CN105772098B - Catalyst for removing NOx by ammonia selective catalytic reduction and preparation method thereof - Google Patents
Catalyst for removing NOx by ammonia selective catalytic reduction and preparation method thereof Download PDFInfo
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- CN105772098B CN105772098B CN201610292200.8A CN201610292200A CN105772098B CN 105772098 B CN105772098 B CN 105772098B CN 201610292200 A CN201610292200 A CN 201610292200A CN 105772098 B CN105772098 B CN 105772098B
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- molecular sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 title abstract description 4
- 239000002808 molecular sieve Substances 0.000 claims abstract description 83
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000843 powder Substances 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001768 cations Chemical class 0.000 claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000005341 cation exchange Methods 0.000 claims abstract description 5
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000002562 thickening agent Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract 2
- 239000011324 bead Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- -1 iron ion Chemical class 0.000 claims description 5
- 238000009938 salting Methods 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 3
- 210000002421 cell wall Anatomy 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 239000008188 pellet Substances 0.000 abstract 2
- 239000011230 binding agent Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical compound [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- KTNUFJVOTPQPES-UHFFFAOYSA-N oxotungsten titanium vanadium Chemical group [W]=O.[Ti].[V] KTNUFJVOTPQPES-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a preparation method of a catalyst for removing NOx by ammonia selective catalytic reduction, which comprises the following steps: (1) cation exchanging the molecular sieve with a salt solution of one or more metal cations by an ion exchange process; (2) after cation exchange, washing the molecular sieve with deionized water, drying at 50-200 ℃, and calcining at 200-600 ℃, so that cations exchanged into the molecular sieve are stably combined; (3) dispersing the molecular sieve treated in the step (2) in water, and mixing with a certain proportion of hollow alumina pellet powder, wherein the mass ratio of the molecular sieve to the hollow alumina pellet powder is from 2:1 to 15: 1, adding a binder and a thickening agent after fully dispersing, and then coating the mixture on a cordierite honeycomb carrier to form a catalyst coating with the thickness of tens of microns on the walls of fine pore channels of the honeycomb carrier. The catalyst prepared by the method is loaded by a molecular sieve, and has high-temperature activity and hydrothermal stability.
Description
Technical field
The invention belongs to the technical fields of tail gas denitrating catalyst, and in particular, the present invention relates to one kind being used for ammine selective
The molecular sieve carried catalyst and preparation method thereof of catalysis reduction removing NOx.
Background technology
In diesel car engine tail gas containing hydrocarbon (HC), carbon monoxide (CO), nitrogen oxides (NOx) and
The pernicious gases such as grain object (PM), tail gas itself have certain temperature, after first passing around direct oxidation catalyst (DOC), carbon
Hydrogen compound and carbon monoxide are oxidized to the innocuous gas such as carbon dioxide and water, and nitrogen oxides and particulate matter cannot be converted,
It subsequently enters in denitrifying catalyst with selective catalytic reduction (SCR catalyst), sprays urea liquid between the two catalyst,
Urea is broken down into ammonia and carbon dioxide, and wherein ammonia reacts under the action of SCR catalyst with nitrogen oxides, generates
The innocuous gas such as nitrogen and water.SCR catalyst, DOC catalyst and urea injection system are emphasis in this process.
There are mainly two types of the existing catalyst for ammine selectivity catalytic reduction removing oxynitrides.
The first is vanadium titanium tungsten oxide catalyst, and using titanium oxide as carrier, barium oxide is main active component, tungsten oxygen
Compound then mainly plays a part of to improve catalyst hydrothermal stability as auxiliary agent.But the shortcomings that this catalyst, which is barium oxide, to be had
Prodigious toxicity, no matter in catalyst production process, or after installation catalyst, it is de- that powder occurs at work for catalyst
It falls, can all be caused to environment in very big harm, such as dust sucking human body.
Second is copper, iron, ZSM5 molecular sieve catalysts, and wherein ZSM5 molecular sieves are carrier, and copper and iron are active component.
The shortcomings that this catalyst is that catalyst operating temperature section is narrow, and hydrothermal stability is poor, in actual operation due to diesel oil
The presence of water in motor exhaust, copper and iron are easy to be lost in molecular sieve pore passage, to which catalytic activity reduces quickly.
Therefore, it is necessary to prepare it is a kind of there is more high activity and hydrothermal stability, and can in broader temperature range and
SCR catalyst with high NOx conversion efficiency under conditions of high-speed.
Invention content
Technical problem to be solved by the invention is to provide a kind of molecular sieves removing NOx for ammine selectivity catalytic reduction
Catalyst of load and preparation method thereof.The catalyst that the method for the present invention is prepared is that molecular sieve is load, is had higher
High temperature active and hydrothermal stability；And there is high NOx conversion efficiency under conditions of broader temperature range and high-speed.
Technical solution is used by the present invention solves above-mentioned technical problem：NOx is removed for ammine selectivity catalytic reduction
Catalyst preparation method, in turn include the following steps：
(1) salting liquid of molecular sieve and one or more kinds of metal cations is made to carry out cationic friendship by ion-exchange
It changes.
(2) after cation exchanges, the molecular sieve is washed with deionized, then dry at 50~200 DEG C, then
200~600 DEG C of temperature lower calcinations combine to make to exchange to the cationic stabilized in molecular sieve；
(3) the step (2), treated that molecular sieve disperses in water, remixes into a certain proportion of hollow alumina
Bead powder, the mass ratio of the molecular sieve and the hollow alumina bead powder is from 2:1 to 15：1, add after fully dispersed
Enter adhesive and thickener, be then applied on cordierite honeycomb carrier, thickness is formed in the tiny cell walls of honeycomb substrate
Tens microns of catalyst coat.
In above-mentioned technical proposal, in preferred embodiment, molecular sieve of the present invention is used with existing for aluminosilicate form
ZSM-35 molecular sieve, silica alumina ratio are more than 30.Also, the ZSM-35 molecular sieve can be obtained by commercially available means, example
The ZSM-35 molecular sieve produced such as Shanghai Shen Tan environmental friendly materials Co., Ltd.
In above-mentioned technical proposal, exchanged by cation, by original cation in molecular sieve, be substituted for active metal from
Son constitutes catalytic reaction activity position to which active metallic ion to be introduced into molecular sieve pore passage.
In above-mentioned technical proposal, temperature, swap time and friendship when can be exchanged by adjusting metal cation salting liquid
Number etc. is changed to control the amount of metal cation exchange.The basic pore passage structure of molecular sieve is constant after ion exchange.Specifically, originally
Invention swaps under (20~25 DEG C) preferably at room temperature.Specifically, the operating procedure of the ion exchange is：By molecular sieve
It is distributed to formation molecular sieve slurry in the water of room temperature, meanwhile, in another reaction kettle, the cation exchanged will be needed at room temperature
Salt dissolves, and is subsequently poured into molecular sieve slurry, is stirred continuously, 1.5~4 hours；This process is 1 to 3 times repeatable.
In the step (1), the metal cation is copper ion, iron ion, titanium ion, vanadium ion and rare earth metal sun
It is one or more in ion；The salting liquid is chloride, acetate, nitrate, sulfate or other halide.
In the step (1), metal cation and the molecular sieve ratio of exchange are from 0.5% to 40%.
Further include following steps before the step (1)：By molecular sieve precalcining.The precalcining refer to 120~
It is calcined 0.5~1 hour at a temperature of 150 DEG C.It is handled by precalcining, removes having for molecular sieve pore passage and the template on surface
Machine object, is more advantageous to ion exchange in this way.
In the step (2), dry drying time is 2~5 hours at described 50~200 DEG C；Described 200~600 DEG C
The calcination time of temperature lower calcination is 2~8 hours.
In the step (3) of above-mentioned technical proposal, described adhesive is boehmite, and the thickener is ethoxy
Cellulose.
In the step (3) of above-mentioned technical proposal, the specific painting method of " being coated to cordierite honeycomb carrier " is：Very
Empty cladding process, upper end feed, vacuum valve is opened in posterior end within several seconds, under being inhaled slurry by negative pressure.
In one embodiment, the molecular sieve is one or both of ZSM-35 molecular sieve and Titanium Sieve Molecular Sieve.
In another embodiment, the molecular sieve is ZSM-22 molecular sieves, Cu-ZSM-5 molecular sieves, Beta molecular sieves
In any one.
In preferred technical solution, the mass ratio of the molecular sieve and the hollow alumina bead powder is 8：1
To 10:1.It is further preferred that the mass ratio of the molecular sieve and the hollow alumina bead powder is 8：1.
The molecular sieve is ZSM-22 molecular sieves compared with prior art, the present invention having the following advantages that：
(1) it by the present invention in that being catalyst main carriers with ZSM-35 molecular sieve, and adulterates with hollow alumina bead
With improve its dynamics distribution, by ion-exchange by copper ion, iron ion, titanium ion, vanadium ion and rare earth metal sun from
Son is supported in molecular sieve pore passage, so that the catalyst that the present invention is prepared has higher high temperature active and hydro-thermal steady
It is qualitative.
(2) catalyst that the present invention is prepared can have height under conditions of broader temperature range and high-speed
NOx conversion efficiency.
Specific implementation mode
In order to better understand the content of the present invention, it is described further with reference to specific embodiment.It should be understood that these
Embodiment is only used for that the present invention is further described, rather than limits the scope of the invention.In addition, it should also be understood that, having read this
After the invention content, person skilled in art makes some nonessential changes or adjustment to the present invention, still falls within this
The protection domain of invention.
Embodiment 1
For ammine selectivity catalytic reduction remove NOx molecular sieve carried catalyst preparation method, include successively with
Lower step：
1, precalcining：ZSM-35 molecular sieve is calcined 0.5 hour at a temperature of 120 DEG C.It is handled, is removed by precalcining
The organic matter of template on molecular sieve pore passage and surface is more advantageous to subsequent ion exchange in this way.
2, ion exchange：ZSM-35 molecular sieve after precalcining is distributed to formation molecular sieve slurry in the water of room temperature；Together
When, in another reaction kettle, at room temperature by chlorination copper dissolution, it is subsequently poured into molecular sieve slurry, is stirred continuously, stirring 3
A hour.Wherein, the weight ratio of copper ion and ZSM-35 molecular sieve is 1%.
3, the molecular sieve after cation exchanges is washed with deionized, then 3 hours dry at 50 DEG C, then
500 DEG C of temperature lower calcinations 3 hours combine to make to exchange to the cationic stabilized in molecular sieve.
4, treated after the ion exchange with catalytic activity and drying and calcining, molecular sieve disperses in water, then mixes
It is incorporated into a certain proportion of hollow alumina bead powder, the matter when molecular sieve is mixed with the hollow alumina bead powder
Amount ratio is from 2:1, boehmite and hydroxyethyl cellulose is added after fully dispersed, cordierite honeycomb is coated to after stirring evenly
On carrier, the catalyst coat of tens microns of thickness is formed in the tiny cell walls of honeycomb substrate.
Embodiment 2
The present embodiment is substantially the same manner as Example 1, differs only in：The molecular sieve is Cu-ZSM-5 molecular sieves
In.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, differs only in：The molecular sieve is Beta molecular sieves.
The performance test results for the molecular sieve carried catalyst that embodiment 1-3 is prepared are as shown in table 1 below：
Table 1
Reaction velocity is 90000 (h-1), 800ppmNH3, 800ppmNO, 8%O2,
By table 1 as it can be seen that the catalyst that embodiment 1 is prepared can be under conditions of broader temperature range and high-speed
With high NOx conversion efficiency.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, differs only in：The ZSM-35 molecular sieve and the hollow oxygen
Mass ratio when changing the mixing of aluminium bead powder is 4:1.
Embodiment 5
The present embodiment is substantially the same manner as Example 1, differs only in：The ZSM-35 molecular sieve and the hollow oxygen
Mass ratio when changing the mixing of aluminium bead powder is 8:1.
Embodiment 6
The present embodiment is substantially the same manner as Example 1, differs only in：The ZSM-35 molecular sieve and the hollow oxygen
Mass ratio when changing the mixing of aluminium bead powder is 10:1.
Embodiment 7
The present embodiment is substantially the same manner as Example 1, differs only in：The ZSM-35 molecular sieve and the hollow oxygen
Mass ratio when changing the mixing of aluminium bead powder is 12:1.
Embodiment 8
The present embodiment is substantially the same manner as Example 1, differs only in：The ZSM-35 molecular sieve and the hollow oxygen
Mass ratio when changing the mixing of aluminium bead powder is 15:1.
The performance test results for the molecular sieve carried catalyst that embodiment 4-8 is prepared are as shown in table 2 below：
Table 2
Reaction velocity is 90000 (h-1), 800ppmNH3, 800ppmNO, 8%O2,
By table 2, it is seen then that mass ratio when ZSM-35 molecular sieve is mixed with the hollow alumina bead powder is to catalysis
Agent performance has significant impact.And the mixing quality of ZSM-35 molecular sieve and the hollow alumina bead powder is 8:When 1,
Conversion rate of NOx (%) under the conditions of 150~550 DEG C is above 70, and the conversion ratio is significantly higher than other ratio mixing
Embodiment.
As described above, the present invention can be realized preferably.
Claims (9)
1. the preparation method of the catalyst for ammine selectivity catalytic reduction removing NOx, which is characterized in that include following step successively
Suddenly：
(1) make molecular sieve carry out cation with the salting liquid of one or more kinds of metal cations by ion-exchange to exchange；
(2) after cation exchanges, the molecular sieve is washed with deionized, then dry at 50~200 DEG C, then 200~
600 DEG C of temperature lower calcinations combine to make to exchange to the cationic stabilized in molecular sieve；
(3) the step (2), treated that molecular sieve disperses in water, remixes into a certain proportion of hollow alumina bead
Powder, the mass ratio of the molecular sieve and the hollow alumina bead powder is from 2:1 to 15：1, it is added after fully dispersed viscous
Mixture and thickener, are then applied on cordierite honeycomb carrier, and thickness tens is formed in the tiny cell walls of honeycomb substrate
The catalyst coat of micron.
2. the preparation method for the catalyst of ammine selectivity catalytic reduction removing NOx, feature exist as described in claim 1
In in the step (1), the metal cation is copper ion, iron ion, titanium ion, vanadium ion and rare earth metal cations
In it is one or more；The salting liquid is chloride, acetate, nitrate, sulfate or other halide.
3. the preparation method for the catalyst of ammine selectivity catalytic reduction removing NOx, feature exist as described in claim 1
In in the step (1), metal cation and the molecular sieve ratio of exchange are from 0.5% to 40%.
4. the preparation method for the catalyst of ammine selectivity catalytic reduction removing NOx, feature exist as described in claim 1
In further including following steps before the step (1)：By molecular sieve precalcining.
5. the preparation method for the catalyst of ammine selectivity catalytic reduction removing NOx as described in claim 1, the step
(2) in, dry drying time is 2~5 hours at described 50~200 DEG C；The calcining of 200~600 DEG C of temperature lower calcinations
Time is 2~8 hours.
6. the preparation method for the catalyst of ammine selectivity catalytic reduction removing NOx, feature exist as described in claim 1
In the molecular sieve is ZSM-35 molecular sieve.
7. the preparation method for the catalyst of ammine selectivity catalytic reduction removing NOx, feature exist as described in claim 1
In the molecular sieve is one or both of ZSM-35 molecular sieve and Titanium Sieve Molecular Sieve.
8. the preparation method for the catalyst of ammine selectivity catalytic reduction removing NOx, feature exist as described in claim 1
In the molecular sieve is any one in ZSM-22 molecular sieves, Cu-ZSM-5 molecular sieves, Beta molecular sieves.
9. the catalyst for ammine selectivity catalytic reduction removing NOx, which is characterized in that use claim 1-8 any one
The method is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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