CN108176394A - A kind of denitration SCR catalyst and its preparation process - Google Patents
A kind of denitration SCR catalyst and its preparation process Download PDFInfo
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- CN108176394A CN108176394A CN201711489019.7A CN201711489019A CN108176394A CN 108176394 A CN108176394 A CN 108176394A CN 201711489019 A CN201711489019 A CN 201711489019A CN 108176394 A CN108176394 A CN 108176394A
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- 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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- 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
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- B01J23/30—Tungsten
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention provides a kind of denitration SCR catalyst and its preparation process, includes the following steps：Titanium dioxide, tungstic acid, silica flour are sent into milling equipment, and high-temperature water vapor are passed through in milling equipment, carries out grinding and activation, carrier is made；Lubricant, ammonium metavanadate aqueous solution, plasticizer, binding agent are sequentially added in above-mentioned carrier, is sent into blender, is added in distilled water while agitating, stir evenly, slurry is made；It is required with slurry obtained according to catalyst shape, is sent into extruder and is squeezed into cellular catalyst blank；Catalyst blank drying, calcining, are made finished catalyst.Its simple production process of the invention, catalyst has good activity and anti-erosion performance, service life is long, so as to significantly reduce the manufacture cost of catalyst and the operating cost of denitration process, it ensure that the plasticity of mixing materials, mixing cycle is greatly shortened simultaneously, improves yield rate, improves the compression strength and wear resistance of finished product.
Description
Technical field
The present invention relates to denitrating catalyst technical field more particularly to a kind of denitration SCR catalysts and its preparation process.
Background technology
Nitrogen oxides is one of main harmful substance for polluting air, and fire coal is the main path for generating a large amount of nitrogen oxides
One of, especially coal-fired power plant accounts for about the 50% of discharged nitrous oxides.For other technologies, selective catalysis is also
Former method (SCR) is reducing agent using ammonia, urea and lower carbon number hydrocarbons, and the nitrogen oxides in exhaust gas is selectively restored by catalyst
Be converted into non-polluting element molecule nitrogen and water, have the characteristics that it is at low cost and efficient, be most widely used at present it is de-
Nitre technology.
In the prior art, the common catalyst of SCR methods the use of titanium dioxide is generally carrier, vanadic anhydride be activity into
Divide and add the ternary component that tungstic acid is stable elements.This catalyst is by Japan earliest in nineteen seventies
It invents, advantage is that denitration activity is high and side reaction is small, but carrier titanium dioxide manufacture cost is higher.Due in China's coal
Flyash loss on ignition is higher in charcoal combustion process, and free calcium oxide, magnesia, sulfur trioxide are also higher in chemical composition, in addition
The universal load fluctuation of boiler operatiopn is larger, cause existing SCR system device often occur in operation catalyst blockage, poisoning,
The problems such as abrasion failure, it is necessary to regularly replace, so as to make operation and cost of investment higher.Existing catalyst is with boiler fly ash
For carrier, carrier needs to first pass through pickling processes when preparing, and is then impregnated and is molded, then use distilled water flushing with concentrated nitric acid solution again
The molding fly ash granule filtered out is finally sent into the SCR denitration that drying box is modified by primary drying, generation flying dust to neutrality
Catalyst carrier；Carrier obtained is immersed again in the metal oxide salting liquid being made of unsaturated copper nitrate solution, made
Metal oxide is supported as active constituent on carrier, then through redrying and calcining, catalyst is made；This catalyst into
Though this more traditional catalyst decreases, but still higher, preparation process is complex, and during applied to high cloud of dust gas, carries
The anti-erosion performance of body is poor.
Invention content
Present invention seek to address that the deficiencies in the prior art, and a kind of denitration SCR catalyst and its preparation process are provided.
The present invention to achieve the above object, using following technical scheme：
A kind of denitration SCR catalyst, the raw material components for preparing the catalyst are as follows：55~75 parts by weight of titanium dioxide,
6~9 parts by weight of tungstic acid, 3~4 parts by weight of silica flour, 8~14 parts by weight of ammonium hydroxide, 16~33 parts by weight of distilled water, lubricant 4
~5 parts by weight, 11~14 parts by weight of ammonium metavanadate aqueous solution, 4~5 parts by weight of plasticizer, 16~24 parts by weight of binding agent；Its
In, lubricant is glycerine or triethanolamine, and plasticizer is dioctyl phthalate or dibutyl phthalate, and binding agent is
One or both of polyvinyl alcohol, carboxylic propyl methocel.
A kind of preparation process of denitration SCR catalyst, includes the following steps：
(1) grinding of carrier and activation：Titanium dioxide, tungstic acid, silica flour are sent into milling equipment, grinding 10~15
Minute, and 100~120 DEG C of high-temperature water vapor is passed through in milling equipment, grinding and activation are carried out, carrier is made；
(2) preparation of slurry：Lubricant, ammonium metavanadate aqueous solution, plasticizer, bonding are sequentially added in above-mentioned carrier
Agent is sent into blender, adds in distilled water while agitating, stir evenly, slurry is made；
(3) molding of catalyst：It is required with slurry obtained according to catalyst shape, is sent into extruder and is squeezed into honeycomb fashion
Board-like catalyst blank is made in catalyst blank or the board-like catalyst preparation device of feeding；Catalyst blank drying, calcining,
Finished catalyst is made.
In above-mentioned steps (2), lubricant is firstly added, continues to stir, mixing speed is 400~600r/min, is stirred
Time is 5~10min, then adds in a part of water, adjusts water content to 36~38%, then adds in a part of ammonium hydroxide and adjust pH
For value to 8~9, system temperature is 40~60 DEG C；Water and ammonium hydroxide are added in distinguish the water content of regulation system and pH value, and heat up
To certain temperature, coordinate high-speed stirred, be conducive to the mixing of raw material；Sequentially add ammonium metavanadate aqueous solution, plasticizer, bonding
Agent continues to stir, and mixing speed is 80~120r/min, and mixing time is 5~10min, adjusts water content to 40~45%, body
Be temperature be 50~55 DEG C；It is stirred again using low temperature, by the auxiliary materials such as ammonium metavanadate aqueous solution, plasticizer, binding agent and major ingredient
It stirs evenly together, and strictly controls water content and temperature.
Manufactured slurry water content is below 25% in above-mentioned steps (2).
In above-mentioned steps (3), the drying is in closed climatic chamber, is first dried at a temperature of 60~63 DEG C
It is 46~49 hours dry, then dried 66~74 hours at a temperature of 76~84 DEG C.
In above-mentioned steps (3), the calcining is first in 252~254 DEG C of temperature lower calcination 46~49 hours, then 375
~385 DEG C of temperature lower calcinations 24 hours, then in 446~454 DEG C of temperature lower calcinations 12 hours.
The beneficial effects of the invention are as follows：The present invention, as carrier, produces work using titanium dioxide, tungstic acid, silica flour
Skill is simple, and catalyst has good activity and anti-erosion performance, and service life is long, so as to significantly reduce the system of catalyst
The operating cost of this and denitration process is caused, in mixing process, in a manner that segmentation is stirred, low temperature stirring and high temperature stir
Mix cross-reference, the curing temperatures of mixing materials, water content, pH value controlled, so as to ensure the plasticity of mixing materials, so as to get mixing
Material plasticity reaches 250~300, while greatly shorten mixing cycle, improves yield rate, effectively prevent the mixing materials of honeycomb catalyst
Cracking in follow-up drying, calcination process, while improve the compression strength and wear resistance of finished product.
Specific embodiment
With reference to embodiment, the invention will be further described：
As shown in the figure, a kind of denitration SCR catalyst, the raw material components for preparing the catalyst are as follows：Titanium dioxide 55~
75 parts by weight, 6~9 parts by weight of tungstic acid, 3~4 parts by weight of silica flour, 8~14 parts by weight of ammonium hydroxide, 16~33 weight of distilled water
Part, 4~5 parts by weight of lubricant, 11~14 parts by weight of ammonium metavanadate aqueous solution, 4~5 parts by weight of plasticizer, binding agent 16~24
Parts by weight；Wherein, lubricant is glycerine or triethanolamine, and plasticizer is two fourth of dioctyl phthalate or phthalic acid
Ester, binding agent are one or both of polyvinyl alcohol, carboxylic propyl methocel.
A kind of preparation process of denitration SCR catalyst, includes the following steps：
(1) grinding of carrier and activation：Titanium dioxide, tungstic acid, silica flour are sent into milling equipment, and are set in grinding
100~120 DEG C of high-temperature water vapor is passed through in standby, carries out grinding and activation, carrier is made；
(2) preparation of slurry：Lubricant, ammonium metavanadate aqueous solution, plasticizer, bonding are sequentially added in above-mentioned carrier
Agent is sent into blender, adds in distilled water while agitating, stir evenly, slurry is made；
(3) molding of catalyst：It is required with slurry obtained according to catalyst shape, is sent into extruder and is squeezed into honeycomb fashion
Board-like catalyst blank is made in catalyst blank or the board-like catalyst preparation device of feeding；Catalyst blank drying, calcining,
Finished catalyst is made.
In above-mentioned steps (2), lubricant is firstly added, continues to stir, mixing speed is 400~600r/min, is stirred
Time is 5~10min, then adds in a part of water, adjusts water content to 36~38%, then adds in a part of ammonium hydroxide and adjust pH
For value to 8~9, system temperature is 40~60 DEG C；Water and ammonium hydroxide are added in distinguish the water content of regulation system and pH value, and heat up
To certain temperature, coordinate high-speed stirred, be conducive to the mixing of raw material；Sequentially add ammonium metavanadate aqueous solution, plasticizer, bonding
Agent continues to stir, and mixing speed is 80~120r/min, and mixing time is 5~10min, adjusts water content to 40~45%, body
Be temperature be 50~55 DEG C；It is stirred again using low temperature, by the auxiliary materials such as ammonium metavanadate aqueous solution, plasticizer, binding agent and major ingredient
It stirs evenly together, and strictly controls water content and temperature.
Manufactured slurry water content is below 25% in above-mentioned steps (2).
In above-mentioned steps (3), the drying is in closed climatic chamber, is first dried at a temperature of 60~63 DEG C
It is 46~49 hours dry, then dried 66~74 hours at a temperature of 76~84 DEG C.
In above-mentioned steps (3), the calcining is first in 252~254 DEG C of temperature lower calcination 46~49 hours, then 375
~385 DEG C of temperature lower calcinations 24 hours, then in 446~454 DEG C of temperature lower calcinations 12 hours.
Embodiment one
A kind of denitration SCR catalyst, the raw material components for preparing the catalyst are as follows：55 parts by weight of titanium dioxide, three oxygen
Change 9 parts by weight of tungsten, 3 parts by weight of silica flour, 14 parts by weight of ammonium hydroxide, 16 parts by weight of distilled water, 5 parts by weight of lubricant, ammonium metavanadate water
14 parts by weight of solution, 5 parts by weight of plasticizer, 16 parts by weight of binding agent；Wherein, lubricant be glycerine or triethanolamine, plasticizer
For dioctyl phthalate or dibutyl phthalate, binding agent is one in polyvinyl alcohol, carboxylic propyl methocel
Kind or two kinds.
A kind of preparation process of denitration SCR catalyst, includes the following steps：
(1) grinding of carrier and activation：Titanium dioxide, tungstic acid, silica flour are sent into milling equipment, grinding 15 divides
Clock, and 100 DEG C of high-temperature water vapor is passed through in milling equipment, grinding and activation are carried out, carrier is made；
(2) preparation of slurry：Lubricant, ammonium metavanadate aqueous solution, plasticizer, bonding are sequentially added in above-mentioned carrier
Agent is sent into blender, adds in distilled water while agitating, stir evenly, slurry is made；
(3) molding of catalyst：It is required with slurry obtained according to catalyst shape, is sent into extruder and is squeezed into honeycomb fashion
Board-like catalyst blank is made in catalyst blank or the board-like catalyst preparation device of feeding；Catalyst blank drying, calcining,
Finished catalyst is made.
In above-mentioned steps (2), lubricant is firstly added, continues to stir, mixing speed 600r/min, mixing time is
5min, then adds in a part of water, adjusts water content to 38%, then adds in a part of ammonium hydroxide and adjusts pH value to 8, system temperature
It is 60 DEG C；Water and ammonium hydroxide are added in distinguish the water content of regulation system and pH value, and be warming up to certain temperature, coordinates high-speed stirring
It mixes, is conducive to the mixing of raw material；Ammonium metavanadate aqueous solution, plasticizer, binding agent are sequentially added, continues to stir, mixing speed
For 80r/min, mixing time 10min, water content is adjusted to 40%, system temperature is 55 DEG C；It is stirred again using low temperature, it will
The auxiliary materials such as ammonium metavanadate aqueous solution, plasticizer, binding agent stir evenly together with major ingredient, and strictly control water content and temperature.
Manufactured slurry water content is below 25% in above-mentioned steps (2).
In above-mentioned steps (3), the drying is in closed climatic chamber, first dries 49 at a temperature of 60 DEG C
Hour, then dried 74 hours at a temperature of 76 DEG C.
In above-mentioned steps (3), the calcining is first in 252 DEG C of temperature lower calcination 49 hours, then forged at a temperature of 375 DEG C
24 hours are burnt, then in 454 DEG C of temperature lower calcinations 12 hours.
Embodiment two
A kind of denitration SCR catalyst, the raw material components for preparing the catalyst are as follows：75 parts by weight of titanium dioxide, three oxygen
It is water-soluble to change 6 parts by weight of tungsten, 4 parts by weight of silica flour, 8 parts by weight of ammonium hydroxide, 33 parts by weight of distilled water, 4 parts by weight of lubricant, ammonium metavanadate
14 parts by weight of liquid, 4 parts by weight of plasticizer, 24 parts by weight of binding agent；Wherein, lubricant is glycerine or triethanolamine, and plasticizer is
Dioctyl phthalate or dibutyl phthalate, binding agent is polyvinyl alcohol, one kind in carboxylic propyl methocel
Or two kinds.
A kind of preparation process of denitration SCR catalyst, includes the following steps：
(1) grinding of carrier and activation：Titanium dioxide, tungstic acid, silica flour are sent into milling equipment, grinding 10 divides
Clock, and 120 DEG C of high-temperature water vapor is passed through in milling equipment, grinding and activation are carried out, carrier is made；
(2) preparation of slurry：Lubricant, ammonium metavanadate aqueous solution, plasticizer, bonding are sequentially added in above-mentioned carrier
Agent is sent into blender, adds in distilled water while agitating, stir evenly, slurry is made；
(3) molding of catalyst：It is required with slurry obtained according to catalyst shape, is sent into extruder and is squeezed into honeycomb fashion
Board-like catalyst blank is made in catalyst blank or the board-like catalyst preparation device of feeding；Catalyst blank drying, calcining,
Finished catalyst is made.
In above-mentioned steps (2), lubricant is firstly added, continues to stir, mixing speed 400r/min, mixing time is
10min, then adds in a part of water, adjusts water content to 36%, then adds in a part of ammonium hydroxide and adjusts pH value to 9, system temperature
Spend is 40 DEG C；Water and ammonium hydroxide are added in distinguish the water content of regulation system and pH value, and be warming up to certain temperature, cooperation is at a high speed
Stirring, is conducive to the mixing of raw material；Ammonium metavanadate aqueous solution, plasticizer, binding agent are sequentially added, continues to stir, stirring speed
It spends for 120r/min, mixing time 5min, adjusts water content to 45%, system temperature is 50 DEG C；It is stirred again using low temperature,
The auxiliary materials such as ammonium metavanadate aqueous solution, plasticizer, binding agent together with major ingredient are stirred evenly, and strictly control water content and temperature
Degree.
Manufactured slurry water content is below 25% in above-mentioned steps (2).
In above-mentioned steps (3), the drying is in closed climatic chamber, first dries 46 at a temperature of 63 DEG C
Hour, then dried 66 hours at a temperature of 84 DEG C.
In above-mentioned steps (3), the calcining is first in 254 DEG C of temperature lower calcination 46 hours, then forged at a temperature of 385 DEG C
24 hours are burnt, then in 446 DEG C of temperature lower calcinations 12 hours.
Embodiment three
A kind of denitration SCR catalyst, the raw material components for preparing the catalyst are as follows：60 parts by weight of titanium dioxide, three oxygen
Change 8 parts by weight of tungsten, 3.5 parts by weight of silica flour, 9 parts by weight of ammonium hydroxide, 20 parts by weight of distilled water, 4.5 parts by weight of lubricant, ammonium metavanadate
10 parts by weight of aqueous solution, 4.5 parts by weight of plasticizer, 20 parts by weight of binding agent；Wherein, lubricant is glycerine or triethanolamine, is increased
It is dioctyl phthalate or dibutyl phthalate to mould agent, and binding agent is polyvinyl alcohol, in carboxylic propyl methocel
One or two.
A kind of preparation process of denitration SCR catalyst, includes the following steps：
(1) grinding of carrier and activation：Titanium dioxide, tungstic acid, silica flour are sent into milling equipment, grinding 11 divides
Clock, and 110 DEG C of high-temperature water vapor is passed through in milling equipment, grinding and activation are carried out, carrier is made；
(2) preparation of slurry：Lubricant, ammonium metavanadate aqueous solution, plasticizer, bonding are sequentially added in above-mentioned carrier
Agent is sent into blender, adds in distilled water while agitating, stir evenly, slurry is made；
(3) molding of catalyst：It is required with slurry obtained according to catalyst shape, is sent into extruder and is squeezed into honeycomb fashion
Board-like catalyst blank is made in catalyst blank or the board-like catalyst preparation device of feeding；Catalyst blank drying, calcining,
Finished catalyst is made.
In above-mentioned steps (2), lubricant is firstly added, continues to stir, mixing speed 500r/min, mixing time is
6min, then adds in a part of water, adjusts water content to 37%, then adds in a part of ammonium hydroxide and adjusts pH value to 8.5, system temperature
Spend is 50 DEG C；Water and ammonium hydroxide are added in distinguish the water content of regulation system and pH value, and be warming up to certain temperature, cooperation is at a high speed
Stirring, is conducive to the mixing of raw material；Ammonium metavanadate aqueous solution, plasticizer, binding agent are sequentially added, continues to stir, stirring speed
It spends for 100r/min, mixing time 8min, adjusts water content to 42%, system temperature is 51 DEG C；It is stirred again using low temperature,
The auxiliary materials such as ammonium metavanadate aqueous solution, plasticizer, binding agent together with major ingredient are stirred evenly, and strictly control water content and temperature
Degree.
Manufactured slurry water content is below 25% in above-mentioned steps (2).
In above-mentioned steps (3), the drying is in closed climatic chamber, first dries 47 at a temperature of 61 DEG C
Hour, then dried 70 hours at a temperature of 80 DEG C.
In above-mentioned steps (3), the calcining is first in 253 DEG C of temperature lower calcination 47 hours, then forged at a temperature of 380 DEG C
24 hours are burnt, then in 450 DEG C of temperature lower calcinations 12 hours.
The present invention is exemplarily described above in conjunction with specific embodiment, it is clear that present invention specific implementation is not by upper
The limitation of mode is stated, as long as employing the various improvement or not improved straight of inventive concept and technical scheme of the present invention progress
It scoops out for other occasions, within protection scope of the present invention.
Claims (6)
1. a kind of denitration SCR catalyst, which is characterized in that the raw material components for preparing the catalyst are as follows：Titanium dioxide 55~
75 parts by weight, 6~9 parts by weight of tungstic acid, 3~4 parts by weight of silica flour, 8~14 parts by weight of ammonium hydroxide, 16~33 weight of distilled water
Part, 4~5 parts by weight of lubricant, 11~14 parts by weight of ammonium metavanadate aqueous solution, 4~5 parts by weight of plasticizer, binding agent 16~24
Parts by weight；Wherein, lubricant is glycerine or triethanolamine, and plasticizer is two fourth of dioctyl phthalate or phthalic acid
Ester, binding agent are one or both of polyvinyl alcohol, carboxylic propyl methocel.
2. a kind of preparation process of denitration SCR catalyst described in claim 1, which is characterized in that include the following steps：
(1) grinding of carrier and activation：Titanium dioxide, tungstic acid, silica flour are sent into milling equipment, 10~15 points of grinding
Clock, and 100~120 DEG C of high-temperature water vapor is passed through in milling equipment, grinding and activation are carried out, carrier is made；
(2) preparation of slurry：Lubricant, ammonium metavanadate aqueous solution, plasticizer, binding agent are sequentially added in above-mentioned carrier, is sent
Enter in blender, add in distilled water while agitating, stir evenly, slurry is made；
(3) molding of catalyst：It is required with slurry obtained according to catalyst shape, is sent into extruder and is squeezed into cellular catalysis
Board-like catalyst blank is made in agent blank or the board-like catalyst preparation device of feeding；Catalyst blank drying, calcining, are made
Finished catalyst.
3. the preparation method of a kind of denitration SCR catalyst according to claim 2, which is characterized in that in above-mentioned steps (2)
In, lubricant is firstly added, continues to stir, mixing speed is 400~600r/min, and mixing time is 5~10min, Ran Houjia
Enter a part of water, adjust water content to 36~38%, then add in a part of ammonium hydroxide and adjust pH value to 8~9, system temperature 40
~60 DEG C；Water and ammonium hydroxide are added in distinguish the water content of regulation system and pH value, and be warming up to certain temperature, coordinates high-speed stirring
It mixes, is conducive to the mixing of raw material；Ammonium metavanadate aqueous solution, plasticizer, binding agent are sequentially added, continues to stir, mixing speed
For 80~120r/min, mixing time is 5~10min, adjusts water content to 40~45%, system temperature is 50~55 DEG C；Again
It is secondary to be stirred using low temperature, the auxiliary materials such as ammonium metavanadate aqueous solution, plasticizer, binding agent are stirred evenly together with major ingredient, and stringent
Control water content and temperature.
4. the preparation method of a kind of denitration SCR catalyst according to claim 3, which is characterized in that in above-mentioned steps (2)
In manufactured slurry water content below 25%.
5. the preparation method of a kind of denitration SCR catalyst according to claim 3, which is characterized in that in above-mentioned steps (3)
In, described drying is in closed climatic chamber, is first dried 46~49 hours at a temperature of 60~63 DEG C, then 76~
It is dried 66~74 hours at a temperature of 84 DEG C.
6. the preparation method of a kind of denitration SCR catalyst according to claim 3, which is characterized in that in above-mentioned steps (3)
In, the calcining is then small in 375~385 DEG C of temperature lower calcinations 24 for first in 252~254 DEG C of temperature lower calcinations 46~49 hours
When, then in 446~454 DEG C of temperature lower calcinations 12 hours.
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Cited By (1)
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| CN112717921A (en) * | 2020-09-01 | 2021-04-30 | 江苏峰业科技环保集团股份有限公司 | SCR denitration catalyst and preparation process thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112717921A (en) * | 2020-09-01 | 2021-04-30 | 江苏峰业科技环保集团股份有限公司 | SCR denitration catalyst and preparation process thereof |
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