CN106902813A - A kind of samarium doped, the manganese based denitration catalyst of zirconium and preparation method - Google Patents
A kind of samarium doped, the manganese based denitration catalyst of zirconium and preparation method Download PDFInfo
- Publication number
- CN106902813A CN106902813A CN201710158922.9A CN201710158922A CN106902813A CN 106902813 A CN106902813 A CN 106902813A CN 201710158922 A CN201710158922 A CN 201710158922A CN 106902813 A CN106902813 A CN 106902813A
- Authority
- CN
- China
- Prior art keywords
- manganese
- zirconium
- samarium
- catalyst
- titanium
- 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.)
- Granted
Links
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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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 invention discloses a kind of samarium doped, the manganese based denitration catalyst of zirconium and preparation method, manganese, titanium, zirconium, the composite oxides of samarium prepared with coprecipitation, wherein, manganese, samarium, zirconium, the mol ratio of titanium are (0.1~0.3) in the composite oxides:(0.05~0.15):(0.05~0.15):1.Samarium doped, the manganese based denitration catalyst of zirconium prepared by the present invention, by adding samarium, zirconium in the denitrating catalyst to manganese titanium composite oxide so that catalyst possesses low temperature NH higher3Selective catalysis reduction NO activity and water resistant resistance to SO_2, by the ratio of each metallic element in the manganese based denitration catalyst for adjusting samarium doped, zirconium, discovery can not only improve low temperature NH using the catalyst of said ratio3Selective catalysis reduction NO activity and water resistant resistance to SO_2, and substantially increase the N of catalyst2Selectivity, N2Selectivity more than 94%.
Description
Technical field
It is few the invention belongs to contain in the fixed source emission flue gas such as coal-burning power plant, kiln and chemical plant in environmental catalysis field
The oxynitrides treatment of sulfur dioxide is measured, is related to a kind of method for improving manganese-based catalyst nitrogen selectivity and water resistant resistance to SO_2,
Specifically related to a kind of samarium doped, the manganese based denitration catalyst of zirconium and preparation method.
Background technology
The nitrogen oxides of the exhaust emissions of stationary source (coal-burning power plant, industrial furnace and chemical plant etc.) causes serious big
Gas pollutes.China's coal storage capacity and consumption are the first in the world, and energy consumption structure based on coal will be grown in China
Phase is present.And a large amount of NO can be given off after coal combustionx, cause eutrophication, photochemical fog and the mist of acid rain, water body and soil
The problem of environmental pollutions such as haze, and seriously threaten the life and health of people.Therefore, effectively control stationary source NOxDischarge has been compeled
The eyebrows and eyelashes.
V in recent decades2O5-WO3/TiO2, always as business denitrating catalyst, the catalyst is in the reaction for catalyst
Active temperature range be 300~400 DEG C, therefore before denitrification apparatus are arranged on dedusting and desulfurization.But due to V2O5High temperature bar
N under part2Poor selectivity, easily distillation and with bio-toxicity, secondary pollution is caused to environment.According to low-temperature denitration technology, i.e.,
After electrostatic precipitator and desulfurizer, secondary pollution problem will be readily solved denitrification apparatus.But based on China's coal
The characteristics of matter sulfur-bearing is higher, contains SO higher in the flue gas of Discharged form Coal Combustion2Even if flue gas after desulfurizer by still containing
A small amount of SO2, therefore denitrating catalyst must possess excellent anti-SO2Poisoning performance.In sum, research and development have N high2Selection
Property and anti-SO2The non-vanadium based low-temperature denitration catalyst of the green non-pollution of poisoning is significant.
Manganese-based catalyst is to study and report most low temperature NH at present3- SCR catalyst.The high catalytic activity of manganese oxide
May be relevant with the valence electron structure of manganese species, manganese has seven valence electrons, has more variable valences with respect to other transition metal,
And easily change between its various valence state under cryogenic, so it is to NH3- SCR catalytic reactions have stronger low-temperature catalyzed work
Property.Manganese-based catalyst is broadly divided into two classes：The first kind is one pack system manganese oxide catalyst, refers to that certain presoma is straight by it
Connect the manganese-based catalyst for preparing high activity；Equations of The Second Kind is the manganese-based catalyst of composite oxides, refers to be adulterated in Mn oxide
The catalyst of other metal species synthesis, such as MnOx-CeO2、MnOx-FeOx、MnOx- CuO and MnOx-TiO2Deng.Manganese-based catalyst
Though there is preferable low temperature active, its low temperature N2Poor selectivity, operation temperature window narrows, and the H in flue gas2O and SO2
Catalyst can be made to inactivate so as to limit its further industrial applications.Therefore, the N of manganese-based catalyst how is improved2Selectivity
And water resistant sulfur resistance has turned into the focus and difficult point of the art research.
The content of the invention
In order to overcome the defect of prior art, an object of the present invention to be to provide the manganese base denitration of a kind of samarium doped, zirconium
Catalyst, the catalyst can improve N during catalytic denitration2Selectivity, also with the performance of water resistant sulfur resistive.
To achieve these goals, samarium doped of the invention, the technical scheme of the manganese based denitration catalyst of zirconium are：
The manganese based denitration catalyst of a kind of samarium doped, zirconium, the manganese prepared with coprecipitation, titanium, zirconium, the composite oxygen of samarium
Compound, wherein, manganese, samarium, zirconium, the mol ratio of titanium are (0.1~0.3) in the composite oxides:(0.05~0.15):(0.05
~0.15):1.
Samarium doped, the manganese based denitration catalyst of zirconium prepared by the present invention, by the denitration catalyst to manganese-titanium composite oxide
Samarium, zirconium are added in agent so that catalyst possesses low temperature NH higher3Selective catalysis reduction NO activity and water resistant resistance to SO_2, pass through
The ratio of each metallic element in adjustment samarium doped, the manganese based denitration catalyst of zirconium, it is found that manganese, samarium, zirconium, the mol ratio of titanium are
(0.1~0.3):(0.05~0.15):(0.05~0.15):1 catalyst can not only improve low temperature NH3Selective catalysis are reduced
NO activity and water resistant resistance to SO_2, and substantially increase the N of catalyst2Selectivity, N2Selectivity more than 94%.
There is N higher during catalytic denitration in order to prepare2Selectivity and water resistant sulfur resistance catalyst, this
The second purpose of invention is to provide a kind of samarium doped, the preparation method of the manganese based denitration catalyst of zirconium, and its technical scheme is：
The preparation method of a kind of samarium doped, the manganese based denitration catalyst of zirconium, prepared by manganese salt, samarium salt, zirconates, titanium salt dissolving
Into salting liquid, the salting liquid and the solution containing alkaline matter are prepared into manganese, titanium, zirconium, samarium using coprecipitation method and is answered
Oxide is closed, wherein, manganese, samarium, zirconium, the mol ratio of titanium are (0.1~0.3) in the composite oxides:(0.05~0.15):
(0.05~0.15):1.
The present invention can be prepared with N higher2Selectivity and water resistant sulfur resistance denitrating catalyst, party's legal system
Standby process is simple, it is easy to operate.
The third object of the present invention there is provided a kind of above-mentioned catalyst in SCR denitration technique or SCR denitration system
Using.
Beneficial effects of the present invention are：
1. raw material of the present invention is easy to get, and preparation process is simple, is participated in without toxic chemical substance, environmental protection.
2. prepared catalyst of the present invention shows good NH in the range of 100~300 DEG C3Selective catalysis reduce NO
Activity, its catalysis activity is close to 100% especially in the range of 125~275 DEG C.
3. prepared catalyst of the present invention studies N in temperature range whole2Selectivity is more than 94%.
4. prepared catalyst of the present invention shows good water resistant sulfur resistance.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrated for explaining the application, does not constitute the improper restriction to the application.
Fig. 1 is the curve map of the catalysis activity of catalyst prepared by embodiment 1~8；
Fig. 2 is the N of catalyst prepared by embodiment 1~82The curve map of selectivity；
Fig. 3 be 200 DEG C of reaction temperatures under, SO2The curve of the catalysis activity influence of the catalyst prepared on embodiment 1~8
Figure；
Fig. 4 be 200 DEG C of reaction temperatures under, H2O and SO2The catalysis activity influence of the catalyst prepared on embodiment 1~8
Curve map；
Fig. 5 is the scanning electron microscopic picture of catalyst prepared by embodiment 1.
Specific embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
Be also intended to include plural form, additionally, it should be understood that, when in this manual use term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Heretofore described coprecipitation includes positive coprecipitation and reverse coprecipitation, wherein, it is described positive common
The precipitation method are during the solution containing alkaline matter dropped into metal salt solution, and the reverse coprecipitation to be intended to slaine molten
Drop is added in the solution containing alkaline matter.
Heretofore described alkaline matter is to contain the material that can be dissolved in solvent hydroxy, such as hydroxide
Potassium, NaOH, ammoniacal liquor etc..
Heretofore described manganese salt is that metal ion is the ionic compound of manganese ion, such as manganese nitrate, manganese sulfate, phosphorus
Sour manganese etc..
Heretofore described titanium salt is that metal ion is the ionic compound of titanium ion, such as Titanium Nitrate, titanium sulfate, phosphorus
Sour titanium etc..
Heretofore described zirconates is that metal ion is the ionic compound of zirconium ion, such as zirconium nitrate, zirconium sulfate, phosphorus
Sour zirconium etc..
Heretofore described samarium salt is that metal ion is the ionic compound of samarium ion, such as samaric nitrate, samarium sulphate, phosphorus
Sour samarium etc..
As background technology is introduced, there is manganese-based catalyst low temperature N in the prior art2Poor selectivity, operation temperature
H in window narrows, flue gas2O and SO2The deficiency that can inactivate catalyst, in order to solve technical problem as above, the application is proposed
A kind of samarium doped, the manganese based denitration catalyst of zirconium.
In a kind of typical implementation method of the invention, there is provided a kind of samarium doped, the manganese based denitration catalyst of zirconium, with altogether
Manganese, titanium, zirconium, the composite oxides of samarium that the precipitation method are prepared, wherein, manganese in the composite oxides, samarium, zirconium, titanium rub
You are than being (0.1~0.3):(0.05~0.15):(0.05~0.15):1.
Samarium doped, the manganese based denitration catalyst of zirconium prepared by the present invention, by the denitration catalyst to manganese-titanium composite oxide
Samarium, zirconium are added in agent so that catalyst possesses low temperature NH higher3Selective catalysis reduction NO activity and water resistant resistance to SO_2, pass through
The ratio of each metallic element in adjustment samarium doped, the manganese based denitration catalyst of zirconium, it is found that manganese, samarium, zirconium, the mol ratio of titanium are
(0.1~0.3):(0.05~0.15):(0.05~0.15):1 catalyst can not only improve low temperature NH3Selective catalysis are reduced
NO activity and water resistant resistance to SO_2, and substantially increase the N of catalyst2Selectivity, N2Selectivity more than 94%.
In order to control the dimensional structure of catalyst, present embodiment is preferred, and the coprecipitation is reverse coprecipitation.
The catalyst prepared using reverse coprecipitation is substantially spherical in shape, as shown in figure 5, the particle diameter of particle is smaller and than more uniform.
Preferably, the oxide of the manganese in the composite oxides is MnO2、Mn2O3、Mn3O4In one or more, titanium
Oxide be TiO2, the oxide of zirconium is ZrO2, the oxide of samarium is Sm2O3。
Present embodiment additionally provides a kind of samarium doped, the preparation method of the manganese based denitration catalyst of zirconium, by manganese salt, samarium
Salt, zirconates, titanium salt dissolving are prepared into salting liquid, and the salting liquid and the solution containing alkaline matter are used into coprecipitation method system
It is standby go out manganese, titanium, zirconium, the composite oxides of samarium, wherein, manganese in the composite oxides, samarium, zirconium, titanium mol ratio for (0.1~
0.3):(0.05~0.15):(0.05~0.15):1.
The implementation method can be prepared with N higher2Selectivity and water resistant sulfur resistance denitrating catalyst, the party
Method preparation process is simple, it is easy to operate.
Preferably, the coprecipitation is reverse coprecipitation.Using reverse coprecipitation prepare catalyst be in substantially
Spherical, the particle diameter of particle is smaller and than more uniform.
In order to ensure the reaction completely of raw material, the granular size of catalyst is further controlled, it is further preferred that salt is molten
During drop adds to the solution containing alkaline matter, pH >=10 are kept.
In order to further control the formation of catalyst, it is further preferred that after salting liquid completion of dropping, stirring 5h, then
Ageing 24h.
Preferably, the manganese salt is manganese nitrate, and the samarium salt is samaric nitrate, and the zirconates is zirconium nitrate, and the titanium salt is
Titanium sulfate.The dissolubility of these slaines is preferable, it is easy to dissolve, and can preferably control the formation size of catalyst.
Preferably, CTAB (CTAB) is added in the salting liquid.Slaine can be increased molten
Solubility property in agent, so as to control the particle diameter to form precipitation particle.
It is further preferred that the concentration of CTAB is 30~35mmol/L in the salting liquid.
Preferably, the solvent in the salting liquid is the mixed liquor of water and ethanol.Ethanol is added in water, by increasing capacitance it is possible to increase gold
Belong to the solubility of salt, so as to further control the particle diameter of catalyst granules.
Preferably, the solution containing alkaline matter is ammoniacal liquor.With the alkalescence such as sodium hydroxide solution, potassium hydroxide solution
The solution ratio of material, addition ammoniacal liquor is prevented from adding other metallic elements in the catalyst for preparing, so as to influence catalysis
The catalytic performance of agent.
It is further preferred that the concentration of the ammoniacal liquor is 25~28wt.%.Industrial ammonia is 25~28wt.%, and raw material is easy
, cost is relatively low.
Preferably, the material for being prepared using coprecipitation method sequentially passes through washing, drying, calcining.By washing, energy
Most of diffluent ion is enough removed, then by drying and calcining, foreign ion is further removed, it is ensured that the catalysis of catalyst
Performance.
It is further preferred that the step of washing using ethanol first to be washed, then adopt and be washed with deionized, preferably adopt
Washed with ethanol
It is further preferred that it is 105~115 DEG C that the dry condition is temperature, the time is 10~24h.
It is further preferred that the process of the calcining for 2 DEG C/min speed from room temperature to 250 DEG C, be incubated 2h, then
500 DEG C are warming up to from 250 DEG C, and are incubated 4h.
Present embodiment additionally provides a kind of application of above-mentioned catalyst in SCR denitration technique or SCR denitration system.
In order that obtaining those skilled in the art can clearly understand the technical scheme of the application, below with reference to tool
The embodiment of body describes the technical scheme of the application in detail with comparative example.
Embodiment 1.Sm, Zr codope MnOx-TiO2The preparation of composite oxide catalysts.
(1) by Mn (NO3)2(50wt.%), Zr (NO3)4·5H2O,Sm(NO3)3·6H2O and Ti (SO4)2It is dissolved in 40-
In 50 times of deionized waters of mole, stirring 10min to clear solution.Wherein, Mn:Sm:Zr:Ti mol ratios are 0.2:0.1:
0.1:1。
(2) a certain amount of CTAB is added under 30-40 DEG C of temperature conditionss, CTAB concentration is about 30~35mmol/L, stirred
After 30min, a small amount of ethanol dilute solution is added, be stirred for 10min.
(3) in solution prepared by (2) dropwise being instilled into excessive 25wt.% ammoniacal liquor, whole titration process keeps pH >=10,
And continue to stir 5h, then it is aged 24h.
(4) filtration washing will be precipitated 2 times with absolute ethyl alcohol, deionized water is washed 3 times, and absolute ethanol washing 1 is finally used again
It is secondary.Gained solid is placed in drying >=10h in 110 DEG C of baking ovens.
(5) sample is put in Muffle furnace in air atmosphere, the heating rate of 2 DEG C/min is warming up to 250 at room temperature
DEG C, 2h is incubated, then 500 DEG C are warming up to from 250 DEG C, and it is incubated 4h.The scanning electron microscopic picture of the catalyst for preparing such as Fig. 5 institutes
Show, catalyst particle substantially spherical in shape, than more uniform, its particle diameter is 40~80nm to particle.
Embodiment 2
Preparation process is same as Example 1, and difference is：Mn:Sm:Zr:Ti mol ratios are 0.2:0.02:0.1:1.
Embodiment 3
Preparation process is same as Example 1, and difference is：Mn:Sm:Zr:Ti mol ratios are 0.2:0.06:0.1:1.
Embodiment 4
Preparation process is same as Example 1, and difference is：Mn:Sm:Zr:Ti mol ratios are 0.2:0.14:0.1:1.
Embodiment 5
Preparation process is same as Example 1, and difference is：Mn:Sm:Zr:Ti mol ratios are 0.2:0.18:0.1:1.
Embodiment 6
Preparation process is same as Example 1, and difference is：Mn:Sm:Zr:Ti mol ratios are 0.2:0.22:0.1:1.
Embodiment 7
Preparation process is same as Example 1, and difference is：Mn:Sm:Zr:Ti mol ratios are 0.2:0.1:0:1.
Embodiment 8
Preparation process is same as Example 1, and difference is：Mn:Sm:Zr:Ti mol ratios are 0.2:0:0.1:1.
The catalyst n H of the invention of embodiment 93Selective catalysis reduction NO activity and the test of water resistant resistance to SO_2.
Catalytic perfomance test is carried out on the fixed bed system that reacting gas continuously flows, and reaction velocity is 30,
000ml·g─1·h─1, reacting gas is constituted includes 500ppm NO, 500ppm NH3, 5vol.%O2, 100ppm SO2(when making
Used time) and 2.5vol.%H2O (when deployed), Balance Air is N2.Sample is in 200 DEG C of high-purity Ns before test2After lower pretreatment 1h,
It is cooled to room temperature.Open NO, NH3And O2, make Catalyst Adsorption to saturation state.Temperature programming afterwards to target temperature, every 25 DEG C
One data point of collection, catalytic performance data are collected after stabilization 0.5h under target temperature.NO, NH of outflow3、N2O、NO2Gas
Concentration use Thermo-fisher IS10 FTIR spectrometer online records.NO conversion ratios and N2Selectivity is respectively
Drawn by below equation (1) and formula (2)：
Wherein, in formula (1) and formula (2), [NO]inIt is the molar concentration into the NO of fixed bed system,
[NO]outIt is the molar concentration of the NO from fixed bed system discharge,
[NH3]inIt is the NH into fixed bed system3Molar concentration,
[N2O]outIt is the N from fixed bed system discharge2The molar concentration of O,
[NO2]outIt is the NO from fixed bed system discharge2Molar concentration.
The characterization result for obtaining is calculated by formula (1) and (2) as shown in figures 1-4, as can be seen that real from Fig. 1~4
The catalyst for applying the preparation of example 1~6 can not only improve low temperature NH3Selective catalysis reduction NO activity and water resistant resistance to SO_2, Er Qie great
The big N that improve catalyst2Selectivity, N2Selectivity more than 94%.
Although above-mentioned be described with reference to accompanying drawing to specific embodiment of the invention, not to invention protection domain
Limitation, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not required to
The various modifications or deformation made by paying creative work are still within the scope of the present invention.
Claims (10)
1. the manganese based denitration catalyst of a kind of samarium doped, zirconium, it is characterized in that, manganese, titanium, zirconium, the samarium prepared with coprecipitation
Composite oxides, wherein, manganese in the composite oxides, samarium, zirconium, the mol ratio of titanium are (0.1~0.3):(0.05~
0.15):(0.05~0.15):1.
2. manganese based denitration catalyst as claimed in claim 1, it is characterized in that, the coprecipitation is reverse coprecipitation.
3. manganese based denitration catalyst as claimed in claim 1, it is characterized in that, the oxide of the manganese in the composite oxides is
MnO2、Mn2O3、Mn3O4In one or more, titanyl compound is TiO2, the oxide of zirconium is ZrO2, the oxide of samarium is
Sm2O3。
4. a kind of samarium doped, the preparation method of the manganese based denitration catalyst of zirconium, it is characterized in that, by manganese salt, samarium salt, zirconates, titanium salt
Dissolving is prepared into salting liquid, by the salting liquid and the solution containing alkaline matter using coprecipitation method prepare manganese, titanium,
The composite oxides of zirconium, samarium, wherein, manganese, samarium, zirconium, the mol ratio of titanium are (0.1~0.3) in the composite oxides:(0.05
~0.15):(0.05~0.15):1.
5. preparation method as claimed in claim 4, it is characterized in that, the coprecipitation is reverse coprecipitation；
Preferably, during salting liquid being dropped into the solution containing alkaline matter, pH >=10 are kept；
Preferably, after salting liquid completion of dropping, 5h is stirred, is then aged 24h.
6. preparation method as claimed in claim 4, it is characterized in that, the manganese salt is manganese nitrate, and the samarium salt is samaric nitrate, institute
Zirconates is stated for zirconium nitrate, the titanium salt is titanium sulfate.
7. preparation method as claimed in claim 4, it is characterized in that, cetyl trimethyl bromination is added in the salting liquid
Amine；
Or, the solvent in the salting liquid is water and the mixed liquor of ethanol.
8. preparation method as claimed in claim 4, it is characterized in that, the solution containing alkaline matter is ammoniacal liquor.
9. preparation method as claimed in claim 4, it is characterized in that, the material prepared using coprecipitation method is sequentially passed through
Washing, dry, calcining；
Preferably, the step of washing using ethanol first to be washed, then adopted and be washed with deionized, and is finally carried out using ethanol
Washing；
Preferably, the dry condition is that temperature is 105~115 DEG C, and the time is 10~24h；
Preferably, the process of the calcining is the speed of 2 DEG C/min from room temperature to 250 DEG C, is incubated 2h, then is risen from 250 DEG C
Temperature is incubated 4h to 500 DEG C.
10. prepared by a kind of any described catalyst of claims 1 to 3 or any described preparation method of claim 4~9
Application of the catalyst in SCR denitration technique or SCR denitration system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710158922.9A CN106902813B (en) | 2017-03-16 | 2017-03-16 | The manganese based denitration catalyst and preparation method of a kind of samarium doped, zirconium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710158922.9A CN106902813B (en) | 2017-03-16 | 2017-03-16 | The manganese based denitration catalyst and preparation method of a kind of samarium doped, zirconium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106902813A true CN106902813A (en) | 2017-06-30 |
| CN106902813B CN106902813B (en) | 2019-09-24 |
Family
ID=59187526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710158922.9A Active CN106902813B (en) | 2017-03-16 | 2017-03-16 | The manganese based denitration catalyst and preparation method of a kind of samarium doped, zirconium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106902813B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108212147A (en) * | 2018-01-31 | 2018-06-29 | 东北大学秦皇岛分校 | A kind of rare-earth-doped modification mangano-manganic oxide and its preparation method and application |
| CN108435189A (en) * | 2018-03-27 | 2018-08-24 | 山东师范大学 | A kind of samarium doping iron-based denitrating catalyst and preparation method thereof with water resistant sulfur resistance |
| CN108579728A (en) * | 2018-01-26 | 2018-09-28 | 华东理工大学 | A kind of catalyst and preparation method of high thermal stability ammonia selective reducing nitrogen oxide |
| CN109772471A (en) * | 2019-01-31 | 2019-05-21 | 北京科技大学 | One kind low-temperature denitration catalyst containing samarium and preparation method thereof |
| CN111569866A (en) * | 2020-06-10 | 2020-08-25 | 太原理工大学 | Low-temperature SCR denitration catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1457921A (en) * | 2001-11-30 | 2003-11-26 | Omg股份公司及两合公司 | Catalyst for reducing nitrogen oxide content in wast gas of impoverished burning engine |
| CN102008956A (en) * | 2010-12-27 | 2011-04-13 | 国电科学技术研究院 | Preparation method of low-temperature selective catalytic reduction (SCR) catalyst by removing NOx from flue gas |
| CN102319560A (en) * | 2011-05-27 | 2012-01-18 | 东南大学 | Preparation method of manganese titanium catalysts |
-
2017
- 2017-03-16 CN CN201710158922.9A patent/CN106902813B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1457921A (en) * | 2001-11-30 | 2003-11-26 | Omg股份公司及两合公司 | Catalyst for reducing nitrogen oxide content in wast gas of impoverished burning engine |
| CN102008956A (en) * | 2010-12-27 | 2011-04-13 | 国电科学技术研究院 | Preparation method of low-temperature selective catalytic reduction (SCR) catalyst by removing NOx from flue gas |
| CN102319560A (en) * | 2011-05-27 | 2012-01-18 | 东南大学 | Preparation method of manganese titanium catalysts |
Non-Patent Citations (3)
| Title |
|---|
| BONINGARI THIRUPATHI 等: "Co-doping a metal (Cr, Fe, Co, Ni, Cu, Zn, Ce, and Zr) on Mn/TiO2 catalyst and its effect on the selective reduction of NO with NH3 at low-temperatures", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| DONGMEI MENG 等: "A highly effective catalyst of Sm-Mn mixed oxide for the selectivecatalytic reduction of NOx with ammonia: Effect of the calcinations temperature", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 胡强等: "铈钛掺杂促进铁氧化物低温SCR脱硝性能的机理", 《中国环境科学》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108579728A (en) * | 2018-01-26 | 2018-09-28 | 华东理工大学 | A kind of catalyst and preparation method of high thermal stability ammonia selective reducing nitrogen oxide |
| CN108579728B (en) * | 2018-01-26 | 2021-04-13 | 华东理工大学 | Catalyst for high-thermal-stability selective reduction of nitrogen oxide by ammonia and preparation method |
| CN108212147A (en) * | 2018-01-31 | 2018-06-29 | 东北大学秦皇岛分校 | A kind of rare-earth-doped modification mangano-manganic oxide and its preparation method and application |
| CN108435189A (en) * | 2018-03-27 | 2018-08-24 | 山东师范大学 | A kind of samarium doping iron-based denitrating catalyst and preparation method thereof with water resistant sulfur resistance |
| CN108435189B (en) * | 2018-03-27 | 2021-01-08 | 山东师范大学 | Samarium-doped iron-based denitration catalyst with water resistance and sulfur resistance and preparation method thereof |
| CN109772471A (en) * | 2019-01-31 | 2019-05-21 | 北京科技大学 | One kind low-temperature denitration catalyst containing samarium and preparation method thereof |
| CN111569866A (en) * | 2020-06-10 | 2020-08-25 | 太原理工大学 | Low-temperature SCR denitration catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106902813B (en) | 2019-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106902813B (en) | The manganese based denitration catalyst and preparation method of a kind of samarium doped, zirconium | |
| CN105214679B (en) | A kind of water resistant sulfur resistive type denitrating flue gas powder catalyst, preparation method and its usage | |
| CN111229212B (en) | CO-SCR denitration catalyst, preparation method and application | |
| CN105056923B (en) | A kind of water resistant sulfur resistive type denitrating catalyst, preparation method and its usage | |
| CN108435189A (en) | A kind of samarium doping iron-based denitrating catalyst and preparation method thereof with water resistant sulfur resistance | |
| WO2015101275A1 (en) | High-concentration carbonyl sulfide conversion-absorption type desulfurizer and carbon disulfide conversion-absorption type desulfurizer and preparation method thereof | |
| CN105413715B (en) | Low-temperature denitration of flue gas is acidified the sulfur resistant catalyst and preparation method thereof of manganese cobalt cerium with composite carrier load type | |
| CN105080566A (en) | Flue gas denitrification powder catalyst as well as preparation method and application thereof | |
| CN102941083B (en) | Medium/low-temperature core-shell denitration catalyst and preparation method and application thereof | |
| CN108393085B (en) | Attapulgite-loaded cerium-doped MnTiOX ternary-component low-temperature denitration catalyst and preparation method thereof | |
| CN101411984A (en) | Other transitional metals doped ferrotitanium composite oxides catalyst for selectively reducing nitrous oxides by ammonia | |
| CN105833901A (en) | PrOx-MnOx/SAPO-34 low-temperature SCR smoke denitration catalyst and preparation method and application thereof | |
| CN112742413B (en) | Low-temperature SCR denitration catalyst and preparation method and application thereof | |
| CN104069861B (en) | A kind of mesoporous iron-based composite oxide catalysts, preparation method and the application in ammonia selective catalysis nitrogen oxides reduction thereof | |
| CN109433254A (en) | A kind of confinement molecular sieve denitrating catalyst and preparation method thereof | |
| CN104209115A (en) | Vanadium-series loading type high-temperature SCR catalyst and preparation method thereof | |
| CN110339832A (en) | A kind of sheet Detitanium-ore-type TiO2For the manganese cerium compound of carrier and preparation and application | |
| CN105214652A (en) | Efficient Ce 1-xmn xo 2-δthe preparation method of solid solution low-temperature denitration catalyst and application | |
| CN104258840A (en) | Cerium supported medium temperature SCR (selective catalytic reduction) catalyst and preparation method thereof | |
| CN104084213B (en) | For the method for making of ferrimanganic titanium catalyst and the catalyst of preparation thereof of the denitration of stationary source flue gas low-temperature | |
| CN104857952A (en) | Sulfur-resistant nitrogen-oxide-removing attapulgite manganese-based SCR catalyst and preparation method and application thereof | |
| CN113042066A (en) | Flue gas denitration catalyst and preparation method thereof | |
| CN106111123A (en) | A kind of support type manganio composite oxides selective denitrification catalyst containing tourmaline | |
| CN105727965B (en) | A kind of copper zirconium cerium and titanium compound oxide catalyst and its preparation method for denitrating flue gas | |
| CN106362733A (en) | High-temperature resistant manganite catalyst and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |