CN115739074A - High-activity yellow smoke-eliminating denitration catalyst for gas engine and preparation method thereof - Google Patents
High-activity yellow smoke-eliminating denitration catalyst for gas engine and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 230000000694 effects Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 19
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000779 smoke Substances 0.000 claims abstract description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 18
- 238000002485 combustion reaction Methods 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 239000002073 nanorod Substances 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 150000000703 Cerium Chemical class 0.000 claims abstract description 3
- 150000001879 copper Chemical class 0.000 claims abstract description 3
- 150000002696 manganese Chemical class 0.000 claims abstract description 3
- 150000003657 tungsten Chemical class 0.000 claims abstract description 3
- 150000003681 vanadium Chemical class 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a high-activity yellow smoke-eliminating denitration catalyst for a gas turbine and a preparation method thereof, belonging to the technical field of denitration catalysts. The technical scheme is as follows: the carrier is cordierite honeycomb ceramic, a titanium dioxide nanorod array grows on the cordierite honeycomb ceramic in situ, and active components are loaded on the carrier and are three or four of vanadium salt, tungsten salt, manganese salt, cerium salt and copper salt. The catalyst prepared by the invention has large specific surface area and can remove NO at low temperature 2 And NO has high activity, and can be suitable for eliminating 'yellow smoke' when a combustion engine is started and stopped.
Description
Technical Field
The invention relates to the technical field of denitration catalysts, and particularly relates to a high-activity yellow smoke-eliminating denitration catalyst for a gas turbine and a preparation method thereof.
Background
With the improvement of national standards for controlling the emission concentration of NOx, the deep emission reduction of NOx of a gas turbine unit (hereinafter referred to as a combustion engine) is gradually promoted. In the operation of the existing gas turbine, the phenomenon of yellow smoke emission of different degrees in the starting stage partially exists, which causes high-concentration NO in the exhaust smoke with the change of combustion modes in the starting and stopping stages of the gas turbine 2 Related to this, it brings great pressure to environmental protection governance and survival of fuel power plants.
At present, most of domestic in-service gas turbines are not provided with an SCR denitration device, and an SCR unit of the gas turbine which is put into operation can only meet the requirement of the normal operation working condition of the gas turbine, and the NOx emission reduction and the 'yellow smoke' control of low-load low-temperature sections such as start and stop of the unit are not considered. In addition, because the denitration space reserved in the existing waste heat boiler matched with the gas turbine is very narrow, the smoke content in the gas turbine smoke is very low. Therefore, the denitration catalyst for the combustion engine generally adopts a catalyst with high pore number, large specific surface area and high catalytic activity, so as to reduce the volume of the catalyst while meeting the denitration efficiency and meet the installation space inside the waste heat boiler. At present, the low-temperature denitration activity of commercial vanadium-tungsten-titanium catalyst is low, especially NO 2 At higher concentration, it is free of NO 2 The activity of the composition is lower, and the composition is not suitable for eliminating 'yellow smoke' when a combustion engine is started and stopped.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, provides a high-activity yellow smoke-eliminating denitration catalyst for a gas turbine and a preparation method thereof, and the prepared catalyst has large specific surface area and can remove NO at low temperature 2 And NO activity is high, and the smoke eliminating agent can be suitable for eliminating 'yellow smoke' when a combustion engine is started and stopped.
The technical scheme of the invention is as follows:
on one hand, the invention provides a high-activity yellow smoke eliminating denitration catalyst for a combustion engine, wherein a carrier is cordierite honeycomb ceramic, a titanium dioxide nanorod array grows on the cordierite honeycomb ceramic in situ, and active components are loaded on the carrier and are three or four of vanadium salt, tungsten salt, manganese salt, cerium salt and copper salt.
On the other hand, the invention also provides a preparation method of the high-activity yellow smoke-eliminating denitration catalyst for the gas engine, wherein a titanium dioxide nanorod array is grown in situ on a carrier by adopting a hydrothermal in-situ growth method, and then an active component is loaded on the carrier by adopting an impregnation method.
Preferably, the preparation method of the high-activity yellow smoke-eliminating denitration catalyst for the combustion engine comprises the following steps:
s1, washing a cordierite honeycomb ceramic carrier with deionized water and ethanol, and drying;
s2, putting the carrier pretreated in the step S1 on TiO 2 Ultrasonically dipping in sol, drying, transferring to a muffle furnace, and annealing at 450-550 ℃ for 20-30min to obtain paved TiO 2 A cordierite honeycomb ceramic carrier of seeds;
s3, adding hydrochloric acid, deionized water and tetrabutyl titanate into the lining of the hydrothermal reaction kettle, mixing and stirring, and then putting the carrier with the seeds paved in the step S2 into the mixed solution; putting the inner liner of the reaction kettle into the reaction kettle, carrying out hydrothermal reaction at 180-200 ℃ for 10-12h, naturally cooling to room temperature, washing with deionized water and ethanol respectively, and drying to obtain a cordierite honeycomb ceramic carrier with an in-situ grown titanium dioxide nanorod array;
s4, putting the carrier obtained in the step S3 into an active substance solution, carrying out ultrasonic impregnation, then drying, and calcining in a muffle furnace at 450-550 ℃ for 10-12h to obtain the high-activity yellow smoke-eliminating denitration catalyst for the gas engine.
Preferably, in the steps S1, S2 and S3, the drying temperature is 110-120 ℃, and the drying time is 2-4h; in the step S4, the drying temperature is 110-120 ℃, and the drying time is 20-24h.
Preferably, in step S2, tiO 2 The concentration of the sol is 0.1-0.8mol/L.
Preferably, in the step S3, the volume ratio of the hydrochloric acid to the deionized water to the tetrabutyl titanate is 1.
Preferably, in step S4, the concentration of the active substance solution is 0.5-1mol/L.
Preferably, in step S2, tiO 2 The sol is prepared by the following method:
s21, mixing ethanol, deionized water and hydrochloric acid, and stirring to prepare a solution A;
s22, mixing ethanol, acetylacetone and tetrabutyl titanate, and stirring to prepare a solution B;
s23, dripping the solution A into the solution B, stirring, and aging at normal temperature to obtain TiO 2 And (3) sol.
Preferably, in step S21, the volume ratio of ethanol, deionized water and hydrochloric acid is 200; in step S22, the volume ratio of ethanol to acetylacetone to tetrabutyl titanate is (2-16): 1.
Preferably, in step S23, the normal temperature aging time is 20-24h.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, a titanium dioxide nanorod array is grown in situ on a cordierite carrier by a hydrothermal in-situ growth method, so that the carrier with a large specific surface area is prepared; then, the impregnation method is adopted to load the carrier with alum, tungsten, manganese, cerium, copper and the like to remove NO at higher and lower temperature 2 And transition metal elements with NO activity, and creatively develops a high-activity denitration catalyst for eliminating 'yellow smoke' when a combustion engine is started or stopped. The catalyst of the invention has large specific surface area and can remove NO at low temperature 2 And NO activity is high, and the smoke eliminating agent can be suitable for eliminating 'yellow smoke' when a combustion engine is started and stopped.
Detailed Description
Example 1
Pretreatment of S1 cordierite honeycomb ceramic carrier
Cutting the cordierite honeycomb ceramic carrier into a plurality of small blocks with the size of 1cm multiplied by 1cm, washing the small blocks with deionized water and ethanol for three times, drying the small blocks for 2 hours at the temperature of 115 ℃, and then placing the small blocks in a dryer.
S2 TiO 2 Seed crystal laying
（1）TiO 2 Preparation of the Sol
Mixing 60mL of ethanol, 3mL of deionized water and 300uL of hydrochloric acid (37 wt%), and magnetically stirring for 20min to obtain a solution A; mixing 12mL of ethanol, 6mL of acetylacetone and 30mL of tetrabutyl titanate, and magnetically stirring for 20min to prepare a solution B; dripping the solution A into the solution B, and magnetically stirring for 30min, aging for 24 hours at normal temperature to obtain 0.8mol/L TiO 2 And (3) sol.
（2）TiO 2 Seed crystal laying
Placing the cordierite honeycomb ceramic carrier pretreated in the step S1 on TiO 2 Ultrasonically dipping the sol for 30min, taking out the sol, drying the sol in a drying oven at 115 ℃ for 2h, transferring the sol to a muffle furnace, and annealing the sol at 500 ℃ for 20min to obtain the paved TiO 2 A seeded cordierite honeycomb ceramic carrier.
S3 hydrothermal in-situ growth of TiO 2 Titanium dioxide nanorod array
Adding 15mL of hydrochloric acid, 15mL of deionized water and 300uL of tetrabutyl titanate into the inner liner of the hydrothermal reaction kettle, mixing and magnetically stirring for 20min, and then paving the TiO 2 And putting the carrier of the seeds into the mixed solution, then putting the liner of the reaction kettle into the reaction kettle, putting the reaction kettle into an oven, carrying out hydrothermal reaction for 10h at 190 ℃, respectively washing the reaction kettle for three times by using deionized water and ethanol after the reaction kettle is naturally cooled to room temperature, and drying the reaction kettle for 1h at 115 ℃ to obtain the cordierite honeycomb ceramic carrier with the in-situ grown titanium dioxide nanorod array.
S4 impregnation of the active component
And (3) soaking the carrier obtained in the step (S3) into a mixed solution of 0.5mol/L ammonium metavanadate, ammonium metatungstate, cerium nitrate and manganese nitrate (the concentrations of four salts in the mixed solution are all 0.5 mol/L) for 2 hours by ultrasonic soaking, then drying at 115 ℃ for 20 hours, and calcining at 500 ℃ in a muffle furnace for 10 hours. Obtaining the high-activity yellow smoke-eliminating denitration catalyst for the gas engine.
Example 2
The difference from example 1 is that: the TiO of example 1 2 The sol concentration was adjusted to 0.1mol/L and the volume of tetrabutyl titanate in step S3 was adjusted to 500uL.
Example 3
The difference from example 1 is that: the TiO of example 1 2 The sol concentration was adjusted to 0.3mol/L and the volume of tetrabutyl titanate in step S3 was adjusted to 400uL.
Example 4
The difference from example 1 is that: the TiO of example 1 2 The sol concentration was adjusted to 0.5mol/L, and the volume of tetrabutyl titanate in step S3 was adjusted to 400uL.
Example 5
The differences from example 4 are: the concentration of the mixed solution in step S4 of example 4 was changed to 1mol/L.
Example 6
The difference from example 5 is that: the mixed liquid in step S4 of example 4 was changed to a mixed liquid of ammonium metavanadate, ammonium metatungstate, cerium nitrate and copper nitrate.
Example 7
The differences from example 5 are: the mixed solution in step S4 of embodiment 4 is changed to a mixed solution of ammonium metavanadate, ammonium metatungstate and copper nitrate.
Comparative example 1
Comparative example 1A 200 mesh commercial honeycomb catalyst (TiO as support) 2 Active ingredient was 2.5% V 2 O 5 -5%WO 3 ) Specific surface area of 45.123m 2 / g。
The specific surface area measurement data of the cordierite honeycomb ceramic carrier and the catalysts of examples 1 to 7 and comparative example 1 are shown in table 1:
TABLE 1
The catalysts of examples 1 to 7 and comparative example 1 were subjected to activity detection under the following conditions: 100ppmNO +200ppmNO 2 +400ppmNH 3 +N 2 +20ppmSO 2 +15%H 2 O, the space velocity of the catalyst is 100000h -1 The temperature of the flue gas is 200-500 ℃. The denitration efficiency of each catalyst was measured as shown in table 2:
TABLE 2
As can be seen from tables 1-2, the catalysts prepared in examples 1-7 of the present invention have very high specific surface areas and the removal of NO and NO as compared with comparative example 1 2 Has high activity and strong yellow smoke eliminating capacity. NO 2 Is a reddish brown gas, and is yellowish brown after dilutionThe visible yellow smoke during the start-up of the combustion engine is derived from NO 2 Thus, to eliminate yellow smoke, NO is required 2 The emission concentration decreases. NH 3 The selective catalytic reduction method is an effective method for removing NO 2 And method of NO, NH 3 NH during the SCR reaction 3 The adsorption on the surface of the catalyst is divided into two types: 1. adsorbed at the acid position B and denoted as NH 4+ (ii) a 2. Adsorbed at the L acid position and denoted as NH 3 (a)。NO 2 Easily combined with NH adsorbed at the B acid site 3 Species reaction to NH 4 NO 3 . NH on the surface of the catalyst at low temperature 4 NO 3 Species may cover the active sites of the SCR reaction, causing a reduction in activity, but at high temperatures, NH is formed 4 NO 3 Part of the species will be reduced to N by NO 2 And the other part is directly thermally decomposed into N 2 O, causing a decrease in the selectivity of the catalyst; and NH adsorbed at the L acid position 3 (a) Without being affected thereby. Therefore, increase of NH 3 NO in SCR reactions 2 The removal efficiency and selectivity of (2) are improved by decreasing the number of B acid sites and increasing the number of L acid sites of the catalyst to improve the removal of NO 2 The efficiency of (c). According to the catalyst prepared by the hydrothermal in-situ growth method, the active substances have interaction, so that better dispersion is promoted, the number of L acids is increased, more L acid sites, larger specific surface area, more surface active oxygen and stronger reduction capability are provided, and therefore, the catalyst has higher NO removal capability 2 Activity and yellow smoke eliminating ability.
Claims (10)
1. The high-activity yellow smoke eliminating denitration catalyst for the gas engine is characterized in that a carrier is cordierite honeycomb ceramic, a titanium dioxide nanorod array grows on the cordierite honeycomb ceramic in situ, active components are loaded on the carrier, and the active components are three or four of vanadium salt, tungsten salt, manganese salt, cerium salt and copper salt.
2. The preparation method of the high-activity yellow smoke-eliminating denitration catalyst for the gas turbine as claimed in claim 1, wherein a titanium dioxide nanorod array is grown in situ on the carrier by a hydrothermal in-situ growth method, and then an active component is loaded on the carrier by an impregnation method.
3. The preparation method of the high-activity yellow smoke-eliminating denitration catalyst for the combustion engine as claimed in claim 2, characterized by comprising the following steps:
s1, washing a cordierite honeycomb ceramic carrier with deionized water and ethanol, and drying;
s2, putting the carrier pretreated in the step S1 on TiO 2 Ultrasonically dipping in sol, drying, transferring to a muffle furnace, annealing at 450-550 ℃ for 20-30min to obtain paved TiO 2 A cordierite honeycomb ceramic carrier of seeds;
s3, adding hydrochloric acid, deionized water and tetrabutyl titanate into the lining of the hydrothermal reaction kettle, mixing and stirring, and then putting the carrier with the seeds laid in the step S2 into the mixed solution; putting the inner liner of the reaction kettle into the reaction kettle, carrying out hydrothermal reaction at 180-200 ℃ for 10-12h, naturally cooling to room temperature, washing with deionized water and ethanol respectively, and drying to obtain a cordierite honeycomb ceramic carrier with an in-situ grown titanium dioxide nanorod array;
s4, putting the carrier obtained in the step S3 into an active substance solution, carrying out ultrasonic impregnation, then drying, and then calcining for 10-12h in a muffle furnace at 450-550 ℃ to obtain the high-activity yellow smoke-eliminating denitration catalyst for the gas engine.
4. The method for preparing the high-activity yellow smoke-eliminating denitration catalyst for the combustion engine as claimed in claim 3, wherein in the steps S1, S2 and S3, the drying temperature is 110-120 ℃, and the drying time is 2-4h; in the step S4, the drying temperature is 110-120 ℃, and the drying time is 20-24h.
5. The method for preparing high-activity yellow smoke-eliminating denitration catalyst for the gas turbine as claimed in claim 3, wherein in the step S2, tiO is used 2 The concentration of the sol is 0.1-0.8mol/L.
6. The method for preparing the high-activity yellow smoke-eliminating denitration catalyst for the combustion engine as claimed in claim 3, wherein in the step S3, the volume ratio of hydrochloric acid, deionized water and tetrabutyl titanate is 1.
7. The method of claim 3, wherein in step S4, the concentration of the active material solution is 0.5-1mol/L.
8. The method for preparing the high-activity yellow smoke-eliminating denitration catalyst for the combustion engine as claimed in claim 3, wherein in the step S2, tiO is added 2 The sol is prepared by the following method:
s21, mixing ethanol, deionized water and hydrochloric acid, and stirring to obtain a solution A;
s22, mixing ethanol, acetylacetone and tetrabutyl titanate, and stirring to prepare a solution B;
s23, dripping the solution A into the solution B, stirring, and aging at normal temperature to obtain TiO 2 And (3) sol.
9. The method for preparing a highly active anti-smoke denitration catalyst for a combustion engine according to claim 8, wherein in step S21, the volume ratio of ethanol, deionized water and hydrochloric acid is 200; in step S22, the volume ratio of ethanol to acetylacetone to tetrabutyl titanate is (2-16): 1.
10. The method for preparing the high-activity yellow smoke-eliminating denitration catalyst for the combustion engine as claimed in claim 8, wherein in the step S23, the normal temperature aging time is 20-24h.
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