CN116786108B - A high-space-velocity SCR denitration catalyst for a gas generator set and a preparation method thereof - Google Patents
A high-space-velocity SCR denitration catalyst for a gas generator set and a preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 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 class [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 107
- 239000000843 powder Substances 0.000 claims abstract description 70
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002002 slurry Substances 0.000 claims abstract description 46
- 238000001291 vacuum drying Methods 0.000 claims abstract description 41
- -1 titanate compound Chemical class 0.000 claims abstract description 34
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 33
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 45
- 239000011148 porous material Substances 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 20
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000010248 power generation Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 2
- JEKYCZIXYPVKNQ-BQGNPDQISA-N (Z)-octadec-9-enoic acid propan-2-ol titanium Chemical compound [Ti].CC(C)O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O JEKYCZIXYPVKNQ-BQGNPDQISA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 claims 1
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000003546 flue gas Substances 0.000 abstract description 9
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 description 24
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- 238000000227 grinding Methods 0.000 description 11
- 229910052878 cordierite Inorganic materials 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004576 sand Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000003245 coal Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- 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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- 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
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention relates to a preparation method of a high-airspeed SCR denitration catalyst for a gas generator set, which comprises the following steps of immersing a modified cordierite framework in titanate compound solution, drying the immersed modified cordierite, immersing the dried modified cordierite framework in hydrophobic modified catalyst active powder slurry to obtain a catalyst precursor, vacuum drying the obtained catalyst precursor, and roasting the dried catalyst precursor to obtain the high-airspeed SCR denitration catalyst. According to the preparation method, the modified cordierite skeleton is pretreated by using the titanate solution, the hydrophobic group V 2O5-WO3/TiO2 catalytic layer and the modified cordierite skeleton treated by the titanate form chemical bonds and actions, the bonding force between the catalytic layer and the modified cordierite skeleton is increased, and meanwhile, the high dispersion of the hydrophobic group V 2O5-WO3/TiO2 powder of the active component of the catalyst on the modified cordierite greatly improves the denitration activity of the catalyst. The catalyst prepared by the invention can be used for high-space-velocity denitration of the flue gas of the gas generator set.
Description
Technical Field
The invention belongs to the technical field of flue gas denitration, and particularly relates to a high-airspeed SCR denitration catalyst for a gas generator set and a preparation method thereof.
Background
Coalbed methane is known as coal mine methane in coal mines. The main component of the coal bed gas is methane, and when the concentration of the methane in the air reaches 5% -16%, the methane can explode when meeting open fire, which is the root of coal mine gas explosion accidents. Coal bed gas is not utilized and is directly discharged into the atmosphere, and the greenhouse effect is about 21 times that of carbon dioxide.
The gas power generation can effectively solve the problem of coal mine gas accidents, improve the safe production conditions of coal mines, and is beneficial to increasing clean energy supply and reducing greenhouse gas emission, thereby achieving the multiple aims of protecting life, resources and environment. However, the gas generator set has a special structure, so that the NOx concentration of the set smoke is high, and the NOx concentration interval is 2000-800mg/Nm 3. NOx in flue gas is a highly polluting component that can cause acid rain and photochemical smog, and Selective Catalytic Reduction (SCR) denitration technology using NH 3 as a reducing agent is the best choice for NOx treatment.
Because the concentration of NOx in the flue gas of the gas generator set is too high, and the compact structure of the set requires that the SCR denitration catalyst has extremely high activity and smaller volume, namely, the high-space-velocity high-activity denitration operation of the catalyst is required. The conventional mature commercial SCR denitration catalyst cannot meet the requirement of high-space-velocity high-activity denitration of the gas generator set smoke due to the low activity.
Disclosure of Invention
The invention aims to provide a high-airspeed SCR denitration catalyst for a gas generator set and a preparation method thereof, which can meet the requirement of high airspeed use of the catalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A preparation method of a high-airspeed SCR denitration catalyst for a gas generator set comprises the following steps:
firstly, pre-treating a cordierite framework, namely soaking the modified cordierite framework in a titanate compound solution, and then drying the soaked modified cordierite;
Impregnating the dried modified cordierite skeleton with hydrophobic modified catalyst active powder slurry to obtain a catalyst precursor, wherein the catalyst active powder slurry comprises 35% -50% of hydrophobic modified catalyst powder, 1% -3% of silica sol and 43% -64% of organic solvent;
step three, vacuum drying, namely vacuum drying the catalyst precursor obtained in the step two;
And step four, roasting the catalyst precursor after the drying in the step three at a high temperature to obtain the high-space-velocity SCR denitration catalyst.
Preferably, in the first step, the titanate compound is dissolved in deionized water to form a titanate compound solution, the modified cordierite skeleton is soaked in the titanate compound solution for 2 hours, and then the modified cordierite skeleton is taken out and dried for 3 hours under the environment of 110 ℃.
Preferably, the mass ratio of titanate compounds in the titanate compound solution is 60% -80%, and the titanate compound is one of isopropyl di (dioctyl phosphite acyloxy) titanate or isopropyl trioleate acyloxy titanate.
Preferably, the modified cordierite skeleton is an 80-108-pore honeycomb body, and the pore volume of the modified cordierite skeleton is 0.05-0.2 ml/g.
Preferably, the modified cordierite framework comprises 5.5% MgO, 13.5% Al 2O3, and 81% SiO 2.
Preferably, the step (2) is preceded by a step of preparing catalyst active powder slurry, namely weighing hydrophobic modified catalyst active powder, dispersing the hydrophobic modified catalyst active powder in an organic solvent, stirring for 1h to form a solution A, adding silica sol into the solution A to form a mixed solution B, grinding the mixed solution B, and grinding for 2h to obtain the catalyst active powder slurry.
Preferably, the hydrophobically modified catalyst active powder is a hydrophobic V 2O5-WO3/TiO2 powder, V 2O5-WO3/TiO2 is present in a mass ratio of 1.9% -4.0%/94.1%, the silica sol is an alkaline silica sol having a solids content of 40%, and the organic solvent is dimethylformamide (DMF, CAS: 68-12-2).
Preferably, in the third step, the volatilized organic solvent is condensed by a condensing device, wherein the temperature of the vacuum drying is 75 ℃, the vacuum pressure is-0.03 MPa, and the time of the vacuum drying is 5 hours.
Preferably, in the fourth step, the highest temperature of the roasting is 550 ℃, and the highest temperature roasting time is 2h.
The high-airspeed SCR denitration catalyst for the gas generator set is prepared by adopting the preparation method.
The invention has the following beneficial effects:
Aiming at the flue gas conditions of the gas generator set, the invention prepares the high-performance SCR denitration catalyst meeting the use requirements of flue gas denitration of the gas generator set, and the catalyst has the following excellent performances:
(1) The modified cordierite skeleton is pretreated by titanate solution, and the hydrophobic group V 2O5-WO3/TiO2 catalytic layer and the modified cordierite skeleton treated by titanate form chemical bonds and actions, so that the cohesive force of the catalytic layer and the modified cordierite skeleton is further increased, and the high airspeed usage of the catalyst is satisfied;
(2) The catalyst powder slurry is prepared by using the hydrophobic group V 2O5-WO3/TiO2 powder and the low surface tension organic solvent, the hydrophobic group V 2O5-WO3/TiO2 powder is highly dispersed in the organic solvent, the uniform distribution of the catalytic active powder on the cordierite skeleton and the high dispersion of the catalytic components are ensured, and the catalyst activity is improved. Meanwhile, the selection of the low-surface-tension organic solvent can enable bubbles brought in during slurry grinding to be quickly defoamed, so that shrinkage holes of a catalytic layer are avoided being formed during the catalyst drying process, the utilization rate of catalyst powder on a cordierite framework in unit area is greatly improved, the denitration activity of the catalyst is improved, and the denitration use of high-NOx-concentration flue gas is satisfied.
(3) The catalyst preparation process is energy-saving and environment-friendly, the catalyst is dried at a low temperature by using vacuum drying equipment, so that the defects of orange peel, shrinkage cavity, cracking and the like of a catalytic layer caused by high-temperature drying are avoided, and the volatile organic solvent is condensed and recycled by using condensing equipment in the low-temperature drying and vacuumizing process, so that the aim of recycling resources is fulfilled.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
The preparation method of the high-airspeed SCR denitration catalyst for the gas generator set comprises the following steps of:
firstly, pre-treating a cordierite framework, namely selecting 80-pore modified cordierite honeycomb bodies as framework materials, wherein the outer dimensions of the 80-pore modified cordierite honeycomb bodies are 150mm, 150mm and 150mm, the chemical components of the 80-pore modified cordierite honeycomb bodies are a mixture of MgO, al 2O3 and SiO 2, the mass ratio of MgO, al 2O3 and SiO 2 is 5.5 percent to 13.5 percent to 81 percent, and the pore volume of the modified cordierite is 0.17ml/g;
80g of isopropyl di (dioctyl phosphite acyloxy) titanate is dissolved in 20g of deionized water to form a titanate compound solution, a modified cordierite framework is soaked in the titanate compound solution for 2 hours, then the modified cordierite framework is taken out and dried for 3 hours under the environment of 110 ℃, and the pretreatment of the modified cordierite framework is completed;
Step two, dipping catalyst active powder slurry, namely weighing 35 parts of conventional commercial hydrophobic V 2O5-WO3/TiO2 powder (wherein the mass ratio of V 2O5-WO3/TiO2 is 1.9% -4.0%/94.1%) respectively, dispersing in 62 parts of dimethylformamide (DMF, CAS: 68-12-2) to form solution A, adding 3 parts of silica sol with the solid content of 40% into the solution A to form mixed solution B, grinding the mixed solution B for 2 hours by using a sand mill to obtain catalyst active powder slurry, dipping the dried modified cordierite skeleton in the catalyst active powder slurry for 10 minutes to obtain a catalyst precursor, and finishing dipping the hydrophobic modified catalyst active powder slurry;
vacuum drying, namely vacuum drying the catalyst precursor obtained in the step two at the temperature of 75 ℃ and the vacuum pressure of-0.03 MPa for 5 hours, wherein a condensing device is arranged on vacuum drying equipment, and the dried and volatilized condensed dimethylformamide (DMF, CAS: 68-12-2) is reused in the preparation of catalyst active powder slurry;
and step four, high-temperature roasting, namely roasting the catalyst precursor dried in the step three in a sintering furnace, wherein the highest roasting temperature is 550 ℃ and the highest roasting time is 2 hours.
Example 2
The preparation method of the high-airspeed SCR denitration catalyst for the gas generator set comprises the following steps of:
firstly, pre-treating a cordierite framework, namely selecting 80-pore modified cordierite honeycomb bodies as framework materials, wherein the outer dimensions of the 80-pore modified cordierite honeycomb bodies are 150mm, 150mm and 150mm, the chemical components of the 80-pore modified cordierite honeycomb bodies are a mixture of MgO, al 2O3 and SiO 2, the mass ratio of MgO, al 2O3 and SiO 2 is 5.5 percent to 13.5 percent to 81 percent, and the pore volume of the modified cordierite is 0.17ml/g;
60g of isopropyl di (dioctyl phosphite acyloxy) titanate is dissolved in 40g of deionized water to form titanate compound solution, a modified cordierite framework is soaked in the titanate compound solution for 2 hours, then the modified cordierite framework is taken out and dried for 3 hours under the environment of 110 ℃, and the pretreatment of the modified cordierite framework is completed;
Step two, dipping catalyst active powder slurry, namely weighing 35 parts of conventional commercial hydrophobic V 2O5-WO3/TiO2 powder (wherein the mass ratio of V 2O5-WO3/TiO2 is 1.9% -4.0%/94.1%) respectively, dispersing in 62 parts of dimethylformamide (DMF, CAS: 68-12-2) to form solution A, adding 3 parts of silica sol with the solid content of 40% into the solution A to form mixed solution B, grinding the mixed solution B for 2 hours by using a sand mill to obtain catalyst active powder slurry, dipping the dried modified cordierite skeleton in the catalyst active powder slurry for 10 minutes to obtain a catalyst precursor, and finishing dipping the hydrophobic modified catalyst active powder slurry;
Step three, vacuum drying, namely vacuum drying the catalyst precursor obtained in the step two, wherein the vacuum drying temperature is 75 ℃, the vacuum pressure is-0.03 MPa, and the vacuum drying is carried out for 5 hours;
And step four, high-temperature roasting, namely roasting the catalyst precursor dried in the step three in a sintering furnace, wherein the highest roasting temperature is 550 ℃, and the highest roasting time is 2 hours.
Comparative example 1
Firstly, pre-treating a cordierite framework, namely selecting 80-pore modified cordierite honeycomb bodies as framework materials, wherein the outer dimensions of the 80-pore modified cordierite honeycomb bodies are 150mm, 150mm and 150mm, the chemical components of the 80-pore modified cordierite honeycomb bodies are a mixture of MgO, al 2O3 and SiO 2, the mass ratio of MgO, al 2O3 and SiO 2 is 5.5 percent to 13.5 percent to 81 percent, and the pore volume of the modified cordierite is 0.17ml/g;
placing the modified cordierite framework in 100% deionized water for soaking time for 2 hours, then taking out the modified cordierite framework, and drying for 3 hours at 110 ℃ to complete pretreatment of the modified cordierite framework;
Step two, dipping catalyst active powder slurry, namely weighing 35 parts of conventional commercial hydrophobic V 2O5-WO3/TiO2 powder (wherein the mass ratio of V 2O5-WO3/TiO2 is 1.9% -4.0%/94.1%) respectively, dispersing in 62 parts of dimethylformamide (DMF, CAS: 68-12-2) to form solution A, adding 3 parts of silica sol with the solid content of 40% into the solution A to form mixed solution B, grinding the mixed solution B for 2 hours by using a sand mill to obtain catalyst active powder slurry, dipping the dried modified cordierite skeleton in the catalyst active powder slurry for 10 minutes to obtain a catalyst precursor, and finishing dipping the hydrophobic modified catalyst active powder slurry;
Step three, vacuum drying, namely vacuum drying the catalyst precursor obtained in the step two, wherein the vacuum drying temperature is 75 ℃, the vacuum pressure is-0.03 MPa, and the vacuum drying is carried out for 5 hours;
And step four, high-temperature roasting, namely roasting the catalyst precursor dried in the step three in a sintering furnace, wherein the highest roasting temperature is 550 ℃, and the highest roasting time is 2 hours.
Example 3
The preparation method of the high-airspeed SCR denitration catalyst for the gas generator set comprises the following steps of:
Firstly, pre-treating a cordierite framework, namely selecting 80-pore modified cordierite honeycomb bodies as framework materials, wherein the outer dimensions of the 80-pore modified cordierite honeycomb bodies are 150mm, 150mm and 150mm, the chemical components of the 80-pore modified cordierite honeycomb bodies are a mixture of MgO, al 2O3 and SiO 2, the mass ratio of MgO, al 2O3 and SiO 2 is 5.5 percent to 13.5 percent to 81 percent, and the pore volume of the modified cordierite is 0.17ml/g;
60g of isopropyl di (dioctyl phosphite acyloxy) titanate is dissolved in 20g of deionized water to form titanate compound solution, a modified cordierite framework is soaked in the titanate compound solution for 2 hours, then the modified cordierite framework is taken out and dried for 3 hours under the environment of 110 ℃, and the pretreatment of the modified cordierite framework is completed;
Step two, dipping catalyst active powder slurry, namely weighing 50 parts of conventional commercial hydrophobic V 2O5-WO3/TiO2 powder (wherein the mass ratio of V 2O5-WO3/TiO2 is 1.9% -4.0%/94.1%) respectively, dispersing in 49 parts of dimethylformamide (DMF, CAS: 68-12-2) to form solution A, adding 1 part of silica sol with the solid content of 40% into the solution A to form mixed solution B, grinding the mixed solution B for 2 hours by using a sand mill to obtain catalyst active powder slurry, dipping the dried modified cordierite skeleton in the catalyst active powder slurry for 10 minutes to obtain a catalyst precursor, and finishing dipping the hydrophobic modified catalyst active powder slurry;
Step three, vacuum drying, namely vacuum drying the catalyst precursor obtained in the step two, wherein the vacuum drying temperature is 75 ℃, the vacuum pressure is-0.03 MPa, and the vacuum drying is carried out for 5 hours;
And step four, high-temperature roasting, namely roasting the catalyst precursor dried in the step three in a sintering furnace, wherein the highest roasting temperature is 550 ℃, and the highest roasting time is 2 hours.
Example 4
The preparation method of the high-airspeed SCR denitration catalyst for the gas generator set comprises the following steps of:
Firstly, pre-treating a cordierite framework, namely selecting 80-pore modified cordierite honeycomb bodies as framework materials, wherein the outer dimensions of the 80-pore modified cordierite honeycomb bodies are 150mm, 150mm and 150mm, the chemical components of the 80-pore modified cordierite honeycomb bodies are a mixture of MgO, al 2O3 and SiO 2, the mass ratio of MgO, al 2O3 and SiO 2 is 5.5 percent to 13.5 percent to 81 percent, and the pore volume of the modified cordierite is 0.17ml/g;
60g of isopropyl trioleate acyloxy titanate is dissolved in 20g of deionized water to form titanate compound solution, a modified cordierite framework is soaked in the titanate compound solution for 2 hours, then the modified cordierite framework is taken out and dried for 3 hours under the environment of 110 ℃, and the pretreatment of the modified cordierite framework is completed;
Step two, dipping catalyst active powder slurry, namely weighing 50 parts of conventional commercial hydrophobic V 2O5-WO3/TiO2 powder (wherein the mass ratio of V 2O5-WO3/TiO2 is 1.9% -4.0%/94.1%) respectively, dispersing in 49 parts of dimethylformamide (DMF, CAS: 68-12-2) to form solution A, adding 1 part of silica sol with the solid content of 40% into the solution A to form mixed solution B, grinding the mixed solution B for 2 hours by using a sand mill to obtain catalyst active powder slurry, dipping the dried modified cordierite skeleton in the catalyst active powder slurry for 10 minutes to obtain a catalyst precursor, and finishing dipping the hydrophobic modified catalyst active powder slurry;
Step three, vacuum drying, namely vacuum drying the catalyst precursor obtained in the step two, wherein the vacuum drying temperature is 75 ℃, the vacuum pressure is-0.03 MPa, and the vacuum drying is carried out for 5 hours;
And step four, high-temperature roasting, namely roasting the catalyst precursor dried in the step three in a sintering furnace, wherein the highest roasting temperature is 550 ℃, and the highest roasting time is 2 hours.
Example 5
The preparation method of the high-airspeed SCR denitration catalyst for the gas generator set comprises the following steps of:
Firstly, pre-treating a cordierite framework, namely selecting 80-pore modified cordierite honeycomb bodies as framework materials, wherein the outer dimensions of the 80-pore modified cordierite honeycomb bodies are 150mm, and the chemical components of the 80-pore modified cordierite honeycomb bodies are a mixture of MgO, al 2O3 and SiO 2, the mass ratio of MgO, al 2O3 and SiO 2 is 5.5 percent to 13.5 percent to 81 percent, and the pore volume of the modified cordierite is 0.05ml/g;
60g of isopropyl trioleate acyloxy titanate is dissolved in 20g of deionized water to form titanate compound solution, a modified cordierite framework is soaked in the titanate compound solution for 2 hours, then the modified cordierite framework is taken out and dried for 3 hours under the environment of 110 ℃, and the pretreatment of the modified cordierite framework is completed;
Step two, dipping catalyst active powder slurry, namely weighing 50 parts of conventional commercial hydrophobic V 2O5-WO3/TiO2 powder (wherein the mass ratio of V 2O5-WO3/TiO2 is 1.9% -4.0%/94.1%) respectively, dispersing in 49 parts of dimethylformamide (DMF, CAS: 68-12-2) to form solution A, adding 1 part of silica sol with the solid content of 40% into the solution A to form mixed solution B, grinding the mixed solution B for 2 hours by using a sand mill to obtain catalyst active powder slurry, dipping the dried modified cordierite skeleton in the catalyst active powder slurry for 10 minutes to obtain a catalyst precursor, and finishing dipping the hydrophobic modified catalyst active powder slurry;
Step three, vacuum drying, namely vacuum drying the catalyst precursor obtained in the step two, wherein the vacuum drying temperature is 75 ℃, the vacuum pressure is-0.03 MPa, and the vacuum drying is carried out for 5 hours;
And step four, high-temperature roasting, namely roasting the catalyst precursor dried in the step three in a sintering furnace, wherein the highest roasting temperature is 550 ℃, and the highest roasting time is 2 hours.
Comparative example 2
Firstly, pre-treating a cordierite framework, namely selecting 80-pore modified cordierite honeycomb bodies as framework materials, wherein the outer dimensions of the 80-pore modified cordierite honeycomb bodies are 150mm, and the chemical components of the 80-pore modified cordierite honeycomb bodies are a mixture of MgO, al 2O3 and SiO 2, the mass ratio of MgO, al 2O3 and SiO 2 is 5.5 percent to 13.5 percent to 81 percent, and the pore volume of the modified cordierite is 0.05ml/g;
60g of isopropyl trioleate acyloxy titanate is dissolved in 20g of deionized water to form titanate compound solution, a modified cordierite framework is soaked in the titanate compound solution for 2 hours, then the modified cordierite framework is taken out and dried for 3 hours under the environment of 110 ℃, and the pretreatment of the modified cordierite framework is completed;
Step two, dipping catalyst active powder slurry, namely weighing 50 parts of conventional commercial hydrophilic V 2O5-WO3/TiO2 powder (wherein the mass ratio of V 2O5-WO3/TiO2 is 1.9% -4.0%/94.1%) and dispersing in 49 parts of deionized water to form solution A, adding 1 part of silica sol with the solid content of 40% into the solution A to form mixed solution B, grinding the mixed solution B for 2 hours by using a sand mill to obtain catalyst active powder slurry, dipping the dried modified cordierite skeleton in the catalyst active powder slurry for 10 minutes to obtain a catalyst precursor, and finishing dipping the hydrophobic modified catalyst active powder slurry;
Step three, vacuum drying, namely vacuum drying the catalyst precursor obtained in the step two, wherein the vacuum drying temperature is 75 ℃, the vacuum pressure is-0.03 MPa, and the vacuum drying is carried out for 5 hours;
And step four, high-temperature roasting, namely roasting the catalyst precursor dried in the step three in a sintering furnace, wherein the highest roasting temperature is 550 ℃, and the highest roasting time is 2 hours.
Example 6
The preparation method of the high-airspeed SCR denitration catalyst for the gas generator set comprises the following steps of:
Firstly, pretreating a cordierite framework, namely selecting 108-pore modified cordierite honeycomb bodies as framework materials, wherein the external dimensions of the 108-pore modified cordierite honeycomb bodies are 150mm, 150mm and 150mm, the chemical components of the modified cordierite honeycomb bodies are a mixture of MgO, al 2O3 and SiO 2, the mass ratio of MgO, al 2O3 and SiO 2 is 5.5 percent to 13.5 percent to 81 percent, and the pore volume of the modified cordierite is 0.05ml/g;
60g of isopropyl trioleate acyloxy titanate is dissolved in 20g of deionized water to form titanate compound solution, a modified cordierite framework is soaked in the titanate compound solution for 2 hours, then the modified cordierite framework is taken out and dried for 3 hours under the environment of 110 ℃, and the pretreatment of the modified cordierite framework is completed;
Step two, dipping catalyst active powder slurry, namely weighing 50 parts of conventional commercial hydrophobic V 2O5-WO3/TiO2 powder (wherein the mass ratio of V 2O5-WO3/TiO2 is 1.9% -4.0%/94.1%) respectively, dispersing in 49 parts of dimethylformamide (DMF, CAS: 68-12-2) to form solution A, adding 1 part of silica sol with the solid content of 40% into the solution A to form mixed solution B, grinding the mixed solution B for 2 hours by using a sand mill to obtain catalyst active powder slurry, dipping the dried modified cordierite skeleton in the catalyst active powder slurry for 10 minutes to obtain a catalyst precursor, and finishing dipping the hydrophobic modified catalyst active powder slurry;
Step three, vacuum drying, namely vacuum drying the catalyst precursor obtained in the step two, wherein the vacuum drying temperature is 75 ℃, the vacuum pressure is-0.03 MPa, and the vacuum drying is carried out for 5 hours;
And step four, high-temperature roasting, namely roasting the catalyst precursor dried in the step three in a sintering furnace, wherein the highest roasting temperature is 550 ℃, and the highest roasting time is 2 hours.
Description of the above comparative examples:
(1) Comparative example 1 in comparison with examples 1 and 2, the pretreatment solutions for the modified cordierite skeleton of examples 1 and 2 were changed from titanate-based solutions to deionized water of comparative example 1;
(2) Comparative example 2 in comparison with example 5, the hydrophobe V 2O5-WO3/TiO2 powder in example 5 (wherein the V 2O5-WO3/TiO2 mass ratio is 1.9% -4.0%/94.1%, respectively) and the organic solvent dimethylformamide (DMF, CAS: 68-12-2) were replaced with the hydrophilic V 2O5-WO3/TiO2 powder in comparative example 2 (wherein the V 2O5-WO3/TiO2 mass ratio is 1.9% -4.0%/94.1%, respectively) and deionized water.
Description of the above embodiments:
(1) Examples 1 and 2. Compared with the example 1, the example 2 reduces the content of titanate mixture in the modified cordierite skeleton titanate pretreatment liquid in the step one;
(2) Example 2 and example 3. Example 3 increased the level of hydrophobic-based catalyst active powder in the catalyst active powder slurry of step two compared to example 2;
(3) Examples 3 and 4. Compared with example 3, example 4 is characterized in that isopropyl di (dioctyl phosphite acyloxy) titanate in the modified cordierite skeleton titanate pretreatment liquid in the step one of example 3 is replaced by isopropyl trioleate acyloxy titanate;
(4) Examples 4 and 5. Example 5 reduced the pore volume of the modified cordierite framework in step one of example 4 compared to example 4;
(5) Example 6 and example 5. Example 6 compared to example 5, the number of pores of the modified cordierite skeleton was increased from 80 to 108 pores.
Referring to a detection method of denitration activity in DL/T1286-2021 technical Specification for detection of flue gas denitration catalyst in a thermal power plant, wherein the test working condition of denitration activity is that the flue gas temperature is 350 ℃, the catalyst test airspeed is 150000h -, the catalyst test area speed is 23m/h, the test inlet NOx concentration is 500mg/Nm 3, and the test inlet SO2 concentration is 6500mg/Nm 3.
The method for detecting the mass shedding rate of the catalytic layer in XB/T607-2011 'experimental method for coating materials for purifying exhaust catalysts of gasoline vehicles'.
The performance indexes of the catalysts prepared in the above examples and comparative examples are shown below:
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