CN106902809B - Reproducible SCR catalyst and preparation method thereof - Google Patents
Reproducible SCR catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN106902809B CN106902809B CN201710237645.0A CN201710237645A CN106902809B CN 106902809 B CN106902809 B CN 106902809B CN 201710237645 A CN201710237645 A CN 201710237645A CN 106902809 B CN106902809 B CN 106902809B
- Authority
- CN
- China
- Prior art keywords
- reproducible
- powder
- scr catalyst
- temperature
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000011148 porous material Substances 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 230000006835 compression Effects 0.000 claims abstract description 19
- 238000007906 compression Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000004321 preservation Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 230000001413 cellular effect Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 7
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 239000003546 flue gas Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000012495 reaction gas Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/61—
-
- B01J35/64—
-
- 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
Abstract
The present invention discloses a kind of preparation method of reproducible SCR catalyst.Include the following steps: to take Ti powder, W powder, V powder, and be by mass percentage (70-80): (10-20): (5-10) mixing；Addition accounts for the medium temperature pore creating material of total weight 10-20% and accounts for the high temperature pore creating material of total weight 5-10%；Cellular carrier blank is made in mixture；Carrier blank is successively carried out to low temperature, medium temperature, hot stage roasting heat preservation method in vacuum calcining furnace；Cool down under vacuum conditions with furnace, when temperature is reduced to 450-500 DEG C, air is passed through into furnace, makes the Surface Creation oxidation film of carrier blank；60-120min is kept the temperature under 450-500 DEG C of vacuum state, obtains reproducible SCR catalyst.The preparation method of reproducible SCR catalyst provided by the invention, the catalyst being prepared have the advantages that compression strength is high, porosity is big, reproducible.The present invention also provides a kind of reproducible SCR catalysts being prepared by the preparation method.
Description
[technical field]
The present invention relates to field of material technology, and in particular to a kind of reproducible SCR catalyst and preparation method thereof.
[background technique]
The principle of selective catalytic reduction (Selective Catalytic Reduction, SCR) is made in catalyst
Under, reducing agent NH3Selectively by NO and NO at 290-400 DEG C2It is reduced into N2, and hardly happen NH3With O2Oxidation
Reaction, to improve N2Selectivity, reduce NH3Consumption.
Catalyst is the key that entire SCR system, and the design and selection of catalyst are determined by flue gas condition, component
, the factor for influencing three interactions of its design is NOxRemoval efficiency, NH3Escapement ratio and catalyst volume.
In the related technology, the active constituent of SCR catalyst is V2O5, carrier is the TiO of Detitanium-ore-type2, WO3Or MoO3It helps
Urge agent.SCR catalyst ingredient and ratio are different according to the difference of component content in flue gas and denitration performance guarantee value.Its
In, catalyst carrier primarily serves support, dispersion, the effect of stabilizing active ingredient, and structure is mainly honeycomb structure, has
The characteristic that large specific surface area, activity are high, carrier itself is catalyst, with good application prospect.
However, honeycombed catalyst in the related technology, main active V2O5、WO3Or MoO3All be by physics or
It is chemisorbed on catalyst support surface, after being catalyzed reaction, sweep of gases for a long time, catalyst active component compares regular meeting
It is lower and lower, so catalyst needs to carry out catalyst regeneration after general 1 to 2 years；And low, the anti-impact brush wear energy with mechanical strength
The low disadvantage of power, will affect the application effect of catalyst.
Therefore, it is necessary to provide a kind of new technique solution above-mentioned technical problem.
[summary of the invention]
The purpose of the present invention is overcoming above-mentioned technical problem, a kind of preparation method of reproducible SCR catalyst is provided, is made
Standby obtained catalyst has the advantages that compression strength is high, porosity is big, reproducible.
The technical scheme is that
A kind of preparation method of reproducible SCR catalyst, includes the following steps:
Step S1: taking the W powder that Ti powder, partial size that partial size is 10-50 μm are 10-50 μm, the V powder that partial size is 10-50 μm, and
Ti powder by mass percentage: W powder: V powder=(70-80): (10-20): (5-10) mixing；
Step S2: addition accounts for the medium temperature pore creating material of total weight 10-20% and accounts for the high temperature pore creating material of total weight 5-10%, and
It is uniformly mixed；Wherein total weight be Ti powder, W powder, V powder, medium temperature pore creating material and high temperature pore creating material quality and；
Step S3: cellular carrier blank is made in mixture；
Step S4: carrier blank after molding is successively carried out to low temperature, medium temperature, hot stage roasting in vacuum calcining furnace
Heat preservation method: from room temperature to 105 DEG C, 5 DEG C/min of heating rate, and in 105 DEG C of 30~60min of heat preservation；From 105 DEG C to 500 DEG C,
5~10 DEG C/min of heating rate keeps the temperature 60~120min at 500 DEG C；From 500 DEG C to 1000 DEG C, 2~5 DEG C of heating rate/
Min, in 1000 DEG C of 60~120min of heat preservation；
Step S5: cooling down with furnace under vacuum conditions, and when temperature is reduced to 450-500 DEG C, vacuum state is converted to
It is passed through air into furnace, makes the Surface Creation oxidation film of carrier blank；
Step S6: after oxidation and sinter technique, 60-120min is kept the temperature under 450-500 DEG C of vacuum state, is obtained renewable
SCR catalyst.
Preferably, the vacuum degree in the vacuum calcining furnace is 1.0 × 10-2Pa-1.0×10-1Pa。
Preferably, in the step S2, the medium temperature pore creating material is one of PEG200, PEG400, AEO-3, glycerol
Or two kinds.
Preferably, the high temperature pore creating material is nano-calcium carbonate calcium powder, partial size 50-100nm.
Preferably, in the step S5, the thickness of the oxidation film is passed through time control by air, with a thickness of 20-60 μ
m。
The present invention provides a kind of reproducible SCR catalyst, is prepared by the preparation method of the reproducible SCR catalyst
It obtains.
Preferably, the porosity of the reproducible SCR catalyst is 60-80%, and aperture is 50-100 μm.
Preferably, the reproducible SCR catalyst is greater than 8MPa in 300 DEG C of compression strength, in 400 DEG C of pressure resistance
Degree is greater than 4MPa.
Compared with the relevant technologies, reproducible SCR catalyst provided by the invention and preparation method thereof has following beneficial
Effect:
One, the present invention is using Ti, W, V as primary raw material, and the pore creating material of medium and high temperature different decomposition temperature is added, and passes through tune
The parameter in proportion and processing technology between whole each material composition, making the catalyst being prepared both has good pressure resistance
Degree and flushing resistance, show as being greater than 8MPa in 300 DEG C of compression strength, are greater than 4MPa in 400 DEG C of compression strength, simultaneously
Also there is biggish porosity, showing as porosity is 60-80%, and aperture is 50-100 μm, because of its large specific surface area, thus
The performance of catalyst can be improved.
Two, the preparation method provided through the invention, the catalyst surface being prepared have layer oxide film, the oxidation
The main component of film is the oxide of tri- kinds of elements of Ti, W, V, the especially V of the active constituent of SCR catalyst2O5、WO3.Make
With in the process, surface catalyst active constituent V is caused due to being catalyzed a variety of causes such as reaction, sweep of gases, soot blowing2O5、WO3Subtract
Thin or after falling off, in high-temperature flue gas under the oxidation of oxygen, V, W metal can regenerate active constituent V2O5、WO3, and it is raw
It is proportional to be fully equivalent to former design proportion, make the SCR catalyst Regenrable catalyzed, thus reduce its use at
This.
Three, the reproducible SCR catalyst that the present invention is prepared, the thickness of surface film oxide being passed through by air
Time controls at 20-60 μm, further increases the performance of the reproducible SCR catalyst.
Four, the reproducible SCR catalyst that the present invention is prepared has the characteristics that resistant to high temperature, can be acidproof up to 500 DEG C
Caustic corrosion, long service life.
[specific embodiment]
It below will the invention will be further described by specific embodiment.
Embodiment one
A kind of preparation method of reproducible SCR catalyst, includes the following steps:
Step S1: taking the W powder that Ti powder, partial size that partial size is 10-50 μm are 10-50 μm, the V powder that partial size is 10-50 μm, and
It is calculated by mass percentage, Ti powder 70%, W powder 20%, V powder 10% is added, and be uniformly mixed；
Step S2: addition accounts for the medium temperature pore creating material of total weight 10% and accounts for the high temperature pore creating material of total weight 5%, and mixes equal
It is even；Wherein total weight be Ti powder, W powder, V powder, medium temperature pore creating material and high temperature pore creating material quality and；
Specifically, medium temperature pore creating material is one or both of PEG200, PEG400, AEO-3, glycerol, made for high temperature
Hole agent is nano-calcium carbonate calcium powder, partial size 50-100nm.
Step S3: cellular carrier blank is made in mixture；
Step S4: carrier blank after molding is successively carried out to low temperature, medium temperature, hot stage roasting in vacuum calcining furnace
Heat preservation method: from room temperature to 105 DEG C, 5 DEG C/min of heating rate, and in 105 DEG C of heat preservation 30min；From 105 DEG C to 500 DEG C, heating
8 DEG C/min of speed, keeps the temperature 120min at 500 DEG C；From 500 DEG C to 1000 DEG C, 2 DEG C/min of heating rate is kept the temperature at 1000 DEG C
100min；
Vacuum degree in the vacuum calcining furnace is 1.0 × 10-2Pa；
Step S5: cooling down with furnace under vacuum conditions, and when temperature is reduced to 450-500 DEG C, vacuum state is converted to
It is passed through air into furnace, makes the Surface Creation oxidation film of carrier blank；
Specifically, it is 5-10min that control air, which is passed through the time, make 20-60 μm of oxide thickness generated；
Step S6: after oxidation and sinter technique, 60min is kept the temperature under 450-500 DEG C of vacuum state, is obtained reproducible
SCR catalyst, wherein vacuum degree is 1.0 × 10-2Pa。
Through detecting, the porosity of the reproducible SCR catalyst is 72%, and aperture is 50-100 μm；It can be again by described in
Raw SCR catalyst carries out intensity test, test result under condition of different temperatures are as follows: reaches in 300 DEG C of compression strength
8.7MPa reaches 4.4MPa in 400 DEG C of compression strength.
The reproducible SCR catalyst is applied to denitrification test, specific test method and result are as follows:
The reaction temperature of simulated flue gas in the catalyst is arranged at 350 DEG C, because temperature is that existing coal-burning boiler SCR is anti-thus
It answers in temperature range.In denitrification test, reaction gas composition are as follows: 750ppmNO, 900ppmNH3, 5%O2, 750ppmSO2, N2Make
For Balance Air, gas flow 1.5L/min.The removal efficiency of NO is 95.5%.
Embodiment two
A kind of preparation method of reproducible SCR catalyst, includes the following steps:
Step S1: taking the W powder that Ti powder, partial size that partial size is 10-50 μm are 10-50 μm, the V powder that partial size is 10-50 μm, and
It is calculated by mass percentage, Ti powder 75%, W powder 20%, V powder 5% is added, and be uniformly mixed；
Step S2: addition accounts for the medium temperature pore creating material of total weight 20% and accounts for the high temperature pore creating material of total weight 10%, and mixes
Uniformly；Wherein total weight be Ti powder, W powder, V powder, medium temperature pore creating material and high temperature pore creating material quality and；
Specifically, medium temperature pore creating material is one or both of PEG200, PEG400, AEO-3, glycerol, made for high temperature
Hole agent is nano-calcium carbonate calcium powder, partial size 50-100nm.
Step S3: cellular carrier blank is made in mixture；
Step S4: carrier blank after molding is successively carried out to low temperature, medium temperature, hot stage roasting in vacuum calcining furnace
Heat preservation method: from room temperature to 105 DEG C, 5 DEG C/min of heating rate, and in 105 DEG C of heat preservation 60min；From 105 DEG C to 500 DEG C, heating
5 DEG C/min of speed, keeps the temperature 60min at 500 DEG C；From 500 DEG C to 1000 DEG C, 3 DEG C/min of heating rate is kept the temperature at 1000 DEG C
80min；
Vacuum degree in the vacuum calcining furnace is 1.0 × 10-1Pa；
Step S5: cooling down with furnace under vacuum conditions, and when temperature is reduced to 500 DEG C, vacuum state is converted to furnace
It is inside passed through air, makes the Surface Creation oxidation film of carrier blank；
Specifically, it is 5-10min that control air, which is passed through the time, make 20-60 μm of oxide thickness generated；
Step S6: after oxidation and sinter technique, 60min is kept the temperature under 450-500 DEG C of vacuum state, is obtained reproducible
SCR catalyst, wherein vacuum degree is 1.0 × 10-1Pa。
Through detecting, the porosity of the reproducible SCR catalyst is 74%, and aperture is 50-100 μm；It can be again by described in
Raw SCR catalyst carries out intensity test, test result under condition of different temperatures are as follows: reaches in 300 DEG C of compression strength
9MPa reaches 4.8MPa in 400 DEG C of compression strength.
The reproducible SCR catalyst is applied to denitrification test, specific test method and result are as follows:
The reaction temperature of simulated flue gas in the catalyst is arranged at 350 DEG C, because temperature is that existing coal-burning boiler SCR is anti-thus
It answers in temperature range.In denitrification test, reaction gas composition are as follows: 750ppmNO, 900ppmNH3, 5%O2, 750ppmSO2, N2Make
For Balance Air, gas flow 1.5L/min.The removal efficiency of NO is 95.7%.
Embodiment three
A kind of preparation method of reproducible SCR catalyst, includes the following steps:
Step S1: taking the W powder that Ti powder, partial size that partial size is 10-50 μm are 10-50 μm, the V powder that partial size is 10-50 μm, and
It is calculated by mass percentage, Ti powder 80%, W powder 15%, V powder 5% is added, and be uniformly mixed；
Step S2: addition accounts for the medium temperature pore creating material of total weight 12% and accounts for the high temperature pore creating material of total weight 8%, and mixes equal
It is even；Wherein total weight be Ti powder, W powder, V powder, medium temperature pore creating material and high temperature pore creating material quality and；
Specifically, medium temperature pore creating material is one or both of PEG200, PEG400, AEO-3, glycerol, made for high temperature
Hole agent is nano-calcium carbonate calcium powder, partial size 50-100nm.
Step S3: cellular carrier blank is made in mixture；
Step S4: carrier blank after molding is successively carried out to low temperature, medium temperature, hot stage roasting in vacuum calcining furnace
Heat preservation method: from room temperature to 105 DEG C, 5 DEG C/min of heating rate, and in 105 DEG C of heat preservation 40min；From 105 DEG C to 500 DEG C, heating
10 DEG C/min of speed, keeps the temperature 100min at 500 DEG C；From 500 DEG C to 1000 DEG C, 5 DEG C/min of heating rate is kept the temperature at 1000 DEG C
120min；
Vacuum degree in the vacuum calcining furnace is 1.0 × 10-2Pa；
Step S5: cooling down with furnace under vacuum conditions, and when temperature is reduced to 450 DEG C, vacuum state is converted to furnace
It is inside passed through air, makes the Surface Creation oxidation film of carrier blank；
Specifically, it is 5-10min that control air, which is passed through the time, make 20-60 μm of oxide thickness generated；
Step S6: after oxidation and sinter technique, 60min is kept the temperature under 450-500 DEG C of vacuum state, is obtained reproducible
SCR catalyst, wherein vacuum degree is 1.0 × 10-2Pa。
Through detecting, the porosity of the reproducible SCR catalyst is 65%, and aperture is 50-100 μm；It can be again by described in
Raw SCR catalyst carries out intensity test, test result under condition of different temperatures are as follows: reaches in 300 DEG C of compression strength
8.2MPa reaches 4MPa in 500 DEG C of compression strength.
The reproducible SCR catalyst is applied to denitrification test, specific test method and result are as follows:
The reaction temperature of simulated flue gas in the catalyst is arranged at 350 DEG C, because temperature is that existing coal-burning boiler SCR is anti-thus
It answers in temperature range.In denitrification test, reaction gas composition are as follows: 750ppmNO, 900ppmNH3, 5%O2, 750ppmSO2, N2 work
For Balance Air, gas flow 1.5L/min.The removal efficiency of NO is 95.2%.
Example IV
A kind of preparation method of reproducible SCR catalyst, includes the following steps:
Step S1: taking the W powder that Ti powder, partial size that partial size is 10-50 μm are 10-50 μm, and partial size is 10-50 μm of V, and presses
Mass percent calculates, and Ti powder 72%, W powder 10%, V powder 8% is added, and be uniformly mixed；
Step S2: addition accounts for the medium temperature pore creating material of total weight 15% and accounts for the high temperature pore creating material of total weight 7%, and mixes equal
It is even；Wherein total weight be Ti powder, W powder, V powder, medium temperature pore creating material and high temperature pore creating material quality and；
Specifically, medium temperature pore creating material is one or both of PEG200, PEG400, AEO-3, glycerol, made for high temperature
Hole agent is nano-calcium carbonate calcium powder, partial size 50-100nm.
Step S3: cellular carrier blank is made in mixture；
Step S4: carrier blank after molding is successively carried out to low temperature, medium temperature, hot stage roasting in vacuum calcining furnace
Heat preservation method: from room temperature to 105 DEG C, 5 DEG C/min of heating rate, and in 105 DEG C of heat preservation 50min；From 105 DEG C to 500 DEG C, heating
7 DEG C/min of speed, keeps the temperature 80min at 500 DEG C；From 500 DEG C to 1000 DEG C, 4 DEG C/min of heating rate is kept the temperature at 1000 DEG C
60min；
Vacuum degree in the vacuum calcining furnace is 1.0 × 10-2Pa；
Step S5: cooling down with furnace under vacuum conditions, and when temperature is reduced to 480 DEG C, vacuum state is converted to furnace
It is inside passed through air, makes the Surface Creation oxidation film of carrier blank；
Specifically, it is 5-10min that control air, which is passed through the time, make 20-60 μm of oxide thickness generated.
Step S6: after oxidation and sinter technique, 100min is kept the temperature under 450-500 DEG C of vacuum state, is obtained reproducible
SCR catalyst, wherein vacuum degree is 1.0 × 10-2Pa。
Through detecting, the porosity of the reproducible SCR catalyst is 80%, and aperture is 50-100 μm；It can be again by described in
Raw SCR catalyst carries out intensity test, test result under condition of different temperatures are as follows: reaches in 300 DEG C of compression strength
10MPa reaches 5.2MPa in 500 DEG C of compression strength.
The reproducible SCR catalyst is applied to denitrification test, specific test method and result are as follows:
The reaction temperature of simulated flue gas in the catalyst is arranged at 350 DEG C, because temperature is that existing coal-burning boiler SCR is anti-thus
It answers in temperature range.In denitrification test, reaction gas composition are as follows: 750ppmNO, 900ppmNH3, 5%O2, 750ppmSO2, N2Make
For Balance Air, gas flow 1.5L/min.The removal efficiency of NO is 96.2%.
Embodiment five
A kind of preparation method of reproducible SCR catalyst, includes the following steps:
Step S1: taking the W powder that Ti powder, partial size that partial size is 10-50 μm are 10-50 μm, the V powder that partial size is 10-50 μm, and
It is calculated by mass percentage, Ti powder 76%, W powder 17%, V powder 7% is added, and be uniformly mixed；
Step S2: addition accounts for the medium temperature pore creating material of total weight 18% and accounts for the high temperature pore creating material of total weight 6%, and mixes equal
It is even；Wherein total weight be Ti powder, W powder, V powder, medium temperature pore creating material and high temperature pore creating material quality and；
Specifically, medium temperature pore creating material is one or both of PEG200, PEG400, AEO-3, glycerol, made for high temperature
Hole agent is nano-calcium carbonate calcium powder, partial size 50-100nm.
Step S3: cellular carrier blank is made in mixture；
Step S4: carrier blank after molding is successively carried out to low temperature, medium temperature, hot stage roasting in vacuum calcining furnace
Heat preservation method: from room temperature to 105 DEG C, 5 DEG C/min of heating rate, and in 105 DEG C of heat preservation 50min；From 105 DEG C to 500 DEG C, heating
6 DEG C/min of speed, keeps the temperature 110min at 500 DEG C；From 500 DEG C to 1000 DEG C, 3 DEG C/min of heating rate is kept the temperature at 1000 DEG C
90min；
Vacuum degree in the vacuum calcining furnace is 1.0 × 10-2Pa；
Step S5: cooling down with furnace under vacuum conditions, and when temperature is reduced to 460 DEG C, vacuum state is converted to furnace
It is inside passed through air, makes the Surface Creation oxidation film of carrier blank；
Specifically, it is 5-10min that control air, which is passed through the time, make 20-60 μm of oxide thickness generated.
Step S6: after oxidation and sinter technique, 120min is kept the temperature under 450-500 DEG C of vacuum state, is obtained reproducible
SCR catalyst, wherein vacuum degree is 1.0 × 10-2Pa。
Through detecting, the porosity of the reproducible SCR catalyst is 78%, and aperture is 50-100 μm；It can be again by described in
Raw SCR catalyst carries out intensity test, test result under condition of different temperatures are as follows: reaches in 300 DEG C of compression strength
9.7MPa reaches 5MPa in 500 DEG C of compression strength.
The reproducible SCR catalyst is applied to denitrification test, specific test method and result are as follows:
The reaction temperature of simulated flue gas in the catalyst is arranged at 350 DEG C, because temperature is that existing coal-burning boiler SCR is anti-thus
It answers in temperature range.In denitrification test, reaction gas composition are as follows: 750ppmNO, 900ppmNH3, 5%O2, 750ppmSO2, N2Make
For Balance Air, gas flow 1.5L/min.The removal efficiency of NO is 95.8%.
Compared with the relevant technologies, reproducible SCR catalyst provided by the invention and preparation method thereof has following beneficial
Effect:
One, the present invention is using Ti, W, V as primary raw material, and the pore creating material of medium and high temperature different decomposition temperature is added, and passes through tune
The parameter in proportion and processing technology between whole each material composition, making the catalyst being prepared both has good pressure resistance
Degree and flushing resistance, show as being greater than 8MPa in 300 DEG C of compression strength, are greater than 4MPa in 400 DEG C of compression strength, simultaneously
Also there is biggish porosity, showing as porosity is 60-80%, and aperture is 50-100 μm, because of its large specific surface area, thus
The performance of catalyst can be improved.
Two, the preparation method provided through the invention, the catalyst surface being prepared have layer oxide film, the oxidation
The main component of film is the oxide of tri- kinds of elements of Ti, W, V, the especially V of the active constituent of SCR catalyst2O5、WO3.Make
With in the process, surface catalyst active constituent V is caused due to being catalyzed a variety of causes such as reaction, sweep of gases, soot blowing2O5、WO3Subtract
Thin or after falling off, in high-temperature flue gas under the oxidation of oxygen, V, W metal can regenerate active constituent V2O5、WO3, and it is raw
It is proportional to be fully equivalent to former design proportion, make the SCR catalyst Regenrable catalyzed, thus reduce its use at
This.
Three, the reproducible SCR catalyst that the present invention is prepared, the thickness of surface film oxide being passed through by air
Time controls at 20-60 μm, further increases the performance of the reproducible SCR catalyst.
Four, the reproducible SCR catalyst that the present invention is prepared has the characteristics that resistant to high temperature, can be acidproof up to 500 DEG C
Caustic corrosion, long service life.
Above-described is only embodiments of the present invention, it should be noted here that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, improvement can also be made, but these belong to protection model of the invention
It encloses.
Claims (7)
1. a kind of preparation method of reproducible SCR catalyst, which comprises the steps of:
Step S1: the W powder that Ti powder, partial size that partial size is 10-50 μm are 10-50 μm, the V powder that partial size is 10-50 μm are taken, and presses matter
Measure percentage Ti powder: W powder: V powder=(70-80): (10-20): (5-10) mixing；
Step S2: addition accounts for the medium temperature pore creating material of total weight 10-20% and accounts for the high temperature pore creating material of total weight 5-10%, and mixes
Uniformly；Wherein total weight be Ti powder, W powder, V powder, medium temperature pore creating material and high temperature pore creating material quality and；The medium temperature pore creating material is
One or both of PEG200, PEG400, AEO-3, glycerol；The high temperature pore creating material is nano-calcium carbonate calcium powder；
Step S3: cellular carrier blank is made in mixture；
Step S4: carrier blank after molding is successively carried out to low temperature, medium temperature, hot stage roasting heat preservation in vacuum calcining furnace
Technique: from room temperature to 105 DEG C, 5 DEG C/min of heating rate, and in 105 DEG C of 30~60min of heat preservation；From 105 DEG C to 500 DEG C, heating
5~10 DEG C/min of speed keeps the temperature 60~120min at 500 DEG C；From 500 DEG C to 1000 DEG C, 2~5 DEG C/min of heating rate,
1000 DEG C of 60~120min of heat preservation；
Step S5: cooling down with furnace under vacuum conditions, and when temperature is reduced to 450-500 DEG C, vacuum state is converted to furnace
It is inside passed through air, makes the Surface Creation oxidation film of carrier blank；
Step S6: after oxidation and sinter technique, 60-120min is kept the temperature under 450-500 DEG C of vacuum state, is obtained reproducible
SCR catalyst.
2. the preparation method of reproducible SCR catalyst according to claim 1, which is characterized in that the vacuum calcining
Vacuum degree in furnace is 1.0 × 10-2Pa-1.0×10-1Pa。
3. the preparation method of reproducible SCR catalyst according to claim 1, which is characterized in that the high temperature pore-creating
The partial size of agent is 50-100nm.
4. the preparation method of reproducible SCR catalyst according to claim 1, which is characterized in that in the step S5,
The thickness of the oxidation film is passed through time control by air, with a thickness of 20-60 μm.
5. a kind of reproducible SCR catalyst, which is characterized in that by reproducible SCR of any of claims 1-4
The preparation method of catalyst is prepared.
6. reproducible SCR catalyst according to claim 5, which is characterized in that the reproducible SCR catalyst
Porosity is 60-80%, and aperture is 50-100 μm.
7. reproducible SCR catalyst according to claim 5, which is characterized in that the reproducible SCR catalyst exists
300 DEG C of compression strength is greater than 8MPa, is greater than 4MPa in 400 DEG C of compression strength.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710237645.0A CN106902809B (en) | 2017-04-12 | 2017-04-12 | Reproducible SCR catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710237645.0A CN106902809B (en) | 2017-04-12 | 2017-04-12 | Reproducible SCR catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106902809A CN106902809A (en) | 2017-06-30 |
| CN106902809B true CN106902809B (en) | 2019-08-27 |
Family
ID=59194816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710237645.0A Active CN106902809B (en) | 2017-04-12 | 2017-04-12 | Reproducible SCR catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106902809B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115282973A (en) * | 2022-08-11 | 2022-11-04 | 中国科学院上海高等研究院 | 3D printing-based monolithic catalyst, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1936045A (en) * | 2005-09-22 | 2007-03-28 | 中南大学 | Three-dimensional through-hole or part-hole interconnecting porous metal foam and its preparing method |
| CN105126887A (en) * | 2015-08-21 | 2015-12-09 | 成都易态科技有限公司 | Catalyst support body and preparation method and application thereof |
-
2017
- 2017-04-12 CN CN201710237645.0A patent/CN106902809B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1936045A (en) * | 2005-09-22 | 2007-03-28 | 中南大学 | Three-dimensional through-hole or part-hole interconnecting porous metal foam and its preparing method |
| CN105126887A (en) * | 2015-08-21 | 2015-12-09 | 成都易态科技有限公司 | Catalyst support body and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106902809A (en) | 2017-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105289648B (en) | A kind of spherical low-temperature denitration of flue gas catalyst and preparation method and application | |
| CN104646022B (en) | A kind of honeycomb fashion low-temperature denitration catalyst and preparation method thereof | |
| CN106140143B (en) | A kind of non-homogeneous honeycomb type denitrating catalyst and preparation method thereof | |
| CN103240078B (en) | Wear-resistant SCR (Selective Catalytic Reduction) denitration catalyst and preparation method thereof | |
| CN103301863B (en) | Steel-slag-based selective catalytic reduction (SCR) denitration catalyst and preparation method thereof | |
| CN102728346B (en) | MnO2-TiO2 carbon nanotube-porous inorganic ceramic membrane low-temperature catalytic denitrification self-cleaning material and its preparation method | |
| CN105536884B (en) | Regeneration method of waste denitration catalyst selectively implanted with active ingredients | |
| CN114570435A (en) | Honeycomb catalyst and preparation method and application thereof | |
| CN106902809B (en) | Reproducible SCR catalyst and preparation method thereof | |
| CN103657632A (en) | Alkali liquor treated integral chrome oxide catalyst, preparation method and application | |
| CN103866151A (en) | Preparation method of foaming stainless steel plate, and preparation method of heat-engine plant denitration catalyst | |
| CN102886255B (en) | MnO2-TiO2-carbon nano tube porous inorganic ceramic membrane low-temperature denitration catalyst and preparation method thereof | |
| CN103433081A (en) | Regeneration method for honeycomb type SCR (Selective Catalytic Reduction) denitration catalyst | |
| CN113750783A (en) | Method of two-section type SCR reaction device suitable for wide-temperature-zone denitration | |
| CN105148941A (en) | Regeneration impregnation liquid and regeneration technology for vanadium-titanium honeycomb type denitrification catalyst | |
| CN109759078B (en) | Gamma-Fe load 2 O 3 Preparation method of molded SCR catalyst | |
| CN104324591A (en) | Method for removing nitric oxide in coking process | |
| CN106914252B (en) | Porous material is the SCR catalyst and preparation method thereof of carrier between TiFeAl metal | |
| CN112473683B (en) | Powder sintering filtering catalytic material based on gradient pore structure and preparation method thereof | |
| CN103406127A (en) | Non-toxic low-temperature denitrating catalytic catalyst and preparation method thereof | |
| CN105498789B (en) | A kind of flexible fibreglass base catalyst for VOCs catalysis burnings and its preparation method and application | |
| CN106902841B (en) | Porous material supporter and preparation method thereof between TiFe metal | |
| CN103990448A (en) | Monolithic chromium oxide catalyst as well as preparation method and application thereof | |
| CN103433051A (en) | Honeycombed SCR denitration catalyst and preparation method thereof | |
| CN104772039B (en) | A kind of coke oven combustion exhaust gas denitration system and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190806 Address after: 318027 No. 13 Jinniu Road, Xinqian Development Zone, Huangyan District, Taizhou City, Zhejiang Province Applicant after: TAIZHOU THREE-WAY VEHICLE CATALYTIC CONVERTER Co.,Ltd. Address before: 410205 Room 3219, Pixel Building, 109 Guyuan Road, Changsha High-tech Development Zone, Hunan Province Applicant before: HUNAN YUNPING ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No.3 Shuangnan Village, Toutuo Town, Huangyan District, Taizhou City, Zhejiang Province, 318020 Patentee after: Zhejiang Sanyuan Longxing Technology Co.,Ltd. Address before: 318027 No. 13 Jinniu Road, Xinqian Development Zone, Huangyan District, Taizhou City, Zhejiang Province Patentee before: TAIZHOU THREE-WAY VEHICLE CATALYTIC CONVERTER Co.,Ltd. |