CN106563490B - Method for preparing composite catalyst that is a kind of while purifying N2O and NH3 - Google Patents
Method for preparing composite catalyst that is a kind of while purifying N2O and NH3 Download PDFInfo
- Publication number
- CN106563490B CN106563490B CN201610952646.9A CN201610952646A CN106563490B CN 106563490 B CN106563490 B CN 106563490B CN 201610952646 A CN201610952646 A CN 201610952646A CN 106563490 B CN106563490 B CN 106563490B
- Authority
- CN
- China
- Prior art keywords
- cordierite
- coated
- molecular sieve
- zsm
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Abstract
N is purified simultaneously the invention discloses a kind of2O and NH3Composite catalyst preparation method, this method be on cordierite monolithic substrate covering include catalytic component A and catalytic component B.Catalytic component A is one layer of Ce-Mx(M=Mn, Fe, Cu, Co, Ni, Al, Ti) oxide catalyst；Catalytic component B is a metal ion species (copper, manganese, iron, cobalt, nickel) modified ZSM-5 molecular sieve film.N can be purified simultaneously by being prepared2O and NH3Catalyst.The catalyst can be at a lower temperature by N2O and NH3It purifies simultaneously, and there is synergistic effect, N in purification process2O and NH3Removal efficiency is high.
Description
Technical field
N is purified simultaneously the present invention relates to a kind of2O and NH3Method for preparing composite catalyst, belong to atmospheric cleaning technology neck
Domain.
Background technique
Automobile is one of most important vehicles of modern society, is brought convenience in the life and work for people same
When, the tail gas that it is discharged also causes serious pollution to atmospheric environment.Most typically nineteen forty-three and the Lip river of the U.S. in 1954
The photochemical fog poisoning twice that Shan Ji occurs, arch-criminal is exactly vehicle exhaust.The motor vehicle in China in 2014 is protected
The amount of having has reached 2.46 hundred million, and still in accelerated growth.The rapid growth of car ownership, the N of motor vehicle exhaust emission2O
Amount is consequently increased, in addition, the NH in vehicle maintenance service3There is excessive NH during-SCR3Discharge.This all makes atmosphere
Pollute health that is increasingly severe, while also greatly endangering us.
In recent years in N2A few class catalyst that O catalytic decomposition field is widely noticed, including metal oxide catalyst, load
Type noble metal catalyst and molecular sieve catalyst.And NH is eliminated at present3Main be absorption, high temperature incineration, catalytic decomposition,
And selective catalytic oxidation ammonia.Absorption, absorption, high temperature incineration, catalytic decomposing method be easy to cause secondary pollution and energy consumption is high, choosing
Selecting property catalytic oxidation ammonia is a more promising technology, currently, mainly having for ammoxidation catalyst: precious metal catalyst
Agent, single metal oxide catalyst and cerium-based composite oxides catalyst.But it is possible to be catalyzed N simultaneously2O and NH3Catalysis
System is seldom mentioned.
The carrier of the auto-exhaust catalyst of current application of having gone into operation on the market is mainly cordierite honeycomb ceramic, is urged
Agent active component is mainly noble metal, but noble metal expensive price, higher cost.So developing transition metal or base metal
It is more and more important for the catalyst system of main active component.CeO2It is a kind of common co-catalyst, there is excellent storage oxygen energy
Power, d electron orbit effect and unique redox property.CeO2Addition can effectively improve metal oxide catalyst catalysis
Decompose N2The ability of O.Studies have reported that crossing using cordierite as carrier, cerium-carrying base catalyst has good N2O catalytic decomposition
Ability.
Molecular screen membrane has been to be concerned by more and more people in recent years, with agraphitic carbon and SiO2Equal films are compared, its aperture
It is single and adjustable；Compared with organic film, it has, and the service life is long, mechanical strength is big, resistant to chemical etching and separation selectivity is high
The characteristics of.The aperture of molecular screen membrane is uniform, has good separation selectivity, and regular cellular structure can guarantee that gas quickly expands
It dissipates.Therefore, it can constitute membrane reactor with catalyst, carry out reaction process simultaneously with diffusion, to improve the conversion of reaction
Rate or selectivity.The molecular screen membrane widely studied now, it be allow zeolite molecular sieve the porous carrier with some strength (such as
Porous ceramics, porous metals and cellular glass etc.) it grows on surface, one layer of densification, continuous film layer are formed, this film layer is utilized
Carry out the transmission and separation of substance.And molecular screen membrane is modified by metal ion and makes it have preferable N2O decomposability
Energy.
The present invention relates to a kind of integral catalyzer preparation method and applications of catalytic purification ammonia-contaminated gas.Monolithic catalyst
It is made of cordierite honeycomb structural body and catalytic active component two parts, cellular structure ceramic carrier material is cordierite, is urged
Change active component to be made of metal active constituent and inorganic oxide carrier.
Summary of the invention
N is purified simultaneously the object of the present invention is to provide a kind of2O and NH3Method for preparing composite catalyst, it is whole in cordierite
One layer of Ce-M is covered on body formula carrierx(M=Mn, Fe, Cu, Co, Ni, Al, Ti) composite oxides are bottom and a metal ion species
(copper, manganese, iron, cobalt and nickel) modified ZSM-5 molecular sieve film catalyst group is divided into surface layer, preparation method the following steps are included:
(1) Ce-M is preparedxComposite oxides: with the nitrate (M=Mn, Fe, Cu, Co, Ni, Al, Ti) of M and Ce (NO3)3·
6H2O is raw material, and using coprecipitation, (precipitating reagent is (NH4)2CO3、NH3·H2O or K2CO3), hydro-thermal method or sol-gal process, system
Obtain Ce-MxComposite oxides；X is the molar ratio of M and Ce, x > 0；
(2) by Ce-M obtainedxComposite oxide power is added in colloidal sol, stirs evenly, and Ce-M is madexComposite oxides
Colloidal sol；
(3) pretreated cordierite carrier is immersed into Ce-M made from step (2)xIn composite oxide sol, take out
Extra colloidal sol is blown away with air pump afterwards, in 80-100 DEG C of drying, 300-500 DEG C of roasting 1-3h, repeatedly in cordierite carrier
The uniform coating of surface formation 100-180mg/mL；
(4) it is being coated with Ce-MxOne layer of ZSM-5 molecular sieve film is prepared on the cordierite of composite oxides: using water in situ
Thermal synthesis method or secondary growth method prepare ZSM-5 molecular sieve film；
(5) one of copper, manganese, iron, cobalt and nickel metal is selected to be modified to get described one kind ZSM-5 molecular sieve film
N is purified simultaneously2O and NH3Composite catalyst.
Coprecipitation, hydro-thermal method or sol-gal process described in step (1) are conventional method.
Colloidal sol described in step (2) is silica solution (main component SiO2), or it is routinely square using boehmite
Colloidal sol (the main component Al of method preparation2O3), Ce-MxComposite oxides and SiO2Or Al2O3Mass ratio be 9-50:1.
Be to the preprocess method of cordierite carrier in step (3): first by cordierite honeycomb ceramic wash with distilled water after,
It is immersed in the nitric acid of 0.5-1mol/L and impregnates 2h, fall remaining nitric acid after taking-up wash with distilled water, it is dry；
Ce-M is being coated in step (4)xThe method that the cordierite surface of composite oxides prepares ZSM-5 molecular sieve film
It is:
Method one: Vacuum-assisted method method
A, mother liquor, template: Si:Al:H are prepared by raw material of template, silicon source, silicon source and water2The molar ratio of O is
(0.02-0.06): 1:(0.03-0.05): (10-1000), wherein template be TPAOH or TPABr, silicon source include silica solution,
Tetraethyl orthosilicate etc., silicon source include sodium metaaluminate, four aluminium isopropoxides, aluminium hydroxide, aluminum nitrate etc.；Raw material is mixed at room temperature
It closes, stirs 20-60min；
B, the hydrothermal synthesis of film: it is coated with Ce-MxThe cordierite of composite oxides, is put into crystallizing kettle, then to crystallizing kettle
In be slowly added into the mother liquor of step a preparation and make its submergence, crystallizing kettle is put into insulating box after sealing, it is brilliant at 160-200 DEG C
After changing 32-56h, it is cooled fast to room temperature, is rinsed with deionized water, then the dry 1h at 100 DEG C, that is, be coated with Ce-Mx
The cordierite surface of composite oxides forms one layer of ZSM-5 molecular sieve film；
C, the roasting of film: it is coated with Ce-MxThe cordierite of composite oxide layer and ZSM-5 molecular sieve film is in furnace with 1
DEG C/min is warming up to 100 DEG C, constant temperature 1h, then is warming up to 200 DEG C of constant temperature 1h with 1 DEG C/min, then be warming up to 300 DEG C with 1 DEG C/min
Then constant temperature 1h is warming up to 540 DEG C of constant temperature 3h again with 1 DEG C/min, is finally down to room temperature with 1 DEG C/min.
Method two: secondary growth method
A, it prepares molecular sieve seed suspension: preparing mother liquor by raw material of template, silicon source, silicon source and water, template:
Si:Al:H2The molar ratio of O be (0.02-0.06): 1:(0.03-0.05): (10-1000), wherein template be TPAOH or
TPABr, silicon source include silica solution, tetraethyl orthosilicate etc., and silicon source includes sodium metaaluminate, four aluminium isopropoxides, aluminium hydroxide, nitric acid
Aluminium etc.；Aging overnight after raw material is mixed, the hydrothermal crystallizing 32-56h at 150-180 DEG C are rinsed to neutrality with deionized water, are dried
It is dry to obtain zeolite powder, zeolite powder plus water are made into the crystal seed suspension of 0.1-1wt%；
B, it prepares seed layer: being coated with Ce-MxThe cordierite of composite oxides, the crystal seed for immersing step a synthesis suspend
After liquid 1-5min, vertically lifted with the rate of about 0.5cm/s, dry 30min under field conditions (factors), then the drying at 100 DEG C
30min, this step carry out 2 times；
C, kind: being had the cordierite supporter of crystal seed, is put into crystallizing kettle by the hydrothermal synthesis of film, then is slowly added into crystallizing kettle
Enter by template described in step a: Si:Al:H2The molar ratio of O is (0.02-0.06): 1:(0.03-0.05): (10-1000) system
The mother liquor obtained makes its submergence, and crystallizing kettle is put into insulating box after sealing, at 150-200 DEG C after crystallization 32-56h, fast quickly cooling
But room temperature is arrived, is rinsed with deionized water, then dry 1h at 100 DEG C, dry 12h at 120 DEG C.
Step is to be coated with Ce-M in (5)xThe cordierite of composite oxide layer and ZSM-5 molecular sieve film is placed in 0.001-
12-36h is impregnated in Cu, Fe, Mn, Co, Ni of 5mol/L in the nitrate solution of any one metal, with a large amount of distillations after taking-up
Water rinses, then in 200-600 DEG C of activation 4-6h.
The present invention has the advantages that compared with prior art
1, the present invention covers one layer of Ce-M on cordierite monolithic substratex(M=Mn, Fe, Cu, Co, Ni, Al, Ti) is multiple
The table for the ZSM-5 molecular sieve film catalyst component that the bottom and a kind of metal (copper, manganese, iron, cobalt, nickel) for closing oxide component are modified
Layer.Wherein bottom is catalysis oxidation layer, and upper layer is catalyzing hydrolysis coupling and catalyzing decomposition layer.The working principle of catalyst such as Fig. 4 institute
Show；N2The active oxygen species that O catalytic decomposition generates can quickly and NH3Reaction, and NH3Catalysis oxidation consume N2O, which is decomposed, to be produced
Raw oxygen, so that reaction be promoted to carry out.In addition, N2The ratedeterming step of O catalytic decomposition is the diffusion rate for generating oxygen, and this catalysis
The molecular sieve of agent outer layer is also beneficial to N2O decomposes the transmitting of the oxygen generated, to promote cartalytic decomposition effect.In short, the catalysis
Agent can not only purify N in vehicle exhaust simultaneously2O and NH3, and there are synergistic effects for two kinds of reactions, therefore the catalyst has catalysis
The high characteristic of activity.
2, the present invention provides a kind of coating method for being suitable for Ce base catalyst, it can be achieved that catalyst load factor is high, de-
The low purpose of rate, simple process are fallen, catalyst is firmly combined with ceramic honey comb, coating uniform, catalyst long service life, is reduced
Production cost, industrialization easy to accomplish.
Detailed description of the invention
Fig. 1 is the catalytic activity figure of composite catalyst made from embodiment 1；
Fig. 2 is the catalytic activity figure of composite catalyst made from embodiment 2；
Fig. 3 is the catalytic activity figure of composite catalyst made from embodiment 3；
Fig. 4 principle schematic diagram of the present invention.
Specific embodiment
Elaborate below with reference to embodiment and attached drawing to the present invention: following embodiment is before technical solution of the present invention is
Implementation is put, detailed embodiment and operating process are given.But the protection scope of invention is not limited to following examples.
Embodiment 1
(1) Ce-M is prepared using the method for co-precipitationxComposite oxides: 4.04g Fe (NO is taken3)3·9H2O and 10.85g
Ce(NO3)3·6H2O is dissolved in 100mL water, using saturation (NH4)2CO3Or NH3·H2O or K2CO3Solution as precipitating reagent,
Adjusting pH value at room temperature is 10, and gained is precipitated and stands aging 2h, after standing in water-bath heating water bath 5h, stand overnight,
Gained precipitating is washed with deionized, and filters, and gained filter cake is dried in 75 DEG C, finally obtains CeO in 400 DEG C of roasting 5h2-Fe2O3
(Fe/Ce=0.4) composite oxides；
(2) CeO is prepared2-Fe2O3(Fe/Ce=0.4) composite oxide sol: weighing diaspore, then presses its mass fraction
Deionized water dissolving is used for 10%, after stirring 10min, hydrochloric acid solution is added by 0.24 acid/aluminium mass ratio, by CeO obtained2-
Fe2O3(Fe/Ce=0.4) composite oxide power is added in colloidal sol, CeO2-Fe2O3(Fe/Ce=0.4) composite oxides and Al2O3
Mass ratio be 9:1, stir evenly；
(3) first by cordierite honeycomb ceramic wash with distilled water after, be immersed in the nitric acid of 0.5mol/L and impregnate 2h, take out
Fall remaining nitric acid wash with distilled water afterwards, just obtains pretreated cordierite honeycomb ceramic after dry；
(4) CeO is being coated by pretreated cordierite surface2-Fe2O3(Fe/Ce=0.4) composite oxides:
Pretreated cordierite honeycomb ceramic carrier is immersed into CeO made from step (2)2-Fe2O3(Fe/Ce=0.4) is multiple
It closes in oxide sol, blows away extra colloidal sol with air pump after taking-up, in 100 DEG C of drying, 500 DEG C of roasting 1h, repeatedly exist
The CeO of cordierite carrier surface formation 100mg/mL2-Fe2O3(Fe/Ce=0.4) composite oxide coating；
(5) CeO is being coated with using secondary growth method2-Fe2O3It is prepared on the cordierite of (Fe/Ce=0.4) composite oxides
ZSM-5 molecular sieve film:
A, molecular sieve seed suspension is prepared: with silica solution, sodium metaaluminate, 4-propyl bromide (TPABr) and deionization
Water is raw material, is TPABr:Si:Al:H according to molar ratio2The ratio of O=0.02:1:0.03:10 prepares solution, stays overnight aging,
Hydrothermal crystallizing 48h at 160 DEG C, filtering are rinsed with deionized water to neutrality, and drying obtains zeolite powder, with zeolite powder plus water
It is made into the crystal seed suspension of 0.8wt%；
B, it prepares seed layer: being coated with CeO2-Fe2O3The cordierite supporter of (Fe/Ce=0.4) composite oxides soaks
After the crystal seed suspension 3min for entering above-mentioned synthesis, vertically lifted with the rate of about 0.5cm/s, dry 30min under field conditions (factors),
Dry 30min, this step carry out 2 times at 100 DEG C again；
C, kind: being had the cordierite supporter of crystal seed, is put into crystallizing kettle by the hydrothermal synthesis of film, then is slowly added into crystallizing kettle
Enter using silica solution, sodium metaaluminate, 4-propyl bromide (TPABr) and deionized water as raw material, be TPABr:Si according to molar ratio:
Al:H2The mother liquor that the ratio of O=0.02:1:0.03:50 is prepared makes its submergence, and crystallizing kettle is put into insulating box after sealing,
At 200 DEG C after crystallization 48h, it is cooled fast to room temperature, is rinsed with deionized water, then dry 1h at 100 DEG C, it is dry at 120 DEG C
12h；
(6) Cu (NO of 0.005mol/L is prepared3)2The catalyst that step (5) prepares is placed in Cu (NO by solution3)2It is molten
36h is impregnated in liquid, with a large amount of distilled water flushings after taking-up, activated at 600 DEG C 4h to get.
Embodiment 2
(1) Ce-M is prepared using sol-gal processxComposite oxides: the molar ratio according to Ti/Ce is 0.5, takes 1.48g nitre
Sour titanium, 4.34g Ce (NO3)3·6H2O and 15g citric acid is dissolved in 100mL water, stirs plastic in 80 DEG C of water-baths, then
It is dried in 100 DEG C of baking ovens, finally obtains Ce-Ti in 400 DEG C of roasting 4h0.5Composite oxides；
(2) CeO is prepared2-TiO2(Ti/Ce=0.5) composite oxide sol: weighing diaspore, then presses its mass fraction
Deionized water dissolving is used for 10%, after stirring 10min, adds hydrochloric acid solution by 0.15 acid/aluminium mass ratio, by CeO obtained2-
TiO2(Ti/Ce=0.5) composite oxide catalysts powder is added in colloidal sol, CeO2-TiO2(Ti/Ce=0.5) composite oxides with
Al2O3Mass ratio be 30:1, stir evenly；
(3) first by cordierite honeycomb ceramic wash with distilled water after, 2h is impregnated in the nitric acid of 0.5mol/L, is used after taking-up
Distilled water washes remaining nitric acid, obtains pretreated cordierite honeycomb ceramic after dry；
(4) by load C eO on pretreated cordierite2-TiO2(Ti/Ce=0.5) composite oxides:
Pretreated cordierite honeycomb ceramic carrier is immersed into CeO made from step (2)2-TiO2(Ti/Ce=0.5) is multiple
It closes in oxide sol, blows away extra colloidal sol with air pump after taking-up, then in 80 DEG C of drying, 400 DEG C of roasting 2h, repeatedly
The CeO of 140mg/mL is formed on cordierite carrier surface2-TiO2(Ti/Ce=0.5) composite oxide coating；
(5) CeO is being coated with using Vacuum-assisted method method2-TiO2On the cordierite of (Ti/Ce=0.5) composite oxides
Prepare ZSM-5 molecular sieve film:
A, it is according to the molar ratio of tetrapropylammonium hydroxide (TPAOH), tetraethyl orthosilicate (TEOS), sodium metaaluminate and water
0.06:1:0.05:200 prepares molecular sieve synthesis mother liquid, stirs 30min；
B, the hydrothermal synthesis of film: it is coated with CeO2-TiO2The cordierite of (Ti/Ce=0.5) composite oxides, is put into crystallization
Kettle, then be slowly added into synthesis mother liquid into crystallizing kettle and make its submergence, crystallizing kettle is put into insulating box after sealing, at 200 DEG C
Crystallization 32h, is then cooled fast to room temperature, is rinsed with deionized water, dry 1h at 100 DEG C；
C, the roasting of film: it is coated with CeO2-TiO2The violet of (Ti/Ce=0.5) composite oxide layer and ZSM-5 molecular sieve film
Green stone is placed in furnace, with 1 DEG C/min temperature programming to 100 DEG C, constant temperature 1h, then with 1 DEG C/min is warming up to 200 DEG C of constant temperature 1h, then
300 DEG C of constant temperature 1h are warming up to 1 DEG C/min, 540 DEG C of constant temperature 3h are then warming up to 1 DEG C/min again, are finally down to 1 DEG C/min
Room temperature；
(6) Mn (NO of 0.2mol/L is prepared3)2The catalyst that step (5) prepares is placed in Mn (NO by solution3)2Solution
Middle dipping for 24 hours, with a large amount of distilled water flushings after taking-up, 200 DEG C of activation 6h to get.
Embodiment 3
(1) Ce-M is prepared using hydro-thermal methodxComposite oxides: the molar ratio according to Co/Ce is 0.4, takes 1.16g cobalt nitrate
And 4.34g Ce (NO3)3·6H2O is dissolved in 50mL water, with the pH value of ammonium hydroxide adjusting mixed solution to about 10, by mixed solution
It is put into reaction kettle, the constant temperature 72h at 150 DEG C is filtered after taking-up, uses water and ethanol washing respectively, and gained filter cake is dried in 100 DEG C
It is dry, finally CeO is obtained in 400 DEG C of roasting 5h2-Co3O4(Co/Ce=0.4) composite oxides；
(2) CeO is prepared2-Co3O4(Co/Ce=0.4) composite oxide sol: commercially available silica solution is weighed by CeO obtained2-
Co3O4(Co/Ce=0.4) composite oxide catalysts powder is added in silica solution, CeO2-Co3O4(Co/Ce=0.4) combined oxidation
Object and SiO2Mass ratio be 50:1, stir evenly；
(3) first by cordierite honeycomb ceramic wash with distilled water after, be immersed in the nitric acid of 1mol/L and impregnate 2h, after taking-up
Fall remaining nitric acid wash with distilled water, is dried to obtain pretreated cordierite honeycomb ceramic；
(4) by load C eO on pretreated cordierite2-Co3O4(Co/Ce=0.4) composite oxides:
Pretreated cordierite honeycomb ceramic carrier is immersed into CeO made from step (2)2-Co3O4(Co/Ce=0.4) is multiple
It closes in oxide sol, blows away extra colloidal sol with air pump after taking-up, in 100 DEG C of drying, 300 DEG C of roasting 3h, repeatedly exist
The CeO of cordierite carrier surface formation 180mg/mL2-Co3O4(Co/Ce=0.4) composite oxide coating；
(5) CeO is being coated with using Vacuum-assisted method method2-Co3O4On the cordierite of (Co/Ce=0.4) composite oxides
Prepare ZSM-5 molecular sieve film:
A, it is according to the molar ratio of tetrapropylammonium hydroxide (TPAOH), tetraethyl orthosilicate (TEOS), sodium metaaluminate and water
0.03:1:0.05:800 prepares molecular sieve synthesis mother liquid, they are mixed at room temperature, stirs 40min；
B, the hydrothermal synthesis of film: it is coated with CeO2-Co3O4The cordierite of (Co/Ce=0.4) composite oxides, is put into crystalline substance
Change kettle, then be slowly added into synthesis mother liquid into crystallizing kettle to make its submergence, crystallizing kettle is put into insulating box after sealing, at 180 DEG C
Lower crystallization 48h, is cooled fast to room temperature after taking-up, dries 1h after being rinsed with deionized water at 100 DEG C；
C, the roasting of film: it is coated with CeO2-Co3O4(Co/Ce=0.4) composite oxide layer and ZSM-5 molecular sieve film
Cordierite is placed in furnace, with 1 DEG C/min temperature programming to 100 DEG C, constant temperature 1h, then with 1 DEG C/min is warming up to 200 DEG C of constant temperature 1h,
300 DEG C of constant temperature 1h are warming up to 1 DEG C/min again, 540 DEG C of constant temperature 3h are then warming up to 1 DEG C/min again, finally with 1 DEG C/min drop
To room temperature；
(6) Fe (NO of 3mol/L is prepared3)3The catalyst that step (5) prepares is placed in Fe (NO by solution3)3In solution
Impregnate 12h, after taking-up use a large amount of distilled water flushings, at 300 DEG C activation 5h to get.
Claims (10)
1. a kind of purify N simultaneously2O and NH3Composite catalyst preparation method, as follows carry out:
(1) with the nitrate of M and Ce (NO3)3·6H2O is raw material, using conventional coprecipitation, hydro-thermal method or sol-gal process
Prepare Ce-MxComposite oxides, x are the molar ratio of M and Ce, x > 0；Wherein M is one of Mn, Fe, Cu, Co, Ni, Al, Ti；
(2) by Ce-M obtainedxComposite oxide power is added in colloidal sol, stirs evenly, and Ce-M is madexComposite oxide sol；
(3) Ce-M is being coated by pretreated cordierite carrier surfacexComposite oxide coating；
(4) it is being coated with Ce-MxZSM- is prepared using Vacuum-assisted method method or secondary growth method on the cordierite of composite oxides
5 molecular screen membranes；
(5) to ZSM-5 molecular sieve film be modified to get；Wherein method of modifying is to be coated with Ce-MxComposite oxide layer and
The cordierite of ZSM-5 molecular sieve film, which is placed in the metal-nitrate solutions of 0.001-5mol/L, impregnates 12-36h, with steaming after taking-up
Distilled water is rinsed, then in 200-600 DEG C of activation 4-6h.
2. preparation method according to claim 1, which is characterized in that the precipitating reagent of coprecipitation is (NH in step (1)4)2CO3、NH3·H2O or K2CO3。
3. preparation method according to claim 1, which is characterized in that colloidal sol described in step (2) is silica solution, or is adopted
The colloidal sol prepared according to a conventional method with boehmite, Ce-MxComposite oxides and SiO2Or Al2O3Mass ratio be 9-50:
1。
4. preparation method according to claim 1, which is characterized in that the pretreatment side of cordierite carrier in step (3)
Method is: first by cordierite honeycomb ceramic wash with distilled water after, be immersed in the nitric acid of 0.5-1mol/L and impregnate 2h, used after taking-up
Distilled water washes remaining nitric acid, dry.
5. preparation method according to claim 1, it is characterised in that: coat Ce- on cordierite carrier surface in step (3)
MxThe method of composite oxide coating is: pretreated cordierite carrier is immersed Ce-M made from step (2)xCombined oxidation
In object colloidal sol, extra colloidal sol is blown away with air pump after taking-up, in 80-100 DEG C of drying, 300-500 DEG C of roasting 1-3h, repeatedly
The uniform coating of 100-180mg/mL is formed on cordierite carrier surface.
6. preparation method according to claim 1, which is characterized in that step (4) is being coated using Vacuum-assisted method method
There is Ce-MxZSM-5 molecular sieve film is prepared on the cordierite of composite oxides, comprising the following steps:
A, mother liquor is prepared by raw material of template, silicon source, silicon source and water, raw material is mixed at room temperature, stir 20-60min；
B, the hydrothermal synthesis of film: it is coated with Ce-MxThe cordierite of composite oxides is put into crystallizing kettle, then slowly into crystallizing kettle
The mother liquor that step a is prepared, which is added, makes its submergence, crystallizing kettle is put into insulating box after sealing, the crystallization 32- at 160-200 DEG C
After 56h, it is cooled fast to room temperature, is rinsed with deionized water, then the dry 1h at 100 DEG C, that is, be coated with Ce-MxComposite oxygen
The cordierite surface of compound forms one layer of ZSM-5 molecular sieve film；
C, the roasting of film: it is coated with Ce-MxThe cordierite of composite oxide layer and ZSM-5 molecular sieve film is in furnace with 1 DEG C/min
100 DEG C, constant temperature 1h are warming up to, then 200 DEG C of constant temperature 1h are warming up to 1 DEG C/min, then 300 DEG C of constant temperature 1h are warming up to 1 DEG C/min,
Then 540 DEG C of constant temperature 3h are warming up to 1 DEG C/min again, room temperature is finally down to 1 DEG C/min.
7. preparation method according to claim 1, which is characterized in that step (4) is being coated with Ce- using secondary growth method
MxZSM-5 molecular sieve film is prepared on the cordierite of composite oxides, comprising the following steps:
A, it prepares molecular sieve seed suspension: mother liquor is prepared by raw material of template, silicon source, silicon source and water, after raw material is mixed
Aging overnight, the hydrothermal crystallizing 32-56h at 150-180 DEG C are rinsed with deionized water to neutrality, and drying obtains zeolite powder, will
Zeolite powder adds water to be made into the crystal seed suspension of 0.1-1wt%；
B, it prepares seed layer: being coated with Ce-MxThe cordierite of composite oxides immerses the crystal seed suspension 1- of step a synthesis
After 5min, vertically lifted with the rate of 0.5cm/s, dry 30min under field conditions (factors), then the dry 30min at 100 DEG C, this
Step carries out 2 times；
C, the hydrothermal synthesis of film: having the cordierite supporter of crystal seed for kind, be put into crystallizing kettle, then be slowly added into crystallizing kettle by
Mother liquor made from step a makes its submergence, and crystallizing kettle is put into insulating box after sealing, at 150-200 DEG C after crystallization 32-56h,
It is cooled fast to room temperature, is rinsed with deionized water, then dry 1h at 100 DEG C, dry 12h at 120 DEG C.
8. preparation method according to claim 6 or 7, which is characterized in that template in step a: Si:Al:H2Mole of O
Than for (0.02-0.06): 1:(0.03-0.05): (10-1000).
9. according to preparation method according to claim 6 or 7, which is characterized in that in step a template be TPAOH or
TPABr, silicon source are silica solution or tetraethyl orthosilicate, and silicon source is sodium metaaluminate, in four aluminium isopropoxides, aluminium hydroxide, aluminum nitrate
One kind.
10. the method according to claim 1, wherein the metal nitrate is to appoint in Cu, Fe, Mn, Co, Ni
It anticipates the nitrate of metal a kind of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610952646.9A CN106563490B (en) | 2016-10-25 | 2016-10-25 | Method for preparing composite catalyst that is a kind of while purifying N2O and NH3 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610952646.9A CN106563490B (en) | 2016-10-25 | 2016-10-25 | Method for preparing composite catalyst that is a kind of while purifying N2O and NH3 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106563490A CN106563490A (en) | 2017-04-19 |
| CN106563490B true CN106563490B (en) | 2019-07-16 |
Family
ID=58535361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610952646.9A Active CN106563490B (en) | 2016-10-25 | 2016-10-25 | Method for preparing composite catalyst that is a kind of while purifying N2O and NH3 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106563490B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107913665B (en) * | 2017-11-29 | 2020-07-17 | 中南大学 | Metal-doped boehmite as well as preparation method and application thereof |
| CN110882687B (en) * | 2019-12-18 | 2022-05-06 | 西南石油大学 | Application method of cerium-based composite oxide coating type monolithic catalyst |
| CN112076803B (en) * | 2020-09-16 | 2023-02-17 | 包头稀土研究院 | Ammonia oxidation catalyst, preparation method and application |
| CN113019430A (en) * | 2021-03-11 | 2021-06-25 | 北京工业大学 | Molecular sieve monolithic catalyst, preparation method and application thereof |
| CN113198525B (en) * | 2021-05-08 | 2023-05-09 | 北京工业大学 | Catalyst for synergistic purification of laughing gas decomposition and NOx catalytic reduction under low-temperature condition and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4082837A (en) * | 1975-03-10 | 1978-04-04 | University Of Southern California | Process for the selective catalytic oxidation of partially oxidized inorganic compounds |
| CN101549301A (en) * | 2009-01-20 | 2009-10-07 | 昆明贵研催化剂有限责任公司 | Natural gas vehicle tai-gas clean-up catalyst and preparation method thereof |
| CN102416343A (en) * | 2011-09-16 | 2012-04-18 | 中国汽车技术研究中心 | NOx selective catalytic reduction molecular sieve catalyst and preparation method |
| CN103316709A (en) * | 2007-10-29 | 2013-09-25 | 优美科触媒日本有限公司 | Catalyst for the removal of nitrogen oxides and method for the removal of nitrogen oxides with the same |
-
2016
- 2016-10-25 CN CN201610952646.9A patent/CN106563490B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4082837A (en) * | 1975-03-10 | 1978-04-04 | University Of Southern California | Process for the selective catalytic oxidation of partially oxidized inorganic compounds |
| CN103316709A (en) * | 2007-10-29 | 2013-09-25 | 优美科触媒日本有限公司 | Catalyst for the removal of nitrogen oxides and method for the removal of nitrogen oxides with the same |
| CN101549301A (en) * | 2009-01-20 | 2009-10-07 | 昆明贵研催化剂有限责任公司 | Natural gas vehicle tai-gas clean-up catalyst and preparation method thereof |
| CN102416343A (en) * | 2011-09-16 | 2012-04-18 | 中国汽车技术研究中心 | NOx selective catalytic reduction molecular sieve catalyst and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106563490A (en) | 2017-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106563490B (en) | Method for preparing composite catalyst that is a kind of while purifying N2O and NH3 | |
| WO2020063360A1 (en) | Method for preparing molecular sieve scr catalyst, and catalyst prepared thereby | |
| EP2586528A1 (en) | Catalyst having monolithic structure for manufacturing ethylene glycol by oxalate hydrogenation, preparation method and application thereof | |
| CN101811049B (en) | Method for preparing honeycomb ceramic catalyst for catalytically ozonizing organic matters in water | |
| CN111036280B (en) | Preparation method of Fe/Cu-SSZ-13 molecular sieve | |
| CN109731609B (en) | Cu-SSZ-13/porous ceramic catalyst with controllable coating and preparation method and application thereof | |
| KR101460437B1 (en) | Nano-catalytic filter and manufacturing method thereof | |
| CN101269326B (en) | Integral catalyst for producing cyclohexene with benzene hydrogenation and method for producing the same | |
| CN105833899A (en) | Preparation method for SCR catalyst for purifying oxynitride in motor vehicle exhaust | |
| CN106622356A (en) | Copper modified molecular sieve selective reduction catalyst, preparation method and applications thereof | |
| CN104722331A (en) | Preparation method of Cu-SAPO-44 microporous molecular sieve and application thereof as NH3-SCR catalyst | |
| CN108067218A (en) | The preparation method of denitrating catalyst | |
| US9468918B2 (en) | Metal-supported crystalline silicoaluminophosphate NOx-reducing catalyst | |
| CN107983365A (en) | Using titanium foam as VOCs catalyst of carrier and preparation method thereof | |
| CN111530463A (en) | Denitration catalyst of honeycomb ceramic load double oxide rice hull ash carrier, preparation method and application | |
| CN107233895B (en) | Oxidation catalyst for purifying motor vehicle tail gas and preparation method thereof | |
| WO2022214655A1 (en) | One-pot synthesis of transition metal-promoted chabazites | |
| CN107744830B (en) | Method for preparing Cu-based molecular sieve SCR catalyst by one-step method | |
| CN111111642B (en) | Denitration catalyst and preparation method and application thereof | |
| CN104324728B (en) | Mesoporous composite oxide catalyst for purifying tail gases and preparation method thereof | |
| CN101618323B (en) | Structural catalyst for catalyzing and reducing nitrogen oxide and preparation method thereof | |
| CN112844452A (en) | Modified molecular sieve, preparation method thereof, catalyst for preparing methyl acetate by carbonylation of dimethyl ether and method | |
| CN109985663A (en) | The method that the Cu-SSZ-13 molecular sieve of a kind of pair of one kettle way fabricated in situ is post-processed | |
| CN109622027A (en) | A kind of catalyst and preparation method thereof for nitrous oxide | |
| CN109562366A (en) | The SCR activity material of thermal stability with enhancing |
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 |