CN101952023A - 具有催化性能的成型体作为反应器内件的用途 - Google Patents
具有催化性能的成型体作为反应器内件的用途 Download PDFInfo
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Abstract
本发明涉及具有催化性能的成型体,其中该成型体可通过包括如下步骤的方法得到:a)借助基于粉末的快速成型方法制备成型体,b)任选对所述成型体进行热处理,c)任选向成型体施加至少一种催化活性组分,d)任选对所述成型体进行另一热处理。其中步骤b)、c)和/或d)可进行多次。所述成型体在非均相催化化学反应中用作反应器内件。
Description
本发明涉及具有催化性能的成型体在非均相催化化学反应中作为反应器内件的用途。
背景技术
在现代化学工业中非均相催化起着核心作用。非均相催化剂经常包含金属和/或金属氧化物,它们的表面与待催化反应的反应物相互作用。除了该相互作用的性质外,将反应物转移至表面的活性位点以及将产物从表面除去也起着关键作用。此外,必须尽可能快地除去反应释放的热或者引入反应所需的热。
催化剂的物理形式
由于广泛的各种非均相催化反应以及有时非常困难的反应条件,对非均相催化剂建立了各种物理形式,以确保最佳传质和各个反应的热量输送。在床中,催化剂以无序排列存在于反应器中,而在填料中,其以排列和有序方式安装在反应器中。作为床引入反应器中的颗粒、挤出物、粒料、环或碎材料的催化剂使用形式是最广泛的。这类成型体可填充整个反应器空间或借助间隔以各种段排列在反应器内。在反应器入口或在反应器的其他位置可配有额外的混合装置、换热器或其他内件。为了优化所需产物的产率,可沿着流动方向使用各种催化剂床(如不同的物理形式、活性组分量不同的催化剂或具有不同掺杂剂的催化剂)。然而,催化剂的这种使用方式的缺点在于所述床经常在反应器中导致高的压降。此外,可易于发生具有停滞的气体和/或液体移动的通道或区域的形成,从而使催化剂仅非常不均匀地暴露于反应物。此外,例如在管壳式反应器或具有大量管的盐浴反应器的情况下,在更换催化剂时所需的成型体除去和安装可变得非常复杂。
为了降低压降,描述了用于防止催化剂在反应器中过高密集填充的反应器内件。WO 03/047747描述了由金属制成的多通道填料,其中将具有不同几何形状表面区域的填料层交替装配并在它们之间引入催化剂。选择填料层,以使催化剂仅可滴入具有低比表面积的填料通道中,该通道已知为催化剂通道。由于几何形状的原因,催化剂不可滴入具有高比表面积的层中。该体系尤其用于反应性蒸馏。其缺点在于,由于增加的填料孔隙率,需要较大的反应器体积并且内件赋予大的金属表面积。需要额外的填料形式的金属,导致材料成本增加。此外,可发生腐蚀并且金属离子可溶解。
由于尺寸小而不能用作成型体床的催化剂经常可通过装入渗透性容器,如织物网袋中而使用。该网袋包括金属网(如K,购自Sulzer AG,CH-8404 Winterthur,参见J.P.Stringaro等,Chemical Plantsand Processing 1992年7月,第6-10页)并用作反应性蒸馏的催化活性内件。其他设计由Montz和CDTech提供并且根据类似的原理起作用(如“bales”,来自美国Houston,CDTech)。使用这些填料的缺点在于在其中催化剂由气体/液体混合物围绕的工艺中,必须精确地遵守合适的液体滴流密度,这在实际操作中证明是有困难的。当液体流动太快时,这导致溢出催化剂袋,当液体流动太慢时,导致催化剂“干燥”。
对于具体应用,催化剂也以具有连续通道的单块、蜂窝或肋片结构的形式使用,例如如DE-A-270900所述。单块赋予非常低的压降,同时损害横向混合。这在实际操作中可导致浓度、温度和流动速率的不均匀分布以及不令人满意的径向热分布。催化剂(负载)间隔物料与反应器体积的低比例通常是不利的。尽管存在所述缺点,由于没有更好的用于机动车的替换形式,单块的物理形式已经用于废气催化剂中。
因此,需要具有催化性能的成型体,其可用作反应器内件且对于各反应条件具有优化的几何形状。可能的话,它们应允许高的横向混合,即反应器中的浓度和温度相同,并且仅具有微弱的返混和足够高的传质和热输送并仅导致非常小的压降并且输送或引入可能发生的任何正反应热或负反应热。
制备方法“快速成型(rapid prototyping)”
本领域技术人员已知用于成型组件的所谓“快速成型(RP)”的制备方法,借助该方法,在事实上没有人工操作程序或模具的情况下,借助可获得的CAD数据可直接且快速地制备甚至任何复杂工件。快速成型的原理基于利用物理和/或化学作用的组件的层状构造。此处建立了许多方法,如选择性激光烧结(SLS)或立体平板印刷术(SLA)。方法本身的区别在于借助其构造层的材料(聚合物、树脂、纸页、粉末等),和借助其使这些材料结合的方法(激光、加热、粘合剂或粘合剂体系等)。该方法描述于许多出版物中。
一种快速成型方法描述于EP-A0431 924中且包括由粉末和粘合剂层状构建三维组件。在结束时除去未粘合的粉末并留下具有所需几何形体的工件。
由WO 2004/112988已知,也可以使用超过一种粉状原料,并且US 2005/0017394公开了使用导致粘合剂固化的活化剂。
例如在Galvanotechnik 1/2004,第196-204页中,R.Knitter等描述了用于微型反应器技术的陶瓷反应器。成型借助快速成型方法链进行,还插入额外的中间步骤,即1)由通过立体平板印刷术得到的原始塑料模型制备聚硅氧烷凹模,然后2)用陶瓷浆料在低压喷射模塑中填充该模具。所得陶瓷微型反应器尤其用作向其施加真正催化剂的催化剂载体,例如作为悬浮液施加。该制备方法的缺点为其中首先制备凹模,然后以浇注形式进行最终制备的额外工艺步骤。
在cfi/Ber.DKG 82(2005),第13期,第99-103页中,U.Kaufmann等描述了借助一种其中基于在粉末床中构建层状组件的方法而制备3D陶瓷组件。并讨论了将这些组件用作植入物的可能性。
本发明的目的和主题
本发明的目的是改善催化剂在非均相催化化学反应中的使用并且避免上述已知催化剂的缺点。在使用催化剂时,应可实现与床相当的低压降,优选非常高的横向混合,以及仅仅小的与流动方向相反的返混,以及足够高的传质和热量输送,包括径向热量输送。
因此,本发明提供了具有催化性能的成型体在非均相催化化学反应中作为反应器内件的用途,其中该成型体可通过包括如下步骤的方法得到:
a)借助基于粉末的快速成型方法制备成型体,
b)合适的话,对成型体进行热处理,优选烧结和/或煅烧,
c)合适的话,向成型体施加至少一种催化活性组分,
d)合适的话,进行另一热处理,
其中步骤b)、c)和/或d)可进行多次。
优选选择粘合剂或粘合剂混合物,以使粘合剂本身或其残留物不影响或没有不利地影响随后使用该催化剂(载体)的化学反应。
根据本发明,该目的因此通过使用具有催化性能且其几何形状对反应器中的各料流和反应条件优化的成型体实现。该反应器内件可根据所需反应条件设计,而这借助常规技术如挤出或注射模塑是不可行的。
与这些常规制备技术相比,快速成型技术的优点在于理论上可借助计算机控制使用设定为相应三维组件的CAD数据转化为任何所需几何形体,包括例如具有空心空间或微通道的复杂组件,而无需预先制备浇注凹模,无需切割、研磨、磨削、焊接等。这使得可以制备如下反应器内件,该反应器内件由于其优化的几何形体,在化学反应中就传质和热量输送而言优于常规反应器内件。该工艺强化了在更高产率、转化率和选择性以及可靠的反应条件方面的结果并且由于降低了装置尺寸或减少了催化剂量导致化学工业中的现有方法或新方法的成本节约。
发明内容
待根据本发明使用的成型体通过由催化活性材料或其前体制备或由于包含其上施加了催化活性组分的惰性材料(用作载体)(参见方法步骤c)而获得其催化性能。也可将其他催化活性组分,如金属或促进剂施加至已经是催化活性的材料上。
材料
适用于制备待根据本发明使用的成型体的材料优选为金属氧化物、金属氧化物氢氧化物、水滑石、尖晶石、钙钛矿、金属、合金、金属磷酸盐,天然产生和合成的层或架状硅酸盐,如粘土材料,沸石,云母,长石,陶瓷材料,如滑石、堇青石、瓷料,碳化物,如SiC、B4C,氮化物,如Si3N4、AlN,玻璃等。优选材料为二氧化硅、氧化铝、二氧化钛、二氧化锆、氧化镁、氧化钙、混合金属氧化物、水滑石、尖晶石、钙钛矿、金属磷酸盐、硅酸盐、沸石、滑石、堇青石、碳化物、氮化物或其混合物或共混物。特别优选二氧化硅,氧化铝,二氧化钛,二氧化锆,氧化镁,氧化钙,滑石,堇青石和混合物氧化物,如SiO2-Al2O3、ZnO-Al2O3-CuO、SiO2-TiO2、ZrO2-SiO2、ZrO2-Al2O3,或两种或更多种这些材料的混合物。如果所用材料以多种变型存在,各种变型可单独或以混合物使用,并且由于在制备方法中可能进行的热处理也可发生相变。可使用且具有各种已知变型的材料实例为α-Al2O3、γ-Al2O3、θ-Al2O3、单斜ZrO2、立方ZrO2、四方ZrO2、具有金红石结构的TiO2、具有锐钛矿结构的TiO2,呈许多稳定或亚稳定变型的SiO2,如α-和β-石英、α-和β-方石英、α-和β-鳞石英等。
粉末形式
在待根据本发明使用的快速成型方法中使用粉状原料,该粉状原料可以具有或不具有粘合剂使用。其它信息适用于这两种变型。可使用单分散和多分散粉末。当使用较细颗粒时,自然可获得较薄的层,因此,在构建所需成型体时可比使用粗颗粒具有更多数目的层并因此具有更高的空间分辨率。优选平均粒度为约0.5μm至约450μm,特别优选约1μm至约300μm,非常特别优选10-100μm的粉末。需要的话,所用粉末也可以目标方式预处理,如借助煅烧、压缩、混合、造粒、筛分、聚集或研磨至特定粒度级分中的至少一个步骤而预处理。
制备
已知的是,待根据本发明使用的快速成型方法包括将其重复直至由各层完全构建所需成型体的如下步骤。粉状原料或原料混合物以薄层施加至基材,随后在该层的所选位置上与粘合剂和任何所需助剂混合或经受辐照或以其它方式处理,以使粉末在这些位置粘结,其结果是粉末在该层内以及与相邻层粘结。当对于在形成的粉末床中完全复制所需工件形状是必须的时候重复该程序之后,除去没有被粘合剂粘结的粉末并留下呈所需形状的粘结粉末。
粘合剂和助剂
作为粘合剂,通常可使用能够将粉状原料的相邻颗粒相互牢固结合的任何材料。此处,优选二氧化硅或铝硅酸盐的溶胶或胶体溶液,硅石或硅酸酯,硅氧烷或聚硅氧烷。其它合适的粘合剂为有机材料,尤其是可交联或可以其它方式相互共价连接的有机材料,例如酚醛树脂,多异氰酸酯,聚氨酯,环氧树脂,呋喃树脂,脲醛缩合物,糠醇,丙烯酸分散体和丙烯酸酯分散体,聚合物醇,过氧化物,碳水化合物,糖,糖醇,蛋白质,淀粉,羧甲基纤维素,黄原胶,明胶,聚乙二醇,聚乙烯醇,聚乙烯基吡咯烷酮或其混合物。粘合剂作为溶液或分散体以液体形式使用,其中可使用有机溶剂(如甲苯)和水。优选使用其本身或其残留物不影响或没有不利地影响随后使用该催化剂(载体)的化学反应
粘合剂例如借助喷嘴、压头或允许在粉末层上精确定位非常细的粘合剂液滴的其它装置。粉末与粘合剂的重量比随着所用物质的功能而变化且通常为约40∶60至约99∶1,优选约70∶30至约99∶1,特别优选约85∶15至约98∶2。
合适的话,也可使用一种或多种助剂,该助剂例如可对粘合剂的交联有影响或用作固化剂。所用助剂尤其为水、无机酸或碱以及可快速水解或缩合的化合物,如金属醇盐(如钛醇盐)。助剂可分开施用或合适的话可加入粉末床和/或粘合剂或粘合剂溶液中。
热处理
在步骤b)中,热处理可以呈烧结和/或煅烧形式。烧结或煅烧优选在350-2100℃的温度下进行。热处理也可通过快速进行粘合剂的除去,然后进行烧结和/或煅烧而进行。烧结和煅烧的定义如下文所给出。
成型体的几何形体
成型体的几何形体取决于各应用领域的要求并且由于基于粉末的快速成型方法的灵活性可在宽范围内变化。优选如下成型体,其在非均相催化化学反应中用作催化剂时导致非常高的横向混合并且在反应器中导致非常低的压降以及仅仅小的与流动方向相反的返混,以及足够高的传质和热量输送,包括向周围环境进行热量输送。有利的成型体例如可基于具有交叉通道结构的填料,本领域技术人员由蒸馏技术已知该填料并且该填料由诸如Montz、Sulzer或Kühni的制造商提供。这些成型体具有反应介质经由其流过的通道;这些通道与主流动方向以0°-70°,优选30°-60°的角度倾斜。通道可具有任何横截面形状,其中优选正方形、矩形或圆形横截面。
填料可优选以多通道填料构造,该填料具有其中优先进行化学反应的通道且额外包含其中优先进行对流热输送的通道。用于热输送的通道优选以较大角度倾斜且优选具有2-10倍于用于催化的通道直径的水力直径(hydraulic diameter)。
多通道填料优选以在各层中具有穿孔而制备,例如如网形铁,以确保更好地传质。
然而,有利地具有定位孔和/或将各通道相互连接的开口并因此增强横向混合的单块结构相比于现有形状也具有决定性的优点。这类单块的实例详细描述于Emitec的文章中(参见因特网:http://www.emitec.com/index.php?lang=de&mid=d5&doc=s7)。然而,其中描述的结构的缺点在于制备方法仅适用于制备金属单块,而不适用于制备陶瓷成型体。此外,向外的径向热输送是有问题的并且由于单块和反应器壁之间的间隙可形成旁路(或在多个经由其平行流过横截面的单块的情况下,也可在单块之间形成旁路)。
在反应器中安装成型体
根据本发明使用的成型体用作反应器内件。它们可以作为床以未排列形式存在,或以空间排列形式存在,如作为柱形反应器中的填料,这原则上对单块是已知的。根据本发明使用的成型体可延伸至(柱形)反应器的边缘。结构化催化剂在反应器中的安装可以多种方式进行,如在管式或管壳式反应器的情况下将圆柱形组件一个在另一个之上排列。此时,所有催化剂部分并不一定需要具有相同形状、结构、掺杂等,但是垂直/纵向分段也是可行的:如贵金属负载低的催化剂成型体可安装在反应器入口并且更多贵金属可提供在出口方向的结构上或者反之亦然。具有不同的热输送性能等的组件也可在反应器的长度方向上安装。此外,催化剂成型体也可以分段方式安装在横向方向上(如在通过4个四分之一圆柱体或通过许多六边形的饼式区段,相互相邻排列的蜂窝状组件的情况下)。组件也可作为无序床安装。
作为床安装成型体
传统的成型体偶尔具有使得存在流化或破裂或磨损风险的小尺寸。本发明成型体可更大,而在催化、传质和热输送或压降性能的其它方面相同,从而当使用这些成型体的床时可消除流化风险。
作为填料安装成型体
根据本发明使用的成型体也可以空间排列的形式用作反应器内件,如作为填料。此处,可使反应介质流过包含作为填料的成型体的柱形反应器,其中填料由一个元件构成或由多个在纵向方向上排列的形成填料区段的元件构成,其中各填料元件由多个纵向排列的层构成,各层包含紧密包裹的通道,相邻层的通道交叉并且在填料元件内的通道具有可渗透或不可渗透流体的侧壁。也可使用作为床描述的成型体。
为了抑制经由外表面通过,填料优选a)围绕外侧配有密封以确保均匀流过填料的整个横截面或者优选b)具有如下结构:其在外表面不具有较高孔隙率。
几何形状的实例
根据本发明使用的成型体的合适形状或结构例如描述于Montz和Sulzer公司的如下文献中。根据本发明,这些结构可以陶瓷材料形式用作催化剂或催化剂载体。可提及的结构的实例描述于WO 2006/056419、WO2005/037429、WO 2005/037428、EP-A-1 362 636、WO 01/52980、EP-B-1251 958、DE-A-38 18 917、DE-A-32 22 892、DE-A-29 21 270、DE-A-29 21269、CA-A-10 28 903、CN-A-1 550 258、GB-A-1 186 647、WO 97/02880、EP-A-1 477 224、EP-A-1 308 204、EP-A-1 254 705、EP-A-1 145 761、US6,409,378、EP-A-1 029 588、EP-A-1 022 057和WO 98/55221中。
这类成型的实例例如具有多个大约垂直排列的波纹板或边缘,该板或边缘沿着其侧面接触并且其紧密间隔的肋大约以弧的形式从顶部向下走向,其中两个相邻板的肋相互交叉并且在板上部区域的肋是直的并且向板的上部,尤其是水平的边缘倾斜并且在板的下部区域以弧的形式弯曲,肋的上端的纵线与板的上部,尤其是水平的边缘形成30-70°,优选45-60°的角,其中肋的下端的纵线与板的下部,尤其是水平的边缘形成75-90°,优选80-85°的角,其中纵线的走向在上端可以与肋的方向相同或相反方向。这种设计例如由Montz描述于EP-B-1 251 958中。也可提供在顶部和底部弯曲的肋,这例如由Sulzer提供。
适合用作优化反应器内件的另一成型体呈由垂直层构成的交叉通道填料形式,该层包含波纹或褶皱的金属氧化物形成的流动通道,其中相邻层的流动通道以开放方式相互交叉并且相互交叉的通道之间的角度小于约100°。这种交叉通道的填料例如描述于EP-A-1 477 224中;也参见其中的角度定义。
可用作成型体的填料实例为Sulzer BX网填料、Sulzer Mellapak薄层填料,高性能填料如Mellapak Plus,购自Sulzer(Optiflow)、Montz(BSH)和Kühni(Rombopak)的结构化填料,以及购自Emitec(www.emitec.com)的填料。
成型体例如可具有购自Montz的填料类型A3、B1、BSH、Cl和M的形状。此处,填料成型体由波纹板(薄层)构成。波纹以与垂直成角度走向并且与相邻薄层形成交叉流动通道。
用于反应
根据本发明使用的成型体,例如上文所定义的成型体优选用于吸收或放出热量的反应,即用于吸热或放热反应。反应可以为液相反应、气相反应或多相反应,如三相反应。
制备
成型体如上对快速成型所述制备。可参考上文引用的文献,以及Gebhardt,Rapid Prototyping(快速成型),Werkzeuge für die schnelleProduktentstehung,Carl Hanser Verlag,Munich,2000,J.G.Heinrich,New Developments in the Solid Freeform Fabrication of CeramicComponents,cfi/Ber.DKG 66(1999),第29-35页,R.Knitter,W.Bauer,Keramische Reaktoren für den Einsatz in der Mikroreaktor-Technik,Nachrichten-Forschungszentrum Karlsruhe 34(2002),第143-152页,A.Nagy,R.Lenk,Rapid Prototyping-Fertigungsverfahren für die schnelleBereitstellung keramischer Funktionsmuster:Kriegesmann(编辑),Technische keramische Werkstoffe,2004,ke 12/2005,第54-55页;对于适用于快速成型的标准,也参见Rapid Prototyping(快速成型),在www.werkstoffzentrum.de中。
在制备成型体之后,需要的话对其进行热处理,该热处理可以多段或根据温度程序或曲线进行。通常而言,热处理在约300-2100℃的范围内进行。例如,可首先将粉末床与位于其中的成型体一起加热至300-700℃,优选300-550℃的温度。这用于例如通过水解和/或缩合并消除水或醇而完成粘合剂交联,并且有机成分可至少部分通过氧化除去。随后可为第二温度段,该温度段通常包括加热至900-2100℃,优选1100-1800℃的温度。这位于烧结的范围,其中粉末颗粒变得相互连接并且成型体的机械强度因此增加。在烧结工艺中可发生一些收缩并且在印刷过程中这必须考虑到CAD模型中。没有被粘合剂粘结的粉末必须最迟在烧结步骤之前除去,这例如可借助压缩空气进行或吹掉。这留下呈所需形状的粘结的粉末。可选择第二温度段,以使所得材料具有高或低的孔隙率。取决于待催化反应的要求,可借助该步骤优化材料的机械稳定性、结构和孔隙率.
在本发明的实施方案中,制备的成型体本身是催化活性的。在本发明的另一实施方案中,制备的成型体用作催化剂的载体。
在根据本发明制备成型体之后,合适的话可通过施加至少一种(其他)催化活性组分而将其改性。这类组分例如可为金属盐,如元素如铁、铝、铜、镍、钴、铬、钒、钼、钛、锆、锰、锌、钯、铑、银、金、钨、铂、铋、锡、钾、钠、铯、钙、钡、镁、硒、锑、镧、铈、钇等的氢氧化物、硝酸盐、硫酸盐、卤化物、磷酸盐、乙酸盐、草酸盐或碳酸盐。也可使用盐的混合物。铵盐,如硫酸铵、磷酸铵、钨酸铵或钒酸铵以及杂多酸或其盐,如钨磷酸、钼硅酸(molybdosilicic acid)等也可用于改性。这些催化活性组分例如可通过用金属盐的水溶液和/或有机溶液浸渍成型体而施加。需要的话,浸渍之后可为另一热处理,其中将施加的金属盐活化或使其分解。也可在制备成型体之后,通过本领域技术人员已知的方法施加具有本领域技术人员已知的组成的基面涂层(washcoat)。
用作催化剂
以此方式得到的具有催化性能的成型体可用作许多化学反应的反应器内件。通常可以用于所有使用非均相催化剂操作的反应器,例如固定床管式反应器、移动床反应器、管壳式反应器、盐浴反应器或流化床反应器,或用于反应性蒸馏或反应性萃取的反应器。通常而言,所有其中涉及在催化剂上反应的工艺工程操作均是可行的。优选用于连续反应的反应器。
根据本发明,具有催化性能的成型体可用于任何非均相催化化学反应,例如氧化、氨氧化、加氢、脱氢、异构化、水合、脱水、胺化、硝化、烷基化、脱烷基化、歧化、酰化、烷氧基化、环氧化、酯化、酯交换、易位反应、二聚、低聚或重排。这可以为单个气相或液体反应或多相反应(如气-液或液-液反应)。
定义
对本发明而言,如下定义是重要的:
煅烧为其中从成型体中除去有机成分的热处理。
烧结为其中使相邻粉末颗粒相互连接在一起的热处理。
单位质量的表面积A为通过氮气吸附使用根据DIN-ISO 9277或DIN 66131的BET方法测定的基于其质量的催化剂表面积。
单位质量的表面积为材料相关的并且在根据本发明使用的催化剂的情况下为0.25-1500m2/g,优选0.5-1000m2/g,特别优选1-600m2/g。
为了测定外部表面积A颗粒,总共,设想内部自由体积由固体填充,即仅考虑颗粒或多孔介质表面。外部表面积也称作几何形体表面积。
以类似的方式,总颗粒体积V颗粒,总共为所有颗粒的总体积,其中内部自由体积认为是由固体填充。
总的或床体积V床为多孔介质的总体积。其同样通过设想外部自由体积为0而计算,即床认为是实心材料。
单位体积的外部表面积σ为催化剂成型体的几何形体或外部表面积与反应器体积的比例。
σ=A颗粒,总共/V床
在根据本发明使用的催化剂的情况下,单位体积的外部表面积优选为1-10 000m2/m3,特别优选10-5000m2/m3,尤其是100-3000m2/m3。
催化剂的孔隙率为ε为(总体积-颗粒体积)与总体积的比例。
ε=(V床-V颗粒,总共)/V床
孔隙率再划分为两部分。外部孔隙率为各种成型体之间的间隙体积。在成型体内具有大自由体积的成型体的情况下,这些自由空间同样视为外部孔隙率的一部分。实例为在环形催化剂成型体内的圆柱形体积。
内部孔隙率定义为成型体内的孔隙体积,其原因为成型体并不是完全由实心材料组成而且包含一些自由体积。在颗粒内的这些自由体积例如可归因于颗粒包含小的初级颗粒。
孔隙率例如借助水银孔隙率测定法根据DIN 66133测定。该测量给出了催化剂中的孔尺寸分布。在在非常低的表压下,仅测量外部孔隙率。
在根据本发明使用的成型体的情况下,孔隙率优选为10-99%,特别优选20-90%,尤其是25-75%.
沙得直径(sauter diameter)dS为床尺寸的度量或通常为多孔介质中的等价颗粒的度量。其定义为6倍的总体积V颗粒,总共与几何形体的总表面积A颗粒,总共的比例:
dS=6*V颗粒,总共/A颗粒,总共
在多孔介质的情况下,沙得直径通常可更简单地表示为dS=6*(1-ε)/σ,其中σ为单位体积的外部表面积。
根据本发明使用的成型体的沙得直径优选为1-50mm,特别优选1.5-15mm,尤其是1.5-5mm。
水力直径dh在替换模型中的原型为具有任何形状的过流横截面。其定义为4倍的横截面积A与周长U的比例或4倍的流体流过的体积V=V床-V颗粒,总共与被流体润湿的表面积A颗粒,总共的比例:
dh=4*A/U=4*V/A颗粒,总共
具有任何横截面的流动通道可以这种方式归属于具有直径dh的管横截面。因此,该管横截面具有与任何横截面的通道相同的面积与周长之比。在管具有圆形横截面的情况下,例如,管内径等于水力直径。
如果具有局部或局部化的浓度梯度的流体料流流过床,则这些梯度在床内减小。这首先通过分子扩散发生,其次由于局部湍流,这导致对流的传质。此外,粘附作用可导致浓度均化。后面的两种作用称作分散。扩散作用可由材料性能描述,分散性能额外取决于流速和床性能。在径向和轴向分散过程之间有区别。轴向分散作用可借助停留时间的测量而量化。径向分散(横向混合)较难以测定。为了测量该径向分散,可在局部位置,如在床中间加入跟踪气体。因此,跟踪气体的局部浓度必须在床的末端测定。
皮克里特数(Peclet number)(Pe)为对流传质或热输送与热或材料的扩散输送无量纲的比例。皮克里特数为轴向上的返混或浓度或温度梯度的平坦化的特征量度。皮克里特数变为0时,在几何形体中流体流过其的条件对应于理想化的混合搅拌釜,即完全返混体系。随着皮克里特数增加,热或材料的轴向对流输送与分散作用相比变为主要的,并且返混在体系中重要性变小。皮克里特数的分子中的对流输送可由流体流过的结构的直径计算。如果使用特征颗粒尺寸代替对流输送中的直径,可进一步定义无量纲的参数,但是它们对于轴向返混的信息功能保持与上述参数相同。
轴向或径向皮克里特数Pe轴向或Pe径向定义为自由起始流速u0和颗粒直径dS的乘积与轴向分散系数D轴向或径向分散系数D径向的比例。其为对流率和分散传质过程的量度。
自由起始流速u0为在设想不存在成型体时经过流动横截面的平均流速。分散系数D轴向和D径向为几何形体或床的特定参数,其量度了通过其产生流动的结构体的不是由分子扩散过程引起的分散传质和热输送性能。
在根据本发明使用的成型体的情况下,皮克里特数可为0至任何更大的值。在单分散的球的床情况下,当分子扩散可忽略的低时,轴向皮克里特数Pe轴向=2。
除了上面考虑的传质过程外,也可考虑向外或向内的壁热输送。壁热输送表示额外的限制。这是因为与远离壁的内部床相比,临近壁的床中的孔隙率更大。
对本发明而言,主流动方向表示其中流体组分在反应器中优先流动的方向。取决于反应器构造,主流动方向也可在局部不同,如当在反应器中使用板以引导流动的情况下。具有入口和出口的反应器中主流动方向例如可借助示踪剂测定。示踪剂会以料流的形式移动通过反应器。主流动方向由这些料流的运动方向给出。
因此,例如在圆柱体的相对端面具有入口和出口的圆柱形反应器中,从入口到出口的圆柱体轴描述了主流动方向。在具有平行管的管壳式反应器中,主流动方向同样与管平行排列。
对本发明而言,流动横截面为与主流动方向垂直的平面。在反应器中偏转的情况下,流动横截面因此有时也可仅在反应器的一部分上延伸。
如下实施例阐述本发明而不是限制其范围。
实施例
实施例1:
如图1所示的三维结构化的“交叉通道结构”由α-Al2O3制备。长度为50mm且直径为14mm。
成型体的基料为借助Turbula混合器(Willy A.Bachofen AG,4058Basel,瑞士)与固体粘合剂黄原胶,200目(购自& Wiegand,40472Düsseldorf)混合的颗粒氧化铝CT 3000 SDP(购自Almatis,67065Ludwigshafen)。基于氧化铝,固体粘合剂的比例为10重量%。三维印刷借助Z-Printer 310(Z-Corporation,Burlington,MA 01803,美国)使用水基粘合剂溶液ZB 54(Z-Corporation,Burlington,MA 01803,美国)进行。使用2重量%的液体粘合剂。在印刷之后,首先将部件在60℃下干燥8小时,然后借助压缩空气吹扫干净。陶瓷灼烧在1600℃下进行并维持2小时。
实施例2:
将3.12g Bi(NO3)3·5H2O与3.36g Pd(NO3)2·2H2O和48.6mgCo(NO3)2·6H2O一起置于玻璃烧杯中。加入18.17g蒸馏水和9.08g浓硝酸并将全部混合物搅拌1小时。将通过实施例1中的快速成型制备且总质量为42.8g的7个Al2O3成型体置于皮氏培养皿中并加入所述金属硝酸盐溶液。每隔30分钟转动溶液中的成型体并在3小时后从溶液中取出。随后将成型体干燥(120℃下4小时)并煅烧(以2K/min加热至500℃并在500℃下维持10小时)。这产总重量为44.0g且包含1.4%Bi、1.4%Pd和0.01%Co的7个成型体。
对比例2:
将3.54g Bi(NO3)3·5H2O与3.81g Pd(NO3)2·2H2O和55mgCo(NO3)2·6H2O一起置于玻璃烧杯中。加入30g蒸馏水和15g浓硝酸并将全部混合物搅拌1小时。将该金属硝酸盐溶液加入呈平均长度为5-10mm的1.5mm挤出物形式的97g Al2O3中。在浸渍之后,将成型体干燥(120℃下4小时)并煅烧(以2K/min加热至500℃,并在500℃下保持10小时)。这产生包含1.5%Bi、1.5%Pd和0.011%Co的98.2g挤出物。
实施例3
将50ml催化剂装入盐浴反应器中;在顶部和底部存在10ml滑石层作为惰性材料。使催化剂达到350℃的温度。首先使120标准l/h氮气和35标准l/h空气通过催化剂,15分钟后额外加入32.5g/h水,在另一15分钟后加入22.4g/h环己酮。收集输出物并且所需反应产物环己烯酮的含量借助气相色谱法测定。下表显示了实施例2的催化剂和对比例2的催化剂对三种不同温度的结果。
m催化剂/g | 温度/℃ | 转化率/% | 选择性/% | 产率/% | |
实施例2 | 32 | 350370390 | 59.665.168.4 | 59.451.543.3 | 35.433.529.6 |
对比例2 | 48 | 350370390 | 48.648.151.0 | 31.729.725.2 | 15.414.312.8 |
转化率=环己酮的转化率
选择性=至环己烯酮的选择性
产率=环己烯酮的产率
尽管在相当的掺杂剂含量下较低的催化剂质量,当在相同反应条件下使用本发明催化剂时得到了更高的选择性和更高的产率。产率比对比例的2倍还高。
实施例4:
如图2所示的三维结构化的“交叉通道结构”由SiO2制备。长度为100mm且直径为80mm。
借助快速成型的成型在ProMetal RCT S15(购自ProMetal RCTGmbH,86167 Augsburg)上通过交替施加粉末和粘合剂层而进行。将粒径为140μm的硅沙GS 14(购自Strobel Quarzsand GmbH,92271Freihung)用作粉末并将呋喃树脂酸混合物用作粘合剂。Askuran 120(购自Ashland-Südchemie,40721 Hilden)和RPT 100(购自Ashland-Südchemie,40721Hilden)的该粘合剂混合物以100∶40的混合比使用,其中将树脂加入粉末中并经由压头喷嘴引入固化剂。将树脂以约1.5%的量加入粉末中。成型体通过构建47个层并在室温下干燥过夜而制备。
实施例5:
测量了当气体流过流量管中的通过实施例4中的快速成型制备的SiO2成型体时产生的压降。为了对比,测量了SiO2挤出物(直径:1.5mm;平均长度:5-10mm)床中的压降。为此,将成型体装入直径为80mm的不锈钢管中或将SiO2挤出物作为固定床(床高度:592mm)引入,并使氮气在25℃和大气压力下以各种流速通过管。将流速逐步增加并借助压力传感器(NetScanner 9116,购自Esterline Pressure Systems,压力范围高达100kPa)测量经过反应器内件或床的压力差。为了评价结果,作为空塔速度的函数描绘经过反应器内件或床高度的压降。
下表显示与SiO2挤出物相比的结构化成型体所测得的压降,选用3个流速。
可以看出通过快速成型制备的结构化的SiO2成型体比1.5mm挤出物组成的催化剂床产生显著更低的压降。
实施例6:
制备了如图2所示的包含α-Al2O3的三维结构化的“交叉通道结构”。长度为50mm且直径为80mm。
成型体的基料为借助Turbula混合器(Willy A.Bachofen AG,4058Basel,瑞士)与固体粘合剂黄原胶,200目(购自& Wiegand,40472Düsseldorf)混合的颗粒氧化铝CT 3000 SDP(购自Almatis,67065Ludwigshafen)。基于氧化铝,固体粘合剂的比例为10重量%。三维印刷借助Z-Printer 310(Z-Corporation,Burlington,MA 01803,美国)使用水基粘合剂溶液ZB 54(Z-Corporation,Burlington,MA 01803,美国)进行。使用2重量%的液体粘合剂。在印刷之后,首先将部件在60℃下干燥8小时,然后借助压缩空气吹扫干净。陶瓷灼烧在1600℃下进行并维持2小时。
Claims (15)
1.具有催化性能的成型体在非均相催化化学反应中作为反应器内件的用途,其中该成型体可通过包括如下步骤的方法得到:
a)借助基于粉末的快速成型方法制备成型体,
b)合适的话,对成型体进行热处理,
c)合适的话,向成型体施加至少一种催化活性组分,
d)合适的话,进行另一热处理,
其中步骤b)、c)和/或d)可进行多次。
2.根据权利要求1的用途,其中选择用于步骤a)中的粘合剂或粘合剂混合物,以使粘合剂本身或其残留物不影响或没有不利地影响随后使用该催化剂(载体)的化学反应。
3.根据权利要求1或2的用途,其中在步骤a)中将二氧化硅或铝硅酸盐的溶胶或胶体溶液,硅石,硅酸酯,硅氧烷或聚硅氧烷,或加入乙烯基聚合物或其他润湿剂的水基液体粘合剂用作粘合剂。
4.根据权利要求1-3中任一项的用途,其中成型体由二氧化硅、氧化铝、二氧化钛、二氧化锆、氧化镁、氧化钙、混合金属氧化物、水滑石、尖晶石、钙钛矿、金属磷酸盐、硅酸盐、沸石、滑石、堇青石、碳化物、氮化物或其混合物或共混物制成。
5.根据权利要求1-4中任一项的用途,其中将平均粒度为1-450μm粉状原料用于步骤a)中。
6.根据权利要求1-5中任一项的用途,其中步骤b)中的热处理在350-2100℃的温度下作为煅烧进行。
7.根据权利要求1-6中任一项的用途,其中对用于步骤a)的粉末进行包括研磨、筛分、煅烧、造粒、压缩、混合、聚集中的至少一个步骤的预处理。
8.根据权利要求1-7中任一项的用途,其中成型体具有反应介质经由其流过的通道且该通道与主流动方向以0°-70°,优选30°-60°的角度倾斜
9.根据权利要求1-8中任一项的用途,其中将成型体构造为多通道填料,该填料具有其中优先进行化学反应的通道且额外包含其中优先进行对流热输送的通道,其中用于热输送的通道优选以较大角度倾斜且优选具有2-10倍于用于催化的通道直径的水力直径。
10.根据权利要求9的用途,其中将成型体构造为多通道填料,该填料的各层穿孔以获得更好的传质。
11.根据权利要求1-10中任一项的用途,其中使反应介质流过包含作为填料或床的成型体的柱形反应器,其中填料由一个元件构成或由多个在纵向方向上排列的形成填料区段的元件构成,其中各填料或床元件由多个纵向排列的层构成,各层包含紧密包裹的通道,相邻层的通道交叉并且在填料元件内的通道具有可渗透或不可渗透流体的侧壁。
12.根据权利要求1-11中任一项的用途,其中将成型体填充在柱形反应器中,为了抑制经由外边缘通过,成型体a)围绕外侧配有密封以确保均匀流过填料的整个横截面或者b)具有如下结构:其在外边缘不具有较高孔隙率。
13.根据权利要求1-12中任一项的用途,其中所述化学反应吸热或放热进行。
14.根据权利要求1-13中任一项的用途,其中所述反应选自氧化、氨氧化、加氢、脱氢、异构化、水合、脱水、胺化、硝化、烷基化、脱烷基化、歧化、酰化、烷氧基化、环氧化、酯化、酯交换、易位反应、二聚、低聚和重排。
15.根据权利要求1-14中任一项的用途,其中反应器内件作为床或填料存在于柱形反应器,优选管壳式反应器中。
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PCT/EP2008/062956 WO2009047141A1 (de) | 2007-10-08 | 2008-09-26 | Verwendung von formkoerpern mit katalytischen eigenschaften als reaktoreinbauten |
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EP (1) | EP2200736B1 (zh) |
JP (1) | JP5322119B2 (zh) |
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CN108160011A (zh) * | 2018-01-23 | 2018-06-15 | 上海尚信化工装置科技有限公司 | 一种涓流床反应器 |
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CN114307634A (zh) * | 2022-01-05 | 2022-04-12 | 嘉兴沃特泰科环保科技股份有限公司 | 颗粒态脱硝剂及其制备方法和应用 |
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CA2701851C (en) | 2017-01-17 |
US20100222209A1 (en) | 2010-09-02 |
US8119554B2 (en) | 2012-02-21 |
WO2009047141A1 (de) | 2009-04-16 |
JP5322119B2 (ja) | 2013-10-23 |
EP2200736B1 (de) | 2016-11-30 |
CA2701851A1 (en) | 2009-04-16 |
EP2200736A1 (de) | 2010-06-30 |
CN101952023B (zh) | 2013-09-04 |
JP2011501691A (ja) | 2011-01-13 |
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