CN1267183C - 催化剂或吸附剂床 - Google Patents
催化剂或吸附剂床 Download PDFInfo
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Abstract
本发明涉及一种包含经受高温操作的颗粒催化剂或者吸附剂材料(10)的固定床,所述固定床具有相对于流体流过床的方向倾斜的特定形状的边界元件(16),所述边界元件(16)能够在经过一系列热膨胀和热收缩循环后使所述催化剂或者吸附剂的深度保持在床的边界处。通过保持床的深度,特定形状的边界元件(16)例如可防止通过颗粒氨氧化催化剂床的氨旁通。
Description
技术领域
本发明涉及催化剂或者吸附剂的固定床,特别涉及通过一系列热膨胀-热收缩循环保持床厚度以提高床的效率的装置。
背景技术
固定床通常包括至少一层采用挤出物、球粒或者粒状物形式的颗粒材料形式的催化剂或者吸附剂,所述催化剂或者吸附剂层由处理流体不渗透的边界元件界定并且被设置在带孔元件上,例如孔板、格栅或者网,通过该床的处理流体能够通过所述带孔元件。该床设置在容器内,其中例如利用凸耳直接由容器壁支撑该床,或者利用与容器壁相连的诸如篮或者框架的处理流体不渗透的床支撑装置支撑该床。
边界元件可以固定或者不固定到带孔元件上。但是,该边界元件通常平行于流体流过床的方向并且防止颗粒与该床设置在其中的容器的壁接触。在床经受高温的情况下,由于边界元件保护容器壁或者床支撑元件不受处于高温的颗粒催化剂或者吸附剂的影响,因此这样一种边界元件可被描述为热防护装置。
最好,通过催化剂或者吸附剂床的气流或者液流是均匀的以在催化剂床的情况下在转变方面或者在吸附剂床的情况下在吸收方面提供一致的操作。为了达到这种效果,颗粒的尺寸,特别是颗粒层的厚度通常被精心控制以获得均匀的通过处理流体可流过的床的渗透率。这对于薄的固定床,即深度小于容器直径的床是特别重要的。
包含催化剂或者吸附剂床颗粒的固定床,特别是经受高温的薄固定床所遇到的一个问题是,在颗粒与边界元件接触的情况下,发现例如与启动-停止程序相关的床的热膨胀和热收缩可导致床的深度减小,特别是在床与边界元件接触的区域中。因此,通过床的气流路径在边界元件附近缩短,因而通过床的气流或者液流,即,渗透率在高区域升高。
通过床的流量增大会减少流体和催化剂或者吸附剂之间的接触时间,并且可导致流体旁通的问题。对于要求基本上为100%的转化率的催化过程,这可导致非反应物质进入产品流,而对于类似地需要基本上完全去除污染物的吸附剂床,这可导致所不希望的在任何下游工艺和/或产品中存在污染物。
我们发现,使用特定形状的边界元件可保持通过一系列热膨胀和热收缩的循环后的床的厚度,从而减少旁通的问题。
发明内容
因此,本发明提供一种可使处理流体流过的固定床,所述固定床包括设置在带孔元件上并且由处理流体不渗透边界元件界定的颗粒材料,其中,所述边界元件的至少一部分以相对于流体流过所述床的方向形成20至70度之间的总角度至少在床的基本深度上界定所述颗粒材料。
在本发明中,固定床可经受可为气体或者液体的处理流体的轴向和/或径向流动。最好,本发明的床经受轴向流并且例如可沿着基本水平的方向设置在容器中,而处理流体基本垂直流过床。
所述床包括设置在诸如具有适合尺寸的用于防止颗粒流过的孔的孔板、网或者格栅的带孔元件上的催化剂或者吸附剂颗粒。一种例如作为支撑层的惰性颗粒材料也可存在于催化剂或者吸附剂下方,也构成了床的部分深度。所述床可利用与容器壁相连的凸耳或者利用与容器壁相连的篮、托架或者框架通过带孔元件或者边界元件被容器壁支撑。最好,所述床利用与容器壁相连的处理流体不渗透的篮或者框架通过带孔元件被支撑。这样的装置根据床、容器和工艺的类型而改变,并且可被称为“床支撑装置”。该床可具有提供所需作业所需的任何形状。通常,床的形状与将其设置在其中的容器的横截面的形状相符。例如,该床可是圆形的、椭圆形、正方形、矩形、六边形或者八边形。该床的宽度可0.25米至6米的范围内,最好在0.5米至3.5米的范围内。
本发明特别适用于床较薄的情况,即床的深度小于容器直径。最好,本发明的床的深度在5和500毫米之间,在25和300毫米之间较好,最好在25和100毫米之间。
催化剂或者吸附剂颗粒或者惰性颗粒支撑材料(如果有的话)采用球、小板、方块、挤出物、圆柱形弹丸、粒状物或者其他规则的或者不规则的形状,高宽比,即最大尺寸被最小尺寸除,通常小于2。颗粒的尺寸根据需要可是均匀的或者不同的以在气体或者液体与催化剂或者吸附剂之间产生所需的接触时间。
本发明的边界元件的尺寸和形状将根据床的尺寸和容器壁的性质或者床支撑装置改变。本发明的边界元件可或者不固定在支撑床的带孔元件上。在一个优选实施例中,为了降低由于床的热膨胀和热收缩而产生的应变作用,边界元件不固定在带孔元件上。在该实施例中,边界元件将界定催化剂或者吸附剂的颗粒以使颗粒材料不能通过在边界元件和带孔元件之间的任何保留间隙,在床的至少基本深度上延伸并且与容器或者床支撑装置相连,例如在适合位置处独立支撑带孔元件的篮,所述适合的位置可在床的上方或者下方。或者,如上所述,边界元件可与带孔元件相连。无论边界元件如何与其相连,任何床支撑装置都应该围绕床的周边提供处理流体不渗透阻挡层以使基本上所有的流体直接通过设置在带孔元件上的颗粒材料。
边界元件从带孔元件至少延伸床的深度并且以相对于流体流过所述床的方向形成20至70度之间的总角度相对于床的深度倾斜。如果总角度小于20度,那么在一系列热膨胀和热收缩循环后床的深度将不能被有效地保持;如果总角度大于70度,那么可能被边界元件占据的床表面积的一部分太大。总角度最好在相对于流体流过所述床的方向形成20至60度之间。对于术语“总角度”,我们指的是,流体流过大部分床的基本方向和在边界元件的下端与边界元件与床的上表面基本上相交的点之间绘制的直线之间的角度。边界元件包括至少一个基本上从带孔元件延伸到容器壁或者床支撑装置的小面。最好,边界元件包括在1和50个小面。每一个小面可具有各种形状,例如直的或者曲面并且提供在所需范围内的总角度的这些小面的任何组合可被使用。但是,最好这些小面的任何组合不封闭颗粒材料或者防止处理流体流过与边界元件接触的大部分颗粒材料。这样,在小面是曲面的情况下,小面的下端最好相对于流体流过所述床的方向形成的角度不大于90度。
已经发现,在床的表面下方提供至少一个台阶的小面组合可提高边界元件在结果一系列热膨胀和热收缩循环后保持床的周边深度方面的性能。对于术语“台阶”,我们指的是,以大于在其紧上方的小面相对于流体流过所述床的方向的角度的角度在床中延伸一定距离,例如等于床的深度的10%至50%之间的距离的至少一个直的或者曲面的小面。最好,提供在1和10个之间的台阶。台阶可具有相同或者不同的尺寸,并且包括不同台阶的小面可具有相同的或者不同的相对于流体流过所述床的大部分的方向的角度。在一个优选实施例中,提供台阶,并且所述台阶最好位于床的深度的25%至75%之间的深度处。最好,台阶角度相对于流体流过所述床的大部分的方向为90度。
边界元件的厚度取决于多种因素,包括容器和/或床的尺寸,但在1-25毫米的范围内较好,最好在1-10毫米的范围内。
边界元件可利用任何适用于催化剂或者吸附剂处理条件下的材料制成。通常,边界元件是由抗氧化合金制成的,例如310不锈钢。
本发明的固定床的具有特定形状的边界元件具有或者没有用于在一系列热膨胀和热收缩循环后保持构成床的颗粒材料的厚度的台阶,从而减少了反应剂或者污染物旁通的可能性。
在另一个可选择的实施例中,固定床包括上述基本上从带孔元件延伸到在床表面上方的一个位置的第一外边界元件和设置在第一边界元件和从在床的表面下方远离带孔元件的位置延伸到在床的表面上方的位置的第二内边界元件之间的颗粒材料,例如催化剂、吸附剂或者惰性材料的存储区。
第二边界元件可具有任何任何适于限定颗粒材料的存储区的形状;例如,在床的表面上方的小面与流过所述床的流体流对准或者可平行或者以一定角度远离第一边界元件。最好,在床内的第二边界元件的形状是这样的,即,它具有相对于流体流过所述床的方向成20至70度之间的总角度以防止第二边界元件影响床的厚度。第一和第二边界元件的形状和它们延伸到床的表面上方的距离以及它们的间距可用于限定存储区的体积。最好,第一和第二边界元件延伸到床的表面上方的距离在5和300毫米之间,并且第一和第二边界元件之间的最近距离最好在10和100毫米之间。最好,第二边界元件在床的表面的下方延伸到小于床深度的60%的深度处以减小第二边界元件影响床的厚度的可能性。最好利用能够使处理流体流过存储区进入床中的固定装置,例如与通过所述存储区的处理流体流对准的螺栓、支柱、隔销或者板将第二边界元件固定到第一边界元件上。最好,以使颗粒可在重力作用下通向床的方式设置存储区。
第二边界元件的厚度在1-25毫米的范围内较好,最好在1-10毫米的范围内,并且可利用与第一边界元件相同的材料制造。
通过以这样的方式形成存储区,固定床的深度以及周边的渗透率可被控制,例如在经过一系列热膨胀和热收缩循环后。在第一和第二边界元件之间的增大的床厚度能够减少在该区域中的渗透率,并且如果出现颗粒收缩,也可利用来自于存储区的催化剂或者吸附剂颗粒来维持床的体积。
如上所述,本发明的固定床可是固定催化剂床。最好,催化剂可是适用于薄床中的任何催化剂。可在薄床中使用催化剂的处理例如包括:例如使用颗粒钴基催化剂的氨的氧化、例如使用钼酸钴或者钼酸镍氢化脱硫催化剂的氢化脱硫、例如使用银催化剂的甲醛制造、氰化氢制造和部分氧化反应,例如用于作为所谓的“气到液”(GTL)工艺的一部分的碳氢化合物的部分氧化。诸如氧化铝丸的惰性颗粒也可存在,例如在催化剂的下方作为支撑层。惰性颗粒的尺寸可与颗粒催化剂相同或者不同。
本发明的固定床也可是固定吸附剂床。对于术语“吸附剂”,我们必需包括吸附剂和吸附材料。任何适用于从处理流体中去除硫、汞、砷或者其化合物、水和/或氯化氢的吸附剂可被使用。吸附材料的示例包括用于去除硫的碱式碳酸锌、锰的氧化物和铜/锌氧化物、用于去除汞和去除砷的硫化铜以及用于去除氯化氢的铝酸钠或者碳酸铅。
特别是,本发明适用于床经受高温的情况。床的温度大于100℃较好,大于200℃更好,最好大于500℃。
附图说明
现将参照附图对本发明进行描述,在附图中:
图1是第一实施例所涉及的圆形固定催化剂或者吸附剂床的边界区域的截面图;
图2是第二实施例所涉及的圆形固定催化剂或者吸附剂床的边界区域的截面图;以及
图3是第三实施例所涉及的圆形固定催化剂或者吸附剂床的边界区域的截面图。
具体实施方式
在图1、2和3中,处理流体流过床的大部分的方向用箭头“A”表示,该方向基本上是垂直的。为了清楚起见,附图1、2、3示出了在处理流体流过床的大部分的方向(A)和在边界元件下端(C)与床的表面(B)之间绘制的直线之间的总角度(θ)。
参见附图,图1示出了例如用于氨氧化的催化剂床。该床是由设置在具有能够使气体流过床的孔13的带孔元件12上的在一层尺寸较大的惰性氧化铝颗粒11上的一层含钴催化剂颗粒10提供的。该床通过带孔元件12被支撑,带孔元件12抵靠在与容器壁15相连的凸耳14上。
边界元件包括防止床10接触容器壁15的直的小面16、17和18。小面16在床上方的连接点19处与容器壁15相连并且以相对于处理流体流过床的方向成30度的角度朝向床向下延伸到基本上处于连接点19和床10的表面之间的一半距离的位置处;小面17以0度,即基本上平行于处理气体的流向从小面16的下端在床的表面下方延伸到基本上等于床的厚度的50%的深度处;以及小面18以相对于处理流体流过床的方向成35度的角度从小面17的下端延伸到带孔元件12,延伸到基本上等于床的厚度的97%的深度处。边界元件的总角度(θ)(即,处理流体流过床的方向A和点B-C之间绘制直线之间的角度)相对于处理流体流过床的方向成20度。
在图2中,例如用于氨氧化的催化剂床由设置在具有能够使气体流过床的孔22的带孔元件21上的一层含钴催化剂颗粒20提供的。该床通过带孔元件21被支撑,带孔元件21抵靠在与容器壁24相连的凸耳23上。
边界元件包括防止床20接触容器壁24的直的小面25、26和曲面的小面27。台阶28设置在第二直小面26和曲小面27之间。直的上部小面25从在床上方的连接点27处从容器壁24以相对于处理流体流过床的方向成50度的角度延伸到基本上处于连接点27和床20的表面之间的一半距离的位置处;小面26以5度的角度从直的上部小面25的下端延伸到基本上等于床的厚度的33%的深度处;台阶28包括第一直台阶小面29和第二直台阶小面30,第一直台阶小面29以相对于处理流体流过床的方向成90度的角度从直的上部小面26的下端延伸等于床的厚度的15%的距离,第二直台阶小面30沿着远离床的方向以35度的角度从第一直台阶小面29的端部延伸基本上等于第一直台阶小面29长度的距离。曲小面27与第二直台阶小面30的端部相连并且以45度的弦角朝向床延伸到基本上等于床的厚度的97%的深度处。边界元件的总角度(θ)(即,处理流体流过床的方向A和点B-C之间绘制直线之间的角度)相对于处理流体流过床的方向成30度。
在图3中,例如用于氨氧化的催化剂床由设置在具有能够使气体流过床的孔42的带孔元件41上的一层含钴催化剂颗粒40提供的。该床通过带孔元件41被支撑,带孔元件21抵靠在与容器壁44相连的凸耳43上。
第一边界元件包括防止床40接触容器壁44的直的小面45、46和曲面的小面47。小面45在床上方的连接点48处与容器壁44相连并且以相对于处理流体流过床的方向成30度的角度朝向床向下延伸到基本上处于连接点48和床40的表面之间的一半距离的位置处;小面46以0度,即基本上平行于处理气体的流向从小面45的下端在床的表面下方延伸到基本上等于床的厚度的50%的深度处;以及曲小面47以45度的弦角从小面46的下端延伸到基本上等于床的厚度的97%的深度处。边界元件的总角度(θ)(即,处理流体流过床的方向A和点B-C之间绘制直线之间的角度,其中B与床的大部分的表面平齐)相对于处理流体流过床的方向成20度。
含钴的催化剂颗粒49的存储区设置在第一边界元件和第二边界元件50之间,第二边界元件50从基本上与所述第一边界元件的连接点48平齐的点处延伸到床中并且延伸到基本上等于床的厚度的50%的深度处。利用安装在第一边界元件上的分隔支柱(未示出)使第二边界元件定位。第二边界元件包括从床的表面上方延伸到床的表面的基本上垂直的直小面和以45度的弦角从与床垂直的小面的下端延伸到床中的曲小面。存储区具有基本上等于床的厚度的50%的深度并且第二边界元件以大约为床的厚度的四分之一的最近距离与所述第一元件隔开。第二边界元件的总角度(即,处理流体流过床的方向A和点B′-C′之间绘制直线之间的角度)相对于处理流体流过床的方向也成20度。
在本发明的一个优选实施例中,如在WO98/28073中所述的处于800℃和900℃之间的用于氨氧化的50毫米深的钴-稀土钙钛矿的催化剂床被设置在0.5-6米的圆形横截面的反应器中,所述催化剂床具有从床支撑装置朝向床延伸的连续周边边界元件,所述边界元件包括直的上部小面和曲面的下部小面并且在所述小面之间具有延伸到床中5至15毫米的台阶。在曲小面的下端和边界元件与床的表面相交的点之间的总角度为相对于流体通过床的方向成20至70度之间。该催化剂颗粒通常为3毫米长和直径为3毫米的圆柱形丸粒。它们可被支撑在深度例如为25毫米的直径通常为3-10毫米的α氧化铝丸粒层上。在经过一系列热膨胀和热收缩循环后边界元件保持床的厚度。
尽管前面参照氨氧化工艺对上述实施例进行了描述,但是应该理解的是,本发明的固定床也可用于许多工艺,特别是如上所述的使用催化剂或者吸附剂的薄床的工艺。
Claims (8)
1.一种固定床,该固定床的深度小于其所处的容器的直径,该固定床的深度在5和500mm之间,所述固定床包括设置在带孔元件上并且由处理流体不渗透边界元件界定的颗粒材料,其特征在于,所述边界元件不固定在带孔元件上并且所述边界元件的至少一部分以相对于流体流过所述床的方向形成20至70度之间的总角度至少在床的基本深度上界定所述颗粒材料,所述边界元件总角度(θ)为流体流过床的体积的方向(A)和边界元件的下端与边界元件与床的上表面相交点之间形成的直线(B-C)之间的角度。
2.如权利要求1所述的固定床,其特征在于,所述边界元件包括在1至50个之间的曲面和/或直的小面。
3.如权利要求2所述的固定床,其特征在于,提供可在所述床的表面下方设置至少一个台阶的小面的组合。
4.如权利要求1至3中任何一项所述的固定床,其特征在于,所述固定床具有基本上从带孔元件延伸到在床表面上方的一个位置的第一外边界元件和设置在第一外边界元件和第二内边界元件之间的颗粒材料存储区,第二内边界元件从在床的表面下方远离带孔元件的位置延伸到在床的表面上方的位置。
5.如权利要求1所述的固定床,其特征在于,所述颗粒材料包括催化剂或者吸附剂,还可选择地包括一种惰性材料。
6.如权利要求1所述的固定床的用途,其特征在于,所述床经受大于100℃的温度。
7.如权利要求1所述的固定的吸附剂床的用途,其用于从处理流体中去除含硫、汞、砷、水和/或氯化氢的材料。
8.如权利要求1所述的固定的催化剂床的用途,其用于氨的氧化、氢化脱硫、氰化氢制造、甲醛制造或碳氢化合物的部分氧化反应。
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DE102011112781A1 (de) | 2011-09-09 | 2013-03-14 | Thyssenkrupp Uhde Gmbh | Vorrichtung zur Bypass-Minderung in Ammoniak-Oxidationsbrennern |
DE102011112782A1 (de) | 2011-09-09 | 2013-03-14 | Thyssenkrupp Uhde Gmbh | Vorrichtung zur Bypass-Minderung in Ammoniak-Oxidationsbrennern |
WO2015022247A1 (de) | 2013-08-16 | 2015-02-19 | Basf Se | Korbartige vorrichtung mit wandisolierung |
DE102014223813A1 (de) * | 2014-11-21 | 2016-05-25 | Thyssenkrupp Ag | Brennerkorb für einen Ammoniak-Oxidationsbrenner |
EP3501633A1 (en) | 2017-12-19 | 2019-06-26 | Yara International ASA | Catalyst support systems for ammonia oxidation burners |
FR3083718B1 (fr) | 2018-07-11 | 2020-07-03 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Dispositif en toile permettant de limiter ou supprimer la migration de particules entre deux couches |
FR3083717B1 (fr) * | 2018-07-11 | 2020-06-26 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Dispositif permettant de limiter ou supprimer la migration de particules entre deux couches |
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Publication number | Priority date | Publication date | Assignee | Title |
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BE792236A (fr) * | 1971-12-17 | 1973-06-01 | Inst Francais Du Petrole | Appareil pour la conversion d'hydrocarbures |
US3909209A (en) * | 1973-11-05 | 1975-09-30 | Gould Inc | Method of treating aluminum and aluminum alloys and article produced thereby |
JPS55116439A (en) * | 1979-03-02 | 1980-09-08 | Koei Chem Co Ltd | Catalyst support |
JPS5959244A (ja) | 1982-09-27 | 1984-04-05 | Mitsui Eng & Shipbuild Co Ltd | 気相流動層反応器 |
SE447819B (sv) | 1983-09-16 | 1986-12-15 | Ifoe Sanitaer Ab | Anordning for neutralisering av forsurat vatten |
FR2590499B1 (fr) * | 1985-11-27 | 1988-06-10 | Flork Sa Laboratoires | Colonne de traitement physique ou chimique en phase heterogene |
US5710089A (en) * | 1995-06-07 | 1998-01-20 | Phillips Petroleum Company | Sorbent compositions |
FR2741823B1 (fr) * | 1995-12-05 | 1998-01-23 | Air Liquide | Installation de traitement d'au moins un fluide et utilisation pour la separation d'au moins un constituant d'un melange gazeux |
JPH09315801A (ja) | 1996-03-26 | 1997-12-09 | Toyota Motor Corp | 燃料改質方法と燃料改質装置ならびに該燃料改質装置を備えた燃料電池システム |
GB9626516D0 (en) | 1996-12-20 | 1997-02-05 | Ici Plc | Ammonia oxidation |
-
2001
- 2001-07-27 GB GBGB0118322.7A patent/GB0118322D0/en not_active Ceased
-
2002
- 2002-07-03 RU RU2004105850/12A patent/RU2290987C2/ru not_active IP Right Cessation
- 2002-07-03 EP EP02735664A patent/EP1412074A1/en not_active Withdrawn
- 2002-07-03 KR KR1020047001108A patent/KR100823422B1/ko not_active IP Right Cessation
- 2002-07-03 CA CA002454933A patent/CA2454933A1/en not_active Abandoned
- 2002-07-03 JP JP2003516673A patent/JP4334340B2/ja not_active Expired - Fee Related
- 2002-07-03 BR BR0211495-0A patent/BR0211495A/pt not_active IP Right Cessation
- 2002-07-03 CN CNB028163974A patent/CN1267183C/zh not_active Expired - Fee Related
- 2002-07-03 US US10/485,049 patent/US7323152B2/en not_active Expired - Fee Related
- 2002-07-03 WO PCT/GB2002/003075 patent/WO2003011448A1/en active IP Right Grant
- 2002-07-03 AU AU2002310553A patent/AU2002310553B2/en not_active Ceased
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2004
- 2004-01-23 IN IN64MU2004 patent/IN2004MU00064A/en unknown
- 2004-01-26 NO NO20040343A patent/NO20040343L/no not_active Application Discontinuation
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IN222892B (zh) | 2009-02-06 |
JP4334340B2 (ja) | 2009-09-30 |
US20040234433A1 (en) | 2004-11-25 |
WO2003011448A1 (en) | 2003-02-13 |
US7323152B2 (en) | 2008-01-29 |
BR0211495A (pt) | 2004-08-17 |
RU2290987C2 (ru) | 2007-01-10 |
RU2004105850A (ru) | 2005-02-27 |
CA2454933A1 (en) | 2003-02-13 |
KR100823422B1 (ko) | 2008-04-17 |
KR20040021652A (ko) | 2004-03-10 |
EP1412074A1 (en) | 2004-04-28 |
AU2002310553B2 (en) | 2007-05-31 |
CN1545434A (zh) | 2004-11-10 |
IN2004MU00064A (en) | 2005-04-29 |
NO20040343L (no) | 2004-02-23 |
JP2004536704A (ja) | 2004-12-09 |
GB0118322D0 (en) | 2001-09-19 |
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