CN113117667A - Preparation method of integral honeycomb denitration catalyst - Google Patents
Preparation method of integral honeycomb denitration catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910001868 water Inorganic materials 0.000 claims abstract description 26
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 18
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 9
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 43
- 230000032683 aging Effects 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910021389 graphene Inorganic materials 0.000 claims description 22
- 229920002472 Starch Polymers 0.000 claims description 21
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 21
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 21
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 21
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 21
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 21
- 239000008107 starch Substances 0.000 claims description 21
- 235000019698 starch Nutrition 0.000 claims description 21
- 239000003365 glass fiber Substances 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229910003437 indium oxide Inorganic materials 0.000 claims description 17
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 17
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical group [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 16
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical group [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 16
- 229960001471 sodium selenite Drugs 0.000 claims description 16
- 235000015921 sodium selenite Nutrition 0.000 claims description 16
- 239000011781 sodium selenite Substances 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 14
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
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- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- 238000007580 dry-mixing Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003546 flue gas Substances 0.000 abstract description 7
- 239000004480 active ingredient Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 27
- 239000007789 gas Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 229910052738 indium Inorganic materials 0.000 description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910052716 thallium Inorganic materials 0.000 description 6
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 6
- 208000005374 Poisoning Diseases 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
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- 231100000719 pollutant Toxicity 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 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 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229940091258 selenium supplement Drugs 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000026015 thallium poisoning Diseases 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 206010057190 Respiratory tract infections Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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Abstract
The preparation method of the integral honeycomb denitration catalyst is characterized in that the catalyst mainly comprises manganese oxide, selenium oxide and praseodymium oxide as active ingredients and TiO2The catalyst is composed of a catalyst carrier, sulfur-resistant active components are adsorbed on the surface of an integral honeycomb denitration catalyst, the specific surface area of the honeycomb denitration catalyst is more than 200m2/g, mesopores are intensively distributed between 3 nm and 5nm, the axial strength of the catalyst is 2.27 Mpa to 2.34Mpa, the radial strength is 0.62 Mpa to 0.71Mpa, and the conversion rate of NOx is maintained under the condition of flue gas containing water and sulfur oxide80-85% conversion.
Description
Technical Field
The invention belongs to the technical field of denitration catalysts, and relates to a preparation method of a sulfur poisoning resistant honeycomb catalyst for flue gas denitration.
Background
Nitrogen oxides, as one of the main atmospheric pollutants, have adverse effects on both the environment and human health: the acid rain can pollute the soil and rivers and damage the growth of crops; may cause respiratory tract infection of human, aggravate the illness of patients, cause various discomfort, etc. The nitrogen oxides are widely available and mainly come from tail gas of industrial boilers/kilns of thermal power plants, steel plants, waste incineration plants, cement plants and the like. GB13223-2011 'emission Standard of atmospheric pollutants for thermal power plant' stipulates that the emission concentration of nitrogen oxides in tail gas of newly-built coal-fired boiler is not more than 100mg/Nm3The nitrogen oxide emission concentration of the tail gas of the gas turbine set is not more than50mg/Nm3. GB 13271-2014 emission Standard of atmospheric pollutants for boilers stipulates that the emission concentration of nitrogen oxides in tail gas of newly-built coal-fired boilers is not more than 300mg/Nm3The nitrogen oxide emission concentration of the tail gas of the newly-built gas boiler is not more than 200mg/Nm3. Local atmospheric pollutant emission standards are set by all regions according to actual conditions aiming at nitrogen oxide emission under the condition of meeting national standard requirements, and some regions require that the nitrogen oxide emission concentration of tail gas of a coal/gas fired boiler is not more than 50mg/Nm3。
At present, the SCR denitration technology is one of the most widely applied and mature and effective flue gas denitration technologies. The SCR denitration device of the coal-fired power plant is mainly installed between an economizer and an air preheater and contains a large amount of fly ash and high-concentration SO2 gas, and after 24000 hours of operation, the SCR catalyst is inactivated and replaced to be abandoned due to the problems of poisoning, ash blockage, abrasion and the like. The catalyst poisoning problem is common, and the main substances causing the poisoning are as follows: alkali metals, heavy metals, H2O, and SO2, and the like.
In order to control the emission concentration of nitrogen oxides to be maintained below relevant national and local standards, the denitration of the tail gas generally adopts SNCR or SCR or SNCR and SCR denitration. The SCR denitration is a process of converting NOX and NH3 in flue gas into water and N2 under the catalysis of a denitration catalyst, and is widely applied to industrial kiln/boiler tail gas denitration due to the advantages of high denitration activity, long chemical life, low ammonia escape rate, low SO2 oxidation rate and the like. The conventional SCR denitration catalyst is generally high in denitration activity at medium temperature (280-420 ℃), but low-temperature (160-280 ℃) denitration activity is low, the denitration rate at low temperature of 160 ℃ is about 79% generally, the denitration rate at 200 ℃ is only about 84%, and the denitration efficiency is not ideal.
In addition, when water and SO2 are added into the feed gas, the catalytic activity of the catalyst is obviously reduced, and the conversion rate is rapidly reduced, for example, CN202010755439 discloses a thallium poisoning resistant core-shell honeycomb catalyst for cement kiln flue gas denitration and a preparation method thereof. The catalyst is a core-shell catalyst, V-W/TiO2 added with a thallium-resistant additive is used as a core structure, and a metal oxide film is used as a shell structure; the thallium resistant additive comprises element gallium and/or element indium. The thallium poisoning resistance of the prepared denitration catalyst is 2-3 times higher than that of the existing catalyst, the denitration efficiency is stably maintained at more than 90%, and breakthrough of the denitration catalyst technology under the condition of thallium-containing flue gas in a cement kiln is realized. By adopting the catalyst provided by the invention, the service life of the SCR denitration catalyst can be prolonged, the use cost of a denitration system is reduced, the adaptability of the SCR denitration catalyst under the thallium-containing flue gas condition is improved, the production cost of denitration operation management is reduced, and the catalyst has great economic value. The catalyst has the following problems, and the preparation method of the catalyst comprises the following steps: ammonium metavanadate, ammonium metatungstate, a thallium-resistant auxiliary agent (indium nitrate) and water are mixed, stirred, heated and dissolved, and mixed with titanium dioxide powder to obtain slurry, and the slurry is dried to obtain V-W/TiO2 powder of the thallium-resistant auxiliary agent, namely the V-W/TiO2 powder is simply mixed.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of an integral honeycomb denitration catalyst, the preparation method can obtain a catalyst with a high specific surface area, active sulfur-resistant components are dispersed on the surface of the catalyst, and the indium active components are found to have extremely high sulfur-resistant activity, so that the industrial problems of poor sulfur-resistant activity, high denitration efficiency reduction speed, low strength, short service life and the like of the denitration catalyst in the prior art are solved, and the integral honeycomb denitration catalyst can be industrially applied.
A preparation method of a honeycomb denitration catalyst comprises the following steps:
(1) uniformly mixing precursors of manganese oxide, selenium oxide and praseodymium oxide with deionized water, and adding TiO2Obtaining a mixed material A;
(2) carrying out dry mixing on stearic acid, glass fiber and graphene oxide to obtain a mixed material B;
(3) adding the mixed material B into a mixer containing the mixed material A, and performing primary mixing;
(3) then adding a mixed binder consisting of hydroxypropyl methyl cellulose, silica sol, starch and water into a mixer, and performing secondary mixing to obtain a paste;
(4) aging and forming treatment;
(5) pugging;
(6) extrusion molding;
(7) primary drying;
(8) dipping an indium oxide precursor;
(9) secondary drying;
(10) and (4) roasting.
In some embodiments of the present invention, the manganese oxide precursor is manganese nitrate, the selenium oxide precursor is sodium selenite, and the praseodymium oxide precursor is praseodymium nitrate.
In some embodiments of the invention, the mass ratio of the manganese oxide, the selenium oxide and the praseodymium oxide is 7: 1-3: 1-2, and the mass ratio of the total mass usage of the manganese oxide, the selenium oxide and the praseodymium oxide to the mass usage of the TiO2 is 1: (5-6).
In some embodiments of the invention, the mass ratio of sodium stearate, glass fiber, graphene oxide and titanium oxide is (0.03-0.05): 0.05-0.07: (0.02-0.04): 1.
In some embodiments of the invention, the mass ratio of hydroxypropyl methylcellulose, silica sol, starch and titanium oxide is (0.03-0.05): (0.04-0.5): (0.03-0.05): 1.
In some embodiments of the invention, the amount of water used in step (1) and step (3) is adjusted; the aging time and the temperature in the step (4) enable the molding of the mixed material obtained by aging molding to be 9-11, the water content to be 20-30%, and the temperature of the aging molding treatment to be 30 +/-2oC, the time is 20-25 h.
In some embodiments of the invention, the time for the first mixing is 10-15min, the time for the second mixing is 30-40min,
in some embodiments of the inventionThe temperature of the primary drying is 60-70 DEGoC, the time is 24-48h, and the secondary drying is carried out at the normal temperature of 1-2oC/min is increased to 50-60oC, keeping for 3-4h, then 1-2oC/min is increased to 90-100oC, keeping for 10-12h, then 1-2oC/min is increased to 200-oAnd C, keeping for 24-48 h.
In some embodiments of the present invention, the indium oxide precursor is 3-5wt.% indium nitrate, and the soaking process is assisted by a vacuum pump for pumping until no significant bubbles overflow, and the temperature is normal temperature.
In some embodiments of the invention, the firing is followed by a secondary drying step to 15-6oC/min is raised to 500-oAnd C, keeping for 3-4 h.
The Mn is a main active component and provides an active site for catalytic reaction, the selenium and the praseodymium are main catalyst promoter components and improve the SCR reaction activity, and the graphene is used for improving the specific surface area of the honeycomb catalyst; and after the primary drying and forming, the indium active component is soaked before the secondary drying, so that the situation that the indium active component is buried and cannot contact with the feed gas because of direct mixing is avoided.
The preparation process is optimized, and process parameters such as temperature programming parameters are adjusted, so that the mechanical strength of the catalyst is effectively improved, and the industrial requirements are met as shown in figure 1.
The prepared catalyst has pores of 16-20 × 16-20, and specific surface area of more than 200g/cm2。
Advantageous technical effects
(1) By adding the graphene material, the specific surface area of the catalyst is effectively improved, the contact between the reaction raw material gas and the active component is facilitated, particularly the contact between the active component in the whole catalyst is facilitated, the catalytic activity of the catalyst is improved, and the active sites are increased.
(2) By introducing the selenium and praseodymium promoters, the catalytic activity is remarkably improved.
(3) The honeycomb denitration catalyst block catalyst has high mechanical strength and meets industrial requirements.
(4) By controlling the loading position of the indium on the catalyst, the sulfur-resistant activity of the catalyst is effectively ensured, and the sulfur-resistant activity of the catalyst is increased while the using amount of the indium is obviously reduced.
Drawings
FIG. 1 is a schematic representation of a honeycomb catalyst of the present invention.
FIG. 2 is a BET-BJH graph showing gas adsorption and desorption of example 1 and comparative examples 1 to 3.
FIG. 3 shows the present invention at 175oC, water-resistant and sulfur-resistant performance test chart.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
A preparation method of a honeycomb denitration catalyst is characterized by comprising the following steps:
(1) uniformly mixing manganese nitrate, sodium selenite and praseodymium nitrate with the mass ratio of 7:1:1 in deionized water, and adding TiO2Mixing the obtained mixed material A and the obtained TiO2The mass dosage of the (B) is 5 times of the total dosage of (manganese nitrate, sodium selenite and praseodymium nitrate);
(2) carrying out dry mixing on stearic acid, glass fiber and graphene oxide to obtain a mixed material B, wherein the mass ratio of sodium stearate, glass fiber, graphene oxide to titanium oxide is 0.03: 0.05: 0.02: 1;
(3) adding the mixed material B into a mixer containing the mixed material A, and performing primary mixing for 10 min;
(3) adding a mixed binder consisting of hydroxypropyl methyl cellulose, silica sol, starch and water into a mixer, and carrying out secondary mixing to obtain a paste, wherein the mass ratio of the hydroxypropyl methyl cellulose to the silica sol to the starch to the titanium oxide is 0.03: 0.04: 0.03:1, and the secondary mixing time is 30 min;
(4) aging and forming treatment; the temperature of the aging molding treatment is 30 +/-2oC, the time is 20 h.
(5) Pugging;
(6) extrusion molding;
(7) primary drying; the temperature of primary drying is 60 deg.CoC, the time is 24 hours,
(8) dipping an indium oxide precursor; the indium oxide precursor is 3wt.% indium nitrate, and the soaking process is assisted with the suction treatment of a vacuum pump for a time period until no obvious bubbles overflow, and the temperature is normal temperature.
(9) Secondary drying; secondary drying to normal temperature 1oC/min is increased to 50oC, holding for 3h, then 1oC/min is increased to 90oC, holding for 10h, then 1oC/min is increased to 200oC, keeping for 24 h.
(10) Roasting 5oC/min is increased to 500oAnd C, keeping for 3 hours, and naturally cooling.
Example 2
A preparation method of a honeycomb denitration catalyst is characterized by comprising the following steps:
(1) uniformly mixing manganese nitrate, sodium selenite and praseodymium nitrate with the mass ratio of 7:1.5:1.5 in deionized water, and adding TiO2Mixing the obtained mixed material A and the obtained TiO2The mass dosage of the (B) is 5.5 times of the total dosage of (manganese nitrate, sodium selenite and praseodymium nitrate);
(2) carrying out dry mixing on stearic acid, glass fiber and graphene oxide to obtain a mixed material B, wherein the mass ratio of sodium stearate, glass fiber, graphene oxide and titanium oxide is (0.04): 0.06): 0.03): 1;
(3) adding the mixed material B into a mixer containing the mixed material A, and performing primary mixing for 12.5 min;
(3) adding a mixed binder consisting of hydroxypropyl methyl cellulose, silica sol, starch and water into a mixer, and carrying out secondary mixing to obtain a paste, wherein the mass ratio of the hydroxypropyl methyl cellulose to the silica sol to the starch to the titanium oxide is (0.04): 0.045: 0.04): 1, and the secondary mixing time is 35 min;
(4) aging and forming treatment; the temperature of the aging molding treatment is 30 +/-2oC, the time is 22.5 h.
(5) Pugging;
(6) extrusion molding;
(7) primary drying; the temperature of primary drying is 65 deg.CoC, the time is 36h,
(8) dipping an indium oxide precursor; the indium oxide precursor is 4wt.% indium nitrate, and the soaking process is assisted with the suction treatment of a vacuum pump for a period of time until no obvious bubbles overflow, and the temperature is normal temperature.
(9) Secondary drying; the secondary drying is carried out at normal temperature of 1.5oC/min is increased to 55oC, keeping for 3.5h, then 1.5oC/min is increased to 95oC, holding for 11h, then 1.5oC/min is increased to 210oC, keeping for 36 h.
(10) Roasting 5.5oC/min is increased to 550oAnd C, keeping for 3.5 hours, and naturally cooling.
Example 3
A preparation method of a honeycomb denitration catalyst is characterized by comprising the following steps:
(1) uniformly mixing manganese nitrate, sodium selenite and praseodymium nitrate with the mass ratio of 7:3:2 in deionized water, and adding TiO2Mixing the obtained mixed material A and the obtained TiO2The mass dosage of the (B) is 6 times of the total dosage of (manganese nitrate, sodium selenite and praseodymium nitrate);
(2) carrying out dry mixing on stearic acid, glass fiber and graphene oxide to obtain a mixed material B, wherein the mass ratio of sodium stearate, glass fiber, graphene oxide and titanium oxide is (0.05): 0.07): 0.04): 1;
(3) adding the mixed material B into a mixer containing the mixed material A, and performing primary mixing for 15 min;
(3) then adding a mixed binder consisting of hydroxypropyl methyl cellulose, silica sol, starch and water into a mixer, and carrying out secondary mixing to obtain a paste, wherein the mass ratio of the hydroxypropyl methyl cellulose to the silica sol to the starch to the titanium oxide is (0.05): 1, and the secondary mixing time is 40 min;
(4) aging and forming treatment; the temperature of the aging molding treatment is 30 +/-2oC, the time is 25 h.
(5) Pugging;
(6) extrusion molding;
(7) primary drying; the temperature of primary drying is 70 deg.CoC, the time is 48 hours,
(8) dipping an indium oxide precursor; the indium oxide precursor is 5wt.% indium nitrate, and the soaking process is assisted with the pumping treatment of a vacuum pump for a time period until no obvious bubbles overflow, and the temperature is normal temperature.
(9) Secondary drying; secondary drying to normal temperature 2oC/min is increased to 60oC, holding for 4h, then 2oC/min is increased to 100oC, holding for 12h, then 2oC/min is increased to 220oC, keeping for 48 h.
(10) Roasting 6oC/min is increased to 600oAnd C, keeping for 4 hours, and naturally cooling.
Comparative example 1
A preparation method of a honeycomb denitration catalyst is characterized by comprising the following steps:
(1) uniformly mixing manganese nitrate, sodium selenite and praseodymium nitrate with the mass ratio of 7:1.5:1.5 in deionized water, and adding TiO2Mixing the obtained mixed material A and the obtained TiO2The mass dosage of the (B) is 5.5 times of the total dosage of (manganese nitrate, sodium selenite and praseodymium nitrate);
(2) mixing stearic acid and glass fiber in a dry mode to obtain a mixed material B, wherein the mass ratio of the sodium stearate to the glass fiber to the titanium oxide is (0.04): 0.06): 1;
(3) adding the mixed material B into a mixer containing the mixed material A, and performing primary mixing for 12.5 min;
(3) adding a mixed binder consisting of hydroxypropyl methyl cellulose, silica sol, starch and water into a mixer, and carrying out secondary mixing to obtain a paste, wherein the mass ratio of the hydroxypropyl methyl cellulose to the silica sol to the starch to the titanium oxide is (0.04): 0.045: 0.04): 1, and the secondary mixing time is 35 min;
(4) aging and forming treatment; the temperature of the aging molding treatment is 30 +/-2oC, the time is 22.5 h.
(5) Pugging;
(6) extrusion molding;
(7) primary drying; the temperature of primary drying is 65 deg.CoC, the time is 36h,
(8) dipping an indium oxide precursor; the indium oxide precursor is 4wt.% indium nitrate, and the soaking process is assisted with the suction treatment of a vacuum pump for a period of time until no obvious bubbles overflow, and the temperature is normal temperature.
(9) Secondary drying; the secondary drying is carried out at normal temperature of 1.5oC/min is increased to 55oC, keeping for 3.5h, then 1.5oC/min is increased to 95oC, holding for 11h, then 1.5oC/min is increased to 210oC, keeping for 36 h.
(10) Roasting 5.5oC/min is increased to 550oAnd C, keeping for 3.5 hours, and naturally cooling.
Comparative example 2
A preparation method of a honeycomb denitration catalyst is characterized by comprising the following steps:
(1) uniformly mixing manganese nitrate and deionized water, and adding TiO2Mixing the obtained mixed material A and the obtained TiO2The mass dosage of the manganese nitrate is 5.5 times of that of the manganese nitrate;
(2) carrying out dry mixing on stearic acid, glass fiber and graphene oxide to obtain a mixed material B, wherein the mass ratio of sodium stearate, glass fiber, graphene oxide and titanium oxide is (0.04): 0.06): 0.03): 1;
(3) adding the mixed material B into a mixer containing the mixed material A, and performing primary mixing for 12.5 min;
(3) adding a mixed binder consisting of hydroxypropyl methyl cellulose, silica sol, starch and water into a mixer, and carrying out secondary mixing to obtain a paste, wherein the mass ratio of the hydroxypropyl methyl cellulose to the silica sol to the starch to the titanium oxide is (0.04): 0.045: 0.04): 1, and the secondary mixing time is 35 min;
(4) aging and forming treatment; the temperature of the aging molding treatment is 30 +/-2oC, the time is 22.5 h.
(5) Pugging;
(6) extrusion molding;
(7) primary drying; the temperature of primary drying is 65 deg.CoC, the time is 36h,
(8) dipping an indium oxide precursor; the indium oxide precursor is 4wt.% indium nitrate, and the soaking process is assisted with the suction treatment of a vacuum pump for a period of time until no obvious bubbles overflow, and the temperature is normal temperature.
(9) Secondary drying; the secondary drying is carried out at normal temperature of 1.5oC/min is increased to 55oC, keeping for 3.5h, then 1.5oC/min is increased to 95oC, holding for 11h, then 1.5oC/min is increased to 210oC, keeping for 36 h.
(10) Roasting 5.5oC/min is increased to 550oAnd C, keeping for 3.5 hours, and naturally cooling.
Comparative example 3
A preparation method of a honeycomb denitration catalyst is characterized by comprising the following steps:
(1) uniformly mixing manganese nitrate, sodium selenite and praseodymium nitrate with the mass ratio of 7:1.5:1.5 in deionized water, and adding TiO2Mixing the obtained mixed material A and the obtained TiO2The mass dosage of the (B) is 5.5 times of the total dosage of (manganese nitrate, sodium selenite and praseodymium nitrate);
(2) carrying out dry mixing on stearic acid, glass fiber and graphene oxide to obtain a mixed material B, wherein the mass ratio of sodium stearate, glass fiber, graphene oxide and titanium oxide is (0.04): 0.06): 0.03): 1;
(3) adding the mixed material B into a mixer containing the mixed material A, and performing primary mixing for 12.5 min;
(3) adding a mixed binder consisting of hydroxypropyl methyl cellulose, silica sol, starch and water into a mixer, and carrying out secondary mixing to obtain a paste, wherein the mass ratio of the hydroxypropyl methyl cellulose to the silica sol to the starch to the titanium oxide is (0.04): 0.045: 0.04): 1, and the secondary mixing time is 35 min;
(4) aging and forming treatment; the temperature of the aging molding treatment is 30 +/-2oC, the time is 22.5 h.
(5) Pugging;
(6) extrusion molding;
(7) primary drying; the temperature of primary drying is 65 deg.CoC, the time is 36h,
(8) dipping an indium oxide precursor; the indium oxide precursor is 4wt.% indium nitrate, and the soaking process is assisted with the suction treatment of a vacuum pump for a period of time until no obvious bubbles overflow, and the temperature is normal temperature.
(9) Secondary drying; secondary drying to normal temperature 5oC/min is increased to 210oC, keeping for 36 h.
(10) Calcination 10oC/min is increased to 550oAnd C, keeping for 3.5 hours, and naturally cooling.
TABLE 1
As shown in Table 1 above, by performing specific surface area tests on the above example 2 and comparative examples 1, 2 and 3, as shown in FIG. 2, the specific surface area of the honeycomb catalyst obtained by the preparation method of the present invention was significantly greater than 200 g/m2The main contribution to the specific surface area is in the doped graphene component, which burns out during the firing process, leaving mesoporous channels with a mode pore diameter of 3.27nm, which is not significantly changed from that of comparative example 2, and is 3.61nm, but the specific surface area is less than that of example 2, mainly because the reduction of the additive reduces the adjacent channels at the interface between different oxides, and the specific surface area of comparative example 2 is reduced to 161g/m2Since the graphene oxide is not contained in the comparative document 1, the specific surface area is obviously reduced to 71g/m2(ii) a Comparative example 3 mainly considers the contribution of the firing temperature to the mechanical strength, of comparative document 3The mechanical strength of the catalyst is greatly reduced by improper control of the roasting temperature, which is far from the mechanical strength of the catalyst of the embodiment of the invention with axial strength of 2.27-2.34Mpa and radial strength of 0.62-0.71Mpa, and in addition, if the hydroxypropyl methyl cellulose, silica sol and starch adhesive in the embodiment 2 are cancelled, the honeycomb catalyst cannot be molded and is easy to break.
Comparative example 4
A preparation method of a honeycomb denitration catalyst is characterized by comprising the following steps:
(1) uniformly mixing manganese nitrate, sodium selenite and praseodymium nitrate with the mass ratio of 7:1.5:1.5 and 4wt.% of indium nitrate deionized water, and adding TiO2Mixing the obtained mixed material A and the obtained TiO2The mass dosage of the (B) is 5.5 times of the total dosage of (manganese nitrate, sodium selenite and praseodymium nitrate);
(2) carrying out dry mixing on stearic acid, glass fiber and graphene oxide to obtain a mixed material B, wherein the mass ratio of sodium stearate, glass fiber, graphene oxide and titanium oxide is (0.04): 0.06): 0.03): 1;
(3) adding the mixed material B into a mixer containing the mixed material A, and performing primary mixing for 12.5 min;
(3) adding a mixed binder consisting of hydroxypropyl methyl cellulose, silica sol, starch and water into a mixer, and carrying out secondary mixing to obtain a paste, wherein the mass ratio of the hydroxypropyl methyl cellulose to the silica sol to the starch to the titanium oxide is (0.04): 0.045: 0.04): 1, and the secondary mixing time is 35 min;
(4) aging and forming treatment; the temperature of the aging molding treatment is 30 +/-2oC, the time is 22.5 h.
(5) Pugging;
(6) extrusion molding;
(7) primary drying; the temperature of primary drying is 65 deg.CoC, cooling for 36 hours;
(8) secondary drying; the secondary drying is carried out at normal temperature of 1.5oC/min is increased to 55oC, keeping for 3.5h, then 1.5oC/min is increased to 95oC, holding for 11h, then 1.5oC/min is increased to 210oC, keeping for 36 h.
(9) Roasting 5.5oC/min is increased to 550oAnd C, keeping for 3.5 hours, and naturally cooling.
Comparative example 5
A preparation method of a honeycomb denitration catalyst is characterized by comprising the following steps:
(1) uniformly mixing manganese nitrate, sodium selenite and praseodymium nitrate with the mass ratio of 7:1.5:1.5 in deionized water, and adding TiO2Mixing the obtained mixed material A and the obtained TiO2The mass dosage of the (B) is 5.5 times of the total dosage of (manganese nitrate, sodium selenite and praseodymium nitrate);
(2) carrying out dry mixing on stearic acid, glass fiber and graphene oxide to obtain a mixed material B, wherein the mass ratio of sodium stearate, glass fiber, graphene oxide and titanium oxide is (0.04): 0.06): 0.03): 1;
(3) adding the mixed material B into a mixer containing the mixed material A, and performing primary mixing for 12.5 min;
(3) adding a mixed binder consisting of hydroxypropyl methyl cellulose, silica sol, starch and water into a mixer, and carrying out secondary mixing to obtain a paste, wherein the mass ratio of the hydroxypropyl methyl cellulose to the silica sol to the starch to the titanium oxide is (0.04): 0.045: 0.04): 1, and the secondary mixing time is 35 min;
(4) aging and forming treatment; the temperature of the aging molding treatment is 30 +/-2oC, the time is 22.5 h.
(5) Pugging;
(6) extrusion molding;
(7) primary drying; the temperature of primary drying is 65 deg.CoC, the time is 36h,
(8) secondary drying; the secondary drying is carried out at normal temperature of 1.5oC/min is increased to 55oC, keeping for 3.5h, then 1.5oC/min is increased to 95oC, holding for 11h, then 1.5oC/min is increased to 210oC, keeping for 36 h.
(9) Roasting 5.5oC/min is increased to 550oAnd C, keeping for 3.5 hours, and naturally cooling.
The catalytic activity tests were carried out for example 2, comparative example 4, comparative example 5: test temperature range 175oC. The reaction gas contained 500 ppm NO, 500 ppm NH3、5 vol. % O2、5 vol. % H2O (as required), 200 ppm SO2(as required) and N2As a balance gas. The total flow rate of the NH3-SCR test is 100 ml/min, and the space velocity (GHSV) is 30000 h-1。
As shown in figure 3, the denitration catalytic activity obtained by subsequently loading indium oxide is higher, and when NO boiled water is added and NO SO2 is introduced, the full conversion rate of example 2 can be used for completely converting NOXThe catalyst shown in comparative example 4 was prepared by mixing indium nitrate with a main co-active component at 175oC, almost completely purifying NOXComparative example 5 catalyst without indium nitrate at 175oAnd C, the conversion rate is 93.8%, namely, the fact that the indium nitrate can also play a role of an auxiliary agent to synergistically improve the catalytic activity under the anhydrous SO 2-free condition can be proved, but the research focus is not the research focus of the invention.
The water vapor is introduced into the raw material gas, the competitive adsorption of H2O and NH3/NO in the reaction gas on the active sites on the surface of the catalyst is reduced, the catalytic activity of the catalyst in the embodiment 2 and the comparative examples 4-5 is reduced obviously after the SO2 is further introduced, for the comparative example 4, the sulfur resistance and the water resistance of the catalytic active component, particularly indium, are obviously consistent due to the fact that cerium nitrate and the main auxiliary active component are mixed together, and when the water and the SO2 are removed, the denitration catalytic activity is improved to a certain extent. As can be seen from the attached figure 3, the catalyst prepared by the invention has extremely high catalytic activity after water and SO2 exist simultaneously, and the catalytic conversion rate of NOx is more than 80 percent and less than 85 percent.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (10)
1. A preparation method of a honeycomb denitration catalyst is characterized by comprising the following steps:
(1) uniformly mixing precursors of manganese oxide, selenium oxide and praseodymium oxide with deionized water, and adding TiO2Obtaining a mixed material A;
(2) carrying out dry mixing on stearic acid, glass fiber and graphene oxide to obtain a mixed material B;
(3) adding the mixed material B into a mixer containing the mixed material A, and performing primary mixing;
(3) then adding a mixed binder consisting of hydroxypropyl methyl cellulose, silica sol, starch and water into a mixer, and performing secondary mixing to obtain a paste;
(4) aging and forming treatment;
(5) pugging;
(6) extrusion molding;
(7) primary drying;
(8) dipping an indium oxide precursor;
(9) secondary drying;
(10) and (4) roasting.
2. The method for preparing a honeycomb denitration catalyst as claimed in claim 1, wherein the manganese oxide precursor is manganese nitrate, the selenium oxide precursor is sodium selenite, and the praseodymium oxide precursor is praseodymium nitrate.
3. The preparation method of the honeycomb denitration catalyst according to claim 1, wherein the mass ratio of the manganese oxide, the selenium oxide and the praseodymium oxide is 7: 1-3: 1-2, and the mass ratio of the total mass usage of the manganese oxide, the selenium oxide and the praseodymium oxide to the mass usage of the TiO2 is 1: (5-6).
4. The method for preparing a honeycomb denitration catalyst according to claim 1, wherein the mass ratio of the sodium stearate, the glass fiber, the graphene oxide and the titanium oxide is (0.03-0.05): (0.05-0.07): (0.02-0.04):1.
5. The method for preparing a honeycomb denitration catalyst according to claim 1, wherein the mass ratio of the hydroxypropyl methyl cellulose, the silica sol, the starch and the titanium oxide is (0.03-0.05): (0.04-0.5): (0.03-0.05):1.
6. The method for preparing a honeycomb denitration catalyst according to claim 1, wherein the amount of water used in the step (1) and the step (3) is adjusted; the aging time and the temperature in the step (4) enable the molding of the mixed material obtained by aging molding to be 9-11, the water content to be 20-30%, and the temperature of the aging molding treatment to be 30 +/-2oC, the time is 20-25 h.
7. The method of claim 1, wherein the primary mixing time is 10-15min, and the secondary mixing time is 30-40 min.
8. The method for preparing a honeycomb denitration catalyst according to claim 1, wherein the temperature of the primary drying is 60-70%oC, the time is 24-48h, and the secondary drying is carried out at the normal temperature of 1-2oC/min is increased to 50-60oC, keeping for 3-4h, then 1-2oC/min is increased to 90-100oC, keeping for 10-12h, then 1-2oC/min is increased to 200-oAnd C, keeping for 24-48 h.
9. The method for preparing a honeycomb denitration catalyst according to claim 1, wherein the indium oxide precursor is 3-5wt.% indium nitrate, and the immersion process is performed by an auxiliary vacuum pump until no obvious bubbles overflow and the temperature is normal temperature.
10. The method of claim 1, wherein the firing is followed by a secondary drying step to obtain 5-6 wt% of the denitration catalystoC/min is raised to 500-oAnd C, keeping for 3-4h, and naturally cooling.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263914A (en) * | 2013-05-03 | 2013-08-28 | 北京工业大学 | Honeycomb-shaped SCR denitration catalysis material for cement kiln and preparation method thereof |
| US20170128883A1 (en) * | 2015-11-06 | 2017-05-11 | Paccar Inc | High efficiency and durability selective catalytic reduction catalyst |
| CN107456981A (en) * | 2017-09-01 | 2017-12-12 | 天津市职业大学 | A kind of exhaust gas denitration composite catalyst and preparation method thereof |
| CN108067296A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of preparation method of cellular Mn based low-temperature denitration catalysts |
| CN108212146A (en) * | 2018-01-09 | 2018-06-29 | 上海大学 | Nucleocapsid denitrating catalyst of metallic monoliths and preparation method thereof |
| US20190358586A1 (en) * | 2013-03-29 | 2019-11-28 | Korea University Research And Business Foundation | Nano-catalyst filter and production method for same |
| CN111939757A (en) * | 2020-08-10 | 2020-11-17 | 暨南大学 | Method for removing nitrogen oxides in low-temperature flue gas |
-
2021
- 2021-04-11 CN CN202110385861.6A patent/CN113117667B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190358586A1 (en) * | 2013-03-29 | 2019-11-28 | Korea University Research And Business Foundation | Nano-catalyst filter and production method for same |
| CN103263914A (en) * | 2013-05-03 | 2013-08-28 | 北京工业大学 | Honeycomb-shaped SCR denitration catalysis material for cement kiln and preparation method thereof |
| US20170128883A1 (en) * | 2015-11-06 | 2017-05-11 | Paccar Inc | High efficiency and durability selective catalytic reduction catalyst |
| CN108067296A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of preparation method of cellular Mn based low-temperature denitration catalysts |
| CN107456981A (en) * | 2017-09-01 | 2017-12-12 | 天津市职业大学 | A kind of exhaust gas denitration composite catalyst and preparation method thereof |
| CN108212146A (en) * | 2018-01-09 | 2018-06-29 | 上海大学 | Nucleocapsid denitrating catalyst of metallic monoliths and preparation method thereof |
| CN111939757A (en) * | 2020-08-10 | 2020-11-17 | 暨南大学 | Method for removing nitrogen oxides in low-temperature flue gas |
Non-Patent Citations (2)
| Title |
|---|
| DONG YANG: "Selective catalytic reduction of NOx with methane over indium supported on tungstated zirconia", 《CATALYSIS COMMUNICATIONS》, vol. 8, no. 12, XP022317271, DOI: 10.1016/j.catcom.2007.04.035 * |
| 吴爽: "铟基车用SCR整体催化剂的制备及脱硝性能研究", 《中国博士学位论文全文数据库 (工程科技Ⅰ辑)》, pages 014 - 33 * |
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