CN103118782B - 催化剂制造方法 - Google Patents

催化剂制造方法 Download PDF

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Publication number
CN103118782B
CN103118782B CN201180043238.7A CN201180043238A CN103118782B CN 103118782 B CN103118782 B CN 103118782B CN 201180043238 A CN201180043238 A CN 201180043238A CN 103118782 B CN103118782 B CN 103118782B
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catalyst
forming unit
metal
powder
layer
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CN103118782A (zh
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D·R·库普兰德
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Johnson Matthey PLC
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Johnson Matthey PLC
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Priority to CN201510484676.7A priority Critical patent/CN105107551A/zh
Priority to CN201510611136.0A priority patent/CN105195235A/zh
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Abstract

本发明描述了一种使用叠层法制造催化剂的方法，所述方法包括：(i)形成催化剂或催化剂载体粉末材料层；(ii)根据预定图案使所述层中的所述粉末结合或熔合；(iii)层压层地重复(i)和(ii)以形成成形单元；以及(iv)任选地将催化材料施加至所述成形单元。

Description

催化剂制造方法
本发明涉及通过叠层制造来制造催化剂。
典型地通过对粉末催化金属化合物进行造粒、挤出或成粒，随后煅烧和/或任选的还原阶段，制造非均相催化剂。或者利用催化剂化合物的溶液对通过对催化惰性材料进行造粒或挤出而形成的催化剂载体进行浸渍、干燥，然后经历煅烧和/或还原阶段。造粒、挤出和成粒方法在高效的同时，限制催化剂几何形状和物理性质的变化。
叠层制造(ALM)是顺序放置粉末材料的2-维层并熔合或结合在一起以形成3-维固体物体的技术。已经开发了制作用于航空和医疗用途中的金属和陶瓷部件的技术。
我们已经实现，ALM提供制造具有复杂几何形状和性质的催化剂结构的可能性，这是利用常规成形技术所不能实现的。
因此，本发明提供使用叠层法制造催化剂的方法，所述方法包括：
(i)形成催化剂或催化剂载体粉末材料层；
(ii)根据预定图案使所述层中的所述粉末结合或熔合；
(iii)层压层地重复(i)和(ii)以形成成形单元；以及
(iv)任选地将催化材料施加至所述成形单元。
本发明还提供可通过上述方法得到的催化剂和所述催化剂在催化反应中的用途。
ALM技术提供的主要改进在于催化剂性能和新的设计选项范围，包括更高的几何表面积对体积之比、更低的比重、受控的孔的几何形状、受控的气体/流体流动路径、受控的气体/流体湍流、受控的气体/流体停留时间、强化的填充、受控的热量、受控的热传递、受控的热损失以及更高的转化率和更好的催化选择性。
可使用已知技术将ALM法应用于催化剂设计，所述ALM法也称作层的制造、结构性制造、生成性制造、直接数字制造、自由形式的制作、固体自由形式的制作或随意成型（fabbing）。在所有情况中，通过常规3D设计计算机包能够实施所述ALM法，所述3D设计计算机包使得可将成形单元设计为所谓的“STL文件”，所述“STL文件”是3D形状的简单网眼描述。使用设计软件将STL文件切割成多个二维层，所述二维层是制作工艺的基础。然后，读取二维图案的制作设备以与2D切片相对应的方式顺序层压层地沉积粉末材料。为了成形单元具有结构整体性，在沉积层的同时将粉末材料结合或熔合在一起。重复层的沉积和结合或熔合的工艺，直至产生强壮(robust)的成形单元。未结合或未熔合的粉末易于因例如重力或鼓吹而从成形单元分离。
可获得大量ALM结合和熔合制作技术，显著的是3D印刷和激光烧结技术。然而，可使用任意一种技术。
在激光烧结中，所述工艺包括三个步骤，其中使用刮刀、辊或移动料斗首先将粉末材料的薄层施加到基础板上。对所述层的厚度进行控制。以二维方式施加激光辐射以熔合所述层。例如使用检流计镜根据期望图案对激光位置进行控制。在熔合所述层之后，将在其上放置层的板向下移动一个层的厚度并随后在熔合的层上遮盖新鲜的粉末层。重复所述程序，由此产生三维形式的成形单元。在形成形状之后，简单地通过重力或通过将其吹离，将未熔合的粉末与成形单元分离。
直接激光烧结使用固态纤维激光器在高温下实施所述工艺。这种系统商购得自PhenixSystems，例如如同在WO2005002764中所述的。
替代方法是使用具有聚合涂层的粉末材料或包含粉末材料和聚合粘合剂的组合物。在此情况中，激光用于熔化粘合剂。该技术具有优势，激光功率明显低于熔合方法的激光的功率。聚合涂布技术可商购得自EOSGmbH。
称作光固化快速成型（stereolithography）的其他替代方案使用分散在单体中的粉末，该单体在通过使用UV激光器进行光聚合在层中“固化”以充当粘合剂。所述粉末材料在单体中高达约60体积%。用于实施该工艺的合适设备商购得自Cerampilot。
在这些方法中，但尤其是后者，可对成形单元进行随后的热处理，实施所述热处理以烧掉并除去所有聚合粘合剂和/或改变成形单元的物理化学性质如其强度。
作为激光烧结或光固化快速成型的替代，所述ALM法可以基于将粘合剂印刷在粉末材料上并随后实施或不实施加热。通常，该方法使用多阵列喷墨印刷头将液体粘合剂层喷施在粉末层上以将粒子保持在一起。以与先前相同的方式将载体板向下移动并再次重复所述程序以按上述累积成形单元。在此情况中的层可以为0.02～5.0mm厚。通常应用随后的热处理以除去粘合剂。用于实施该工艺的合适设备可商购得自美国的Z-Corporation。
通过ALM法制造的催化剂成形单元可以为横断面尺寸为1～50mm的微粒或所述成形单元可以为横断面为100～1000mm的诸如蜂巢的独块形式。对于微粒成形单元或独块成形单元，长宽比即长度/宽度可以为0.5～5。
对可使用ALM技术制作的催化剂成形单元的几何形状几乎没有限制。复杂性可以为从骨架框架和晶格或饰边工作结构变化到多特征的且小平面的强壮结构。例如，成形单元可以为在其内含有空隙空间的线-框或骨架框架结构形式且其可具有多个内部增强棒，或成形单元可以为任意形式的蜂巢或固体单元如圆柱体，其可构造有圆顶端、多个叶片和/或通孔。
骨架框架结构是优选的且可包含3个以上的开放面，所述开放面可以为三角形、正方形、五边形或另一个多边形形状。因此，制得的结构可以为四面体、五面体(金字塔形)、六面体(立方体或正方形柱)、七面体、八面体、九面体、十面体、十二面体、二十面体等。还可通过外部棒对骨架架构进行连接以产生2-维或3-维结构。
优选地，成形单元包含一个或多个通孔，其横断面可以为圆形、椭圆形或多边形如三角形、正方形、矩形或六边形。所述通孔可包含平行延伸的两个以上的通孔、或在各种角度下延伸穿过所述成形单元到达成形单元纵轴的不平行的孔。还可使用ALM技术制造弯曲的通孔，这在目前使用常规造粒和挤出技术是不可能实现的。
所述成形单元可以由催化材料制备，或可以由非催化载体材料制备并涂布有催化材料，以提供催化剂。可以以单次或多次施加的方式，将多于一种的催化材料施加于载体上。如果期望，可利用相同或不同催化材料进一步对由催化材料制备的成形单元进行涂覆。
在一个实施方案中，所述粉末材料为催化剂粉末。所述催化剂粉末可包含金属粉末或粉末金属化合物。优选地，所述催化剂粉末包含一种或多种金属或金属化合物，该一种或多种金属或金属化合物含有选自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Ce中的金属。
在催化剂粉末为金属粉末的情况中，优选所述催化剂粉末包含贵金属催化剂粉末，例如任选地与一种或多种过渡金属混合的Pt、Pd、Ir、Ru、Re中的一种或多种。
在催化剂粉末为粉末金属化合物的情况中，优选所述催化剂粉末包含一种或多种过渡金属化合物，包括镧系金属化合物和锕系金属化合物。所述过渡金属化合物可以为金属氧化物、金属氢氧化物、金属碳酸盐、金属碱式碳酸盐或其混合物。过渡金属氧化物可包含单种或混合的金属氧化物如尖晶石或钙钛矿、或包含两种或更多种过渡金属氧化物的组合物。
所述催化剂粉末可还包含一种或多种粉末惰性材料如氧化铝、氧化硅、氮化硅、碳化硅、碳及其混合物。还可存在诸如堇青石的陶瓷类物质。
或者，所述催化剂粉末可包含沸石。
在替代实施方案中，粉末材料为催化剂载体粉末且所述方法包括将催化剂材料施加在所述成形单元上。催化剂载体粉末包含一种或多种惰性材料如氧化铝、氧化硅、氮化硅、碳化硅、碳及其混合物。还可使用常规的陶瓷类催化剂载体。所述催化剂载体粉末可还包含一种或多种过渡金属化合物，包括镧系金属化合物和锕系金属化合物，所述过渡金属化合物选自金属氧化物、金属氢氧化物、金属碳酸盐、金属碱式碳酸盐或其混合物。过渡金属化合物可包含单种或混合的金属氧化物或包含两种或更多种过渡金属氧化物的组合物。优选地，所述催化剂载体粉末包含氧化铝、金属-铝酸盐、氧化硅、铝硅酸盐、氧化钛、氧化锆、氧化锌或其混合物。
或者，所述催化剂载体粉末可以为金属粉末如贵金属粉末或非贵金属粉末如铁合金或钢粉末。
或者，催化剂载体粉末可包含沸石。
施加至成形单元的催化材料可包含金属、金属化合物或沸石。
通过金属气相沉积可将催化金属施加至成形单元。或者，可从金属、金属化合物或沸石的溶液或分散液将金属、金属化合物或沸石施加至成形单元。特别合适的用于从溶液中施加的金属化合物为水溶性盐如金属硝酸盐、金属醋酸盐、甲酸盐或草酸盐。
可施加至成形催化剂载体单元的金属或金属化合物优选包含选自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Ce中的一种或多种金属。
所述ALM法使用粉末材料。可将所述材料形成为粉末或使用各种技术如喷雾干燥将所述材料转化成粉末。喷雾干燥的优势在于，可制备不同粉末材料的混合物、施加粘合剂材料或制备自由流动的粉末。
无论通过何种方法制备粉末材料，粉末材料优选具有1～200微米的平均粒径D50。
所述叠层制造方法优选包括3D印刷或激光烧结技术。由此，在一个实施方案中，通过激光对各个层中的粉末进行熔合。在另一个实施方案中，利用粘合剂将各个层中的粉末结合在一起，所述粘合剂可以为无机粘合剂如铝酸钙水泥或有机粘合剂如酚醛树脂聚合物、纤维素、树胶或多糖粘合剂。
在催化剂粉末或粘合剂中可包括烧除性添加剂以控制得到的成形单元的孔隙率。
无论通过何种方法形成成形单元，可期望将其经历随后的加热步骤，可实施所述加热步骤以烧掉有机材料例如粘合剂或孔改性材料，和/或以改进物理化学性质，例如将非氧化金属化合物转化成相应的金属氧化物和/或对粉末材料进行熔合。可在300～1400℃、优选500～1200℃的最高温度下实施该加热步骤。
当成形单元包含一种或多种可还原的金属化合物时，可将成形单元经历还原步骤以将金属化合物转化成相应的金属。这可直接在成形单元上实施而不需要先前的加热步骤，或可在加热步骤之后实施，以将可还原的金属氧化物转化成相应的金属。通过在150～800℃、优选150～600℃的温度下将成形单元暴露在含氢气的气体流股中实现还原。包含还原的金属的催化剂可能是能自燃的，因此期望通过将成形单元受控暴露在含氧气的气体流股下以在所述还原的金属上形成钝化层，将成形单元中的还原的金属钝化。
本发明包括使用ALM方法制备的催化剂。
使用ALM方法制备的催化剂适用于任意催化工艺中，其中在实施催化反应的条件下将反应物混合物与该催化剂成形单元接触。或者，可将该成形单元用于吸附工艺以从工艺流体中催化除去物质，所述工艺流体可以为液体或气体。
催化反应可选自：加氢处理，包括加氢脱硫、氢化；蒸汽转化，包括预转化、催化蒸汽转化、自热转化和二次转化以及用于直接还原铁的转化工艺；催化部分氧化；水煤气变换，包括等温变换、酸变换（sourshift）、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(Fischer-Tropsch)反应合成烃；甲醇的合成；氨的合成；氨的氧化和一氧化二氮的分解反应；或内燃机或发电站废气的选择性氧化或还原反应。
所述ALM法特别适用于制造用于氨的氧化和蒸汽转化的微粒催化剂和用于对源自内燃机或发电站的废气成分进行选择性氧化和还原的独块催化剂。
所述吸附工艺可以为吸附，该吸附选自从污染的气态或液态流体流股中回收硫的化合物或重金属如汞和砷、或从内燃机和发电站的废气中回收微粒物质。特别地，可将所述方法用于制造称作催化烟粒过滤器的蜂巢型独块结构。
参考附图对本发明做进一步说明，其中：
图1描绘了可通过本发明方法得到的线-框催化剂结构；
图2是通过本发明方法制备的激光烧结的氧化铝催化剂载体的图像，所述载体具有图1的十二面体框架结构；且
图3是通过本发明方法制备的烧结的3D印刷的铝硅酸盐催化剂载体的图像，其处于四面体框架的形式。
在图1和2中，对“线-框”催化剂结构进行了描绘，所述催化剂结构包含具有在所述结构中心处连接的十二个内部“棒”的十二个五边形面。使用常规的造粒、挤出或成粒技术不能制造这种结构。
参考如下实例对本发明做进一步说明。
实施例1
将根据图1描绘的线-框氨氧化催化剂与商购获得的造粒的氨氧化催化剂进行了比较。
根据图1的成形单元中的活性面积为约545mm2。所述形状的体积为约135mm3。填充的体积估计为约90mm3。
在此基础上可预测，在相同的操作条件下，通过常规小球数目的15～16%就可提供相同的转化效率。
实施例2
使用PhenixSystemsPX系列激光烧结机械，由氧化铝制备了图2的十二面体框架结构。采用平均尺寸为约10微米的未改性的氧化铝粉末并在激光熔化之前在对各个新粉末层机械压缩的条件下使用约100微米的步长完成了构造。沿着由标准软件驱动的轨迹，使用300W的纤维激光器将氧化铝熔化。刚构造的该部件是易碎的并需要小心地从粉末床中移出、通过在高达约1800℃的温度下的构造后的烧结，可实现增加的强度。
实施例3
使用Z-Corp的3D印刷机和标准商购的结合介质，实现图3的氧化铝-氧化硅四面体形状的“3D-印刷”。使用例行加工条件，在100微米的步长下印刷约30微米中值粒径的粉末。在约8小时时间内使用缓慢升温将制得的原始结构焚烧至约1000℃以将粘合剂烧掉并在不损失整体性的条件下使得组分致密化(收缩)。在完成时，许多制造的3D形状的强度足以承受催化剂涂覆。

Claims (9)

1.使用3D印刷叠层法制造横断面尺寸为1～50mm且长宽比为0.5～5的微粒催化剂的方法，所述方法包括：
(i)形成粉末状催化剂载体材料的层，所述催化剂载体材料选自氧化铝、金属-铝酸盐、氧化硅、铝硅酸盐、氧化钛、氧化锆、氧化锌或其混合物；
(ii)根据预定图案使所述层中的所述粉末结合，其中利用粘合剂将各个层中的粉末结合在一起，和在所述粘合剂中包括烧除性添加剂以控制所制得的成形单元的孔隙率；
(iii)层压层地重复(i)和(ii)以形成成形单元；
(iv)将所述成形单元经历加热步骤；以及
(v)将包括金属、金属化合物或沸石的催化材料的分散液施加至所述成形单元。
2.根据权利要求1的方法，其中所述金属或金属化合物包含选自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Ce中的一种或多种金属。
3.根据权利要求1的方法，其中所述粉末材料具有1～200微米的平均粒径D50。
4.根据权利要求1的方法，其中将包含一种或多种可还原金属化合物的所述成形单元经历还原步骤。
5.根据权利要求1的方法，其中所述成形单元为含有空隙空间的线-框或骨架框架结构，在所述结构内具有多个内部增强棒。
6.根据权利要求1的方法，其中所述成型单元是固体单元，包含通孔。
7.根据权利要求1的方法，其中所述催化材料是氨氧化催化剂。
8.一种氨氧化催化剂，其通过根据权利要求7的方法得到。
9.根据权利要求8的催化剂的使用方法，包括在实施催化反应的条件下将反应物混合物与所述催化剂成形单元接触，其中所述催化反应选自氨氧化和一氧化二氮分解反应。
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