CN102149466A - 成型异相催化剂 - Google Patents
成型异相催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
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- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J23/74—Iron group metals
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Abstract
描述了一种具有长度为C和直径为D的圆柱体形式的催化剂单元,其含有沿着它的长度延伸的两个或更多个沟槽,其中所述圆柱体含有长度为A和B的圆顶端,并满足(A+B+C)/D在0.50至2.00范围内,和(A+B)/C在0.40至5.00范围内的条件。催化剂可以尤其用于其中氢为反应物的反应,例如加氢处理,氢化,水煤气变换反应,甲烷化,通过费-托反应的烃合成,甲烷合成和氨合成。
Description
本发明涉及成型异相催化剂。
异相催化剂通常作为粒子床提供,液体和/或气体反应混合物经常在增加的温度和压力下通过其中。因此异相催化剂材料通常以成型体的形式提供以平衡催化活性和生产量。一般来说较小催化剂颗粒具有较高比表面积因此活性较高,但是因为通过催化剂床层的压降比较大造成生产量较低。考虑到这点,为了使压降最小化的同时增加几何表面积,已采用可具有一个或多个沿着外表面延伸的沟槽或通道的多种催化剂设计形式。
US 4328130揭示一种圆柱体形式的成型催化剂,其具有从圆柱状圆周径向延伸和在其间定义凸出部的多个纵向通道,其中,突出部最大的宽度大于通道最大的宽度。催化剂被描述为含有2,3或者4个截短的V-型通道。
WO2004/014549揭示一种用于气体反应的成型异相催化剂,包含直径和高度比例在约0.5∶1至1∶1之间和含有多个通过其中的非圆形横截面的成型的孔的圆柱体单元。一些实施例中还含有沿着圆柱体的外部长度延伸的两个,三个或四个的V-型沟槽或通道。
其中沟槽或孔可增加理论几何表面积,申请人发现当把单元放在填料床中时通过催化剂的装填可能显著降低有效的几何表面积。申请人设计的催化剂单元可以克服这些设计产生的问题。
因此本发明提供一种长度为C和直径为D的圆柱体催化剂单元,其中单元的外表面具有沿着它的长度延伸的两个或更多个沟槽,其中圆柱体含有长度为A和B的圆顶端,使得(A+B+C)/D在0.50至2.00范围,和(A+B)/C在0.40至5.00范围。
本发明进一步提供制备催化剂单元的方法,包括以下步骤:(i)将粉末状材料,任选与造粒助剂一起,置于造粒模具中,(ii)压制粉末形成成型单元和然后(iii)可选加热成型单元形成催化剂单元,所述模具成型使得催化剂单元为具有长度C和直径D的圆柱体形式,其中单元的外表面含有沿着它的长度延伸的两个或更多个沟槽,所述圆柱体含有长度为A和B的圆顶端,使得(A+B+C)/D在0.50至2.00范围,和(A+B)/C在0.40至5.00范围。
本发明进一步提供在实现催化反应的条件下通过使反应混合物与催化剂单元接触而使用催化剂单元的催化方法。
申请人发现本发明的含有这些比例的沟槽催化剂单元,其中圆顶端尺寸相对增加,比现有技术催化剂具有更大的有效几何表面积。
催化剂单元的长径比,被定义为全部长度除以直径,即(A+B+C)/D在0.5至2.0范围内。优选(A+B+C)/D在0.50至1.50范围内,因为这样减少单元破裂的趋势。
圆柱体的一个或者两个端部,优选两个端部都是圆顶形。圆顶形的端部的长度A和B,二者可以相同或者不同。不对称的圆顶形的端部,即A和B不同,可能提供在制备时的优势。更进一步,不对称的圆顶形的端部可以改善表面积/空隙度关系。催化剂单元的圆顶与圆柱部分的比例(即(A+B)/C)在0.40至5.00范围,以提供相对高的圆顶形结构。优选(A+B)/C在0.40至3.00范围,更优选0.50至2.50。圆顶形的端部可以形成圆形或者椭圆形的一部分的横截面,以及期望半径R≥D/2。
对于多数催化反应的使用,C优选在1至25mm范围和D优选在4至40mm范围。
催化剂单元含有两个或更多个沿着其长度延伸的沟槽。本发明中,“沟槽”和“通道”可以互换使用。沟槽可能是弯曲或者直的或者两者的结合。优选沟槽是直的和沿着催化剂单元外部的轴向延伸,因为这简化制备。沟槽的形状可以为半圆,椭圆形,U-形,V-形,∏-形或者这些的变形。
催化剂单元可含有2至12之间或者更多的沟槽,并期望对称设置,即相等间隔在催化剂单元的圆周。优选2-7个沟槽,尤其3,4或者5沟槽或者通道。当沟槽是半圆或者椭圆它们独立地具有直径d”,宽度或深度在0.05D至0.5D范围内,优选0.15D至0.4D。申请人尤其发现期望限制总的沟槽宽度,即组合开口,为单元圆周的≤35%,即≤0.35(πD),因为这样阻止与催化剂床层中相临单元的不希望的互锁。互锁可以减少流动但是由于杠杆作用也易于使催化剂破裂。
在优选的实施方案中,沟槽具有圆形的边缘。这样减少互锁和移除其它情况下容易磨损的尖锐的边缘。互锁和磨损可产生细粉和/或破碎的催化剂单元,它们使催化剂有效性降低并增加了通过催化剂床层的压降。优选圆形的边缘半径在0.03D至0.09D范围内。
与之前的催化剂相比,具有一个或多个高度圆顶端部与多个沟槽的组合的催化剂单元其几何表面积和空隙度有所改善。如果希望,催化剂单元可含有一个或多个轴向延伸通过其的孔。单元可以含有1至12个延伸通过其的孔,更优选1-10个孔,尤其是1-6个孔。孔应该期望关于圆柱体横截面相等间隔和对称设置以使催化剂由此产生的强度最大化。因此1个孔可设置在中心,3个孔可以为三角形图案,4个孔可以是四边形图案,5个孔可以是四边形图案和一个中心孔,6个孔可以是六边形图案,等等。当D≤6mm时,优选1个中心放置的孔。当多于1个孔,它们应被设置在沟槽或通道间产生的凸起部中。由于多孔单元的中心孔会降低单元强度因而不优选该种形式。孔的横截面为圆形或具有一个或多个前述WO2004/014549中公开的多种横截面。在优选的实施方案中,孔或多个孔的横截面是圆形。孔可以是相同或不同的尺寸。优选孔或多个孔具有圆形横截面和独立地具有在0.05D至0.5D范围的直径d’,更优选0.15D至0.3D。然而孔在本发明中不是必须的。
为了有助于制备过程,可以放置一个或两个圆顶端以提供成型单元圆柱形部分一个或者两个端部上的凸缘。凸缘的宽度,w’,希望在0.2至2.0mm范围内。
催化剂单元可由含有一种或多种催化活性金属的粉末组合物制备从而直接生成催化剂或者由一种或多种粉末催化剂载体材料来制备然后处理制得的单元,例如通过浸渍或者沉积一种或多种金属化合物而形成催化剂。
催化剂单元可采用粉末金属,金属氧化物,金属氢氧化物,金属碳酸盐,金属碱式碳酸盐或其混合物来制备。
含有催化活性金属的粉末状组合物可将各自金属氧化物,碳酸盐,氢氧化物或者碱式碳酸盐混合而制得,或者可通过已知的沉淀技术形成,由此沉淀可溶性盐混合物,例如使用碱性沉淀剂,干燥和可选的煅烧和/或还原和钝化。
优选的催化剂载体材料可选自含有一种或多种稳定化合物的粉末状氧化铝,二氧化硅,二氧化钛,氧化锆,金属-铝酸盐,或者它们的混合物。用这些制备的催化剂单元可以叫做成型的催化剂载体单元,和成品催化剂将因此进一步包含浸渍和/或沉积在所述的成型的催化剂载体单元上的一种或多种属化合物。
催化剂单元优选包含一种或多种选自Na,K,Mg,Ca,Ba,Al,Si,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Y,Zr,Nb,Mo,Ru,Rh,Pd,Ag,Sn,Sb,La,Hf,W,Re,Ir,Pt,Au,Pb,或者Ce的金属。
催化剂单元可以使用确定方法以任何已知的催化剂配方来制备。
在一种实施方案中,催化剂单元包含以金属,氧化物,氢氧化物,碳酸盐或碱式碳酸盐形式存在的一种或多种过渡金属例如镍,钴,铁或者铜,和/或一种或多种贵金属例如铂,钯,铑,铱或钌。
在可选实施方案中,催化剂单元包含浸渍在耐火催化剂载体材料例如氧化铝,铝酸钙,铝酸镁或者氧化锆基成型催化剂载体单元中或沉积在所述耐火催化剂载体材料上的一种或多种过渡金属例如镍,铜,钴或者铁,和/或贵金属例如铂,钯,铑,铱或钌。
这种催化剂中过渡金属和贵金属以重量计可为至多85%,但是优选以重量计在1-60%范围内。
造粒是本发明优选的制备方法。因此制备催化剂单元的方法可以包括以下步骤:(i)将粉末状材料,任选与造粒助剂或润滑剂例如石墨或硬脂酸镁一起,置于造粒模具中,(ii)压制粉末形成成型单元和然后(iii)可选加热成型单元形成催化剂单元。可以进行可选的加热步骤(可以包括煅烧),以增加催化剂单元的强度。粉末状材料可包含一种或多种还原和/或氧化形式的催化活性金属,或者可以是催化剂载体材料,在这种情况下通过浸渍金属化合物到该成型的催化剂载体单元中和/或沉积金属化合物到该成型的催化剂载体单元上的单独步骤制备成品催化剂。为了实现如此,可以应用已知的技术。例如,在一种实施方案中,将硝酸镍溶液浸渍到成型的催化剂载体单元中,干燥,并煅烧导致硝酸镍分解由此形成含有氧化镍的催化剂。或者,粉末状材料可以是包含已经干燥和可选煅烧和/或还原和钝化的一种或多种催化金属的沉淀组合物。
可以使用替代的制备方法,例如注射成型,或者可能的挤出形成成型挤出物,然后在挤出物上形成圆顶的两步程序。
可以对含催化金属化合物的催化剂单元进行多种处理,例如用含氢气和/或一氧化碳的气体物流还原,或者例如用硫化氢进行硫化,以使它们在使用中具有活性。后处理可以异位或原位进行,即安放在待使用的反应器之前或之后进行。
根据本发明制备的催化剂单元可应用到任一异相催化过程,但是优选应用到固定床过程,更优选使用气体反应物的固定床过程。催化过程因此包括在实现催化反应的条件下使催化剂接触反应混合物,优选气体反应物混合物。催化过程可以选自加氢处理过程,包括:加氢脱硫,氢化,蒸汽重整(包括预重整),催化蒸汽重整,自热重整和二段转化和用于直接还原铁的重整过程,催化部分氧化,水煤气变换包括等温变换、酸性变换、低温变换、中间温度变换、中等温度变换和高温变换反应,甲烷化,通过费托反应的烃合成,甲醇合成,氨合成,氨氧化和氧化亚氮分解反应。催化剂单元也可以用于从污染的气态或液态流体物流中回收重金属如汞和砷。
本发明优选催化过程是以氢气作为反应物和包括加氢处理的反应,所述加氢处理包括加氢脱硫,氢化,水煤气变换包括低温变换、中间温度变换、中等温度变换和高温变换反应,甲烷化,通过费托反应的烃合成,甲醇合成,和氨合成。
参考附图解释本发明,其中:
图1是本发明催化剂单元的侧视图,
图2是图1催化剂单元顶部的端视图,和
图3是图1催化剂单元的等视图。
图1和图2一起描述具有长度C和直径D的圆柱体12形式的催化剂单元10,其含有沿着长度的相等间隔围绕单元10的圆周的四个沟槽14。圆柱体12具有横截面是椭圆形、长度为A和B的圆顶端16,18。A和B是相同的。(A+B+C)/D是约0.73。(A+B)/C是约3.0。图2和3可以看出,四个沟槽14产生四个等尺寸的凸起部20。沟槽都是宽度约0.25D和深度约0.16D的椭圆形横截面。形成凸起部的沟槽的边缘具有圆形部分22。圆形部分的半径约0.05D。
本发明通过以下实施例进一步阐释。
实施例1
使用计算机模拟一系列催化剂单元。实施例1a-f涉及与图1-3描述类似的4沟槽的高度圆顶形圆柱体小球。对比例X是目前所用的标准平顶催化剂单元。对比例Y是没有沟槽的高度圆顶形圆柱体小球。
下面给出了相同的条件下反应容器模拟;
相对GSA m2/m3 | 相对空隙度 | 相对压降 | |
X | 100.0 | 100.0 | 100.0 |
Y | 93.7 | 103.1 | 85.4 |
1a | 127.4 | 136.0 | 50.7 |
1b | 129.7 | 135.5 | 52.1 |
1c | 117.6 | 121.3 | 65.8 |
1d | 120.3 | 119.1 | 71.3 |
1e | 119.9 | 121.4 | 67.0 |
1f | 118.7 | 122.9 | 63.9 |
以上结果证明根据本发明的催化剂单元比对比的催化剂拥有更高的GSA,更好的空隙度和更低的压差。
实施例2
将根据US4788175的公开内容制备的100份包含碱式碳酸Cu和Zn与氧化铝的混合物的共沉淀组合物与2份石墨混合,并加入旋转压片机,成功形成具有根据实施例1d的形状的小球。
Claims (24)
1.一种具有长度C和直径D的圆柱体形式的催化剂单元,其中单元外表面具有两个或更多个沿着其长度延伸的沟槽,所述圆柱体具有长度为A和B满足(A+B+C)/D在0.50至2.00范围内,和(A+B)/C在0.40至5.00范围内的圆顶端。
2.根据权利要求1所述的催化剂单元,其中A和B相同或者不同。
3.根据权利要求1或2所述的催化剂单元,其中(A+B+C)/D在0.50至1.50范围内.
4.根据权利要求1-3任一项所述的催化剂单元,其中(A+B)/C在0.4至3.00范围内.
5.根据权利要求1-4任一项所述的催化剂单元,其中单元含有3至12个沿着其长度轴向延伸的沟槽。
6.根据权利要求1-5任一项所述的催化剂单元,其中沟槽相等间隔围绕单元圆周。
7.根据权利要求6所述的催化剂单元,其中沟槽呈半圆,椭圆形,U-形,V-形,∏-形或者这些的变形。
8.根据权利要求1-7任一项所述的催化剂单元,其中整个的沟槽宽度≤单元圆周的35%。
9.根据权利要求1-8任一项所述的催化剂单元,其中沟槽有圆形的边缘。
10.根据权利要求9所述的催化剂单元,其中圆形的边缘半径在0.03D至0.09D范围内。
11.根据权利要求1-10任一项所述的催化剂单元,含有1至12个延伸通过其的孔。
12.根据权利要求11所述的催化剂单元,其中的孔或多个孔具有圆形横截面和独立地具有在0.05D至0.5D之间的直径d’。
13.根据权利要求1-12任一项所述的催化剂单元,其中布置一个或两个圆顶端以提供圆柱体一个或两个端部上的凸缘。
14.根据权利要求1-13任一项所述的催化剂单元,包含选自金属氧化物,金属氢氧化物,金属碳化盐,金属碱式碳酸盐或其混合物的金属或金属化合物。
15.根据权利要求14所述的催化剂单元,其中金属或金属化合物包含一种或多种选自Na,K,Mg,Ca,Ba,Al,Si,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Y,Zr,Nb,Mo,Ru,Rh,Pd,Ag,Sn,Sb,La,Hf,W,Re,Ir,Pt,Au,Pb,或者Ce的金属。
16.根据权利要求1-15任一项所述的催化剂单元,包含氧化铝,二氧化钛,氧化锆或者金属铝酸盐,或它们的混合物。
17.根据权利要求1-16任一项所述的催化剂单元,包含一种或多种浸渍在所述单元中和/或沉积在所述单元上的金属化合物。
18.根据权利要求17所述的催化剂单元,其中金属化合物包含一种或多种选自Na,K,Mg,Ca,Ba,Al,Si,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Y,Zr,Nb,Mo,Ru,Rh,Pd,Ag,Sn,Sb,La,Hf,W,Re,Ir,Pt,Au,Pb,或者Ce的金属。
19.制备根据权利要求1-18任一项所述的催化剂单元的方法,包括以下步骤(i)将粉末状材料,任选与造粒助剂一起,置于造粒模具中,(ii)压制粉末形成成型单元和然后(iii)可选加热成型单元形成催化剂单元,所述模具成型使得催化剂单元为具有长度C和直径D的圆柱体形式,其中单元的外表面含有沿着它的长度延伸的两个或更多个沟槽,所述圆柱体含有长度为A和B的圆顶端,使得(A+B+C)/D在0.50至2.00范围,和(A+B)/C在0.40至5.00范围。
20.根据权利要求19所述的方法,其中的粉末状材料是包含一种或多种已经干燥和可选煅烧和/或还原和钝化的催化金属的沉淀组合物。
21.根据权利要求19所述的方法,其中的粉末状材料是催化载体材料。
22.根据权利要求21所述的方法,其中所述方法进一步包括通过用一种或多种金属化合物浸渍或沉积从而处理所得单元的步骤。
23.利用权利要求1-18任一项所述的或根据权利要求19-22任一项制备的催化剂单元的催化方法,包括在实现催化反应的条件下使反应混合物与催化剂单元接触。
24.根据权利要求23所述的催化方法,选自加氢处理,包括:加氢脱硫,氢化,蒸汽重整、包括预重整,催化蒸汽重整,自热重整和二段转化和用于直接还原铁的重整过程,催化部分氧化,水煤气变换包括等温变换、酸性变换、低温变换、中间温度变换、中等温度变换和高温变换反应,甲烷化,通过费托反应的烃合成,甲醇合成,氨合成,氨氧化和氧化亚氮分解反应,或用于从污染的气态或液态流体物流中回收重金属如汞和砷。
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- 2009-08-24 DK DK09785518.3T patent/DK2323763T3/en active
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CN108349731A (zh) * | 2015-10-29 | 2018-07-31 | 庄信万丰股份有限公司 | 水煤气转变催化剂 |
CN108349731B (zh) * | 2015-10-29 | 2022-04-29 | 庄信万丰股份有限公司 | 水煤气转变催化剂 |
Also Published As
Publication number | Publication date |
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EP2323763B1 (en) | 2016-07-27 |
EG26770A (en) | 2014-08-19 |
WO2010029325A1 (en) | 2010-03-18 |
DK2323763T3 (en) | 2016-11-28 |
RU2011114080A (ru) | 2012-10-20 |
NZ591370A (en) | 2012-10-26 |
RU2487757C2 (ru) | 2013-07-20 |
EP2323763A1 (en) | 2011-05-25 |
US20110166013A1 (en) | 2011-07-07 |
CL2011000500A1 (es) | 2011-08-05 |
MY161206A (en) | 2017-04-14 |
AU2009290702A1 (en) | 2010-03-18 |
CN102149466B (zh) | 2014-01-15 |
US8557729B2 (en) | 2013-10-15 |
CA2735980A1 (en) | 2010-03-18 |
ZA201101822B (en) | 2011-11-30 |
BRPI0918784A2 (pt) | 2015-12-01 |
AU2009290702B2 (en) | 2014-03-13 |
GB0816709D0 (en) | 2008-10-22 |
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