CN101227976A - 催化剂载体 - Google Patents

催化剂载体 Download PDF

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CN101227976A
CN101227976A CNA2006800142839A CN200680014283A CN101227976A CN 101227976 A CN101227976 A CN 101227976A CN A2006800142839 A CNA2006800142839 A CN A2006800142839A CN 200680014283 A CN200680014283 A CN 200680014283A CN 101227976 A CN101227976 A CN 101227976A
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N·林格
G·泽利希
H-J·米勒
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Abstract

本发明涉及一种圆柱形的催化剂体(1)，其特征为，在催化剂体(1)的圆周面(3)上设有压痕。这些压痕尤其是设计成凹槽(4)和筋(5)，它们平行于催化剂体(1)的纵轴线(2)分布。

Description

催化剂载体
技术领域
本发明涉及一种例如可用于碳氢化合物蒸汽重整的催化剂载体。
背景技术
为了在放热催化反应时在气相得到尽可能高的流通量和尽可能高的产出量，应该在气相和催化剂表面之间提供尽可能大的接触面，从而使催化剂和气态反应组分之间可以剧烈地交换。因此对于放热催化反应开发了反应器，在它里面提供小的催化剂体的松散散装物作为催化剂。这里散装物必须做成这样，使得一方面提供大的表面作为固态催化剂和气态反应物之间的接触面，但是另一方面在反应器上的压降不能太大，否则通过反应器的气体流量将下降或要求反应气体强烈压缩。加入反应器的催化剂应该以尽可能大的份量供给催化反应。因此催化剂散装物应该具有不太高的密度，因为否则设置在催化剂体较深处的区域内的、因此不能用于反应的催化的催化剂份量便大大上升，亦即催化剂体应该具体尽可能大的表面积与重量之比。催化剂体仅仅必须具有足够的机械稳定性，使它们在受机械载荷时不碎裂和粉碎成细的粉末或颗粒，粉末或颗粒堵塞催化剂组件内部的流动路径，并导致压降上升。催化剂体仅仅必须做成这样的形状，使它们在装入反应器时形成希望的散装物，亦即催化剂体例如不允许歪斜，使得在反应器内不形成没有填充催化剂的较大空腔。
因此除了简单的球或颗粒外还开发出整个一个系列的催化剂体，它们提供均匀的散装物和尽可能大的表面。尽管已经存在对于催化剂体的大量的形状多样性，但是始终还有进一步开发的空间。
装灌催化剂或催化剂体的反应器大多在几个月直至几年的较长时间段内连续地运行，因此在制造希望的化合物时在产量方面小的增加对设备的盈利性便已经具有大的经济效果。
同样一个即使在催化剂成形体稳定性方面的很小的增加大多意味着有意义的经济利益，因为可以延长设备的运行时间，并且为了更换催化剂组件只需要少的制造过程中断。
在DE3935073中介绍了一种在提高温度的情况下以水蒸汽和金属氧化物催化剂成形体对流使碳氢化合物、特别是烷基芳香物质(Alkylaromaten)催化脱氢的方法。成形体具有一种带至少三个齿的齿轮形结构，其中遵照以下尺寸比：
a)顶圆直径(d2)与根圆直径(d1)之比约为1.2至2.5∶1；
b)在齿根处的齿间宽度(b1)与齿顶处的齿宽(b2)之比为0.1至0.9∶1；
c)在齿根处的齿间宽度(b1)至少为0.1mm。
在DE3934032A1中介绍了一种热传递元件或填充物元件，它具有一沿纵向延伸的芯部区域，在它上面设置沿纵向分布的具有T形横截面的凸台。
在DE3141942A1中介绍了一种具有基本上圆柱形造型的催化剂成形体，它具有许多纵向凹槽，各纵向凹槽从圆柱体圆周沿径向向内延伸，并围成位于它们之间的突起，突起的最大宽度大于凹槽宽度。
在DE3118835A1中介绍了一种用于n-丁烷的部分氧化以制造马来酸酐(Maleinsureanhydrid)的催化剂结构。催化剂具有薄片形状，在其中心设一孔或空腔。
在DE2914079中介绍了具有活性材料的更换散装体，它们特别适合于从大量水中采选原踪物质。散装体具有机械稳固的外轮廓和一防止受相邻物体机械作用的液体可接触的活性表面。
在DE2719543A中介绍了一种用来存放催化剂的、特别是用于碳氢化合物转化的陶瓷体。陶瓷体具有管子形状，在其内部空腔内设置一些从纵轴线的径向向外伸展的筋。
在DE2425058中介绍了一种由陶瓷材料组成的填充体，它们具有管段形状。管段具有许多相互平行分布的纵向通道。其中围绕一中央纵向通道可以设置许多纵向通道。
发明内容
因此本发明的目的是，提供一种催化剂体，它使得可以制造尽可能均匀的催化剂散装物，其中应该提供尽可能大的催化剂体表面。
这个目的用具有权利要求1特征的催化剂体实现，优良的改进结构是从属权利要求的内容。
按照本发明提供一种圆柱形的催化剂体，该催化剂体在其圆周面上具有平行于催化剂体纵轴线分布的凹槽以及分布在凹槽之间的筋，此催化剂体的特征是，凹槽和分布在凹槽之间的筋在其横截面中具有圆弧段的形状。
通过设置在催化剂体圆周面上的凹槽和筋，扩大了催化剂体的表面积，因此与纯圆柱形相比在同样数量的活性物质的情况下提供在催化剂和气态反应物之间的更大的接触面。由此可以在催化剂量不变的情况下实现流过反应器的反应物的更大流量，其结果是单位时间内产量的提高。凹槽在其横截面内具有圆弧段的形状。这里把垂直于催化剂体纵轴线的剖面看作横截面。通过凹槽的圆弧形结构避免应力集中，它们可能导致催化剂体破裂。在凹槽之间分布筋，其横截面也具有圆弧段的形状，通过筋表面的横截面的圆弧形形状避免棱边，棱边例如在催化剂体装入反应器时可能断裂。在本发明的催化剂体中筋的圆弧段的半径选择得与凹槽的圆弧段的半径不同。因此催化剂体不能用这样的方法堆放，即一个催化剂体的筋贴合在另一个催化剂体的凹槽上，其中筋和凹槽的相配对的表面相互平整贴合，并造成可供使用的催化剂表面减小。如果筋的横截面的半径小于凹槽的半径，筋虽然能紧靠在凹槽内，但是凹槽和筋的表面相互不是平整贴合。在优选的实施形式中，筋的圆弧段的半径大于凹槽的圆弧段的半径。用这种方法使筋不能进入凹槽内和贴合在那里。凹槽圆弧段的半径最好在1至5mm之间，特别优选选择在2至3mm之间。筋的圆弧段半径最好为2至5mm之间，特别优选在3至4mm之间。
催化剂体最好具有一中央通道，它沿催化剂体纵轴线延伸。用这种方法可以进一步扩大催化剂体表面积，和进一步降低催化剂体的密度和重量，而不必在催化剂体的稳定性方面忍受大的损失。
中央通道最好具有圆形横截面。
按照一种优选实施形式，催化剂体还具有平行于纵轴线、但与纵轴线偏心分布的副通道。通过副通道达到催化剂体表面积的进一步扩大和更加减少对于产生催化剂体所必要的活性材料量。
副通道最好具有圆形横截面。
副通道的数量最好选择得大于7，特别优选大于8和特别优选等于9。副通道的数量最好选择得尽可能大，以便能够将催化剂体的表面积设计得尽可能大，并使由催化剂体引起的压降尽可能小。另一方面必须找到与催化剂体稳定性的平衡点。副通道之间的副通道与中央通道之间的筋必须足够宽，以便还能承受由散装物在单个催化剂载体上引起的负荷。
副通道的纵轴线最好设置在一圆或圆柱面上，其圆心或其轴线由催化剂体的纵轴线构成，因此催化剂载体得到一基本上旋转对称的造型，由此达到催化剂体在反应器组件内的布局方面的更高自由度，亦即提高催化剂体组件的均匀性，从而达到气体均匀地流过反应器组件。副通道的圆心或纵轴线所设置在的圆的直径最好在10至20mm之间，优选在12至16mm之间。
筋的圆弧段的圆心最好设置在相应副通道的纵轴线上。由此使从催化剂体外侧限定副通道的筋得到均匀的厚度，以及作用在催化剂体外侧上的力可以通过筋的圆弧形形状传入催化剂体，因此可提高催化剂体的稳定性。在朝催化剂体端面的视图中可看到筋的圆弧形状。
设置在催化剂体内的副通道优选具有比中央通道小的直径，中央通道的直径可以选得比较大，以便由此加大催化剂体的表面积和减小由单个催化剂体引起的压降。这里中央通道的直径这样选择，使得设置在中央通道和副通道之间的筋具有足够的厚度。以保证催化剂体必要的稳定性。
中央通道的直径最好选择在4至8mm之间，副通道的直径优选在1.5至3mm之间。在催化剂体外侧围成副通道的筋和设在副通道之间或在副通道和中央通道之间的筋的厚度最好大于1mm，优选大于1.5mm，特别优选在1.6至4mm之间选择。
为了达到催化剂体在反应器内尽可能均匀的散装，本发明的催化剂体最好设计成这样，使其沿纵轴线方向的尺寸近似地相当于催化剂体的垂直于纵轴线的直径，催化剂体的直径与其纵向尺寸之比最好在0.9至1.5之间选择。催化剂体的直径最好选择在15至30mm之间，优选在18至25mm之间和特别优选约为21mm。催化剂体在纵轴线方向的尺寸最好在15mm至30mm之间，优选在18至25mm之间，特别优选约为16mm。
为了达到催化剂体散装物尽可能长的使用寿命，催化剂体必须具有足够高的强度。这一方面可以通过催化剂体的几何结构，另一方面通道制造催化剂体的材料强度达到。催化剂体最好具有大于700N的侧向抗压强度。侧压强度可以通过这样的方法测量，即在将催化剂体夹在两个平夹爪之间并且夹爪的平表面平行于催化剂体的纵轴设置时确定促使催化剂体破裂至少所需要的力。
催化剂体特别适合于用在碳氢化合物的蒸汽重整中，在一种用作碳氢化合物的蒸汽重整的催化剂的结构中，催化剂体最好主要如下构成，分别作为金属氧化物计算：
-NiO      10-20重量％；
-CaO      10-20重量％；
-Al2O3    其余100重量％。
催化剂体可以包含少量杂质，催化剂体中Na以及SiO2的份量最好小于0.05重量％。
本发明的催化剂体可以用普通方法制造，例如通过挤出，这时催化剂体的组成部分磨成细的粉末，使得尤其是具有5至500μm的平均粒度D50，必要时掺入滑动剂，如石墨或长链脂肪酸，然后必要时在与水混合后转变成希望的形状。
本发明的另一主题是上述催化剂体用于碳氢化合物的蒸汽重整。
附图说明
下面参照附图详细说明本发明。
图1显示本发明催化剂体的一个实施形式的横剖视图。
具体实施方式
图1表示本发明催化剂体1的垂直于催化剂体1纵轴线2或朝向本发明催化剂体端面的横剖视图。催化剂体1的外围表面3由一个凹槽4和筋5的序列组成。在朝横剖视图观察时凹槽4和筋5分别做成圆弧段，其中凹槽4的圆弧段的半径6选择得小于筋5的圆弧段的半径7。因此在催化剂体并排放置时催化剂体1的筋5不会平整地紧贴在另一个催化剂体的凹槽4的表面上。一中央通道8沿催化剂体1的纵轴线2分布，围绕中央通道8在一其圆心与催化剂体1的纵轴线2重合的图9上按规则的间距设置九个副通道10，它们平行于中央通道8分布。副通道10的直径小于中央通道8的直径12。其中副通道10的纵轴线13与对应筋5的圆弧段的纵轴线或圆心重合，使得副通道朝催化剂体1的外侧由圆弧形的筋14限定，该筋具有基本上恒定的厚度。其中设置在两个副通道10之间的筋15的厚度大致相当于圆弧形筋14的厚度。在所示实施形式中设置在中央通道8和副通道10之间的筋16的厚度选择得大于设置在两个副通道10之间的筋15的厚度。催化剂体1的直径17大致相当于催化剂体沿纵轴线2方向的纵向尺寸。
图形标记列表
1     催化剂体    2     纵轴线
3     圆周面      4     凹槽
5     筋          6     半径
7     半径        8     中央通道
9     圆          10    副通道
11    直径        12    直径
13    纵轴线      14    筋
15    筋          16    筋
17    直径

Claims (17)

1.圆柱形的催化剂体，该催化剂体在其圆周面(3)上具有平行于催化剂体(1)纵轴线(2)分布的凹槽(4)以及分布在凹槽(4)之间的筋(5)，其特征为：凹槽(4)和分布在凹槽(4)之间的筋(5)在其横截面内具有圆弧段的形状，其中筋(5)的圆弧段的半径(7)不同于凹槽(4)的圆弧段的半径。
2.按权利要求1的催化剂体，其特征为：筋(5)的圆弧段的半径(7)选择得大于凹槽(4)的圆弧段的半径(6)。
3.按权利要求1或2的催化剂体，其特征为：催化剂体(1)具有一中央通道(8)，该中央通道沿催化剂体(1)的纵轴线(2)延伸。
4.按权利要求3的催化剂体，其特征为：中央通道(8)具有一圆形横截面。
5.按上述权利要求之任一项的催化剂体，其特征为：催化剂体(1)具有副通道(10)，各副通道平行于催化剂体(1)的纵轴线(2)，但是与该纵轴线偏心分布。
6.按权利要求5的催化剂体，其特征为：副通道(10)具有一圆形横截面。
7.按权利要求5或6的催化剂体，其特征为：副通道(10)的数量大于7，尤其是大于8，特别优选等于9。
8.按权利要求5至7之任一项的催化剂体，其特征为：副通道(10)的纵轴线(13)设置在一圆(9)上，其圆心由催化剂体(1)的纵轴线(2)构成。
9.按权利要求5至9之任一项的催化剂体，其特征为：筋(5)的圆弧段的圆心设置在副通道(10)的纵轴线(13)上。
10.按权利要求5至9之任一项的催化剂体，其特征为：副通道(10)具有比中央通道(8)小的直径。
11.按权利要求3至10之任一项的催化剂体，其特征为：中央通道(8)的直径在4至8mm之间选择。
12.按权利要求5至11之任一项的催化剂体，其特征为：副通道(8)的直径在1.5至3mm之间选择。
13.按上述权利要求之任一项的催化剂体，其特征为：催化剂体的直径(17)与其纵向尺寸之比在0.9至1.5之间选择。
14.按上述权利要求之任一项的催化剂体，其特征为：催化剂体(1)具有大于700N的侧压强度。
15.按上述权利要求之任一项的催化剂体，其特征为：催化剂体(1)主要如下构成，分别以金属氧化物计算：
-NiO      10-20重量％
-CaO      10-20重量％
-Al2O3    其余100重量％
16.按上述权利要求之任一项的催化剂体，其特征为：催化剂体(1)中Na和SiO2的份额少于0.05重量％。
17.按权利要求18或19的催化剂体用于碳氢化合物的蒸汽重整的应用。
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