CN111511458A - Scr催化剂和废气清洁系统 - Google Patents
Scr催化剂和废气清洁系统 Download PDFInfo
- Publication number
- CN111511458A CN111511458A CN201980006715.9A CN201980006715A CN111511458A CN 111511458 A CN111511458 A CN 111511458A CN 201980006715 A CN201980006715 A CN 201980006715A CN 111511458 A CN111511458 A CN 111511458A
- Authority
- CN
- China
- Prior art keywords
- scr catalyst
- exhaust gas
- coating
- carrier substrate
- palladium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 238000004140 cleaning Methods 0.000 title claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000010457 zeolite Substances 0.000 claims abstract description 59
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 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 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims description 50
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 49
- 230000003647 oxidation Effects 0.000 claims description 27
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 239000003638 chemical reducing agent Substances 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 25
- 229910021529 ammonia Inorganic materials 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000000446 fuel Substances 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000004071 soot Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 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 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 229910052878 cordierite Inorganic materials 0.000 description 6
- 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 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- -1 copper cations Chemical class 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 3
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 3
- 229910052676 chabazite Inorganic materials 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 206010021198 ichthyosis Diseases 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000010354 integration Effects 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
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient 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
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- B01D53/34—Chemical or biological purification of waste gases
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- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- 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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Abstract
本发明涉及一种SCR催化剂,该SCR催化剂包括具有长度L的载体基材以及包括小孔沸石、铜和钯的涂层A,该具有长度L的载体基材为流通式基材。
Description
本发明涉及可在紧密耦接位置中使用的SCR催化剂,以及涉及包括紧密耦接的SCR催化剂的废气清洁系统。
用稀燃内燃机(诸如柴油发动机)操作的机动车辆的废气含有一氧化碳(CO)、氮氧化物(NOx)、以及因燃料在气缸的燃烧室中不完全燃烧而产生的组分。这些组分包括通常也主要以气体形式存在的残余烃(HC),以及粒子排放物,也称为“柴油炭烟”或“炭烟粒子”。粒子排放物是主要来自含碳颗粒物和粘附液相的复杂团聚体,通常主要包括长链烃缩合物。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”。
为了清洁这些废气,上述组分必须尽可能完全地转化为无害化合物。这只有在使用合适催化剂的情况下才有可能实现。
在氧的存在下除去废气中所含氮氧化物的已知方法是在SCR催化剂的存在下用氨进行选择性催化还原。该方法包括用作为还原剂的氨将待从废气中除去的氮氧化物转化成氮气和水。
合适的SCR催化剂例如是与铁,特别是与铜进行离子交换的沸石,参见例如WO2008/106519A1、WO2008/118434A1和WO2008/132452A2。
用于用氨转化氮氧化物的SCR催化剂通常不含贵金属,特别是不含铂。这是因为在这些金属的存在下,优选用氧将氨氧化成氮氧化物,并且SCR反应(氨与氮氧化物的转化)将落在后面。在文献中,一些作者说明了与铂交换的“SCR催化剂”。然而,这并不是指NH3-SCR反应,而是指用烃还原氮氧化物。由于后一反应的选择性非常有限,因此更准确的是将其称为“HC-DeNOx-反应”而非“SCR反应”。
SCR反应中使用的氨可以通过将氨前体诸如尿素、氨基甲酸铵或甲酸铵给料到废气管线中并随后水解而可用。
目前用于低排放应用的柴油后处理系统通常由柴油氧化催化剂(DOC)、之后是催化柴油微粒过滤器(cDPF)和SCR催化剂组成。在该系统中,SCR催化剂在循环早期(例如,冷启动期间)的温度受到组分(尤其是cDPF)的热质量的限制,在此之前,其延迟热能的传递。
一种解决方案是将SCR催化剂与微粒过滤器组合,从而制备SDPF(DPF上的SCR),也称为SCRF(过滤器上的SCR),参见例如WO2005/016497A1。
然而,在该配置中,SDPF中收集的炭烟的高温暴露所导致的主动再生(燃烧)过程会导致以下情况中的任一种:如果过滤器再生温度足够高以进行良好、快速的清理(约575℃以上),则系统的NOx控制有损失,其中SDPF的SCR转化较差;或者通过在SDPF内可以进行一些SCR转化但炭烟再生较差的温度(约525℃以下)下进行操作来减少再生时间/完整性。
该问题的另一个解决方案是两阶段系统,其中在DOC和系统的其余部分之前放置了具有自身尿素或氨供应的额外SCR催化剂,因此它比cDPF下游的初级SCR更快变暖。在各种类型的SCR催化剂中,可考虑的是用于该紧密耦接位置的钒基和铜基催化剂。钒的优点在于,其不需要在冷启动时具有预储存的氨,并且其不是硫敏感的。然而,钒在没有NO2增强的情况下具有较差的低温NOx转化,该增强通常是通过将NO2放置在DOC和/或cDPF后面来提供的。铜基SCR催化剂在没有NO2辅助的情况下具有好得多的低温转化,但易受硫中毒的影响,并且根据类型,需要在高于400-500℃的温度下周期性地脱硫。通常,如果铜基SCR催化剂在DOC和/或cDPF的下游,则如果正常的发动机操作温度不够高(通常与DPF再生结合),则可以在铜基SCR催化剂之前的设备中燃烧燃料以提供附加温度。
然而,如果铜基SCR催化剂被放置在系统的其余部分之前,则在铜基SCR催化剂之前的设备中燃烧的燃料不会产生热量。具有良好低温转化特性和低N2O形成的现代小孔沸石SCR催化剂也不能有效燃烧燃料,因此注入其中的燃料不会通过内部热释放使SCR催化剂脱硫。因此,这些SCR催化剂不能紧密耦接使用。
因此,仍然需要在低温下(例如在冷启动期间)提供足够NOx转化的技术解决方案。
现已令人惊讶地发现,包括一定量钯的基于小孔沸石和铜的SCR催化剂可解决该问题。
因此,本发明涉及SCR催化剂,其包括:
-具有长度L的载体基材,该具有长度L的载体基材为流通式基材,
和
-包括小孔沸石、铜和钯的涂层A。
沸石是二维或三维结构,其由SiO4-和AlO4-四面体作为最小的结构单元组成。此类四面体组合成更大的结构,其中每两个经由共同的氧原子连接。这产生不同尺寸的环,例如四个、六个或更多个四面体硅原子或铝原子的环。不同的沸石类型通常经由环尺寸来定义,因为该尺寸决定哪个客体分子可进入沸石结构以及哪个客体分子不进入沸石结构。通常区分最大环尺寸为12的大孔沸石、最大环尺寸为10的中孔沸石和最大环尺寸为8的小孔沸石。
此外,国际沸石协会结构委员会(Structure Commission of the InternationalZeolite Association)将沸石分类为结构类型,每个结构类型具有三字母代码,参见例如沸石骨架类型图集,爱思唯尔出版公司(Atlas of Zeolite Framework Types,Elsevier),第六修订版,2007年。
因此,如根据本发明所用的小孔沸石具有8个四面体原子的最大环尺寸。
在本发明的实施方案中,涂层A包括属于骨架类型代码为AEI、AFX、CHA、ERI、KFI或LEV的骨架类型的小孔沸石。
骨架类型为AEI的沸石是例如SSZ-39和AlPO-18。骨架类型为AFX的沸石是例如SAPO-56。骨架类型为CHA的沸石是例如SSZ-13、SAPO-34、LZ-218、ZK-14和菱沸石。骨架类型为ERI的沸石是例如ZSM-34、LZ-220和SAPO-17。骨架类型为KFI的沸石是例如ZK-5。骨架类型为LEV的沸石是例如插晶菱沸石、LZ-132、Nu-3、ZK-20和SAPO-35。
在本发明的上下文中,术语沸石包括有时被称为“类沸石”的分子筛。如果分子筛属于上述结构代码之一,则它们是优选的。示例是被称为SAPO的硅铝磷酸盐-沸石和被称为AlPO的铝磷酸盐-沸石。
此外,优选的沸石具有的SAR(二氧化硅与氧化铝比率)值为2至100、特别是5至50。
在本发明的实施方案中,涂层A包括铜,其量基于小孔沸石的重量并且以CuO计算为1至20重量%。具体地讲,基于小孔沸石的重量并且以CuO计算,铜的量为1至10重量%或优选地为2至6重量%。
铜特别地作为铜阳离子,即以离子交换形式存在于沸石结构中。此外,铜可以完全或部分地以氧化铜的形式存在于沸石结构内和/或沸石结构的表面上。
在本发明的实施方案中,涂层A包括钯,其量基于小孔沸石的重量并且以钯金属计算为0.003至2重量%,例如0.005至1.5、0.007至1或0.009至0.5重量%。具体地讲,基于小孔沸石的重量并且以钯金属计算,钯的量为0.04至0.1重量%并且优选地为0.06至0.08重量%。
钯特别地作为钯阳离子,即以离子交换形式存在于沸石结构中。此外,钯可以完全或部分以钯金属的形式和/或以氧化钯的形式存在于沸石结构内和/或沸石结构的表面上。
在本发明的实施方案中,除了小孔沸石之外,涂层A还包括铜和钯铈,特别是呈二氧化铈(CeO2)的形式或呈铈/锆混合氧化物的形式。
在这种情况下,基于载体基材的体积计,二氧化铈和铈/锆混合氧化物的量具体地讲分别为10至80g/L。
在本发明的实施方案中,基于载体基材的体积计,涂层A以50至300g/L,特别是100至250g/L的量存在。
根据本发明使用的载体基材是例如由堇青石或金属制成的通常的流通式基材。此类载体基材在文献中有描述,并且可在市场上获得。
作为另外一种选择,根据本发明的载体基材为所谓的波纹基材。这些载体基材是特别蜂窝形状的,由波纹片材形成并且具有开放通道,使得废气可直接流过。
具体地讲,波纹基材包括非织造材料,例如E-玻璃纤维,其在波纹化并形成为波纹片材之前被涂覆有陶瓷材料。陶瓷材料优选地包括二氧化钛、二氧化硅和/或高岭土。
通过将多个经涂覆的波纹片材堆叠成矩形或圆柱形主体来形成蜂窝形状的基材。这样的主体具有由波纹片材的波形成的多个平行流通式通道。
包括小孔沸石、铜和钯的涂层A通常延伸到载体基材的总长度L。然而,在本发明的实施方案中,涂层A仅延伸到长度L的一部分。在这种情况下,载体上可存在一个或多个附加的催化活性涂层。例如,可存在包括小孔沸石和铜但不含钯的涂层B。具体地讲,涂层A和B仅在涂层B中不存在钯的情况下不同。
涂层A和B可以以不同方式布置在载体基材上。在一个实施方案中,涂层A从载体基材的一个端部开始延伸到长度L的10%至80%,并且涂层B也从载体基材的另一个端部开始延伸到长度L的20%至90%。通常,L=LA+LB适用,其中LA是涂层A的长度,并且LB是涂层B的长度。
当使用时,将涂层A布置在上游,并且将涂层B布置在下游。
根据本发明的SCR催化剂可以通过已知的方法制造,例如根据常规浸涂方法或泵涂和吸涂方法,随后进行热后处理(煅烧和可能使用合成气体或氢气进行还原)。这些方法在现有技术中是充分已知的。因此,在第一步骤中,制备包括小孔沸石、铜和钯的载体涂料,该载体涂料在第二步骤中被涂覆到载体基材上。
在本发明的实施方案中,SCR催化剂与还原剂的定量给料单元连接。
合适的定量给料单元可见于文献(参见例如T.Mayer,Feststoff-SCR-System aufBasis von Ammonium-carbamat,Dissertation,Technical University ofKaiserslautern,Germany,2005),并且技术人员可以选择它们中的任何一种。氨可以以原样或以在废气流的环境条件下形成氨的前体的形式定量给料到废气流中。合适的前体是例如尿素或铵形式的水溶液,以及固体氨基甲酸铵。还原剂及其前体通常分别被携带在与定量给料单元连接的储罐中。
因此,本发明还涉及系统,该系统包括:
SCR催化剂,该SCR催化剂包括:
-具有长度L的载体基材,该具有长度L的载体基材为流通式基材,
和
-包括小孔沸石、铜和钯的涂层A,和还原剂的定量给料单元。
当使用时,本发明的系统被布置到废气流中,使得定量给料单元在SCR催化剂的上游。
本发明的SCR催化剂具有增加的在高于300℃下氧化烃的能力,主要目的是产生足够的内部放热以达到允许其脱硫的温度。令人惊讶的是,这对低温SCR性能没有不利影响或甚至增强低温SCR性能。换句话讲,SCR催化剂在循环早期,例如在冷启动期间提供足够的NOx转化。除了自脱硫外,加热后的废气(可能仍含有一些或很大部分的烃)使得下游的DOC和cDPF能够在有或没有附加燃料的情况下进行主动炭烟再生。
特别令人惊讶的是,本发明SCR催化剂氧化烃的能力不会增加氨的氧化,特别是在300℃以下。
因此,本发明的SCR催化剂特别适合作为紧密耦接的SCR催化剂。这意味着当使用时,在本发明SCR催化剂的上游不存在催化剂。
因此,本发明还涉及废气清洁系统,其依次包括:
·还原剂的第一定量给料单元,
·第一SCR催化剂,该第一SCR催化剂包括:
-具有长度L的载体基材,该具有长度L的载体基材为流通式基材,和
-包括小孔沸石、铜和钯的涂层A,
·氧化催化剂,
·微粒过滤器,
·还原剂的第二定量给料单元,和
·第二SCR催化剂。
在本发明的废气清洁系统的实施方案中,将氧化催化剂和微粒过滤器组合以形成催化的微粒过滤器(cDPF)。
在本发明的废气清洁系统的另一个实施方案中,将微粒过滤器和第二SCR催化剂组合以形成所谓的SDPF。在这种情况下,第二定量给料单元布置在SDPF的上游。
在本发明的废气清洁系统的另外的实施方案中,氧化催化剂在载体材料上包括贵金属,例如铂、钯或铂和钯。在后一种情况下,铂和钯的重量比为例如4:1至14:1。
作为载体材料,可以使用本领域技术人员已知的所有材料。它们的BET表面积为30m2/g至250m2/g,优选100m2/g至200m2/g(根据德国标准DIN 66132确定),并且特别是氧化铝、二氧化硅、氧化镁、二氧化钛以及包括这些材料中的至少两种的混合物或混合氧化物。
优选氧化铝、氧化铝/二氧化硅混合氧化物和氧化镁/氧化铝混合氧化物。在使用氧化铝的情况下,优选例如用1重量%至6重量%,特别是4重量%的氧化镧使其稳定。
氧化催化剂通常以涂层的形式存在于载体基材上,特别是由堇青石或金属制成的流通式基材。
在氧化催化剂与微粒过滤器组合的情况下,氧化催化剂以涂层形式存在于微粒过滤器上,该微粒过滤器通常是由堇青石制成的壁流式过滤器基材。
本发明的废气清洁系统的第二SCR催化剂可以主要选自在催化氮氧化物与氨的SCR反应中有活性的所有催化剂。这是特别真实的,因为当使用时,紧密耦接布置的第一SCR催化剂在低操作温度下具有良好的性能,并且因此消除了第二SCR催化剂具有良好低温性能的需要。因此,优选的是使用在适度温度下具有良好性能并且可用NO2来控制N2的第二SCR催化剂,而不损害总体低温系统性能。这使得能够使用混合氧化物类型的SCR催化剂(该催化剂例如包括钒、钨和钛),以及基于沸石的催化剂,特别是与过渡金属交换的沸石,特别是与铜、铁或铁和铜交换的沸石。
在本发明的实施方案中,第二SCR催化剂包括最大环尺寸为八个四面体原子的小孔沸石,以及过渡金属,例如铜、铁、或铜和铁。此类SCR催化剂例如公开于WO2008/106519A1、WO2008/118434A1和WO2008/132452A2中。
此外,也可以使用与过渡金属交换的大孔和中孔尺寸的沸石。受到关注的特别是属于结构代码BEA的沸石。
特别优选的沸石属于结构代码BEA、AEI、CHA、KFI、ERI、LEV、MER或DDR,并且特别地与铜、铁或铜和铁进行离子交换。
沸石包括过渡金属,以金属氧化物(比如Fe2O3或CuO)计算,该过渡金属的量特别为1重量%至10重量%,优选地为2重量%至5重量%。
在本发明的废气清洁系统的优选实施方案中,第二SCR催化剂包括β型(BEA)、菱沸石型(CHA)或插晶菱沸石型(LEV)的沸石或分子筛。此类沸石或分子筛为例如ZSM-5、β、SSZ-13、SSZ-62、Nu-3、ZK-20、LZ-132、SAPO-34、SAPO-35、AlPO-34和AlPO-35,参见例如US6,709,644和US8,617,474。
本发明的废气清洁系统任选地包含所谓的氨逃逸催化剂(ASC)作为附加元素。氨逃逸催化剂的目的是氧化突破SCR催化剂的氨,并因此避免其释放到大气中。因此,氨逃逸催化剂被涂覆在单独的载体基材上并位于第二SCR催化剂的下游,或者其被涂覆在第二SCR催化剂的下游部分上。
在本发明的废气清洁系统的实施方案中,氨逃逸催化剂包括一种或多种铂族金属,特别是铂或铂和钯。
此外,本发明涉及用于清洁从稀燃发动机排放并且含有氮氧化物的废气的方法,该方法包括使废气流穿过废气清洁系统,该废气清洁系统依次包括:
·还原剂的第一定量给料单元,
·第一SCR催化剂,该第一SCR催化剂包括:
-具有长度L的载体基材,该具有长度L的载体基材为流通式基材,和
-包括小孔沸石、铜和钯的涂层A,
·氧化催化剂,
·微粒过滤器,
·还原剂的第二定量给料单元,和
·第二SCR催化剂。
其中还原剂的第一定量给料单元和第一SCR催化剂被布置成紧密耦接的,并且其中氧化催化剂、微粒过滤器、还原剂的第二定量给料单元和第二SCR催化剂被布置在底板下,并且
其中废气在还原剂的第一定量给料单元之前进入废气清洁系统,并且在第二SCR催化剂之后离开该废气清洁系统。
本发明的方法可根据废气清洁系统的某些部件的温度进行微调,具体地讲经由还原剂的定量给料来微调,例如如下所述。
在第二SCR催化剂(处于底板位置)的温度介于约200和225℃之间的情况下,优选地进行第一定量给料单元(处于紧密耦接位置)处的尿素定量给料,以考虑到需要限制下游氧化催化剂上的氨逃逸氧化来优化氨储存和NOx转化。
在第一SCR催化剂(处于紧密耦接位置)的温度在约225至275℃之间(其中下游cDPF中的被动炭烟氧化可能不明显)的情况下,优选地控制第一定量给料单元(处于紧密耦接位置)处的尿素定量给料以保持一定的最小氨储存,最大化整体系统性能,同时最小化完整废气清洁系统中N2O的形成。在第一SCR催化剂(处于紧密耦接位置)的温度高于约275℃的情况下,优选地最小化或完全停止第一定量给料单元(处于紧密耦接位置)处的尿素定量给料,以在第二SCR催化剂(处于底板位置)处于完全转化电势时实现足够的被动炭烟氧化。
当第一SCR催化剂(处于紧密耦接位置)需要被脱硫时,应采取发动机措施以将废气温度升高至约300至350℃,并且优选地进行后期缸内燃料后喷射,使得第一SCR催化剂(处于紧密耦接位置)使其中一些裂化的、部分氧化的烃氧化,以达到约400至450℃的内部脱硫温度目标。从第一SCR催化剂(处于紧密耦接位置)的烃逃逸在DOC和/或cDPF中被氧化,并且可在第一SCR催化剂(处于紧密耦接位置)下游补充有排气喷射的柴油燃料,以同时实现cDPF再生。如果在经历脱硫的同时用第一SCR催化剂(处于紧密耦接位置)实现足够的NOx转化,则下游cDPF可积极地再生,而无需保持在约550至600℃以下的良好SCR转化温度窗口中。如果从第一SCR催化剂(处于紧密耦接位置)获得不充分的NOx转化,则优选地将第二SCR催化剂(处于底板位置)保持在可获得更好SCR转化的温度范围内,低于约500℃。
当需要cDPF再生但不需要将第一SCR催化剂(处于紧密耦接位置)脱硫时,NOx转化可仅由第一SCR催化剂(处于紧密耦接位置)提供,并且主要在其下游注入的燃料将用于实现cDPF再生。然而,在第一SCR催化剂(处于紧密耦接位置)中燃烧的燃料仍然可能是提高DOC或cDPF入口温度以增强其燃料燃烧所需的,并且可能有利的是总是将脱硫和DPF再生组合以管理两者的条件。
实施例1
a)将SSZ-13型沸石(骨架类型代码CHA)悬浮在水中,基于沸石的重量计并且以CuO计算,该沸石包含量为3.85重量%的铜。
b)将硝酸钯形式的钯在可商购获得的铝硅载体材料上沉淀至1.4重量%的钯重量。
c)将在上述步骤a)中获得的含沸石浆料与去矿质水混合,然后以一定量添加在上述步骤b)中获得的含钯粉末,达到30ppm的钯。接下来,将获得的浆料与12重量%的可商购获得的基于勃姆石的粘结剂混合,并在球磨机中研磨。随后,将获得的载体涂料以200g/L的负载涂覆在堇青石的可商购获得的流通式基材上。
d)将上述步骤c)中获得的SCR催化剂(下文称为催化剂E1)与可商购获得的定量给料单元组合,以用于定量给料尿素的水溶液。
比较例1
重复实施例1,不同之处在于省略步骤b)。所获得的催化剂在下文中称为催化剂CE1。
实验:
催化剂E1和CE1在针对其SCR以及其氧化能力的测试过程中进行表征。SCR能力由NO与NH3在存在氧气的情况下的反应(所谓的“标准SCR反应”)表示,并且氧化能力由CO的氧化表示。
测试过程在浓度和温度方面是瞬态的。其包括用于不同温度步骤的预调节和测试循环。所施加的气体混合物如下:
气体混合物 | 1 | 2 | 3 |
N<sub>2</sub> | 平衡 | 平衡 | 平衡 |
O<sub>2</sub> | 10体积% | 10体积% | 10体积% |
NOx | 0ppm | 500ppm | 500ppm |
NO<sub>2</sub> | 0ppm | 0ppm | 0ppm |
NH<sub>3</sub> | 0ppm | 0ppm | 750ppm |
CO | 350ppm | 350ppm | 350ppm |
C<sub>3</sub>H<sub>6</sub> | 100ppm | 100ppm | 100ppm |
H<sub>2</sub>O | 5体积% | 5体积% | 5体积% |
GHSV/h-1 | 60.000 | 60.000 | 60.000 |
测试程序:
1.在N2下于600℃下预调节10分钟,同时经由旁路线识别精确的气体浓度(气体混合物3)。
2.测试循环,其针对每个目标温度(在这种情况下为350、250、225和175℃)重复。
a.使用气体混合物1达到目标温度
b.添加NOx(气体混合物2)
c.添加NH3(气体混合物3),等待直至达到20ppm NH3的突破
d.程序升温脱附,直到达到500℃(气体混合物3)
组分NO的测试结果示于图1中,组分NH3的测试结果示于图2中,并且组分CO的测试结果示于图3中。
由于NO和NH3的排放数据对于E1和CE1几乎相同(参见图1和图2),因此催化剂E1和CE1的SCR反应能力相同。
由于E1的CO排放与CE1的CO排放相比明显减少(参见图3),因此在E1中添加钯导致氧化能力的改善。这可用于加热功能以及催化剂的自脱硫能力。
实施例2
通过在定量给料单元的相对侧处向SCR催化剂添加来将上文实施例1d)中获得的SCR催化剂集成到废气清洁系统中
·以壁流式过滤器的体积计,涂覆有100g/L氧化催化剂的可商购获得的堇青石壁流式过滤器,该氧化催化剂由承载在氧化铝上的铂组成,
·第二定量给料单元,以及
·SCR催化剂,该SCR催化剂包括可商购获得的堇青石流通式基材,其涂覆有包括铁交换的β-沸石的载体涂料。
Claims (12)
1.一种SCR催化剂,包括:
-具有长度L的载体基材,所述具有长度L的载体基材为流通式基材,和
-包括小孔沸石、铜和钯的涂层A。
2.根据权利要求1所述的SCR催化剂,其中所述小孔沸石属于骨架类型代码为AEI、AFX、CHA、ERI、KFI或LEV的骨架类型。
3.根据权利要求1和/或2所述的SCR催化剂,其中涂层A包括铜,其量基于所述小孔沸石的重量并且以CuO计算为1至20重量%。
4.根据权利要求1至3中任一项所述的SCR催化剂,其中涂层A包括钯,其量基于所述小孔沸石的重量并且以钯金属计算为0.003至2重量%。
5.根据权利要求1至4中任一项所述的SCR催化剂,其中涂层A包括铈。
6.根据权利要求1至5中任一项所述的SCR催化剂,其中基于所述载体基材的体积计,涂层A以50至300g/L的量存在。
7.根据权利要求1至6中任一项所述的SCR催化剂,其中所述载体基材包括催化活性涂层B,所述催化活性涂层B包括小孔沸石和铜并且不含钯。
8.一种包括SCR催化剂的系统,所述SCR催化剂包括:
-具有长度L的载体基材,所述具有长度L的载体基材为流通式基材,和
-包括小孔沸石、铜和钯的涂层A,以及还原剂的定量给料单元。
9.一种废气清洁系统,依次包括:
·还原剂的第一定量给料单元,
·第一SCR催化剂,所述第一SCR催化剂包括:
-具有长度L的载体基材,所述具有长度L的载体基材为流通式基材,和
-包括小孔沸石、铜和钯的涂层A,
·氧化催化剂,
·微粒过滤器.
·还原剂的第二定量给料单元,和
·第二SCR催化剂。
10.根据权利要求9所述的废气清洁系统,其中将所述氧化催化剂和所述微粒过滤器组合以形成催化的微粒过滤器(cDPF)。
11.根据权利要求9所述的废气清洁系统,其中将所述微粒过滤器和所述第二SCR催化剂组合以形成所谓的SDPF。
12.一种用于清洁从稀燃发动机排放并且含有氮氧化物的废气的方法,所述方法包括使所述废气流穿过废气清洁系统,所述废气清洁系统依次包括:
·还原剂的第一定量给料单元,
·第一SCR催化剂,所述第一SCR催化剂包括:
-具有长度L的载体基材,所述具有长度L的载体基材为流通式基材,和
-包括小孔沸石、铜和钯的涂层A,
·氧化催化剂,
·微粒过滤器,
·还原剂的第二定量给料单元,和
·第二SCR催化剂。
其中还原剂的所述第一定量给料单元和所述第一SCR催化剂被布置成紧密耦接的,并且其中所述氧化催化剂、所述微粒过滤器、还原剂的所述第二定量给料单元和所述第二SCR催化剂被布置在底板下,并且
其中所述废气在还原剂的所述第一定量给料单元之前进入所述废气清洁系统,并且在所述第二SCR催化剂之后离开所述废气清洁系统。
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Also Published As
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US20190226372A1 (en) | 2019-07-25 |
CN111511458B (zh) | 2022-08-09 |
WO2019145198A1 (en) | 2019-08-01 |
US10898889B2 (en) | 2021-01-26 |
EP3743198A1 (en) | 2020-12-02 |
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