CN1292303A - 多相催化三相反应的等温操作 - Google Patents

多相催化三相反应的等温操作 Download PDF

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CN1292303A
CN1292303A CN001305980A CN00130598A CN1292303A CN 1292303 A CN1292303 A CN 1292303A CN 001305980 A CN001305980 A CN 001305980A CN 00130598 A CN00130598 A CN 00130598A CN 1292303 A CN1292303 A CN 1292303A
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F·J·布雷克尔
M·哈尔克
G·凯贝尔
G·罗尔巴赫尔
E·施瓦尔
M·斯特雷策尔
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Abstract

本发明涉及用于多相催化反应的等温操作的方法和装置,所述反应涉及呈气相、液相和固相的至少三相。本发明提供了进行涉及三相的反应的装置,包括:(i)用于在液相中分散气相以产生反应流体的分散元件,(ii)至少一个反应器,其具有一个入口、一个出口和由散热壁界定的反应器空间,所述散热壁沿反应流体的主流动轴线基本均一地间隔排布,且其上设有涂覆了催化剂的金属织物,和(iii)加料管线,其将反应流体由分散元件发送至反应器入口,且其足够短以使得反应流体的分散度在流经所述加料管线通道时不发生明显的改变。

Description

多相催化三相反应的等温操作
本发明涉及用于多相催化反应等温操作的方法和装置，所述反应涉及呈气相、液相和固相的至少三相。
本发明具体涉及这类反应的操作，所述反应中至少一种反应物是液体，且一种反应物是气体，且所述催化剂是固体物质。
这类反应的操作存在相当大的困难。气-液迁移经常发生问题。再有，等温条件难以实现，所用的等温的意义是，通过输入或移出热量使反应热量基本上稳定，使得在反应器中的瞬时或局部温度波动不重要。
在G．Eigenberger，Ullmann，5th edition，vol．4，p．199ff(1992)Wiley-VCH，Weinheim，Berlin，New York中叙述了已建立的方法。
EP-B0305203(US-A-4985230)叙述了在非绝热的条件下进行的多相催化反应的操作。为达此目的，具有热传递壁的反应器中装入整体式催化剂。所述整体式催化剂是具有足够大催化表面积的粘结(coherent solid)固体，这些物体的可计数量足以使催化反应达到工业上可行的程度。所述整体式催化剂具有与总体流动方向成角度的沟槽，使得所述反应流体的路径以锐角从一个反应器壁至另一反应器壁，据说这样可改进热传递。在反应器壁附近施加在反应流体上的剪应力极高(高压降)，而另外方面相当低(不良传质)。这导致在反应器壁附近有不必要的大的压降。所述反应器制造复杂，因为所述压降决定性地取决于反应器壁与整体式催化剂之间的几何形状。
EP-B0201614(US-A-4731229)叙述了含有部分波纹带形催化剂体的反应器，所述波纹以与主流动轴呈倾斜角的方式设置，且正对着邻接板，催化剂体的波纹间距小于邻接的波纹板的间距，且所述催化剂体的表面积大于邻接的波纹板的表面积。这种装置不是设计用来产生气-液分散。塔板的复杂的波纹利于形成旁路，抑制产生涡流，从而协调了传质。此外，预计的致密装填元件不能有效地除去反应热。
EP-B0068862(CA-A1146148)公开了用于气相和液体间转移反应的固定床反应器。在这种反应器中，所述固定床包括交替的平面层和波纹片，它们盘绕在一起形成卷筒，所述波纹片包括具有由高分子量有机聚合物质构成的至少一个外表面层的开口网状物质，而所述有机聚合物质列所提到的液体具有固有的憎水性，且所述平面片包括纺织品芯料物质的针织、编织或毡制织物，而所述芯料物质对液体或气-液转移反应是亲水性的且其对所提到的液体提供了在所述卷筒端部之间的不间断的吸液通道。这类反应器的缺点是所述反应器的纺织品组分限制了断面流动速度。再有，所述吸液通道抑制了快速液体转移，从而有利于气液间分离，而抑制气液间的传质。此外，所述反应器是用于绝热操作的。
本发明的目的之一是提供用于进行涉及液相、气相和固相反应的装置和方法，改进气相和液体之间的传质，并以等温操作来进行。
我们发现，这一目的通过用于进行涉及液相、气相和固相的反应的装置得以实现，所述装置包括
-用于在液相中分散气相以生成反应流体的分散元件，
-至少一个反应器，其具有一个入口、一个出口和由散热壁界定的反应器空间，所述散热壁沿反应流体的主流动轴线基本均匀地间隔排布，且其上设置有涂覆了催化剂的金属织物，和
-加料管线，其将反应流体由分散元件发送至反应器入口，且其足够短以使得反应流体的分散度在流经所述加料管线的过程中不发生明显的改变。
本发明人已确定，仅在如下条件下可获得改进的传质，即如反应流体是由气相(作为分散相)和液体(作为分散介质)形成的分散液，且所述方法和装置的设计方式使得所述分散液流经反应器时保持稳定，即，基本上不出现气泡尺寸的增加。
本发明的反应器设计用来对反应流体保持高但均一的剪应力。一方面，它经受高的横截面流速而不磨损催化剂。另一方面，所述反应流体在金属织物中受均一的高剪应力作用。这对反应流体提供了均一的混合并从而在所述反应流体流经反应器时提供恒定的分散度。
本发明的涂覆有催化剂的金属织物是编织或编结的金属织物。丝线直径一般范围为0．01至5．0mm，优选为0．04至1．0mm。网眼尺寸可在宽范围内变化。
这些编织物或编结物可通过在EP-B0564830(CA-A2090930)或EP-A0965384中叙述的方法进行涂覆。EP-B0564830没有清楚地叙述用催化剂涂覆金属编结物，但它们以与编织金属织物相同的方式进行处理。对于本发明的目的，编结的金属织物是由一根连续的金属线形成的金属织物。相反，编织的金属织物是由至少两根金属线形成的织物。
编织或编结金属织物涂覆催化剂还可通过通用的浸渍方法来实现，例如按照在EP-A-0056435中叙述的方法。
如形成编织或编结金属织物的金属本身是有催化活性的(可在处理后)，则完全可不进行涂覆。
编织或编结金属织物可以条带的形式来使用。涂覆有催化剂的编织和编结金属织物可通过带齿的轮筒进行波纹化处理。在反应器中引入波纹化的编织或编结金属织物可改变编织或编结金属织物的填充密度。例如，可向反应器空间中引入多层波纹化和平坦的编织或编结金属织物。相似地，可在编织和编结金属织物之间插入惰性的金属片。在任何情况下，引入涂覆有催化剂的编织或编结金属织物的方式必须使得所述反应器空间在导热壁之间很均一地填充。均一地填充抑制了旁路的形成，并支持热量传导至散热壁，这又使得所述反应能够在等温条件下进行。
在另外的实施方案中，所述分散元件是液体喷射气体压缩机。这些通用的分散装置是用于输送并压缩气体的喷射泵。
在喷射泵中，驱动液体的喷射在离开驱动喷嘴时破裂成单独的液滴。这些液滴沿混合喷嘴横截面上均一地分布，通过冲击和磨擦夹带周围的气体将其压缩为更高的压力。可达到的分散度由设置驱动喷嘴和扩散器来决定。而这又取决于驱动液体的压力、吸入压力、反压力、驱动液体的流动、气体抽吸物流和混合物物流。
在本发明装置的另外的实施方案中，所述反应器建造为热交换器。当在背向反应器空间的反应器壁表面上的流体介质吸收反应热量并将其运走时，经反应器壁的热传递明显增加。这种热交换器反应器可建造为平板型热交换器或螺旋管型热交换器。本发明的平板型热交换器具有特别是正方或矩形反应器空间，该空间被附加的导热壁细分区，所述导热壁使反应流体以之字形流程流经反应器空间。在变向最大处不使用涂覆催化剂的编织或编结金属织物以避免过大的压降。本发明螺旋管型热交换器具有特别是圆筒形反应器空间，其中很均一地填充涂覆了催化剂的编织或编结金属织物。本发明的热交换器反应器的所述壁的间隔优选为1至30mm，尤其是为2至20mm，特别是为4至10mm。
本发明还提供了进行涉及气相、液相和固相的反应的方法，包括如下步骤：
-通过将气相分散于液相中生成反应流体，
-使生成的反应流体流经反应器，所述反应器空间设置有涂覆了催化剂的编织或编结金属织物，
-传递界定反应器空间的壁处的反应热量，及
-将反应流体分离为气相和液相。
可使用通用的分离器来实现反应流体的分离。
优选以在反应器中反应流体的总流动方向为向上的方式来进行所述方法。
本发明方法的另外的实施方案是以单独的部分循环气相和／或液相来进行操作。单独的部分循环的意义是将反应产物从气相和／或液相中分离。残余的气体和残余的液体可完全或部分再分散并返送到反应器中。
在本发明方法的另一实施方案中，在所述反应器中表层液体速度为100至600m3／(m2．h)，优选为150至300m3／(m2．h)。表层液体速度为在反应条件(压力和温度)下分散液的液体组分的体积流量除以与主流动轴线垂直的反应器空间横截面积。因为，作为引入的编织或编结金属织物的结果，所述反应器空间不能完全提供给反应流体，所以，实际的微观表层液体速度对应的更高。
在本发明方法的另一实施方案中，表气体速度为0．5至15cm／s，优选为2．5至10cm／s。在这里定义的表层气体速度与表层液体速度相似。
在本发明方法的另一实施方案中，在反应器中的反应流体处于0．1至200巴的压力，优选1至100巴，尤其是1至10巴。
在本发明的另一实施方案中，在反应器中的反应流体的温度为25至250℃，优选为25至200℃，特别是为50至150℃。
现在参照附图1至4对本发明进行更具体的说明。
图1所示为进行产物循环的三相反应的装置，循环气体操作使用液体喷射气体压缩机和平板型热交换器反应器。
图2所示为进行产物循环的三相反应的装置，循环气体操作使用液体喷射气体压缩机和螺旋管型热交换器反应器。
图3所示为螺旋管型热交换器反应器内部的侧视图。
图4所示为螺旋管型热交换器反应器的侧视图。
图1和2图示了一种装置，其中在反应器1中的金属织物20承载的催化剂已进行活化(例如通过H2还原)，所述装置通过循环泵21充填产物液体，所述循环泵21将来自分离器10的液体经非必需的预加热器16和液体喷射气体压缩机的加料管线5泵送至液体喷射气体压缩机6，并从该处输送至热交换器反应器1，从热交换器反应器1经加料管线输送至分离器9返回至分离器10中。循环气体从分离器10中经加料管线11排出并通过循环气体泵13经液体喷射气体压缩机的加料管线8加入到液体喷射气体压缩机6中，在所述压缩机6中气体压缩并同时在液体中分散形成反应混合物。使用足够短的反应器加料管线7来向反应器1中加入反应流体，使得反应流体的分散度经这一距离不发生明显的改变。一旦使用产物起动了循环，即使用液体喷射气体压缩机的加料管线4引入反应物，并使用在分离器10上的恒定流充填液面系统来经排料管线14从循环液体中排出对应数量的产物。在保持压力的条件下，经液体喷射气体压缩机的加料管线17向循环气体中加入新鲜的气体来置换消耗掉的反应气体，并经废气管线12从循环气体中排出废气。在放热反应的情况下，经冷却循环系统22从反应器中除去反应热量，而在吸热反应的情况下，引入热量。
图3所示为本发明螺旋管型热交换器反应器的侧视图。31表示的是加入到反应器中的反应流体的进料(反应器入口)。32表示的是反应器通道，其容纳涂覆了催化剂的金属织物，且其以或大或小的填充密度占有全部空间。33表示冷却通道，其中容纳冷却流体。
图4是螺旋管型热交换器反应器的侧视图，并表示了进料和排料短管的排布。41：反应流体进料(反应器入口)，42：冷却流体排料，43：反应流体排料(反应器出口)，44：冷却流体进料。反应流体和冷却流体在这里逆流排布以使热传导最大化。如特别是在反应器入口释出的热量相对于如选择性和催化剂稳定性来说是关键的，则并流排布是适宜的。
以下以实施例对本发明进行说明。
实施例
苯加氢为环己烷的放热量△H=-214KJ／mol。
苯加氢产物在环己烷和甲基环戊烷之间平衡，除非除去反应热量并保持较低的温度。
研究还表明，所述反应是基物限制的，因为氢在苯和环己烷中的低溶解度使得反应混合物沿催化剂层耗尽溶解的H2。因而，使用本发明来改进溶解氢的供给是有利的。
使用按照图2的本发明装置来进行苯加氢方法，所述装置包括按照图3和4的螺旋管型热交换器反应器。为达此目的，在宽5mm、深25mm、长960mm(容积120ml)的反应器通道中装填8层编结的催化剂织物带，所述催化剂织物带是通过先对V2A不锈钢(德国物质号1．4301)编结载体带在650℃下热处理3小时、然后真空涂覆6nm铂来制备的。活性组分的数量为46mg。装填了催化剂的热交换器反应器安装到绘于图3中的装置中。在用氮吹扫并用氢在80℃下还原催化剂2小时后，经加料管线4将苯泵入充填有环己烷的液体循环系统。反应参数为p=20巴，T=90℃，表层液体和氢速度为400m3／m2h。
在反应器出口测量反应产物的温度。相对于设定的反应温度观察到的最大温差为0．2℃。
以98％的转化度获得了100％的选择性。基于反应器通道容积的空时产率为0．5kg／(l．h)。

Claims (16)

1．进行涉及气相、液相和固相的反应的装置，包括：
-用于在液相中分散气相以产生反应流体的分散元件，
-至少一个反应器(1)，其具有一个入口(31，41)、一个出口(43)和由散热壁界定的反应器空间，所述散热壁沿反应流体的主流动轴线基本均一地间隔排布，且其上设有涂覆了催化剂的金属织物(20，32)，和
-加料管线(7)，其将反应流体由分散元件(6)发送至反应器入口(31，41)，且其足够短以使得反应流体的分散度在流经所述加料管线通道的过程中不发生明显的改变。
2．如权利要求1的装置，其中所述金属织物是编织的金属织物。
3．如权利要求1的装置，其中所述金属织物是编结的金属织物。
4．如权利要求1至3任一项的装置，其中所述分散元件(6)是液体喷射气压缩机。
5．如权利要求1至3任一项的装置，其中所述反应器(1)构造为热交换器。
6．如权利要求5的装置，其中所述反应器(1)构造为平板型热交换器。
7．如权利要求5的装置，其中所述反应器(1)构造为螺旋型热交换器。
8．如权利要求5的装置，其中在反应器中的所述壁的间隔为1至30mm。
9．如权利要求5的装置，其中在反应器中的所述壁的间隔为2至20mm。
10．如权利要求5的装置，其中在所述反应器中的所述壁的间隔为4至10mm。
11．一种进行涉及气相、液相和固相的反应的方法，其包括如下步骤：
-通过将气相分散于液相中生成反应流体，
-使生成的反应流体流经反应器，所述反应器空间设置有涂覆了催化剂的编织或编结金属织物，
-传递界定反应器空间的壁处的反应热量，及
-将反应流体分离为气相和液相。
12．如权利要求11的方法，以独立地部分循环气相和／或液相来进行操作。
13．如权利要求11的方法，其中在反应器中的表层液体速度为100至600m3／(m2．h)。
14．如权利要求11的方法，其中所述表层气体速度为0．5至15cm／s。
15．如权利要求11的方法，其中在反应器中的反应流体的压力为0．1至200巴。
16．如权利要求11的方法，其中在反应器中的反应流体的温度为25至250℃。
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