also discloses a preparation method of the rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst. The rare earth-based low-vanadium medium-low-temperature flue gas denitration catalyst obtained by the invention has high denitration efficiency under medium-low temperature condition, and SO2Low conversion rate and strong resistance to arsenic and alkali metal poisoning.
Description
Technical Field
The invention relates to a honeycomb catalyst, in particular to a rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst and a preparation method thereof.
Background
NOXIs the main component of acid rain, and the main component of inhalable particles (PM 2.5). NOXAnd hydrocarbon compounds can easily generate photochemical smog under the action of lightThe chemical smog is a secondary pollutant with strong toxicity, and seriously harms the natural environment and the health of people. Domestic to NOXThe emission control is becoming stricter, so the new denitration technology is a new hot spot for research and development in the domestic environmental protection field. The Selective Catalytic Reduction (SCR) method is one of the most widely applied and most efficient methods for eliminating air pollution worldwide at present, and the catalyst is the core part of the SCR technology and determines the denitration efficiency and the economical efficiency of an SCR system.
The SCR flue gas denitration catalyst which is most widely applied in the industrial production at present is V2O5-WO3/TiO2The service life of the catalyst is 2-3 years. In order to maintain the activity of the SCR catalyst, studies on the deactivation problem of the SCR catalyst have been conducted, and these studies can provide references for improving the performance of the catalyst and regenerating the deactivated catalyst. The catalyst has an activity temperature window of 320-400 ℃, and when the temperature is lower than 300 ℃, the V is2O5Has strong oxidizing power and high loading amount of SO2Will be towards SO3Conversion of, SO produced3And NH3The ammonium sulfate generated by combination can be attached to the surface of the catalyst and equipment, thereby causing catalyst poisoning and equipment corrosion and blockage; if the temperature exceeds 400 ℃, the catalyst is thermally sintered, and the catalyst is permanently disabled. In addition, the catalyst is poisoned and deactivated during the use of the SCR catalyst due to the access of arsenic oxides to catalyst micropores and the reaction of alkali metals at the active sites of the catalyst.
Disclosure of Invention
The invention aims to provide a rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst and a preparation method thereof, and the obtained catalyst has high denitration efficiency and SO (sulfur oxide) content under the medium-low temperature condition2Low conversion rate and strong resistance to arsenic and alkali metal poisoning.
The technical scheme is as follows:
a rare earth-based low-vanadium medium-low temperature flue gas honeycomb denitration catalyst comprises: CeO (CeO)21-5wt％、V2O50.01-0.5wt％、WO30.01-5wt％、MoO30.01-6 wt%, glass fiber 5-8 wt%, TiO263.0-88.20wt％、Ba(OH)20.01-1wt％。
Further, the carrier is TiO2Composite CeO2、ZrO2One or two of them. The carrier being TiO2Composite CeO2，TiO2With CeO2In a weight ratio of TiO2：CeO299.5-96.9: 0.05-3%. The carrier being TiO2Composite CeO2And ZrO2，TiO2、CeO2And ZrO2In a weight ratio of TiO2：CeO2：ZrO2＝99.0％～93.9％：0.05～3％：0.05～3％。
The invention uses CeO2As active center, by adding three transition metal oxides V2O5、WO3、MoO3As the auxiliary agent, the catalytic efficiency under medium and low temperature conditions can be further improved due to the synergistic effect among the active component, the auxiliary agent and the carrier. By adding small amounts of ZrO2The compressive strength of the catalyst can be improved, the wear rate of the catalyst is reduced, the service life of the catalyst is prolonged, and the acid-base performance and the active sites on the surface of the catalyst can be further regulated and controlled. Meanwhile, auxiliary agent Ba (OH)2Can effectively absorb SO3Further reducing the generation of ammonium sulfate salt, improving the sulfur resistance of the catalyst and prolonging the service life of the catalyst.
A preparation method of a rare earth-based low-vanadium medium-low temperature flue gas honeycomb denitration catalyst comprises the following steps:
heating pure water to 70-90 ℃, adding cerium precursor cerium nitrate or cerium carbonate, stirring, dissolving, adding tungsten precursor and molybdenum precursor, stirring, fully dissolving, and recording as an active component solution A;
adding pure water and monoethanolamine into a reaction kettle, adding ammonium metavanadate into the reaction kettle when the temperature reaches 60-70 ℃, stirring the mixed solution in the container, heating to 90-100 ℃, keeping the temperature unchanged, continuously stirring (30-40 minutes) until the mixed solution is completely dissolved, and recording the mixed solution as an active component solution B;
weighing a carrier, a release agent, a pore-forming agent and an adhesive, and adding the carrier, the release agent, the pore-forming agent and the adhesive into a mixer for mixing; adding an active component solution A, an active component solution B, a forming aid and titanium zirconium powder in the mixing process, and mixing to form slurry;
filtering and vacuum kneading the mixed slurry, sealing and ageing; the aging condition is as follows: the environmental temperature is 20-30 ℃, the environmental humidity is 60-80%, and the time is 48-72 h;
extruding and molding the aged raw materials by a powerful extruder according to specification requirements to form a honeycomb type ceramic precursor, and drying the honeycomb type ceramic precursor;
and calcining the dried honeycomb ceramic precursor, and cutting the calcined honeycomb ceramic precursor according to the size requirement to obtain the required honeycomb denitration catalyst.
Preferably, the tungsten precursor is ammonium paratungstate or ammonium metatungstate, and the molybdenum precursor is ammonium heptamolybdate.
Preferably, the adhesive is carboxymethyl cellulose, and the dosage of the carboxymethyl cellulose is 0.2-2% of the dry weight of the honeycomb denitration catalyst; the pore-forming agent is polyoxyethylene, and the using amount of the pore-forming agent is 0.5-2% of the dry weight of the honeycomb denitration catalyst; the forming auxiliary agent is glass fiber, paper pulp fiber and lactic acid, and the dosage of the forming auxiliary agent is 5-8 wt%, 0.1-1.5 wt% and 0.1-3 wt% of the dry weight of the honeycomb type denitration catalyst in sequence.
Preferably, the release agent is stearic acid, and the amount of the release agent is 0.5-1.5% of the dry weight of the honeycomb denitration catalyst.
Preferably, the formed honeycomb type ceramic precursor is subjected to primary drying and secondary drying; the temperature of the drying environment of primary drying is 20-60 ℃, the humidity is 85-10%, the low-temperature high humidity is gradually changed into high-temperature low humidity, and the drying time is 10-15 days; the drying environment temperature of the secondary drying is 50-60 deg.C, humidity is 10-3%, and drying time is 1-2 days.
Preferably, the calcining kiln is a continuous mesh belt kiln, a parabolic temperature curve is adopted, the calcining is started from 80-120 ℃, the highest temperature is 450-550 ℃, the product discharging temperature is 60-80 ℃, and the calcining time is controlled to be 30-40 hours.
Compared with the prior art, the invention has the technical effects that:
CeO is adopted as the catalyst prepared by the invention2、V2O5、WO3、MoO3As the main active component, the sintering phenomenon of the catalyst can be effectively reduced, and the thermal stability and the service life of the catalyst can be greatly improved. Meanwhile, auxiliary agent Ba (OH)2Can effectively absorb SO3Further reducing the generation of ammonium sulfate salt, improving the sulfur resistance of the catalyst and prolonging the service life of the catalyst.
The invention uses CeO2As active center, by adding three transition metal oxides V2O5、WO3、MoO3As the auxiliary agent, the catalytic efficiency under medium and low temperature conditions can be further improved due to the synergistic effect among the active component, the auxiliary agent and the carrier. By adding small amounts of ZrO2The compressive strength of the catalyst can be improved, the wear rate of the catalyst is reduced, the service life of the catalyst is prolonged, and the acid-base performance and the active sites on the surface of the catalyst can be further regulated and controlled. Therefore, the rare earth-based low-vanadium medium-low temperature denitration catalyst disclosed by the invention effectively widens the working temperature range (200-420 ℃) of the catalyst by adding a small amount of transition metal oxide as an auxiliary agent, and improves the denitration efficiency of the catalyst. And the water resistance, alkali metal resistance and sulfur resistance of the catalyst can be enhanced, the catalyst is suitable for the fields of thermal power plants, glass plants, chemical plants and the like, and the catalyst has better application prospect and economic benefit.
Adding CeO to the catalyst carrier2The catalyst is beneficial to improving the activity of the catalyst and inhibiting the formation of ammonium sulfate; v2O5With MoO3Can improve the activity of the catalyst under the low temperature condition (200 ℃ C. and 300 ℃ C.), and simultaneously MoO3Has strong arsenic poisoning resistance; adding ZrO2The catalyst forming efficiency is improved while the strength and the abrasion performance of the catalyst are improved, so that the catalyst is not easy to crack in the drying and calcining process, and the forming qualification rate can reach more than 95%.
The rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst prepared by the invention has a simple preparation process and is easy to realize batch production.
Detailed Description
The following description sufficiently illustrates specific embodiments of the invention to enable those skilled in the art to practice and reproduce it.
The preparation method of the rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst comprises the following steps:
(1) preparing an active solution; heating pure water to 70-90 deg.C, adding cerium precursor (cerium nitrate or cerium carbonate), stirring, dissolving, adding tungsten precursor (ammonium paratungstate or ammonium metatungstate) and molybdenum precursor (ammonium heptamolybdate), stirring, and dissolving completely, and recording as active component solution A.
Adding pure water and monoethanolamine into a reaction kettle, adding ammonium metavanadate into the reaction kettle when the temperature reaches 60-70 ℃, stirring the mixed solution in the container, heating to 90-100 ℃, keeping the temperature unchanged, continuously stirring (30-40 minutes) until the mixed solution is completely dissolved, and recording the mixed solution as an active component solution B;
(2) pug mixing process;
a. mixing for the first time;
weighing carrier titanium dioxide, titanium zirconium powder, release agent (stearic acid), Ba (OH)2And adding pure water into a mixer, and mixing at high speed (the rotating speed is 300-.
b. Mixing for the second time;
and weighing the titanium dioxide again, slowly adding the active component solution A, adding ammonia water, and mixing at a high speed (the rotating speed is 300-.
c. Mixing for the third time;
slowly adding the forming aid, the interfacial agent and the active component solution B, and mixing at a high speed. The forming auxiliary agent is glass fiber and wood pulp, and the dosage of the forming auxiliary agent is 5-8% and 0.1-1.5% of the dry weight of the catalyst (medium-low temperature flue gas denitration catalyst) in sequence. The interfacial agent is monoethanolamine, and the dosage of the interfacial agent is 1-3% of the dry weight of the catalyst (the medium-low temperature flue gas denitration catalyst).
d. Mixing for the fourth time;
adding adhesive and pore-forming agent, and high-speed mixing. The adhesive is carboxymethyl cellulose, and the dosage of the adhesive is 0.4 to 2 percent of the dry weight of the catalyst; the pore-forming agent is polyoxyethylene, and the dosage of the pore-forming agent is 0.5-2% of the dry weight of the catalyst (the medium-low temperature flue gas denitration catalyst).
e. Mixing for the fifth time;
adding adhesive and pore-forming agent, mixing at low speed (rotation speed of 120-.
(3) Extrusion molding and drying and calcining.
a. Filtering, vacuum kneading, sealing and aging the pug after mixing;
aging conditions are as follows: the environmental temperature is 15-30 ℃, the environmental humidity is 60-80%, and the time is 48-72 h.
b. Extruding the aged pug into a honeycomb catalyst blank by a powerful extruder according to the specification requirement;
c. primary drying is carried out on the honeycomb type catalyst green body;
primary drying conditions: the ambient temperature is 20-60 deg.C, humidity is 85-20%, and drying time is 10-15 days.
d. Carrying out secondary drying on the honeycomb type catalyst green body;
the secondary drying is gradually changed from low-temperature high-humidity to high-temperature low-humidity. Secondary drying conditions: the ambient temperature is 50-60 deg.C, humidity is 10-3%, and drying time is 1-2 days.
e. Calcining the dried honeycomb catalyst green body;
the calcining kiln is a continuous mesh belt kiln, is provided with 24 temperature points and a parabolic temperature curve, and is calcined from 80-120 ℃, the highest temperature is 450-80 ℃, the temperature of the product discharged from the kiln is 60-80 ℃, and the calcining time is controlled within 30-35 hours.
f. And finally, cutting the calcined catalyst according to the size requirement to obtain the rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst.
The analysis and evaluation method of each example and comparative example of the invention is as follows:
the activity evaluation was determined on a self-made catalyst evaluation device, and the evaluation conditions were: taking an integral honeycomb type denitration catalyst, wherein the reaction temperature is 180-480 ℃, and the gas conditions are as follows: simulated industrial flue gas 2000ppmNH3+2000ppmNO+500ppmSO2+5％O2，N2Balanced at normal pressure and airThe speed is 5000ml mg-1h-1The reaction activity of the catalyst was measured as the conversion of NO, and the product was analyzed with a KM9106 flue gas analyzer.
Example 1
a. Weighing 25.25kg of cerium nitrate, adding 100.00L of water for dissolving, heating to 85 ℃, adding 28.89kg of ammonium metatungstate and 32.50kg of ammonium molybdate, stirring for full reaction, and recording as an active component solution A; 40.0L of pure water was taken, 2kg of monoethanolamine was added, 3.16kg of ammonium metavanadate was weighed and added to the mixed solution, heated, stirred to be sufficiently dissolved, and recorded as active ingredient solution B.
b. Mixing for the first time, weighing 422kg of titanium dioxide, 6.5kg of stearic acid, 7.55kg of lactic acid and 1.95kg of barium hydroxide, adding into a mixer, adding 150L of pure water, and mixing for 30min at a high speed; mixing for the second time, weighing 150kg of titanium dioxide, adding into a mixer, slowly adding the active component solution A, adding 15kg of ammonia water, and stirring at high speed for 40 min; mixing for the third time, adding 4.5kg of forming auxiliary agent pulp fiber and 42kg of glass fiber, slowly adding the solution B, and stirring at high speed for 30 min; mixing for the fourth time, adding 4.8kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 10min at a high speed; mixing for the fifth time, adding 4.8kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 30min at a high speed; adjusting pH to 7-8 with ammonia water, controlling water content at 28.0%, filtering, vacuum kneading, sealing, and aging for 48 hr.
c. Extruding the aged raw materials by a powerful extruder, packaging, and drying at 20-60 deg.C and 80-20% humidity for 10 days. And calcining the dried honeycomb catalyst, wherein the calcining kiln is a continuous mesh belt kiln, is provided with 24 temperature points and a parabolic temperature curve, calcining is started from 100 ℃, the highest temperature is 500 ℃, the kiln discharging temperature of the product is 60 ℃, and the calcining time is controlled to be 35 hours. Finally, cutting the calcined catalyst according to the size requirement to obtain the required catalyst. The catalyst is noted as CAT-01.
Example 2
a. Weighing 25.25kg of cerium nitrate, adding 100.0L of water for dissolving, heating to 85 ℃, adding 25.28kg of ammonium metatungstate and 24.38kg of ammonium molybdate, stirring for full reaction, and recording as an active component solution A; 40.0L of pure water was taken, 2kg of monoethanolamine was added, 3.16kg of ammonium metavanadate was weighed and added to the mixed solution, heated, stirred to be sufficiently dissolved, and recorded as active ingredient solution B.
b. First mixing, weighing the mixture containing 1.5 percent of ZrO2433kg of titanium zirconium powder, 6.5kg of stearic acid, 7.00kg of lactic acid and 1.95kg of barium hydroxide are added into a mixer, 150L of pure water is added, and the mixture is mixed for 30min at a high speed; mixing for the second time, weighing the mixture containing 1.5 percent of ZrO2Adding 150kg of titanium zirconium powder into a mixer, slowly adding the active component solution A, adding 15kg of ammonia water, and stirring at a high speed for 40 min; mixing for the third time, adding 4.5kg of forming auxiliary agent pulp fiber and 39kg of glass fiber, slowly adding the solution B, and stirring at high speed for 30 min; mixing for the fourth time, adding 4.5kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 10min at a high speed; mixing for the fifth time, adding 4.5kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 30min at a high speed; (ii) a Adjusting pH to 7-8 with ammonia water, controlling water content at 28.0%, filtering, vacuum kneading, sealing, and aging for 48 hr.
c. Extruding the aged raw materials by a powerful extruder, packaging, and drying at 20-60 deg.C and 80-20% humidity for 10 days. And calcining the dried honeycomb catalyst, wherein the calcining kiln is a continuous mesh belt kiln, is provided with 24 temperature points and a parabolic temperature curve, calcining is started from 80 ℃, the highest temperature is 500 ℃, the discharging temperature of the product is 60 ℃, and the calcining time is controlled to be 35 h. Finally, cutting the calcined catalyst according to the size requirement to obtain the required catalyst. The catalyst was noted as CAT-02.
Example 3
a. Weighing 35.12kg of cerium nitrate, adding 100.00L of water for dissolving, heating to 85 ℃, adding 28.89kg of ammonium metatungstate and 24.38kg of ammonium molybdate, stirring for full reaction, and recording as an active component solution A; 30.0L of pure water was taken, 2kg of monoethanolamine was added, 3.16kg of ammonium metavanadate was weighed and added to the mixed solution, heated, stirred to be sufficiently dissolved, and recorded as active ingredient solution B.
b. Mixing for the first time, weighing 418.5kg of titanium dioxide, 6.5kg of stearic acid, 7.26kg of lactic acid and 1.95kg of barium hydroxide, adding into a mixer, adding 150L of pure water, and mixing for 30min at high speed; mixing for the second time, weighing 150kg of titanium dioxide, adding into a mixer, slowly adding the active component solution A, adding 15kg of ammonia water, and stirring at high speed for 40 min; mixing for the third time, adding 4.5kg of forming auxiliary agent pulp fiber and 42kg of glass fiber, slowly adding the solution B, and stirring at high speed for 30 min; mixing for the fourth time, adding 4.5kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 10min at a high speed; mixing for the fifth time, adding 4.5kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 30min at a high speed; (ii) a Adjusting pH to 7-8 with ammonia water, controlling water content at 28.0%, filtering, vacuum kneading, sealing, and aging for 48 hr.
c. Extruding the aged raw materials by a powerful extruder, packaging, and drying at 20-60 deg.C and 85-15% humidity for 10 days. And calcining the dried honeycomb catalyst, wherein the calcining kiln is a continuous mesh belt kiln, is provided with 24 temperature points and a parabolic temperature curve, calcining is started from 80 ℃, the highest temperature is 500 ℃, the discharging temperature of the product is 60 ℃, and the calcining time is controlled to be 35 h. Finally, cutting the calcined catalyst according to the size requirement to obtain the required catalyst. The catalyst is denoted as CAT-03.
Example 4
a. Weighing 25.25kg of cerium nitrate, adding 100.00L of water for dissolving, heating to 85 ℃, adding 28.89kg of ammonium metatungstate and 32.50kg of ammonium molybdate, stirring for full reaction, and recording as an active component solution A; 40.0L of pure water was taken, 3.00kg of monoethanolamine was added, 4.12kg of ammonium metavanadate was weighed and added to the mixed solution, heated, stirred to be sufficiently dissolved, and recorded as an active ingredient solution B.
b. Mixing for the first time, weighing 420.5kg of titanium dioxide, 6.5kg of stearic acid, 7.00kg of lactic acid and 1.95kg of barium hydroxide, adding into a mixer, adding 150L of pure water, and mixing for 30min at high speed; mixing for the second time, weighing 150kg of titanium dioxide, adding into a mixer, slowly adding the active component solution A, adding 15kg of ammonia water, and stirring at high speed for 40 min; mixing for the third time, adding 3.5kg of forming auxiliary agent pulp fiber and 42kg of glass fiber, slowly adding the solution B, and stirring at high speed for 30 min; mixing for the fourth time, adding 3.16kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 10min at a high speed; mixing for the fifth time, adding 3.16kg of pore-forming agent polyoxyethylene and carboxymethyl cellulose, and stirring and mixing for 30min at a high speed; (ii) a Adjusting pH to 7-8 with ammonia water, controlling water content at 28.0%, filtering, vacuum kneading, sealing, and aging for 60 hr.
c. Extruding the aged raw materials by a powerful extruder, packaging, and drying at 20-60 deg.C and 85-15% humidity for 10 days. And calcining the dried honeycomb catalyst, wherein the calcining kiln is a continuous mesh belt kiln, is provided with 24 temperature points and a parabolic temperature curve, calcining is started from 80 ℃, the highest temperature is 500 ℃, the discharging temperature of the product is 60 ℃, and the calcining time is controlled to be 35 h. Finally, cutting the calcined catalyst according to the size requirement to obtain the required catalyst. The catalyst is noted as CAT-04.
Comparative example 1
a. Weighing 35.12kg of cerium nitrate, adding 80.00L of water for dissolving, heating to 85 ℃, adding 28.89kg of ammonium metatungstate and 24.38kg of ammonium molybdate, stirring for full reaction, and recording as an active component solution A;
b. mixing for the first time, namely weighing 423kg of titanium dioxide, 6.5kg of stearic acid, 7.00kg of lactic acid and 1.95kg of barium hydroxide, adding into a mixer, adding 150L of pure water, and mixing for 30min at a high speed; mixing for the second time, weighing 150kg of titanium dioxide, adding into a mixer, slowly adding the active component solution A, adding 15kg of ammonia water, and stirring at high speed for 40 min; mixing for the third time, adding 3.5kg of forming auxiliary agent pulp fiber and 42kg of glass fiber, and stirring at high speed for 30 min; mixing for the fourth time, adding 4.5kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 10min at a high speed; mixing for the fifth time, adding 4.5kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 30min at a high speed; adjusting pH to 7-8 with ammonia water, controlling water content at 28.0%, filtering, vacuum kneading, sealing, and aging for 48 hr.
c. Extruding the aged raw materials by a powerful extruder, packaging, and drying at 20-60 deg.C and 85-15% humidity for 10 days. And calcining the dried honeycomb catalyst, wherein the calcining kiln is a continuous mesh belt kiln, is provided with 24 temperature points and a parabolic temperature curve, calcining is started from 120 ℃, the highest temperature is 500 ℃, the discharging temperature of the product is 60 ℃, and the calcining time is controlled to be 33 h. Finally, cutting the calcined catalyst according to the size requirement to obtain the required catalyst. The catalyst is noted KB-01.
Comparative example 2
a. Weighing 25.25kg of cerium nitrate, adding 80.00L of water for dissolving, heating to 85 ℃, adding 25.28kg of ammonium metatungstate and 24.38kg of ammonium molybdate, stirring for full reaction, and recording as an active component solution A;
b. mixing for the first time, namely weighing 423kg of titanium dioxide, 6.5kg of stearic acid, 7.00kg of lactic acid and 1.95kg of barium hydroxide, adding into a mixer, adding 150L of pure water, and mixing for 30min at a high speed; mixing for the second time, weighing 150kg of titanium dioxide, adding into a mixer, slowly adding the active component solution A, adding 15kg of ammonia water, and stirring at high speed for 40 min; mixing for the third time, adding 3.5kg of forming auxiliary agent pulp fiber and 39kg of glass fiber, and stirring at high speed for 30 min; mixing for the fourth time, adding 4.5kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 10min at a high speed; mixing for the fifth time, adding 4.5kg of pore-forming agent polyoxyethylene and 2.14kg of carboxymethyl cellulose, and stirring and mixing for 30min at a high speed; adjusting pH to 7-8 with ammonia water, controlling water content at 28.0%, filtering, vacuum kneading, sealing, and aging for 48 hr.
c. Extruding the aged raw materials by a powerful extruder, packaging, and drying at 20-60 deg.C and 85-15% humidity for 10 days. And calcining the dried honeycomb catalyst, wherein the calcining kiln is a continuous mesh belt kiln, is provided with 24 temperature points and a parabolic temperature curve, calcining is started from 120 ℃, the highest temperature is 500 ℃, the discharging temperature of the product is 60 ℃, and the calcining time is controlled to be 33 h. Finally, cutting the calcined catalyst according to the size requirement to obtain the required catalyst. The catalyst was noted KB-02.
TABLE 1 catalyst Activity in the examples and comparative examples
As can be seen from Table 1, the catalyst prepared by the method can effectively widen the working temperature interval of the denitration catalyst and improve the denitration efficiency of the catalyst.
The terminology used herein is for the purpose of description and illustration, rather than of limitation. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.
Claims (10)
1. A rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst is characterized by comprising: CeO (CeO)21-5wt％、V2O50.01-0.5wt％、WO30.01-5wt％、MoO30.01-6 wt%, glass fiber 5-8 wt%, TiO263.0-88.20wt％、Ba(OH)20.01-1wt％。
2. The rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst as claimed in claim 1, wherein the carrier of the rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst is TiO2Composite CeO2、ZrO2One or two of them.
3. The rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst as claimed in claim 2, wherein the carrier is TiO2Composite CeO2，TiO2With CeO2In a weight ratio of TiO2：CeO2＝99.5～96.9：0.05～3％。
4. The rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst as claimed in claim 2, wherein the carrier is TiO2Composite CeO2And ZrO2，TiO2、CeO2And ZrO2In a weight ratio of TiO2：CeO2：ZrO2＝99.0％～93.9％：0.05～3％：0.05～3％。
5. A preparation method of a rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst comprises the following steps:
preparing an active solution; heating pure water to 70-90 ℃, adding cerium precursor cerium nitrate or cerium carbonate, stirring, dissolving, adding tungsten precursor ammonium paratungstate or ammonium metatungstate and molybdenum precursor ammonium heptamolybdate, stirring, and fully reacting to obtain an active component solution A; adding pure water and monoethanolamine into a reaction kettle, adding ammonium metavanadate into the reaction kettle when the temperature reaches 60-70 ℃, stirring the mixed solution in the container, heating to about 90-100 ℃, keeping the temperature unchanged, continuously stirring for 30-40 minutes until the mixed solution is completely dissolved, and recording the mixed solution as an active component solution B;
pug mixing; weighing carrier titanium dioxide, release agent, Ba (OH)2Adding pure water into a mixer, and mixing at high speed; weighing titanium dioxide and titanium zirconium powder again, adding the active component solution A slowly, adding ammonia water, and mixing; adding a forming aid, an interfacial agent and an active component solution B, and mixing; adding a bonding agent and a pore-forming agent, and mixing at high speed; adding the adhesive and the pore-forming agent again, mixing at low speed, and controlling the water content of the pug to be 28-29%;
filtering, vacuum kneading, sealing and aging the pug after mixing; extruding the aged pug by a powerful extruder to form a honeycomb catalyst blank; drying the honeycomb catalyst green body; and calcining the dried honeycomb type ceramic precursor, and cutting the calcined honeycomb type catalyst blank according to the size requirement to obtain the required honeycomb type denitration catalyst.
6. The preparation method of the rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst as claimed in claim 5, wherein the release agent is stearic acid, and the dosage of the release agent is 0.5-1.5% of the dry weight of the catalyst; the forming auxiliary agent is glass fiber and wood pulp, and the dosage of the forming auxiliary agent is 5-8% and 0.1-1.5% of the dry weight of the catalyst in sequence; the interfacial agent is monoethanolamine, and the dosage of the interfacial agent is 1-3% of the dry weight of the catalyst; the adhesive is carboxymethyl cellulose, and the dosage of the adhesive is 0.1 to 2 percent of the dry weight of the catalyst; the pore-forming agent is polyoxyethylene, and the dosage of the pore-forming agent is 0.5-2% of the dry weight of the catalyst.
7. The preparation method of the rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst of claim 5, wherein the aging condition is as follows: the environmental temperature is 15-30 ℃, the environmental humidity is 60-80%, and the time is 48-72 h.
8. The preparation method of the rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst of claim 5, wherein the primary drying conditions are as follows: the ambient temperature is 20-60 deg.C, humidity is 85-20%, and drying time is 10-15 days.
9. The preparation method of the rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst as claimed in claim 5, wherein the ambient temperature is 50-60 ℃, the humidity is 10-3%, and the drying time is 1-2 days.
10. The preparation method of the rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst as claimed in claim 5, wherein the calcination kiln is a continuous mesh belt kiln, 24 temperature points are arranged, and a parabolic temperature curve is adopted for calcination; the calcination is started from 80 to 120 ℃, the highest temperature is 450-550 ℃, the kiln discharging temperature of the product is 60 to 80 ℃, and the calcination time is controlled to be 25 to 35 hours.
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