CN101203584B - 用于fcc工艺的co氧化促进剂 - Google Patents
用于fcc工艺的co氧化促进剂 Download PDFInfo
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- CN101203584B CN101203584B CN2006800157251A CN200680015725A CN101203584B CN 101203584 B CN101203584 B CN 101203584B CN 2006800157251 A CN2006800157251 A CN 2006800157251A CN 200680015725 A CN200680015725 A CN 200680015725A CN 101203584 B CN101203584 B CN 101203584B
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Classifications
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Abstract
一种用于在FCC工艺期间促进CO氧化和使NOx排放最小化的组合物,其包含(i)酸性氧化物载体、(ii)用于促进CO氧化的至少一种贵金属、和(iii)能够在CO氧化期间减少NOx形成的金属或金属氧化物,至少一种贵金属(ii)被主要分布在颗粒添加剂的中心内部,和所述金属或金属氧化物(iii)被主要分布在所述颗粒添加剂中作为围绕所述贵金属的壳。
Description
发明领域
本发明涉及用于在FCC处理期间在无增加的NOx生成的情况下氧化CO的改进催化剂添加剂。
背景技术
一个主要的工业问题涉及开发减少空气污染物浓度的有效方法,这些污染物例如为在加工和燃烧含有硫、碳和氮的燃料所产生的废气流中的一氧化碳、硫氧化物和氮氧化物。在常规操作中经常遇到的硫氧化物、一氧化碳和氮氧化物浓度下,这些废气流向大气中的排放就环境而言是不希望的。在对含硫和氮的烃原料催化裂化中已被焦炭沉积物钝化的裂化催化剂的再生是可以导致含有相对高水平的一氧化碳、硫氧化物和氮氧化物的废气流的一个典型工艺实例。
重质石油馏分的催化裂化是在将原油转化成有用制品(诸如内燃机使用的燃料)中所采取的主要精炼操作之一。在流化催化裂化(FCC)工艺中,将高分子量的烃液体和蒸气与热的精细的固体催化剂颗粒在流化床反应器中或在延长的管道反应器中接触,并在升高的温度下保持处于流化或分散状态达足以实现所希望程度的向通常存在于发动机汽油和馏出燃料中的那种较低分子量烃类裂化的一段时间。
在烃类的催化裂化中,一些不挥发的含碳物质或焦炭被沉积在所述催化剂颗粒上。焦炭包含高度缩合的芳烃,和一般含有约4~约10wt%的氢。当所述烃原料包含有机硫和氮化合物时,所述焦炭也会含有硫和氮。由于焦炭积聚在所述裂化催化剂上,因此用于生产汽油调合料(gasolineblending stock)的催化剂的活性和选择性降低。从所述反应区中连续取出已经由于焦炭沉积而实质上被钝化的催化剂。该钝化催化剂被输送到气提区,在那里于升高的温度下以惰性气体除去挥发性的沉积物。然后通过在适合的再生过程中实质上除去所述焦炭沉积物而使得所述催化剂颗粒再活化基本上至其初始能力。然后将被再生的催化剂连续地返回到所述反应区以重复该循环。
催化剂再生通过用含氧气体如空气燃烧来自所述催化剂表面的焦炭沉积物而实现。这些焦炭沉积物的燃烧可以被以简化方式看作碳的氧化和所述产物是一氧化碳和二氧化碳。
来自再生器的烟道气中一氧化碳的高残留浓度从催化裂化工艺的一开始就是个问题。FCC的发展已经导致在FCC再生器中使用越来越高的温度以便获得所述再生催化剂中要求的低碳水平。通常,当不使用促进剂时,目前再生器现于约1100~1400的温度下操作,并会导致CO2/CO比率为36或更高、在完全燃烧装置(full burn unit)中直至0.5的烟道气。一氧化碳的氧化是强烈放热的,并可导致所谓的“一氧化碳迟燃”,这可能在稀催化剂相中、在旋风分离器中或在烟道气管线中发生。迟燃已经引起了对工厂设备的严重损害。另一方面,向大气排放的烟道气中未燃烧的一氧化碳代表燃料值损失并且就生态而言是不希望的。
对可以排放到大气中的一氧化碳量的限制和由一氧化碳的更加完全氧化带来的工艺优点已经激发了若干解决方案以提供在再生器中实现一氧化碳完全燃烧的手段。
建议用于在FCC再生中获得一氧化碳完全燃烧的方法包括(1)相对于标准再生而言增加引入再生器中的氧气量;和要么(2)提高再生器中的平均操作温度,要么(3)在所述裂化催化剂中包括不同的一氧化碳氧化促进剂以促进一氧化碳燃烧。对于一氧化碳迟燃的问题,也已经提出了多种解决方案,例如加入外来可燃物或使用水或热量接收固体以吸收一氧化碳的燃烧热。
应用于以完全燃烧模式操作的再生的处理方式的具体实例包括向所述催化剂中或向所述再生器中添加CO燃烧促进剂金属。例如,美国专利2,647,860提出向裂化催化剂中加入0.1~1wt%氧化铬以促进CO的燃烧。美国专利3,808,121教导在再生器内使用包含CO燃烧促进金属的相对大尺寸的颗粒。将所述小尺寸的催化剂在所述裂化反应器和所述催化剂再生器之间循环,而所述燃烧促进颗粒保留在所述再生器中。另外,美国专利4,072,600和4,093,535教导基于整个催化剂总量以0.01~50ppm的浓度在裂化催化剂中使用Pt、Pd、Ir、Rh、Os、Ru和Re,从而促进在完全燃烧装置(complete burn unit)中的CO燃烧。
在FCC装置的再生器中使用贵金属来催化一氧化碳的氧化已经获得广泛的商业认可。这种发展的部分历史在美国专利4,171,286和4,222,856中得到描述。在该发展的早期阶段,所述贵金属被沉积在裂化催化剂的颗粒上。目前的做法一般是提供含有贵金属的固体可流化颗粒形式的促进剂,所述颗粒与裂化催化剂颗粒在物理上是分开的。所述贵金属或其化合物被担载在合适载体物质的颗粒上,和所述促进剂颗粒通常与裂化催化剂颗粒分开被引入所述再生器中。在裂化/气提/再生循环期间,不将所述促进剂颗粒作为细料从该体系中除去,而将其与裂化催化剂颗粒一起共循环。通过控制(较热的)稀相、旋风分离器或烟道气管线与密相之间的温度差异ΔT的能力来评价促进剂的CO燃烧效率。大多数FCC装置现在使用Pt CO燃烧促进剂。尽管燃烧促进剂如铂的使用可减少CO排放,但是这种CO排放的减少通常伴随着再生器烟道气中氮氧化物(NOx)的增加。
商业上用于FCC装置中的促进剂制品包括经煅烧、喷雾干燥的、以少量(例如100~1500ppm)铂浸渍的高岭土多孔微球体。参见(上述)美国专利4,171,286。大多数商业上使用的促进剂通过将铂源浸渍到高纯度多孔氧化铝、通常是γ-氧化铝的微球体上而获得。选择铂作为多种商业制品中的贵金属似乎反映出对这种金属的优先选择,这与现有技术的公开一致,该公开认为对于FCC再生器中的一氧化碳氧化促进作用来说,铂是最有效的VIII族金属。参见例如美国专利4,107,032中的图3以及美国专利4,350,614中同样的图。该图说明了不同贵金属促进剂物种的浓度从0.5ppm提高到10ppm对CO2/CO比率的影响。
美国专利4,608,357教导了当将钯担载在特定形式的二氧化硅-氧化铝(即沥滤过的莫来石)的颗粒上时,在例如那些常见于FCC装置的再生器中的条件下,在促进将一氧化碳氧化成二氧化碳方面钯异乎寻常地有效。所述钯可以是所述促进剂中唯一具有催化活性的金属组分,或者它可以与其他金属如铂混合。
美国专利5,164,072和5,110,780涉及具有在La-稳定化的氧化铝上的Pt的FCC CO促进剂,优选约4-8wt%的La2O3。它公开了二氧化铈“必须被排除”。在第3栏中,它公开了“在足够量的La2O3存在下,例如约6-8%、2%的Ce是没有用的。如果La2O3的量较少则实际上是有害的。”在示例性的实例中,’072和’780证明8%Ce对于担载在γ-氧化铝上的铂的CO促进作用的不利影响以及La的积极影响。
当在催化裂化工艺中使用含硫和氮的原料时,沉积在所述催化剂上的焦炭含有硫和氮。在结焦的钝化催化剂的再生过程中,所述焦炭从该催化剂表面被燃烧掉,这于是导致一部分所述硫和氮分别转化成硫氧化物和氮氧化物。
不幸的是,活性更高的燃烧促进剂如铂和钯也会用来促进再生区中氮氧化物的形成。已有报道现有技术CO促进剂的使用会导致NOx的急剧增加(例如>300%)。在催化剂再生器中难以完全燃烧焦炭和CO而不使再生器烟道气的NOx含量增加。由于将氮氧化物排放到大气中是环境上不利的,因此这些促进剂的使用具有用一种不希望的排放替代另一种不希望的排放的效果。许多管辖区域限制可存在于排放到大气中的烟道气流中的NOx量。为了响应环境方面的关注,已经在寻找减少NOx排放的途径方面付出了诸多努力。
已经使用多种方法来减少NOx的形成或在其形成后进行处理。最典型的是,使用添加剂作为FCC催化剂颗粒的组成部分(integral part)或作为与FCC催化剂混合的单独颗粒。
已经开发出将起到CO促进作用和同时控制NOx排放的多种添加剂。
美国专利4,350,614、4,072,600和4,088,568提及将稀土添加到Pt基CO促进剂中。一个实例是显示出一些优点的4%REO。不存在有关REO对降低来自FCCU的NOx排放的任何影响的教导。
美国专利4,199,435教导了无机载体上的选自Pt、Pd、Ir、Os、Ru、Rh、Re和铜的燃烧促进剂。
美国专利4,290,878教导了Pt--Ir和Pt--Rh双金属促进剂,其与常规Pt促进剂相比可减少NOx。
美国专利4,300,997教导了Pd-Ru促进剂在CO氧化中的用途,该促进剂没有导致过度的NOx形成。
美国专利4,544,645描述了Pd与除Ru以外每一种其他VIII族金属组成的双金属。
W.R.Grace的美国专利6,165,933和6,358,881描述了包含下述组分的组合物以在FCC工艺中促进CO燃烧并同时使NOx的形成最小化,该组分含有(i)酸性氧化物载体、(ii)碱金属和/或碱土金属或其混合物、(iii)具有氧储存能力的过渡金属氧化物、和(iv)钯。
美国专利6,117,813教导由VIII族过渡金属氧化物、IIIB族过渡金属氧化物和IIA族金属氧化物构成的CO促进剂。
然而,仍然需要在FCC工艺中具有NOx排放控制作用的改进CO氧化促进剂。
发明概述
本发明提供了适用于FCC工艺中的新型组合物,该组合物能够提供改进的CO氧化促进活性连同NOx排放控制作用。
一方面,本发明提供了用于在FCC工艺中促进CO氧化的组合物,所述组合物包含(i)酸性氧化物载体、(ii)二氧化铈、(iii)除二氧化铈以外镧系元素的至少一种氧化物、(iv)任选的选自周期表Ib族和IIb族的过渡金属的至少一种氧化物和(v)至少一种贵金属。所述酸性氧化物载体优选包含氧化铝。氧化镨是优选的除二氧化铈以外的镧系元素氧化物。Cu和Ag是优选的Ib族过渡金属和Zn是优选的IIb族过渡金属。
另一方面,本发明包括使用本发明的CO氧化促进组合物的FCC工艺,所述组合物作为所述FCC催化剂颗粒的组成部分或者作为与所述FCC催化剂混合的单独颗粒。与现有技术的CO氧化促进剂相比,所述组合物可提供更低的NOx排放。
在本发明的另一方面中,通过将用于促进CO氧化的铂族金属和用于分解NOx的金属组分引入单一颗粒中而提供用于CO氧化的添加剂,其中所述铂族金属和其他金属被分布在所述颗粒的分开区域中以实现在NOx减少方面的改进。
以下进一步详细描述本发明的这些和其他方面。
附图简述
图1是说明CO氧化促进剂和NOx分解组分分布的本发明添加剂的图示描述。
发明详述
一方面,本发明包括发现某些类型的组合物对于FCC工艺中氧化CO和减少NOx气体排放这两者都非常有效。本发明的CO氧化组合物的特征在于它们包含(i)酸性氧化物载体、(ii)二氧化铈、(iii)除二氧化铈以外镧系元素的至少一种氧化物、(iv)任选的选自周期表Ib族和IIb族的过渡金属的至少一种氧化物和(v)至少一种贵金属。
所述酸性氧化物应该具有足够的酸性,使得所述组合物充当用于CO氧化促进有效的添加剂。酸性氧化物催化剂载体对本领域的技术人员来说是公知的,包括例如过渡氧化铝如γ和η氧化铝,所述氧化铝的二氧化硅稳定化形式,包括二氧化硅稳定化的氧化铝尖晶石,其通过从被煅烧经其特征放热而形成尖晶石或莫来石的高岭土沥滤二氧化硅而形成。所述载体可以是结晶的或无定形的。优选地,所述酸性氧化物载体含有至少一些氧化铝。更优选地,所述氧化物载体含有至少50wt%氧化铝。所述氧化物载体优选是选自氧化铝和二氧化硅-氧化铝的氧化物。当使用无定形的二氧化硅-氧化铝载体时,该载体优选具有约1∶1直至约50∶1的氧化铝与二氧化硅的摩尔比。市售酸性氧化物氧化铝载体的实例可以以诸如PURALOX、CATAPAL和VERSAL等商品名得到。市售酸性二氧化硅-氧化铝载体的实例可以以诸如SIRAL和SIRALOX等商品名得到。
可以任选地通过从预制高岭土微球体中将二氧化硅苛性沥滤而制得所述二氧化硅-氧化铝载体,如美国专利4,847,225和4,628,042中所述,因此对于其在此方面的教导通过引用并入本文。优选地,将经受苛性沥滤的高岭土煅烧实质上通过其特征放热以形成尖晶石和/或莫来石。更优选地,该苛性沥滤的高岭土载体是微球体,由此在将其煅烧通过所述放热之前使得所述苛性沥滤的高岭土与羟基氯化铝(aluminum chlorohydroxide)结合。
所述酸性氧化物载体进一步优选具有足够的表面积以促进CO氧化和控制。优选地,所述氧化物载体的表面积为至少约20m2/g,更优选从约50m2/g直至约300m2/g。当用作FCC催化剂的组成部分或者微球体或颗粒时,优选当用作与FCC催化剂的混合物时,所述酸性氧化物载体可优选为粉末。
存在于本发明添加剂组合物中的二氧化铈的量可以相对于所述酸性氧化物载体的量显著地变化。优选地,所述添加剂组合物包含以每100重量份酸性氧化物载体物质计至少约0.5重量份二氧化铈,更优选以每100重量份酸性氧化物载体物质计至少约1重量份直至约25重量份二氧化铈。
除二氧化铈以外的镧系元素氧化物包括除二氧化铈以外的镧系元素的至少一种金属氧化物。优选地,所述除二氧化铈以外的镧系元素氧化物为氧化镨。所述添加剂组合物中的除二氧化铈以外的镧系元素氧化物的量可以相对于所述酸性氧化物载体的量显著地变化。优选地,相对于该组合物中存在的二氧化铈,所述添加剂组合物包含较少量的除二氧化铈以外的镧系元素氧化物。通常,存在于本发明添加剂组合物中的二氧化铈相当于除二氧化铈以外的镧系元素氧化物的量以重量计是5∶1~20∶1,优选5∶1~10∶1。
所述Ib和/或IIb族过渡金属可以是选自周期表那些族中的任何金属或金属组合。优选地,所述过渡金属选自Cu、Ag、Zn及其混合物。过渡金属的存在量优选为以每百万份氧化物载体物质计至少约100重量份(按金属氧化物计),更优选以每100份氧化物载体物质计约0.1直至约5重量份。
贵金属的量可以根据所希望的CO燃烧促进水平而显著改变。贵金属的典型含量可以是整个添加剂和/或催化剂的50-1500ppm。如本文所用的,所述贵金属包括选自Pt、Pd、Ir、Os、Ru、Rh、Re以及它们的前体如盐和胺络合物及其混合物的那些,优选该贵金属是Pt、Pd或其混合物。
所述添加剂组合物可以包含少量的其他物质,其优选不会显著地对CO氧化或NOx控制功能产生不利影响。本文提及的NOx控制通常是指减少来自FCC工艺的NOx排放,然而在本发明中可以考虑其他类型的控制,包括例如在其中预期增加的NOx排放的FCC装置中保持NOx排放水平。所述添加剂组合物可以基本上由上述第(i)-(v)项组成,第(iv)项是任选的。当本发明的组合物用作FCC工艺用的添加剂颗粒时(与将它们并入FCC催化剂颗粒本身中相反),所述添加剂组合物可以与填料(例如粘土、二氧化硅-氧化铝、二氧化硅和/或氧化铝颗粒)和/或粘结剂(例如硅溶胶、氧化铝溶胶、二氧化硅氧化铝溶胶等)组合以形成适合用于FCC工艺中的颗粒,优选在煅烧步骤前通过喷雾干燥形成。更优选地,由酸性氧化物载体形成多孔颗粒,也称为微球体,其通常通过在以个体成分沥滤之前或之后将与粘结剂/填料结合的粉末氧化物载体物质喷雾干燥而形成。优选地,任何所添加的粘结剂或所用的填料不会显著地对所述添加剂组分的性能产生不利影响。
当所述添加剂组合物用作添加剂颗粒时(与将它们并入FCC催化剂颗粒本身中相反),所述添加剂颗粒中的添加剂组分的量优选为至少50wt%,更优选为至少75wt%。最优选地,所述添加剂颗粒完全由所述添加剂组分组成。所述添加剂颗粒优选具有适合与FCC工艺中的催化剂投料量一起循环的尺寸。优选地,所述添加剂颗粒的平均粒度为约20-200μm。优选添加剂颗粒具有的磨损特性使得它们可以耐受FCCU的严峻环境。
如前面所提及的,本发明的添加剂组合物可以被并入FCC催化剂颗粒本身中。在这种情形中,可以将任何常规的FCC催化剂颗粒组分与本发明的添加剂组合物组合使用。如果被并入FCC催化剂颗粒中,本发明的添加剂组合物优选占该FCC催化剂颗粒的至少约0.02wt%。
尽管本发明不限于任何特定的制造方法,但是本发明的添加剂组合物可以通过下列过程制造:
(a)将所述酸性氧化物载体颗粒与二氧化铈源、除二氧化铈以外的至少一种镧系元素氧化物源和任选的Ib/IIb族元素的至少一种来源共浸渍,
(b)煅烧步骤(a)的经过浸渍的载体,
(c)将步骤(b)中形成的物质用所希望水平和所选择的贵金属或前体盐或络合物进行浸渍,
(d)任选地再煅烧来自步骤(c)的经过浸渍的添加剂。
所述氧化物源优选为金属氧化物本身或煅烧时分解成氧化物的相应金属的盐、或者氧化物和盐组合的浆料、溶胶和/或溶液。希望的话,可以将个体成分单独加入到所述载体颗粒中,每次添加之间进行煅烧步骤。所述煅烧步骤优选在约450-750℃下进行。
所述添加剂组合物可以被用作单独的添加剂颗粒或作为FCC催化剂颗粒的组成部分。如果用作添加剂,所述添加剂组分可以自身成型为适合用于FCC工艺中的颗粒。作为选择,所述添加剂组分可以与粘结剂、填料等通过任何常规技术结合。参见例如在美国专利5,194,413中所述的方法,其所公开的内容通过引用并入本文。
在将本发明的添加剂组分并入FCC催化剂颗粒中的情况下,优选首先形成该组分,然后将其与构成FCC催化剂颗粒的其他成分结合。可以通过任何已知的技术将所述添加剂组合物直接并入FCC催化剂颗粒中。适合于这一目的的技术的实例在美国专利3,957,689;4,499,197;4,542,188和4,458,623中得到描述,其公开内容通过引用并入本文。
本发明的组合物通常不含碱金属和/或碱土金属。不存在碱金属和/或碱土金属的量应当是指小于约1%、优选小于约0.5%、更优选小于约0.1%的碱金属和碱土金属存在于本发明的添加剂组合物中。在本发明的另一方面中,碱金属和/或碱土金属可以存在于本发明的添加剂组合物中,只要这些金属适当地分布在所述添加剂颗粒中,如以下进一步说明的那样。
本发明的组合物可以用于任何常规的FCC工艺中。典型的FCC工艺是在450-650℃的反应温度和600-850℃的催化剂再生温度下进行的。本发明的组合物可以用于任何典型烃原料的FCC工艺中。优选地,本发明的组合物被用于包括对含有高于平均量氮的烃原料、尤其是氮含量为至少0.1wt%的原料或残留原料进行裂化的FCC工艺中。所用的本发明添加剂组分的量可以根据特定的FCC工艺而改变。优选地,基于在循环催化剂投料量中的FCC催化剂的重量,所用的添加剂组分的量(在循环投料量中)为约0.05-15wt%。在FCC工艺催化剂再生步骤期间,本发明组合物的存在有效地促进CO的氧化,同时也使得NOx形成的最终水平最小化。
在本发明的另一方面中,用于并入FCC工艺的颗粒添加剂被描述成具有贵金属的规定分布以使得在促进一氧化碳的氧化并同时使NOx形成最小化方面有效。本发明这一方面的添加剂基于以下思想:使所述贵金属CO氧化促进剂分布在所述颗粒添加剂的中心和使发现在分解NOx方面有用的任何金属或金属氧化物分布遍及该颗粒。本发明添加剂的图示显示在图1中。如图1所示,多孔的颗粒添加剂10将包含诸如前面所述的标记为“Pt”的贵金属,其主要分布在添加剂10的中心12。根据本发明理论化的是,主要分布在多孔添加剂10的中心区域12中的贵金属如Pt、Pd、Ir、Os、Ru、Rh和/或Re将能够促进CO氧化成CO2。然而,如先前所述,上述铂族金属不仅促进CO氧化成CO2,而且通常形成显著量的NOx。根据本发明,围绕着所述贵金属的中心分布12和甚至分布穿过该中心分布12的是标记为“NOx”的金属或金属氧化物,其已知与所述贵金属一起合作用于分解NOx。图1中描绘的是壳14,其可以包含大比例的这些用于分解NOx的其他金属或金属氧化物。
例如,壳分布14和甚至中心分布12可以包括二氧化铈以及如上所述的除二氧化铈以外的镧系金属氧化物,例如氧化镨,或其他稀土氧化物。另外被引入遍及颗粒10(包括壳分布14在内)的是选自周期表Ib和IIb族的过渡金属的至少一种氧化物,如前所述。所述NOx分解组分可以作为选择地包含碱金属或碱土金属和过渡金属氧化物,如前面提及的W.R.Grace专利中所述的。上述美国专利6,165,933和6,358,881的全部内容通过引用并入本文。另外,除了所述中心分布12中所含的贵金属以外的贵金属可以被引入遍及颗粒10。因而,在包括前述专利在内的现有技术中,已知双金属的贵金属CO氧化促进剂也可以分解NOx。再次参照图1,据认为添加剂10中通过贵金属形成的任何NOx组分现将被导向该颗粒的外部表面,和将会被捕获或甚至另外被分解成氮,例如在含有已知与贵金属合作用于分解NOx的金属或金属氧化物组分的壳分布14中。据认为图1所示的分布使得由贵金属促进CO氧化期间NOx的形成最小化。据理解在中心分布12中的贵金属与壳分布14中的其他金属或金属氧化物之间的细微分离可以不存在。在NOx分解组分与中心12之间存在一些重叠是可能和优选的。然而,通常贵金属的主要分布将在该多孔颗粒基体的极靠内部处,而其他金属或金属氧化物将被主要分布在所述颗粒外部表面附近。
为实现金属催化组分如图1所示的在本发明添加剂中的期望分布,本发明可以使用任何已知方法。在一种这样的方法中,可以首先用所述贵金属浸渍所述多孔基体。当浸渍和煅烧以活化该金属时,然后可以以另外的氧化物涂布所述载体,其可以接着以所述NOx分解金属浸渍。可以作为选择地将该NOx分解金属混合或浸渍入所述涂布组合物中。该方法在美国专利5,935,889中得到描述,其全部内容通过引用并入本文。在该方法中,随后以一个或多个递增壳层涂布所述贵金属的中心分布,所述壳层可以包含一种或多种所述NOx分解金属,其围绕着所述中心贵金属分布。可以通过使用流化床涂布技术的沉积方法形成所述壳层,该技术包括反复施加和干燥少量含有所述壳层物质的浆料,其中该浆料呈胶体分散体或溶胶或非常微细的颗粒形式。
另外已知形成“蛋黄(egg yolk)”催化剂分布,其中催化剂组分在这种情况下是贵金属,并集中在所述颗粒中心处。所述方法包括用贵金属溶液或络合物单独地或与共浸渍剂一起浸渍该颗粒。已知通过该颗粒的液体对流可能受到特定干燥模式影响,所述干燥模式可以将金属有效地分布到所期望的多孔颗粒内部。随后的浸渍可以将一种或多种另外的金属分布在所述多孔载体的外部表面上。不同干燥工艺对催化剂分布的影响在“Predicting the Effect of Drying on Supported CoimpregnationCatalysts”,Lekhal等,Ind.Eng.Chem.Res.2001,40,第3989-3999页中有述。该论文的全部内容也通过引用并入本文。
铂族金属的内部分布也已知通过用铂族盐和与所述铂族盐竞争吸附在所述多孔载体内的酸浸渍多孔载体如氧化铝而实现。例如,可以使高表面积的多孔载体与所述活性组分的液体溶液接触。所述活性组分通过毛细管作用和扩散而进入该多孔载体并吸附在可以利用的表面位点上。当仅用六氯铂酸浸渍氧化铝载体时,已发现所得的催化剂形态通常为“蛋壳”型的,即所述铂位于载体表面处的薄壳中。已知通过将所述六氯铂酸与诸如HCl或柠檬酸的酸共浸渍,可以使得所述铂分布更加均匀或使其分布在催化剂的中心,其中所述铂现在处于次表面带中或在所述多孔基体的中心内。为了改变所述铂组分的分布已经研究了其他共浸渍剂。根据共浸渍剂的相对扩散和吸附强度,可以将活性组分“推”到所述颗粒内部。这类方法的综述在 “Preparation of Pt/Gamma-Al2O3 Pellets with InternalStep-Distribution of Catalyst:Experiments and Theory”,Papageorgiou等,Journal of Catalysis 158,1996,第439-451页,和“Catalysis:AnIntegrated Approach,Second,revised and enlarged eddition”,NetherlandsInstitute for Catalysis Research,1999,第10章中有述,其全部内容通过引用并入本文。
下面的实施例举例说明本发明的实施方案,并非旨在限制由构成本申请一部分的权利要求所包括的发明内容。
实施例1
2%Pr6O11/10%CeO2/2%CuO/氧化铝
实施例2
3%Pr6O11/18%CeO2/0.5%CuO/氧化铝
实施例3
2%Pr6O11/10%CeO2/氧化铝
实施例4
从单乙醇胺络合物的水溶液将铂浸渍到实施例1中制得的产物上直至500ppm的含量。将干燥过的物质在1200下煅烧2小时。
实施例5
实施例6
实施例7
实施例8
实施例9
比较例
例A
氧化铝上500ppm Pt
例B
氧化铝上500ppm Pd
CO氧化测试
通过在100%蒸汽中于1500下对添加剂与FCC催化剂的50/50共混物仅蒸汽加工4小时而使得被测试的添加剂钝化。使用化学标记物以确保在蒸汽加工后保留所述共混组合物。在1100下用具有5%CO/3%O2/5%CO2/余量N2的气流在流化床中进行CO氧化测试。通过改变供入所述流化床反应器的添加剂来获得不同的CO转化率。活性定义为-ln(1-x)对时空关系的斜率,其中x为CO的转化率。CO氧化活性测试的数据示于表1中。
表1
活性 | |
实施例5 | 59 |
比较例A | 55 |
表1的结果表明具有相当贵金属负载量的本发明的添加剂组合物比现有技术的物质具有更好的CO氧化促进活性。
NOx减少
使用固定流化床实验室反应器。通过在100%蒸气中于1500下对所述添加剂进行蒸汽加工4小时而使其钝化。将包含0.2wt%所述添加剂与低金属ECAT的共混物用于测试。通过裂化瓦斯油,使焦炭沉积在该共混物上。将用过的催化剂于1300下在空气中再生。来自所得烟道气的NOx排放通过化学发光的手段来确定。在恒定焦炭的情况下给出NOx排放。NOx减少的典型结果如表2所示。
表2
NOx减少(%) | |
比较例A | 基准 |
实施例5 | 17 |
实施例6 | 28 |
表2的结果表明,与现有技术的添加剂相比,本发明的添加剂组合物可减少NOx排放。
实施例10
形成上述实施例1中所述的添加剂。煅烧后,用氯铂酸和柠檬酸的混合物浸渍该颗粒添加剂。氯铂酸的用量使得在添加剂中提供300ppm Pt。柠檬酸用量明显更大,提供柠檬酸从而与颗粒的全部表面羟基反应以便提高氯铂酸向颗粒内部和中心区域的扩散。将干燥过的物质在1200下煅烧2小时以产生颗粒添加剂,其包含铂和Pr6O11的中心分布,而CeO2和CuO被主要分布围绕该中心分布。
Claims (10)
1. 一种适合于在流化催化裂化工艺中的催化剂再生期间促进CO氧化的添加剂颗粒组合物,所述组合物包含(i)颗粒酸性氧化物载体,(ii)用于促进CO氧化的至少一种贵金属,和(iii)能够分解NOx的金属或金属氧化物,所述至少一种贵金属(ii)被主要分布在所述颗粒添加剂的中心内部,所述金属或金属氧化物(iii)被主要分布遍及所述颗粒添加剂,包括作为围绕所述至少一种贵金属的壳在内。
2. 权利要求1的组合物,其中所述酸性氧化物载体选自氧化铝和二氧化硅-氧化铝。
3. 权利要求1的组合物,其中所述金属或金属氧化物(iii)包含二氧化铈和除二氧化铈以外的镧系元素的至少一种氧化物。
4. 权利要求3的组合物,其中所述金属或金属氧化物(iii)进一步包括选自铜、银、锌和其混合物的Ib和IIb族过渡金属。
5. 一种流化裂化催化剂组合物,其包含(a)适合于催化所述烃类裂化的裂化组分,和(b)颗粒添加剂组合物,所述添加剂组合物包含(i)酸性氧化物载体、(ii)用于促进CO氧化的至少一种贵金属、和(iii)能够分解NOx的金属或金属氧化物,所述至少一种贵金属(ii)被主要分布在所述颗粒添加剂的中心内部,所述金属或金属氧化物(iii)被主要分布遍及所述颗粒添加剂,包括作为围绕所述至少一种贵金属的壳在内,所述添加剂组合物是与所述催化剂组分分开的颗粒和以足够的减少CO排放的量存在于所述裂化催化剂中。
6. 权利要求5的裂化催化剂组合物,其中所述添加剂组分(b)占所述裂化催化剂组合物的约0.05-15wt%。
7. 权利要求5的裂化催化剂组合物,其中所述金属或金属氧化物(iii)包含二氧化铈和除二氧化铈以外的镧系元素的至少一种氧化物。
8. 权利要求7的裂化催化剂组合物,其中所述除二氧化铈以外的镧系元素的氧化物是氧化镨。
9. 一种在将烃原料流化催化裂化成较低分子量组分期间促进CO氧化的方法,所述方法包括于升高的温度下将烃原料与适合于催化所述烃类裂化的裂化催化剂接触,由此在颗粒CO氧化促进组合物的存在下形成较低分子量的烃组分,其中所述颗粒组合物包含(i)酸性氧化物载体、(ii)用于促进CO氧化的至少一种贵金属、和(iii)能够分解NOx的金属或金属氧化物,所述至少一种贵金属(ii)被主要分布在所述颗粒组合物的中心内部,所述金属或金属氧化物(iii)被主要分布遍及所述颗粒组合物,包括作为围绕所述至少一种贵金属的壳在内,所述CO减少组合物以足以减少所述CO排放的量存在。
10. 权利要求9的方法,其中在与烃原料接触期间所述裂化催化剂是流化的。
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US60/659,821 | 2005-03-09 | ||
US11/366,651 | 2006-03-02 | ||
US11/366,651 US7959792B2 (en) | 2005-03-09 | 2006-03-02 | CO oxidation promoters for use in FCC processes |
PCT/US2006/007731 WO2006098914A1 (en) | 2005-03-09 | 2006-03-03 | Co oxidation promoters for use in fcc processes |
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CN (1) | CN101203584B (zh) |
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WO2008148683A1 (en) * | 2007-06-08 | 2008-12-11 | Albemarle Netherlands, B.V. | Fcc co oxidation promoters |
US11208514B2 (en) | 2008-03-20 | 2021-12-28 | Chevron Phillips Chemical Company Lp | Silica-coated alumina activator-supports for metallocene catalyst compositions |
US7884163B2 (en) | 2008-03-20 | 2011-02-08 | Chevron Phillips Chemical Company Lp | Silica-coated alumina activator-supports for metallocene catalyst compositions |
US7959892B2 (en) * | 2008-06-18 | 2011-06-14 | Praxair Technology, Inc. | Reduction of CO and NOx in full burn regenerator flue gas |
US9533286B2 (en) * | 2012-08-21 | 2017-01-03 | Toyota Motor Engineering & Manufacturing North America, Inc. | Sinter resistant catalytic material and process of producing the same |
WO2015004530A2 (en) * | 2013-07-11 | 2015-01-15 | Sabic Global Technologies B.V. | Use of lanthanide oxides to reduce sintering of catalysts |
US9943836B2 (en) * | 2013-10-22 | 2018-04-17 | China Petroleum & Chemical Corporation | Metal modified Y zeolite, its preparation and use |
IN2013MU04120A (zh) | 2013-12-30 | 2015-08-07 | Indian Oil Corp Ltd | |
US9868111B2 (en) | 2016-02-27 | 2018-01-16 | Toyota Motor Engineering & Manufacturing North America, Inc. | Catalyst for direct NOx decomposition and a method of forming and using the catalyst |
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WO2019195088A2 (en) * | 2018-04-02 | 2019-10-10 | Cochise Technology, Llc | A co to co2 combustion promoter |
CN113262606A (zh) * | 2021-03-17 | 2021-08-17 | 中煤科工集团沈阳研究院有限公司 | 一种煤矿用一氧化碳复合抑制吸收剂及其制备方法 |
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US7959792B2 (en) | 2011-06-14 |
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EP1879982A1 (en) | 2008-01-23 |
EP1879982B1 (en) | 2009-12-09 |
US20060204420A1 (en) | 2006-09-14 |
TWI398509B (zh) | 2013-06-11 |
DK1879982T3 (da) | 2010-03-29 |
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WO2006098914A1 (en) | 2006-09-21 |
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