CN106179339A - 作为用于柴油氧化应用的高抗硫催化剂的铁板钛矿氧化物和低载荷pgm组合 - Google Patents
作为用于柴油氧化应用的高抗硫催化剂的铁板钛矿氧化物和低载荷pgm组合 Download PDFInfo
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- CN106179339A CN106179339A CN201610274712.1A CN201610274712A CN106179339A CN 106179339 A CN106179339 A CN 106179339A CN 201610274712 A CN201610274712 A CN 201610274712A CN 106179339 A CN106179339 A CN 106179339A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 19
- 239000011593 sulfur Substances 0.000 title abstract description 19
- 239000002283 diesel fuel Substances 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims 3
- 239000001117 sulphuric acid Substances 0.000 claims 3
- 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 claims 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 20
- 231100000572 poisoning Toxicity 0.000 abstract description 14
- 230000000607 poisoning effect Effects 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 9
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- 230000019635 sulfation Effects 0.000 description 33
- 238000005670 sulfation reaction Methods 0.000 description 33
- 238000010998 test method Methods 0.000 description 23
- 238000012360 testing method Methods 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 description 12
- 238000010586 diagram Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
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- 229910009202 Y—Mn Inorganic materials 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
- 239000003795 chemical substances by application Substances 0.000 description 6
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- OTIJDYHLLCTUJA-UHFFFAOYSA-N aluminum oxygen(2-) platinum(2+) Chemical compound [Pt+2].[O-2].[Al+3] OTIJDYHLLCTUJA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000002879 macerating effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- UUAPOGVVFCUHAD-UHFFFAOYSA-N niobium(5+) oxygen(2-) zirconium(4+) Chemical compound [O-2].[Zr+4].[Nb+5] UUAPOGVVFCUHAD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
公开了具有显著氧化能力的抗硫增效铂系金属(SPGM)催化剂。SPGM催化剂试样的催化层使用常规合成技术制备以建立完全或基本不含PGM材料的修补基面涂层。SPGM催化剂包含含有YMn2O5(铁板钛矿)的修补基面涂层和包含具有5.0g/ft3或以下总PGM负载的Pt/Pd组合物的罩面层。在5.2gS/L条件下观察对硫中毒的抗性和催化稳定性以评估NO氧化以及HC和CO转化率的显著改进。
Description
背景
公开内容领域
本公开内容一般性地涉及用于处理来自柴油机的废气排放的柴油氧化催化剂,更特别是,根据包含至少两个不同层的催化剂结构,具有低铂系金属(PGM)负载的抗硫增效铂系金属(SPGM)催化剂体系。
背景信息
柴油氧化催化剂(DOC)包含沉积于金属载体氧化物上的PGM。DOC用于处理柴油机废气以降低氮氧化物(NOX)、烃(HC)和一氧化碳(CO)气体污染物。DOC通过将它们氧化而降低气体污染物。
常规催化转化器厂商在其柴油废气系统中使用单一PGM催化剂。由于催化体系的PGM部分内的铂(Pt)和钯(Pd)催化剂的混合物提供改进的稳定性,催化转化器制造工业移向制造Pt/Pd基DOC。
在柴油机中,存在于废气排放中的硫由于强金属-硫键的形成,可导致显著的催化剂减活,甚至在非常低的浓度下也是如此。强金属-硫键在硫化学吸着并与金属的活性催化剂部位反应时产生。稳定的金属-吸附物键可产生改变表面化学的非选择性副反应。
解决该问题的现有尝试引导厂商生产具有改进的抗硫性的催化剂体系。通常,这些催化剂体系通过使用高PGM负载制造。不幸的是,在催化剂体系内使用高PGM负载提高了催化剂体系的成本,因为PGM是昂贵的。PGM是昂贵的,因为它们是稀有的,具有小的市场流通量,并且除其它问题外,显示出恒定的价格波动和恒定的稳定供应风险。
因此,由于世界范围内连续采用较严格的规则标准以控制排放,越来越需要开发具有关于增强催化效率和硫中毒稳定性的改进性能的DOC。
概述
本公开内容描述了用于柴油氧化催化剂(DOC)应用的具有低PGM负载的增效PGM(SPGM)催化剂。
本公开内容的目的是描述具有高催化活性和抗硫中毒性的SPGM催化剂体系的实施方案。在这些实施方案中,将具有5g/ft3PGM活性组分的催化层用分开催化剂层中的包含铁板钛矿结构的Zero-PGM(ZPGM)催化剂组合物增效。在一些实施方案中,所述双层SPGM催化剂可提供显示出高氧化活性以及抗硫性的催化剂体系。
根据本公开内容中的一些实施方案,可配置所述SPGM DOC体系以包含沉积在具有所选择的贱金属负载的多种载体氧化物上的ZPGM材料组合物的修补基面涂层(WC)。在这些实施方案中,WC层可使用沉积在掺杂ZrO2载体氧化物上的YMn2O5铁板钛矿结构形成。
在其它实施方案中,所述SPGM DOC体系的第二层配置为罩面层(OC)。OC层包含在载体氧化物上的多种低PGM材料组合物。在这些实施方案中,OC层可使用氧化铝类载体氧化物形成,所述氧化铝类载体氧化物使用低载荷PGM溶液如铂(Pt)和钯(Pd)溶液金属化以形成氧化铝类载体氧化物/低载荷PGM淤浆。然后将氧化铝类载体氧化物/低载荷PGM淤浆沉积到WC层上,随后煅烧。
在其它实施方案中,使用于DOC应用的所述SPGM催化剂经受DOC/硫试验方法以评估/验证显著的NO氧化活性和抗硫中毒性。在这些实施方案中,进行DOC点火试验以证明层状SPGM构型中ZPGM催化活性材料的协同效果。进一步,对这些实施方案而言,所述SPGM催化剂试样的抗硫性和NO氧化在多种DOC条件下在约54,000h-1的空速(SV)下根据试验方法中的多个步骤确定。
又进一步,对这些实施方案而言,SPGM催化剂体系中层的组合催化性能可提供NO氧化方面的更多效率和对抗硫中毒的更多稳定性。
本公开内容的大量其它方面、特征和优点可从以下详细描述连同附图中获悉,所述附图可阐述本公开内容的实施方案,结合在此处用于参考。
附图简述
本公开内容可参考以下图更好地理解。图中的组件未必按比例绘制,而是强调阐述公开内容的原理。在图中,在整个不同的视图中,参考数字表示相应的部件。
图1为阐述根据一个实施方案,用于SPGM催化剂试样的催化剂结构的图示。
图2为阐述根据一个实施方案,用于评估SPGM催化剂试样的催化剂活性和抗硫性的DOC试验方法的步骤图的图示。
图3为阐述根据一个实施方案,根据图2所述DOC试验方法测试的SPGM催化剂试样的NO转化率LO结果的图示。
图4为阐述根据一个实施方案,根据图2所述DOC试验方法测试的SPGM催化剂试样的NO转化率LO结果的图示。
图5为阐述根据一个实施方案,根据图2所述DOC试验方法测试的SPGM催化剂试样的NO、CO和THC转化稳定性结果的图示。
详述
此处参考图中所述实施方案详细描述本公开内容,所述实施方案形成此处的一部分。可使用其它实施方案和/或可不偏离本公开内容的精神或范围地做出其它改变。详述中描述的说明性实施方案不意欲限制此处呈现的主题。
定义
如此处所用,以下术语具有以下定义:
“催化剂”指可用于一种或多种其它材料的转化的一种或多种材料。
“修补基面涂层”指包含可沉积于基质上的至少一种氧化物固体的至少一个涂层。
“基质”指得到用于沉积修补基面涂层和/或罩面层的足够表面积的具有任何形状或构型的任何材料。
“罩面层”指可沉积在至少一个修补基面涂层或浸渍层上的至少一个涂层。
“载体氧化物”指用于提供帮助氧分布和催化剂暴露于反应物如NOx、CO和烃的高表面积的多孔固体氧化物,通常混合金属氧化物。
“Zero PGM(ZPGM)催化剂”指完全或基本不含铂系金属的催化剂。
“增效PGM(SPGM)催化剂”指在不同构型下由ZPGM化合物增效的PGM催化剂体系。
“催化剂体系”指任何包含具有至少两个层,包括基质、修补基面涂层和/或罩面层的催化剂,例如PGM催化剂或ZPGM催化剂的体系。
“柴油氧化催化剂(DOC)”指利用化学方法使来自柴油机或贫燃汽油机的废气料流中的污染物分解,将它们转化成较无害组分的装置。
“铁板钛矿”指具有AB2O5材料结构的ZPGM催化剂,所述材料可通过将元素“A”和“B”贱金属用合适的非铂系金属部分取代而形成。
“初始润湿(IW)”指将催化材料的溶液加入干载体氧化物粉末中直至载体氧化物的所有孔体积被溶液填充且混合物轻微接近饱和点的方法。
“金属化”指将金属涂覆在金属或非金属物体的表面上的方法。
“转化”指至少一种材料变成一种或多种其它材料的化学改变。
“中毒或催化剂中毒”指催化剂由于其暴露于发动机废气中的铅、磷或硫而失活。
公开内容描述
本发明公开内容涉及柴油氧化催化剂(DOC)体系构型。DOC构型包括具有Zero-PGM(ZPGM)催化剂的修补基面涂层(WC)和罩面层(OC)的双层催化剂。罩面层(OC)为低载荷PGM催化剂。该双层催化剂改进由柴油机中排放的废气包含的NOX、HC和CO的转化率。
SPGM催化剂体系的构型、材料组成和制备
图1为阐述根据一个实施方案,用于SPGM催化剂试样的催化剂结构的图示,其包括在修补基面涂层内作为ZPGM组合物实施的负载型铁板钛矿结构,和包含低载荷PGM组合物的罩面层。在图1中,SPGM催化剂结构100包括WC层102、OC层104和基质106。WC层102沉积于基质106上且OC层104沉积于WC层102上。在一些实施方案中,WC层102作为ZPGM组合物实施,且OC层104作为低PGM组合物实施。
在一些实施方案中,实施包括沉积在载体氧化物上的含有AB2O5铁板钛矿氧化物结构的WC层102的SPGM催化剂试样。在这些实施方案中,实施包含沉积在载体氧化物上的一种或多种PGM材料组合物的OC层104。
适于形成具有通式AB2O5的铁板钛矿的示例材料包括但不限于银(Ag)、锰(Mn)、钇(Y)、镧(La)、铈(Ce)、铁(Fe)、镨(Pr)、钕(Nd)、锶(Sr)、镉(Cd)、钴(Co)、钪(Sc)、铜(Cu)和铌(Nb)。除其它外,可用于WC和OC层中的合适载体氧化物包括氧化锆(ZrO2)、包含掺杂如镧系金属的任何掺杂ZrO2、五氧化铌、铌-氧化锆、氧化铝类载体氧化物、二氧化钛、氧化锡、沸石、二氧化硅或其混合物。PGM材料组合物包括铂、钯、钌、铱和铑本身或者具有不同负载的其组合。
在一个实例中,用于SPGM催化剂结构的WC层中的ZPGM催化剂包括沉积于掺杂ZrO2载体氧化物上的YMn2O5铁板钛矿组合物。
在一些实施方案中,WC层的制备以Y-Mn溶液的制备开始。在这些实施方案中,Y-Mn溶液的制备包括将硝酸钇溶液与硝酸锰溶液和水混合以产生合适摩尔比的溶液。在一个实例中,使用1:2的Y:Mn摩尔比。
在其它实施方案中,使用常规初始润湿(IW)技术将Y-Mn硝酸盐溶液加入掺杂ZrO2粉末中,形成Y-Mn/掺杂ZrO2淤浆。在这些实施方案中,将Y-Mn/掺杂ZrO2淤浆干燥并在约750℃下煅烧约5小时。进一步,对这些实施方案而言,然后将煅烧的Y-Mn/掺杂ZrO2粉末研磨成细粒用于制备例如YMn2O5/掺杂ZrO2粉末。在一个实例中,随后将YMn2O5/掺杂ZrO2粉末用水研磨以产生淤浆。在该实例中,然后将淤浆涂覆在合适的基质上用于在约750℃下煅烧约5小时。以这种方式涂覆和煅烧的基质形成WC层。
在一些实施方案中,用于OC层中的PGM催化剂包括沉积在氧化铝类载体氧化物上的铂(Pt)和钯(Pd)硝酸盐的PGM溶液。
在一个实例中,OC层的制备包括掺杂Al2O3载体氧化物的研磨。在该实例中,将研磨的掺杂Al2O3载体氧化物与水混合以形成含水淤浆。进一步,对该实例而言,将掺杂Al2O3载体氧化物淤浆通过Pt和Pd硝酸盐溶液以约5g/ft3,优选约4.5g/ft3Pt和约0.25g/ft3Pd内的总PGM负载金属化。随后将OC层沉积在WC层上并在约550℃下煅烧约4小时。
DOC LO和硫酸盐化试验方法
在一些实施方案中,DOC/硫试验方法可应用于如图1所述的SPGM催化剂体系。在这些实施方案中,DOC/硫试验方法提供用于DOC应用的包括ZPGM(YMn2O5铁板钛矿结构)的WC层与具有低PGM的OC层的所述催化剂体系显示出提高的气体污染物转化率的证明。进一步,对这些实施方案而言,以加入ZPGM催化剂材料中的低量PGM制备的SPGM催化剂能够提供抗硫性的明显改进。
图2为阐述根据一个实施方案,用于评估SPGM催化剂试样的催化剂活性和抗硫性的DOC试验方法的步骤的图示。
在图2中,DOC试验方法200使用在整个以下步骤中给予的标准气流组成:DOC点火(LO)、在等温DOC条件下浸泡(soaking)和在等温硫酸盐化DOC条件下浸泡。对于这些实施方案,DOC试验方法200步骤能够在选择用于评估SPGM催化剂试样的催化活性和抗硫性的不同时间期间。DOC试验方法200中的步骤在约340℃的等温温度和约54,000h-1的空速(SV)下进行。
在一些实施方案中,DOC试验方法200以DOC LO试验210开始。DOC LO试验使用流动反应器以约100ppm NO、约1,500ppm CO、约4%CO2、约4%H2O、约14%O2和约430ppmC1混合烃的流动DOC气体组成进行,同时在约54,000h-1的SV下将温度从约100℃提高至约340℃。随后,在约340℃下,进行在DOC条件下的等温浸泡220约1小时以在约340℃下使催化剂性能稳定化。在该时间结束时,在点230处,通过将约3ppm浓度的SO2加入气流中而开始在等温硫酸盐化DOC条件下的浸泡试验240约4小时。在该时间结束时,在点250处,当进入催化剂中的SO2的量为约0.9gS/L(克硫/升)基质时,硫酸盐化方法停止。随后,使流动气流在点260处冷却至约100℃。在该点以后,DOC试验方法200通过进行试验步骤的另一循环而继续,包括DOC LO试验210、在DOC条件下的等温浸泡220约1小时,和硫酸盐化DOC条件240,其中气流中流动约3ppmSO2约2小时,直至在气流的硫酸盐化停止时,点270处达到约1.3gS/L基质的进入催化剂中的总SO2。最后,通过在硫酸盐化浸泡总计约6小时以后的另一DOC LO和浸泡测定SPGM催化剂试样的催化剂活性。在关于所有DOC条件的试验结束时(例如在试验方法中,在硫酸盐化以前和以后),对比NO转化率和抗硫性。
在其它实施方案中,DOC试验方法200以DOC LO试验210开始,其使用流动反应器以约100ppm NO、约1,500ppm CO、约4%CO2、约4%H2O、约14%O2和约430ppmC1混合烃的流动DOC气体组合物进行,同时在约54,000h-1的SV下将温度从约100℃提高至约340℃。随后,在约340℃下进行在DOC条件下等温浸泡220约1小时以在约340℃下使催化剂性能稳定化。在该时间结束时,在点230处,通过将约5.8ppm SO2加入气流中而开始在等温硫酸盐化DOC条件下浸泡试验240约6小时。在该时间结束时,在点250处,当进入催化剂中的SO2的量为约2.6gS/L基质时,硫酸盐化方法停止。随后,使流动气流在点260处冷却至约100℃。DOC试验方法200通过进行试验步骤的另一循环而继续,包括DOC LO试验210、在DOC条件下的等温浸泡220约1小时,和硫酸盐化DOC条件240,其中气流中流动约5.8ppm SO2约6小时,直至在气流的硫酸盐化停止时,在点270处达到约5.2gS/L基质的进入催化剂中的总SO2。最后,通过在硫酸盐化浸泡总计约12小时以后的另一DOC LO和浸泡测定SPGM催化剂试样的催化剂活性。在关于所有DOC条件的试验结束时(例如在试验方法中,在硫酸盐化以前和以后),对比NO转化率和抗硫性。
硫酸盐化条件以前和以后SPGM体系的催化剂活性
图3为阐述根据一个实施方案,根据图2所述DOC试验方法测试的SPGM催化剂试样的NO转化率LO结果的图。
在图3中,3个具体转化率曲线详述如下:转化率曲线302阐述在DOCLO试验210和DOC条件下的等温浸泡220下,硫酸盐化以前的%NO转化率LO;转化率曲线304阐述在硫酸盐化DOC条件下的硫酸盐化240约4小时以后的%NO转化率LO,其中SO2浓度为约0.9gS/L;转化率曲线306阐述在硫酸盐化DOC条件下的硫酸盐化240约2小时的第二时间(约6小时的总硫酸盐化时间)以后的%NO转化率,其中SO2浓度为约1.3gS/L。
在图3中,可以观察到在硫酸盐化NO氧化以前,如转化率曲线302所示,在约252℃下达到约48%的NO转化率。约61%的最大NO转化率在约340℃下实现。另外,在具有约0.9gS/L或约1.3gS/L的硫酸盐化中毒以后,如转化率曲线304和转化率曲线306所示,NO转化率的降低在较低温度范围下观察到。然而,在较高温度范围(约290℃至约340℃)下,硫酸盐化SPGM催化剂的NO转化率基本类似于非硫酸盐化SPGM催化剂。该NO氧化LO水平表示SPGM催化剂在较高温度范围下具有显著抗硫性。最后,SPGM催化剂的显著抗硫性通过在具有约0.9gS/L或约1.3gS/L的硫酸盐化中毒以后在340℃下约61%的稳定NO转化率证明。
图4为阐述根据一个实施方案,根据图2所述DOC试验方法测试的SPGM催化剂试样的NO转化率LO结果的图示。
在图4中,三个具体转化率曲线详述如下:转化率曲线402阐述在DOCLO试验210和DOC条件下的等温浸泡220下,在硫酸盐化以前的%NO转化率LO;转化率曲线404阐述在硫酸盐化DOC条件下的硫酸盐化240约6小时以后的%NO转化率LO,其中SO2浓度为约2.6gS/L;转化率曲线406阐述在硫酸盐化DOC条件下的硫酸盐化240约6小时的第二时间(约12小时的总硫酸盐化时间)以后的%NO转化率,其中SO2浓度为约5.2gS/L。
在图4中,可观察到在硫酸盐化NO氧化以前,如转化率曲线402所示,在约252℃下达到约48%的NO转化率。约61%的最大NO转化率在约340℃下实现。另外,在具有约2.6gS/L或5.2gS/L的硫酸盐化中毒以后,如分别通过转化率曲线404和转化率曲线406所示,在较低温度范围下观察到NO转化率的降低。然而,在较高温度范围(约290℃至约340℃)下,硫酸盐化SPGM催化剂的NO转化率基本类似于非硫酸盐化SPGM催化剂。该NO氧化LO水平表示SPGM催化剂在较高温度范围下具有显著抗硫性。最后,SPGM催化剂的显著抗硫性通过在具有约2.6gS/L或约5.2gS/L的硫酸盐化中毒以后的稳定NO转化率证明。
图3和4的试验结果证明,所述SPGM催化剂体系具有显著的催化剂性能效率和抗硫性。
SPGM催化剂的抗硫性
图5为阐述根据一个实施方案,根据图2所述DOC试验方法测试的SPGM催化剂试样的NO、CO和THC转化稳定性结果的图示。
在图5中,三个具体转化率曲线详述如下:转化率曲线502、转化率曲线504和转化率曲线506分别阐述对于如图2所述DOC试验方法的完整方案,在约340℃下的%CO转化率、%THC转化率和%NO转化率。虚线508和510阐述在所述SPGM催化剂试样的硫酸盐化方法期间的不同时间下通过SPGM催化剂体系的总硫浓度。线508阐述其中硫浓度为约2.6gS/L,线510阐述其中硫浓度为约5.2gS/L。
在图5中,可观察到在约340℃下,所述SPGM催化剂体系显示出CO和THC的高%转化率和稳定转化率水平。约100.0%CO转化率和约88.0%THC转化率的这些水平对在DOC应用中操作的SPGM体系而言是非常理想的催化性能。
在图5中,从转化率曲线506的分析中还可以观察到,在SPGM催化剂试样以多个硫浓度长期硫酸盐化中毒期间,在约2.6gS/L的硫酸盐化中毒最初约6小时时间以后,NO转化率从约64.0%降至约57.0%。另外,转化率曲线506的分析表明,在SPGM催化剂试样的长期硫酸盐化中毒期间,在约5.2gS/L的硫酸盐化中毒另外约6小时时间以后,NO转化率从约57.0%降至约49.0%。这些结果证明,所述SPGM催化剂体系可提供在约2.6gS/L或约5.2gS/L的硫酸盐化下对DOC应用而言显著的抗硫性能。
在本公开内容中,在SPGM催化剂试样的试验期间实现的结果证明,生产以包含加在ZPGM催化剂材料层上的低量PGM催化剂材料层的SPGM催化剂体系能够提供抗硫性的显著改进。如图5中所观察到的,所述SPGM催化剂的THC和CO转化率在长期硫酸盐化暴露以后显著稳定,并且显示出高水平的NO转化稳定性接受性。
所述双层SPGM催化剂体系的柴油氧化性能表明,在贫燃条件下,化学组成与常规DOC体系相比更有效。
尽管公开了各个方面和实施方案,可预期其它方面和实施方案。此处公开的各个方面和实施方案用于阐述,且不意欲为限定性的,其中真实范围和精神由以下权利要求书指示。
Claims (16)
1.催化组合物,其包含铂系金属和YMn2O5。
2.根据权利要求1的组合物,其中YMn2O5具有铁板钛矿结构。
3.适于柴油氧化催化剂应用的催化组合物,其包含:铂系金属和至少一种铁板钛矿结构化合物。
4.根据权利要求3的组合物,其中铁板钛矿结构化合物具有通式AB2O5。
5.根据权利要求3的组合物,其中铁板钛矿结构化合物选自银、锰、钇、镧、铈、铁、镨、钕、锶、镉、钴、钪、铜和铌。
6.根据权利要求3的组合物,其中铂系金属选自铂、钯、钌、铱、铑及其组合。
7.催化剂体系,其包含:
至少一种基质;
至少一个包含铁板钛矿结构化合物的修补基面涂层;和
至少一个包含铂系金属的罩面层。
8.根据权利要求7的催化剂体系,其中铁板钛矿结构化合物具有通式AB2O5。
9.根据权利要求7的催化剂体系,其中铁板钛矿结构化合物选自银、锰、钇、镧、铈、铁、镨、钕、锶、镉、钴、钪、铜和铌。
10.根据权利要求7的催化剂体系,其中铂系金属选自铂、钯、钌、铱、铑及其组合。
11.根据权利要求7的催化剂体系,其中铁板钛矿结构化合物在ZrO2载体氧化物上。
12.根据权利要求7的催化剂体系,其中铂系金属以5.0g/ft3施涂于修补基面涂层上。
13.根据权利要求7的催化剂体系,其中CO转化率在5.2g/L的硫酸盐化下为约100%。
14.根据权利要求7的催化剂体系,其中NO转化率在5.2g/L的硫酸盐化下为约50%。
15.根据权利要求7的催化剂体系,其中HC转化率在5.2g/L的硫酸盐化下为约88%。
16.根据权利要求7的催化剂体系,其中NO转化率在约340℃下为约60%。
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