CN1164362C - 涂层催化剂、其制备方法及其用途 - Google Patents
涂层催化剂、其制备方法及其用途 Download PDFInfo
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- CN1164362C CN1164362C CNB018072232A CN01807223A CN1164362C CN 1164362 C CN1164362 C CN 1164362C CN B018072232 A CNB018072232 A CN B018072232A CN 01807223 A CN01807223 A CN 01807223A CN 1164362 C CN1164362 C CN 1164362C
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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Abstract
本发明涉及一种具有芯和包围所述芯的至少一层壳的涂层催化剂,所述芯由惰性载体材料组成,所述至少一层壳由多孔载体物质组成。所述壳以物理方式附着在所述芯上,所述至少一层壳含有选自元素周期表第ⅧB族中的Ni、Pd和Pt和第ⅠB族中的Cu、Ag和Au金属的细分散形式的催化活性金属或均匀分散形式的所述催化活性金属的前体。本发明涂层催化剂适用于不饱和烃的还原,可实现比以前已知涂层催化剂更好的选择性。本发明还涉及所述涂层催化剂的生产方法。
Description
技术领域
本发明涉及具有芯和包围所述芯的至少一层壳的涂层催化剂,所述涂层催化剂的生产方法及用途。
背景技术
用于不饱和烃氢化的金属催化剂通常涂于均质多孔载体例如碳酸钙或活性炭上。所述催化剂通过用金属盐溶液浸渍所述载体生产。干燥后,利用氢气使所述金属盐还原,从而使所述催化剂活化。这种催化剂有高反应速率,但氢化选择性通常不令人满意。原因在于此催化剂的结构。用金属盐溶液浸渍载体并非总能使活性组分均匀分布在多孔载体中。本文中,活性组分可以是催化活性金属本身或其前体化合物例如金属盐。因此,相对于全部多孔载体体积上所述活性组分的平均浓度而言,所述多孔载体有活性组分浓度较高的区域或活性组分浓度较低的区域。这在进行所述反应中造成困难,因为载体体积上反应条件可能不同。另一困难是所述多孔载体内各分子与其它分子的停留时间不同。这是因各分子的渗透深度或扩散速率不同所致。
因此要求氢化催化剂首先表现出足够的转化速率,其次显示出高选择性。此外,要求所述催化剂在再生之间的使用期长,而且特别是在贵金属催化剂的情况下,在催化剂寿命结束时再加工简单。
DE-A-27 15 094描述一种用于使高度不饱和烃选择氢化的催化剂。其中将钯涂于粒状多孔氧化铝载体上,所述钯主要分布在所述催化剂粒子的几何表面下不大于150μm的区域。所述载体颗粒可全部由氧化铝构成。但所述氧化铝也可以作为在另一种材料上的涂层形式存在。所述氧化铝载体最有利地是假勃姆石的焙烧产物。所述载体的全部体积内都是多孔的,在多层结构的情况下,所述载体的组分通过化学键结合,例如在焙烧假勃姆石的情况下,在所述芯和所述壳之间形成的化学键。所述钯优选通过湿法、通过将所述载体浸入钯化合物溶液中或将所述溶液喷涂至载体上而涂于所述载体上。通过加热或用氢气还原释放所述钯金属。实施例中,用钯盐的水溶液喷涂氧化铝颗粒。
EP 0 075 314描述了包含γ-氧化铝和氧化镍(II)的双功能催化剂及其生产。所述催化剂用于通过部分氧化使燃料裂化。所用催化剂是涂层催化剂,其具有非活性芯和以薄层形式存在于所述芯上的催化活性组分。所述催化剂的惰性密实芯包含α-氧化铝和/或富铝红柱石和/或烧结陶瓷材料和/或氧化镁和/或菱镁矿。所述催化剂的壳包括γ-氧化铝和氧化镍(II)。该催化剂通过交替地用镍盐溶液和包含γ-氧化铝和氧化镍(II)或氧化铝的粒度小于100μm的粉末喷涂所述惰性载体颗粒生产。作为备选方案,也可用γ-氧化铝和氧化镍(II)制成的悬浮液和镍盐溶液喷涂所述惰性载体颗粒。涂布所述壳后,点燃所述催化剂。
US4,255,253描述一种用于降低例如在石油加工中得到的烃馏分的硫、氮或金属含量的涂层催化剂。所述涂层催化剂包括至少在某些区域是多孔的载体,具有至少20μm的直径,并涂有催化活性物质。此物质包括催化活性的氧化物组分和可与所述载体表面形成牢固结合的载体材料。为生产所述涂层催化剂,首先使所述载体湿润。然后通过在粉末中轻轻地搅动所述载体将粉状催化活性物质滚压在所述载体的外表面上。作为备选方案,提出先用载体材料涂布所述润湿的载体,焙烧后,用所述金属氧化物的前体化合物的溶液浸渍。
DE 196 07 437 A1公开一种有蛋壳状活性金属分布的负载型金属催化剂的生产方法。为此,使金属如Pd、Ni、Co、Mo、Cu、Pt、Fe、Ag、Ir、Pb、Pi、Sm、V、Zn等金属的有机金属化合物溶于纯有机溶剂。通过湿浸渍和/或喷涂法使所述金属化合物转移至载体表面。可通过选择适合的溶剂和/或工艺条件精确地控制所述金属的浓度分布和金属载荷。所述催化剂的载体材料是均匀的,即所述载体外侧没有涂布其它载体材料层。
EP 0 542 528描述一种使蜡加氢异构化的方法。所述异构化使用含铂的涂层催化剂。为生产所述催化剂,将一层勃姆石或假勃姆石涂于催化惰性的芯上,将催化活性物质引入此层中。焙烧过程中,所述勃姆石/假勃姆石转变成γ-氧化铝并与下面的芯形成化学键。
EP 0 547 756 A1描述一种涂层催化剂,其涂层包括担载在氟化氧化铝之上的铂。为生产所述催化剂,将催化活性物质和勃姆石或假勃姆石的浆液涂于惰性的非催化活性材料如α-氧化铝上。然后加热所述颗粒使所述勃姆石/假勃姆石转化成γ-氧化铝,从而在所述壳和所述芯之间形成化学键。
WO 98/37967描述一种用于芳烃的气相催化氧化的涂层催化剂的生产方法。其中将一层催化活性的金属氧化物以壳的形式涂于惰性材料的芯上。作为所述催化活性组合物的催化活性组分,一般使用锐钛矿改性形式的二氧化钛及五氧化钒。也可存在少量的能影响催化剂活性和选择性的起促进剂作用的许多其它氧化化合物。为生产所述催化剂,通过适合的前体化合物的悬浮液喷雾干燥生产催化活性组合物粉末。然后在添加水与有机溶剂的混合物的情况下在涂料桶中将其涂于成型体。然后使所述涂层催化剂载体干燥。
DE 29 09 671描述一种涂层催化剂的生产方法。所述催化剂可用于用氧气使丙烯醛氧化生产丙烯酸。为生产所述涂层催化剂,先用在其重量的至少0.1%至其吸水容量的95%范围内的水预湿润用于形成所述涂层催化剂芯的多孔惰性载体。然后,将催化活性物质和水连续地和彼此物理分离地以恒定的添加速率涂于剧烈搅拌的载体上。形成所述壳的含水量低于所述催化活性物质壳的最大饱和度。所述催化剂的壳包括钼和钒以及氧化形式的其它过渡金属。
EP 0 714 700 A2描述一种包括芯和涂于芯表面的催化活性氧化物组合物的催化剂的生产方法。为此,先用常压下沸点高于100℃的有机物质的水溶液作为提供粘合力的液体湿润用于形成所述涂层催化剂芯的载体,然后通过与干燥的细分散活性氧化物组合物接触,使一层活性氧化物组合物粘附于所述润湿载体的表面上。然后从已涂有活性氧化物组合物的润湿载体中除去所述提供粘合力的液体。所述催化活性氧化物组合物包括金属形式的钼和钒以及其它金属。
发明内容
本发明的目的是提供一种用于不饱和烃的气相氢化的催化剂,该催化剂显示出提高的选择性。
我们发现一种具有芯和包围所述芯的至少一层壳的涂层催化剂可实现此目的,其中所述芯由惰性载体材料组成,所述壳由多孔载体物质组成,所述壳以物理方式附着在所述芯上,选自元素周期表第VIIIB族中的Ni、Pd和Pt和第IB族中的Cu、Ag和Au金属的至少一种催化活性金属或所述催化活性金属的前体以均匀分布的细分散形式存在于所述壳中。
本发明涂层催化剂可实现气相中氢化选择性的显著提高。所述壳能产生规定的均匀反应条件。由于所述芯不含活性组分,所以催化反应仅在所述涂层催化剂的壳中发生,可按规定的方式选择其厚度和组成。反应物在所述壳内的扩散程短而且对于所有分子近似相等。所述芯与其周围壳之间只有物理连接,例如通过壳的收缩实现。在芯和壳之间未形成化学键。但各粒子之间和壳与芯之间的粘合力足以确保所述催化剂粒子的结构稳定。所述涂层催化剂已达到其寿命终点之后,可容易地通过壳与芯的机械分离处理。
所述催化活性金属可直接以细分散形式存在于所述壳中,或者在氢化条件下由例如通过喷涂溶液均匀地分布在壳中的催化活性金属的前体形成。
特别地,可用于所述芯的材料是氧化铝、二氧化硅、硅酸盐如粘土、高岭土、滑石、浮石、硅酸铝和硅酸镁、碳化硅、二氧化锆和二氧化钍。所述芯可由多孔载体材料组成。但所述孔的总体积相对于所述载体材料的体积优选小于1%(体积)。原则上,任何几何形状的芯都可以。但优选用球或圆柱体、特别是中空圆柱体作芯。它们的纵向尺寸一般为1-10mm。
如果用圆柱体作芯,其长度优选为2-10mm,其外径优选为4-10mm。此外,在环的情况下,壁厚通常为1-4mm。特别优选的环形芯长3-6mm,外径4-8mm,壁厚1-2mm。特别优选的是7mm×3mm×4mm(外径×长度×内径)的环。
所述芯的表面有利地是粗糙的,因为表面粗糙度的增加一般使涂布壳的粘合力增加。所述芯的表面粗糙度Rz一般在40-200μm的范围内,优选40-100μm(用来自Hommelwerke的“用于DIN-ISO表面测量的Hommel测试仪”按DIN4768part1测定)。用于芯的载体物质有很高的孔隙率。作为所述壳的原料,可使用与芯相同的材料。特别优选氧化铝、二氧化锆、二氧化钛和二氧化硅。所述壳的载体物质一般是化学惰性的,即基本上不参与本发明涂层催化剂催化的气相氢化。取决于被催化的反应,也可使用酸性或碱性载体物质。所述贵金属催化剂以细分散形式掺入所述壳内。
所述金属也可以均匀分布形式的前体形式存在于所述涂层催化剂的壳内。这些前体在所述催化反应的氢化条件下可转化成活性形式的纯金属。适用的所述催化金属的前体是相应的金属氧化物或水溶性金属盐。优选使用氯化物、硝酸盐、C1-C10羧酸盐、碳酸盐、碳酸氢盐、硫酸盐、硫酸氢盐或磷酸盐。所述盐的水溶性的优点在于可非常简单地通过浸渍或喷涂将所述化合物在液相中均匀地引入所述壳材料中。原则上,也可使用水不溶性化合物,在产生所述壳催化剂之前先使之与形成壳的载体物质充分混合。
可在所述涂层催化剂的芯周围形成多层叠置的壳。所述壳可包含不同的催化活性金属。各层壳中所述催化活性金属的浓度也可不同。这样,可进一步改善所述氢化反应的选择性。
根据本发明涂于所述芯上的壳的厚度有利地为1-1000μm。特别是在环形芯的情况下,优选壳厚在10-500μm的范围内,特别是50-300μm。
根据本发明,所述涂层催化剂可通过包括以下步骤的方法生产:
a)提供包含惰性载体材料的载体以形成所述涂层催化剂的芯;
b)在使所述载体保持运动的同时在所述载体上喷撒氧化的粉状载体物质以形成壳;
c)用包含常压下沸点高于100℃的有机化合物的水溶液的粘合剂喷涂所述载体;
d)加入选自元素周期表第VIIIB族中的Ni、Pd和Pt和第IB族中的Cu、Ag和Au金属的催化活性金属或这些金属的前体化合物;
e)使挥发性组分蒸发;
f)适当时,使所述金属的前体化合物活化,其中步骤b)、c)和d)可同时进行或以任何顺序相继进行,需要时也可进行两次或多次。
一般通过将待涂布的芯放在优选倾斜(倾斜角一般为30-90°)旋转的容器(例如旋转盘或涂布转鼓)中进行涂布。所述旋转容器借助相隔一定距离的两个相继计量装置输送所述芯,特别是球形或圆柱形的芯,特别优选中空圆柱形的芯。这两个计量装置的第一个有利地对应于喷嘴,借助该喷嘴用本发明所用液体粘合剂喷涂在所述旋转盘中滚动的所述芯,以受控的方式使之润湿。所述第二计量装置位于喷入的液体粘合剂的雾化锥形区之外,用于供入形成所述壳的细分散的载体物质(例如通过振动斜槽)。已经以受控方式润湿的芯聚集所加入的载体物质,利用所述滚动运动将其压在所述圆柱形或球形芯的外表面上,形成粘附的壳。
需要时,已经以此方式涂底层的芯在后续旋转过程中又在所述喷嘴下面经过,从而以受控的方式润湿以致在进一步移动的过程中可再吸收一层细分散的载体物质等(一般不需中间干燥)。在此情况下,具有以前涂布的壳的芯构成所述待涂布的壳的载体。
在所述涂层催化剂的生产中,先通过在所述芯上喷撒少量干粉状氧化载体物质有利地形成薄壳。然后通过用粘合剂喷涂使之固定。再通过进一步喷撒粉状氧化载体物质使所述壳积累至要求的厚度。
要涂于芯表面的粉状氧化载体物质的细度与所要求的壳厚匹配。对于在10-500μm范围内的优选壳厚而言,粉末粒子的50%能通过筛孔为1-10μm的筛且纵向尺寸大于50μm的粒子比例小于1%的粉状载体物质特别适用。一般地,所述粉末粒子纵向尺寸的分布因生产方法而对应于高斯分布。
特别地,所述液体粘合剂的适用有机组分是一元和多元有机醇如乙二醇、1,4-丁二醇、1,6-己二醇或甘油,一元或多元有机羧酸如丙酸、草酸、丙二酸、戊二酸或马来酸,氨基醇如乙醇胺或二乙醇胺,单官能或多官能有机酰胺如甲酰胺,单糖或低聚糖如葡萄糖、果糖、蔗糖或乳糖。所述粘合剂优选由含有20-90重量%水和10-80重量%溶于水中的常压下沸点或升华温度高于100℃的有机化合物的溶液组成。所用液体粘合剂的有机物比例优选为10-50重量%,特别优选20-30重量%。
所述涂层催化剂的生产中,用粘合剂润湿以受控的方式进行是必要的。有利地使所述芯或预先形成的壳的表面润湿至这样的程度,以致液体粘合剂以吸附形式存在于其中,但所述表面上看不见液相。如果所述表面太湿,则所述粉状载体物质附聚形成分开的附聚物而非附着在所述表面上。
选自元素周期表第VIIIB族中的Ni、Pd和Pt和第IB族中的Cu、Ag和Au金属、特别是铂、钯和银的所述催化活性金属或所述金属的前体化合物可以各种方式涂布。在优选实施方案中,使所述催化活性金属或前体化合物分散在所述粉状载体物质中。可这样实现:先用所述催化活性金属的化合物在适合溶剂中的溶液浸渍所述粉状载体物质,然后需要时使所述溶剂蒸发。然后在所述涂布步骤中将所述催化活性金属或前体化合物与所述粉状载体物质一起涂于所述涂层催化剂的芯上。
另一实施方案中,使催化活性金属或前体化合物溶解或悬浮于所述粘合剂中。形成所述壳时,在用所述粘合剂喷涂载体的过程中使所述催化活性金属或前体化合物掺入所述涂层催化剂的壳中。
所述方法的再一实施方案中,通过单独的喷嘴将所述催化活性金属或前体化合物的溶液或悬浮液喷涂在所述载体上,可在形成壳的过程中或只在所述壳已形成之后进行。
所述壳已形成之后,以受控的方式最后除去所述挥发性组分,例如通过蒸发和/或升华。最简单的情况下,可在适当温度(通常为50-150℃)下通过热气的作用进行。但对于仅预干燥而言也可通过热气的作用实现。然后可在例如任何类型的干燥箱(例如带式干燥机)中进行最终干燥。所述温度应这样选择以致所述壳的孔隙率不发生显著变化。
本发明方法的特殊优点在于可在一个工艺步骤中生产具有两或多层不同组成的叠置壳的涂层催化剂。本发明方法不仅使相继层之间的粘合力好,而且使最下层与芯表面的粘合力好。在环形芯的情况下也是如此。
本发明方法中,一般不必采用高温处理(焙烧)以通过部分熔合粘结所述粉状载体物质的粒子。但为提高所述涂层催化剂的稳定性,挥发性组分蒸发后在200-600℃下焙烧所述涂层催化剂可能是有利的。所述焙烧在相对较低的温度下进行。
本发明涂层催化剂在氢化反应中显示出极好的选择性。因而,本发明涂层催化剂优选用于烃馏分、优选C2-C4馏分的气相氢化。
具体实施方式
通过以下实施例说明本发明。
实施例
实施例1:对比催化剂的生产
通过在室温下用硝酸银形式的0.045重量%银和硝酸钯形式的0.025重量%钯(基于所用载体的质量)的硝酸水溶液喷涂来浸渍BET表面积为8m2/g的挤出物形式的氧化铝载体。所述溶液体积为所述载体吸水容量的90%。将所述催化剂在80℃下干燥,然后在400℃下焙烧。光学显微镜法显示所述挤出物外部区域形成约250-300μm宽的活性组分区。
实施例2:本发明催化剂1
如下生产本发明催化剂1:通过平行添加包含增粘剂(甘油)和以硝酸银形式使用的0.045%银和以硝酸钯的硝酸溶液形式使用的0.0925%钯(基于Versal的用量)的溶液,用100g Versal(来自La Roche的氧化铝,在1050℃焙烧5小时,BET表面积:40m2/g)涂布500g直径2.5-3mm的非多孔性滑石球,干燥和在300℃下焙烧。光学显微镜法显示所得壳的厚度最大为200μm。
实施例3:本发明催化剂2
如下生产本发明催化剂:用以硝酸银形式使用的0.045%银和以硝酸钯的硝酸溶液形式使用的0.0925%钯浸渍Versal(在1100℃焙烧6小时,BET表面积:55m2/g),干燥和在400℃下焙烧。在添加增粘剂(甘油)水溶液的情况下用80g所述浸渍银和钯的Versal涂布500g直径2.5-3mm的非多孔性滑石球,干燥和在300℃下焙烧。
常压下在实验室装置中测试实施例1至3中所述催化剂的性能。
在固定床反应器中使99%(体积)乙烯和1%(体积)乙炔的预混物通过66ml的各催化剂,加入所述预混物中的氢气与乙炔之比为1.8∶1,GHSV为3000l/h。
在乙炔的转化率为90%的情况下,为了获得对所需产品乙烯的各选择性需要以下温度:
催化剂 | 温度[℃] | 对乙烯的选择性[%] |
对比催化剂 | 69 | 25 |
催化剂1 | 85 | 57 |
催化剂2 | 100 | 61 |
由于所述限定的活性组分分布,本发明催化剂显示出与传统通过浸渍生产的催化剂相比显著提高的对所需产品乙烯的选择性。
Claims (15)
1.一种生产具有芯和包围所述芯的至少一层壳的涂层催化剂的方法,其中
所述芯由惰性载体材料组成,
所述壳由多孔载体物质组成,所述壳以物理方式附着在所述芯上,和选自元素周期表第VIIIB族中的Ni、Pd和Pt和第IB族中的Cu、Ag和Au金属的至少一种催化活性金属或所述催化活性金属的前体以均匀分布的细分散形式存在于所述壳中,
所述方法包括以下步骤:
a)提供包含惰性载体材料的载体以形成所述涂层催化剂的芯;
b)在使所述载体保持运动的同时在所述载体上喷撒氧化的粉状载体物质以形成壳;
c)用包含常压下沸点或升华点高于100℃的有机化合物的水溶液的液体粘合剂喷涂所述载体;
d)加入选自元素周期表第VIIIB族中的Ni、Pd和Pt和第IB族中的Cu、Ag和Au金属的催化活性金属或这些金属的前体化合物;
e)使挥发性组分蒸发;
f)适当时,使所述金属的前体化合物活化,其中步骤b、c和d可同时进行或以任何顺序相继进行,需要时也可进行两次或多次,
其中所述催化活性金属或所述前体化合物溶解或悬浮于所述粘合剂中,并在用所述粘合剂喷涂所述载体的过程中使所述催化活性金属或前体化合物掺入所述涂层催化剂的壳中,或者将所述催化活性金属或前体化合物的溶液或悬浮液单独喷涂在所述载体上,这可以在形成壳的过程中或在所述壳已形成之后进行。
2.权利要求1的方法,其中所述芯的载体材料是多孔性的,所述载体材料的孔的总体积相对于所述载体材料的体积是≤1%体积。
3.权利要求1或2的方法,其中所述催化金属的前体是金属氧化物或水溶性金属盐。
4.权利要求3的方法,其中所述催化金属的前体是氯化物、硝酸盐、C1-C10-羧酸盐、碳酸盐、碳酸氢盐、硫酸盐、硫酸氢盐或磷酸盐。
5.权利要求1或2的方法,其中提供多层叠置的壳,其中所述壳包含不同的催化活性金属和/或相邻壳内所述催化活性金属的浓度不同。
6.权利要求1或2的方法,其中所述壳的厚度为1-1000μm。
7.权利要求6的方法,其中所述壳的厚度为10-500μm。
8.权利要求6的方法,其中所述壳的厚度为50-300μm。
9.权利要求1或2的方法,其中先在所述载体上涂布一层干粉状载体物质,然后用粘合剂润湿,再通过喷撒干粉状载体材料产生所述壳。
10.权利要求1或2的方法,其中所述用粉状载体材料喷撒所述载体和用粘合剂喷涂所述载体是利用物理上分开的进料管线同时进行的。
11.权利要求1或2的方法,其中在所述载体上涂布第一层壳,然后涂布其组成与所述第一层壳不同的另一层壳。
12.权利要求1或2的方法,其中挥发性组分蒸发后,在200-600℃下焙烧所述涂层催化剂。
13.一种通过权利要求1或2的方法获得的涂层催化剂。
14.权利要求13的涂层催化剂用于不饱和烃的还原或纯化的用途。
15.权利要求14的用途,其中不饱和烃是C2-C4馏分。
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JP4025891B2 (ja) * | 1997-02-27 | 2007-12-26 | ビーエーエスエフ アクチェンゲゼルシャフト | 芳香族炭化水素の接触気相酸化用シェル触媒の製造方法 |
US6177381B1 (en) * | 1998-11-03 | 2001-01-23 | Uop Llc | Layered catalyst composition and processes for preparing and using the composition |
-
2000
- 2000-03-28 DE DE10015250A patent/DE10015250A1/de not_active Withdrawn
-
2001
- 2001-03-20 TW TW090106481A patent/TW592807B/zh not_active IP Right Cessation
- 2001-03-23 RU RU2002129002/04A patent/RU2002129002A/ru unknown
- 2001-03-23 AU AU2001260150A patent/AU2001260150A1/en not_active Abandoned
- 2001-03-23 US US10/221,275 patent/US20030036476A1/en not_active Abandoned
- 2001-03-23 EP EP01933749A patent/EP1278600B1/de not_active Expired - Lifetime
- 2001-03-23 CA CA002403899A patent/CA2403899A1/en not_active Abandoned
- 2001-03-23 WO PCT/EP2001/003376 patent/WO2001072415A1/de active IP Right Grant
- 2001-03-23 AT AT01933749T patent/ATE261339T1/de not_active IP Right Cessation
- 2001-03-23 JP JP2001570371A patent/JP2003527962A/ja not_active Withdrawn
- 2001-03-23 KR KR1020027012878A patent/KR20030003241A/ko not_active Application Discontinuation
- 2001-03-23 CZ CZ20023237A patent/CZ20023237A3/cs unknown
- 2001-03-23 CN CNB018072232A patent/CN1164362C/zh not_active Expired - Fee Related
- 2001-03-23 DE DE50101660T patent/DE50101660D1/de not_active Expired - Fee Related
-
2002
- 2002-09-27 NO NO20024648A patent/NO20024648L/no unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102215963B (zh) * | 2008-11-19 | 2013-11-13 | 环球油品公司 | 用于进行选择性氢化的层状球催化剂配制剂 |
Also Published As
Publication number | Publication date |
---|---|
CA2403899A1 (en) | 2001-10-04 |
DE10015250A1 (de) | 2001-10-04 |
EP1278600A1 (de) | 2003-01-29 |
NO20024648D0 (no) | 2002-09-27 |
DE50101660D1 (de) | 2004-04-15 |
WO2001072415A1 (de) | 2001-10-04 |
ATE261339T1 (de) | 2004-03-15 |
CZ20023237A3 (cs) | 2003-01-15 |
JP2003527962A (ja) | 2003-09-24 |
CN1419474A (zh) | 2003-05-21 |
KR20030003241A (ko) | 2003-01-09 |
EP1278600B1 (de) | 2004-03-10 |
RU2002129002A (ru) | 2004-02-27 |
AU2001260150A1 (en) | 2001-10-08 |
NO20024648L (no) | 2002-09-27 |
TW592807B (en) | 2004-06-21 |
US20030036476A1 (en) | 2003-02-20 |
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