CN117916019A - 用于天然气发动机的排气系统的催化剂制品 - Google Patents
用于天然气发动机的排气系统的催化剂制品 Download PDFInfo
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- CN117916019A CN117916019A CN202280061381.7A CN202280061381A CN117916019A CN 117916019 A CN117916019 A CN 117916019A CN 202280061381 A CN202280061381 A CN 202280061381A CN 117916019 A CN117916019 A CN 117916019A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 239000003345 natural gas Substances 0.000 title claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011572 manganese Substances 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002485 combustion reaction Methods 0.000 claims abstract description 22
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000011068 loading method Methods 0.000 claims description 22
- 239000002019 doping agent Substances 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 abstract description 24
- 239000011593 sulfur Substances 0.000 abstract description 24
- 230000001976 improved effect Effects 0.000 abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 11
- 239000000446 fuel Substances 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 231100000572 poisoning Toxicity 0.000 description 7
- 230000000607 poisoning effect Effects 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000003949 liquefied natural gas Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003878 thermal aging Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 239000003112 inhibitor Substances 0.000 description 2
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- 239000000543 intermediate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010011906 Death Diseases 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000001668 ameliorated effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
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- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- XSKIUFGOTYHDLC-UHFFFAOYSA-N palladium rhodium Chemical compound [Rh].[Pd] XSKIUFGOTYHDLC-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B01J23/656—Manganese, technetium or rhenium
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Abstract
本发明涉及具有改进的耐硫和/或耐水性的用于天然气发动机的排气系统的催化剂制品。该催化剂制品包括掺杂的钯‑氧化铝催化剂,其中该钯‑氧化铝催化器掺杂有锰和/或锌。本发明还涉及一种排气处理系统、一种天然气燃烧发动机以及一种用于处理来自天然气燃烧发动机的排气的方法。
Description
本发明涉及一种用于天然气发动机的排气系统的催化剂制品,特别地涉及由于在Pd氧化铝催化剂中存在额外的Mn和/或Zn而具有改进的耐硫性和耐水性的催化剂制品。
天然气作为传统上使用汽油和柴油燃料的车辆和固定式发动机的替代燃料越来越受到关注。天然气主要由甲烷(通常为70-90%)与可变比例的其它碳氢化合物如乙烷、丙烷和丁烷(在一些沉积物中高达20%)和其它气体组成。天然气可从石油或天然气田商业生产,并广泛用作发电、工业热电联供和家用供暖的燃烧能源。它还可以用作车辆燃料。
天然气可用作压缩天然气(CNG)和液化天然气(LNG)形式的运输燃料。CNG装在压力为3600磅/平方英寸(~248巴)的储罐中,每单位体积的能量密度约为汽油的35%。LNG的能量密度是压缩天然气的2.5倍,主要用于重型车辆。它在–162℃下冷却成液态,因此体积减少了600倍,这意味着LNG比CNG更容易运输。生物液化天然气可以是天然气(化石)的替代品,天然气由沼气产生,沼气是通过厌氧消化垃圾填埋场废物或粪肥等有机物而产生的。
天然气具有许多环境益处:它是通常包含很少杂质的更清洁的燃烧燃料,它的每碳能量(Bti)比传统的碳氢化合物燃料高,因此二氧化碳排放量低(温室气体排放量减少25%),并且它与柴油和汽油相比具有更低的PM和NOx排放。沼气可以进一步减少这种排放。
与其他化石燃料相比,采用天然气的进一步驱动因素包括高丰度和低成本。
与重型和轻型柴油发动机相比,天然气发动机排放的PM和NOx非常低(分别低达95%和70%)。然而,由NG发动机产生的排气通常含有大量的甲烷(所谓的“甲烷泄漏”)。限制这些发动机排放的法规目前包括欧洲VI和美国环境保护局(EPA)温室气体法规。这些规定了甲烷、氮氧化物(NOx)和颗粒物(PM)的排放限值。
甲烷燃料发动机使用的两种主要操作模式是化学计量条件(λ=1)和贫燃条件(λ≥1.3)。众所周知,钯基催化剂是在两种条件下用于甲烷氧化的最具活性类型的催化剂。通过分别应用钯铑三元催化剂(TWC)或铂钯氧化催化剂,可以满足化学计量和贫燃压缩天然气发动机两者的规定排放限制。
这种钯基催化剂技术的发展取决于克服由于硫、水和热老化而导致的成本和催化剂失活方面的挑战。
甲烷是反应性最低的碳氢化合物,并且需要高能量使初级C–H键断裂。烷烃的点燃温度通常随着燃料空气比的增加和碳氢链长度的增加而降低,这与C–H键强度有关。众所周知,对于Pd基催化剂,甲烷转化的起燃温度高于其他碳氢化合物(其中“起燃温度”是指转化率达到50%的温度)。
当在化学计量条件(λ=1)下操作时,TWC被用作燃烧甲烷的有效且经济高效的后处理系统。大多数双金属Pd-Rh催化剂具有>200gft–3的高总铂族金属(pgm)负载量,需要用于高水平的甲烷转化,以满足寿命终止总碳氢化合物(THC)的规定,因为这种碳氢化合物的反应性非常低,并且催化剂通过热效应和化学效应失活。使用高pgm负载量将提高化学计量CNG发动机中的总HC转化率。然而,基于发动机校准,可以用相对低的pgm来实现高甲烷转化率,即控制空气-燃料比以便在接近化学计量或富含化学计量下操作;pgm负载量也可以根据关于甲烷和非甲烷转化率的区域立法要求而变化。
NOx的还原和甲烷的氧化在非常氧化的条件下也更加困难。对于贫燃CNG应用,在较低温度下进行甲烷燃烧需要高总pgm负载量(>200gft–3)的Pd-Pt。与化学计量发动机不同,还需要将还原剂喷射到排气流中,以便能够在过量氧气的存在下还原NOx。这通常是氨(NH3)的形式,因此贫燃应用需要与化学计量的催化剂体系完全不同的催化剂体系,其中可以在稍微富或化学计量的条件下使用CO或HC来实现有效的NOx还原。
由于甲烷在较低温度下的非反应性(或反应性差),在冷启动和怠速情况下,甲烷排放量增加,主要是在排气温度低于化学计量的贫燃情况下。为了提高甲烷在较低温度下的反应性,其中一种选择是使用高pgm负载量,这增加了成本。
天然气催化剂,尤其是Pd基催化剂,可能会受到水(5-12%)和硫(润滑油中的SO2<0.5ppm)的毒害,尤其是在贫条件下,这会导致催化剂的转化率随着时间的推移急剧降低。由于在催化剂表面形成羟基、碳酸盐、甲酸酯和其他中间体,水导致的失活是显著的。这种活性是可逆的,如果去除水,可以完全恢复。然而,这是不实际的,因为甲烷燃烧进料由于甲烷中高含量的H而总是含有高水平的水。
H2O可以是抑制剂或促进剂,这取决于空气燃料比,即λ。在化学计量和还原条件下,λ>1,H2O可以通过CNG和汽油发动机两者中的蒸汽重整反应作为碳氢化合物氧化的促进剂。然而,对于在λ>1下操作的贫燃CNG,H2O起到甲烷氧化抑制剂的作用。理解水的抑制作用并设计对H2O的存在更耐受的催化剂是至关重要的。当试图控制稀燃CNG的甲烷排放时,这将允许进行改进。
尽管发动机排气中的硫含量非常低,但由于形成稳定的硫酸盐,Pd基催化剂在暴露于硫后会显著失活。为了在硫中毒后恢复活性而对催化剂进行再生是具有挑战性的,并且通常需要高温、富操作或两者兼而有之。这在化学计量操作中容易实现,但在稀燃中更难实现。稀燃车辆以比化学计量车辆高得多的空燃比运行,并且将需要喷射高得多浓度的还原剂以切换到富操作。由于发动机瞬态控制和点火系统差而引起的高水平失火事件所导致的热失活破坏了催化剂,并相应地导致高水平的废气排放。
催化剂在两种条件下失活,但硫中毒比贫操作中的热老化具有更显著的影响。硫中毒可以通过向Pd催化剂中添加少量Pt来改善。这是因为在添加Pt时,由于硫酸钯的形成导致的硫抑制可以显著降低。然而,Pt的添加进一步增加了成本。
因此,希望提供一种用于天然气燃烧发动机的改进催化剂,以通过抑制催化剂失活(诸如通过硫、水和热老化)来减少甲烷排放,而不增加催化剂的成本。本发明的一个目的是解决这个问题,解决与现有技术相关的缺点,或者至少提供一种商业上有用的替代方案。
根据第一方面,提供一种用于处理来自天然气燃烧发动机的排气的催化剂制品,所述制品包含掺杂的钯-氧化铝催化剂,其中所述钯-氧化铝催化剂掺杂有锰(Mn)和/或锌(Zn)。
在以下段落中,更详细地定义了不同方面/实施方案。除非有明确相反的说明,否则如此定义的每个方面/实施方案可与任何其他方面/实施方案或多个方面/实施方案组合。特别地,任何被指示为优选或有利的特征可与任何其他被指示为优选或有利的一个或多个特征组合。
催化剂制品是适用于排气系统中的组分。典型地,这样的制品是蜂窝整料,其也可以被称为“砖”。这些具有适于使待处理的气体与催化剂材料接触以实现排气组分的转换或转化的高表面积构造。其它形式的催化剂制品是已知的并且包括板构造以及包裹的金属催化剂基材。本文所述的催化剂适用于所有这些已知形式,但特别优选的是,它采用蜂窝整料的形式,因为这些催化剂提供了成本和制造简单性的良好平衡。
优选地,掺杂的钯-氧化铝催化剂作为载体涂层提供在基材上。或者,掺杂的钯-氧化铝催化剂作为挤出基材的组分提供。优选地,在任何一种情况下,基材是流通式整料。优选地,其中所述催化剂以载体涂层的形式提供在基材上,所述基材为流通陶瓷整料。
该催化剂制品用于处理来自天然气燃烧发动机的排气。也就是说,催化剂制品用于对来自天然气燃烧发动机的排气进行催化处理,以便在气体被排放到大气中之前转换或转化气体组分,以便满足排放法规。当天然气燃烧时,它会产生二氧化碳和水,但排气中还含有一定量的额外甲烷(和其他短链碳氢化合物),在排气被排放到大气中之前,这些甲烷需要被催化去除。排气通常还含有大量的水和硫,这些水和硫会累积并使催化剂失活。
在移动应用中,天然气燃烧可以被配置为以贫燃或化学计量配置运行。“移动应用”是指该系统通常可适用于汽车或其他车辆(例如越野车辆)-在这种系统中,根据操作员的要求(诸如加速度),燃料供应和需求在操作过程中可能会发生变化。在移动应用中,通常可以暂时以富燃模式运行系统,这与温度的显著升高有关,这有助于烧掉使催化剂中毒的硫并除去积聚的水。
在固定系统中,天然气燃烧也可被构造成在贫燃或化学计量条件下操作。固定系统的示例包括燃气轮机和发电系统-在这种系统中,燃烧条件和燃料组成通常在长操作时间内保持恒定。这意味着,与移动应用相比,具有去除硫和水分污染物的再生步骤的机会较少。因此,本文所述的益处对于固定应用可以是特别有益的。即,当再生催化剂的机会有限时,特别希望提供一种具有高耐硫性和耐湿性的催化剂。
尽管上述“稀”和“化学计量”系统被描述为“移动”和“固定”,但应该理解的是,这两种系统类型都可以在一系列不同的应用中使用。
该催化剂制品包括掺杂的钯-氧化铝催化剂。即,该制品包含这样的催化剂,该催化剂包含作为组分(优选作为唯一的催化活性组分)的氧化铝载体和掺杂剂,所述氧化铝载体被提供作为负载钯的载体。氧化铝是用于催化剂应用的极常见载体,并且选择合适的氧化铝是本领域常见的。如本文所讨论的,选择用于形成催化剂的氧化铝的合适的量将取决于基材的形式。
氧化铝可以以一种或多种不同的晶体形式提供。由于其热稳定性,γ氧化铝通常是最优选的。氧化铝可以包含一种或多种掺杂剂以帮助改善其稳定性,并且典型的掺杂剂包括Si和La。用于稳定氧化铝的掺杂剂优选以小于氧化铝重量的15wt%,更优选小于10wt%的量存在。用于氧化铝的这些掺杂剂可以按氧化铝的重量计1至10wt%的量存在。
取决于催化剂制品的形式,催化剂还可包含另外的非催化组分。例如,载体涂层通常包括粘合剂,该粘合剂包括粘土和其他氧化铝组分。例如,挤出的催化剂整料通常包括额外的填料和加工助剂如玻璃纤维和粘土。
优选地,催化剂制品具有50-300g/ft3,优选70-250g/ft3,并且更优选100-200g/ft3的Pd负载量。这些水平对于处理排气中的甲烷是有效的,并且可以显著高于TWC的水平。
钯-氧化铝催化剂掺杂有锰和/或锌。最优选该催化剂掺杂有Mn或Zn。优选地,催化剂制品的Mn和/或Zn的总负载量为5至100g/ft3,优选20至80g/ft3,并且更优选40至60g/ft3。总负载量是指存在的所有Mn和Zn的总和(例如当不存在Zn时,存在的Mn的量)。如下文所解释,已发现这两种元素在促进钯和在用硫和/或水分挑战时提供催化剂的改进性能方面特别有效。
优选地,催化剂制品的Pd负载量与Mn和/或Zn的总负载量之比大于1∶1,优选1∶1至10∶1,更优选2∶1至5∶1,并且最优选约3∶1。Mn和/或Zn的存在是为了促进由Pd实现的反应,因此掺杂剂的量通常等于或小于所促进的Pd的量。
本发明人寻求提供能够在较低温度下燃烧甲烷的天然气发动机后处理系统。本发明人惊奇地发现,包含Mn和/或Zn对(i)在湿和干条件下的甲烷转化性能和(ii)催化剂的耐硫性具有积极影响。特别地,实验SCAT分析表明,Mn和Zn掺杂的Pd/Al2O3催化剂在低温、干和湿条件下对甲烷的起燃活性都有所提高。这表明,用Mn或Zn掺杂Pd/Al2O3比Pt掺杂的Pd/Al2O3催化剂更好地提高了催化剂的性能。还对这些催化剂进行了耐硫性测试,其中Mn和Zn掺杂的催化剂在耐硫性方面都表现出类似的改善。
在不希望受理论约束的情况下,用Mn掺杂Pd似乎比其他掺杂剂更好地降低了活化能(Ea)并增强了其对OH中毒的抵抗力。用Zn观察到类似的性能。
使用计算模拟,开发了有助于理解这些反应的基本原理的模型。在该模型中,PdO(100)表面掺杂有如表1所列的一系列+2氧化态元素。计算了甲烷在掺杂表面的活化能垒(Ea)和各种中间物质的吸附能,建立了模型。该模型预测,用Mn或Zn掺杂降低活化能并可增强对OH或SO2中毒的抗性。
表1:各种掺杂的PdO(100)表面、活化能垒、OH、O和SO2物质的吸附能。
为了证实这些掺杂的PdO(100)表面的活性,然后使用三个变量,即δG(CH4_TS*)、δG(OH*)和δG(O*),建立了动力学模型。其中,δG(CH4_TS*)是CH4的第一个离解步骤,被认为是速率决定步骤,δG(OH*)表示对水中毒的耐受性,并且δG(O*)是氧在Pd表面的吸附以产生活性位点。Mn被认为在较低的温度下增强了PdO(100)表面的活性。
优选地,掺杂的钯-氧化铝催化剂还包含铂,优选负载量为50至300g/ft3,优选70至250g/ft3,并且更优选100至200g/ft3。优选地,Pt与Pd的重量比小于1∶1,优选1∶2至1∶10。Pt是众所周知的互补pgm,其存在是为了提高催化剂整体的氧化性能。
上表中清楚地显示Mn和Zn在所有情况下均优于单独的PdO。然而,所示的其它要素是优点和缺点的平衡。优选地,掺杂的钯-氧化铝催化剂包括选自Se、Cu、Cd、Ge、Ba、Sr和Sn的一种或多种另外的掺杂元素。如上表所示,这些掺杂剂中的每一种对活化能、OH、O和SO2吸收的能量具有不同的平衡效果。这意味着,取决于所需的具体应用,可能希望添加具有特定益处的组分,即使被一些缺点抵消。例如,Cd在耐水性方面会有很大的改善,而在活化能方面只会有轻微的缺点。
优选地,一种或多种另外的掺杂剂元素以5至100g/ft3、优选20至80g/ft3,并且更优选40至60g/ft3的负载量存在。优选地,一种或多种另外的掺杂剂以相对于Mn和Zn的总量小于1:1、优选小于3:1,并且更优选小于5:1的质量比存在。这是因为Mn和Zn通常具有积极效果,而通常提供另外的掺杂剂以获得次要益处。
根据另一方面,提供了废气处理系统,其包括如本文所述的催化剂制品。排气处理系统通常具有被构造成接收来自燃烧室的排气的入口端和用于将处理后的排气释放到大气中的出口。与排气系统中的催化剂制品一致,可以有一个或多个其他催化或过滤组分,其适合于处理排气的其他组分或为甲烷提供额外的处理以避免漏失。
根据另一方面,提供了一种包括如本文所述的排气处理系统的天然气燃烧发动机。优选地,天然气燃烧发动机被配置为在贫条件下运行。天然气燃烧发动机可以是固定式发动机。如上所述,由于催化剂再生在固定系统中更加困难,因此催化剂对硫和水分污染的稳定性尤为关键。否则,催化剂将需要离线并单独再生,这可导致工艺低效和成本。
根据另一方面,提供了一种用于处理来自天然气燃烧发动机的排气的方法,该方法包括使排气与本文所述的催化剂制品接触。优选地,所述排气通过燃烧天然气获得,所述排气包含至少0.5ppm的二氧化硫。优选地,所述排气通过燃烧天然气获得,所述排气包含5至12wt%的水。应当理解,当处理来自天然气燃烧的排气时,这些类型的排气是常规的,并且正是这些排气最明显地受益于本文所述的具有改进的耐水性和耐硫性的催化剂制品。
优选地,在使排气与催化剂制品接触的步骤期间,排气的温度低于550℃,优选低于500℃。例如,排气可以具有大约450℃的温度。这些条件在贫操作的系统中尤其常见。
附图说明
现在将结合以下非限制性附图来进一步讨论本发明,其中:
图1显示了在干和湿条件下甲烷转化率(%)作为温度的函数。在该图中,在50%转化率下,从左至右,线是Zn掺杂(干)、Mn掺杂(干)、未掺杂(干)、Pt掺杂(干),然后是Zn掺杂(湿)、Mn掺杂(湿)、未掺杂(湿)和Pt掺杂(湿)。
图2显示了使用0.5ppm SO2反应气体进料的甲烷转化率(%)作为温度的函数。在该图中,在425℃,用Mn然后用Zn获得最佳的转化率。
实施例
现在将结合以下非限制性实施例来进一步描述本发明。
-实施例1
如下制备包含1wt%Mn-2.85wt%Pd/在未掺杂氧化铝上的催化剂组合物(SCFA140)。
将0.9g四水合硝酸锰溶解在最少量的水中,并加入3.75g硝酸钯中,然后用约1ml水进一步稀释。在不断搅拌下将该混合物逐滴加入20g氧化铝载体中,然后冲洗。将混合物在烘箱中干燥3小时,然后在500℃下煅烧2小时。
该催化剂中Pd的总负载量为约128g/ft3,并且Mn的总负载量为约45g/ft3。
-实施例2
如下制备包含在未掺杂氧化铝(SCFA 140)上的1wt%Zn-2.85wt%Pd的另一催化剂组合物。
将0.9g六水合硝酸锌溶解在最少量的水中,并加入3.77g硝酸钯中,然后用约1ml水进一步稀释。在不断搅拌下将该混合物逐滴加入20g氧化铝载体中,然后冲洗。将混合物在烘箱中干燥3小时,然后在500℃下煅烧2小时。
该催化剂中Pd的总负载量为约128g/ft3,并且Zn的总负载量为约45g/ft3。
-催化剂测试
在合成催化活性测试(SCAT)装置中测试实施例1和2中制备的催化剂组合物的造粒样品(0.2-0.4g,250-300μm)的耐水性和耐硫性,使用下述入口气体混合物,空速(SV)为45k,在温度范围内(以10-15℃/分钟的升温速率从150℃升温至450℃)。
对于耐水性测试,使用以下入口气体混合物:
干燥:4000ppm CH4,8%O2,余量N2
湿:4000ppm CH4,8%O2,10%H2O,余量N2
对于耐硫性测试,使用以下入口气体混合物:4000ppm CH4、30ppm C3H8、100ppmC2H6、1000ppm CO、5%CO2、500ppm NO、8%O2、10%H2O、0.5ppm SO2、余量N2。
如图所示,与未掺杂的Pd催化剂相比,这两个实施例均显示出改善的耐硫性、改善的耐湿性和更好的催化活性。
虽然本文已详细描述了本公开的优选实施方案,但是本领域的技术人员应当理解,在不脱离本发明或所附权利要求书的范围的情况下,可以对本公开进行各种改变。
Claims (17)
1.一种用于处理来自天然气燃烧发动机的排气的催化剂制品,所述催化剂制品包含掺杂的钯-氧化铝催化剂,其中所述钯-氧化铝催化剂掺杂有锰和/或锌。
2.根据权利要求1所述的催化剂制品,其中所述催化剂制品的Pd负载量为50-300g/ft3,优选70-250g/ft3,并且更优选100-200g/ft3。
3.根据权利要求1或权利要求2所述的催化剂制品,其中所述催化剂制品具有5至100g/ft3,优选20至80g/ft3,并且更优选40至60g/ft3的Mn和/或Zn的总负载量。
4.根据前述权利要求中任一项所述的催化剂制品,其中所述Pd负载量与所述Mn和/或Zn的总负载量之比大于1∶1,优选1∶1至10∶1,更优选2∶1至5∶1,并且最优选约3∶1。
5.根据前述权利要求中任一项所述的催化剂制品,其中所述掺杂的钯-氧化铝催化剂作为载体涂层提供在基材上。
6.根据权利要求1至4中任一项所述的催化剂制品,其中所述掺杂的钯-氧化铝催化剂作为挤出基材的组分提供。
7.根据前述权利要求中任一项所述的催化剂制品,其中所述基材为流通陶瓷整料。
8.根据前述权利要求中任一项所述的催化剂制品,其中所述掺杂的钯-氧化铝催化剂还包含铂,负载量优选为50至300g/ft3,优选为70至250g/ft3,并且更优选为100至200g/ft3。
9.根据权利要求8的催化剂制品,其中Pt与Pd的重量比小于1∶1,优选为1∶2至1∶10。
10.根据前述权利要求中任一项所述的催化剂制品,其中所述掺杂的钯-氧化铝催化剂包含一种或多种选自Se、Cu、Cd、Ge、Ba、Sr和Sn的另外的掺杂剂元素。
11.根据权利要求10的催化剂制品,其中所述一种或多种另外的掺杂剂元素以5-100g/ft3,优选20-80g/ft3,并且更优选40-60g/ft3的负载量存在。
12.根据权利要求10或权利要求11所述的催化剂制品,其中所述一种或多种另外的掺杂剂以相对于Mn和/或Zn的总量小于1:1、优选小于3:1,并且更优选小于5:1的质量比存在。
13.一种排气处理系统,包括根据前述权利要求中任一项所述的催化剂制品。
14.一种天然气燃烧发动机,包括根据权利要求13所述的排气处理系统,优选地,其中所述天然气燃烧发动机被构造为在贫条件下运行。
15.一种用于处理来自天然气燃烧发动机的排气的方法,所述方法包括使所述排气与根据权利要求1至12中任一项所述的催化剂制品接触。
16.根据权利要求15所述的方法,其中所述排气通过燃烧天然气获得,所述排气包含至少0.5ppm二氧化硫和/或5-12wt%水。
17.根据权利要求15或权利要求16所述的方法,其中在使所述排气与所述催化剂制品接触的步骤期间,所述排气的温度低于550℃,优选低于500℃。
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