CN109107373A - A kind of denitrfying agent and preparation method thereof can be used for coal-fired flue gas denitration - Google Patents
A kind of denitrfying agent and preparation method thereof can be used for coal-fired flue gas denitration Download PDFInfo
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- CN109107373A CN109107373A CN201810936955.6A CN201810936955A CN109107373A CN 109107373 A CN109107373 A CN 109107373A CN 201810936955 A CN201810936955 A CN 201810936955A CN 109107373 A CN109107373 A CN 109107373A
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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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
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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
- B01D53/81—Solid phase processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
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Abstract
A kind of denitrfying agent and preparation method thereof can be used for coal-fired flue gas denitration, by mass percentage, the denitrfying agent include 1~5% reducing agent and 95~99% dispersing agent, wherein reducing agent is Hyperbranched Polymer with Terminal Amido.First Hyperbranched Polymer with Terminal Amido is dissolved in alcohols solvent, formed solution, then reproducibility powder is added in solution and is impregnated, refilter, dry after grind, obtain the denitrfying agent that can be used for coal-fired flue gas denitration.Reducing agent is Hyperbranched Polymer with Terminal Amido in denitration agent prescription disclosed by the invention, itself contains a large amount of NH in molecular structure2, denitration activity center can be directly formed at high temperature, and therefore, denitration agent prescription is relatively easy (two components), is also easier to obtain high denitration efficiency.Two kinds of components can be uniformly mixed by denitrfying agent preparation method disclosed by the invention in molecular level, so that it is guaranteed that the stability of denitration efficiency.Preparation process of the invention is simple, is suitble to large-scale production.
Description
Technical field
The invention belongs to power environment protection fields, are related to coal-fired flue gas denitration, and in particular to it is de- that one kind can be used for coal-fired flue-gas
Denitrfying agent of nitre and preparation method thereof.
Background technique
Attention with country to environmental protection, industrial pot (kiln) kiln gas denitration have also been put on agenda.Due to industrial pot
(kiln) furnace smoke temperature is usually lower, obtains widely applied SCR method in coal fired power plant and is not appropriate for industrial pot (kiln) kiln gas denitration,
And certain denitrfying agent is sprayed into burner hearth, using SNCR technique carry out denitration become one of industrial pot (kiln) denitrating flue gas it is important
Technological approaches (efficient selective reduction method).Different from traditional SCR method and SNCR method, efficient selective reduction method is in industrial pot
It can express higher removal efficiency in terms of the denitration of (kiln) kiln gas, but the factor for influencing denitration efficiency is more, including boiler
Residence time, smoke temperature and the cigarette of combustion system, denitrfying agent the amount of injection, denitrfying agent and flue gas mixability, denitrfying agent in flue gas
Gas composition etc..Analysis finds that denitrfying agent structure or formula are the fundamental factors for determining efficient selective reduction denitration efficiency.Cause
This, the exploitation of NO_x Reduction by Effective agent in recent years receives significant attention.Such as CN106861431A discloses a kind of quadruple effect denitrfying agent, by
Nine kinds of component structures such as reducing agent, catalyst, adsorbent, promotor, dispersing agent, activator, bleeding agent, corrosion inhibiter and initiator
At.The characteristics of denitrfying agent is and NOxThat react is not NH3But the very high ammonia free radical of activity, therefore effectively overcome
The disadvantage that traditional SNCR reaction temperature is high, denitration efficiency is low, in flue gases such as circulating fluidized bed boiler, chain furnace, coal water slurry boilers
Very high denitration efficiency (>=80%) has been shown in terms of denitration.Patent CN103977701A discloses a kind of by sludge, urine
The denitrfying agent of element, ammonium salt and water composition, the denitrfying agent have also shown higher removal efficiency in cement kiln denitrating flue gas
(70% or so).Patent CN105771645A discloses one kind by urea, silica, sodium carbonate, bentonite, anhydrous sodium sulphate and page
The macromolecule Dry denitration agent of rock powder composition；Patent CN107149867A discloses one kind by Organic Alcohol, organic amine, urea, hydroxyl
The Environment-friendlylow-temperature low-temperature denitrfying agent of propyl methocel and water composition；CN107952346A discloses one kind by one acyl of melamine
The biomass denitrfying agent that amine, modified plant fibers element, ammelide, peroxidating phosphinylidyne ammonia and adsorbent form.It is above-mentioned
Denitrfying agent all has higher denitration efficiency under fixed flue gas condition, but due to these denitrfying agent complicated components, on the one hand meeting
Increase denitration cost, while also increasing the unstability of denitration efficiency, in other words, when boiler combustion type or flue gas condition
When changing, to maintain certain removal efficiency, denitrfying agent each component content needs re-optimization to adjust.Therefore, simplify denitration
The component of agent increase its universality seem it is particularly necessary with it is important.
Summary of the invention
In order to overcome the problems, such as that existing denitrfying agent exists, it is an object of that present invention to provide one kind can be used for coal-fired flue gas denitration
Denitrfying agent and preparation method thereof.
In order to achieve the above object, The technical solution adopted by the invention is as follows:
A kind of denitrfying agent can be used for coal-fired flue gas denitration, by mass percentage, the denitrfying agent include 1~5% also
Former agent and 95~99% dispersing agent, wherein reducing agent is Hyperbranched Polymer with Terminal Amido.
A further improvement of the present invention lies in that the repeat unit structure of Hyperbranched Polymer with Terminal Amido is as follows:
Hyperbranched Polymer with Terminal Amido is made by following procedure: methyl acrylate and diethylene triamine are added to first
In alcohol, react 4 hours at room temperature；Wherein, the ratio of methyl acrylate, diethylene triamine and methanol is 43:52:100.
A further improvement of the present invention lies in that the reproducibility powder is active powdered carbon or active coke powder.
Hyperbranched Polymer with Terminal Amido, is first dissolved in by the preparation method of the above-mentioned denitrfying agent that can be used for coal-fired flue gas denitration
In alcohols solvent, formed solution, then reproducibility powder is added in solution and is impregnated, refilter, dry after grind, obtaining can
Denitrfying agent for coal-fired flue gas denitration.
A further improvement of the present invention lies in that the alcohols solvent is methanol, ethyl alcohol or propyl alcohol.
A further improvement of the present invention lies in that the mass concentration of solution is 1~5%.
The soaking temperature is room temperature, and soaking time is 2~4 hours.
Dry temperature is 90 DEG C, and the time is 5 hours.
Compared with prior art, the invention has the following beneficial effects:
(1) efficient selective reduction denitration is based primarily upon NH2With reacting for NO, in existing denitrfying agent system, NH2Shape
At the NH generated dependent on reducing agent component in formula3The interaction such as OH or O for generating with other components, leads to existing denitration
The relative complex problem of agent prescription.Reducing agent is Hyperbranched Polymer with Terminal Amido in denitration agent prescription disclosed by the invention, point
Itself contains a large amount of NH in minor structure2, denitration activity center can be directly formed at high temperature, and therefore, denitration agent prescription is relatively simple
Single (two components), is also easier to obtain high denitration efficiency.The denitration efficiency of denitrfying agent prepared by the present invention reaches 90~94%.
(2) existing denitrfying agent usually contains various solid components of different nature, is difficult to be uniformly mixed, and causes prepared
Denitrfying agent homogeneity is poor, influences the stability of denitration efficiency.Denitrfying agent preparation method disclosed by the invention can be in molecular level
Two kinds of components are uniformly mixed, so that it is guaranteed that the stability of denitration efficiency.Preparation process of the invention is simple, is suitble to scale metaplasia
It produces.
Detailed description of the invention
Fig. 1 is the repetitive unit chemical structural drawing of Hyperbranched Polymer with Terminal Amido in the present invention.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The denitrfying agent that can be used for coal-fired flue gas denitration of the invention, by mass percentage, the denitrfying agent include 1~5%
Reducing agent and 95~99% dispersing agent.
Wherein, referring to Fig. 1, reducing agent is Hyperbranched Polymer with Terminal Amido, the repetition of the Hyperbranched Polymer with Terminal Amido
Cellular construction is as follows:
Hyperbranched Polymer with Terminal Amido by using methyl acrylate and diethylene triamine as raw material, methanol is reaction medium,
It reacts 4 hours and obtains at room temperature.Wherein, the ratio of methyl acrylate, diethylene triamine and methanol is 43:52:100.
Dispersing agent is reproducibility powder；Specifically, the reproducibility powder is active powdered carbon or active coke powder.
Hyperbranched Polymer with Terminal Amido, is first dissolved in by the preparation method of the above-mentioned denitrfying agent that can be used for coal-fired flue gas denitration
In alcohols solvent, the solution that mass fraction is 1~5% is formed, then reproducibility powder is added in solution and is soaked at room temperature
Bubble 2~4 hours, refilter, 90 DEG C grind after drying 5 hours, obtain the denitrfying agent that can be used for coal-fired flue gas denitration.
The alcohols solvent is methanol, ethyl alcohol or propyl alcohol.
On 1MW One Dimensional Furnace, denitrfying agent denitration performance is investigated using true coal-fired flue-gas.It the results are shown in Table 1.
The preparation condition and its result of the denitrfying agent embodiment disclosed by the invention of table 1
As it can be seen from table 1 the denitration efficiency of denitrfying agent prepared by the present invention is between 90~94%.
Claims (9)
1. a kind of denitrfying agent that can be used for coal-fired flue gas denitration, which is characterized in that by mass percentage, which includes 1
~5% reducing agent and 95~99% dispersing agent；Wherein, reducing agent is Hyperbranched Polymer with Terminal Amido.
2. a kind of denitrfying agent that can be used for coal-fired flue gas denitration according to claim 1, which is characterized in that amine-terminated hyperbranced
The repeat unit structure of fluidized polymer is as follows:
3. a kind of denitrfying agent that can be used for coal-fired flue gas denitration according to claim 1 or 2, which is characterized in that Amino End Group
Dissaving polymer is made by following procedure: methyl acrylate and diethylene triamine being added in methanol, at room temperature
Reaction 4 hours；Wherein, the ratio of methyl acrylate, diethylene triamine and methanol is 43:52:100.
4. a kind of denitrfying agent that can be used for coal-fired flue gas denitration according to claim 1, which is characterized in that the reproducibility
Powder is active powdered carbon or active coke powder.
5. a kind of preparation method of the denitrfying agent that can be used for coal-fired flue gas denitration as described in any one of claim 1-4,
It is characterized in that, first Hyperbranched Polymer with Terminal Amido is dissolved in alcohols solvent, solution is formed, then adds reproducibility powder
Enter and impregnated into solution, refilter, dry after grind, obtain the denitrfying agent that can be used for coal-fired flue gas denitration.
6. a kind of preparation method of denitrfying agent that can be used for coal-fired flue gas denitration according to claim 5, which is characterized in that
The alcohols solvent is methanol, ethyl alcohol or propyl alcohol.
7. a kind of preparation method of denitrfying agent that can be used for coal-fired flue gas denitration according to claim 5 or 6, feature exist
In the mass concentration of solution is 1~5%.
8. a kind of preparation method of denitrfying agent that can be used for coal-fired flue gas denitration according to claim 7, which is characterized in that
The soaking temperature is room temperature, and soaking time is 2~4 hours.
9. a kind of preparation method of denitrfying agent that can be used for coal-fired flue gas denitration according to claim 5, which is characterized in that
Dry temperature is 90 DEG C, and the time is 5 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810936955.6A CN109107373B (en) | 2018-08-16 | 2018-08-16 | Denitration agent for coal-fired flue gas denitration and preparation method thereof |
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|---|---|---|---|
| CN201810936955.6A CN109107373B (en) | 2018-08-16 | 2018-08-16 | Denitration agent for coal-fired flue gas denitration and preparation method thereof |
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| CN109107373B CN109107373B (en) | 2020-12-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950550A (en) * | 2022-05-09 | 2022-08-30 | 安徽潜隆机电科技有限公司 | Chromium-free environment-friendly catalyst material for civil air defense |
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| CN101428237A (en) * | 2008-12-12 | 2009-05-13 | 华东理工大学 | Urea supported carbon based denitration catalyst, preparation and application method thereof |
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| CN101428237A (en) * | 2008-12-12 | 2009-05-13 | 华东理工大学 | Urea supported carbon based denitration catalyst, preparation and application method thereof |
| CN102361678A (en) * | 2009-03-20 | 2012-02-22 | 巴斯夫欧洲公司 | Method for separating acid gases using metal-organic frameworks impregnated with amines |
| CN102151585A (en) * | 2011-03-22 | 2011-08-17 | 华东理工大学 | Melamine-supported denitration catalyst and preparation method thereof |
| CN102553412A (en) * | 2012-02-10 | 2012-07-11 | 山东大学 | Method for denitrifying flue gas by using amino reducing agent with high reaction activity |
| EP3181223A1 (en) * | 2014-08-15 | 2017-06-21 | Kyushu University, National University Corporation | Gas absorption material, use of same for gas absorption, gas absorption body, gas absorption method, acidic gas absorption device, acidic gas recovery device, water vapor absorption device, water vapor recovery device, heat exchanger, and heat recovery device |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950550A (en) * | 2022-05-09 | 2022-08-30 | 安徽潜隆机电科技有限公司 | Chromium-free environment-friendly catalyst material for civil air defense |
| CN114950550B (en) * | 2022-05-09 | 2024-02-20 | 安徽潜隆机电科技有限公司 | Chromium-free environment-friendly catalyst material for civil air defense |
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