CN104349839B - Scr catalyst and preparation method thereof - Google Patents
Scr catalyst and preparation method thereof Download PDFInfo
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- CN104349839B CN104349839B CN201280073796.2A CN201280073796A CN104349839B CN 104349839 B CN104349839 B CN 104349839B CN 201280073796 A CN201280073796 A CN 201280073796A CN 104349839 B CN104349839 B CN 104349839B
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- scr catalyst
- base material
- catalyst composition
- zeolite
- ferrum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- 239000010457 zeolite Substances 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002657 fibrous material Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000002241 glass-ceramic Substances 0.000 claims description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 13
- 230000037452 priming Effects 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Abstract
The present invention relates to a kind of NH3SCR catalyst and preparation method thereof, this NH3SCR catalyst includes that ferrum promotes β zeolite, cerium oxide and titanium dioxide, and optionally farther includes at least one in tungsten oxide, Dineodymium trioxide, silicon oxide and kieselguhr.
Description
The present invention relates to a kind of carbon monoxide-olefin polymeric (SCR) and the method preparing this SCR catalyst composition, described catalysis
Agent compositions is for by reacting, with ammonia, the nitrogen oxides optionally reducing in waste gas.
Especially, the present invention provides NH3-SCR catalyst, it contains ferrum and promotes beta-zeolite, cerium oxide and titanium dioxide, and
Comprise at least one in tungsten oxide, Dineodymium trioxide, silicon oxide and kieselguhr the most further.
SCR is for removing nitrogen oxides (NO from flue and waste gasx) it is well-known method.Many catalyst are at literary composition
For at NO disclosed in offeringxReaction (DeNO with ammonia to nitrogenxActive catalyst in).
Known DeNOxThe problem of catalyst is that these catalyst have low activity under the high temperature higher than 500 DEG C.
Now, we have found a kind of particularly carbon monoxide-olefin polymeric, this carbon monoxide-olefin polymeric is in the temperature higher than 500 DEG C
It is activity NH under degree3-SCR catalyst.
Thus, the present invention provides a kind of SCR catalyst composition, its comprise the ferrum being deposited on base material promote beta-zeolite,
Cerium oxide and titanium dioxide.
Display further, as at least comprised in the composition in tungsten oxide, Dineodymium trioxide, silicon oxide and kieselguhr
When planting, the catalysis activity of described catalyst can be further enhanced.
Certain form of flue gas contains substantial amounts of suspended solid, i.e. dust and flue dust, causes high corrosion tendency
(erosion propensity)。
Have been found that adding kieselguhr in titanium dioxide obtains the repellence improving corrosion.
So, depend on application, in carbon monoxide-olefin polymeric, preferably comprise silicon with the diatomaceous amount of up to 60wt%
Diatomaceous earth.
If not otherwise specified, all amounts that are above-mentioned and that hereinafter mention are calculated in weight percent, to comprise base material
Carbon monoxide-olefin polymeric total amount calculate.
In embodiments of the invention, described carbon monoxide-olefin polymeric preferably further comprises tungsten oxide, Dineodymium trioxide, oxidation
At least one in silicon and kieselguhr.
Base material preferably includes fibrous material and is configured to corrugated (corrugated shape).
In a preferred embodiment of the present invention, described carbon monoxide-olefin polymeric comprise 5 to 60wt% ferrum promote beta-zeolite,
The cerium oxide of 2 to 20wt% and the titanium dioxide of 20 to 70wt%, and the WO of optional 2 to 6wt%3With 2 to 6wt%'s
SiO2。
In beta-zeolite the amount of ferrum preferably with the gauge of beta-zeolite between 0.5 to 15wt%.
Catalyst according to the invention compositions provides the High-temperature scr catalyst with long-time stability.
The compositions of the present invention has extensively at engine exhaust with in the denitrogenation of the waste gas of stationary source such as electric station
General application.
In some application above-mentioned, it is preferable that described carbon monoxide-olefin polymeric is provided at en-block construction base material
On (monolithic structured substrate).
Preferably fiber base material is bellows-shaped.
Described catalyst can also be provided at wall flow particulate filters (particulate wall flow
Filter) in, such as in the waste gas cleaning system of compression ignition engine.
The present invention further provides the preparation method of SCR catalyst that is disclosed above and that limit, the method include with
Lower step:
Base material is provided；
Thering is provided priming paint (wash coat), this priming paint comprises ferrum and promotes beta-zeolite and titanium dioxide, and wraps the most further
Silicon oxide-containing and/or kieselguhr；
It is coated with cloth base material with described priming paint and is dried and calcines this base material being coated with priming paint；
Then, should with the aqueous impregnation containing cerium oxide precursor and optional tungsten oxide precursor and/or Dineodymium trioxide precursor
The base material being coated with priming paint through calcining；And
Calcine this base material being through impregnation with, cerium oxide precursor to be converted into cerium oxide, and by optional tungsten oxide precursor
And/or Dineodymium trioxide precursor is converted into tungsten oxide and/or Dineodymium trioxide.
Preferably, described priming paint comprise with the total amount of priming paint and base material be calculated as 5 to 60wt% ferrum promote beta-zeolite, 2 to
The cerium oxide of 20wt% and the titanium dioxide of 20 to 70wt%.
If any, it is preferable that in carbon monoxide-olefin polymeric in terms of the total amount of priming paint and base material the amount of tungsten oxide be 2 to
6wt%, the amount of silicon oxide are 2 to 6wt% and diatomaceous amount is 0 to 60%.
In beta-zeolite, the amount of ferrum accelerator is preferably 0.5 to 15wt% with the gauge of beta-zeolite.
In embodiments of the invention, base material includes fibrous material, is preferably made up of glass fibre or ceramic fibre.
Embodiment
Embodiment 1
According to one embodiment of the invention, the preparation of catalyst comprises the steps of:
Corrugated fibrous glass base material is provided；
Thering is provided priming paint, by the ferrum of 30%, described priming paint promotes that the titanium dioxide of beta-zeolite and 40wt% forms, described ferrum promotees
Enter the ferrum that beta-zeolite comprises 0.5wt%；
Described component is mixed with butanol；
It is coated with cloth base material with priming paint and is dried and calcines this base material being coated with priming paint；
Then, with the aqueous solution containing the cerous nitrate as cerium oxide precursor at 550 DEG C, impregnate this coating through calcining
There is the base material of priming paint；
This base material being through impregnation with is calcined, cerium oxide precursor to be changed into cerium oxide, and in the catalysis made at 450 DEG C
Agent reaches the cerium oxide of 10wt%.
Embodiment 2
Catalyst test
The present embodiment is given following catalyst at 550 DEG C through time activity level comparison:
1) reference Fe β/TiO2Catalyst.
2) reference Fe β/TiO2Catalyst+5%CeO2。
3) reference Fe β/TiO2Catalyst+10%CeO2。
4) reference Fe β/TiO2Catalyst+20%CeO2。
5) reference Fe β/TiO2Catalyst+10%CeO2And 10%Nd2O3。
6) reference Fe β/TiO2Catalyst+5%CeO2, 4%WO3And 4%SiO2。
In laboratory reactor, test catalyst, use the sample cut from monolithic sample (monolith sample)
Product plate (plates), and by sample panel alignment (aligned) so that gas is along sample panel Surface runoff.Reactor is mounted with 4
Block sample panel (long 3.5cm, wide 1.1cm, thick 0.8mm).Inlet gas comprises 5%H2O, 4%O2And N2As surplus.Entrance
NO concentration is 500ppm and entrance NH3/ NO ratio is 1.5.Temperature is 550 DEG C and equivalent airspeed (EAS) (equivalent GHSV)
For 72000Nm3/m3/h.The air-flow of unit catalyst weight is 80Nm3/h/kg。
Activity coefficient (activity coefficient) is calculated as below:
KNOx=-NHSV*ln (1-NO conversion).
The characteristic of catalyst 1-6 listed above is summarized in Fig. 1 of accompanying drawing.
Claims (6)
1. a SCR catalyst composition, it is deposited on base material, and described SCR catalyst composition comprises and combines with catalyst
The total amount meter of thing and base material,
The ferrum of 5 to 60wt% promotes beta-zeolite,
The titanium dioxide of 20 to 70wt%,
The cerium oxide of 2 to 20wt%,
The tungsten oxide of 2 to 6wt%,
The silicon oxide of 2 to 6wt%, and
The kieselguhr of 0 to 60wt%.
SCR catalyst composition the most according to claim 1, wherein said ferrum promotes that beta-zeolite comprises the amount with beta-zeolite
It is calculated as the ferrum of 0.5 to 15wt%.
SCR catalyst composition the most according to claim 1 and 2, wherein said base material includes fibrous material.
SCR catalyst composition the most according to claim 3, wherein said fibrous material is by glass fibre or ceramic fibre
Constitute.
SCR catalyst composition the most according to claim 1, is wherein configured to corrugated by described base material.
SCR catalyst composition the most according to claim 1, wherein said base material is wall flow particulate filters.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA201270304 | 2012-06-06 | ||
| DKPA201270304 | 2012-06-06 | ||
| PCT/EP2012/066976 WO2013182255A1 (en) | 2012-06-06 | 2012-08-31 | Scr catalyst and method of preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104349839A CN104349839A (en) | 2015-02-11 |
| CN104349839B true CN104349839B (en) | 2016-11-30 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Address after: Denmark City Applicant after: Topsoe A/S Address before: Denmark City Applicant before: Haldor Topse A/S |
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| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180212 Address after: Hanau, Germany Patentee after: Limited Partnership On shares Address before: Denmark City Patentee before: Topsoe A/S |