CN103252232B - A kind of vanadium oxide catalyst, preparation method and its usage of zirconium doping - Google Patents

A kind of vanadium oxide catalyst, preparation method and its usage of zirconium doping Download PDF

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CN103252232B
CN103252232B CN201310208338.1A CN201310208338A CN103252232B CN 103252232 B CN103252232 B CN 103252232B CN 201310208338 A CN201310208338 A CN 201310208338A CN 103252232 B CN103252232 B CN 103252232B
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catalyst
zirconium
vanadium
oxide
dryness
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CN103252232A (en
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贺泓
单文坡
刘福东
连志华
谢利娟
杨卫卫
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Research Center for Eco Environmental Sciences of CAS
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Abstract

The present invention relates to vanadium oxide catalyst that a kind of zirconium for ammine selectivity catalytic reduction nitrous oxides adulterates and preparation method thereof.Described catalyst is the oxide carried metal oxide catalyst formed to titanium tungsten powder surface of zirconium and vanadium.The present invention significantly can improve high-temperature stability and the N of traditional catalytic component based on vanadium by the method that zirconium adulterates 2generate selective catalytic performance of Denging, the vanadium oxide catalyst of prepared zirconium doping be applicable to exhaust gas from diesel vehicle be representative moving source and take coal-fired plant flue gas as the stationary source catalytic purification of nitroxide device of representative.

Description

A kind of vanadium oxide catalyst, preparation method and its usage of zirconium doping
Technical field
The present invention relates to a kind of catalyst, be specifically related to the vanadium tungsten titanium oxide catalyst that a kind of zirconium for catalytic cleaning nitrogen oxide adulterates, particularly a kind of moving source for taking exhaust gas from diesel vehicle as representative and take coal-fired plant flue gas as the vanadium tungsten titanium oxide catalyst of zirconium doping of stationary source catalytic purification of nitroxide of representative.
Background technology
Nitrogen oxide (NO x, mainly refer to NO and NO 2) be the important pollutant of one in air.NO xthere is stronger bio-toxicity, can to health, especially respiratory system produces and directly endangers.In addition, NO xthe great environmental problem such as acid rain, photochemical fog can also be caused.Control NO xdischarge be the major issue that current field of environment protection needs solution badly.
At stationary source NO xwith moving source NO xin emission control technique, NH 3selective Catalytic Reduction of NO x(i.e. NH 3-SCR) technology is widely used in the stationary source NO such as coal-burning power plant xcatalytic removal, be also hopeful most large-scale application in moving source NO such as exhaust gas from diesel vehicle xpurification.By NH 3-SCR technology is applied to stationary source NO xcatalytic elimination be that first 20 century 70s grow up in Japan, subsequently the U.S. and Europe etc. countries and regions be widely used.Owing to being equipped with NH 3there is certain danger in storage tank, NH 3-SCR technology is used for moving source NO xduring catalytic elimination, usually by reducing agent NH 3be replaced with the urea liquid that security is higher.
The NH of industrial applications 3-SCR catalyst is normally containing the V of vanadium (V) 2o 5-WO 3/ TiO 2catalyst, wherein with TiO 2as carrier, with V 2o 5as active component, with WO 3as catalyst aid.This traditional vanadium-based catalyst systems from the seventies in last century by industrial applications since coal-fired plant flue gas denitration, experienced by the test of nearly 40 years, although also there is certain problem in actual applications, but still is NH 3classical formalism in-SCR catalyst.In view of implementing in full of China diesel vehicle state IV stage emission standard is day by day closed on, People, Weihe River bavin, Shang Chaideng domestic enterprise all will adopt NH 3-SCR technology path carries out exhaust aftertreatment, to meet the requirement of this standard.NH 3-SCR technology is widely used in exhaust gas from diesel vehicle NO xremoving has been trend of the times, and the most ripe all vanadium-based catalyst systems of investigation and application becomes the first-selection of present stage.In addition, China also has numerous inland river marine diesel, and due to bunker fuel oil complicated component, especially sulfur content is high, can practical application under this tail gas condition SCR catalyst system also non-catalytic component based on vanadium do not belong to.
At present, the major issue that vanadium tungsten titanium oxide catalyst system is faced in actual applications is high temperature deactivation.Therefore, the high-temperature stability improving this catalyst system has very important significance.The patent (CN102523735A) of Millennium Inorganic Chem discloses composition and the method for the ultra-fine anatase titania of a kind of silica stabilisation, by utilizing the low molecular weight forms of silica and/or little form of nanoparticles to TiO 2particle carries out process to realize surface stabilization, can improve the high-temperature stability of vanadium-titanium catalyst system; With traditional take titanium dioxide as the V of the oxide of carrier loaded vanadium and the Preparation of tungsten 2o 5-WO 3/ TiO 2catalyst is compared, and take titanium tungsten powder as the V of the Preparation of carrier loaded vanadium 2o 5/ WO 3-TiO 2catalyst has more excellent high-temperature stability usually, discloses two kinds of preparation methods for the titanium tungsten powder of SCR catalyst in patent (CN102764662A) and patent (CN102698737A); Be the oxide of carrier loaded vanadium with titanium tungsten powder in the present invention, by the doping of zirconium, prepared ZrO 2-V 2o 5/ WO 3-TiO 2catalyst, this catalyst has and compares V 2o 5/ WO 3-TiO 2more excellent high-temperature stability and N 2generate selective.
Summary of the invention
For existing NH 3the deficiency that-SCR catalyst exists, in order to solve the shortcomings such as vanadium oxide catalyst system high-temperature poor stability, the present invention provides vanadium tungsten titanium oxide catalyst and preparation method thereof of a kind of zirconium doping first, can be used as with exhaust gas from diesel vehicle be representative moving source and take coal-fired plant flue gas as the stationary source NO of representative xcatalytic purification, the present invention is preferred for the NO of exhaust gas from diesel vehicle xcatalytic purification.
Therefore, an object of the present invention is the vanadium tungsten titanium oxide catalyst that provides a kind of zirconium for catalytic cleaning nitrogen oxide to adulterate.
In order to achieve the above object, present invention employs following technical scheme:
For the vanadium tungsten titanium oxide catalyst that the zirconium of catalytic cleaning nitrogen oxide adulterates, the oxide carried metal oxide catalyst formed to titanium tungsten powder surface that described catalyst is zirconium and vanadium, i.e. ZrO x-VO x/ WO x-TiO 2.
Described catalyst comprises vanadium (V), zirconium (Zr), tungsten (W) and titanium (Ti) four kinds of metal components.
In the catalyst, V, Zr, W and Ti element all exists with oxidation state.
In the catalyst, in titanium tungsten powder, titanium dioxide is anatase crystal, the content of tungstic acid is 3 ~ 30wt% of the quality of titanium tungsten powder, preferably 5 ~ 15wt%, such as 8wt%, 10wt%, 12wt%, 4wt%, 6wt%, 14wt%, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%.
In the quality of described titanium tungsten powder for 100wt%, the load capacity of described barium oxide is 0.1 ~ 10wt%, such as 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, preferably 1 ~ 5wt%.
In the quality of described titanium tungsten powder for 100wt%, the load capacity of described Zirconium oxide is 0.5 ~ 30wt%, such as 2wt%, 5wt%, 10wt%, 8wt%, 12wt%, 15wt%, 18wt%, 21wt%, 24wt%, 27wt%, 29wt%, preferably 1 ~ 15wt%.
The oxide of described V is VO x, it is the oxide mixture of different valence state V, such as V 4+and V 5+mixture; The oxide of described Zr is ZrO x, it is the oxide mixture of different valence state Zr, such as Zr 3+and Zr 4+mixture; The oxide of described W is WO x, it is the oxide mixture of different valence state W, such as W 5+and W 6+mixture.
Two of object of the present invention is the preparation method of the vanadium tungsten titanium oxide catalyst providing a kind of zirconium to adulterate, and described method is infusion process, and it comprises the steps:
(1) mixed solution in zirconium source and vanadium source is prepared;
(2) in mixed solution, add titanium tungsten powder, stir under normal temperature condition;
(3) carry out evaporate to dryness, obtain solid content;
(4) by the roasting of gained solid content, the vanadium tungsten titanium oxide catalyst of described zirconium doping is obtained.
In step (1), described zirconium source is selected from the mixture of any one or at least two kinds in zirconium chloride, zirconium nitrate or zirconium sulfate.The mixture of described mixture such as zirconium chloride and zirconium nitrate, the mixture of zirconium chloride and zirconium sulfate, the mixture of zirconium nitrate and zirconium sulfate, the mixture of zirconium chloride, zirconium nitrate and zirconium sulfate.The molecular formula of zirconium nitrate: Zr (NO 3) 45H 2o.
In step (1), described vanadium source is selected from vanadic salts or/and vanadate, the mixture of any one or at least two kinds preferably in ammonium metavanadate, vanadic sulfate, vanadyl oxalate, vanadium tetrachloride or vanadium oxytrichloride.The mixture of described mixture such as ammonium metavanadate and vanadic sulfate, the mixture of vanadyl oxalate and vanadium tetrachloride, the mixture of vanadium oxytrichloride and ammonium metavanadate, the mixture of vanadic sulfate and vanadyl oxalate, the mixture of vanadium tetrachloride and vanadium oxytrichloride.
In step (2), described mixing time is 0.5 ~ 10h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, preferably 0.8 ~ 5h, further preferred 1 ~ 3h.
In step (3), described evaporate to dryness method is direct evaporate to dryness or/and rotate evaporate to dryness, preferably rotates evaporate to dryness.The mixed solution that described direct evaporate to dryness obtains by step (2) is in an oven until distilled-to-dryness.
Preferably, the temperature of described rotation evaporate to dryness is 50 ~ 70 DEG C, such as 52 DEG C, 54 DEG C, 56 DEG C, 58 DEG C, 60 DEG C, 62 DEG C, 64 DEG C, 66 DEG C, 68 DEG C, preferably 53 ~ 67 DEG C, preferably 55 ~ 65 DEG C further.
In step (3), described direct evaporate to dryness evaporate to dryness at 80 ~ 120 DEG C, described evaporate to dryness temperature such as 82 DEG C, 84 DEG C, 88 DEG C, 92 DEG C, 96 DEG C, 100 DEG C, 104 DEG C, 108 DEG C, 112 DEG C, 114 DEG C, 116 DEG C, preferably puts into baking oven in 80 ~ 120 DEG C of evaporates to dryness.
In step (4), described roasting is carried out in air atmosphere, described sintering temperature is 400 ~ 800 DEG C, described sintering temperature such as 420 DEG C, 440 DEG C, 480 DEG C, 520 DEG C, 560 DEG C, 600 DEG C, 640 DEG C, 680 DEG C, 720 DEG C, 740 DEG C, 760 DEG C, 780 DEG C, described roasting time is 1 ~ 24h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, preferably 2 ~ 12h, further preferred 4 ~ 6h.
Three of object of the present invention is the method providing nitrogen oxide in a kind of catalytic purification gas, the vanadium tungsten titanium oxide catalyst that described method uses zirconium of the present invention to adulterate.This catalyst can carry out slurrying according to actual needs, is then coated on various honeycomb ceramic carrier, is prepared into shaping catalyst and uses, and also can use after extruded.
During use, catalyst is placed in exhaust pipe way, reducing agent and tail gas mixing is sprayed in the upstream of catalyst, reducing agent adopts ammonia or urea (can obtain ammonia after hydrolysis), reducing agent consumption is 0.8 ~ 1.2 times of nitrogen oxide in tail gas, can by NO in very wide temperature window under excess oxygen xbe reduced to N 2and H 2o, possesses very high N simultaneously 2generate selective and sulfur resistive water repelling property.
Described tail gas is preferably moving source gas containing nitrogen oxide, such as exhaust gas from diesel vehicle, or stationary source gas containing nitrogen oxide, such as coal-fired plant flue gas.Described gas is preferably exhaust gas from diesel vehicle, and namely the present invention is specially adapted to the catalytic purification of nitrogen oxide in exhaust gas from diesel vehicle.
Compared with prior art, tool of the present invention has the following advantages:
(1) the operating temperature window of the vanadium tungsten titanium oxide catalyst of described zirconium doping is wide, is applicable to the applied environment that motor-vehicle tail-gas range of temperature is large; In stationary source denitrating flue gas, the high-temperature stability due to its excellence is expected to the service life of improving SCR catalyst;
(2) the vanadium tungsten titanium oxide catalyst of described zirconium doping has the high-temperature stability more more excellent than traditional catalytic component based on vanadium;
(3) the vanadium tungsten titanium oxide catalyst of zirconium doping has the N more more excellent than traditional catalytic component based on vanadium 2generate selective;
(4) the vanadium tungsten titanium oxide catalyst of zirconium doping has extraordinary water resistant sulfur resistance.
Detailed description of the invention
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
0.964g ammonium metavanadate is dissolved in oxalic acid solution (mass ratio of ammonium metavanadate and oxalic acid is 1:2), is mixed with 750ml mixed solution, mixes, in this solution, add 25g titanium tungsten powder (10%WO 3-TiO 2), fully stir 1h, then mixed serum carried out rotary evaporation and fully volatilize to moisture, and under 100 DEG C of air atmospheres dry 12h, finally roasting 3h under 550 DEG C of air atmospheres, obtains 3%V 2o 5/ 10%WO 3-TiO 2catalyst.
Obtained catalyst is ground, sieves, gets 40 ~ 60 orders for subsequent use, be called catalyst A.
Embodiment 2
By 0.964g ammonium metavanadate (NH 4vO 3) be dissolved in oxalic acid solution (mass ratio of ammonium metavanadate and oxalic acid is 1:2), and in this solution, add 1.74g five nitric hydrate zirconium (Zr (NO 3) 45H 2o), be mixed with 750mL mixed solution, mix, in this solution, add 25g titanium tungsten powder (10%WO 3-TiO 2), fully stir 1h, then mixed serum carried out rotary evaporation and fully volatilize to moisture, and under 100 DEG C of air atmospheres dry 12h, finally roasting 3h under 550 DEG C of air atmospheres, obtains 3%V 2o 5-2%ZrO 2/ 10%WO 3-TiO 2catalyst.
Obtained catalyst is ground, sieves, gets 40 ~ 60 orders for subsequent use, be called catalyst B.
Embodiment 3
Other condition is as constant in embodiment 2, and changing five nitric hydrate zirconium additions is 4.36g, obtains 5%V 2o 5-2%ZrO 2/ 10%WO 3-TiO 2catalyst.Obtained catalyst is ground, sieves, gets 40 ~ 60 orders for subsequent use, be called catalyst C.
Embodiment 4
Other condition is as constant in embodiment 2, and changing five nitric hydrate zirconium additions is 8.72g, obtains 10%V 2o 5-2%ZrO 2/ 10%WO 3-TiO 2catalyst.Obtained catalyst is ground, sieves, gets 40 ~ 60 orders for subsequent use, be called catalyst D.
Embodiment 5
Catalyst A, B, C, D roasting 8h in 650 DEG C of air is obtained catalyst E, F, G, H.
Vanadium tungsten titanium compound oxide catalyst A, B, C, D, E, F, G, the H obtained with embodiment 1-5 carry out NH on fixed bed reactors 3selective Catalytic Reduction of NO xthe investigation of reactivity.
The use amount of catalyst is 0.6ml, consisting of of reaction mixture gas: [NO]=[NH 3]=500ppm, [O 2]=5%, N 2make Balance Air, total gas flow rate is 500mL/min, and air speed is 50,000h -1, reaction temperature 150 ~ 450 DEG C.NO and NH 3and accessory substance N 2o, NO 2infrared-gas pond is all utilized to measure.NO xconversion ratio and N 2generate selective difference as shown in Table 1 and Table 2.
The V of the different Zr doping of table 1 2o 5/ WO 3-TiO 2the NO of catalyst and the catalyst after high-temperature roasting xconversion ratio
The V of the different Zr doping of table 2 2o 5/ WO 3-TiO 2the N of catalyst and the catalyst after high-temperature roasting 2generate selective
Embodiment 6
Vanadic sulfate is dissolved in oxalic acid solution (mass ratio of vanadic sulfate and oxalic acid is 1:2), and zirconium chloride is added in this solution, be mixed with mixed solution, mix, titanium tungsten powder (content of tungstic acid is 3wt%) is added in this solution, abundant stirring 0.5h, then mixed serum is carried out rotary evaporation at 50 DEG C fully to volatilize to moisture, and under 100 DEG C of air atmospheres dry 12h, finally roasting 24h under 400 DEG C of air atmospheres, obtain the vanadium oxide catalyst of zirconium doping, wherein, with the quality of described titanium tungsten powder for 100wt%, the load capacity of described barium oxide is 0.1wt%, the load capacity of described Zirconium oxide is 30wt%.
Embodiment 7
Vanadium tetrachloride is dissolved in oxalic acid solution (mass ratio of vanadium tetrachloride and oxalic acid is 1:2), and zirconium sulfate is added in this solution, be mixed with mixed solution, mix, titanium tungsten powder (content of tungstic acid is 30wt%) is added in this solution, abundant stirring 10h, then mixed serum is carried out rotary evaporation at 70 DEG C fully to volatilize to moisture, and under 100 DEG C of air atmospheres dry 12h, finally roasting 1h under 800 DEG C of air atmospheres, obtain the vanadium oxide catalyst of zirconium doping, wherein, with the quality of described titanium tungsten powder for 100wt%, the load capacity of described barium oxide is 10wt%, the load capacity of described Zirconium oxide is 0.5wt%.
Embodiment 8
Vanadium oxytrichloride is dissolved in oxalic acid solution (mass ratio of vanadium oxytrichloride and oxalic acid is 1:2), and zirconium nitrate is added in this solution, be mixed with mixed solution, mix, titanium tungsten powder (content of tungstic acid is 10wt%) is added in this solution, abundant stirring 5h, then mixed serum is positioned in baking oven and fully volatilizees to moisture at 80 DEG C of evaporates to dryness, and under 100 DEG C of air atmospheres dry 12h, finally roasting 15h under 500 DEG C of air atmospheres, obtain the vanadium oxide catalyst of zirconium doping, wherein, with the quality of described titanium tungsten powder for 100wt%, the load capacity of described barium oxide is 5wt%, the load capacity of described Zirconium oxide is 3wt%.
Embodiment 9
Vanadium oxytrichloride is dissolved in oxalic acid solution (mass ratio of vanadium oxytrichloride and oxalic acid is 1:2), and zirconium nitrate is added in this solution, be mixed with mixed solution, mix, titanium tungsten powder (content of tungstic acid is 10wt%) is added in this solution, abundant stirring 5h, then mixed serum is positioned in baking oven and fully volatilizees to moisture at 120 DEG C of evaporates to dryness, and under 100 DEG C of air atmospheres dry 12h, finally roasting 15h under 500 DEG C of air atmospheres, obtain the vanadium oxide catalyst of zirconium doping, wherein, with the quality of described titanium tungsten powder for 100wt%, the load capacity of described barium oxide is 5wt%, the load capacity of described Zirconium oxide is 3wt%.
As shown in Table 1, the vanadium oxide catalyst (catalyst A) (catalyst E) after high-temperature roasting process of the Zr that do not adulterate, low temperature and high temperature NO xconversion ratio all obviously reduces.The vanadium oxide catalyst (catalyst B, C, D) after high-temperature roasting process (catalyst F, G, H) of doping Zr, although activity also slightly reduces, compared with the catalyst of the Zr that do not adulterate, its high-temperature stability is all obviously improved.In addition, the catalyst n of doping Zr 2generate selective all apparently higher than the catalyst (table 2) of the Zr that undopes.
Applicant states, the present invention illustrates detailed composition of the present invention and method by above-described embodiment, but the present invention is not limited to above-mentioned detailed composing method, does not namely mean that the present invention must rely on above-mentioned detailed composition and method could be implemented.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (21)

1. for the vanadium tungsten titanium oxide catalyst that the zirconium of catalytic cleaning nitrogen oxide adulterates, it is characterized in that, the oxide carried metal oxide catalyst formed to titanium tungsten powder surface that described catalyst is zirconium and vanadium; In the quality of described titanium tungsten powder for 100wt%, the load capacity of Zirconium oxide is 0.5 ~ 30wt%, and the load capacity of barium oxide is 0.1 ~ 10wt%; In titanium tungsten powder, titanium dioxide is anatase crystal, and the content of tungstic acid is 3 ~ 30wt% of the quality of titanium tungsten powder;
The preparation method of the vanadium tungsten titanium oxide catalyst of described zirconium doping, it comprises the steps:
(1) mixed solution in zirconium source and vanadium source is prepared;
(2) in mixed solution, add titanium tungsten powder, stir under normal temperature condition;
(3) carry out evaporate to dryness, obtain solid content;
(4) by the roasting of gained solid content, the vanadium tungsten titanium oxide catalyst of described zirconium doping is obtained;
Wherein, described zirconium source is selected from the mixture of any one or at least two kinds in zirconium chloride, zirconium nitrate or zirconium sulfate, described vanadium source is selected from vanadic salts or/and vanadate, described mixing time is 0.5 ~ 10h, described roasting is carried out in air atmosphere, described sintering temperature is 400 ~ 800 DEG C, and described roasting time is 1 ~ 24h.
2. catalyst as claimed in claim 1, it is characterized in that, in titanium tungsten powder, titanium dioxide is anatase crystal, and the content of tungstic acid is 5 ~ 15wt% of the quality of titanium tungsten powder.
3. catalyst as claimed in claim 1, it is characterized in that, in the quality of described titanium tungsten powder for 100wt%, the load capacity of barium oxide is 1 ~ 5wt%.
4. catalyst as claimed in claim 1 or 2, it is characterized in that, in the quality of described titanium tungsten powder for 100wt%, the load capacity of Zirconium oxide is 1 ~ 15wt%.
5. catalyst as claimed in claim 1, is characterized in that, described vanadium source is selected from the mixture of any one or at least two kinds in ammonium metavanadate, vanadic sulfate, vanadyl oxalate, vanadium tetrachloride or vanadium oxytrichloride.
6. catalyst as claimed in claim 1, it is characterized in that, described mixing time is 0.8 ~ 5h.
7. catalyst as claimed in claim 6, it is characterized in that, described mixing time is 1 ~ 3h.
8. catalyst as claimed in claim 1, is characterized in that, in step (3), described evaporate to dryness method is direct evaporate to dryness or/and rotate evaporate to dryness.
9. catalyst as claimed in claim 8, it is characterized in that, the temperature of described rotation evaporate to dryness is 50 ~ 70 DEG C.
10. catalyst as claimed in claim 9, it is characterized in that, the temperature of described rotation evaporate to dryness is 53 ~ 67 DEG C.
11. catalyst as claimed in claim 10, is characterized in that, the temperature of described rotation evaporate to dryness is 55 ~ 65 DEG C.
12. catalyst as claimed in claim 8, is characterized in that, described direct evaporate to dryness evaporate to dryness at 80 ~ 120 DEG C.
13. catalyst as claimed in claim 12, is characterized in that, described direct evaporate to dryness puts into baking oven in 80 ~ 120 DEG C of evaporates to dryness.
14. catalyst as claimed in claim 1, it is characterized in that, described roasting time is 2 ~ 12h.
15. catalyst as claimed in claim 14, it is characterized in that, described roasting time is 4 ~ 6h.
In 16. 1 kinds of catalytic purification gases, the method for nitrogen oxide, is characterized in that, the vanadium tungsten titanium oxide catalyst of the zirconium doping that described method uses one of claim 1-15 described.
17. methods as claimed in claim 16, is characterized in that, by described catalyst slurrying, be then coated on honeycomb ceramic carrier, be prepared into shaping catalyst and use.
18. methods as claimed in claim 17, is characterized in that, use after extruded.
19. methods as claimed in claim 17, it is characterized in that, during use, catalyst is placed in exhaust pipe way, spray into reducing agent and tail gas mixing in the upstream of catalyst, reducing agent adopts ammonia or urea, and reducing agent consumption is 0.8 ~ 1.2 times of nitrogen oxide in tail gas.
20. methods as claimed in claim 19, is characterized in that, described tail gas is moving source gas containing nitrogen oxide or stationary source gas containing nitrogen oxide.
21. want the method as described in 19 as right, and it is characterized in that, described tail gas is exhaust gas from diesel vehicle.
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