CN107405613A - 具有含沸石的催化层的改进粘合性的scr‑催化剂 - Google Patents
具有含沸石的催化层的改进粘合性的scr‑催化剂 Download PDFInfo
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- CN107405613A CN107405613A CN201680013831.XA CN201680013831A CN107405613A CN 107405613 A CN107405613 A CN 107405613A CN 201680013831 A CN201680013831 A CN 201680013831A CN 107405613 A CN107405613 A CN 107405613A
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- zeolite
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- catalyst
- catalyst composition
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- 239000010457 zeolite Substances 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 72
- 230000003197 catalytic effect Effects 0.000 title description 6
- 230000006872 improvement Effects 0.000 title description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 claims abstract description 34
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 239000012876 carrier material Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 9
- 239000004575 stone Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002912 waste gas Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 102220076495 rs200649587 Human genes 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000256844 Apis mellifera Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- -1 and depend on this Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 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 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J29/76—Iron group metals or copper
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- B01J37/30—Ion-exchange
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2066—Selective catalytic reduction [SCR]
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- B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
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- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
本发明涉及具有选择性催化还原氮氧化物活性的催化组合物,所述催化组合物包含含有铁的MFI型沸石和含有铁的BEA型沸石,其中MFI型沸石和BEA型沸石的重均粒度d50不同,本发明还涉及用于制备SCR‑催化剂的方法以及由其制备的SCR‑催化剂。由于MFI型沸石和BEA型沸石的重均粒度不同,涂层的粘合性得以改进。
Description
本发明涉及具有选择性催化还原氮氧化物活性的催化组合物,所述催化组合物包含含有铁的MFI型沸石和含有铁的BEA型沸石,其中MFI型沸石和BEA型沸石的重均粒度d50不同。本发明还涉及用于制备具有活性催化组合物的SCR-催化剂的方法以及由其制备的SCR-催化剂。
从一开始尝试废气净化至今,已经做出巨大努力来一再减少内燃机的污染物排放水平。发动机内部的措施将来不足以满足法定要求。因此需要用于废气后处理的先进系统从而能够遵守废气极限值。例如为了进行柴油发动机的废气后处理,特别是已经实现或试用阶段中存在以下系统:
-选择性催化还原(SCR-法),
-NOx-还原催化剂(NSR),
-柴油-氧化催化剂(DOC),
-催化涂布颗粒过滤器,
-不同系统的组合,例如“连续再生捕获”(CRT-系统)、SCRT-法、DPNR-法。
在所述系统中使用的催化剂的表面具有活性涂层从而促进相应的反应。作为将涂层施加在其上的催化剂基材,通常使用陶瓷或金属载体材料的催化剂基材。
尤其是在使用金属载体材料时发现,以活性载体涂层形式施加的催化活性组合物通常在金属载体上仅显示出不足的粘合性。为了在载体材料上施加足够量的催化活性材料,在该情况下需要多次涂布工序。通过多次反复工序涂布载体材料提高了为了制备催化剂必须耗费的花费和成本。
US 8,147,952 B2提供一种用于蜂窝结构的涂布材料,其中涂布材料包括无机颗粒或有机颗粒,所述无机颗粒或有机颗粒具有5至50之间的D90/D10-比例并且D10等于或者小于50μm并且D90等于或者大于4μm(其中D10和D90分别是10%直径和90%直径的值,以通过从小颗粒直径的侧面开始的激光衍射/激光散射法测得的颗粒直径分布的体积份额计)。
US 7,393,804 B2描述了一种具有催化组分的废气净化催化剂,所述催化组分包含铜、ZSM-5和β沸石,其中ZSM-5具有(20-100)/1的SiO2/Al2O3-摩尔比例和在电子显微镜下观察到的不超过0.5μm的平均微晶直径,β沸石具有(10-50)/1的SiO2/Al2O3-比例并且ZSM-5和β沸石的重量比例为1:0.1至1:5。所述废气净化催化剂本身在低温范围内还原氮氧化物并且即使在高热负载下也显示出耐久性。
US 5,589,147描述了一种用于处理废气的方法,其中所述方法使用特别制备的催化剂组合物从而选择性地催化还原废气中包含的NOx。根据该发明的方法的一个实施方案包括在催化剂组合物上选择性地催化还原NOx的催化步骤,所述催化剂组合物包含分子筛,所述分子筛用金属以一定方式处理从而有效最大化金属分散。所述方法的催化剂典型地包含二氧化硅粘合剂、二氧化钛粘合剂或二氧化锆粘合剂,例如包含用羟基官能化的具有高分子量的有机硅树脂的粘合剂。所述催化剂可以例如通过挤出以希望的形式施加,并且可以在潮湿环境中老化。
EP 2123614 A2描述了一种包括蜂窝结构单元的蜂窝结构,所述蜂窝结构包含沸石以及无机粘合剂和大量分离壁,所述分离壁在蜂窝结构单元的纵向方向上设置并且限定由分离壁分离的大量流通开口。所述沸石包含第一沸石和第二沸石,所述第一沸石与选自Cu、Mn、Ag和V的一种或多种类型的金属离子交换,所述第二沸石与选自Fe、Ti和Co的一种或多种类型的金属离子交换。第一沸石的重量与第一和第二沸石的总重量的比例在分离壁的中部比在其表面更大。第二沸石的重量与第一和第二沸石的总重量的比例在分离壁的表面比在其中部更大。
WO 2011/125050 A1基本上描述了组合不同类型的沸石从而制备SCR-催化剂的可能性。然而WO 2011/125050 A1没有提示如何获得催化剂使得活性载体涂层在载体材料上具有更好的粘合性。
因此本发明的目的是提供一种具有涂层的SCR-催化剂,所述涂层与陶瓷和/或金属载体材料显示出更好的粘合性。
通过催化组合物实现上述目的,所述催化组合物包含含有铁的MFI型沸石和含有铁的BEA型沸石,其中沸石的重均粒度d50不同。
MFI型沸石优选具有2至10μm的重均粒度d50,并且BEA型沸石优选具有0.1至3μm的重均粒度d50。
所述催化组合物优选是具有选择性催化还原氮氧化物活性的组合物(SCR-催化剂)。
在本发明的意义上,SCR-催化剂是能够选择性地催化还原来自内燃机和发电厂的废气的氮氧化物的催化剂。SCR-催化剂仅选择性地还原氮氧化物NO和NO2(统称为NOx),其中为了进行反应通常混入NH3(氨)。因此仅产生无害物质水和氮气作为反应产物。
MFI型沸石优选具有2至10μm,特别优选4至8μm的重均粒度d50。
BEA型沸石优选具有0.1至3μm,特别优选0.2至2μm的重均粒度d50。
优选地,MFI型沸石和BEA型沸石的重均粒度d50相差至少5μm,更优选2μm,特别优选0.5μm。
重均粒度d50(或中值)作为平均粒度的量度,在此表示50重量百分比的样品具有小于重均粒度d50的值的粒度并且另外50重量百分比的样品具有大于重均粒度d50的值的粒度。
术语“沸石”通常根据国际矿物学会的定义(D.S.Coombs等人,Can.Mineralogist,35,1997,1571)被理解为具有如下通式的立体网络结构的铝硅酸盐类结晶物质
Mn+ x/n[(AlO2)x(SiO2)y]·z(H2O)
所述硅铝酸盐由SiO4/AlO4四面体组成,所述SiO4/AlO4四面体通过共同的氧原子结合成规则三维网络。沸石骨架包含通道和笼形式的开放空腔,所述开放空腔通常被水分子和可被交换的额外骨架阳离子占据。铝原子上存在过量负电荷,所述负电荷由这些阳离子补偿。根据所谓的“-规则”(阻止相邻出现两个相邻的带负电荷的AlO4-四面体),比例Si/Al=y/x始终≥1。沸石包含的铝越多并且硅越少,则其晶格中的负电荷越密集,并且其内表面越具极性。在此,低的Si/Al-比例下虽然为金属提供更多的交换位置,但是沸石变得更加热不稳定。
沸石结构包含空腔和通道,所述空腔和通道对于每种沸石来说是特征性的。沸石根据其拓扑结构分成不同的结构类型,这些结构类型用三位数代码(骨架类型代码“FTC”)表示。在本发明的说明书的范围内,沸石类型MFI和BEA表示各种结构类型MFI和BEA,正如通过FTC标明的那样。
优选地,MFI型沸石和BEA型沸石的摩尔比例SiO2/Al2O3分别为5至150,特别优选15至100。非常特别优选地,MFI型沸石的摩尔比例SiO2/Al2O3为20至80,还更优选20至50。非常特别优选地,BEA型沸石的摩尔比例SiO2/Al2O3为30至80,还更优选30至50。
MFI型沸石和BEA型沸石分别具有至的相对大的孔直径。
根据本发明的催化组合物优选除了铁之外还具有过渡金属和/或过渡金属氧化物。根据本发明的催化组合物特别优选还具有镍氧化物、铜氧化物、钴氧化物、锰氧化物、铑氧化物、铼氧化物和/或钒氧化物,以及两种或多种所述化合物的混合物。MFI型沸石除了铁之外优选还具有铜,并且取决于此,BEA型沸石除了铁之外同样优选还具有铜。
MFI型沸石优选以0.7至4.9重量%,特别优选1.4至4.2重量%,非常特别优选2.1至3.5重量%的重量含量具有铁,以含铁的MFI型沸石的重量计。BEA型沸石以0.3至3.9重量%,特别优选1至3.1重量%,非常特别优选1.7至2.5重量%的重量含量具有铁。
以Fe2O3计算,MFI型沸石优选以1至7重量%,特别优选2至6重量%,非常特别优选3至5重量%的重量含量具有铁,以含铁的MFI型沸石的重量计。以Fe2O3计算,BEA型沸石以0.4至5.5重量%,特别优选1.4至4.5重量%,非常特别优选2.4至3.5重量%的重量含量具有铁。
根据本发明的催化组合物中的铁优选以阳离子形式(要么是金属阳离子要么是包含铁作为中央原子的阳离子络合物)存在。在此优选的是,所述阳离子补偿沸石基础骨架的负电荷。在此阳离子作为负电荷的反离子存在于沸石的空腔和通道中。但是铁可以完全或部分以氧化铁的形式存在。
MFI型沸石与BEA型沸石的重量比例优选为1:10至10:1,特别优选1:5至5:1,非常特别优选1:2至2:1,还更优选1:1。
根据本发明的SCR-催化剂的BET-表面积优选为100m2/g至1,500m2/g,特别优选150m2/g至1,000m2/g,非常特别优选200m2/g至600m2/g。BET-表面积在此通过氮气吸附根据DIN 66132测定。
在一个特别优选的实施方案中,本发明涉及催化组合物,所述催化组合物包含MFI型沸石和BEA型沸石,所述MFI型沸石具有2至10μm的重均粒度d50,所述BEA型沸石具有0.1至3.0μm的重均粒度d50。
在一个非常特别优选的实施方案中,本发明涉及催化组合物,所述催化组合物包含MFI型沸石和BEA型沸石,所述MFI型沸石具有4至8μm的重均粒度d50,所述BEA型沸石具有0.2至2μm的重均粒度d50,并且在MFI型沸石和BEA型沸石中彼此独立地分别包含0.1至10重量%重量含量的铁。
优选将催化组合物加工成活性载体涂料并且施加在合适的载体材料上。由于催化组合物的性能,由其制备的涂层在载体材料上具有改进的粘合性。
因此本发明的另一个主题是包含上述催化组合物的活性载体涂料。为此,催化剂组合物优选与粘合剂混合。合适的粘合剂为氧化铝-粘合剂、氧化铝-氧化硅-粘合剂或二氧化硅-粘合剂。这些粘合剂为通常用于SCR-催化剂的所有铝氧化物、二氧化硅和氧化硅-铝-混合氧化物。氧化铝-粘合剂可以是(拟)勃姆石或氧化铝-溶胶。氧化铝-粘合剂通常在与沸石和任选的其它组分组合之前或过程中进行胶溶。物料中还可以存在二氧化硅和/或结晶氧化铝并且任选使用填料如粘土,例如高岭土。活性载体涂料中通常存在至多20重量%的粘合剂,优选氧化铝-粘合剂,但是也可以使用其它更高的量。
在另一个实施方案中,本发明涉及用于制备SCR-催化剂的方法,包括如下步骤:
a)提供如上所述的活性载体涂料,
b)使活性载体涂料与载体材料接触,并且
c)干燥根据步骤b)获得的载体材料。
根据一个优选的实施方案,所述方法包括如下步骤:
a)提供活性载体涂料,所述活性载体涂料包含MFI型沸石和BEA型沸石和粘合剂,所述MFI型沸石具有2至10μm的重均粒度d50,所述BEA型沸石具有0.1至3μm的重均粒度d50,
b)使活性载体涂料与载体材料接触,并且
c)干燥根据步骤b)获得的载体材料。
在步骤a)中,使上文已经描述的MFI型沸石和BEA型沸石与粘合剂混合。
在步骤b)中,使载体材料与活性载体涂料接触从而对载体材料进行涂布。合适的催化剂载体或载体材料为金属或陶瓷载体。优选作为载体材料的是分别以整料载体形式存在的金属或陶瓷载体材料。包含载体材料和催化活性涂层的催化剂被称为涂层催化剂。使用所谓的活性载体涂料-悬浮液(即催化活性物质在流体介质中的悬浮体)将涂层施加在催化剂载体上。因此本发明的另一个主题是用于制备SCR-催化剂的方法。
作为陶瓷成形体蜂窝的载体材料,例如使用如堇青石、块滑石、羟钒铜矿或碳化硅的材料,或选自二氧化硅、铝氧化物、铝酸盐或金属和金属合金的成形体。使用金属和金属合金特别能够制备复杂结构的蜂窝体,例如具有开放通道结构或者具有复杂混合系统的蜂窝。
载体材料可以以蜂窝的形式存在。蜂窝要么由所谓的蜂窝体组成,要么完全由陶瓷成形体组成,所述蜂窝体可以由蜂窝壳和插入其中的载体(尤其是部分结构化并且卷绕的片状金属箔)组成。在这种情况下,蜂窝基本上被平行于蜂窝轴线延伸的通道穿过。
在此,涂布可以通过不同方法进行。通常首先用水制备活性载体涂料,任选加入添加剂例如表面活性剂、催化活性组分、成孔剂、流变助剂和其它添加物,然后通过浸渍、渗透或泵送过程用活性载体涂料填充载体材料。使活性载体涂料与载体材料接触的简单方法是将载体材料浸渍在活性载体涂料中并且通过用空气吹扫或抽出空气从而除去过量的活性载体涂料。还能够使用离心机或者通过用活性载体涂料喷洒载体材料从而进行涂布。MFI型沸石和BEA型沸石在此以层的形式施加在载体材料上,其中MFI型沸石和BEA型沸石共同存在于载体材料上的层中。
在步骤c)中干燥用活性载体涂料涂布的载体材料。任选在另外的步骤中煅烧经干燥的载体材料。优选然后在350℃至700℃,特别优选450℃至650℃的温度下煅烧载体材料。
本发明的另一主题是包含上述催化组合物的SCR-催化剂或根据上述方法制备的SCR-催化剂。
根据本发明的SCR-催化剂适合减少移动或静止的燃烧装置的氮氧化物排放。移动燃烧装置例如为机动车的内燃机,特别是柴油发动机、基于内燃机的发电设备或基于内燃机的其它设备。静止燃烧装置通常为发电厂、燃烧设备、垃圾焚化设备和私人加热系统。因此本发明的另一个主题是SCR-催化剂用于选择性还原氮氧化物的用途。
本发明的另一个主题是具包括根据本发明的SCR-催化剂的废气净化系统。废气净化系统还可以包含其它组分,优选用于氧化烃的柴油氧化催化剂(DOC),用于减少颗粒排放的柴油颗粒过滤器,任选的用于尿素加工的氢化催化剂,以及位于SCR-催化剂下游并且充当氨氧化催化剂(泄漏催化剂)的阻断催化剂。
下文通过几个实施例详细解释本发明,但是所述实施例不限制本发明的范围。
实施例
粒度的测定
通过使用Malvern粒度分析仪2000和Malvern Hydro 2000S分散单元测定本发明中使用的沸石的重均粒度d50。由Malvern Instruments(Malvern,英国)制备的所述仪器利用米氏散射并且使用低能量He/Ne-激光。在测量之前首先用超声波在水中将样品分散五分钟从而形成含水分散液。搅拌该分散液,然后用仪器使用说明中描述的测量方法进行测量。Malvern粒度分析仪测量沸石的重均粒度分布。通过由仪器生成的数据容易地获得重均粒度d50。
材料
1.Süd-Chemie Zeolites GmbH的含铁的MFI型沸石(“Fe-MFI”)(商品名:Fe-TZP-302),铁含量:2.8重量%,重均粒度分布:d10=1.98μm,d50=6.42μm,d90=12.21μm。
2.Süd-Chemie Zeolites GmbH的含铁的BEA型沸石(“Fe-BEA”)(商品名:Fe-TZB-223I),铁含量:2.1重量%,重均粒度分布:d10=0.19μm,d50=0.47μm,d90=2.45μm。
3.Süd-Chemie Zeolites GmbH的含铁的MFI型沸石(“FeCZP30.2”),铁含量:2.2重量%,重均粒度分布:d10=2.73μm,d50=7.41μm,d90=13.81μm。
4.Süd-Chemie Zeolites GmbH的含铁的BEA型沸石(“FeCZB 30”),铁含量:2.2重量%,重均粒度分布:d10=0.6μm,d50=6.73μm,d90=13.93μm。
活性载体涂料-悬浮液和经涂布基材的制备
实施例1:
将75g Fe-BEA和75g Fe-MFI分散在275ml水中。然后添加130g Nyacol的AL 20DW(胶态铝溶胶)。将悬浮液分散几分钟。然后通过将基材浸渍在活性载体涂料悬浮液中进行金属基材(1英寸直径,2英寸长度,400cpsi)的涂布,然后抽吸或吹扫从而除去过量的活性载体涂料悬浮液。根据希望的催化剂负载需要进行一至两个涂布步骤。
实施例2:
如实施例1所述进行悬浮液和经涂布基材的制备,但是使用样品FeCZP 30.2和FeCZB 30。
粘合性的测定
借助于所谓的“热冲击试验”测定活性载体涂料的粘合性。为此,将如上所述涂布的金属蜂窝称重,然后加热至650℃至850℃的温度,然后放入具有冷水的容器中。水被突然蒸发。水的蒸发连同突然冷却对活性载体涂层造成巨大的物理负载。然后确定脱落的活性载体涂层的量。为此,在120℃下干燥基材然后称重。确定的重量差对应于脱落的活性载体涂料的量。
上述热冲击试验进行多次,表1汇总了结果
表1
催化剂 | d50 MFI[μm] | d50 BEA[μm] | 损失[%] |
实施例1 | 6.42 | 0.47 | 13.6 |
实施例2 | 7.41 | 6.73 | 33.3 |
Fe-BEA | - | 0.47 | 41.6 |
实施例表明,随着两种沸石类型之间的重均粒度d50(MFI的d50-值和BEA的d50-值)的差异的变大,活性载体涂料在蜂窝上的粘合性增加。实施例1和2中的活性载体涂料的损失分别为13.6%和33.3%,以原始存在的活性载体涂料的量计,相反仅用Fe-BEA涂布的催化剂的损失为41.6%,以原始存在的活性载体涂料的量计。由于活性载体涂料更少的损失表示改进的粘合性,所以根据本发明涂布的催化剂显示出活性载体涂料在载体基材上的改进的粘合性。
Claims (13)
1.催化组合物,所述催化组合物包括含有铁的MFI型沸石和含有铁的BEA型沸石,其中沸石的重均粒度d50不同。
2.根据权利要求1所述的催化组合物,其特征在于,沸石的重均粒度d50相差至少0.5μm。
3.根据权利要求1所述的催化组合物,其特征在于,沸石的重均粒度d50相差至少2μm。
4.根据权利要求1至3所述的催化组合物,其特征在于,BEA型沸石具有0.1至3μm的重均粒度d50,MFI型沸石具有2至10μm的重均粒度d50。
5.根据权利要求1至4任一项所述的催化组合物,其特征在于,BEA型沸石具有0.2至2μm的重均粒度d50。
6.根据权利要求1至5任一项所述的催化组合物,其特征在于,MFI型沸石具有4至8μm的重均粒度d50。
7.根据权利要求1至6任一项所述的催化组合物,其特征在于,MFI型沸石与BEA型沸石的重量比例为1:10至10:1。
8.根据权利要求1至7任一项所述的催化组合物,其特征在于,MFI型沸石包含0.7至4.9重量%,优选2.1至3.5重量%的重量含量的铁,以含铁的MFI型沸石的重量计,并且BEA型沸石包含0.3至3.9重量%,优选1.7至2.5重量%的重量含量的铁,以含铁的BEA型沸石的重量计。
9.根据权利要求1至8任一项所述的催化组合物用于选择性催化还原氮氧化物的用途。
10.包含根据权利要求1至8任一项所述的催化组合物的活性载体涂料。
11.用于制备SCR-催化剂的方法,包括如下步骤:
a)提供根据权利要求10所述的活性载体涂料,
b)使活性载体涂料与载体材料接触,并且
c)干燥根据步骤b)获得的载体材料。
12.根据权利要求11所述的方法,其特征在于,载体材料为金属或陶瓷载体材料。
13.SCR-催化剂,其包含根据权利要求1至8任一项所述的催化组合物或通过根据权利要求11或12所述的方法制备。
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JP2009262098A (ja) * | 2008-04-28 | 2009-11-12 | Ne Chemcat Corp | 選択還元触媒を用いた排気ガス浄化方法 |
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