CN108579731A - A kind of preparation method of low-temperature denitration carbon-supported catalysts - Google Patents
A kind of preparation method of low-temperature denitration carbon-supported catalysts Download PDFInfo
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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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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The present invention relates to chemosynthesis technical field, especially a kind of preparation method of low-temperature denitration carbon-supported catalysts includes the following steps：S1, calcining pretreatment：It is that raw material is added in closed calcining furnace to choose activated carbon, and high-temperature calcination reaming under the conditions of N2 is continually fed into is obtained by pretreated activated carbon；S2, strong acid are modified：It will pass through in pretreated activated carbon addition strong acid solution and impregnate 2 6h, and obtain modified activated carbon；S3, drying is rinsed：Modified activated carbon is rinsed into 1 3h using deionized water, deionized water carries out low temperature drying to the modified activated carbon for rinsing out acid solution later by the way of circulated sprinkling；S4, calcining molding：Modified activated carbon after drying is added in airtight heating stove in N2High-temperature calcination molding is carried out under the conditions of being continually fed into.Catalyst prepared by the present invention can be in high NOX85% or more denitration activity and prolonged denitration stability are realized in concentration and strong flue gas flow rate.
Description
Technical field
The present invention relates to chemosynthesis technical field more particularly to a kind of preparation methods of low-temperature denitration carbon-supported catalysts.
Background technology
With the rapid development of economy, the energy resource structure based on coal makes the discharge capacity of China's coal-fired flue-gas increase greatly
Add.The burning of fuel, can produce in the burning of coal, such as the internal combustion engine of a variety of industrial furnaces of power plant, automobile and other motor vehicles
Raw a large amount of nitrogen oxides (NOX, including N2O、NO、NO2、N2O3、N2O4And N2O5Equal multiple compounds).The excess emissions meeting of NOX
The a series of environmental problems such as acid rain and photochemical fog are caused, health is caused greatly to threaten.Flue gas is net for a long time
In terms of change technology is concentrated mainly on dedusting and desulfurization, but with the gradually understanding that people endanger NOX, remove NOXIt has become and works as
Preceding urgent task.
Denitrating flue gas is to use most NO at presentXAdministering method, and with NH3For the selective catalytic reduction skill of reducing agent
Art (SCR) is that current denitration efficiency highest, technology be most ripe, most widely used power-plant flue gas denitration technology.The technology is usual
Using V2O5-WO3 (or MOO3)/TiO2(or anatase) is used as denitrating catalyst, but the catalyst is of high cost, active temperature window
Mouth easily causes secondary pollution within the scope of 300~400 DEG C.Therefore, green, economic and efficient low-temperature SCR catalysis are developed
Agent is to realize NOXOne of effective way of improvement.
In recent years, the trend concentrated to the oriented carbon-based material of the research of SCR catalyst and catalyst carrier, carbon-based material is not
Pipe is as the carrier of adsorbent or catalyst or catalyst in use, the chemical property on its surface is all with extremely important
Effect, it determines the chemisorption performance of catalyst, wherein chemical property is primarily referred to as the chemical function on carbon-based material surface
Group.It is therefore desirable to be modified to it, to change surface organo-functional group distribution, carbon-based material absorption and catalytic are improved
Energy.And the carbon-based material method of modifying for being used for denitration is concentrated mainly on area load metal oxide modified, a kind of such as " carbon substrate
Expect the medium temperature denitrating catalyst and preparation method thereof of cerium-carrying tungsten " (CN102513095A) patented technology is in carbon-based material table
The oxide of cerium-carrying and tungstic acid prepare denitrating catalyst simultaneously in face.The catalyst preparation process is loaded dilute using infusion process
There is metal oxide as active constituent, good denitration activity is just shown in 230~420 DEG C of mesophilic range, therefore
Energy consumption and cost are higher.Although carbon-based material is modified the extensive concern for having caused people for the research of denitration, have with nitrogenous
The research that machine object carries out carbon-based material nitriding modification is but rarely reported.
Invention content
The purpose of the present invention is to solve disadvantage existing in the prior art, and a kind of low-temperature denitration for proposing is carbon-based urges
The preparation method of agent.
To achieve the goals above, present invention employs following technical solutions：
A kind of preparation method of low-temperature denitration carbon-supported catalysts is designed, is included the following steps：
S1, calcining pretreatment：It is that raw material is added in closed calcining furnace to choose activated carbon, N2High temperature under the conditions of being continually fed into
Reaming is calcined, is obtained by pretreated activated carbon；
S2, strong acid are modified：It will pass through in pretreated activated carbon addition strong acid solution and impregnate 2-6h, and obtain modified active
Charcoal；
S3, drying is rinsed：Modified activated carbon is rinsed into 1-3h using deionized water, deionized water uses the side of circulated sprinkling
Formula carries out low temperature drying to the modified activated carbon for rinsing out acid solution later；
S4, calcining molding：Modified activated carbon after drying is added in airtight heating stove in N2Under the conditions of being continually fed into
Row high-temperature calcination is molded so that catalyst activity component (Mn, Ce, Co, Fe, Sn etc.) and carrier bond strength higher.
Preferably, calcination temperature is 850-900 DEG C in S1, calcination time 3-6h.
Preferably, strong acid solution is the concentrated sulfuric acid, one kind of concentrated nitric acid or mixture in S2.
Preferably, the mass ratio of the concentrated sulfuric acid and concentrated nitric acid is 4:(1-2).
Preferably, low temperature drying temperature is 80-100 DEG C in S3, drying time 2-4h.
Preferably, calcination temperature is 400-500 DEG C in S4, calcination time 3-6h.
A kind of preparation method of low-temperature denitration carbon-supported catalysts proposed by the present invention, advantageous effect are：It is prepared by the present invention
Catalyst, active component (Mn, Ce, Co, Fe, Sn etc.) and carrier bond strength higher, the catalyst of gained can be in high NOX
85% or more denitration activity and prolonged denitration stability are realized in concentration and strong flue gas flow rate.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.
Embodiment 1
A kind of preparation method of low-temperature denitration carbon-supported catalysts is designed, is included the following steps：
S1, calcining pretreatment：It is that raw material is added in closed calcining furnace to choose activated carbon, N2High temperature under the conditions of being continually fed into
Reaming is calcined, is obtained by pretreated activated carbon；
S2, strong acid are modified：It will pass through in pretreated activated carbon addition strong acid solution and impregnate 2h, and obtain modified activated carbon；
S3, drying is rinsed：Modified activated carbon is rinsed into 1h using deionized water, deionized water uses the side of circulated sprinkling
Formula carries out low temperature drying to the modified activated carbon for rinsing out acid solution later；
S4, calcining molding：Modified activated carbon after drying is added in airtight heating stove in N2Under the conditions of being continually fed into
Row high-temperature calcination is molded so that catalyst activity component (Mn, Ce, Co, Fe, Sn etc.) and carrier bond strength higher.The present invention
The catalyst of gained can realize 85% or more denitration activity and prolonged denitration in high NOx concentration and strong flue gas flow rate
Stability.
Calcination temperature is 850 DEG C in S1, calcination time 3h.
Strong acid solution is the concentrated sulfuric acid in S2.
Low temperature drying temperature is 80 DEG C in S3, drying time 2h.
Calcination temperature is 400 DEG C in S4, calcination time 3h.
Embodiment 2
A kind of preparation method of low-temperature denitration carbon-supported catalysts is designed, is included the following steps：
S1, calcining pretreatment：It is that raw material is added in closed calcining furnace to choose activated carbon, N2High temperature under the conditions of being continually fed into
Reaming is calcined, is obtained by pretreated activated carbon；
S2, strong acid are modified：It will pass through in pretreated activated carbon addition strong acid solution and impregnate 3h, and obtain modified activated carbon；
S3, drying is rinsed：Modified activated carbon is rinsed into 2h using deionized water, deionized water uses the side of circulated sprinkling
Formula carries out low temperature drying to the modified activated carbon for rinsing out acid solution later；
S4, calcining molding：Modified activated carbon after drying is added in airtight heating stove in N2Under the conditions of being continually fed into
Row high-temperature calcination is molded so that catalyst activity component (Mn, Ce, Co, Fe, Sn etc.) and carrier bond strength higher.The present invention
The catalyst of gained can realize 85% or more denitration activity and prolonged denitration in high NOx concentration and strong flue gas flow rate
Stability.
Calcination temperature is 860 DEG C in S1, calcination time 4h.
Strong acid solution is concentrated nitric acid in S2.
Low temperature drying temperature is 90 DEG C in S3, drying time 3h.
Calcination temperature is 420 DEG C in S4, calcination time 4h.
Embodiment 3
A kind of preparation method of low-temperature denitration carbon-supported catalysts is designed, is included the following steps：
S1, calcining pretreatment：It is that raw material is added in closed calcining furnace to choose activated carbon, N2High temperature under the conditions of being continually fed into
Reaming is calcined, is obtained by pretreated activated carbon；
S2, strong acid are modified：It will pass through in pretreated activated carbon addition strong acid solution and impregnate 4h, and obtain modified activated carbon；
S3, drying is rinsed：Modified activated carbon is rinsed into 2h using deionized water, deionized water uses the side of circulated sprinkling
Formula carries out low temperature drying to the modified activated carbon for rinsing out acid solution later；
S4, calcining molding：Modified activated carbon after drying is added in airtight heating stove in N2Under the conditions of being continually fed into
Row high-temperature calcination is molded so that catalyst activity component (Mn, Ce, Co, Fe, Sn etc.) and carrier bond strength higher.The present invention
The catalyst of gained can realize 85% or more denitration activity and prolonged denitration in high NOx concentration and strong flue gas flow rate
Stability.
Calcination temperature is 880 DEG C in S1, calcination time 5h.
Strong acid solution is the mixture of the concentrated sulfuric acid, concentrated nitric acid in S2.
The mass ratio of the concentrated sulfuric acid and concentrated nitric acid is 4:1.
Low temperature drying temperature is 90 DEG C in S3, drying time 3h.
Calcination temperature is 450 DEG C in S4, calcination time 5h.
Embodiment 4
A kind of preparation method of low-temperature denitration carbon-supported catalysts is designed, is included the following steps：
S1, calcining pretreatment：It is that raw material is added in closed calcining furnace to choose activated carbon, N2High temperature under the conditions of being continually fed into
Reaming is calcined, is obtained by pretreated activated carbon；
S2, strong acid are modified：It will pass through in pretreated activated carbon addition strong acid solution and impregnate 6h, and obtain modified activated carbon；
S3, drying is rinsed：Modified activated carbon is rinsed into 3h using deionized water, deionized water uses the side of circulated sprinkling
Formula carries out low temperature drying to the modified activated carbon for rinsing out acid solution later；
S4, calcining molding：Modified activated carbon after drying is added in airtight heating stove in N2Under the conditions of being continually fed into
Row high-temperature calcination is molded so that catalyst activity component (Mn, Ce, Co, Fe, Sn etc.) and carrier bond strength higher.The present invention
The catalyst of gained can realize 85% or more denitration activity and prolonged denitration in high NOx concentration and strong flue gas flow rate
Stability.
Calcination temperature is 900 DEG C in S1, calcination time 6h.
Strong acid solution is the mixture of the concentrated sulfuric acid, concentrated nitric acid in S2.
The mass ratio of the concentrated sulfuric acid and concentrated nitric acid is 2:1.
Low temperature drying temperature is 100 DEG C in S3, drying time 4h.
Calcination temperature is 500 DEG C in S4, calcination time 6h.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of preparation method of low-temperature denitration carbon-supported catalysts, which is characterized in that include the following steps：
S1, calcining pretreatment：It is that raw material is added in closed calcining furnace to choose activated carbon, N2High-temperature calcination under the conditions of being continually fed into
Reaming is obtained by pretreated activated carbon；
S2, strong acid are modified：It will pass through in pretreated activated carbon addition strong acid solution and impregnate 2-6h, and obtain modified activated carbon；
S3, drying is rinsed：By modified activated carbon using deionized water rinse 1-3h, deionized water by the way of circulated sprinkling,
Low temperature drying is carried out to the modified activated carbon for rinsing out acid solution later；
S4, calcining molding：Modified activated carbon after drying is added in airtight heating stove in N2High temperature is carried out under the conditions of being continually fed into
Calcining molding so that catalyst activity component (Mn, Ce, Co, Fe, Sn etc.) and carrier bond strength higher.
2. a kind of preparation method of low-temperature denitration carbon-supported catalysts according to claim 1, it is characterised in that：It is calcined in S1
Temperature is 850-900 DEG C, calcination time 3-6h.
3. a kind of preparation method of low-temperature denitration carbon-supported catalysts according to claim 1, it is characterised in that：Strong acid in S2
Solution is the concentrated sulfuric acid, one kind of concentrated nitric acid or mixture.
4. according to a kind of preparation method for low-temperature denitration carbon-supported catalysts that claim 3 is stated, it is characterised in that：The concentrated sulfuric acid with it is dense
The mass ratio of nitric acid is 4:(1-2).
5. a kind of preparation method of low-temperature denitration carbon-supported catalysts according to claim 1, it is characterised in that：Low temperature in S3
Drying temperature is 80-100 DEG C, drying time 2-4h.
6. a kind of preparation method of low-temperature denitration carbon-supported catalysts according to claim 1, it is characterised in that：It is calcined in S4
Temperature is 400-500 DEG C, calcination time 3-6h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772374A (en) * | 2019-01-30 | 2019-05-21 | 四川大学 | Fluorine is grafted supported porous charcoal base catalysis material of manganese and preparation method thereof and its application in low temperature water resistant denitration |
| CN109999901A (en) * | 2019-05-10 | 2019-07-12 | 宫子凡 | A kind of porous graphene-molecular sieve complex carries denitrating catalyst and preparation method thereof |
| CN114471458A (en) * | 2021-10-21 | 2022-05-13 | 北京清新环境技术股份有限公司 | Modified activated carbon and preparation method thereof |
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| CN101422728A (en) * | 2008-12-18 | 2009-05-06 | 哈尔滨工业大学 | Catalyst for denitration of power plant soot fume SCR and preparation method thereof |
| CN103071485A (en) * | 2013-01-24 | 2013-05-01 | 昆明理工大学 | Catalyst as well as preparation method and application thereof |
| CN105032403A (en) * | 2015-07-07 | 2015-11-11 | 四川大学 | Catalyst used for low temperature desulphurization and denitration of flue gas and preparation method thereof |
| CN105170174A (en) * | 2015-10-10 | 2015-12-23 | 武汉科技大学 | Nitriding carbon-based catalyst used for low temperature SCR denitration and preparation method thereof |
| CN107115868A (en) * | 2016-02-24 | 2017-09-01 | 无锡中强电碳有限公司 | A kind of low temperature SCR denitration catalyst based on activated carbon and preparation method thereof |
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2018
- 2018-04-28 CN CN201810398139.4A patent/CN108579731A/en active Pending
Patent Citations (5)
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| CN101422728A (en) * | 2008-12-18 | 2009-05-06 | 哈尔滨工业大学 | Catalyst for denitration of power plant soot fume SCR and preparation method thereof |
| CN103071485A (en) * | 2013-01-24 | 2013-05-01 | 昆明理工大学 | Catalyst as well as preparation method and application thereof |
| CN105032403A (en) * | 2015-07-07 | 2015-11-11 | 四川大学 | Catalyst used for low temperature desulphurization and denitration of flue gas and preparation method thereof |
| CN105170174A (en) * | 2015-10-10 | 2015-12-23 | 武汉科技大学 | Nitriding carbon-based catalyst used for low temperature SCR denitration and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772374A (en) * | 2019-01-30 | 2019-05-21 | 四川大学 | Fluorine is grafted supported porous charcoal base catalysis material of manganese and preparation method thereof and its application in low temperature water resistant denitration |
| CN109772374B (en) * | 2019-01-30 | 2021-10-26 | 四川大学 | Fluorine-grafted manganese-loaded porous carbon-based catalytic material, preparation method thereof and application thereof in low-temperature water-resistant denitration |
| CN109999901A (en) * | 2019-05-10 | 2019-07-12 | 宫子凡 | A kind of porous graphene-molecular sieve complex carries denitrating catalyst and preparation method thereof |
| CN114471458A (en) * | 2021-10-21 | 2022-05-13 | 北京清新环境技术股份有限公司 | Modified activated carbon and preparation method thereof |
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