CN103252232A - Zirconium-doped vanadium-based oxide catalyst, and preparation method and application thereof - Google Patents
Zirconium-doped vanadium-based oxide catalyst, and preparation method and application thereof Download PDFInfo
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- CN103252232A CN103252232A CN2013102083381A CN201310208338A CN103252232A CN 103252232 A CN103252232 A CN 103252232A CN 2013102083381 A CN2013102083381 A CN 2013102083381A CN 201310208338 A CN201310208338 A CN 201310208338A CN 103252232 A CN103252232 A CN 103252232A
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- zirconium
- vanadium
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 37
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 26
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical group 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 28
- UCKLMHXLCUEQPZ-UHFFFAOYSA-N [O-2].[Ti+4].[V+5].[W+4] Chemical compound [O-2].[Ti+4].[V+5].[W+4] UCKLMHXLCUEQPZ-UHFFFAOYSA-N 0.000 claims description 17
- 235000006408 oxalic acid Nutrition 0.000 claims description 16
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 16
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 6
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 claims description 6
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 239000003245 coal Substances 0.000 abstract 1
- 239000000779 smoke Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 229910010413 TiO 2 Inorganic materials 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 6
- 210000002966 serum Anatomy 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000010747 number 6 fuel oil Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a zirconium-doped vanadium-based oxide catalyst for selectively catalyzing and reducing the nitrogen oxide through ammonia, and a preparation method thereof. The catalyst is a metal oxide catalyst which is formed by loading zirconium and vanadium oxide onto the surface of titanium tungsten powder. Through the zirconium doping method, the catalytic properties such as high-temperature stability of the traditional vanadium-based catalyst and the N2 (nitrogen) generation selectivity can be greatly improved, the prepared zirconium-doped vanadium-based oxide catalyst is suitable for a nitrogen oxide catalytic purifying device adopting the diesel exhaust as a representative movable resource and the smoke of a coal plant as a representative fixed source.
Description
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 mixes, particularly a kind of for being the moving source of representative with the exhaust gas from diesel vehicle and being the vanadium tungsten titanium oxide catalyst that the zirconium of the stationary source catalytic purification of nitroxide of representative mixes with the coal-fired plant flue gas.
Background technology
Nitrogen oxide (NO
x, mainly refer to NO and NO
2) be a kind of important pollutant in the atmosphere.NO
xHave stronger bio-toxicity, can be to health, especially respiratory system produces directly harm.In addition, NO
xCan also cause great environmental problem such as acid rain, photochemical fog.Control NO
xDischarging be the major issue that current field of environment protection is needed solution badly.
At stationary source NO
xWith moving source NO
xIn the emission control technique, NH
3Selective Catalytic Reduction of NO
x(be NH
3-SCR) technology has been widely used in stationary source NO such as coal-burning power plant
xCatalysis eliminate, also be hopeful most large-scale application in moving source NO such as exhaust gas from diesel vehicle
xPurify.With NH
3-SCR technology is applied to stationary source NO
xCatalytic elimination be at first to grow up in Japan the seventies in 20th century, be widely used in countries and regions such as the U.S. and Europe subsequently.Owing to be equipped with NH
3Storage tank exists certain danger, NH
3-SCR technology is used for moving source NO
xDuring catalytic elimination, usually with reducing agent NH
3Be replaced with the higher urea liquid of security.
The NH of industrial applications
3-SCR catalyst normally contains the V of vanadium (V)
2O
5-WO
3/ TiO
2Catalyst is 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 the coal-fired plant flue gas denitration, experienced nearly 40 years test, though also exist certain problem in actual applications, but still be NH
3Classical formalism in the-SCR catalyst.In view of implementing in full day by day of China diesel vehicle state IV stage discharge standard closed on, China heavily domestic enterprises such as vapour, Weihe River bavin, last bavin all will adopt NH
3-SCR technology path carries out exhaust aftertreatment, to satisfy 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, studies and use the first-selection that all ripe vanadium-based catalyst systems becomes present stage.In addition, China also has numerous inland river marine diesel, because bunker fuel oil complicated component, especially sulfur content height, SCR catalyst system that can practical application under this tail gas condition yet non-catalytic component based on vanadium does not belong to.
At present, a major issue facing in actual applications of vanadium tungsten titanium oxide catalyst system is high temperature deactivation.Therefore, the high-temperature stability of improving this catalyst system has very important significance.The patent of Millennium Inorganic Chem (CN102523735A) has been announced composition and the method for the ultra-fine anatase titania of a kind of silica stabilisation, and the low-molecular-weight form by utilizing silica and/or little form of nanoparticles are to TiO
2Particle handles to realize surface stabilization, can improve the high-temperature stability of vanadium-titanium catalyst system; With traditional be the V of the oxide preparation of the oxide of carrier loaded vanadium and tungsten with titanium dioxide
2O
5-WO
3/ TiO
2Catalyst is compared, and is the V of the oxide preparation of carrier loaded vanadium with the titanium tungsten powder
2O
5/ WO
3-TiO
2Catalyst has more excellent high-temperature stability usually, has announced two kinds of preparation methods that are used for the titanium tungsten powder of SCR catalyst in patent (CN102764662A) and the patent (CN102698737A); Be the oxide of carrier loaded vanadium with the titanium tungsten powder among the present invention, the doping by zirconium has prepared ZrO
2-V
2O
5/ WO
3-TiO
2Catalyst, this catalyst has the V of ratio
2O
5/ WO
3-TiO
2More excellent high-temperature stability and N
2Generate selective.
Summary of the invention
At existing NH
3The deficiency that-SCR catalyst exists, in order to solve shortcomings such as vanadium oxide catalyst system high-temperature poor stability, the present invention provides vanadium tungsten titanium oxide catalyst that a kind of zirconium mixes and preparation method thereof first, can be used as with the exhaust gas from diesel vehicle to be the moving source of representative and to be the stationary source NO of representative with the coal-fired plant flue gas
xCatalytic purification, the present invention is preferred for the NO of exhaust gas from diesel vehicle
xCatalytic purification.
Therefore, one of purpose of the present invention is to provide a kind of vanadium tungsten titanium oxide catalyst that mixes for the zirconium of catalytic cleaning nitrogen oxide.
In order to achieve the above object, the present invention has adopted following technical scheme:
The vanadium tungsten titanium oxide catalyst that a kind of zirconium for catalytic cleaning nitrogen oxide mixes, described catalyst are the oxide carried formed metal oxide catalyst of titanium tungsten powder surface, the i.e. ZrO of arriving of zirconium and vanadium
x-VO
x/ WO
x-TiO
2
Described catalyst comprises vanadium (V), zirconium (Zr), tungsten (W) and four kinds of metal components of titanium (Ti).
In described catalyst, V, Zr, W and Ti element all exist with the oxidation states of matter.
In described catalyst, titanium dioxide is anatase crystal in the titanium tungsten powder, the content of tungstic acid is 3～30wt% of the quality of titanium tungsten powder, preferred 5～15wt%, for example 8wt%, 10wt%, 12wt%, 4wt%, 6wt%, 14wt%, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%.
Quality in described titanium tungsten powder is 100wt%, and the load capacity of described barium oxide is 0.1～10wt%, for example 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, preferred 1～5wt%.
Quality in described titanium tungsten powder is 100wt%, and the load capacity of described Zirconium oxide is 0.5～30wt%, for example 2wt%, 5wt%, 10wt%, 8wt%, 12wt%, 15wt%, 18wt%, 21wt%, 24wt%, 27wt%, 29wt%, preferred 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 purpose of the present invention is to provide the preparation method of the vanadium tungsten titanium oxide catalyst that a kind of zirconium mixes, and described method is infusion process, and it comprises the steps:
(1) mixed solution in preparation zirconium source and vanadium source;
(2) in mixed solution, add the titanium tungsten powder, under normal temperature condition, stir;
(3) carry out evaporate to dryness, obtain solid content;
(4) with the roasting of gained solid content, obtain the vanadium tungsten titanium oxide catalyst that described zirconium mixes.
In the step (1), described zirconium source is selected from the mixture of any one or at least two kinds in zirconium chloride, zirconium nitrate or the zirconium sulfate.Described mixture is the mixture of zirconium chloride and zirconium nitrate for example, 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 the step (1), described vanadium source is selected from vanadic salts or/and vanadate, preferably the mixture of any one in ammonium metavanadate, vanadic sulfate, oxalic acid vanadyl, vanadium tetrachloride or vanadium oxytrichloride or at least two kinds.Described mixture is the mixture of ammonium metavanadate and vanadic sulfate for example, the mixture of oxalic acid vanadyl and vanadium tetrachloride, the mixture of vanadium oxytrichloride and ammonium metavanadate, the mixture of vanadic sulfate and oxalic acid vanadyl, the mixture of vanadium tetrachloride and vanadium oxytrichloride.
In the step (2), described mixing time is 0.5～10h, for example 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, preferred 0.8～5h, further preferred 1～3h.
In the step (3), described evaporate to dryness method is that direct evaporate to dryness is or/and the rotation evaporate to dryness preferably rotates evaporate to dryness.Described direct evaporate to dryness be about to mixed solution that step (2) obtains in baking oven until distilled-to-dryness.
Preferably, the temperature of described rotation evaporate to dryness is 50～70 ℃, for example 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, and preferred 53～67 ℃, further preferred 55～65 ℃.
In the step (3), described direct evaporate to dryness is in 80～120 ℃ of following evaporates to dryness, for example 82 ℃, 84 ℃, 88 ℃, 92 ℃, 96 ℃, 100 ℃, 104 ℃, 108 ℃, 112 ℃, 114 ℃, 116 ℃ of described evaporate to dryness temperature are preferably put into baking oven in 80～120 ℃ of evaporates to dryness.
In the step (4), described roasting is carried out in air atmosphere, described sintering temperature is 400～800 ℃, for example 420 ℃, 440 ℃, 480 ℃, 520 ℃, 560 ℃, 600 ℃, 640 ℃, 680 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃ of described sintering temperatures, described roasting time is 1～24h, for example 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, preferred 2～12h, further preferred 4～6h.
Three of purpose of the present invention is to provide the method for 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 mix.This catalyst can carry out slurrying according to actual needs, is coated to then on the various honeycomb ceramic carriers, and the catalyst that is prepared into moulding uses, also can be by using after the extrusion modling.
Place exhaust pipe on the way catalyst during use, spray into reducing agent and tail gas mixes in the upstream of catalyst, reducing agent adopts ammonia or urea (can obtain ammonia after the hydrolysis), the reducing agent consumption is 0.8～1.2 times of nitrogen oxide in the tail gas, can be with NO in very wide temperature window under the excess oxygen
xBe reduced to N
2And H
2O possesses very high N simultaneously
2Generate selective and anti-sulphur water repelling property.
Described tail gas is preferably moving source nitrogen-containing oxide gas, for example exhaust gas from diesel vehicle, or stationary source nitrogen-containing oxide gas, for example coal-fired plant flue gas.Described gas is preferably exhaust gas from diesel vehicle, i.e. the present invention is specially adapted to the catalytic purification of nitrogen oxide in the exhaust gas from diesel vehicle.
Compared with prior art, the present invention has following advantage:
(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 the motor-vehicle tail-gas range of temperature is big; Aspect the stationary source denitrating flue gas, because the service life that its excellent high-temperature stability is expected to improve the 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 anti-water sulfur resistance.
The specific embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
The 0.964g ammonium metavanadate is dissolved in oxalic acid solution (mass ratio of ammonium metavanadate and oxalic acid is 1:2), is mixed with the 750ml mixed solution, mix, in this solution, add 25g titanium tungsten powder (10%WO
3-TiO
2), fully stir 1h, then mixed serum is rotated and is evaporated to moisture and fully volatilizees, and under 100 ℃ of air atmospheres dry 12h, roasting 3h under 550 ℃ of air atmospheres obtains 3%V at last
2O
5/ 10%WO
3-TiO
2Catalyst.
The catalyst that makes is ground, sieves, and it is standby to get 40～60 orders, is called catalyst A.
Embodiment 2
With 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 the 750mL mixed solution, mix, in this solution, add 25g titanium tungsten powder (10%WO
3-TiO
2), fully stir 1h, then mixed serum is rotated and is evaporated to moisture and fully volatilizees, and under 100 ℃ of air atmospheres dry 12h, roasting 3h under 550 ℃ of air atmospheres obtains 3%V at last
2O
5-2%ZrO
2/ 10%WO
3-TiO
2Catalyst.
The catalyst that makes is ground, sieves, and it is standby to get 40～60 orders, is called catalyst B.
Embodiment 3
Other condition such as embodiment 2 are constant, and changing five nitric hydrate zirconium additions is 4.36g, obtains 5%V
2O
5-2%ZrO
2/ 10%WO
3-TiO
2Catalyst.The catalyst that makes is ground, sieves, and it is standby to get 40～60 orders, is called catalyst C.
Embodiment 4
Other condition such as embodiment 2 are constant, and changing five nitric hydrate zirconium additions is 8.72g, obtains 10%V
2O
5-2%ZrO
2/ 10%WO
3-TiO
2Catalyst.The catalyst that makes is ground, sieves, and it is standby to get 40～60 orders, is called catalyst D.
Embodiment 5
Catalyst A, B, C, D roasting 8h in 650 ℃ of air is made catalyst E, F, G, H.
The vanadium tungsten titanium compound oxide catalyst A, B, C, D, E, F, G, the H that make with embodiment 1-5 carry out NH at fixed bed reactors
3Selective Catalytic Reduction of NO
xThe investigation of reactivity.
The use amount of catalyst is 0.6ml, the consisting of of reaction mixture gas: [NO]=[NH
3]=500ppm, [O
2]=5%, N
2Make balance gas, total gas flow rate is 500mL/min, and air speed is 50,000h
-1, 150～450 ℃ of reaction temperatures.NO and NH
3And accessory substance N
2O, NO
2All utilize the infrared-gas pond to measure.NO
xConversion ratio and N
2Generate selective difference as shown in Table 1 and Table 2.
The V of the different Zr dopings 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 dopings 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 in this solution, add zirconium chloride, be mixed with mixed solution, mix, in this solution, add titanium tungsten powder (content of tungstic acid is 3wt%), fully stir 0.5h, then mixed serum is rotated at 50 ℃ and is evaporated to moisture and fully volatilizees, and under 100 ℃ of air atmospheres dry 12h, roasting 24h under 400 ℃ of air atmospheres at last obtains the vanadium oxide catalyst that zirconium mixes, wherein, quality with described titanium tungsten powder is 100wt%, and the load capacity of described barium oxide is 0.1wt%, and 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 in this solution, add zirconium sulfate, be mixed with mixed solution, mix, in this solution, add titanium tungsten powder (content of tungstic acid is 30wt%), fully stir 10h, then mixed serum is rotated at 70 ℃ and is evaporated to moisture and fully volatilizees, and under 100 ℃ of air atmospheres dry 12h, roasting 1h under 800 ℃ of air atmospheres at last obtains the vanadium oxide catalyst that zirconium mixes, wherein, quality with described titanium tungsten powder is 100wt%, and the load capacity of described barium oxide is 10wt%, and 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 in this solution, add zirconium nitrate, be mixed with mixed solution, mix, in this solution, add titanium tungsten powder (content of tungstic acid is 10wt%), fully stir 5h, mixed serum is positioned in the baking oven then and fully volatilizees at 80 ℃ of evaporate to dryness to moisture, and under 100 ℃ of air atmospheres dry 12h, roasting 15h under 500 ℃ of air atmospheres at last obtains the vanadium oxide catalyst that zirconium mixes, wherein, quality with described titanium tungsten powder is 100wt%, and the load capacity of described barium oxide is 5wt%, and 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 in this solution, add zirconium nitrate, be mixed with mixed solution, mix, in this solution, add titanium tungsten powder (content of tungstic acid is 10wt%), fully stir 5h, mixed serum is positioned in the baking oven then and fully volatilizees at 120 ℃ of evaporate to dryness to moisture, and under 100 ℃ of air atmospheres dry 12h, roasting 15h under 500 ℃ of air atmospheres at last obtains the vanadium oxide catalyst that zirconium mixes, wherein, quality with described titanium tungsten powder is 100wt%, and the load capacity of described barium oxide is 5wt%, and the load capacity of described Zirconium oxide is 3wt%.
As shown in Table 1, the vanadium oxide catalyst of the Zr that do not mix (catalyst A) is handled back (catalyst E), low temperature and high temperature NO through high-temperature roasting
xConversion ratio all obviously reduces.The vanadium oxide catalyst of doping Zr (catalyst B, C, D) is handled back (catalyst F, G, H) through high-temperature roasting, though activity also slightly reduces, compares with the catalyst of the Zr that do not mix, and 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's statement, 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 mean that namely the present invention must rely on above-mentioned detailed composition and method could be implemented.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a vanadium tungsten titanium oxide catalyst that is used for the zirconium doping of catalytic cleaning nitrogen oxide is characterized in that, described catalyst is the oxide carried to the formed metal oxide catalyst of titanium tungsten powder surface of zirconium and vanadium.
2. catalyst as claimed in claim 1 is characterized in that, titanium dioxide is anatase crystal in the titanium tungsten powder, and the content of tungstic acid is 3～30wt% of the quality of titanium tungsten powder, preferred 5～15wt%.
3. catalyst as claimed in claim 1 or 2 is characterized in that, is 100wt% in the quality of described titanium tungsten powder, and the load capacity of barium oxide is 0.1～10wt%, preferred 1～5wt%;
Preferably, be 100wt% in the quality of described titanium tungsten powder, the load capacity of Zirconium oxide is 0.5～30wt%, preferred 1～15wt%.
4. the preparation method of the vanadium tungsten titanium oxide catalyst of a zirconium doping is characterized in that described method is infusion process, and it comprises the steps:
(1) mixed solution in preparation zirconium source and vanadium source;
(2) in mixed solution, add the titanium tungsten powder, under normal temperature condition, stir;
(3) carry out evaporate to dryness, obtain solid content;
(4) with the roasting of gained solid content, obtain the vanadium tungsten titanium oxide catalyst that described zirconium mixes.
5. method as claimed in claim 4 is characterized in that, described zirconium source is selected from the mixture of any one or at least two kinds in zirconium chloride, zirconium nitrate or the zirconium sulfate;
Preferably, described vanadium source is selected from vanadic salts or/and vanadate, preferably the mixture of any one in ammonium metavanadate, vanadic sulfate, oxalic acid vanadyl, vanadium tetrachloride or vanadium oxytrichloride or at least two kinds;
Preferably, described mixing time is 0.5～10h, preferred 0.8～5h, further preferred 1～3h.
6. as claim 4 or 5 described methods, it is characterized in that in the step (3), described evaporate to dryness method is that direct evaporate to dryness is or/and the rotation evaporate to dryness preferably rotates evaporate to dryness;
Preferably, the temperature of described rotation evaporate to dryness is 50～70 ℃, preferred 53～67 ℃, and further preferred 55～65 ℃.
7. method as claimed in claim 6 is characterized in that, described direct evaporate to dryness is preferably put into baking oven in 80～120 ℃ of evaporates to dryness in 80～120 ℃ of following evaporates to dryness.
8. as the described method of one of claim 4-7, it is characterized in that described roasting is carried out in air atmosphere, described sintering temperature is 400～800 ℃, and described roasting time is 1～24h, preferred 2～12h, further preferred 4～6h.
9. the method for nitrogen oxide in the catalytic purification gas is characterized in that, the vanadium tungsten titanium oxide catalyst that described method right to use requires the described zirconium of one of 1-3 to mix.
10. method as claimed in claim 9 is characterized in that, with described catalyst slurrying, is coated to then on the honeycomb ceramic carrier, and the catalyst that is prepared into moulding uses, or by using after the extrusion modling;
Preferably, during use catalyst placed the exhaust pipe way, spray into reducing agent and tail gas in the upstream of catalyst and mix, reducing agent adopts ammonia or urea, and the reducing agent consumption is 0.8～1.2 times of nitrogen oxide in the tail gas;
Preferably, described tail gas is moving source nitrogen-containing oxide gas or stationary source nitrogen-containing oxide gas, is preferably exhaust gas from diesel vehicle.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103638920A (en) * | 2013-12-03 | 2014-03-19 | 中国重汽集团济南动力有限公司 | Monolithic catalyst for exhausting and treating exhaust gas of diesel engine and preparation process thereof |
| CN106861395A (en) * | 2017-03-09 | 2017-06-20 | 秦皇岛领先康地农业技术有限公司 | It is a kind of for the oxidization processing system waste gas produced in feces of livestock and poultry harmless treatment |
| CN108568296A (en) * | 2018-04-23 | 2018-09-25 | 中国科学院生态环境研究中心 | A kind of vanadium titanium oxide catalyst and its preparation method and application |
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| CN102764643A (en) * | 2012-07-16 | 2012-11-07 | 中国科学院生态环境研究中心 | Vanadium-titanium oxide catalyst, and preparation method and application thereof |
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| CN102764643A (en) * | 2012-07-16 | 2012-11-07 | 中国科学院生态环境研究中心 | Vanadium-titanium oxide catalyst, and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103638920A (en) * | 2013-12-03 | 2014-03-19 | 中国重汽集团济南动力有限公司 | Monolithic catalyst for exhausting and treating exhaust gas of diesel engine and preparation process thereof |
| CN103638920B (en) * | 2013-12-03 | 2015-07-29 | 中国重汽集团济南动力有限公司 | Diesel engine exhaust emission process integer catalyzer and preparation technology thereof |
| CN106861395A (en) * | 2017-03-09 | 2017-06-20 | 秦皇岛领先康地农业技术有限公司 | It is a kind of for the oxidization processing system waste gas produced in feces of livestock and poultry harmless treatment |
| CN108568296A (en) * | 2018-04-23 | 2018-09-25 | 中国科学院生态环境研究中心 | A kind of vanadium titanium oxide catalyst and its preparation method and application |
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