CN111356526B - Scr催化剂 - Google Patents
Scr催化剂 Download PDFInfo
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- CN111356526B CN111356526B CN201880074011.0A CN201880074011A CN111356526B CN 111356526 B CN111356526 B CN 111356526B CN 201880074011 A CN201880074011 A CN 201880074011A CN 111356526 B CN111356526 B CN 111356526B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 142
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 24
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 107
- 239000007789 gas Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 51
- 229910000420 cerium oxide Inorganic materials 0.000 description 41
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 32
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 22
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000004408 titanium dioxide Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 238000011068 loading method Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 239000004576 sand Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 9
- 150000004706 metal oxides Chemical class 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 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 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- -1 for example Chemical compound 0.000 description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003682 vanadium compounds Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 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 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- OLMWLGIOGPZGOZ-UHFFFAOYSA-N antimony cerium Chemical compound [Sb].[Ce] OLMWLGIOGPZGOZ-UHFFFAOYSA-N 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical class [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract
本发明涉及催化剂以及含有所述氧化物的废气系统,所述催化剂包含钒的至少一种氧化物、钨的至少一种氧化物、铈的至少一种氧化物、钛的至少一种氧化物和锑的至少一种氧化物。
Description
技术领域
本发明涉及基于氧化钒的含有氧化锑和氧化铈的SCR催化剂。
背景技术
用稀燃内燃机(诸如柴油发动机)操作的机动车辆的废气除一氧化碳(CO)和氮氧化物(NOx)之外还含有因燃料在气缸的燃烧室中不完全燃烧而产生的组分。除了通常也主要以气态形式存在的残余烃(HC)之外,这些组分还包括颗粒排放物。这些颗粒排放物是主要来自含碳颗粒物和粘附液相的复杂团聚体,通常主要包含长链烃缩合物。粘附到固体组分的液相也称为“可溶性有机馏分SOF”或“挥发性有机馏分VOF”。
为了清洁此类废气,必须将上述组分尽可能完全地转化为无害化合物,这只有通过使用合适的催化剂才可能实现。
用于在存在氧的情况下从废气中去除氮氧化物的熟知的工艺是在合适的催化剂上使用氨的选择性催化还原(SCR工艺)。利用该工艺,使用氨作为还原剂将废气中的待去除的氮氧化物转化为氮和水。
根据公式(I)的所谓“标准SCR反应”
NH3+NO+1/4O2→N2+3/2H2O (I)
以及根据公式(II)的所谓的“快速SCR反应”
NH3+1/2NO+1/2NO2→N2+3/2H2O (II)
被认为是SCR反应的重要反应途径。
由于稀燃内燃机的废气通常仅包含NO2,其量约为氮氧化物总比例的10%,因此通常期望增加其量以便从快速SCR反应中获益。这例如通过上游氧化催化转化器来完成。然而,取决于在特定情况下使用的排气系统,SCR催化剂仍可能面临非常不同的NO2/NOx比,其范围可从NO过量到NO2过量。
用作还原剂的氨可通过将氨前体化合物诸如脲、氨基甲酸铵或甲酸铵按剂量加入排气管道中并随后水解而可用。
所谓的混合氧化物催化剂也可用作SCR催化剂,所述混合氧化物催化剂基于钒的氧化物,并且通常还含有钛的氧化物和另外金属的氧化物,例如钨的氧化物(参见IsabellaNova和Enrico Tronconi(编),Urea-SCR Technology for deNOx After Treatment ofDiesel Exhausts,第3章,Springer Verlag,2014)。
如果废气中所含的氮氧化物以NO的形式存在或至少主要以NO的形式存在,则基于氧化钒的SCR催化剂的特征在于良好的活性和稳定性。然而,在NO2过量的情况下,它们显示出明显的活性降低。尽管在基于氧化钒的SCR催化剂中添加氧化铈在NO2过量的情况下提高了活性,但在NO过量的情况下也损害了低温活性(T<250℃)。
因此,需要对于NO2过量和NO过量以及低温(T<250℃)都具有良好活性的基于氧化钒的SCR催化剂。此外,还需要改善基于钒的SCR催化剂的热稳定性。
已知在基于金属氧化物的SCR催化剂中也使用氧化锑。因此,例如,US 9,662,610公开了一种使用包含二氧化钛、钒化合物和锑化合物的催化剂还原氮氧化物的方法。WO2017/101449 A1公开了包含二氧化钛、含钒和锑的复合氧化物以及任选的硅、钒和锑的氧化物的催化剂组合物的用途。
CN106215929公开了用作脱氮催化剂的铈锑复合氧化物。
最后,US 8,975,206公开了除钒和钛之外还可包含锑的催化剂组合物。
发明内容
现在已经令人惊奇地发现,从含有氧化铈的基于氧化钒的SCR催化剂开始,上述技术问题可通过向催化剂中添加锑的氧化物来解决。
因此,本发明涉及一种催化剂,该催化剂含有
·2重量%至6重量%的量的至少一种钒的氧化物,
·0,5重量%至2重量%的量的至少一种钨的氧化物,
·2重量%至4重量%的量的至少一种铈的氧化物,
·1重量%至7重量%的量的至少一种锑的氧化物,
以及
·经测量的量的至少一种钛的氧化物,以便得到总计100重量%,
在每种情况下基于所述催化剂的总重量并以V2O5、WO3、CeO2、Sb2O5或TiO2计算。
该至少一种钛的氧化物用作载体材料,该至少一种钒的氧化物用作活性催化剂组分,并且该至少一种钨、铈和锑的氧化物用作促进剂。促进剂应被理解为意指保持或增加催化剂活性的物质。
在根据本发明的催化剂的一个实施方案中,其另外含有至少一种硅的氧化物。
在根据本发明的催化剂的另一个实施方案中,其另外含有至少一种钼、铌、锆、钽和/或铪的氧化物。
在根据本发明的催化剂的优选实施方案中,相对于催化剂的重量并以CeO2计算,其含有2重量%至4重量%的量的至少一种铈氧化物。在根据本发明的催化剂的进一步优选的实施方案中,相对于催化剂的重量并以Sb2O5计算,其含有1重量%至7重量%的量的至少一种锑的氧化物。此外,优选的是根据本发明的催化剂的实施方案,其含有以CeO2计算的2重量%至4重量%的量的至少一种铈的氧化物,以及以Sb2O5计算的1重量%至7重量%的量的至少一种的锑的氧化物,在每种情况下均基于催化剂的重量。
在根据本发明的催化剂的进一步优选的实施方案中,其含有
·2重量%至6重量%的量的至少一种钒的氧化物,
·0.5重量%至2重量%的量的至少一种钨的氧化物,
·2重量%至4重量%的量的至少一种铈的氧化物,
·1重量%至7重量%的量的至少一种锑的氧化物,以及
·经测量的量的至少一种钛的氧化物,以便得到总计100重量%,
在每种情况下均基于催化剂的总重量并以V2O5、WO3、CeO2或Sb2O5计算。
如果根据本发明的催化剂含有至少一种硅的氧化物,则其优选以相对于催化剂的重量并以SiO2计算的2重量%至7重量%的量存在。
如果根据本发明的催化剂包含至少一种钼、铌、锆、钽和/或铪的氧化物,则相对于催化剂的重量并以MoO3、Nb2O5、ZrO2、Ta2O5或HfO2计算,这些氧化物的总量优选为0.5重量%至20重量%。
根据本发明的催化剂优选不含镁或镁化合物。
在另一个实施方案中,本发明的催化剂也不含锆或锆化合物。
在本发明的上下文中,术语钒的氧化物包括在根据本发明的催化剂的制备、储存和使用的条件下出现或可能存在的所有氧化物。因此,它包括例如V2O5,但也包括所有其它钒的氧化物。
类似地,术语钨的氧化物包括例如WO3,但也包括钨的所有其它氧化物,术语铈的氧化物包括例如CeO2,但也包括铈的所有其它氧化物,术语锑的氧化物包括例如Sb2O5,但也包括锑的所有其它氧化物,术语钛的氧化物包括例如TiO2,但也包括钛的所有其它氧化物,并且硅的氧化物包括例如SiO2,但也包括硅的所有其它氧化物。术语钼、铌、锆、钽和铪的氧化物也是如此。
根据本发明的催化剂可以简单的方式生产。
因此,例如,可将钒、钨、铈、锑和钛的氧化物以及任选的其它金属氧化物以期望的量以粉末形式充分混合,然后煅烧。然而,通常有利的是将前述氧化物在水中制成浆液,然后干燥并煅烧。
在该方法的一种变型中,最初仅提供一部分金属氧化物,而其余金属以水溶性金属盐的形式添加。例如,可提供钨、铈、锑和钛的氧化物,然后用水溶性钒化合物的水溶液浸渍,随后干燥并煅烧。合适的水溶性钒化合物特别是草酸氧钒,其可通过将五氧化二钒溶解在草酸中获得(参见例如EP 0 345 695 A2)或通过五氧化二钒与胺或乙醇胺的反应产物获得(参见例如WO 89/03366 A1和WO 2011/013006),尤其是偏钒酸铵。DE 11 2007 000 814T5也描述了三氯化氧钒的用途。
另选地,也可提供钒、铈、锑和钛的氧化物,然后用水溶性钨化合物的水溶液浸渍,随后干燥并煅烧。为此目的合适的水溶性钨化合物为偏钨酸铵。
代替使用单独的氧化物,也可以对应的混合氧化物的形式或以掺杂有一种或多种其它金属氧化物的金属氧化物的形式使用两种或更多种金属氧化物。例如,掺杂有二氧化硅和三氧化钨的二氧化钛可用钒和锑的水溶性化合物浸渍,然后干燥并煅烧。
具体取决于生产方法,根据本发明的催化剂可以金属氧化物的混合物、混合氧化物的形式存在,但特别是以金属氧化物的混合物与混合氧化物之间的中间体的形式存在。例如,两种或三种金属可以浸渍有其余金属的混合氧化物的形式存在。
制备根据本发明的催化剂所需的起始化合物(诸如金属氧化物、混合氧化物或水溶性金属盐)是本领域技术人员已知的并且可商购获得。
在优选的实施方案中,根据本发明的催化剂作为涂层存在于载体主体上,该载体主体可作为流通式蜂窝状主体或壁流式过滤器存在。
在本发明的实施方案中,载体主体是催化惰性的并且由陶瓷或金属材料(例如碳化硅、钛酸铝或堇青石)组成。在这些实施方案中,根据本发明的催化剂的所有组分存在于一种涂层中。
经涂覆的载体主体可根据本领域技术人员熟悉的方法来制备,例如根据常用的浸涂方法或泵涂和吸涂方法,随后进行热后处理(煅烧)。
在本发明的另一个实施方案中,根据本发明的催化剂本身是载体主体的组分,在这种情况下该载体主体由根据本发明的催化剂和基质组分形成。
不仅由惰性材料诸如堇青石组成而且还另外含有催化活性材料的载体主体、流通式基材和壁流式基材是本领域技术人员已知的。为了制备它们,根据本身已知的方法挤出由例如10重量%至95重量%的惰性基质组分和5重量%至90重量%的催化活性材料组成的混合物。在该情况下,所有也用于生产催化剂基材的惰性材料都可用作基质组分。这些是例如硅酸盐、氧化物、氮化物或碳化物,其中特别优选的为硅酸镁铝。
根据本发明的催化剂特别适合于还原贫燃内燃机(具体地讲,柴油发动机)的废气中的氮氧化物。
因此,本发明还涉及用于还原贫燃内燃机的废气中的氮氧化物的方法,所述方法包括以下方法步骤:
-将还原剂添加到含有氮氧化物的所述废气中,以及
-使来自含有氮氧化物的废气和还原剂的所得混合物经过根据本发明的催化剂。
作为还原剂,由于其具有特定的优点,特别考虑了氨,不是将氨本身,而是将氨前体(具体地讲,脲)添加到含有氮氧化物的废气中。
具体地讲,根据本发明的催化剂被用作废气清洁系统的组成部分,除了根据本发明的催化剂之外,所述废气清洁系统还包括例如氧化催化剂和布置在流入侧上的柴油机颗粒过滤器。这样,根据本发明的催化剂也可作为涂层存在于柴油机颗粒过滤器上。
因此,本发明还涉及一种用于处理柴油机废气的废气纯化系统,该废气纯化系统在废气的流动方向上包括:
-氧化催化剂,
-柴油机颗粒过滤器,以及
-根据本发明的催化剂,
或
-氧化催化剂以及
-柴油机颗粒过滤器,根据本发明的催化剂作为涂层存在于该柴油颗粒过滤器上。
适用于根据本发明的废气纯化系统的氧化催化剂(特别是铂、钯、或负载在例如氧化铝上的铂和钯)和柴油机颗粒过滤器是本领域技术人员已知的并且是可商购获得的。
根据本发明的废气纯化系统通常包括用于计量还原剂的装置,该装置布置在根据本发明的催化剂的上游。
注射装置可由本领域技术人员任意地选择,其中合适的装置可从文献(参见,例如,T.Mayer,Feststoff-SCR-System auf Basis von Ammonium-carbamat,Dissertation,Technical University of Kaiserslautern,2005)中获得。经由注射装置引入废气流中的还原剂可特别是氨本身或以在环境条件下由其形成氨的化合物的形式。合适的化合物的示例为脲或甲酸铵的水溶液以及固体氨基甲酸铵。一般来说,还原剂或其前体保存在注射装置连带的并连接到注射装置的容器中。
附图说明
下面通过附图和实施例更详细地解释本发明。示出了以下内容:
图1:新制状态下与比较催化剂VK1、VK2、VK3和VK4相比,在根据本发明的催化剂K1和K7上测量的标准SCR反应中的氮氧化物转化率(K1f、VK1f、VK2f、VK3f、VK4f和K7f)。
图2:老化状态下与比较催化剂VK1、VK2、VK3和VK4相比,在根据本发明的催化剂K1和K7上测量的标准SCR反应中的氮氧化物转化率(K1a、VK1a、VK2a、VK3a、VK4a和K7a)。
图3:新制状态下与比较催化剂VK1、VK2、VK3和VK4相比,在根据本发明的催化剂K1和K7上测量的快速SCR反应中的氮氧化物转化率(K1f、VK1f、VK2f、VK3f、VK4f和K7f)。
图4:老化状态下与比较催化剂VK1、VK2、VK3和VK4相比,在根据本发明的催化剂K1和K7上测量的快速SCR反应中的氮氧化物转化率(K1a、VK1a、VK2a、VK3a、VK4a和K7a)。
图5:新制和老化状态下与比较催化剂VK4相比,在根据本发明的催化剂K1、K2和K3上测量的在200℃的标准SCR反应和300℃的快速SCR反应中相对于WO3含量的氮氧化物转化率。
图6:新制和老化状态下与比较催化剂VK3相比,在根据本发明的催化剂K1和K4上测量的在200℃的标准SCR反应和300℃的快速SCR反应中相对于CeO2含量的氮氧化物转化率。
图7:新制和老化状态下与比较催化剂VK2相比,在根据本发明的催化剂K1、K5和K6上测量的在200℃的标准SCR反应和300℃的快速SCR反应中相对于Sb2O5含量的氮氧化物转化率。
具体实施方式
实施例1
a)将掺杂有5重量%二氧化硅的锐钛矿形式的可商购获得的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)、三氧化钨(WO3)、二氧化铈(CeO2)和五氧化二锑(Sb2O5),以便得到组成为86.00重量%TiO2、4.50重量%SiO2、3.75重量%V2O5、1.00重量%WO3、2.00重量%CeO2和2.75重量%Sb2O5的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂K1以新制状态存在,并且因此在下文中称为K1f。
c)使根据b)获得的催化剂K1在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂K1以老化状态存在,并且在下文中称为K1a。
比较例1
a)将掺杂有5重量%二氧化硅的可商购获得的锐钛矿形式的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)和三氧化钨(WO3),以便得到组成为90.5重量%TiO2、4.75重量%SiO2、3.75重量%V2O5、1.00重量%WO3的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂K1以新制状态存在,并且因此在下文中称为VK1f。
c)使根据b)获得的VK1a在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂VK1以老化状态存在,并且在下文中称为VK1a。
比较例2
a)将掺杂有5重量%二氧化硅的可商购获得的锐钛矿形式的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)、三氧化钨(WO3)和二氧化铈(CeO2),以便得到组成为88.60重量%TiO2、4.65重量%SiO2、3.75重量%V2O5、1.00重量%WO3和2.00重量%CeO2的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂VK2以新制状态存在,并且因此在下文中称为VK2f。
c)使根据b)获得的VK2a在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂VK2以老化状态存在,并且在下文中称为VK2a。
比较例3
a)将掺杂有5重量%二氧化硅的可商购获得的锐钛矿形式的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)、三氧化钨(WO3)和五氧化二锑,以便得到组成为87.9重量%TiO2、4.60重量%SiO2、3.75重量%V2O5、1.00重量%WO3和2.75重量%Sb2O5的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂VK3以新制状态存在,并且因此在下文中称为VK3f。
c)使根据b)获得的VK3a在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂VK3以老化状态存在,并且在下文中称为VK3a。
比较例4
a)将掺杂有5重量%二氧化硅的可商购获得的锐钛矿形式的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)、二氧化铈(CeO2)和五氧化二锑,以便得到组成为86.9重量%TiO2、4.60重量%SiO2、3.75重量%V2O5、2.00重量%CeO2和2.75重量%Sb2O5的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂VK4以新制状态存在,并且因此在下文中称为VK4f。
c)使根据b)获得的VK4a在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂VK4以老化状态存在,并且在下文中称为VK4a。
实施例2
a)将掺杂有5重量%二氧化硅的锐钛矿形式的可商购获得的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)、三氧化钨(WO3)、二氧化铈(CeO2)和五氧化二锑(Sb2O5),以便得到组成为86.45重量%TiO2、4.55重量%SiO2、3.75重量%V2O5、0.50重量%WO3、2.00重量%CeO2和2.75重量%Sb2O5的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂K2以新制状态存在,并且因此在下文中称为K2f。
c)使根据b)获得的K2a在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂K2以老化状态存在,并且在下文中称为K2a。
实施例3
a)将掺杂有5重量%二氧化硅的锐钛矿形式的可商购获得的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)、三氧化钨(WO3)、二氧化铈(CeO2)和五氧化二锑(Sb2O5),以便得到组成为85.03重量%TiO2、4.47重量%SiO2、3.75重量%V2O5、2.00重量%WO3、2.00重量%CeO2和2.75重量%Sb2O5的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂K3以新制状态存在,并且因此在下文中称为K3f。
c)使根据b)获得的K3a在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂K3以老化状态存在,并且在下文中称为K3a。
实施例4
a)将掺杂有5重量%二氧化硅的锐钛矿形式的可商购获得的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)、三氧化钨(WO3)、二氧化铈(CeO2)和五氧化二锑(Sb2O5),以便得到组成为84.07重量%TiO2、4.43重量%SiO2、3.75重量%V2O5、1.00重量%WO3、4.00重量%CeO2和2.75重量%Sb2O5的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂K4以新制状态存在,并且因此在下文中称为K4f。
c)使根据b)获得的K4a在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂K4以老化状态存在,并且在下文中称为K4a。
实施例5
a)将掺杂有5重量%二氧化硅的锐钛矿形式的可商购获得的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)、三氧化钨(WO3)、二氧化铈(CeO2)和五氧化二锑(Sb2O5),以便得到组成为84.79重量%TiO2、4.46重量%SiO2、3.75重量%V2O5、1.00重量%WO3、2.00重量%CeO2和4.00重量%Sb2O5的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂K5以新制状态存在,并且因此在下文中称为K5f。
c)使根据b)获得的K5a在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂K5以老化状态存在,并且在下文中称为K5a。
实施例6
a)将掺杂有5重量%二氧化硅的锐钛矿形式的可商购获得的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)、三氧化钨(WO3)、二氧化铈(CeO2)和五氧化二锑(Sb2O5),以便得到组成为81.94重量%TiO2、4.31重量%SiO2、3.75重量%V2O5、1.00重量%WO3、2.00重量%CeO2和7.00重量%Sb2O5的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂K6以新制状态存在,并且因此在下文中称为K6f。
c)使根据b)获得的K6a在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂K6以老化状态存在,并且在下文中称为K6a。
实施例7
a)将可商购获得的锐钛矿形式的二氧化钛分散在水中,然后添加一定量的二氧化钒(VO2)、三氧化钨(WO3)、二氧化铈(CeO2)和五氧化二锑(Sb2O5),以便得到组成为90.5重量%TiO2、3.75重量%V2O5、1.00重量%WO3、2.00重量%CeO2和2.75重量%Sb2O5的催化剂。将浆液剧烈搅拌,然后在可商购获得的搅拌型砂磨机中研磨。
b)以常规方式将根据a)获得的分散体涂覆在可商购获得的陶瓷流式基材上,该陶瓷流式基材的体积为0.5L,孔数为62孔/每平方厘米,在其整个长度上的壁厚为0.17mm,修补基面涂层载量为360g/L。将由此获得的粉末在90℃干燥,然后在600℃煅烧2小时。由此获得的催化剂K7以新制状态存在,并且因此在下文中称为K7f。
c)使根据b)获得的K7a在700℃在气体气氛(10%O2,10%H2O,其余为N2)中经受水热老化48小时。然后催化剂K7以老化状态存在,并且在下文中称为K7a。
表1汇总了所述实施例的催化剂的组成。根据本发明的催化剂的组成不限于明确示出的实施例。
表1:实施例的催化剂的组成
作为SCR活性量度的氮氧化物转化率测定:
在石英玻璃反应器中测定根据上述实施例和比较例制备的催化剂或比较催化剂的NO转化率。在稳态条件下,在200℃和400℃之间测试L=3"且D=1"的钻芯。在实验室模型气体系统中在以下条件下进行测试。
在测量期间,使用合适的分析方法记录流过催化剂后的模型气体的氮氧化物浓度。从已知的、计量的氮氧化物含量(在相应测试流开始时用催化剂前废气分析在调节期间进行验证)和在流过催化剂后测量的氮氧化物转化率含量,如下计算每个温度测量点在催化剂上的相对于NH3与NO的比率的氮氧化物转化率:
其中
c输入/输出(NOx)=c输入/输出(NO)+c输入/输出(NO2)+c输入/输出(N2O)
将所得氮氧化物转化率值UNOx[%]绘制为在催化剂之前测量的温度的函数,以便评估所研究材料的SCR活性。
表2示出了上述实施例在标准SCR反应中的NOx转化率。
表2:标准SCR反应中的NOx转化率
新制催化剂的标准SCR反应的结果在图1中示出。
老化催化剂的标准SCR反应的结果在图2中示出。
表3示出了上述实施例在快速SCR反应中的NOx转化率。
表3:快速SCR反应中的NOx转化率
新制催化剂的快速SCR反应的结果在图3中示出。
老化催化剂的快速SCR反应的结果在图4中示出。
表4示出了在新制和老化状态下,在200℃的标准SCR反应中和在300℃的快速SCR反应中,催化剂的WO3含量对NOx转化率的影响。V2O5、CeO2和Sb2O5的量保持恒定,分别为3.75重量%、2.00重量%或2.75重量%,而WO3含量从0.00重量%(VK4)变化到0.50重量%(K2)、1.00重量%(K1)和2.00重量%(K3)。
表4:WO3含量对NOx转化率的影响
WO3含量的影响的结果在图5中示出。
表5示出了在新制和老化状态下,在200℃的标准SCR反应中和在300℃的快速SCR反应中,催化剂的CeO2含量对NOx转化率的影响。V2O5、WO3和Sb2O5的量保持恒定,分别为3.75重量%、1.00重量%或2.75重量%,而CeO2含量从0.00重量%(VK3)变化到2.00重量%(K1)和2.00重量%(K7)。
表5:CeO2含量对NOx转化率的影响
CeO2含量的影响的结果在图6中示出。
表6示出了在新制和老化状态下,在200℃的标准SCR反应中和在300℃的快速SCR反应中,催化剂的Sb2O5含量对NOx转化率的影响。V2O5、WO3和CeO2的量保持恒定,分别为3.75重量%、1.00重量%或2.00重量%,而Sb2O5含量从0.00重量%(VK2)变化到2.75重量%(K1)、4.00重量%(K5)和7.00重量%(K6)。
表6:Sb2O5含量对NOx转化率的影响
Sb2O5含量的影响的结果在图7中示出。
Claims (7)
1.一种催化剂,由以下物质组成:
·2重量%至6重量%的量的至少一种钒的氧化物,
·0.5重量%至2重量%的量的至少一种钨的氧化物,
·2重量%至4重量%的量的至少一种铈的氧化物,
·1重量%至7重量%的量的至少一种锑的氧化物,
以及
·至少一种硅的氧化物,以及
·任选的,至少一种钼的氧化物、至少一种铌的氧化物、至少一种锆的氧化物、至少一种钽的氧化物和/或至少一种铪的氧化物;以及
·至少一种钛的氧化物作为载体材料,其量经测量以便得到总计100重量%,
在每种情况下基于所述催化剂的总重量并以V2O5、WO3、CeO2、Sb2O5、TiO2、SiO2、MoO3、Nb2O5、ZrO2、Ta2O5或HfO2计算。
2.根据权利要求1所述的催化剂,其特征在于,基于所述催化剂的总重量并以SiO2计算,所述催化剂包含2重量%至7重量%的量的至少一种硅的氧化物。
3.根据权利要求1或2所述的催化剂,其特征在于,所述催化剂包含至少一种钼的氧化物、至少一种铌的氧化物、至少一种锆的氧化物、至少一种钽的氧化物和/或至少一种铪的氧化物,基于所述催化剂的总重量并以MoO3、Nb2O5、ZrO2、Ta2O5或HfO2计算,这些氧化物的总量为0.5重量%至20重量%。
4.根据权利要求1或2所述的催化剂,其特征在于,所述催化剂作为涂层存在于载体主体上。
5.根据权利要求1或2所述的催化剂,其特征在于,所述催化剂作为载体主体的一部分存在。
6.一种用于还原贫燃内燃机的废气中的氮氧化物的方法,包括以下方法步骤
-将还原剂添加到含有氮氧化物的所述废气中,以及
-使含有氮氧化物的废气和还原剂的所得混合物经过根据权利要求1至5中任一项所述的催化剂。
7.一种用于处理柴油机废气的废气纯化系统,包括:
-氧化催化剂,
-柴油机颗粒过滤器,以及
-根据权利要求1至5中任一项所述的催化剂,
或
-氧化催化剂以及
-柴油机颗粒过滤器,根据权利要求1至5中任一项所述的催化剂作为涂层存在于所述柴油机颗粒过滤器上。
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- 2018-11-13 WO PCT/EP2018/081072 patent/WO2019096785A1/de unknown
- 2018-11-13 KR KR1020207017051A patent/KR20200086343A/ko not_active Application Discontinuation
- 2018-11-13 CA CA3082497A patent/CA3082497A1/en active Pending
- 2018-11-13 US US16/763,622 patent/US11135571B2/en active Active
- 2018-11-13 BR BR112020009690-3A patent/BR112020009690B1/pt active IP Right Grant
- 2018-11-13 CN CN202310531105.9A patent/CN116474763A/zh active Pending
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BR112020009690A2 (pt) | 2020-11-10 |
US20200276561A1 (en) | 2020-09-03 |
CN111356526A (zh) | 2020-06-30 |
JP2021502892A (ja) | 2021-02-04 |
EP3710158A1 (de) | 2020-09-23 |
BR112020009690B1 (pt) | 2023-04-11 |
KR20200086343A (ko) | 2020-07-16 |
US11498055B2 (en) | 2022-11-15 |
US11135571B2 (en) | 2021-10-05 |
JP7222996B2 (ja) | 2023-02-15 |
CA3082497A1 (en) | 2019-05-23 |
CN116474763A (zh) | 2023-07-25 |
WO2019096785A1 (de) | 2019-05-23 |
US20210402376A1 (en) | 2021-12-30 |
EP3482825A1 (de) | 2019-05-15 |
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