CN112808264A - Preparation method of vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst - Google Patents
Preparation method of vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst Download PDFInfo
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- CN112808264A CN112808264A CN202110010673.5A CN202110010673A CN112808264A CN 112808264 A CN112808264 A CN 112808264A CN 202110010673 A CN202110010673 A CN 202110010673A CN 112808264 A CN112808264 A CN 112808264A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- DLCOPLYGCSRNAY-UHFFFAOYSA-N molybdenum titanium vanadium Chemical compound [Ti][Mo][V] DLCOPLYGCSRNAY-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 27
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000007790 solid phase Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 8
- 229940010552 ammonium molybdate Drugs 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 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 238000007790 scraping Methods 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 230000001464 adherent effect Effects 0.000 claims 1
- 239000011812 mixed powder Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910016782 Mn2V2O7 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
- B01J23/28—Molybdenum
-
- 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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/30—Improvements relating to adipic acid or caprolactam production
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Abstract
A preparation method of a vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst belongs to the technical field of catalyst preparation. The specific method comprises the following steps: vanadium precursor, molybdenum precursor, organic ligand and carrier TiO2And (4) putting the powder into a ball milling tank for ball milling, and repeatedly processing the adhered materials for multiple times according to the material condition so as to ensure that the uniformly mixed powder is obtained. Then roasting to obtain the vanadium-molybdenum-titanium composite oxide catalyst. The preparation method of the vanadium-molybdenum-titanium composite oxide catalyst has the characteristics of simple process, less material loss, short preparation period, no use of any solvent, low energy consumption and the like, and meets the requirement of green synthesis development.
Description
Technical Field
The invention relates to a preparation method of a vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst and application of the catalyst in ammonia selective catalytic reduction of nitrogen oxides, belonging to the technical field of catalyst preparation.
Background
Industrial waste gas is the main atmospheric pollutionSource of Nitrogen Oxides (NO)x) Is the main atmospheric pollutant causing extreme weather phenomena such as haze, acid rain and the like. Therefore, the research and development of high-efficiency nitrogen oxide removal technology is of great significance. Ammonia Selective catalytic Reduction (NH)3SCR) is the most widely commercialized flue gas denitration technology at home and abroad at present, and is widely applied to the power industry. The core of the SCR denitration technology is catalyst preparation, and the current commercial denitration catalyst is mainly vanadium titanium base (V)2O5-WO3/TiO2Or V2O5-MoO3/TiO2) The working temperature of the catalyst is generally 300-400 ℃. It is difficult to apply to denitration engineering of non-electric boiler (kiln) furnace equipment (such as industrial boilers, glass ceramic furnaces, cement furnaces, metallurgical sintering furnaces, coke ovens, etc.) with low exhaust gas temperature. Therefore, low-temperature SCR denitration catalysts are receiving attention. See reports of: vanadium-based, manganese-based, cerium-based, and the like. The manganese-based and cerium-based catalysts can exhibit excellent low-temperature activity, but are resistant to SO2The performance is poor, and the practical application is difficult. The invention patent CN108236943A discloses a preparation method of a vanadium-based oxide catalyst, in the method, a coprecipitation method is used for preparing a carrier Ce of the catalystaWbTiOxThen loading V on the surface of the carrier by using an impregnation method2O5The vanadium-based catalyst prepared by the method has good low-temperature activity and NO at 200 DEG CxThe conversion rate can reach 100 percent. The invention patent CN111715214A discloses a preparation method of a manganese vanadate catalyst, in the method, the conversion rate of nitrogen oxide of a vanadium-based catalyst synthesized by a sol-gel method reaches 90% within the temperature range of 225-400 ℃. The sol-gel method is adopted to increase the interaction between the active components Mn and V, so that the active component is Mn2V2O7Into the TiO carrier2In (1). The invention patent CN109012712A also discloses a preparation method of the low-temperature vanadium-titanium-based SCR catalyst, in the method, the conversion rate of nitrogen oxide of the vanadium-titanium catalyst prepared by the impregnation method can reach 100% at 200 ℃. In addition, the professor of the subject group who has flood developed a vanadium-titanium SCR catalyst capable of operating at 160-200 DEG CThe denitration efficiency of the catalyst reaches 90 percent, and the catalyst is applied to a plurality of flue gas denitration projects such as coking, glass and the like. The preparation of the low-temperature SCR catalyst adopts a liquid phase method, and has the problems of more synthesis steps, high energy consumption and the like.
The solid phase ball milling method has many applications in the field of environmental catalysis. The mechanochemical synthesis method can effectively regulate and control the particle size and the dispersity of the metal nano particles, increase the specific surface area of the catalyst and further improve the catalytic performance of the catalyst. Uraiwan, K, and the like utilize a solid phase ball milling method to prepare Ag/Al2O3Nanomaterials which show a higher activity in hydrocarbon selective catalytic reduction reactions (Uraiwan. K., et al, ACS Catal.2011,1,10, 1257-. Yan and the like prepare Ce/TiO by utilizing an organic ligand auxiliary ball milling method2Catalyst for obviously improving the content of cerium in TiO2The dispersion of the surface, exhibits good low temperature SCR activity (Yan, et al, chem. commun.,2017,53, 1321-.
The invention provides a method for preparing a vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst by a step-by-step solid-phase ball milling method, aiming at the problems of complicated process flow, high energy consumption and the like in the process of preparing the SCR catalyst by a liquid phase method. The method has the characteristics of less material loss, short preparation period, no solvent, low energy consumption and the like, and meets the requirement of green synthesis development.
Disclosure of Invention
The invention aims to provide a preparation method of a vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst with a simple process and application of the catalyst in ammonia selective catalytic reduction of nitrogen oxides.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst by a step-by-step solid-phase ball milling method is characterized by comprising the following steps:
(1) vanadium precursor, molybdenum precursor, organic ligand and carrier TiO2Putting the mixture into a ball milling tank to perform ball milling for a certain time at a certain rotating speed;
(2) suspending the ball mill, scraping off the adhered materials on the wall of the ball milling tank and the wall of the agate ball, and continuing to perform ball milling for a certain time; the process can be repeated for a plurality of times according to the material condition until the materials are uniformly mixed;
(3) transferring the powder obtained in the step (2) into a muffle furnace for roasting, wherein the roasting temperature is 200-500 ℃;
(4) and (4) grinding the calcined composite oxide obtained in the step (3) to obtain the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst.
In the step (1), the vanadium precursor is any one of sodium metavanadate, ammonium metavanadate or vitriol, and the like, and the vanadium content is 1-10 wt% calculated by vanadium oxide.
In the step (1), the molybdenum precursor is any one of sodium molybdate or ammonium molybdate, and the content of molybdenum is 1-10 wt% calculated as molybdenum oxide.
The mass ratio of the organic ligand to the vanadium precursor in the step (1) is 0-6: 1; the organic ligand is at least one of organic acids such as oxalic acid, terephthalic acid, malonic acid, glutaric acid, adipic acid, citric acid and the like.
The carrier TiO used in the step (1) is TiO2The particle size of the product is 10-50 nm, and the specific surface area (BET) is 60-150 m2/g，TiO2The content is 94.0-99.5%.
The ball milling beads used in the steps (1) and (2) are agate balls with the size of 10-25 mm, the mass ratio of the ball materials is 5: 1-25: 1, the ball milling time is 0.5-12 h, and the ball milling speed is 300-600 r/min.
The step (2) of treating the adhered materials on the wall of the ball milling pot and the wall of the agate ball is repeated for a plurality of times according to the condition of the materials.
The further calcination in step (3) is a stepwise calcination, preferably in an air atmosphere, at 250 ℃ for 2 hours and at 450 ℃ for 2 hours.
The content of vanadium pentoxide in the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst is 1-10 wt%.
The innovation points of the invention are as follows: the invention adopts a step-by-step solid phase ball milling method to prepare the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst, and active components are uniformly dispersed. The obtained low-temperature SCR catalyst has a wide working window and can realize the conversion of the nitrogen oxide by more than 90 percent within the range of 170-410 ℃. Compared with the traditional impregnation method, the preparation method has the advantages of simple preparation process, easy regulation and control of preparation conditions, no solvent participation in the production process, low energy consumption and accordance with the green production concept.
Drawings
FIG. 1 shows NH of catalysts 1#, 2#, 6# prepared in examples 1, 2, 63Comparison of the reactivity of selective catalytic reduction of nitrogen oxides.
FIG. 2 shows NH of catalysts 2#, 3#, 4# prepared in examples 2, 3, 43Comparison of the reactivity of selective catalytic reduction of nitrogen oxides.
FIG. 3 shows NH of catalysis/1 #, 5# prepared in examples 1, 53Comparison of the reactivity of selective catalytic reduction of nitrogen oxides.
FIG. 4 is a graph comparing the sulfur and water resistance activity of catalysts # 1, # 2, and # 6 prepared in examples 1, 2, and 6. (test conditions: 1000ppm NO,1000ppm NH)3，6％O2，100ppm SO2,10％H2O,N2For balancing gas, the space velocity is 30000h-1)。
FIG. 5 is a powder X-ray diffraction pattern of catalysts # 1, # 2 and # 6 prepared in examples 1, 2 and 6.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. Selective catalytic reduction of nitrogen oxides (NH) in ammonia3-SCR) reaction under the following conditions: 1000ppm NO,1000ppm NH3,6％O2,N2The space velocity is 30000h for balancing gas-1. The reaction temperature is 80-450 ℃.
Example 1:
0.62g of ammonium metavanadate, 1.47g of ammonium molybdate and 18.2g of TiO were weighed out2Putting the mixture into a ball milling tank, adding a certain number of 10mm, 15mm, 20mm and 25mm agate balls with the ball-material mass ratio of 10:1, putting the mixture into a planetary ball mill, and grinding the mixture for 1 hour at 500 r/min. And (5) suspending the treatment of the adhered materials on the wall of the ball milling tank and the wall of the agate ball, and continuing ball milling for 1 hour. And (3) putting the uniformly mixed powder into a muffle furnace, and roasting for 2 hours at 250 ℃ and 2 hours at 450 ℃ in an air atmosphere.A sample of catalyst # 1 was obtained.
Example 2:
0.62g of ammonium metavanadate, 1.47g of ammonium molybdate, 0.19g of adipic acid and 18.2g of TiO were weighed out2Putting the mixture into a ball milling tank, adding a certain number of 10mm, 15mm, 20mm and 25mm agate balls with the ball-material mass ratio of 10:1, putting the mixture into a planetary ball mill, and grinding the mixture for 1 hour at 500 r/min. And (5) suspending the treatment of the adhered materials on the wall of the ball milling tank and the wall of the agate ball, and continuing ball milling for 1 hour. And (3) putting the uniformly mixed powder into a muffle furnace, and roasting for 2 hours at 250 ℃ and 2 hours at 450 ℃ in an air atmosphere. A sample of catalyst # 2 was obtained.
Example 3:
0.62g of ammonium metavanadate, 1.47g of ammonium molybdate, 0.31g of adipic acid and 18.2g of TiO were weighed out2Putting the mixture into a ball milling tank, adding a certain number of 10mm, 15mm, 20mm and 25mm agate balls with the ball-material mass ratio of 10:1, putting the mixture into a planetary ball mill, and grinding the mixture for 1 hour at 500 r/min. And (5) suspending the treatment of the adhered materials on the wall of the ball milling tank and the wall of the agate ball, and continuing ball milling for 1 hour. And (3) putting the uniformly mixed powder into a muffle furnace, and roasting for 2 hours at 250 ℃ and 2 hours at 450 ℃ in an air atmosphere. A sample of catalyst # 3 was obtained.
Example 4:
0.62g of ammonium metavanadate, 1.47g of ammonium molybdate, 0.62g of adipic acid and 18.2g of TiO were weighed out2Putting the mixture into a ball milling tank, adding a certain number of 10mm, 15mm, 20mm and 25mm agate balls with the ball-material mass ratio of 10:1, putting the mixture into a planetary ball mill, and grinding the mixture for 1 hour at 500 r/min. And (5) suspending the treatment of the adhered materials on the wall of the ball milling tank and the wall of the agate ball, and continuing ball milling for 1 hour. And (3) putting the uniformly mixed powder into a muffle furnace, and roasting for 2 hours at 250 ℃ and 2 hours at 450 ℃ in an air atmosphere. A 4# catalyst sample was obtained.
Example 5:
0.62g of ammonium metavanadate, 1.47g of ammonium molybdate and 18.2g of TiO were weighed out2Putting the mixture into a ball milling tank, adding a certain number of 10mm, 15mm, 20mm and 25mm agate balls with the ball-material mass ratio of 10:1, putting the mixture into a planetary ball mill, and grinding the mixture for 1 hour at 500 r/min. Suspending treatment of adhered materials on the wall of the ball milling tank and the wall of the agate ballAnd continuing ball milling for 1 hour. And (5) suspending the treatment of the adhered materials on the wall of the ball milling tank and the wall of the agate ball, and continuing ball milling for 1 hour. And (3) putting the uniformly mixed powder into a muffle furnace, and roasting for 2 hours at 250 ℃ and 2 hours at 450 ℃ in an air atmosphere. A sample of catalyst # 5 was obtained.
Example 6 (comparative):
1.3g of oxalic acid is weighed and dissolved in 20mL of water, and stirred in a water bath at 60 ℃ until the oxalic acid is completely dissolved. 0.3g of ammonium metavanadate was added to the solution and stirred until the solution turned from yellow to dark blue. 0.74g of ammonium molybdate was added to the dark blue vanadyl oxalate solution, and 9.1g of TiO was added2And carrying out ultrasonic treatment for 2 hours after uniform stirring. And drying the impregnation liquid at 80 ℃, grinding, putting into a muffle furnace, roasting at 250 ℃ for 2 hours and at 450 ℃ for 2 hours in an air atmosphere to obtain a No. 6 catalyst sample.
Claims (10)
1. A method for preparing a vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst by a step-by-step solid-phase ball milling method is characterized by comprising the following steps:
(1) vanadium precursor, molybdenum precursor, organic ligand and carrier TiO2Putting the mixture into a ball milling tank for ball milling for a certain time;
(2) suspending the ball mill, scraping off the adhered materials on the wall of the ball milling tank and the wall of the agate ball, and continuing to perform ball milling for a certain time; the process can be repeated for a plurality of times according to the material condition until the materials are uniformly mixed;
(3) transferring the powder obtained in the step (2) into a muffle furnace for roasting, wherein the roasting temperature is 200-500 ℃;
(4) and (4) grinding the calcined composite oxide obtained in the step (3) to obtain the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst.
2. The method for preparing the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst by the step-by-step solid-phase ball milling method according to claim 1, wherein in the step (1), the vanadium precursor is any one of sodium metavanadate, ammonium metavanadate or vitriol and the like, the vanadium content is 1-10 wt% calculated by vanadium oxide; the content of vanadium pentoxide in the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst is 1-10 wt%.
3. The method for preparing the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst by the step-by-step solid-phase ball milling method according to claim 1, wherein in the step (1), the molybdenum precursor is any one of sodium molybdate or ammonium molybdate, and the content of molybdenum is 1-10 wt% calculated by molybdenum oxide.
4. The method for preparing the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst by the step-by-step solid-phase ball milling method according to claim 1, wherein the mass ratio of the organic ligand to the vanadium precursor in the step (1) is 0-6: 1; the organic ligand is at least one of organic acids such as oxalic acid, terephthalic acid, malonic acid, glutaric acid, adipic acid, citric acid and the like.
5. The method for preparing the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst by the step-by-step solid-phase ball milling method according to claim 1, wherein the carrier TiO used in the step (1) is TiO2The particle size of the product is 10-50 nm, and the specific surface area (BET) is 60-150 m2/g，TiO2The content is 94.0-99.5%.
6. The method for preparing the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst by the step-by-step solid-phase ball milling method according to claim 1, wherein the ball milling beads used in the steps (1) and (2) are agate balls with the size of 10-25 mm, the mass ratio of the ball materials is 5: 1-25: 1, the ball milling time is 0.5-12 h, and the ball milling speed is 300-600 r/min.
7. The method for preparing the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst by the step-by-step solid-phase ball milling method according to claim 1, wherein the step (2) of treating the adherent materials on the wall of the ball mill pot and the wall of the agate ball is repeated for a plurality of times according to the material conditions.
8. The method for preparing the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst by the step-by-step solid-phase ball milling method according to claim 1, wherein the calcination in the step (3) is step-by-step calcination, and the calcination is carried out at 250 ℃ for 2 hours and at 450 ℃ for 2 hours in an air atmosphere.
9. A vanadium molybdenum titanium composite oxide low temperature SCR catalyst prepared according to the method of any one of claims 1 to 8.
10. The application of the vanadium-molybdenum-titanium composite oxide low-temperature SCR catalyst prepared by the method according to any one of claims 1 to 8 to carry out low-temperature SCR catalysis, wherein the working window is in the range of 170-410 ℃ to realize the conversion of nitrogen oxides by more than 90%.
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| CN115304077A (en) * | 2022-08-10 | 2022-11-08 | 浙江浙能技术研究院有限公司 | Molecular sieve for selective catalytic reduction of nitrogen oxides and preparation method and application thereof |
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