CN102365124B - 用于将排气流中的no氧化成no2的耐老化催化剂 - Google Patents
用于将排气流中的no氧化成no2的耐老化催化剂 Download PDFInfo
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- CN102365124B CN102365124B CN201080015464.XA CN201080015464A CN102365124B CN 102365124 B CN102365124 B CN 102365124B CN 201080015464 A CN201080015464 A CN 201080015464A CN 102365124 B CN102365124 B CN 102365124B
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- zeolite
- catalyst
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- platinum
- platiniferous
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Classifications
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Abstract
本发明涉及一种包含铂的沸石。本发明还涉及制备本发明所述的包含铂的沸石的方法,涉及所述沸石作为氧化催化剂和油气藏的用途以及涉及包含本发明沸石的催化剂组分。
Description
技术领域
本发明涉及一种含铂沸石。本发明还涉及制备本发明所述的含铂沸石的方法,所述沸石作为氧化催化剂和油气藏的用途以及包含本发明沸石的催化剂组分。
背景技术
在早期的内燃机排气的净化中,只有来自汽油机的排气可以用三效催化剂(TWC)净化。氮氧化物用还原烃(HC)和一氧化碳(CO)还原。
在约15年内,也试图用催化剂后处理来自柴油机的排气。来自柴油机的废气包含一氧化碳、未燃烃、氮氧化物和作为空气污染物的烟灰颗粒。未燃烃包括烷烃、烯烃、醛和芳烃。
柴油内燃机的排气系统通常包含下列组件:
●用于氧化烃和作为冷起动油气藏的柴油机氧化催化剂(DOC);
●用于减少颗粒排放的柴油机颗粒过滤器(DPF);
●任选用于分解尿素的水解催化剂;
●用于还原氮氧化物的SCR(选择性催化还原)催化剂;
●作为氨氧化催化剂的阻隔(barrier)催化剂。
对于DOC(柴油机氧化催化剂)本领域技术人员理解为优选作为冷起动油气藏并且在常规操作中氧化未燃烃的催化剂。用催化剂处理来自柴油内燃机的排气需要改变催化剂材料的设计,因为不像汽油机,柴油机通常在氧过量下运行并且因此催化剂从不经历还原状态。
因为颗粒物的问题成为讨论的主题,颗粒过滤器仍然连接至DOC的下游。将颗粒过滤器(DPF,柴油机颗粒过滤器)用于过滤出来自内燃机、特别是柴油机排气的烟灰颗粒,并且由此减少其释放入环境中。使用各种过滤器的设计,例如所谓的“壁流式过滤器”或由陶瓷或金属泡沫制成的过滤器。然而,真正的问题不是烟灰颗粒的过滤,而是所用过滤器的再生。取决于操作控制的颗粒的组成,炭黑仅在500℃和700℃之间的温度下自燃。
新生的颗粒过滤器必须是活性再生的。这意味着必须在DOC上重复产生该高温从而使下游DPF上的烟灰着火并烧除。因此,目前DOC的热老化就起到了十分重要的作用。
新生的柴油机动车目前在柴油机颗粒过滤器的下游安装有可以借助于所谓的SCR催化剂影响氮氧化物选择性催化还原的组件。SCR(选择性催化还原)是指来自内燃机排气以及粉末状态的氮氧化物的选择性催化还原。只有氮氧化物NO和NO2(通常被称为NOX)用SCR催化剂选择性还原,其中通常混合NH3(氨)用于反应。因此,只有无害物质水和氮气作为反应产物形成。
因此,除了烃的氧化,NO到NO2的氧化目前在柴油机氧化催化剂中特别重要。NO2使得下列柴油机颗粒过滤器的再生、即烟灰燃尽更容易(例如参见J.Choo等人,Science of the total environment(2008)396-401;M.Jeguirim等人,Applied Catalysis B:Environmental,76(2007),235-240或K.Yamamoto等人,Proceedings of the Combustion institute,付印的文章(article in press))。另外,NO/NO2混合物可以比纯NO更快地通过用氨选择性催化还原(SCR)而分解成氮气和空气(例如参见A.Grossale等人,Journal of Catalysis,256(2008),312至322或M.Schwidder等人,Journal of Catalysis,259(2008),96至103),因此在催化剂老化之后,对于NO到NO2的氧化,DOC的活性仍然必须非常高。
因此,在后处理柴油机排气的操作条件下,具有比到目前为止在现有技术中已可能的老化趋势更低的老化趋势的催化剂是必须的。
除了Pt基催化剂,包含Pt和Pd的催化剂也在现有技术中也是已知的。另外,DOC通常包含当冷时(冷起动情况)用于储存烃的沸石,从而减少烃的冷起动释放。
典型的DOC例如公开在EP 800 856 A2中。其在3至4g Pt/l催化剂体积的情况下,含有高的贵金属浓度。然而,为了使CO和烃的起燃温度达到尽可能地低,将多数的铂施加到无定形Al/Si混合氧化物上,并且仅将少份额施加到沸石上。根据现有技术,目前为止,在沸石中很均匀地分布非常高浓度的铂以至于其甚至在较高温度负载之后仍然具有良好的铂分布还是不可能的。高的铂含量或分布影响足够的稳定性,这是为什么在现有技术中高的铂含量至今为止只在Al/Si混合氧化物中引入而不在沸石中引入的原因。
含铂沸石在现有技术中是已知的。例如,将铂含量非常低(<1%)的沸石在炼油行业中用作催化剂,例如用于催化、芳构化和裂化反应。不同于柴油机排气中普遍的条件,上述反应在还原条件(即具有过量烃)下进行,并且因此仅需要非常低的贵金属含量。
含铂催化剂的制备,例如通过将铂离子交换进入沸石的孔中,在现有技术中是已知的。然而,这种方法并不在沸石中产生对柴油机氧化催化剂的应用而言将是必须的铂浓度(例如参见J.M.García-Cortés等人,Journal of Catalysis,218(2003),111至122;C.Jiménez等人,Applied Catalysis A:General 249(2003),175至185和J.Pérez-Ramírez等人,Applied Catalysis B:Environmental 29(2001),285-至298)。
具有改进稳定性的DOC还通常通过混合Pt/Pd催化剂提供。特别是具有高Pt份额的Pt/Pd催化剂(6∶1)表现出对热老化的良好耐受性。然 而,缺点在于随着Pd含量增加,NO到NO2的氧化恶化。另外,Pt/Pd催化剂显然对硫的耐受性较低(参见5th International Exhaust Gas andParticulate Emissions Forum,2月19和20日,2008,Ludwigsburg,第126至144页)。这类催化剂通常不能在硫中毒之后热再生,但是在中毒后将其热负载即老化之后,其仍然继续损失活性。
发明内容
因此本发明的目的是提供一种制备催化剂、特别是柴油机氧化催化剂的方法,其具有低的老化趋势和高的活性。
该目的通过用于制备含铂沸石的方法实现,所述方法包括如下步骤:
a)用亚硫酸铂溶液浸渍沸石,
b)在保护气氛下煅烧浸渍的沸石。
优选所述煅烧在保护气氛中进行,其中优选使用氩气气氛、氮气气氛或其它惰性气氛。特别优选氩气气氛。
所述浸渍沸石的煅烧优选在600至900℃、更优选>750至850℃、特别优选>750至830℃、特别是在约800℃的温度下进行。
由于煅烧,形成铂前体化合物,如果必须的话,优选将其在煅烧后还原。然而,理论上,还原也可以在煅烧期间已经进行,然而,其中然后将必须使用还原气氛代替保护气氛。
可以在煅烧之后进行的还原优选使用还原气体(氢气、一氧化碳、乙烯、甲醇、乙醇等)和惰性气体的混合物进行。
优选的惰性气体例如为氩气、氦气、氖气等。在还原步骤中的惰性气体将被当成运载气体,其中优选氢气或其它还原气体的浓度,相 对于还原气体和惰性气体的总体积,为1至10体积%、更优选3至7体积%、特别优选约5体积%。
通常还原进行直到铂前体化合物发生完全或基本完全的转换。优选还原在3至7小时、更优选4至6小时、特别优选约5小时的周期内进行。
优选还原在升高的温度下进行。优选还原在200至500℃、更优选250至350℃、最优选约300℃的温度下进行。对还原而言,通常将催化剂置于催化剂床上并且使还原剂流过它。同样地,催化剂可以用还原气体过载并且有利地被引入升高的温度中。温度的升高可以例如通过加热催化剂床进行。同样可能的是还原气体已经例如通过加热供气管预先加热,其中然后将加热的还原气体引入待还原的催化剂上。
用亚硫酸铂溶液浸渍沸石可以经由浸泡浸渍、喷雾浸渍或初湿含浸法进行。优选浸渍经由初湿含浸法进行,尽管根据现有技术用这种浸渍方法仅有少量金属簇移动到孔中,而大部分保留在沸石的外表面。
然而,令人惊讶地发现通过用亚硫酸铂(PSA)初湿含浸沸石粉末然后在保护气体下在高温下煅烧可以制备甚至在该高温负载后在沸石孔中仍然有多数铂的催化剂。这可以在FTIR中经由X射线衍射(XRD)并经由CO吸附(使在表面的Pt簇选择性中毒后)证明。XRD和FTIR是化学中的标准分析方法。
还令人惊讶地发现由此制备的催化剂与具有已知体系的催化剂相比具有增加的耐硫性。本发明的热老化催化剂的催化活性通过硫中毒随后高温脱硫之后不变。
尽管在一氧化碳的氧化方面,与现有的Pt基催化剂相比改进的催化剂表现出相似的老化性能,但令人惊讶地发现在NO的氧化方面,其 具有显著较好的稳定性。
本发明制备的催化剂与现有技术的催化剂相比,另一优点在于贵金属被施加到一种组分、沸石上,而不是如在其它催化剂的情况下,施加到沸石和其它氧化载体的混合物上。因此,节约了生产步骤以及成本。
由于增加的沸石份额,烃存储容量也显著增加(参见例如EP 691833 B1、US 5,804,155和EP 830 301)。如果催化剂还没有达到必须的操作温度并且形成的排气还没有烧除,则存储容量是十分重要的。
因此,本发明的目的还在于一种特别使用本发明的方法制备的沸石。
根据国际矿物学协会(D.S.Coombs等人,Canadian Mineralogist,35,1979,1571)的定义,本发明范围内的“沸石”是指一种来自铝硅酸盐的晶态物质,其具有如下通式的空间网络结构:
Mx/n[(AlO2)x(SiO2)y]×(H2O)z
其由SiO4/AlO4四面体构成,所述四面体通过常规的氧原子连接以形成规则的三维网络。
根据所谓的“ 规则”所述Si/Al=y/x比例通常>1,其阻止两个临近的负电荷的AlO4四面体相互靠近而存在。尽管具有小的Si/Al比例的金属可获得更多交换点,但沸石逐渐变得更加热不稳定。
所述沸石结构包含各沸石特有的腔、通道。根据其拓扑结构将沸石分成不同结构。沸石骨架包括通道形式的开口腔和通常被水分子占据的笼以及可被取代的其它骨架阳离子。铝原子吸引由这些阳离子补偿的过量负电荷。孔体系的内部代表催化活性表面。沸石含有的铝越多并且硅越少,则其晶格中的负电荷越密集并且其内表面极性越大。 除了制备期间的参数,即模板的使用或类型、pH、压力、温度、晶种存在,孔径和结构通过构成沸石催化特征最大部分的Si/Al比(系数)测定。
本发明的沸石优选包含至少2wt%的铂、优选至少3wt%、最优选3.5wt%或更高的铂,其中至少90%、更优选至少95%、特别是优选至少99%的铂位于沸石的孔中。
优选沸石选自如下类型:AEL、BEA、CHA、EUO、FAU、FER、KFI、LTA、LTL、MAZ、MOR、MEL、MTW、LEV、OFF、TON和MFI。特别优选BEA结构。
优选沸石的SiO2/Al2O3系数为5至300、更优选10至200、最优选15至100。
本发明的沸石通过2070和2110cm-1之间、优选约2080至2095cm-1之间的Pt-C=O伸缩振动表征。所述伸缩振动在甚至用氰基金刚烷毒化后还存在。氰基金刚烷是空间高要求的分子,因为其大小,其不能渗透沸石的孔体系。因此,只有[沸石]外表面上的Pt簇通过吸收氰基金刚烷而中毒。如果在该中毒后吸收CO,则其只能结合到沸石内部未中毒的Pt簇。用氰基金刚烷毒化后存在Pt-C=O伸缩振动表明Pt位于沸石的孔中。中毒后的保留强度与对比催化剂相比约高2至4倍。
另外,在X射线衍射谱图(XRD)中本发明的沸石不具有Pt反射。这同样表明铂位于沸石的孔中。
本发明的另一目的是本发明的沸石作为氧化催化剂和油气藏的用途。沸石作为油气藏是已知的。然而,结合在沸石孔中高的铂分布,其还可显著适合作为具有相应聚积烃存储功能的氧化催化剂。因为铂仅施加到沸石上而不是如现有技术中已知的施加到其它金属氧化物 上,可以在有利成本下制备简单的催化剂体系。
将本发明的沸石加工成载体涂料并相应地施加到催化剂载体上可能是有利的。本领域技术人员已知如何制备载体涂料。涂覆催化剂载体所必需的涂覆技术也同样为本领域技术人员所已知。因此,例如将浸渍并干燥的沸石加工成含水涂层分散体。可将粘结剂例如硅溶胶加入到该分散体中。分散体的粘度可以通过合适的添加剂设置,由此使得在一个单独操作步骤中将所需量的涂层施加到流体通道的壁上成为可能。如果这不可能,则可以重复涂覆几次,其中通过立即干燥和必要时煅烧将各新施加的涂层固定。
对于柴油机的排气净化,涂层的量为50至500g/l、优选250至350g/l,催化剂载体的体积是有利的。
本发明的另一目的是含有本发明沸石的催化剂组分。优选沸石作为在载体上的涂层存在。
可将金属或陶瓷整料、非织造材料或金属泡沫用作催化剂载体。根据本发明,在现有技术中已知的其它催化剂成型体或催化剂载体也是适合的。特别优选金属或陶瓷整料具有配有载体涂料涂层的大量平行的通道孔。优选载体具有圆形、三角形、正方形或多边形横截面的通道孔。特别优选载体形成为整体的蜂窝体。
金属蜂窝体通常由金属片或金属箔形成。例如通过替换结构片或箔的层的排列而制备蜂窝体。优选这些排列由用波纹板替换的平滑片的层组成,其中波纹可例如形成为正弦形、梯形、ω形或锯齿形。合适的金属蜂窝体及其制备方法例如描述在EP 0 049 489 A1或DE 28 56030 A1中。
在催化剂载体领域中,金属蜂窝体的优点在于其更快地加热并且 由此基于金属基体的催化剂载体在冷起动条件下通常表现出较好的响应性能。
优选蜂窝体的孔密度为30至1500cpsi、特别优选200至600cpsi、特别是约400cpsi。
可施加本发明催化剂的催化剂载体可以由任意金属或金属合金形成,并可例如通过挤出、卷绕、堆叠或折叠金属箔制备。在排气净化领域,主要成分为铁、铬和铝的耐热的合金是已知的。对于本发明的催化剂而言,优选具有或不具有用于搅动排气的内部前沿且可被自由流过的整体催化剂载体或具有大的内表面积并且对本发明催化剂吸附良好的金属泡沫。然而,也可以使用在金属箔中具有裂缝、洞、穿孔和压痕的催化剂载体。
能够以相同方式使用由陶瓷材料制成的催化剂载体。优选陶瓷材料是具有小表面积的惰性材料,例如堇青石、多铝红柱石、钛酸铝或α-氧化铝。然而所用催化剂载体也可由具有大表面积的载体材料、例如γ-氧化铝构成。
金属泡沫、例如金属开孔泡沫材料也可以用作催化剂载体。在本发明的范围内,术语“金属开孔泡沫材料”是指由任意金属或任意合金制成的泡沫材料,其还可任选包含添加剂并且具有大量通过管道相互连接的孔,因此,例如可以引导气体通过泡沫材料。
金属开孔泡沫材料因为所述孔和腔而具有非常低的密度,但是具有很大的硬度和强度。例如借助于金属粉末和金属氢化物而进行金属泡沫的制备。通常将两种粉末混合在一起并且然后通过热压或挤出而压成成型材料。然后将成型材料加热至高于金属熔点的温度。金属氢化物释放氢气和混合物泡沫。
然而,仍然还有制备金属泡沫的其它可能,例如通过将气体吹入金属熔体中,所述熔体通过加入固体成分预先被制成发泡的。例如对于铝合金,为稳定加入10至20体积%碳化硅或氧化铝。另外,孔径为10ppi至约50ppi的开孔金属泡沫结构可以通过特殊精度铸造技术制备。
理论上可以将载体挤出并注射成型。在此,可以是金属和陶瓷材料,其中在陶瓷材料的情况下,例如加入模塑辅料、还可加入例如粘结剂及其它添加剂。挤出载体可以呈现任何几何形状,优选上文提及的那些。
现在将借助于一些具体实施方式更详细地描述本发明,所述具体实施方式不被认为限定了本发明的范围。
具体实施方式
实施例1
根据如下过程制备本发明的催化剂:
首先,测量干沸石的吸水性(H-BEA-35:Süd-Chemie AG的商品)。其为92.3%。
用蒸馏水将24.1g亚硫酸铂溶液(Pt含量10.17wt%)加满至62.3g。在研钵中,用该溶液浸渍67.55g干沸石。铂浓度为3.5wt%。湿粉末在120℃下干燥然后在保护气体(V=21/min)下在800℃下煅烧5小时并用含5%H2的N2在300℃下还原5h。
使70g粉末借助于Ultra-Turrax搅拌器悬浮于230ml水中。将悬浮液用具有10-mm钇稳定的氧化锆球的行星式球磨机(Retsch PM 100)研磨至粒度为d50~2μm。用该载体涂料涂覆堇青石蜂窝(400cpsi)并煅烧,由此最后在蜂窝上含有3.5g Pt/L蜂窝体积。
实施例2
为研究还原的影响,将第二蜂窝用未还原的催化剂涂覆(其它方面类似于实施例1)。
对比例1
作为比较,用六羟基铂酸乙醇铵溶液(Pt含量13.59wt%)作为Pt源进行相同的合成。所述Pt浓度同样为3.5wt%。
对比例2
根据基于DE 10 2007 057 305和EP 800 856 B1的如下过程制备DOC:
首先测定氧化铝与二氧化硅的混合氧化物(Siralox 5/140,5%Si,来自Condea)的吸水性。其为53.86%。将110.4g六羟基铂酸乙醇铵溶液(Pt含量13.59%)加满至161.6ml(用蒸馏水)。在行星式混合机中用该溶液浸渍300g Siralox粉末。将湿粉末在炉中于80℃下干燥3h然后在550℃下煅烧3h。
使140g粉末借助于Ultra-Turrax搅拌器悬浮于700ml水中。将悬浮液用具有1-1.2-mm Zr/Ce氧化物小珠的玻珠研磨机(来自WAB的Dynomil)研磨至粒度为d50~3μm。将140g用铁交换的β-沸石(3%Fe2O3,β-35-沸石)加入到该细微研磨的Pt/Siralox分散体中,并将悬浮液加满至1400ml,由此形成含有20%固体的涂层载体涂料。用该载体涂料涂覆堇青石蜂窝(400cpsi)并煅烧,由此最后在蜂窝上含有3.5g Pt/l蜂窝体积。
对比例3
为比较催化剂的活性和老化,另外使用Daimler OM646发动机的常规市售DOC。
对比例4
Pt/Pd(4∶1)催化剂:
首先测定氧化铝与二氧化硅的混合氧化物(来自Condea的具有非常大孔和5%Si的C型Siralox 5/140,)的吸水性。其为151%。将67.39g六羟基铂酸乙醇铵溶液(Pt含量13.85%)用蒸馏水58ml加满。在第一步中,在行星式混合机中,用该溶液浸渍186g Siralox粉末。然后将17.34g硝酸铂溶液用58ml水稀释,并在下一步中作为浸渍溶液进一步滴加到在行星式混合机中的湿粉末中。将湿粉末在炉中于80℃下干燥3h然后在550℃下煅烧3h。粉末总共含有7%贵金属。
使140g粉末借助于Ultra-Turrax搅拌器悬浮于700ml水中。将悬浮液用具有1-1.2-mm Zr/Ce氧化物小珠的玻珠研磨机(来自WAB的Dynomil)研磨至粒度为d50~3μm。用该载体涂料涂覆堇青石蜂窝(400cpsi)并煅烧,由此最后在蜂窝上含有3.5g贵金属/L蜂窝体积。
对比例5
无沸石的Pt催化剂:
首先测定氧化铝与二氧化硅的混合氧化物(来自Condea的具有非常大孔和5%Si的C型Siralox 5/140)的吸水性。其为151%。将73.6[g]六羟基铂酸乙醇铵溶液(Pt含量13.59%)用蒸馏水加满至181ml。在行星式混合机中,用该溶液浸渍200g Siralox粉末。将湿粉末在炉中于80℃下干燥3h然后在550℃下煅烧3h。
使100g粉末借助于Ultra-Turrax搅拌器悬浮于200ml水中。将悬浮液用具有10-mm氧化锆粒子的行星式球磨机(Ra.Retsch)研磨至粒度为d50~3μm。用该载体涂料涂覆堇青石蜂窝(400cpsi)并煅烧,由此最后在蜂窝上含有3.5g Pt/l蜂窝体积。
实施例6
催化剂的比较测试:
在如下条件下在反应器中测试实施例1和2以及对比例中制备的催化剂蜂窝对CO、丙烯和NO的氧化:
空速:70 000h-1
CO:500ppm
NO:500ppm
丙烯:500ppm
氧气:5%
水蒸气:10%
CO2:70-90ppm
氮气:剩余物
用陶瓷纤维篮将催化剂蜂窝引入到石英玻璃试管中。在催化前将气流电加热。对该测试而言,催化剂首先在该气体条件下在390℃下操作30min然后以每次20℃分步冷却。将各个温度保持8min并在7至8min之间测试产物组成。在250℃以下,冷却以每次5℃分步进行以能够或更加准确地测试特别是CO的起燃温度(CO转化率50%)。
在测试之后,使含10%水蒸气的空气以空速5000h-1流过催化剂并在该气体条件下在2h内加热至750℃(在整料中测试)。在这些条件下,使催化剂老化10h。然后重复上述测量。
图1显示了本发明催化剂和对比催化剂的CO转化率。表1显示了从图1中获得的起燃温度(50%CO转化率)。
表1:CO起燃温度(50%转化率)
实施例 | CO新鲜批次[℃] | CO老化批次[℃] |
实施例1 | 196 | 225 |
实施例2 | 189 | 224 |
对比例1 | 245 | 278 |
对比例2 | 191 | 233 |
对比例3 | 200 | 220 |
可以清楚地看出与本发明的催化剂相比,纯沸石催化剂显著更差,所述纯沸石催化剂因为用PtEA浸渍制备而无法避免在表面上也具有较大簇的Pt(对比例1)。
还可以看出在新鲜状态和老化之后,与常规市售DOC(参见实施例3)以及基于无定形Al/Si混合氧化物作为铂载体的现有技术DOC的再生状态(参见实施例2)相比,本发明的催化剂在CO起燃温度上具有可比性。另外,从实施例1和2的比较中可以看出,在反应前催化剂的还原在此不起作用。对本发明的催化剂而言通过在氧化气体混合物下于390℃下30min的测试条件而除去该效果。因此可以使用具有Pt(0)或氧化前体的催化剂。
图2和表2显示了这些催化剂NO2产率。高NO2产率对于结合在DOC下游的DPF的被动再生以及在SCR阶段的情况下在该DOC后对于氮氧化物还原是需要的。
表2:最大NO2产率
可以清楚地看出在老化后仅本发明的催化剂对于氧化NO成NO2仍然具有相对高的活性,并且NO2产率为37%和33%。
实施例7
在硫老化下的比较测试
已知的是Pt/Pd催化剂比纯铂催化剂更耐老化但另一方面对硫更敏感,在老化之后硫中毒的另一测试在老化之后进行。
出于此目的,如实施例6中所述,活性测试首先在从390℃降温进行,然后老化,并且然后如实施例6所述,在热老化之后再次测试。然后在250℃下以空速5000h-1引导20ppm SO2在空气中的气体混合物到催化剂上2h。然后再进行从390℃开始冷却的活性测试。然后通过经过1小时期间从150℃加热至750℃并在750下保持15min,将催化剂在具有10%水蒸气的空气下在5000h-1空速下再次脱硫。在该高温脱硫之后,如实施例6所述,新活性测试从390℃开始冷却而进行。
表3显示了不同催化剂的CO起燃温度:
表3:SO2老化之后的CO起燃温度
可以清楚地看出,此处本发明的催化剂表现非常类似于基于无定形Al/Si氧化物(对比例5)的现有技术的纯铂催化剂。Pt/Pd催化剂(对比例4)是基本上更加热稳定的。通过在制备期间在550℃下煅烧,仍然不形成最佳的Pt/Pd合金,因此催化剂实际上在750℃老化期间变得更好。还可以看出对于Pt/Pd催化剂和本发明的催化剂,硫中毒对于CO氧化基本上都是可逆的。然而,在考虑NO氧化时可以发现本发明的Pt催化剂的很好的优点。最大NO2产率显示在表4中。
表4:硫老化之后的NO氧化
可以清楚地看出,本发明的催化剂比纯铂催化剂(对比例5)表现出较低的热老化,但在该与硫无关的热老化之后保持不变。尽管Pt/Pd催化剂(对比例4)更为热稳定,但其甚至在剧烈热老化之后仍然被硫失活。尤其是,当用硫负载后将催化剂加热至高温时,其在脱硫过程中对于NO氧化极大地失活。从CO氧化再次提高的事实(表3,对比例4)可以看出脱硫反应实际上发生的事实。然而,在该脱硫过程期间,Pt/Pd催化剂对于NO氧化再次显著失活(最大NO2产率28%)。该失活在本发明催化剂的情况下没有发现,但是在实施中非常相关。如果在具有活性再生DPF体系中的DOC必须经常通过烧除烃产生高温用于DPF再生,则该失活是非常确定的。在再生之间的催化剂常规操作阶段中,催化剂通常在含SO2排气中在较低温度下(0-500℃)操作。每次活性再生意味着伴随非常高温度的温度上升并导致此处所述现有技术的Pt/Pd催化剂的失活,但不导致本发明催化剂的失活。
实施例8
Pt分布测试
为测试沸石中的Pt分布,采用IR光谱法。该方法基于在吸收1-氰基金刚烷之前和之后的Pt-C=O伸缩振动的比较。1-氰基金刚烷是空间高要求的分子,因为其大小,其不能渗透沸石体系的孔,因此,其选择性地结合于外表面的铂簇上。如果比较中毒之前和之后结合到Pt簇上的一氧化碳量,则可以测定Pt的分布。
测量过程:
由Pt沸石粉末制备约20mg模塑物。在测量前将该模塑在400℃下在高真空中(~10-7毫巴)干燥过夜。
在测量参考谱图之前,在样品上吸收20毫巴的一氧化碳。然后进行一氧化碳吸收总量的首次测量。(CO峰的积分)。中毒之前,为了释放一氧化碳,将样品重新在400℃下热处理,由此使得1-氰基金刚烷中毒可行。为了毒化,吸收2.5毫巴腈然后在计量的剂量下重新加入20毫巴CO。大约10min之后,测量对照谱图。
图3显示了在1-氰基金刚烷中毒之前和之后PSA-BEA和PtEA-Bea的IR谱图。
左边的谱图表示本发明的催化剂,右边的谱图则表示根据对比例1用六羟基铂酸乙醇铵制备的催化剂。本发明的催化剂在原始状态和中毒状态下都吸收大约相同量的一氧化碳。这表明铂不受腈影响并因此位于沸石内部(在孔中)。相反地,根据对比例1,用氰基金刚烷毒化的催化剂比未毒化的催化剂显然吸收较少的CO。这意味着,在两种沸石上的Pt分布是不同的并且和两种催化剂的活性和稳定性均相关。因此,显然将全部铂引入沸石内部的孔体系中是有利的。
不同的铂分布另外由XRD测量证明。本发明的催化剂谱图显示出无Pt折射,而对比例1的催化剂谱图则显示出清晰的折射。
Claims (18)
1.一种制备催化剂的方法,其中含铂沸石的制备包括如下步骤:
a)用亚硫酸铂溶液浸渍SiO2/Al2O3系数为5至300的沸石,
b)在保护气氛下煅烧浸渍的沸石;
其中将所述含铂沸石加工成载体涂料并施加到催化剂载体上,
其特征在于将铂仅施加到一种组分,沸石上。
2.根据权利要求1所述的制备催化剂的方法,其中所述煅烧在氩气、氦气、氖气或氮气气氛中进行。
3.根据权利要求1或2所述的制备催化剂的方法,其中所述煅烧在600至900℃的温度下进行。
4.根据权利要求1或2所述的制备催化剂的方法,其中在所述煅烧后进行还原。
5.根据权利要求4所述的制备催化剂的方法,其中用还原气体和惰性气体的混合物进行所述还原。
6.根据权利要求4所述的制备催化剂的方法,其中所述还原在3至7小时的周期内进行。
7.根据权利要求4所述的制备催化剂的方法,其中在200至500℃的温度下进行所述还原。
8.根据权利要求1或2所述的制备催化剂的方法,其中所述含铂沸石选自如下类型:AEL、BEA、CHA、EUO、FAU、FER、KFI、LTA、LTL、MAZ、MOR、MEL、MTW、LEV、OFF、TON和MFI。
9.使用根据权利要求1至8中的一项所述的方法制备的催化剂。
10.根据权利要求9所述的催化剂,其特征在于含铂沸石包含至少2wt%的铂,其中所述铂的至少90%位于所述含铂沸石的孔内。
11.根据权利要求9或10所述的催化剂,其特征在于所述铂的至少95%位于所述含铂沸石的孔内。
12.根据权利要求9或10所述的催化剂,其特征在于所述含铂沸石包含至少3wt%的铂。
13.根据权利要求9或10所述的催化剂,其中所述沸石选自如下类型:AEL、BEA、CHA、EUO、FAU、FER、KFI、LTA、LTL、MAZ、MOR、MEL、MTW、LEV、OFF、TON和MFI。
14.根据权利要求9或10所述的催化剂,其中所述沸石的SiO2/Al2O3系数为10至300。
15.根据权利要求9或10所述的催化剂,其中所述沸石为金属交换沸石。
16.根据权利要求9或10所述的催化剂,其中所述含铂沸石的特征在于Pt-C=O伸缩振动在2070至2110cm-1之间,和/或其中X-射线衍射谱图(XRD)不具有Pt反射。
17.根据权利要求16所述的催化剂,其中所述含铂沸石的特征在于Pt-C=O伸缩振动为2080至2095cm-1。
18.根据权利要求9至17中的一项所述的催化剂作为氧化催化剂和油气藏的用途。
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DE102009015592A DE102009015592A1 (de) | 2009-03-30 | 2009-03-30 | Alterungsstabiler Katalysator zur Oxidation von NO zu NO2 in Abgasströmen |
PCT/EP2010/054035 WO2010112431A1 (de) | 2009-03-30 | 2010-03-26 | Alterungsstabiler katalysator zur oxidation von no zu no2 in abgasströmen |
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PL2414079T3 (pl) | 2017-04-28 |
BRPI1015452A8 (pt) | 2017-10-10 |
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EP2414079A1 (de) | 2012-02-08 |
US10265689B2 (en) | 2019-04-23 |
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