CN106362735A - 用于蒸汽重整过程的催化剂 - Google Patents
用于蒸汽重整过程的催化剂 Download PDFInfo
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- CN106362735A CN106362735A CN201610632879.0A CN201610632879A CN106362735A CN 106362735 A CN106362735 A CN 106362735A CN 201610632879 A CN201610632879 A CN 201610632879A CN 106362735 A CN106362735 A CN 106362735A
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Classifications
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Abstract
描述了一种制备适用于蒸汽重整过程的催化剂的方法,包括以下步骤:(i)喷涂含有颗粒催化剂化合物的浆料至平盘涂布机中的成型载体的表面上以形成表层中具有催化金属的涂覆的成型载体材料,所述催化剂化合物包含一种或多种选自Ni、Cu、Pt、Pd、Rh、Ru和Au组成的组的催化金属,(ii)干燥和任选煅烧涂覆的成型载体材料以形成催化剂前体,和(iii)任选地还原催化剂前体中的一种或多种金属至较低氧化态以形成催化剂。蛋‑壳催化剂用于进行蒸汽重整反应。
Description
本申请是基于申请号为201280008945.7、申请日为2012年2月6日、发明名称为“用于蒸汽重整过程的催化剂”的中国专利申请的分案申请。
本发明涉及一种制备适用于蒸汽重整过程的负载型催化剂的方法。
蒸汽重整是公认的,由此使烃类原料如天然气或石脑油,或甲醇,与蒸汽在升高的温度和压力下反应,以生成被称为合成气的含氢气体混合物。用于烃类蒸汽重整的催化剂一般基于将镍催化剂直接负载于成型的耐火金属氧化物载体上,如铝酸钙或铝酸镁或α-氧化铝。在较小规模的蒸汽重整过程中,例如在用于燃料电池的氢气混合物的生产中,或在从生物质生成生物合成气中,可以采用贵金属催化剂如Rh或Pt催化剂。对于甲醇蒸汽重整,可使用Cu或Pd催化剂。
这些催化剂一般通过如下制备:浸渍/煅烧技术,由此将活性金属作为水溶液(通常是金属硝酸盐的水溶液)施用到多孔载体上,然后经煅烧使金属硝酸盐转化为相应的金属氧化物。使用前,还原金属氧化物,一般用含氢气体以生成活性催化剂。浸渍技术已广泛使用,但需要更有效地利用催化活性金属,为了最小化生产成本和减少源自硝酸盐基催化剂的NOx排放量。
现已发现替代的方法,该方法克服了以前制备路线的问题。
因此,本发明提供了一种制备适用于蒸汽重整过程的催化剂的方法,包括以下步骤:
(i)喷涂含有颗粒催化剂化合物的浆料至在平盘涂布机中的成型载体的表面上以形成涂覆的成型载体材料,所述催化剂化合物包含一种或多种选自Ni、Cu、Pt、Pd、Rh、Ru和Au组成的组的催化金属,
(ii)干燥和任选煅烧涂覆的成型载体材料以形成在表层具有催化金属的催化剂前体,和
(iii)任选地还原催化剂前体中的一种或多种金属至较低氧化态以形成催化剂。
本发明进一步提供通过上述方法可获得的的催化剂以及将这样的催化剂用于进行催化蒸汽重整反应的用途。
本发明提供了一种生产特别适合于孔隙-扩散-限制的反应如蒸汽重整反应的涂覆催化剂的方法。
本发明的实施方案包括:
1、一种制备适用于蒸汽重整过程的催化剂的方法,包括以下步骤:
(i)喷涂含有颗粒催化剂化合物的浆料至平盘涂布机中的成型载体的表面上以形成表层中具有催化金属的涂覆的成型载体材料,所述催化剂化合物包含一种或多种选自Ni、Cu、Pt、Pd、Rh、Ru和Au组成的组的催化金属,
(ii)干燥和任选煅烧涂覆的成型载体材料以形成催化剂前体,和
(iii)任选地还原催化剂前体中的一种或多种金属至较低氧化态以形成催化剂。
2、根据实施方案1的方法,其中颗粒催化剂化合物中的催化金属包括Ni,和任选Pt、Pd、Rh、Ru和Au的一种或多种。
3、根据实施方案1的方法,其中颗粒催化剂化合物中的催化金属包括Pt,以及任选Pd、Rh、Ru和Au中的一种或多种,优选Pt和Rh。
4、根据实施方案1的方法,其中颗粒催化剂化合物中的催化金属由Rh组成。
5、根据实施方案1至4任一实施方案的方法,其中颗粒催化剂化合物包含催化活性金属的氧化物、氢氧化物或碳酸盐。
6、根据实施方案1至5任一实施方案的方法,其中颗粒催化剂化合物包括分散在颗粒催化剂载体材料的表面上的一种或多种选自Ni、Cu、Pt、Pd、Rh、Ru和Au组成的组的金属。
7、根据实施方案6的方法,其中颗粒催化剂载体材料选自氧化铝、二氧化钛或氧化锆、氧化锌、氧化镧、氧化镁、氧化铈、金属铝酸盐及其混合物组成的组。
8、根据实施方案6或实施方案7的方法,其中颗粒催化剂载体材料包括氧化铝和/或稳定的氧化锆。
9、根据实施方案1至8任一实施方案的方法,其中在成型载体与催化表层之间施加一层或多层中间层。
10、根据实施方案1至9任一实施方案的方法,其中成型载体包括挤出物、丸粒或颗粒。
11、根据实施方案1至10任一实施方案的方法,其中成型载体长度为1mm至50mm,横截面宽度或直径为1mm至25mm。
12、根据实施方案1至11任一实施方案的方法,其中成型载体单元为多孔-丸粒或挤出物,其横截面为圆形、叶形或槽形。
13、根据实施方案1至12任一实施方案的方法,其中成型载体为耐火氧化物,包括选自氧化铝、氧化铈、氧化镁、二氧化钛或氧化锆、铝酸钙或铝酸镁、及其混合物组成的组的载体氧化物。
14、根据实施方案1至13任一实施方案的方法,其中成型载体为铝酸钙或铝酸镁或α-氧化铝。
15、根据实施方案1至14任一实施方案的方法,其中在30-60℃温度范围内涂覆载体。
16、根据实施方案1至15任一实施方案的方法,其中浆料的固体含量在1-60wt%范围内。
17、根据实施方案1至16任一实施方案的方法,其中干燥材料中含有催化活性金属的涂层的厚度在5至250μm范围内。
18、根据实施方案1至17任一实施方案的方法,其中浆料中含有聚乙烯接枝共聚物。
19、根据实施方案1至18任一实施方案的方法,其中对干燥的涂覆载体材料进行煅烧。
20、根据实施方案1至19任一实施方案的方法,其中对干燥或煅烧的涂覆载体材料进行还原。
21、根据实施方案20的方法,其中在200-600℃的温度范围内,在大气压或更高的压力至高约25巴下,将含氢气体通过催化剂之上持续1至24小时之间的时间而进行还原。
22、根据实施方案20或实施方案21的方法,其中对还原催化剂进行钝化。
23、由实施方案1至22任一方法可获得的催化剂。
24、使用根据实施方案23的催化剂或由实施方案1至22任一方法可获得的催化剂进行蒸汽重整反应的方法。
25、根据实施方案24的方法,包括对烃类进行蒸汽重整。
26、根据实施方案25的方法,其中烃类为天然气、石脑油、液体燃料或气化炉流出物。
27、根据实施方案25或实施方案26的方法,其中重整过程中含有氧。
施用至成型载体的涂层中的颗粒状催化剂化合物包含选自Ni、Cu、Pt、Pd、Rh、Ru和Au组成的组中的一种或多种催化活性金属。包含Ni、Pt和Rh中的一种或多种的催化剂是优选的。因此,在一个实施方案中,颗粒催化剂化合物中的催化金属含有Ni,以及任选Pt、Pd、Rh、Ru和Au中的一种或多种。在另一个实施方案中,催化金属由Rh组成。在另一个实施方案中,颗粒催化剂化合物中的催化金属包含Pt,任选地与Pd、Rh、Ru和Au中的一种或多种,优选包含Pt和Rh,其中Pt:Rh的重量比在1:1至6:1的范围内,优选为2:1至4:1。在另一实施方案中,颗粒状催化剂化合物中的催化金属包含Cu,以及任选Pt、Pd、Rh、Ru和Au中的一种或多种。
施用至成型载体上的涂层中的颗粒状催化剂化合物可包括催化活性金属的氧化物、氢氧化物或碳酸盐,如NiO、CuO或PtO。因此,颗粒状催化剂化合物可包含混合氧化物如CuO-ZnO-Al2O3、NiO-Al2O3、NiO-MgO-SiO2、NiO-MgO-SiO2-Al2O3或NiO-MgO-SiO2-CaO-Al2O3,例如可通过共沉淀形成。因此常规的重整催化剂配制剂可制成粉末形式并作为涂层施涂到成型载体上。然而,优选地,颗粒状催化剂化合物包括一种或多种选自Ni、Cu、Pt、Pd、Rh、Ru和Au组成的组中的金属,其分散于颗粒状催化剂载体材料的表面上。因此,浆料可由携带了一种或多种催化活性金属的颗粒状催化剂载体形成的。合适的颗粒状催化剂载体材料有氧化物如氧化铝,二氧化钛,氧化锆,氧化镧,氧化镁,氧化铈,优选氧化镧、氧化钇或氧化铈稳定的氧化锆;金属铝酸盐如铝酸钙和铝酸镁;以及它们的混合物。也可使用氧化锌,特别是与氧化铝结合用于铜或钯催化剂。特别优选的颗粒状催化剂载体材料包括氧化铝和/或稳定的氧化锆,例如氧化镧稳定的氧化铝,氧化铈-氧化锆-氧化铝,氧化铈-二氧化钛-氧化铝和氧化铈-氧化镁-氧化铝材料。颗粒状催化剂载体颗粒优选的平均粒度在1-80μm范围内,优选1-50μm。分散于颗粒状催化剂载体材料表面上的金属优选为催化剂金属或催化剂金属氧化物的微晶,其由XRD测定的平均微晶粒度在5-50nm范围内。用于形成浆料的负载组合物中金属含量可以是在0.1-50wt%的范围内。由于它们活性不同,优选的贵金属如Pt、Pd、Rh、Ru和Au以0.1-5wt%范围内的量存在,Ni或Cu以10-75wt%范围内的量存在。
可通过将可溶性催化金属化合物常规浸渍于颗粒状催化剂载体上,然后干燥和煅烧以将催化金属化合物转化为它们各自的氧化物,而将一种或多种催化金属分散于颗粒状催化剂载体材料的表面上。替代地,使用金属溶胶通过沉淀或通过使用金属氨络物的沉积-沉淀方法(其在加热时从溶液中将不溶性金属化合物沉积到颗粒状催化剂载体上),将一种或多种催化金属分散于颗粒状催化剂载体材料的表面上。
通过采用分散于颗粒状催化剂载体的表面上的催化金属有可能产生与在高温下煅烧的传统浸渍耐火氧化物负载催化剂相比具有增加的表面积和活性的催化剂。为形成浆料,颗粒状催化剂化合物分散在液体介质中,理想的是水性液体介质中。浆料中的固体含量可适当地在10-60wt%的范围内。可适当地采用用于制备催化剂洗涂层(wash-coats)的研磨技术形成浆料。粘合剂材料如氧化铝或水合氧化铝溶胶可包含在层中并且可以使用其它常规的涂层制备技术,如研磨和混合分散液以在涂覆载体之前达到所需粒径。在优选的实施方案中,浆料中含有聚乙烯接枝共聚物,例如KollicoatTM。已用于医药片剂包衣的这些材料降低了洗涂层的表面张力,从而增加了润湿性和喷涂中液滴的形成,并使涂层有了一定程度的塑性使其能够承受发生在涂覆过程本身的磨损。
成型载体呈成型单元形式,如挤出物,丸粒或颗粒,其可由粉末载体材料制得,也可含有润滑剂或粘结剂。挤出物和丸粒是优选的成型载体。挤出物,丸粒或颗粒可以是市售的,或使用本领域技术人员已知的方法容易地由合适的粉末制备的。
成型载体可具有多种形状和粒径,这取决于在它们制造过程中使用的模具或压模。例如,该单元可以是球体、圆柱体、环、或者多孔(multi-holed)单元(例如2-10个通孔)的形状,其可为多叶形或槽形,如具有苜蓿叶形横截面。也可以使用所谓的“车轮”形。挤出物或丸粒可以是圆柱体,即圆形的横截面,但优选是叶形或槽形以增加它们的几何表面积而未增加通过由这些单元形成的层的压降。这样的优点使通过催化剂的压降减小,同时保持令人满意的几何表面积。可选择成型单元以提供与高几何表面积和低压降组合的高抗压强度。在这方面,优选4孔四叶(4-holed tetralobal)、5孔五叶(5-holed pentalobal)的槽形成型单元。有较大的内部体积的形状,如所谓的车轮形,可以减少磨损造成的催化剂涂层的损失,因此可以是特别有用的。
本发明允许通常被认为不适合使用的高空隙率,高的几何表面积,低压降的形状。这是因为可以煅烧或烧制成型载体至非常高的温度下,例如>900℃,以得到必要的抗压强度而没有如同浸渍催化剂的情况那样破坏孔隙度和催化金属微晶表面积。在随后施涂的涂层中包含金属提供了必要的孔隙度和催化剂的表面积,干燥并任选地在较低温度下煅烧所述在随后施涂的涂层。因此,该方法允许达到最大的强度和催化剂的活性。
成型单元理想地具有最小的单元尺寸,优选地在1mm至50mm范围内。最小尺寸可以是宽度,例如直径,或长度,例如高度。成型单元的长度可从1mm到50mm,优选1.2mm至25mm。成形单元的横截面宽度或直径可从1mm到约25mm,优选从1.2mm至10mm,特别是从1.2mm至5mm。长径比,即最大尺寸除以最小尺寸例如长度/横截面,优选小于10,更优选小于5,最优选≤2。
成型载体优选由耐火氧化物(如氧化铝、氧化镁、氧化铈、二氧化钛或氧化锆、铝酸钙或铝酸镁;以及它们的混合物)制成,包括其中成型载体含有以层状排布的两种或更多种载体氧化物的层状结构。特别优选α-氧化铝和铝酸钙或铝酸镁的成型载体。
催化金属存在于成型载体表面上的层中。可以通过将浆料喷涂到平盘涂布机中加热、翻转的成型载体单元上施涂该层到颗粒状成型单元,其可以是制药或食品行业中用于制备涂覆片剂产品的类型。这样的装置由市售得到。喷涂之间可采用伴随干燥的多次喷涂。优选在30-60℃温度范围内将浆料施涂到载体上,优选为30-50℃。以这种方式载体不会过度润湿,并避免喷雾干燥浆料的可能性。
然后干燥所得的涂覆的成型载体材料。干燥步骤可在20-150℃下,优选在20-120℃下,更优选为95-110℃下,在空气中或在惰性气体如氮气下,或在真空烘箱中,按需要进行至多24小时的一段时间。
干燥材料中含有催化活性金属的层的厚度优选在5到250μm(微米)范围内,但更优选在50-250微米,最优选在10-200微米范围内。越薄的层可越有效地利用所施用的金属。可通过本领域技术人员已知的方法,如光学显微镜或电子微探针分析来测定出含有催化金属的层的厚度。
在本发明的一个实施方案中,将多个层施涂到成型载体上。特别是,在表面催化剂层和成型载体之间可设置一个或多个中间层。这样的中间层可以是未催化的,并优选包括具有介于成型载体的热膨胀系数和催化剂涂层的热膨胀系数之间的中间热膨胀系数的材料。以这种方式可降低由热冲击或磨损造成的来自成型载体的催化剂层的损失。替代地,可施加阻隔层到催化剂以改善化学相容性,特别是对于高温应用。
如果需要的话,可对干燥的催化剂前体进行在空气或惰性气体(如氮气)中的煅烧,即在250℃以上的温度,例如250-900℃下加热,以将成型载体表面上的任何非氧化的金属化合物转化成其各自的氧化物并烧尽任何有机组分如可能存在于浆料中的Kollicoat。
前体表层中的催化金属可包括混合氧化物或具有钙钛矿型,烧绿石,水滑石或分层双氢氧化物结构的涂层。
然后可以将干燥或煅烧的催化剂前体提供至蒸汽重整容器中。如果存在可还原金属,催化剂前体理想地还原以原位生成活性还原催化剂。替代地,催化剂可优选以“预还原”的形式提供,其中对干燥或煅烧的催化剂前体进行还原步骤使至少一部分可还原的金属转化为元素的“零价”态。
因此,还原步骤可通过如下进行:在升高温度下将含氢气体如氢气、合成气、或氢气与氮气或其他惰性气体的混合物通过干燥或煅烧的催化剂前体,例如将含氢气体在200-600℃的温度范围内通过组合物之上,优选在1至24小时之间在大气压或更高的压力(至高约25巴)下。
具有元素或零价态形式的金属催化剂可能难以处理,因为它们可以自发地与空气中的氧反应,这可能会导致不希望的自加热并失去活性。因此优选通过用氧化物薄层使还原的金属表面钝化而对适合于蒸汽重整过程的还原的镍和铜催化剂进行保护。这可以通过用稀释的空气/氮气,稀释的氧气/氮气或CO2气体混合物利用已知的技术处理还原的催化剂制得。
根据本发明制备的催化剂可用于重整过程如初级蒸汽重整,初级重整气体混合物的次级重整,自热重整和预重整。该催化剂也可单独用于通过催化部分氧化的重整,或与蒸汽重整组合。该催化剂也可用于甲烷化反应和加氢反应。
在重整中,烃,一般是含甲烷的气体,如天然气、或石脑油、或液体燃料如甲醇、乙醇柴油、汽油或液体石油气(LPG),与蒸汽和/或(在适当情况下)二氧化碳,在催化活性的材料上反应以生成含氢气和碳氧化物的气体。生成H2的反应为:
“CH2”+H2O→CO+2H2
(“CH2”表示高于甲烷的烃,例如通常为气态的烃类,和通常沸点至高为200℃的液体烃)。类似的与二氧化碳的反应可以单独进行或与蒸汽反应一起进行。
CH4+CO2→2CO+2H2
“CH2”+CO2→2CO+H2
甲醇与蒸汽的反应按照以下反应式。
CH3OH+H2O→CO2+3H2
蒸汽重整反应是强烈吸热反应,该过程特别适合当它们在有外部加热下进行,如在管式蒸汽重整中。替代地可以通过如下供给热量:加热反应物,并使蒸汽通过在绝热床的催化剂之上;或在混合过程中,该过程中氧气也是反应物,以便使氧化反应中放出的热量被吸热的蒸汽重整反应吸收。混合过程可以应用到管状或绝热过程的产物,即“次级重整”中,或应用至新鲜原料(“催化部分氧化”或“自热重整”)。在自热重整中,氧气和蒸汽可同时在重整催化剂上与烃反应或可将重整催化剂布置在非催化部分燃烧步骤的下游。
催化剂也可用于煤或生物质气化炉流出物的重整以将甲烷和更高级的烃类,包括焦油,重整成含有氢气和碳氧化物的气流。
对于从天然气或石脑油使用镍或贵金属催化剂制得的含氢合成气,出口温度优选为至少500℃。而用Ni催化剂的制备合成气的温度一般在750-900℃范围内用于生产氨或甲醇,对于冶金还原气的生产它可高达1100℃,或对于煤气的生产其低至700℃。对于使用氧气的混合过程,在催化剂床层中最热的部分温度可高达1300℃。铜或钯催化剂上的甲醇重整优选在较低的温度下进行,如在200-250℃范围内。
蒸汽重整过程中的压力一般在1-50巴(绝对)的范围内,但也提出了至高120巴(绝对)的压力。通常使用过量的蒸汽和/或二氧化碳,尤其是在1.5至6的范围内,例如2.5至5摩尔蒸汽或二氧化碳每克原料烃中的碳原子。
在含有甲烷和更高级的烃(包括焦油)的气化炉流出物的催化重整中,可在一个或多个步骤中使用本发明的催化剂处理含蒸汽的气化炉流出物。例如负载的Rh催化剂或负载的Pt/Rh催化剂可单独使用,或用于负载Ni重整催化剂的下游以重整气化炉流出物中的焦油和甲烷。优选地,在重整步骤之前将含灰尘和/或含碳固体从气体中分离出来,例如通过物理分离方法,如旋风分离器、过滤器、洗涤器或偏转器。由于催化剂在高温下是稳定的,它们可以直接用于气化后不用冷却气化炉流出物,但因为它们具有高活性,它们也可用于已发生一些流出物的冷却之后。气化炉流出物重整优选在500-1000℃的温度范围内在气化炉流出物的压力下进行。
现在将通过参考以下实施例和图1和2进一步描述本发明。图1是根据实施例1的方法制备的催化剂前体的光学显微镜照片。图2是实施例1的催化剂和对比方法的催化剂的甲烷转化率对温度的图表。
使用Profile Automation Pilot XT台式顶部通风平盘涂布机涂覆丸粒。涂层借由蠕动泵(Watson Marlow 101U/R)给料的喷嘴施涂,蠕动泵通过硅胶管(5毫米内径)将洗涂料供至平盘涂布机。
使用Eiger Torrence小型电机研磨机250并采用用1mmYSZ珠子作为研磨介质对浆料预研磨。利用Malvern Mastersizer激光衍射粒度分析仪测定粒度分布。
使用Jenway 370pH计测定浆液的pH,并使用Sartorius MA45固体含量天平测量浆料的固体含量。
实施例1:催化剂制备
将2%Rh/30%Ce0.75Zr0.25O2-70%Al2O3粉末(470g)分散于去离子水中得到45%固体浆料。以350rpm将浆料研磨8分钟,获得所得的D50为2.2微米。通过加入乙酸将478g洗涂料pH由6.7(属性的)调至4.0,加入Dipseral P3氧化铝(Sasol)(21.5g),然后在Silverson上由高剪切头(20分钟,大约3000rpm)混合。加入预先溶解于去离子水(150毫升)中的Kollicoat IR(17.6克(催化剂重量的8%),洗涂层的最终重量为705g。在平盘涂布机中将388g该洗涂层施涂至1L(1180g)的α-氧化铝三叶草(cloverleaf)形片上。涂覆参数如下:T入口(50℃),平盘速度(20rpm),泵转速(18rpm),平盘压力(-30Pa)。涂覆用29分钟。将产物在500℃下煅烧2小时。将所得催化剂层为100-150微米厚。
图1描述了具有包含在成型α-氧化铝的芯上的催化剂外层的催化剂的催化剂前体。
实施例2:测试
测试实施例1的涂覆丸粒的甲烷蒸汽重整活性。将24粒丸粒加24粒未涂覆丸粒放置在1"直径×2.2"长的反应管中。蒸汽-甲烷重整在蒸汽:碳比为3.25,在1atm的压力下进行。
图2对用Rh的硝酸盐溶液常规始润浸渍制备的0.2%Rh/CaAl2O4催化剂与以上的平盘涂覆催化剂(标记为2Rh/CZA)进行了比较。始润浸渍催化剂的Rh以至多500微米的深度分散在整个载体表面,而在平盘涂布机中制备的涂覆催化剂具有含Rh的外层。平盘涂覆的催化剂,Rh负载量为0.15%,在研究的整个温度范围内的甲烷转化率方面表现优于对比的浸渍催化剂,尽管具有显著较低的Rh含量。
Claims (10)
1.用于蒸汽重整煤或生物质气化炉流出物,以将甲烷和更高级的烃类包括焦油,重整成含有氢气和碳氧化物的气流的方法,该方法使用通过包括以下步骤的方法制备的催化剂:
(i)喷涂含有颗粒催化剂化合物的浆料至平盘涂布机中的成型载体的表面上以形成表层中具有催化金属的涂覆的成型载体材料,所述催化剂化合物包含一种或多种选自Ni、Cu、Pt、Pd、Rh、Ru和Au组成的组的催化金属,
(ii)干燥和任选地煅烧该涂覆的成型载体材料以形成催化剂前体,和
(iii)任选地还原该催化剂前体中的一种或多种金属至较低氧化态以形成该催化剂。
2.根据权利要求1所述的方法,其中该重整过程中含有氧。
3.根据权利要求1所述的方法,其中该颗粒催化剂化合物中的该催化金属包括Ni,以及任选Pt、Pd、Rh、Ru和Au中的一种或多种。
4.根据权利要求1所述的方法,其中该颗粒催化剂化合物中的该催化金属包括Pt,以及任选Pd、Rh、Ru和Au中的一种或多种。
5.根据权利要求4所述的方法,其中该颗粒催化剂化合物中的该催化金属包括Pt和Rh。
6.根据权利要求1所述的方法,其中该颗粒催化剂化合物中的该催化金属由Rh组成。
7.根据权利要求1至6中任一项所述的方法,其中该颗粒催化剂化合物包括分散在颗粒催化剂载体材料的表面上的一种或多种选自Ni、Cu、Pt、Pd、Rh、Ru和Au组成的组的金属。
8.根据权利要求7所述的方法,其中该颗粒催化剂载体材料选自氧化铝、二氧化钛或氧化锆、氧化锌、氧化镧、氧化镁、氧化铈、金属铝酸盐及其混合物组成的组。
9.根据权利要求1至8中任一项所述的方法,其中该成型载体为耐火氧化物,该耐火氧化物包含选自氧化铝、氧化铈、氧化镁、二氧化钛或氧化锆、铝酸钙或铝酸镁;及其混合物组成的组的载体氧化物。
10.根据权利要求1至9中任一项所述的方法,其中经干燥的材料中含有催化活性金属的涂层的厚度在5至250μm范围内。
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BR112013020271B8 (pt) | 2019-12-10 |
US20140005042A1 (en) | 2014-01-02 |
EP2675561A1 (en) | 2013-12-25 |
RU2013142164A (ru) | 2015-03-27 |
CN103442803A (zh) | 2013-12-11 |
WO2012110781A1 (en) | 2012-08-23 |
JP5955868B2 (ja) | 2016-07-20 |
RU2580548C2 (ru) | 2016-04-10 |
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US9511351B2 (en) | 2016-12-06 |
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BR112013020271A2 (pt) | 2016-10-18 |
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CN106362735B (zh) | 2019-07-02 |
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