CN100478073C - 用于净化柴油机废气的催化剂及其制备方法 - Google Patents
用于净化柴油机废气的催化剂及其制备方法 Download PDFInfo
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- CN100478073C CN100478073C CNB2004100477214A CN200410047721A CN100478073C CN 100478073 C CN100478073 C CN 100478073C CN B2004100477214 A CNB2004100477214 A CN B2004100477214A CN 200410047721 A CN200410047721 A CN 200410047721A CN 100478073 C CN100478073 C CN 100478073C
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- catalyst
- silica
- zeolite
- alumina
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- 239000010457 zeolite Substances 0.000 claims abstract description 56
- 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 55
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 52
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
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- 239000002002 slurry Substances 0.000 claims abstract description 12
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- 239000010948 rhodium Substances 0.000 claims abstract description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 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 4
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- 150000004706 metal oxides Chemical class 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001274660 Modulus Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- UVNSJYSGNRRBIJ-UHFFFAOYSA-N azanide dinitroazanide platinum(2+) Chemical compound [N+](=O)([O-])N([Pt]N)[N+](=O)[O-] UVNSJYSGNRRBIJ-UHFFFAOYSA-N 0.000 description 1
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
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- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 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 description 1
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- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
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- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 238000009423 ventilation Methods 0.000 description 1
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
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- B01J29/42—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 containing iron group metals, noble metals or copper
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Abstract
本发明提供一种催化剂及其制备方法，该催化剂清除柴油机废气中的HC、CO和SOF并降低微粒的排放。用于净化柴油机废气的催化剂具有沉积在难熔三维结构体上的催化剂组分，催化剂组分包含二氧化硅一氧化铝和沸石，二氧化硅-氧化铝担载上至少一种选自铂、钯和铑的贵金属元素。这种催化剂通过将贵金属组分加入到二氧化硅-氧化铝的浆液中，在其中引起化学吸附，然后将沸石加入所得的混合物中，从而得到载有贵金属的二氧化硅-氧化铝与沸石的混合浆液，将难熔三维结构体浸入所述混合浆液中，在其中引起催化组分的沉积，随后焙烧所得组合物制得。
Description
技术领域
本发明涉及一种用于净化内燃机废气的催化剂及其制备方法，该催化剂通过氧化作用清除柴油机废气中所含的烃(以下用“HC”表示)、一氧化碳(以下用“CO”表示)和可溶的有机成分(以下用“SOF”表示)并减少内燃机微粒的排放。
背景技术
最近几年中，特别是柴油机废气中的微粒物质(以下用“PM”表示)主要含有实心碳微粒(以下用“SOOT”表示)、硫酸盐(以下用“sulfates”表示)和液态的大分子烃微粒(以下用“SOF”表示)，并引起了有关环境健康的问题。这种忧虑的原因在于这样的事实：由于PM的粒径不超过1μm，所以易于飘浮在空气中并通过呼吸进入人体。因此，官方正在制定政策以加强对柴油机PM排放的控制。
同时，柴油机的最优化操作使柴油机PM的排放量有明显降低，而柴油机最优化操作是通过对旨在提升其压力并配合其定时的燃料喷射***的电子控制实现的。然而，这种降低很难达到预期的满意度。此外，PM中的SOF还含有如致癌物的有害成分。因而，SOF和SOOT的除去也已构成一个重要的问题。
在对去除PM的方法的寻求中，已经对催化体系的可行性进行了研究，催化***捕捉柴油机废气中的PM成分并且去除PM，对PM的捕捉是通过构件，该构件是通过将能燃烧PM的催化物质沉积到诸如闭塞型陶瓷蜂窝体、多孔陶瓷、金属丝网、多孔金属、开流型陶瓷蜂窝体或金属蜂窝体之类难熔三维结构体上形成的；对PM的去除或者是通过强制提升引擎温度，引擎处在经柴油机的通常运转或经控制引擎而得到的废气排放条件(气体组成和温度)下、或者是通过采用如电加热器的加热方法来进行。
通常，由于催化剂用于净化柴油机废气，尤其是用于净化应用于客车这一级中的柴油机废气，因此正在寻找(1)一种催化剂，在通过燃烧去除除PM外诸如未燃烧的烃(以下用“HC”表示)和一氧化碳(以下用“CO”表示)的有害成分的过程中表现出高效率，(2)一种催化剂，具有优秀的所谓高温稳定性，即在高装填量下承受连续操作的能力，以及(3)一种催化剂，具有优秀的所谓抗硫中毒性，即对由硫的氧化物在催化剂上的附着引起的毒化的免疫性，该毒化是在低装填量低排气温度的操作中观察到的。
迄今为止已经提出了各种各样的建议，这些建议的目的是提高燃烧去除柴油机废气中PM、HC和CO的效率。例如，公报JP-A-HEI7-24260公开了一种催化剂，该催化剂具有铂和/或钯及选自钨、锑、钼、镍、钒、锰、铁、铋、钴、锌和稀土金属中至少一种元素的氧化物，它们沉积在难熔无机氧化物上，含量在5-50质量％范围内，基于该无机氧化物的质量。
此外，公报JP-A-HEI10-33986中公开了一种催化剂，该催化剂含有具有不同模数的几种沸石的混合物和一种铂族金属以及一种选自铝的硅酸盐、铝的氧化物和钛氧化物的单个的金属氧化物，使铝的硅酸盐中二氧化硅与氧化铝的硅铝比在0.005-1范围内并使铂族金属只沉积在单个的金属氧化物上。
引擎废气的温度在例如EGR的影响下倾向于下降，EGR是为了降低引擎废气中的NOX而安装到引擎上的。为了使冷启动条件与汽车的真实工作环境接近而对其控制试验模式的改变也会促使废气温度下降。在这些情形下，上述的传统催化剂在PM、HC和CO所处的低温区对仍然总是能力不足，尽管它们明显能够燃烧。在低废气温度运转期间，它们对由硫的氧化物在催化剂上的沉积引起的毒化敏感并因此在PM、HC和CO的燃烧效率的下降中处于不利地位。
基于对事情的真实状态的了解启动了本发明，由此其目标是创造一种用于净化柴油机废气的具有上述(1)-(3)所定义的性质的催化剂，该催化剂能令人满意地具有对用于客车的催化剂所特殊要求的特性。
发明内容
为实现上述目标，本发明人进行了辛勤的研究，从而发现通过将催化组分沉积在难熔三维结构体上来实现目标，催化组分由二氧化硅一氧化铝和沸石组成，其上担载有至少一种选自铂、钯和铑的贵金属。在此认识的基础上完善了本发明。
具体地说，本发明涉及一种用于净化柴油机废气的催化剂，特征在于将催化组分沉积在难熔三维结构体上，催化组分由二氧化硅一氧化铝和沸石组成，其上担载至少一种选自铂、钯和铑的贵金属。
本发明进一步涉及一种用于净化柴油机废气的催化剂的制造方法，特征在于将贵金属组分加入二氧化硅一氧化铝的浆液中，使它们进行化学吸附，然后向其中加入沸石，将难熔三维结构体浸入所得的担载有贵金属的二氧化硅一氧化铝与沸石的混合浆液以使催化组分附着，随后焙烧所得组合物。
根据本发明的用于净化柴油机废气的催化剂具有如上所述的这种结构，因此，在通过燃烧去除除PM外诸如未燃烧的烃和一氧化碳的有害成分的过程中从低温向上表现出高效率，具有优秀的抗高温能力并具有优秀的抗硫中毒能力。
附图说明
附图1是一张表示在欧洲排放测试模式循环中模拟行程上引擎速度和转矩大小之间关系的图，以及
附图2是一张表示引擎排出废气的催化剂进口温度和时间之间关系的图。
具体实施方式
现在，将在以下对本发明进行详细描述。
本发明的特征在于组合了一种组合物，该组合物含有至少一种选自铂、钯和铑的贵金属，贵金属负载在二氧化硅一氧化铝和沸石上，因而能够表现出诸如从低温向上清除废气中如未燃烧的烃、一氧化碳和PM中的SOF这样的有害成分的作用、经得住高温连续运转、耐高温能力极佳、足以抵挡如引擎在低废气温度运转期间所观察到例如由硫氧化物在催化剂上的附着而引起的毒化，及抗硫中毒能力优异。
例如，当氧化铝用作担载贵金属的基物时，随后形成的催化剂确实在净化废气的有害成分如未燃烧的烃、一氧化碳和PM中的SOF的过程中产生了可察觉的影响。然而，当这种催化剂长时间暴露于低废气温度的运转下时，将被硫毒化至它对诸如未燃烧的烃、一氧化碳和PM中SOF之类的有害成分的氧化能力严重降低，因为废气中所含的SO2被贵金属氧化并由于吸附而除去。在采用氧化硅的情形下，尤其是当催化剂长时间暴露于高废气温度的运转下时，催化剂对诸如未燃烧的烃、一氧化碳和PM中SOF之类有害成分的氧化能力显著地降低。
本发明中不必对用作沉积作用基底的二氧化硅一氧化铝的物理性质进行特殊限定。为了应用于真正的内燃机车，建议二氧化硅一氧化铝具有100-400m2/g范围内的比表面积(Brunaer-Emmett-Teller(BET)比表面积)，优选120-350m2/g。如果所用二氧化硅一氧化铝的比表面积不足100m2/g，这种不足将导致它对铂、钯和铑的分散能力降低并削弱催化剂对未燃烧的烃、一氧化碳和PM中SOF之类有害成分的氧化能力。相反，如果所用二氧化硅一氧化铝具有超过400m2/g的比表面积，将不再认为它是热稳定的，它屈从于内燃机排放气的热变化并致使对例如未燃烧的烃、一氧化碳和PM中SOF的有害成分的氧化能力大大降低。由于这种超出进一步导致增加废气中SO2的沉积量并且由此降低催化剂的抗硫中毒能力。
推荐二氧化硅一氧化铝中SiO2与Al2O3的硅铝质量比在0.02-1的范围内，优选在0.05-0.5范围内。如果SiO2与Al2O3的硅铝质量比不到0.02，这种不足将导致二氧化硅一氧化铝组合物与使用单一氧化铝相比的优势降低，组合物的优势在于使SO2易于屈从于吸附而除去，从而导致对例如未燃烧的烃、一氧化碳和PM中SOF之类的有害成分的氧化能力降低。相反，如果SiO2与Al2O3的硅铝质量比超过1，当催化剂长时间暴露于高废气温度的运转下时，这种超出将导致催化剂对例如未燃烧的烃、一氧化碳和PM中SOF之类的有害成分的氧化能力的降低。
上述二氧化硅一氧化铝优选为粉末状。粉末的平均粒径在5-90μm范围内，优选10-45μm。
本发明中沸石的作用在于赋予催化剂一种在低排气温度条件下吸附未燃烧烃并在排气温度升高后使其脱附的功能，在低排气温度下催化剂还未激活，大部分脱附的烃在经升温而激活的催化剂上燃烧。也就是说，沸石起到的作用是拓宽了吸附和燃烧脱除废气中未燃烧烃的温度范围。此外，由于沸石所具有的酸性在抑制催化剂对废气中所含SO2的吸附中是有效的，因此沸石具有提高了催化剂抗硫中毒能力的功能。在所有类型的沸石中，最适宜加入本发明预期的催化剂中的是β沸石。
当不加入沸石时，这种缺失必然导致催化剂尤其在低温范围内氧化未燃烧烃的能力的降低以及催化剂抗硫中毒能力的降低。当采用不是β沸石的沸石，例如ZSM-5或丝光沸石时，尽管其吸附烃的功能是可以察觉的，但其吸附存在于柴油机废气中长链烃的功能比采用β沸石的低而且减少烃的作用也降低。
沸石中SiO2与Al2O3的硅铝质量比在10-150的范围内，优选18-50。如果该硅铝质量比超过150，这种超出将导致减少沸石上的酸性位并尤其在低温范围内降低减少烃的作用。相反，如果硅铝质量比不到10，这种不足将导致沸石热稳定性结构的丧失，使其屈从于柴油机废气中的热变化，并致使吸附烃功能的降低。
上述担载至少一种选自铂、钯和铑的贵金属的二氧化硅一氧化铝和沸石各自具有上述的功能。只有当将它们结合时，由此所得的催化剂才能完全令人满意地获得用于净化柴油机废气的(1)-(3)的催化剂，尤其是用于客车的催化剂，所需具有的性质。
本发明预期的催化剂是通过将催化剂组分沉积在难熔三维结构体上来制备的，催化剂组分由二氧化硅一氧化铝和沸石组成，二氧化硅一氧化铝上负载了至少一种选自铂、钯和铑的贵金属，优选铂，沸石优选β沸石。
不需要特别限定上述贵金属的原料。例如硝酸盐、醋酸盐、氯化物、硫酸盐、氧化物、过氧化物和氢氧化物都是可用的。举例：例如氯化铂、硝酸铂水溶液和二硝基二氨铂(II)水溶液为铂的起始原料，硝酸钯水溶液为钯的起始原料，硝酸铑水溶液为铑的起始原料。
多种方法可用于制备这样的贵金属。例如将上述的贵金属组分加入二氧化硅一氧化铝浆液中并搅拌。搅拌期间，可选地将它们加热以促进贵金属组分与二氧化硅一氧化铝之间的反应。加热所达到的温度在15-500℃范围内，优选在25-150℃范围内。由此，贵金属组分化学吸附到二氧化硅一氧化铝上。
然后，可选地对化学吸附了贵金属的二氧化硅一氧化铝浆液通过加热进行干燥。干二氧化硅一氧化铝或二氧化硅一氧化铝浆液与沸石按指定的量加到一起，随后经过干磨或湿磨。当所得的粉末是湿磨的产物，则直接将其打浆。当所得的粉末是干磨的产物，则在水存在下将其打浆。将难熔三维结构体浸入浆液以使催化剂组分沉积在结构体上。
接下来，使如空气之类的气体通过三维结构体的各个空穴以驱逐出过剩的催化剂组分。进一步干燥结构体然后焙烧。
对催化剂的焙烧气氛可适当地选择空气、真空、如氮气类的惰性气流或例如氢气或一氧化碳类的还原气流，以与所采用的制备催化剂的方法相适应。在还原气体下的焙烧证实是尤其有利的。焙烧温度优选为200-800℃的范围，更优选为300-600℃。再者，焙烧时间优选为30分钟-20小时的范围，更优选为1-5小时的范围。
通过如上所述的将贵金属组分加入二氧化硅一氧化铝浆液中并搅拌从而将它们混合，使通过化学吸附将贵金属组分沉积在二氧化硅一氧化铝上成为可能。
同时，即使在沸石与二氧化硅一氧化铝混合时，实质上也没有沉积发生在沸石上。
为了提高其耐高温能力和抗硫中毒能力以及提升氧化性能，本发明中上述的催化剂组分可以任选地含有至少一种选自钛、锆和稀土金属元素的元素。上述元素与沉积后的催化剂总量的适宜的质量比为在1-50质量份的范围，优选为3-20质量份，基于100质量份的沉积总质量。
本发明催化剂中二氧化硅一氧化铝与沸石适宜的硅铝质量比为0.5-5范围，优选为0.8-3的范围。如果二氧化硅一氧化铝与沸石的硅铝质量比不足0.5，这种不足将不适当地导致增加烃的吸附量，从而增加待脱附的烃的量，相应地阻碍了催化剂上燃烧充分地进行，削弱组分之间作用的平衡。如果不适当地提升吸附烃的能力，这种超出将可能由于空穴的阻塞而导致催化剂阻塞。相反，如果二氧化硅一氧化铝与沸石的硅铝质量比超过5，这种超出将导致低温范围内降低催化剂吸附烃的能力并因而降低减少烃的作用。它还将弱化抑制SO2在催化剂上吸附和降低抗硫中毒能力的影响。
每升(以下用L表示)难熔三维结构体中，本发明催化剂的至少一种选自铂、钯和铑并负载在催化剂上的元素的适宜的量为在0.01-5g/L的范围，特别是0.5-4g/L的范围。
本发明中所用的难熔三维结构体仅是通常所称的“陶瓷蜂窝基体”。准确地说，采用如堇青石、莫来石、α一氧化铝、氧化锆、二氧化钛、磷酸钛、钛酸铝、铬砷铅矿、锂辉石、铝硅酸盐和硅酸镁之类材料的蜂窝基体都是优选的例子。在上面列举之外的蜂窝基体中，那些由堇青石构成的证明是尤其有利的。此外，由例如不锈钢和FeCr-Al合金之类抗氧化难熔金属形成的实心结构的基体也可以使用。
通过挤压成型法或经紧轧片状材料形成实心结构的方法来制备这些整体基体。这种蜂窝构型的通气嘴(蜂房状)可以采取如六边形、四边形、三角形和波纹形的多种形状中的任何一种。只要蜂窝基体的蜂房密度(蜂房数/单位横截面)在150-900蜂房/平方英寸范围内就证实是充分有效的，优选400-600蜂房/平方英寸。
本发明的催化剂在净化柴油机废气的使用中，废气空速优选为5,000-200,000hr-1的范围内。如果气体空速不足5,000hr-1，这种不足将导致要求所需催化剂的容量在牺牲经济的情况下不必要地增加。如果气体空速超过200,000hr-1，这种超出将导致净化柴油机废气效率降低。使用本发明的催化剂净化柴油机废气期间，催化剂床层入口处适宜的废气温度在200℃-700℃范围内，优选在250℃-600℃范围内。如果该温度不到200℃或超过700℃，这种背离将导致净化柴油机废气的能力降低至低于目标值。
下面将结合催化剂的相关制备方法描述本发明用于净化柴油机废气的催化剂的多种实施方式。
实施例1
添加并混合1800g二氧化硅一氧化铝(以下用“二氧化硅一氧化铝A”表示)与含60g铂的硝酸二硝基二氨铂(II)水溶液，二氧化硅一氧化铝具有320m2/g的BET比表面积，二氧化硅与氧化铝的硅铝质量比为0.053，干燥所得混合物并在500℃焙烧1小时，得到载铂二氧化硅一氧化铝粉末(以下用“铂粉末A”表示)。添加铂粉末A、2400gβ沸石(SiO2/Al2O3＝25)(该硅铝比在以下过程中很好地保持)和含水介质并湿磨所得的混合物，得到浆液。然后，将堇青石蜂窝基体(以下过程中很好地保持)浸入浆液，对由此得到的湿蜂窝基体进行吹气以驱除过剩浆液，在150℃下干燥，随后在500℃下焙烧1小时，得到完成的催化剂。该催化剂上覆盖了2.0g铂每升蜂窝、60g二氧化硅一氧化铝每升蜂窝和80gβ沸石每升蜂窝。
蜂窝基体由堇青石形成，测定其体积为1.3升，每平方英寸横截面上含400个蜂房，具有6mils的壁厚。
对照例1
按照实施例1的步骤，但是在湿磨过程中用二氧化硅一氧化铝A代替β沸石，得到完成的催化剂。该催化剂上覆盖了2.0g铂每升蜂窝、140g二氧化硅一氧化铝每升蜂窝。
实施例2
按照实施例1的步骤，但是在湿磨过程中以加入1200gβ沸石和1200g二氧化硅一氧化铝A代替单独加入β沸石，得到完成的催化剂。该催化剂上覆盖了2.0g铂每升蜂窝、100g二氧化硅一氧化铝每升蜂窝和40gβ沸石每升蜂窝。
实施例3
按照实施例1的步骤，但是在湿磨过程中以加入2100gβ沸石和300g二氧化钛代替单独加入β沸石，得到完成的催化剂。该催化剂上覆盖了2.0g铂每升蜂窝、60g二氧化硅一氧化铝每升蜂窝、70gβ沸石每升蜂窝，和10g二氧化钛每升蜂窝。
实施例4
按照实施例1的步骤，但是用具有150m2/g比表面积及所含二氧化硅与氧化铝的重量比为0.05的二氧化硅一氧化铝(以下用“二氧化硅一氧化铝B”表示)代替二氧化硅一氧化铝A，得到完成的催化剂。该催化剂上覆盖了2.0g铂每升蜂窝、60g二氧化硅一氧化铝每升蜂窝和80gβ沸石每升蜂窝。
实施例5
按照实施例4的步骤，但是在湿磨过程中以加入900g二氧化硅一氧化铝B、300g二氧化锆和1200gβ沸石来代替单独加入β沸石，得到完成的催化剂。该催化剂上覆盖了2.0g铂每升蜂窝、90g二氧化硅一氧化铝每升蜂窝、40gβ沸石每升蜂窝，和10g二氧化锆每升蜂窝。
对照例2
按照实施例1的步骤，但是在湿磨过程中用ZSM沸石代替β沸石，得到完成的催化剂。该催化剂上覆盖了2.0g铂每升蜂窝、60g二氧化硅一氧化铝每升蜂窝和80gZSM沸石每升蜂窝。
对照例3
按照实施例1的步骤，但是在铂粉末沉积期间用β沸石代替二氧化硅一氧化铝，得到载铂粉末。按照实施例1的步骤，但是在湿磨过程中用二氧化硅一氧化铝A代替β沸石，得到完成的催化剂。该催化剂上覆盖了2.0g铂每升蜂窝、60gβ沸石每升蜂窝和80g二氧化硅一氧化铝每升蜂窝。
实施例6
根据下列测试方法测定由前述实施例和对照例得到的催化剂的净化废气的能力。
(所用设备和燃料)
采用与功率计相连的商业上可得的附加供应直喷式柴油机(4缸，2500cc)。能自动调整引擎速度和转矩的自动操作控制设备与功率计相连。至于评价过程用燃料，采用硫含量低于0.05质量％的轻油。在耐硫中毒能力的测定中，采用硫含量低于0.20质量％的轻油。
(测定耐硫中毒能力的方法)
采用前述硫含量较高的轻油运转的引擎暴露于废气中50小时，调整其转矩以使引擎速度从1400变化到2200r.p.m.以及使催化剂进口温度从200℃变化到300℃。
(测定耐高温能力的方法)
采用与评价过程中同样的燃料运转的引擎暴露于废气中20小时，调整引擎速度和引擎转矩以设置催化剂进口温度在600℃。
(评价方式)
通过任意改变附图1所示欧洲气体排放控制模式中的假设行程上引擎速度和引擎转矩，引擎释放的废气的催化剂进口温度如附图2所示变动。
(评价方法)
未通过催化剂床层的废气部分由废气分析仪进行分析。对通过催化剂床层的另一部分废气进行采样并测定其对HC、CO和PM的净化净化率。此处记录的净化率始终是由上述评价方式所得数据的平均值。结果列于表1-3中。
表1
表2
表3
Claims (10)
1.一种用于净化柴油机废气的催化剂，通过在难熔三维结构体上沉积催化剂组分形成，该催化剂组分包含(a)其上担载至少一种选自铂、钯和铑的贵金属元素的二氧化硅-氧化铝和(b)不担载贵金属的β沸石。
2.根据权利要求1的催化剂，其中所述的二氧化硅-氧化铝中二氧化硅/氧化铝的质量比在0.05-0.5的范围内。
3.根据权利要求1或2的催化剂，其中所述的β沸石中二氧化硅/氧化铝的质量比在18-50的范围内。
4.根据权利要求1的催化剂，其中所述的二氧化硅-氧化铝具有100-400m2/g范围内的BET比表面积，并且SiO2与Al2O3的质量比在0.05-0.5的范围内。
5.根据权利要求1的催化剂，其中所述的二氧化硅-氧化铝为粉末状。
6.根据权利要求5的催化剂，其中所述的二氧化硅-氧化铝粉末的平均粒径在10-45μm范围内。
7.根据权利要求1的催化剂，其中二氧化硅-氧化铝与β沸石的质量比在0.5-5的范围内。
8.根据权利要求1的催化剂，其中所述贵金属的量在0.01-5g每升催化剂体积的范围内。
9.根据权利要求1的催化剂，其中所述催化剂组分进一步包含至少一种选自钛、锆和稀土元素的元素。
10.一种制备用于净化柴油机废气的催化剂的方法，特征在于，(a’)将选自铂、钯和铑的贵金属组分加入到具有100-400m2/g范围内的比表面积以及硅铝质量比在0.02-1的范围内的二氧化硅-氧化铝的浆液中，在其中引起化学吸附，然后(b’)将β沸石加入所得的混合物中，从而得到(a)载有贵金属的二氧化硅-氧化铝与(b)沸石的混合浆液，其中所述二氧化硅-氧化铝与β沸石的质量比在0.5-5的范围内，(c’)将陶瓷蜂窝基体浸入所述混合浆液中，在其中引起催化组分的沉积，和(d’)接着焙烧由(c’)得到的组合物。
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Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4695962B2 (ja) * | 2005-10-20 | 2011-06-08 | エヌ・イーケムキャット株式会社 | 排気ガス浄化用酸化触媒、それを用いた一体構造型酸化触媒及び排気ガス浄化方法 |
| KR101094241B1 (ko) | 2005-12-16 | 2011-12-14 | 에스케이이노베이션 주식회사 | 디젤엔진의 배기가스 정화용 산화촉매의 제조방법 |
| KR101274468B1 (ko) * | 2006-08-10 | 2013-06-14 | 에스케이이노베이션 주식회사 | 디젤엔진의 배기가스 정화용 산화촉매 |
| RU2438777C2 (ru) * | 2006-08-19 | 2012-01-10 | Умикоре Аг Унг Ко. Кг | Фильтр твердых частиц выхлопных газов дизельного двигателя с каталитическим покрытием, способ его изготовления и его применение |
| FR2907444B1 (fr) * | 2006-10-20 | 2008-12-19 | Rhodia Recherches & Tech | Composition a acidite elevee a base d'oxydes de zirconium,de silicium et d'au moins un autre element choisi parmi le titane,l'aluminium,le tungstene,le molybdene,le cerium,le fer et le manganese |
| US7631488B2 (en) | 2006-10-27 | 2009-12-15 | Postech Foundation | Oxidation catalyst for removing fine soot particulates from exhaust gases and method of removing fine soot particulates using the same |
| DE102007018612A1 (de) * | 2007-04-19 | 2008-10-23 | Süd-Chemie AG | Katalysatorformkörper |
| KR100885682B1 (ko) * | 2007-07-10 | 2009-02-26 | 주식회사 이엔드디 | 고유황유를 사용하는 엔진의 일산화탄소, 탄화수소 및 피엠 제거용 복합촉매의 제조방법 |
| DE102007057305A1 (de) * | 2007-11-28 | 2009-06-04 | Süd-Chemie AG | Beschichtungszusammensetzung für Dieseloxidationskatalysatoren |
| CN107413336A (zh) * | 2011-03-04 | 2017-12-01 | 优美科触媒日本有限公司 | 废气净化用催化剂、其制备方法以及使用该催化剂的废气净化方法 |
| WO2012128297A1 (ja) * | 2011-03-24 | 2012-09-27 | 株式会社アイシーティー | 排ガス浄化用酸化触媒、その製造方法およびそれを用いた排ガス浄化方法 |
| CA2892683A1 (en) | 2012-12-12 | 2014-06-19 | Basf Corporation | Catalyst compositions, catalytic articles, systems and processes using large particle molecular sieves |
| US8980209B2 (en) | 2012-12-12 | 2015-03-17 | Basf Corporation | Catalyst compositions, catalytic articles, systems and processes using protected molecular sieves |
| KR101522857B1 (ko) * | 2013-05-02 | 2015-05-26 | 희성촉매 주식회사 | 복합형 선택적 환원 촉매 |
| US9732648B2 (en) * | 2013-10-23 | 2017-08-15 | Mazda Motor Corporation | Catalyst device for exhaust gas purification and method for exhaust gas purification |
| BR112018005877A2 (pt) | 2015-10-14 | 2018-10-16 | Johnson Matthey Plc | catalisador de oxidação, sistema de escape, veículo, e, método para tratamento de um gás de escape. |
| EP3351300A1 (en) * | 2017-01-20 | 2018-07-25 | SASOL Germany GmbH | Manganese oxide containing alumina composition, a method for manufacturing the same and use thereof |
| CN109248681A (zh) * | 2018-09-06 | 2019-01-22 | 南京蔚岚环境技术研究院有限公司 | 一种一氧化碳氧化催化剂及其制备方法和涂覆该催化剂在载体上的方法 |
| KR102292551B1 (ko) * | 2019-09-30 | 2021-08-25 | 주식회사 포스코 | 황에 대한 내구성이 우수한 scr 촉매 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1162501A (zh) * | 1996-04-12 | 1997-10-22 | 德古萨股份公司 | 柴油催化剂 |
| EP0935055A2 (en) * | 1998-02-05 | 1999-08-11 | Nissan Motor Company, Limited | Device for purifying oxygen rich exhaust gas |
| US5943857A (en) * | 1995-06-06 | 1999-08-31 | Johnson Matthey Public Limited Company | Diesel engine exhaust gas purification method |
| CN1315228A (zh) * | 2000-03-01 | 2001-10-03 | dmc2德古萨金属催化剂塞尔德克股份公司 | 净化柴油机废气的催化剂及其制备方法 |
| US6489259B2 (en) * | 2000-12-29 | 2002-12-03 | Delphi Technologies, Inc. | Mixed zeolite NOx catalyst |
| EP1287886A1 (de) * | 2001-08-09 | 2003-03-05 | OMG AG & Co. KG | Katalysator für die Reinigung der Abgase eines Verbrennungsmotors |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5244852A (en) * | 1988-11-18 | 1993-09-14 | Corning Incorporated | Molecular sieve-palladium-platinum catalyst on a substrate |
| US6869573B2 (en) * | 1990-11-09 | 2005-03-22 | Ngk Insulators, Ltd. | Heater and catalytic converter |
| US6248684B1 (en) | 1992-11-19 | 2001-06-19 | Englehard Corporation | Zeolite-containing oxidation catalyst and method of use |
| JP2891609B2 (ja) | 1993-07-15 | 1999-05-17 | 株式会社アイシーティー | ディーゼルエンジン排ガス浄化用触媒 |
| JPH10202105A (ja) | 1997-01-22 | 1998-08-04 | Toyota Motor Corp | ディーゼル排ガス用酸化触媒 |
| WO1999033549A1 (en) * | 1997-12-24 | 1999-07-08 | Engelhard Corporation | Catalytic converter system for internal combustion engine powere d vehicles |
| JPH11276907A (ja) | 1998-03-30 | 1999-10-12 | Nissan Motor Co Ltd | 排気ガス浄化用触媒及びその製造方法 |
| US6208636B1 (en) * | 1998-05-28 | 2001-03-27 | Northpoint Technology, Ltd. | Apparatus and method for processing signals selected from multiple data streams |
| US6165430A (en) * | 1998-07-20 | 2000-12-26 | Ford Global Technologies, Inc. | Method for treating diesel engine exhaust gas |
| JP4703818B2 (ja) * | 2000-06-20 | 2011-06-15 | 株式会社アイシーティー | 排気ガス浄化用触媒および排気ガス浄化方法 |
| US6759358B2 (en) * | 2001-08-21 | 2004-07-06 | Sud-Chemie Inc. | Method for washcoating a catalytic material onto a monolithic structure |
-
2003
- 2003-05-06 JP JP2003127910A patent/JP4210552B2/ja not_active Expired - Lifetime
-
2004
- 2004-04-29 EP EP04010143A patent/EP1475141B1/en not_active Revoked
- 2004-04-30 CN CNB2004100477214A patent/CN100478073C/zh not_active Expired - Lifetime
- 2004-05-04 KR KR1020040031283A patent/KR100774577B1/ko active IP Right Grant
- 2004-05-04 US US10/838,518 patent/US7763560B2/en not_active Expired - Lifetime
- 2004-05-05 CA CA2466409A patent/CA2466409C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5943857A (en) * | 1995-06-06 | 1999-08-31 | Johnson Matthey Public Limited Company | Diesel engine exhaust gas purification method |
| CN1162501A (zh) * | 1996-04-12 | 1997-10-22 | 德古萨股份公司 | 柴油催化剂 |
| EP0935055A2 (en) * | 1998-02-05 | 1999-08-11 | Nissan Motor Company, Limited | Device for purifying oxygen rich exhaust gas |
| CN1315228A (zh) * | 2000-03-01 | 2001-10-03 | dmc2德古萨金属催化剂塞尔德克股份公司 | 净化柴油机废气的催化剂及其制备方法 |
| US6489259B2 (en) * | 2000-12-29 | 2002-12-03 | Delphi Technologies, Inc. | Mixed zeolite NOx catalyst |
| EP1287886A1 (de) * | 2001-08-09 | 2003-03-05 | OMG AG & Co. KG | Katalysator für die Reinigung der Abgase eines Verbrennungsmotors |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040224837A1 (en) | 2004-11-11 |
| KR20040095166A (ko) | 2004-11-12 |
| US7763560B2 (en) | 2010-07-27 |
| EP1475141B1 (en) | 2012-01-18 |
| KR100774577B1 (ko) | 2007-11-09 |
| CA2466409C (en) | 2010-02-23 |
| JP4210552B2 (ja) | 2009-01-21 |
| EP1475141A1 (en) | 2004-11-10 |
| JP2004330046A (ja) | 2004-11-25 |
| CA2466409A1 (en) | 2004-11-06 |
| CN1575850A (zh) | 2005-02-09 |
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