CN1211162C - 催化剂及其制备方法和利用该催化剂的反应 - Google Patents
催化剂及其制备方法和利用该催化剂的反应 Download PDFInfo
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- CN1211162C CN1211162C CNB018042023A CN01804202A CN1211162C CN 1211162 C CN1211162 C CN 1211162C CN B018042023 A CNB018042023 A CN B018042023A CN 01804202 A CN01804202 A CN 01804202A CN 1211162 C CN1211162 C CN 1211162C
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00835—Comprising catalytically active material
-
- B01J35/56—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49345—Catalytic device making
Abstract
本发明包括具有层式结构的催化剂,该催化剂具有:(1)多孔载体、(2)缓冲层、(3)边界层和任选的(4)催化剂层。本发明还提供了一种方法,在该方法中反应物经过盛有该催化剂的反应室而转化成产物。
Description
发明领域
本发明涉及具有多孔载体、缓冲层和边界层的催化剂、制备该催化剂的方法和利用该催化剂的催化方法。
相关申请
该申请是美国序列号09/123,781的连续部分申请,将其引入作为参考。
发明背景
包括蒸汽重整、水煤气转移反应、甲醇合成和催化燃烧在内的氢气和烃类化合物的转化反应是公知的。这些反应通常于150℃至1000℃进行。最近,在工业上利用催化剂颗粒来进行这些反应,该催化剂颗粒由沉积在高表面积的陶瓷颗粒上的活性催化金属或金属氧化物组成。
泡沫或整体催化剂是公知的,该催化剂具有三层(1)多孔载体、(2)边界层和(3)如[1]中所述的催化剂金属。在制备这些催化剂的过程中,通过包括溶液浸渍技术在内的各种方法将边界层进行沉积。通过溶液浸渍技术来沉积催化剂层。边界层比多孔载体具有更大的表面积,但是多孔载体的机械强度大于边界层。
多孔载体可以是金属或陶瓷泡沫。金属泡沫具有较高的热传导性并易于加工。海绵状的机械性能便于在反应室内通过机械接触而方便地密封。金属泡沫和外壳反应器之间紧密相配的热膨胀使多孔载体的断裂最小化并将较高反应温度下的多孔载体周围的气体通道最小化。Pestryakov等用[1]、不用[2]的中间γ-氧化铝层制备了用于正丁烷氧化的金属泡沫为载体的过渡金属氧化物催化剂。Kosak[3]研究了数种方法来将贵金属分散于各种金属泡沫上,其中将金属泡沫表面用HCl溶液进行预蚀刻,并报道化学沉积提供了贵金属粘附到泡沫载体上的最好粘合。Podyacheva等[4]还用多孔氧化铝中间体合成了用于甲烷氧化的泡沫金属负载的LaCoO3钙钛矿催化剂。尽管所有金属泡沫负载的催化剂具有潜在的优点,但是金属泡沫具有较低的耐腐蚀性,并且其非多孔性和光滑网状表面提供了与陶瓷材料的不良粘合,这些材料在热循环后因其热膨胀的不匹配而易于出现边界层的层裂。
为了增加耐腐蚀性,诸如与Al、Cr和Si形成扩散合金之类的方法已用于制备铁素体钢,通常将铁素体钢用于制造高温加热炉元件(约1200℃)[5]。将含铝的铁素体钢进行适当热处理时,铝迁移到合金表面并形成牢固粘合的氧化物膜,该氧化物膜能阻止氧气扩散。该铁素体钢箔已用于制备具有大于10ppi(孔/英寸)的开孔金属整体[6]。但是,对具有适于催化应用的孔(<20ppi,优选80ppi)的类似合金泡沫的研究还没有结果。这归咎于制备更微细的Al铁素体钢泡沫的不成熟方法和用于制备泡沫的合金前体的缺乏。
因此,在负载催化剂的领域内需要提供多孔的泡沫载体,该泡沫多孔载体具有耐腐蚀性或抗氧化性,并能阻止边界层的断裂。
参考文献
1.A.N.Pestryakov,A.A.Fyodorov,V.A.Shurov,M.S.Gaisinovich,和I.V.Fyodorova,React.Kinet.Catal.Lett.,53[2]347-352(1994)。
2.A.N.Pestryakov,A.A.Fyodorov,M.S.Gaisinovich,V.P.Shurov,I.V.Fyodorova,和T.A.Gubaykulina,React.Kinet.Catal.Lett.,54[1]167-172(1995)。
3.J.R.Kosak.用于H2和O2的直接燃烧生成H2O2的新型固定床催化剂,M.G.Scaros和M.L.Prunier,Eds.,Catalysis of OrganicReactions,Marcel Dekker,Inc.(1995),p115-124。
4.O.Y.Podyacheva,A.A.Ketov,Z.R.Ismagilov,V.A.Ushakov,A.Bos和H.J.Veringa,React.Kinet.Catal.Lett.,60[2]243-250(1997)。
5.A.N.Leonov,O.L.Smorygo和V.K.Sheleg,React.Kinet.Catal.Lett.,60[2] 259-267(1997)。
6.M.V.Twigg和D.E.Webster.金属和涂层金属催化剂,ACybulski和J.A.Moulin,Eds.,Structured Catalysts and Reactors,Marcel Dekker,Inc.(1998),第59-90页。
发明概述
本发明包括至少具有三层(1)多孔载体、(2)缓冲层、(3)边界层以及任选的(4)催化活性层的催化剂。在一些实施方案中,位于多孔载体和边界层之间的缓冲层至少包含两个组成不同的子层。该缓冲层通常提供从多孔载体到边界层的热膨胀系数的转变,因此,当将催化剂加热至较高的操作温度和从较高的操作温度冷却时减小了热膨胀应力。该缓冲层还减小了多孔载体的腐蚀和氧化,并使通过多孔载体表面催化的副反应最小化。
本发明还提供了具有多孔载体、位于多孔载体和边界层之间的缓冲层的催化剂,其中催化剂具有抗氧化性,从而将该催化剂在空气中于580℃加热2500分钟时,催化剂的重量增加小于5%。另一选择,该催化剂的特征也可以在于其在热循环过程中有耐剥落性。
本发明还提供了将至少一种反应物转化成至少一种产物的方法,其中反应物经过含有催化剂的反应室。
本发明的用于制备多层催化剂(至少三层)的方法具有以下步骤:(1)选择多孔载体、(2)在多孔载体上沉积缓冲层、(3)在缓冲层上沉积边界层,和任选地(4)将催化活性层沉积于边界层上或与边界层成一整体;其中该缓冲层位于多孔载体和边界层之间。将缓冲层进行蒸发沉积可以得到更好的结果。将催化活性层在边界层沉积之后或沉积之中进行沉积。
本发明(包括具有缓冲层和边界层的多孔载体)的优点可包括:热膨胀系数的良好匹配和对温度变化的良好稳定性、诸如焦化之类的副反应的减少、所需的金属氧化物的相互作用、牢固粘合到高表面积的边界层上以及对底层多孔载体的保护增强。
将本发明的主题特别提出并在该说明书的结论部分清楚地进行要求。但是,通过参照下面的与附图相连的说明书可最好地理解操作方法和体制以及更多的优点及其目的,其中相似的参考符号是指同一元件。
附图简述
图1是催化剂的截面放大图。
图2a是不锈钢泡沫(顶部线条)和涂有二氧化钛的不锈钢泡沫(底部线条)于580℃(虚线)的重量增加(通过氧化)对时间的示意图。
图2b是镍泡沫(顶部线条)和涂有二氧化钛的镍泡沫(底部线条)于500℃的重量增加(通过氧化)对时间的示意图。
图3是一对显微照片,该显微照片比较了热循环对具有二氧化钛缓冲层和氧化铝修补基面涂层的不锈钢泡沫(左侧)和具有氧化铝修补基面涂层的不锈钢泡沫(无缓冲层,右侧)的影响。
优选实施方案的描述
本发明的催化剂描述于图1中,该催化剂具有多孔载体100、缓冲层102、边界层104和任选的催化剂层106。任何一层以点或圆点形式或以具有间隙或孔的层的形式可以是连续的或非连续的。
多孔载体100可以是多孔陶瓷或金属泡沫。适于本发明使用的其它多孔载体包括碳化物、氮化物和复合材料。在沉积各层之前,按照汞孔隙度测定法测定的多孔载体的孔隙率至少为5%,按照光学和扫描电子显微镜测定的多孔载体的平均孔径(孔直径的和/孔数目)为1μm~1000μm。优选多孔载体的孔隙率为约30%至约99%,更优选70%至98%。多孔载体的优选形式是泡沫、毛毡、填絮及其组合。泡沫是在整个结构内具有连续内壁确定的孔的结构。毛毡是相互之间具有间隙空间的纤维结构。填絮是诸如钢丝之类的缠绕线条的结构。次优选的是,多孔载体还可包括诸如颗粒和蜂窝体之类的其它多孔介质,只要其具有上述的孔隙率和孔径特性。优选金属泡沫的开孔约为20个孔/英寸(ppi)至约3000ppi,更优选约40至约120ppi。PPI定义为每英寸孔的最大量(在各项同性的材料中,与测量方向无关;但是,在各项异性的材料中,在具有最多孔数量的方向上进行测定)。在本发明中,通过扫描电子显微镜测定ppi。已经发现本发明的多孔载体提供了几个优点,该优点包括低压降、比常规的陶瓷颗粒载体具有更高的热传导性并易于在化学反应器内进行装载/卸载。
缓冲层102具有与载体和边界层不同的组成和/或密度,并优选缓冲层的热膨胀系数是多孔载体和边界层的热膨胀系数的中间值。优选该缓冲层是金属氧化物或金属碳化物。申请人发现蒸汽沉积制的层是良好的,因为该沉积层具有良好的粘合以及甚至数次热循环后的耐断裂性。更优选该缓冲层是Al2O3、TiO2、SiO2和ZrO2或其组合。更具体地说,Al2O3是α-Al2O3、γ-Al2O3及其组合。α-Al2O3因其优良的抗氧气扩散性而是更优选的。因此,期望用涂布到多孔载体100上的氧化铝来改善抗高温氧化性。该缓冲层还可由两个或多个组成不同的子层形成。当多孔载体100是诸如不锈钢泡沫之类的金属时,优选实施方案的缓冲层102由两个组成不同的子层(未示出)形成。优选第一子层(与多孔载体100接触)是TiO2,因为TiO2对多孔金属载体100表现出良好的粘合。优选第二子层是置于TiO2上的α-Al2O3。在优选的实施方案中,α-Al2O3子层是对下面的金属表面提供良好保护的致密层。然后将次致密的高表面积氧化铝边界层作为催化活性层的载体进行沉积。
多孔载体100的热膨胀系数通常不同于边界层104的热膨胀系数。因此,对于高温催化(T>150℃),缓冲层102需要在两种热膨胀系数之间进行转变。通过控制组成来特制缓冲层的热膨胀系数,从而得到与多孔载体和边界层的热膨胀系数相适应的膨胀系数。缓冲层102的另一个优点在于其减少了副反应的发生,例如由裸露的金属泡沫表面引起的焦化或裂化。对于不需要大表面积载体的化学反应(例如催化燃烧),缓冲层102因其强烈的金属和金属氧化物之间的相互作用而使催化剂稳定。在需要大表面积载体的化学反应中,缓冲层102更牢固地粘合到高表面积的边界层104上。优选缓冲层没有开孔和针孔,这为下面的载体提供了优良的保护。更优选缓冲层是非多孔的。缓冲层的厚度小于多孔载体的平均孔径的一半。优选缓冲层的厚度为约0.05至约10um,更优选小于5um。缓冲层在高温时表现出热稳定性和化学稳定性。
边界层104可由氮化物、碳化物、硫化物、卤化物、金属氧化物、碳及其组合组成。边界层对负载催化剂提供了高表面积和/或提供了所需的催化剂-载体相互作用。边界层可由常规用作催化剂载体的任何材料组成。优选边界层是金属氧化物。金属氧化物的例子包括但不限于γ-Al2O3、SiO2、ZrO2、TiO2、氧化钨、氧化镁、氧化钒、氧化铬、氧化锰、氧化铁、氧化镍、氧化钴、氧化铜、氧化锌、氧化钼、氧化锡、氧化钙、氧化铝、镧系列氧化物、沸石及其组合。边界层104可在没有任何更多的催化活性材料沉积于其上的条件下用作催化活性层。但是,通常将边界层104与催化活性层106进行结合。边界层还可由两个或多个组成不同的子层组成。边界层的厚度小于多孔载体的平均孔径的一半。优选边界层的厚度为约0.5至约100um,更优选约1至约50um。边界层或者是晶体的或者是无定形的,优选其BET表面积至少为1m2/g。
催化活性材料106(存在时)沉积在边界层104上。另一选择,催化活性材料可同时与边界层进行沉积。催化活性层(存在时)通常紧密地沉积在边界层上。将催化活性层“布置在”或“沉积在”边界层上包括常规理解:即将微观催化活性粒子分散到载体层(即边界层)的表面、载体层内的缝中和载体层内的开孔中。催化活性层可包括:催化剂金属(包括但不限于贵金属、过渡金属及其组合)、金属氧化物(包括但不限于碱金属元素、碱土金属元素、硼、镓、锗、砷、硒、碲、铊、铅、铋、钋、镁、钛、钒、铬、锰、铁、镍、钴、铜、锌、锆、钼、锡、钙、铝、硅、镧系元素的氧化物及其组合)、复合物、沸石、氮化物、碳化物、硫化物、卤化物、磷酸盐及其上述任何的组合。
优选催化剂(包括多孔载体、缓冲层、边界层和可能存在的催化活性层)的大小与反应室相适应。优选催化剂具有相连的孔隙,以便分子可经过催化剂进行扩散。在该优选的实施方案中,催化剂位于反应室内,以便气体基本上流经催化剂而不是从催化剂的周围经过。在优选的实施方案中,催化剂的横截面积至少占反应室的横截面积的80%、更优选至少占95%。在优选的实施方案中,催化活性材料分布于催化剂整个表面上,以便经过该催化剂的反应物能沿着经过催化剂的通道在任何地方发生反应;这是优于颗粒型催化剂的重要地方,该颗粒型催化剂颗粒内部具有较大体积的未使用空间或催化无效使用的空间。本发明的催化剂还胜过粉末形式,因为挤压的粉末可能引起严重的压降。
本发明的催化剂的特征在于其表现出的性能。可控制的用来影响这些性能的因素包括:多孔载体、缓冲层、界面层和催化活性层的选择、热膨胀系数的级数、结晶度、金属载体的相互作用、沉积技术,按照在此的描述其它因素是明显的。将利用这些因素的常规实验与缓冲层相结合使用可以制备用于催化许多化学反应的催化剂。本发明的催化剂的优选实施方案表现出了一种或多种下面的性能:(1)在空气中进行3次热循环后的粘合性,按照SEM(扫描电子显微镜)分析的结果,该催化剂表现出的剥落小于2面积%;(2)抗氧化性。在空气中于580℃加热2500分钟后,该催化剂的重量增加小于5%、更优选小于3%;仍更优选在空气中于750℃加热1500分钟后,该催化剂的重量增加小于0.5%。通过重量热分析(TGA)测定重量增量。每个热循环包括在空气中以10℃/分钟的加热速率从室温加热至600℃、将温度于600℃维持3000分钟以及以10℃/分钟的速率进行冷却。按照通过BET测定的结果,优选催化剂的表面积约为0.5m2/g,更优选大于约2.0m2/g。
本发明还提供了催化方法,该方法包括将至少一种反应物经过含有本发明的催化剂的反应室、将所述的至少一种反应物转化成至少一种产物以及产物从反应室流出。在优选的实施方案中,该催化剂方法在具有微通路的装置中进行。适合的微通路装置的例子以及与各种相关工艺因素记载于美国专利5,611,214、5,811,062、5,534,328和美国专利申请序列号为08/883,643、08/938,228、09/375,610、09/123,779、共同申请的美国专利申请序列号为09/492,246(代理人档案号E1666B-CIP)、09/375,614(1999年8月17日申请)和09/265,227(1999年3月8日申请)中,所有这些专利申请均引入作为参考,就如同将其在下文中完全再现一样。在另一个优选的实施方案中,催化剂是单一整体、相连的多孔结构,催化剂片或数个相连的片堆积在一起(不是挤压粉末床或颗粒或在微通路的器壁上的涂层)并能很容易地插入并从反应室中抽出。催化剂片或堆积的催化剂片优选的宽度为0.1mm至约2cm,优选厚度小于1cm,更优选约1mm至约3mm。本发明的催化剂为催化方法提供了许多优点,例如化学稳定性、对反复热循环的稳定性、热稳定性、催化剂的有效装载和卸载、高速的传热和传质和所需的催化活性的保持。
微通路装置的金属表面可涂有缓冲层和边界层之一或两者都涂。这可通过在此描述的方法中的任何一种来完成,优选利用蒸汽沉积法。优选的涂层材料包括二氧化钛和5-10%的SiO2/Al2O3。反应室、换热器的内表面以及微通路装置的其它表面都可进行涂布。在一些实施方案中,反应室的器壁涂有任选的缓冲层、边界层和催化活性材料,通常将该催化活性材料和边界层进行结合来形成负载催化剂。还可将涂料涂布到管子内的金属壁上,该管子形成与微通路装置的连接或微通路装置内的连接。
本发明的催化方法包括:乙酰化、加成反应、烷基化、脱烷基化、加氢脱烷基化、还原烷基化、氨基化、芳构化、芳基化、自热重整、羰基化、脱羰基作用、还原羰基化、羧基化、还原羧基化、还原偶合、缩合、裂化、加氢裂化、环化、成环低聚反应、脱卤化、二聚、环氧化、酯化、交换、Fischer-Tropsch反应、卤化、氢卤化、同系化反应、水合作用、脱水作用、氢化、脱氢、氢羧基化、加氢甲酰基化、氢解、氢金属化、硅氢化作用、水解、氢化处理、加氢脱硫/加氢脱氮(HDS/HDN)、异构化、甲醇合成、甲基化、脱甲基化、复分解、硝化、氧化、部分氧化、聚合、还原、蒸汽和二氧化碳重整、磺化、调聚反应、酯交换、三聚、水煤气转移(WGS)和逆向水煤气转移(RWGS)。
制备本发明的催化剂的方法包括以下步骤:选择多孔载体100、将缓冲层102沉积于多孔载体100上并随后将边界层104沉积于其上。任选的催化剂层106可沉积于边界层104上或沉积于边界层和催化剂层上,该催化剂层可同时沉积于缓冲层102上。
由于金属具有非多孔的光滑网状表面,所以缓冲层的沉积可能受到阻碍。解决该问题的一种方法是通过化学蚀刻使金属表面变粗糙。当利用诸如0.1~1M HCl的无机酸通过化学蚀刻将金属泡沫变粗糙时,可以明显地改善高表面积γ-氧化铝载体催化剂粘附到金属泡沫上的粘合。粗糙网状表面还能改善在热循环条件下的催化剂层的层裂。在优选的实施方案中,其中将金属泡沫用作多孔载体100,将金属泡沫进行蚀刻,然后蒸汽沉积缓冲层102。蚀刻优选用诸如HCl之类的酸。
缓冲层102的沉积优选通过蒸汽沉积进行,该蒸汽沉积包括但不限于化学蒸汽沉积、物理蒸汽沉积或其组合。出人意料地是,已经发现通常于高温进行的蒸汽沉积生成多晶或无定形相,该多晶或无定形相为缓冲层粘附到多孔载体的表面上提供良好的粘合。该方法在将金属氧化物缓冲层粘合到金属多孔载体上特别有利。另一选择,通过溶液涂布可得到缓冲层102。例如,溶液涂布的步骤为:通过将金属表面置于水蒸汽中进行金属表面官能化而形成表面氢氧根,然后通过表面反应和醇盐的水解来得到金属氧化物涂层。该溶液涂布可优选作为沉积缓冲层102的低成本方法。
利用用于这些技术的已知前体,优选通过蒸汽或溶液沉积形成边界层104。适当前体包括有机金属化合物、卤化物、金属羰化物、丙酮酸盐、醋酸盐、金属、金属氧化物的胶体分散液、硝酸盐、浆液等。例如,多孔的氧化铝边界层可用PQ氧化铝(Nyacol Products,Ashland,MA)胶态分散体进行修补基面涂层,随后在真空烘箱中干燥过夜并于500℃煅烧2小时。
催化活性材料可用任何适当的方法进行沉积。例如,将催化剂前体沉积到胶态的金属氧化物粒子和浆液上,将氧化物粒子和浆液涂布到涂有缓冲层的多孔载体上,然后进行干燥并还原。
实施例1
通过进行实验来说明本发明的缓冲层的某些优点。
将未蚀刻的不锈钢泡沫(Astromet,Cincinnati OH)用1000埃的TiO2通过化学蒸汽沉积进行涂布。将异丙醇钛(Strem Chemical,Newburyport,MA)于温度250~800℃、压力0.1~100托进行蒸汽沉积。在沉积温度600℃、反应器压力3托下,可以得到与泡沫具有良好粘合的二氧化钛涂层。
SEM(扫描电子显微镜)分析表明具有TiO2缓冲层的不锈钢泡沫负载的γ-氧化铝在从室温至600℃进行3次热循环后没有表现出层裂。在对涂有γ-氧化铝而没有TiO2缓冲层的不锈钢泡沫载体进行的对比试验中,在相同的试验条件下可以观察到γ-氧化铝的严重剥落和层裂。抗高温氧化性表示于图2a和2b中。从图2a可以看出,未涂布的不锈钢泡沫迅速被氧化(如重量增量所示,即热重值),然而涂有二氧化钛的不锈钢的氧化相对缓慢一些。从图2b可以看出,未涂布的镍泡沫被氧化,然而在相同的条件下涂有二氧化钛的镍泡沫表现出零氧化(即不可检测的量)。
结束语
虽然已经表示并描述了本发明的优选实施方案,但是对本领域技术人员显而易见的是,可以进行许多改变和修饰而不超出本发明的范围。因此,所附的权利要求旨在覆盖所有这些落在本发明的实质和范围之内的改变和修饰。
Claims (49)
1.一种催化剂,该催化剂包含多孔金属载体、缓冲层、边界层和表面上的催化活性层;其中多孔金属载体的平均孔径为1μm~1000μm;其中多孔金属载体选自蜂窝体、泡沫、毛毡和填絮;其中缓冲层位于多孔载体和边界层之间,边界层位于催化活性层和缓冲层之间;其中缓冲层包含金属碳化物或金属氧化物;其中缓冲层的厚度为0.05至10μm;其中缓冲层用作多孔载体和边界层的热膨胀系数之间的过渡;其中边界层包含金属氧化物或选自氮化物、碳化物、硫化物、卤化物和碳的材料;其中边界层的BET表面积至少为1m2/g;其中边界层的厚度为0.5至100μm。
2.权利要求1所述的催化剂,其中缓冲层的厚度小于5μm。
3.权利要求1所述的催化剂,其中该催化剂具有热循环稳定性,所以若在空气中进行3次热循环,该催化剂表现出的剥落小于2%。
4.权利要求1所述的催化剂,其中该催化剂具有抗氧化性,所以若在空气中将其于580℃加热2500分钟,该催化剂的重量增加小于5%。
5.权利要求1所述的催化剂,其中该催化剂具有抗氧化性,所以若在空气中将其于750℃加热1500分钟,该催化剂的重量增加小于0.5%。
6.权利要求1所述的催化剂,其中多孔载体是金属,并且催化活性层分布于整个催化剂的表面上,因此经过该催化剂的反应物能沿着经过催化剂的通道在任何地方发生反应。
7.权利要求1所述的催化剂,其中所述的缓冲层是非多孔的。
8.权利要求1所述的催化剂,其中多孔载体包含泡沫、毛毡、填絮或其组合。
9.权利要求1所述的催化剂,其中边界层的厚度为1~50μm。
10.一种催化剂,该催化剂包含多孔金属载体、缓冲层和边界层;其中多孔金属载体的平均孔径为1μm~1000μm;其中多孔金属载体选自蜂窝体、泡沫、毛毡和填絮;其中缓冲层位于多孔载体和边界层之间,边界层位于催化活性层和缓冲层之间;其中缓冲层包含金属碳化物或金属氧化物;其中缓冲层的厚度为0.05至10μm;其中缓冲层用作多孔载体和边界层的热膨胀系数之间的过渡;其中边界层包含金属氧化物或选自氮化物、碳化物、硫化物、卤化物和碳的材料;其中边界层的BET表面积至少为1m2/g;其中边界层的厚度为0.5至100μm。
11.权利要求10所述的催化剂,该催化剂还包含边界层上的催化活性层。
12.权利要求10所述的催化剂,其中所述的至少两个子层包括由TiO2组成的、与多孔载体进行接触的第一子层和由α-Al2O3组成的第二子层。
13.权利要求12所述的催化剂,其中边界层包含高表面积的氧化铝层,该氧化铝层比第二子层致密性差些。
14.权利要求13所述的催化剂,其中该催化剂还包含沉积于边界层上的催化活性成分。
15.权利要求10所述的催化剂,其中在无任何其它的催化活性材料沉积于其上时,边界层可用作催化活性层。
16.权利要求10所述的催化剂,其中边界层包含至少两个组成不同的子层。
17.权利要求10所述的催化剂,其中多孔载体的孔隙率为70~98%。
18.权利要求10所述的催化剂,其中多孔载体包含泡沫、毛毡、填絮或其组合。
19.权利要求10所述的催化剂,其中边界层的厚度为1~50μm。
20.一种催化剂,该催化剂包含多孔金属载体、缓冲层和边界层;其中多孔金属载体的平均孔径为1μm~1000μm;其中多孔金属载体选自蜂窝体、泡沫、毛毡和填絮;其中缓冲层位于多孔载体和边界层之间,其中该催化剂具有热循环稳定性,所以若在空气中进行3次热循环,该催化剂表现出的剥落小于2%;其中缓冲层位于多孔载体和边界层之间,边界层位于催化活性层和缓冲层之间;其中缓冲层包含金属碳化物或金属氧化物;其中缓冲层的厚度为0.05至10μm;其中缓冲层用作多孔载体和边界层的热膨胀系数之间的过渡;其中边界层包含金属氧化物或选自氮化物、碳化物、硫化物、卤化物和碳的材料;其中边界层的BET表面积至少为1m2/g;其中边界层的厚度为0.5至100μm。
21.权利要求20所述的催化剂,其中多孔载体是金属;其中该催化剂具有抗氧化性,所以若在空气中将其于580℃加热2500分钟,该催化剂的重量增加小于5%。
22.权利要求20所述的催化剂,其中该催化剂是宽度为0.1mm~约2cm、厚度小于1cm的整体。
23.权利要求20所述的催化剂,其中多孔载体的孔隙率为70~98%。
24.权利要求20所述的催化剂,其中多孔载体包含泡沫、毛毡、填絮或其组合。
25.权利要求20所述的催化剂,其中边界层的厚度为1~50μm。
26.一种制备权利要求1、10或20的催化剂的方法,该方法包括步骤:
选择选自蜂窝体、泡沫、毛毡和填絮的多孔载体;
将缓冲层蒸汽沉积于所述的多孔载体上;
将边界层沉积于所述的缓冲层上。
27.权利要求26所述的方法,其中所述的缓冲层是二氧化钛。
28.权利要求26所述的方法,其中将催化活性材料与边界层同时进行沉积。
29.权利要求26所述的方法,其中将边界层从溶液中进行沉积。
30.权利要求26所述的方法,其中蒸汽沉积步骤包括化学蒸汽沉积。
31.权利要求30所述的方法,其中载体包含金属泡沫,其中化学蒸汽沉积于温度250~800℃进行。
32.权利要求30所述的方法,其中用于化学蒸汽沉积的前体选自:有机金属化合物、卤化物、金属羰化物、丙酮酸盐和醋酸盐。
33.权利要求26所述的方法,该方法包括步骤:蒸汽沉积TiO2层、在TiO2层蒸汽沉积致密的氧化铝层以及在致密的氧化铝层上沉积次致密的、高表面积的氧化铝层。
34.权利要求26所述的方法,其中多孔载体包含金属泡沫并且催化剂的表面积大于2.0g/cm3。
35.权利要求26所述的方法,其中多孔载体包含金属泡沫,将该金属泡沫进行蚀刻,然后蒸汽沉积缓冲层。
36.权利要求26所述的方法,其中载体包含选自蜂窝体、泡沫、毛毡和填絮的金属;催化剂具有抗氧化性,所以若在空气中将其于750℃加热1500分钟,该催化剂的重量增加小于0.5%。
37.权利要求26所述的方法,其中多孔载体的孔隙率为70~98%。
38.权利要求26所述的方法,其中多孔载体包含泡沫、毛毡、填絮或其组合。
39.权利要求38所述的方法,其中蒸汽沉积步骤包括化学蒸汽沉积。
40.将至少一种反应物转化成至少一种产物的方法,该方法包括:将至少一种反应物经过反应室、将所述的至少一种反应物转化成至少一种产物以及产物从反应室流出,其中所述的反应室含有权利要求1所述的催化剂。
41.权利要求40所述的方法,其中所述的方法选自乙酰化、加成反应、烷基化、脱烷基化、加氢脱烷基化、还原烷基化、氨基化、芳构化、芳基化、自热重整、羰基化、脱羰基作用、还原羰基化、羧基化、还原数基化、还原偶合、缩合、裂化、加氢裂化、环化、环低聚反应、脱卤化、二聚、环氧化、酯化、交换、Fischer-Tropsch、卤化、氢卤化、同系化反应、水合作用、脱水作用、氢化、脱氢、氢羧基化、加氢甲酰基化、氢解、氢金属化、硅氢化作用、水解、氢化处理、加氢脱硫/加氢脱氮(HDS/HDN)、异构化、甲醇合成、甲基化、脱甲基化、复分解、硝化、氧化、部分氧化、聚合、还原、蒸汽和二氧化碳重整、磺化、调聚反应、酯交换、三聚、水煤气转移(WGS)和逆向水煤气转移(RWGS)。
42.权利要求40所述的方法,其中所述的反应室具有器壁并且所述器壁中的至少一个上沉积有:缓冲层、边界层和催化活性层。
43.将至少一种反应物转化成至少一种产物的方法,该方法包括:将至少一种反应物经过反应室、将所述的至少一种反应物转化成至少一种产物以及产物从反应室流出,其中所述的反应室含有权利要求10所述的催化剂。
44.权利要求43所述的方法,其中所述的方法选自乙酰化、加成反应、烷基化、脱烷基化、加氢脱烷基化、还原烷基化、氨基化、芳构化、芳基化、自热重整、羰基化、脱羰基作用、还原羰基化、羧基化、还原羧基化、还原偶合、缩合、裂化、加氢裂化、环化、环低聚反应、脱卤化、二聚、环氧化、酯化、交换、Fischer-Tropsch、卤化、氢卤化、同系化反应、水合作用、脱水作用、氢化、脱氢、氢羧基化、加氢甲酰基化、氢解、氢金属化、硅氢化作用、水解、氢化处理、加氢脱硫/加氢脱氮(HDS/HDN)、异构化、甲醇合成、甲基化、脱甲基化、复分解、硝化、氧化、部分氧化、聚合、还原、蒸汽和二氧化碳重整、磺化、调聚反应、酯交换、三聚、水煤气转移(WGS)和逆向水煤气转移(RWGS)。
45.将至少一种反应物转化成至少一种产物的方法,该方法包括:将至少一种反应物经过反应室、将所述的至少一种反应物转化成至少一种产物以及产物从反应室流出,其中所述的反应室含有权利要求11所述的催化剂。
46.权利要求45所述的方法,其中所述的方法选自乙酰化、加成反应、烷基化、脱烷基化、加氢脱烷基化、还原烷基化、氨基化、芳构化、芳基化、自热重整、羰基化、脱羰基作用、还原羰基化、羧基化、还原羧基化、还原偶合、缩合、裂化、加氢裂化、环化、环低聚反应、脱卤作用、二聚、环氧化、酯化、交换、Fischer-Tropsch、卤化、氢卤化、同系化反应、水合作用、脱水作用、氢化、脱氢、氢羧基化、加氢甲酰基化、氢解、氢金属化、硅氢化作用、水解、氢化处理、加氢脱硫/加氢脱氮(HDS/HDN)、异构化、甲醇合成、甲基化、脱甲基化、复分解、硝化、氧化、部分氧化、聚合、还原、蒸汽和二氧化碳重整、磺化、调聚反应、酯交换、三聚、水煤气转移(WGS)和逆向水煤气转移(RWGS)。
47.微通路装置,其中将该装置的内壁中的至少一个用权利要求1的催化剂进行涂布。
48.权利要求47所述的微通路装置,其中缓冲层是蒸汽沉积的。
49.权利要求47所述的微通路装置,其中所述的壁包括反应室的至少一个壁。
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-
2000
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US20030007904A1 (en) | 2003-01-09 |
AU778052C (en) | 2005-09-01 |
AU2005200598B2 (en) | 2007-12-20 |
NO20023080L (no) | 2002-09-13 |
AU2005200598A1 (en) | 2005-03-10 |
CA2396144A1 (en) | 2001-08-02 |
JP5964594B2 (ja) | 2016-08-03 |
US20040188326A1 (en) | 2004-09-30 |
EP2295140A1 (en) | 2011-03-16 |
AU778052B2 (en) | 2004-11-11 |
WO2001054812A1 (en) | 2001-08-02 |
JP4982717B2 (ja) | 2012-07-25 |
JP2012110894A (ja) | 2012-06-14 |
US7498001B2 (en) | 2009-03-03 |
RU2002120794A (ru) | 2004-01-10 |
US6440895B1 (en) | 2002-08-27 |
US6762149B2 (en) | 2004-07-13 |
HK1053996A1 (en) | 2003-11-14 |
CA2396144C (en) | 2013-11-19 |
NO20023080D0 (no) | 2002-06-26 |
KR20020080387A (ko) | 2002-10-23 |
EP1257362A1 (en) | 2002-11-20 |
AU3466601A (en) | 2001-08-07 |
KR100670954B1 (ko) | 2007-01-17 |
CN1400923A (zh) | 2003-03-05 |
EP1257362B1 (en) | 2013-05-08 |
JP2003520675A (ja) | 2003-07-08 |
RU2257955C2 (ru) | 2005-08-10 |
WO2001054812B1 (en) | 2001-11-29 |
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