CN1046639C - 用于分散流化床催化剂颗粒或使其表面重新暴露的方法 - Google Patents

用于分散流化床催化剂颗粒或使其表面重新暴露的方法 Download PDF

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CN1046639C
CN1046639C CN92103676A CN92103676A CN1046639C CN 1046639 C CN1046639 C CN 1046639C CN 92103676 A CN92103676 A CN 92103676A CN 92103676 A CN92103676 A CN 92103676A CN 1046639 C CN1046639 C CN 1046639C
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N·J·布雷默
L·R·特罗特
T·R·麦克唐奈
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Abstract

用于分散流化床催化剂颗粒或使其表面重新暴露的方法，所述表面在生产丙烯睛或马来酐的过程中已被污染或已经受了物理的或化学的变化，该方法包括使所述流化床催化剂颗粒在流化状态下与一种气体接触，所述气体的速度在60.96至365.76米/秒之间，且该速度足以在催化剂颗粒之间引起多次碰撞，所以碰撞至少足以产生下述之一的效果，即分散流化床催化剂颗粒或研磨催化剂颗粒的表面以除去被污染的或已变化的表面。

Description

用于分散流化床催化剂颗粒或使其表面重新暴露的方法
本发明涉及一种提高流化床催化剂性能的方法，所述催化剂由于其表面上的污染或其它物理或化学的变化而丧失了活性或流化品质。本发明特别涉及一种在使用中为从催化剂表面除去一层薄层露出新的催化剂而研磨催化剂表面的方法。另外，本发明还涉及一种用于分散(deagglomerating)催化剂颗粒的方法。
在流化床催化反应器中，被分离的催化剂的细颗粒与特殊的汽态反应介质相接触。催化剂颗粒由反应气态物的一股上升气流托起并被搅拌，因而使其在气态流中呈悬浮状态，并似类于一种沸腾的流体，故称之为“流化床”。
广为人知且为流化床反应器技术的早期应用之一的实例是为生产汽油和其它轻质烃而对石油所进行的催化裂化。其它用途包括残余物的焦化；焦化气化；把苯或丁烷催化氧化成马来酐；把丙烯氨氧化成丙烯腈；并把氯化氢氧化成氯。
本发明的发明点集中在用于流化床反应器中的催化剂上，对于已经用过且过期的情况而言，当催化剂的表面被污染或被反应所生成的副产品弄脏时，或当催化剂的表面经受了物理的或化学的变化而变成一种丧失催化性的结构时，某些流化床催化剂便丧失了活性。另外，由于在催化剂表面上产生污染或物理的、化学的变化，一些催化剂变成“粘附状态”，而一些小的流化床颗粒开始附聚成大颗粒。附聚后的颗粒使得催化表面积减少，由此影响了流化床催化剂的全部性能。此外，附聚颗粒阻止了自然循环和催化剂床的流化。
通常，解决上述问题的方法是更换流化床反应器中的所有或部分催化剂。就催化剂的价格而言，这是非常昂贵的。而且可能要以关掉流化床调整催化剂变化量进而降低产量为代价。
因此本发明的目的是提供一种方法来解决由于附聚作用，污染或在催化剂表面上的物理或化学变化所引起的问题，以延长催化剂的寿命。
本发明公开了一种方法，该方法用以分散流化床催化剂并使流化床催化剂的表面重新暴露，所述表面由于其上的污染或物理、化学的变化而丧失了活性或流化品质。本方法是在工作流化床反应器的内部完成的，但也可随意地以连续或非连续的形式在反应器之外完成。
上述一种至少用于下述两种用途之一的方法，即用于分散流化床催化剂颗粒或使其表面重新暴露，所述表面在生产丙烯腈或马来酐的过程中已被污染或已经受了物理的或化学的变化，该方法包括使所述流化床催化剂颗粒在流化状态下与一种气体接触，所述气体的速度在200至1200英寸/秒之间，且该速度足以在催化剂颗粒之间引起多次碰撞，所述碰撞至少足以产生下述之一的效果，即分散流化床催化剂颗粒或研磨催化剂颗粒的表面以除去被污染的或已变化的表面。上述气体是空气或氮气；上述方法是在下述任一种容器中实施，即在该容器中装有一个使气流与流化催化剂接触的装置。
在优选实施例中，本方法包括，一个至少装有一个喷嘴的流化床反应器，气体从反应器的外部输入该喷嘴。喷嘴设在反应器之内，以使其浸入催化剂床并使从喷嘴排出的气体直接与催化剂接触。所述气体以足以使其能触及被流化的流化床催化剂颗粒的速度排出喷嘴，并引起催化剂颗粒之间的多次碰撞，催化剂颗粒多次碰撞的冲击研磨了催化剂的表面，从而除去在催化剂表面上的污染物或丧失催化的物质，最终暴露出新的催化剂。
附图是本发明实施例流化床反应器的简化剖视图。
一个流化床反应器是任一种反应容器，在该容器中可以产生气一固或液一固接触反应。在该容器中，被分离成细固体颗粒(即流化床催化剂)的床由工作气流或液流使其升起并分离。流化床反应器可以具有任何形状和大小。特别是该反应器的底部附近设有栅格，用以支承催化床并允许所需的反应物通过。以下的描述将侧重于本发明在气一固接触反应中的应用方面，但所述方法同样可用于液一固接触反应。
在气-固接触反应中，反应气态物位于反应器的顶部。由于气态物携带着催化剂颗粒，因此气态物流过分离器便使催化剂颗粒移动，这些颗粒通过浸入管返回催化床，所述分离器可以是任一种固体回收装置，如旋风分离器和过滤器。
流化床催化剂被细分成许多固体颗粒，而这种颗粒的大小、重量、形状及成份依据应用要求而变化。用肉眼看，流化床催化剂常似粉末。但用肉眼观察这种催化剂也可呈小珠粒状。典型的流化床颗粒的大小在10至200微米之间。
在使用一段时间之后，由于在催化剂表面上形成污染物或物理、化学的变化使流化床催化剂丧失了其功能。这种情况可能会引起催化活性降低或使催化剂变为“粘附状态”，在这种状态下，催化剂颗粒趋于附聚，因而降低了流化品质和/或降低了催化剂的活性。
在本发明的实施例中，于流化床反应器的内部装有一个或多个喷嘴，通过这些喷嘴将高速气体送入催化剂床。在实施本发明时，使催化剂保持在流化(即成流体的)下，这种状况是由一种提升气流或其它气流所引起的，这种气流使催化剂颗粒于其中被举起。搅拌并悬浮于其中。气流力引起流化催化剂颗粒之间的多次碰撞，由此而产生的撞击研磨催化剂表面，并除去了其表面的污染物，露出新的催化剂。另外，由催化剂颗粒碰撞所引起的撞击将分散(即分离)任何附聚的催化剂颗粒。本发明亦可在任一种下述容器中得以实施，即在该容器中装有任一种用以使高速气流与流化催化剂颗粒接触的装置(如喷嘴或气体分配栅或具有一个或多个孔的盘)。
最好在装有一个以上喷嘴的流化床反应器中实施本发明。所用的喷嘴可以具有任意的形状或大小，并具有任一种“喷射”结构。这些喷嘴可以是简单的开口管，也可以是端部呈锥形或缩颈的短管，用以使管中的气体加速或定向，对于本发明的实施而言，口颈的大小并无严格要求。已用的口颈直径为0.406毫米(在一个气体分配栅上设有直径为0.406毫米的三个一组的孔)。常用的口颈直径在1.5875毫米至6.35毫米之间，更常用的在3.175毫米至4.7625毫米英寸之间。其优选值为3.5719毫米和3.9687毫米。气体的排放速度必须具有足以使催化剂颗粒产生多次碰撞的推力，以便研磨催化剂表面。通常硬催化剂需要较高的排放速度。所采用的排放速度可高达音速。喷嘴的口颈和气体流量的大小取决于所用的气体流速。优选的流速为60.96米至365.76米/秒，更优选的为182.88至335.28米/秒之间。优选的气体流速使得气体一催化剂“接触区”在喷嘴的前面伸入催化剂床若干英寸，可以调整喷嘴的方向，以便为流化反应气体提供同向气流、反向气流或交叉的高速气流。优选的喷嘴方向是为流化反应气体提供高速同向气流。
所述喷嘴或若干个喷嘴可位于催化剂床内的下述任何位置，即喷嘴能够与流化催化剂颗粒接触的位置。如可以仅将喷嘴设于反应器的壁中，或使其位于反应器的中部。为了最大程度地提高本发明的效果，喷嘴应设置在反应器内催化剂循环最好的地方。这样即可加大与气体接触的一次装入的催化剂总量。为此，喷嘴最好邻近浸入管开口端，即在其附近(即使催化剂从分离器返反应器的进口位置)。应注意的是要确保从喷嘴喷出的气体不会将催化剂推入反应器的任一个内部件中。因为在催化剂和反应器部件之间的碰撞将过多的地研磨催化剂，并且重复的碰撞将损坏反应器元件。
所述高流速气体可以是惰性或有利于反应的任一种气体或气化液体。通常这种气体由反应器的外部的气源供入喷嘴。对于将流化床反应器用于氧化反应的情况，常常使用空气。但也可使用惰性气体(如氮气)或一种反应输入气体。在以工业规模反应器实施(即处于生产状态)本发明的实例中，总气体量的增量可忽略不计。
用于分散催化剂和/或使其表面重新暴露的过程可以是间歇的或连续的，这取决于催化剂的要求和喷嘴的参数，如喷嘴的数量、位置及脱离喷嘴的气体排放速度。
通常将污染物或丧失催化作用的物质一即位于催化剂表面的从催化剂上磨落的物质从具有反应流出物的反应器中清除，然后以适宜的分离方式(如旋风分离装置，过滤器等)将其从反应生成物中分离出来。实施本发明的关键是控制气体流速和喷嘴的位置，以尽可能地增大重新暴露催化剂表面的有益作用和/或分散催化剂的作用。而另一方面又要尽可能地减小对催化剂表面的研磨量，以便减小催化剂的损失。
本发明的实施例如图所示。其流化床催化剂2的床是在流化床反应器1的内部，反应气体借助管3进入反应器并通过气体分配栅4进入催化床。含有被输入的催化剂颗粒的气态反应物产品进入旋风分离器6，反应物产品和催化剂在此被分离。气态反应物产品通过管5排出反应器。催化剂通过浸入管7返回催化剂床2。高流速气体通过管8输入反应器并通过喷嘴9进入催化剂床。
在任一种催化流化床反应中，当表面被反应副产品或催化剂组份中的物理或化学变化污染时，均可采用本发明。在这种情况下，催化剂的活性和/或流化品质将降低。通过研磨催化剂表面使其露出新的催化剂或分散催化剂，来恢复其活性和/或流化品质，并延长催化剂的寿命。采用本发明的有代表性的方法是为生产汽油和其它轻质烃对石油的催化裂化，残余物的焦化，焦化气化、把苯或n-丁烷氧化成马来酐、把丙烯氨氧化成丙烯腈，把氯化氢氧化成氯。
如上所述，在工作状态下，高速气体与反应器内部的流化催化剂接触。本发明还可以通过将喷嘴设置在浸入管内来实现。进一步，流化床反应器装有一个再生器，它用于除去被处理过的或失效的催化剂，然后将其送回反应器，如上所述，在反应器和再生器之间的催化剂输送线上或在再生器中，可使催化剂表面重新暴露和/或分散催化剂。最后，如上所述的那样，还可通过从反应器中除去催化剂，暴露催化剂的表面和/或分散催化剂，然后将催化剂送回反应器来实现本发明。
以上描述不是作为完整的论述或限制本发明所公开的详细结构，根据上述内容，许多明显的改进和变化是可能的。以上描述的目的是解释本发明的原理及其实际应用，并由此而使所属领域的熟练技术人员能够在各种变化的实施例中以及为适应必要的特殊用途而作的各种改进形式中利用本发明。在此仅试以下述各权利要求限定本发明。

Claims (8)

1、一种至少用于下述两种用途之一的方法，即用于分散流化床催化剂颗粒或使其表面重新暴露，所述表面在生产丙烯腈或马来酐的过程中已被污染或已经受了物理的或化学的变化，该方法包括使所述流化床催化剂颗粒在流化状态下与一种气体接触，所述气体的速度在60.96至365.76米/秒之间，且该速度足以在催化剂颗粒之间引起多次碰撞，所述碰撞至少足以产生下述之一的效果，即分散流化床催化剂颗粒或研磨催化剂颗粒的表面以除去被污染的或已变化的表面。
2、如权利要求1所述的方法，其特征在于所述气体是空气或氮气。
3、如权利要求1所述的方法，其特征在于所述方法在下述任一种容器中实施，即在该容器中装有一个使气流与流化催化剂接触的装置。
4、如权利要求1的方法，其中催化剂颗粒是在流化状态下保持于流化床反应器中，其中的流化床反应器至少装有一个喷嘴，气体从反应器之外的气源供入喷嘴，该喷嘴位于反应器之中，以便使其浸入催化剂颗粒中并使从喷嘴排出的气体直接与催化剂颗粒接触。
5、如权利要求4所述的方法，其特征在于，其中的气体是空气或氮气。
6、如权利要求4所述的方法，其特征在于在流化床反应器中设有用以将催化剂与气态流出物流分离的旋风分离器，该旋风分离器装有用于将催化剂送回反应器的浸入管，所述喷嘴位于用于催化剂浸入管的出口附近。
7、如权利要求4所述的方法，其特征在于，当所述流化床反应器用于生产马来酐或丙烯腈时，实施所述的用于重新暴露催化剂表面的方法。
8、如权利要求4所述的方法，其特征在于，喷嘴口颈的直径在3.175至4.7625毫米之间。
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