CN114269471A - 用于减少来自内燃机的废气的氨和氮氧化物排放物的催化剂 - Google Patents
用于减少来自内燃机的废气的氨和氮氧化物排放物的催化剂 Download PDFInfo
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- CN114269471A CN114269471A CN201980099706.9A CN201980099706A CN114269471A CN 114269471 A CN114269471 A CN 114269471A CN 201980099706 A CN201980099706 A CN 201980099706A CN 114269471 A CN114269471 A CN 114269471A
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- catalyst
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- material zone
- zeolite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims description 52
- 229910021529 ammonia Inorganic materials 0.000 title claims description 26
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title description 19
- 239000007789 gas Substances 0.000 title description 10
- 238000002485 combustion reaction Methods 0.000 title description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000010457 zeolite Substances 0.000 claims abstract description 45
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 42
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 description 13
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
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- 239000011149 active material Substances 0.000 description 3
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- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
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- 229910052878 cordierite Inorganic materials 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
- 238000003618 dip coating Methods 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 1
- 231100001143 noxa Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 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
- 238000000746 purification Methods 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
- 239000004071 soot Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种催化剂,该催化剂包含‑长度L的载体基材,该载体基材在第一端面‘a’与第二端面‘b’之间延伸,以及‑布置在载体基材上的不同组成的材料区A和B,其中‑材料区A包含铂且不含钯或包含铂和钯,其中Pt:Pd的重量比为≥1,并且,‑材料区B包含Cu/Al比率为0.355或更高的含铜沸石。
Description
本发明涉及用于减少来自内燃机,特别是稀薄运行的发动机如柴油机的废气的氨和氮氧化物排放物的催化剂,所述催化剂具有若干材料区。
除了一氧化碳CO、烃HC和氮氧化物NOx之外,柴油机的原始废气含有高达15体积%的相对高氧含量。还含有主要由烟灰残留物和可能的有机附聚物组成并且源自发动机气缸中的部分不完全燃料燃烧的颗粒排放物。
虽然带有和不带有催化活性涂层的柴油微粒过滤器都适于去除颗粒排放物,但一氧化碳和碳氢化合物通过在合适的氧化催化剂上氧化而变得无害。在文献中广泛描述了氧化催化剂。例如,它们是流通式基材,其承载贵金属,如铂和钯,作为大面积、多孔、高熔点氧化物(如氧化铝)上必不可少的催化活性组分。
氮氧化物可以在存在氧气的情况下在SCR催化剂上通过氨转化为氮气和水。SCR催化剂也在文献中广泛描述。它们通常是所谓的混合氧化物催化剂,特别是含有钒、钛和钨,或者是所谓的沸石催化剂,它们含有金属交换的沸石,特别是小孔的沸石。SCR催化活性材料可以载于流通式基材或壁流式过滤器上。
用作还原剂的氨可以通过将氨前体化合物进料到废气中而得到,该废气被热解和水解以形成氨。此类前体的示例是氨基甲酸铵、甲酸铵,并且优选尿素。另选地,氨可以通过废气内的催化反应形成。
为了提高SCR催化剂处氮氧化物的转化率,可能需要以比所需量高约10%至20%的量(即,超过化学计量的量)加入氨。这继而导致废气中未反应的氨,鉴于其毒性作用,这是不希望的。氨排放物在废气立法中越来越受到限制。
为了避免氨排放物,已经开发了所谓的氨泄漏催化剂(ASC)。这些催化剂通常包含用于在尽可能低的温度下氧化氨的氧化催化剂。这种氧化催化剂包含至少一种贵金属,如钯,特别是铂。然而,包含贵金属的氧化催化剂不仅将氨氧化成氮,而且还氧化成有害物质,如一氧化二氮(N2O)和氮氧化物(NOx)。通过将氧化催化剂与SCR催化剂结合可以提高氨氧化对氮的选择性。此类结合可以以不同的方式进行,例如两种组分可以混合和/或它们可以各自存在于载体基材上的单独层中。在分层布置的情况下,SCR层通常是上层,并且涂覆在作为下层的氧化层上。ASC催化剂通常涂覆在整体式载体基材上,如流通式基材或壁流式过滤器。
这种类型的ASC催化剂例如公开在EP0410440A1、WO02/100520A1、EP2117702A2和WO2010/062730A2中。
在这些系统中,存在氨氧化活性与对N2O和NOx的选择性之间的权衡。较高的氨氧化与较高的N2O和NOx产生相关联。当将氨和NOx同时进料到这些催化剂中时,观察到对N2O和NOx的高选择性。
因此需要一种解决方案,以在对N2O和NOx的选择性较低的情况下实现更高的氨转化率,并在对N2O和NOx的选择性较低的情况下实现高SCR活性。
本发明的发明人惊奇地发现,该问题可以通过包含作为SCR催化剂的含铜沸石的ASC催化剂来解决,其中Cu/Al比高于特定值。
因此,本发明涉及一种催化剂,其包括:
·载体基材,该载体基材具有在第一端面‘a’和第二端面‘b’之间延伸的长度L,和
·布置在载体基材上的不同组成的材料区A和B,其中
-材料区A包含铂且不含钯,或包含重量比为Pt:Pd≥1的铂和钯,并且
-材料区B包含Cu/Al比率为0.355或更高的含铜沸石。
在材料区A包含铂和钯的情况下,重量比Pt:Pd优选地为20:1至1:1,特别是10:1至4:1。示例为20:1、12:1、10:1、7:1、6:1、4:1、3:1、2:1、1.5:1和1:1。
然而,材料区A优选地仅包含铂且不含钯。
在本发明的优选的实施方案中,材料区A包含呈铂颗粒形式的铂,其中铂颗粒的平均粒径为50nm-200nm,优选地80nm-120nm。
在本发明的上下文中,术语“平均粒径”应理解为是指是基于半最大峰宽(FWHM)处的全宽上大约39.8°处的[111]主反射,根据X射线衍射图像计算出来的。
铂或者铂和钯通常负载在材料区A中的一种或多种载体氧化物上。这些载体氧化物有利地是高熔点的,即它们的熔点足够高于根据本发明的催化剂的特定正常操作期间出现的温度。此外,载体氧化物具有有利的大表面积,并且优选地具有50m2/g至200m2/g的BET表面(根据DIN 66132测定)。
合适的载体氧化物选自由以下项组成的组:氧化铝、掺杂的氧化铝、氧化硅、氧化钛、掺杂的氧化钛、氧化铈、氧化锆以及这些氧化物中的一种或多种的混合氧化物。
掺杂的氧化铝为例如氧化硅掺杂的氧化铝、氧化锆掺杂的氧化铝和/或氧化钛掺杂的氧化铝。有利地使用镧稳定的氧化铝,其中分别以按照La2O3计算的并相对于稳定的氧化铝的重量计1重量%至10重量%,优选地3重量%至6重量%的量使用镧。掺杂的氧化钛为例如氧化硅掺杂的氧化钛。
在本发明的优选的实施方案中,材料区A包含负载在氧化钛上的呈铂颗粒形式的铂,其中铂颗粒的平均粒径为50nm-200nm,优选地80nm-120nm。
在本发明的上下文中,术语“平均粒径”是基于半最大峰宽(FWHM)处的全宽上大约39.8°处的[111]主反射,根据X射线衍射图像计算的平均Pt微晶直径。当使用标准硅时,在大约28.4°2θ处产生一峰,其中FWHM为0.06°2θ。
优选地,氧化钛以二氧化钛的形式存在,特别是包括结晶相锐钛矿和金红石。锐钛矿和金红石相优选地以大于9:1的重量比存在。
氧化钛优选地掺杂有氧化硅,特别是基于掺杂的氧化钛的重量计1重量%至10重量%的氧化硅。
基于载体氧化物的重量计,载体氧化物的铂负载量具体地在0.5重量%至20重量%,优选地3重量%至8重量%的范围内。
在其中铂以平均直径为50nm-200nm、优选地80nm-120nm的铂颗粒形式存在的本发明的实施方案中,载体氧化物不是氧化铝。
负载在载体氧化物上的呈铂颗粒形式的铂(其中铂颗粒的平均直径为50nm-200nm,优选地80nm-120nm)可以例如通过以下步骤来获得:将来自水溶性铂化合物的水溶液的铂沉积在载体氧化物上,之后经由在700℃至900℃的热处理将其干燥并固定在载体氧化物上。
除了负载在载体氧化物上的铂或者Pt:Pd的重量比≥1的铂和钯之外,材料区A还可以包含一种或多种不承载铂和/或钯的金属氧化物。这种金属氧化物可以与载体氧化物相同或不同。例如,材料区A可以包含负载在氧化钛上的铂和不承载铂的附加氧化钛。
沸石是二维或三维结构,其最小结构可以被认为是SiO4和AlO4四面体。这些四面体聚在一起形成更大结构,其中每次经由共用的氧原子连接两个四面体。由此可以形成不同尺寸的环,例如四个、六个或甚至九个四面体配位的硅或铝原子的环。不同类型的沸石通常经由最大的环尺寸来定义,因为该尺寸决定哪个客体分子可穿透沸石结构以及哪个客体分子不穿透沸石结构。通常区分最大环大小为12的大孔沸石、最大环大小为10的中孔沸石和最大环大小为8的小孔沸石。
此外,沸石由国际沸石协会结构委员会(Structural Commission of theInternational Zeolite Association)分组成以三字母代码提供的结构类型。参见例如Atlas of Zeolite Framework Types,Elsevier,5th edition,2001(《沸石框架类型图集》,Elsevier,第5版,2001年)。
材料区B的沸石可以是大孔、中孔或小孔沸石。合适沸石的示例属于结构类型ABW、AEI、AFX、BEA、CHA、DDR、ERI、ESV、FAU、FER、KFI、LEV、LTA、MER MFI、MWW、SOD或STT。
优选地,材料区B的沸石是小孔沸石,并且特别是属于结构类型AEI、AFX、CHA或LEV。
更优选地,材料区B的沸石属于结构类型CHA。
材料区B的沸石优选地具有2至100,更优选地5至50,并且最优选地10至40的SAR(二氧化硅-氧化铝比率)值。
在本发明的上下文中,术语沸石还包括分子筛,其有时也称为“类沸石”化合物。属于上述结构类型之一的分子筛为优选的。示例包括术语名称为SAPO的磷酸硅铝沸石和术语名称为AIPO的磷酸铝沸石。
含铜沸石的Cu/Al比率优选地为0.355至2,例如0.355至1.5、0.355至1或0.355至0.75。更优选地,其为0.355至0.5,并且最优选地0.4至0.45。
为了避免疑义,明确指出仅作为三维沸石结构的一部分的氧化铝和可能存在于沸石结构内的氧化铝用于计算Cu/Al比率。例如可以作为载体涂料(washcoat)的一部分存在的氧化铝粘结剂的氧化铝不计入Cu/Al比率的计算中。
如果沸石的SAR(硅与铝比率)值是已知的,本领域技术人员可以容易地计算按照CuO计算的并基于含铜沸石的重量计的铜的重量%。例如,在沸石的SAR为13的情况下,0.355的Cu/Al比率对应于按照CuO计算的并基于含铜沸石的重量计6重量%的铜。同样,0.5的Cu/Al比率对应于按照CuO计算的并基于含铜沸石的重量计8.26重量%的铜,并且0.42的Cu/Al比率对应于按照CuO计算的并基于含铜沸石的重量计7重量%的铜。
铜优选地作为铜阳离子存在于沸石结构中,即以离子交换形式存在。然而,它们也可全部地或部分地作为铜氧化物存在于沸石结构中和/或沸石结构的表面上。
根据本发明的催化剂包括载体基材。这可为流通式基材或壁流式过滤器。
壁流式过滤器是担载主体,其包括长度为L的通道,该通道在壁流式过滤器的第一端和第二端之间平行地延伸,它们在第一端或第二端处交替地密封,并且由多孔壁分开。具体地,流通式基材与壁流式过滤器的不同之处在于长度为L的通道在其两端是敞开的。
在未涂覆状态下,壁流式过滤器具有例如30%至80%、具体地50%至75%的孔隙率。在未涂覆状态下,它们的平均孔径例如为5微米至30微米。
一般来讲,壁流式过滤器的孔是所谓的开放孔,即它们与通道连接。此外,孔通常彼此互连。这使得一方面能够容易地涂覆内孔表面,并且另一方面使废气容易通过壁流式过滤器的多孔壁。
流通式基材是本领域技术人员已知的,壁流式过滤器也是如此,并且均可商购获得。它们由例如碳化硅、钛酸铝或堇青石组成。
在本发明的实施方案中,使用由惰性材料的波纹状片材构成的载体基材。这种载体基材作为波纹状基材来说是本领域技术人员已知。合适的惰性材料是例如具有50μm至250μm的平均纤维直径和2mm至30mm的平均纤维长度的纤维材料。优选地,纤维材料是耐热的,并且由二氧化硅、特别是玻璃纤维组成。
为了制备此类载体基材,例如,将所述纤维材料的片材以已知的方式波纹化,并且将各个波纹状片材形成为具有贯穿主体的通道的圆柱形整体式结构化主体。优选地,通过将多个波纹状片材层压到层之间具有不同波纹取向的平行层,形成具有纵横交错波纹结构的整体式结构化主体。在一个实施方案中,可以在波纹状片材之间布置非波纹形、即平坦叶片。
由波纹状片材构成的基材可以直接涂覆有本发明的催化剂。然而,优选的是首先用惰性材料,例如二氧化钛涂覆这种基材,然后仅用本发明的催化剂涂覆这种基材。
通常,材料区A和B以涂层的形式存在于载体基材上,换言之,在载体基材上形成载体涂料层或载体涂料区。
在一个实施方案中,材料区A和B都在载体基材的长度L的100%上延伸。在这种情况下,材料区A通常涂覆在载体基材上并形成底层,例如直接位于载体基材上,而材料区B涂覆在材料区A上并形成顶层。
在另一个实施方案中,材料区A仅涂覆在载体基材的长度L的一部分上,例如在长度LA上,其为长度的20%至60%,而材料区B涂覆在长度L的100%上。
在壁流式过滤器的情况下,材料区A和B可位于输入通道的表面上、输出通道的表面上和/或介于输入通道与输出通道之间的多孔壁中。
根据本发明的催化剂(其中材料区A和B以涂层的形式存在于载体基材上)可根据本领域技术人员熟悉的方法制备,例如根据通常的浸涂法或泵吸涂布法以及随后的热后处理(煅烧)。本领域的技术人员知道,在壁流式过滤器的情况下,它们的平均孔径和待涂覆材料的平均粒度可以相互适应,使得它们安置在多孔壁上,该多孔壁形成壁流式过滤器的通道(壁上涂层)。然而,可选择待涂覆的材料的平均粒度,使得所述材料位于形成壁流式过滤器的通道的多孔壁中,使得内孔表面因此被涂覆(壁内涂层)。在这种情况下,待涂覆的材料的平均粒度必须足够小以渗透壁流式过滤器的孔。
根据本发明的催化剂特别适合作为氨泄漏催化剂,即可以避免或至少最小化氨排放,从而满足现行立法标准。
优选地将它们整合到废气净化系统中,使得已经通过SCR催化剂的废气在端面‘a’处进入本发明的催化剂并在端面‘b’处再次离开。
因此,本发明还涉及一种催化剂布置,其相继地包括用于喂入氨或氨前体的第一装置、第一SCR催化剂和根据本发明的催化剂,其中根据本发明的催化剂被布置成使得其端面“a”指向第一SCR催化剂的方向。
用于喂入氨或氨前体的装置优选地为用于喂入尿素水溶液的装置。此类装置是本领域技术人员已知的,并且可以在市场上获得。
尤其考虑将涂覆有SCR活性材料的流通式基材或壁流式过滤器作为第一SCR催化剂。
除了包含铜和/或铁的沸石之外,也可以考虑将混合氧化物催化剂,例如VWT催化剂作为SCR活性材料。VWT催化剂是基于V2O5、WO3和TiO2的催化剂。
第一SCR催化剂优选地包括VWT催化剂,或结构类型AEI、BEA、CHA或LEV的与铜、铁或铜和铁交换的沸石或分子筛。
实施例1
a)通过加入稀硝酸,将铂从六羟基铂酸四乙基铵(EP 3 210 989B1)的水溶液中沉淀到用5重量%的氧化硅稳定的氧化钛粉末上,以获得在氧化钛粉末上Pt浓度为3重量%的材料。随后,将如此制备的粉末过滤出、干燥并在空气气氛下在800℃下固定2小时。
b)然后将根据a)获得的粉末在水中浆化,并且通过添加不含铂的二氧化钛来来调节0.14重量%的Pt(基于总二氧化钛粉末计)的所需负载量。如此获得的载体涂料用于以常规方式在其整个长度上涂覆孔密度为400cpsi且壁厚为110μm的市售陶瓷流通基材。然后将涂覆的基材在110℃下干燥,并且在600℃下煅烧6小时。催化剂的载体涂料负载量为25g/l,催化剂的铂负载量为0.0353g/l。
c)结构类型CHA(SAR=13)的沸石负载有按照CuO计算的并基于含铜沸石的重量计7重量%的量的铜。Cu/Al比率为0.42。如此获得的沸石分散在含有粘结剂材料的水中以获得载体涂料。
d)将根据c)获得的载体涂料作为顶层在其总长度上涂覆到根据b)获得的涂覆的基材上。载体涂料负载量为100g/L。然后将涂覆的基材在110℃下干燥,并且在600℃下煅烧6小时。
如此获得的催化剂被称为K1。
比较例1
重复实施例1,不同之处在于根据步骤c)获得的沸石负载有5.5重量%的量的铜,Cu/Al比率为0.325。
如此获得的催化剂被称为VK1。
比较测试
a)将催化剂K1和VK1在包含10%H2O和10%O2的气氛中在750℃下老化16小时。
b)在进料中加入NH3、O2和H2O的Light Down-Light-up实验中,考虑了light-up阶段,在该阶段中温度以5K/min的速度从100℃增加到600℃。与催化剂VK1相比,根据本发明的催化剂K1显示出改进的NH3转化率、平均N2O形成减少20%、最大N2O浓度减少30%和NO选择性减少5%。结果也显示在图1中,其中灰色图对应于催化剂K1,并且黑色图对应于催化剂VK1。
c)在进料中添加NH3、NO、O2和H2O的映射测试中,当反应器出口处的NH3浓度达到20ppm时,确定获得的NOx转化率和N2O形成。
结果在表2中示出。可以看出,当与VK1(黑色图)相比时,根据本发明的催化剂K1(灰色图)在高于250℃的温度下显示出改进的NOx转化率并且在高达500℃时显着降低了N2O形成。在图2中,实线对应于NOx转化率(左y轴),并且虚线对应于N2O浓度(右y轴)。
Claims (17)
1.催化剂,所述催化剂包含
·载体基材,所述载体基材具有在第一端面‘a’和第二端面‘b’之间延伸的长度L,和
·布置在所述载体基材上的不同组成的材料区A和B,其中
-材料区A包含铂且不含钯,或包含重量比为Pt:Pd≥1的铂和钯,并且
-材料区B包含Cu/Al比率为0.355或更高的含铜沸石。
2.根据权利要求1所述的催化剂,其特征在于,材料区A包含铂且不含钯。
3.根据权利要求1和/或2所述的催化剂,其特征在于,材料区A包含呈铂颗粒形式的铂,其中所述铂颗粒的平均直径为50nm-200nm。
4.根据权利要求1至3中的一项或多项所述的催化剂,其特征在于,材料区A中的铂或者铂和钯负载在一种或多种载体氧化物上。
5.根据权利要求4所述的催化剂,其特征在于,所述载体氧化物选自由以下项组成的组:氧化铝、掺杂的氧化铝、氧化硅、氧化钛、掺杂的氧化钛、氧化铈、氧化锆以及它们中的一种或多种的混合氧化物。
6.根据权利要求1至5中的一项或多项所述的催化剂,其特征在于,材料区A包含负载在氧化钛上的呈铂颗粒形式的铂,其中所述铂颗粒的平均直径为50nm-200nm。
7.根据权利要求6所述的催化剂,其特征在于,氧化钛掺杂有氧化硅。
8.根据权利要求7所述的催化剂,其特征在于,基于所述掺杂的氧化钛的重量计,氧化钛掺杂有1重量%至10重量%的氧化硅。
9.根据权利要求1至8中的一项或多项所述的催化剂,其特征在于,材料区B的沸石属于结构类型ABW、AEI、AFX、BEA、CHA、DDR、ERI、ESV、FAU、FER、KFI、LEV、LTA、MER、MFI、MWW、SOD或STT。
10.根据权利要求1至9中的一项或多项所述的催化剂,其特征在于,材料区B的沸石属于所述结构类型CHA。
11.根据权利要求1至10中的一项或多项所述的催化剂,其特征在于,材料区B的沸石的SAR(二氧化硅与氧化铝比率)值为2至100。
12.根据权利要求1至11中的一项或多项所述的催化剂,其特征在于,材料区B的含铜沸石的Cu/Al比率为0.355至2。
13.根据权利要求1至12中的一项或多项所述的催化剂,其特征在于,材料区B的含铜沸石的Cu/Al比率为0.4至0.45。
14.根据权利要求1至13中的一项或多项所述的催化剂,其特征在于,材料区A和B都在所述载体基材的长度L的100%上延伸。
15.根据权利要求14所述的催化剂,其特征在于,材料区A涂覆在所述载体基材上并形成底层,而材料区B涂覆在材料区A上并形成顶层。
16.根据权利要求1至13中的一项或多项所述的催化剂,其特征在于,材料区A被涂覆在所述载体基材的长度L的20%至60%上,而材料区B被涂覆在所述载体基材的长度L的100%上。
17.催化剂布置,所述催化剂布置相继地包括用于喂入氨或氨前体的第一装置、第一SCR催化剂和根据权利要求1至16中的一项或多项所述的催化剂,其中根据权利要求1至16中的一项或多项所述的催化剂被布置成使得其端面“a”指向所述第一SCR催化剂的方向。
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