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CN1077111C - 聚合方法 - Google Patents

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CN1077111C
CN1077111C CN94192172A CN94192172A CN1077111C CN 1077111 C CN1077111 C CN 1077111C CN 94192172 A CN94192172 A CN 94192172A CN 94192172 A CN94192172 A CN 94192172A CN 1077111 C CN1077111 C CN 1077111C
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CN1124029A (zh
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Ｊ·－Ｃ·程
M·C·H·菲利佩利
D·牛顿
M·B·包瓦
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Abstract

本发明涉及烯烃，特别是乙烯、丙烯或它们与其它α-烯烃的混合物的连续气相流化床聚合，其中采用流化床的含单体的循环气流进行冷却，冷凝出至少一些液态烃。可能是单体或不活泼液态烃的冷凝液与循环气流分离，并将其直接加入床，通过蒸发潜热产生冷却效果。可以通过气一致雾化喷嘴(图2)或液体喷雾喷嘴将液体加入床。本方法显著地提高了烯烃气相流化床聚合的生产率。

Description

聚合方法
本发明涉及在流化床反应器中进行烯烃气相聚合的连续方法，更具体地讲，涉及一种提高生产率的方法。
在气相中进行烯烃的均聚和共聚的方法是该技术领域内公知的方法。例如通过将气态单体引入包括预制聚烯烃和聚合用的成型催化剂的搅动床和/或流化床可以上进行这些方法。
在烯烃的流化床聚合反应中，聚合反应是在流化床反应器中进行，利用包括气态反应单体的上行气流维持聚合物颗粒床的流化状态。这种聚合反应的启动一般都采用与要求制备的聚合物相似的预制聚物颗粒床。在聚合反应过程中、通过单体的催化聚合，产生新的聚合物，并排出聚合物产品，保持床体积基本上不变。在工业上有利的方法采用流化栅板分布到床的流化气，当供气切断时，该栅板用作床的支撑体。产生的聚合物通常经设置在反应器下部，靠近栅板处的排放管排出。流化床包括生长的聚合物颗粒、聚合物产品颗粒和催化剂颗粒。通过流化气从反应器底部连续地向上流动维持反应混合物的流化状态，所述的流化气包括来自反应器顶部的循环气和补充的原料气。
流化气进入反应器底部，并优选经流化栅板通到流化床。
烯烃的聚合反应是放热反应，因此必须设置冷却床以除去聚合反应热的装置。在没有这种冷却装置的情况下，床将会升温，例如升温直到催化剂失活或床开始熔化为止。在烯烃的流化床聚合反应中，通过向聚合反应器供给一种气体，优选流化气，且该气体的温度低于要求的聚合反应温度，使该气体通过流化床，导走聚合反应热，是排除聚合反应热的优选方法，从反应器排除气体并用通过外部换热器的方法将其冷却后，再循环到床。循环气体的温度可以在换热器中调节，以保持流化床处于所要求的聚合反应温度。在α-烯烃聚合的这种方法中，循环气一般包括单体烯烃、任选的例如和稀释剂或气态的链转移剂例如氢气。这样，循环气就用来将单体输送到床，并流化床，还使床保持在所要求的温度下。由聚合反应所消耗的单体一般通过将补充气加入循环气流中来补充。
众所周知，在上述类型的工业化气相流化床反应器中，生产率(即时空产率，每单位时间反应器空间每单位体积所产生的聚合物重量)受从反应器除去热量的最大速率的限制。例如通过提高循环气的速度和/或降低循环气的温度可以提高热量的除去速率。然而在工业实践中，可以利用的循环气速度有限。超过这种限制，该床就可能变得不稳定，或甚至脱离反应器在气流中提升，导至循环管堵塞和毁坏循环气压缩机或鼓风机。而且在实践中循环气的冷却也有限。这主要是由经济方面的考虑来决定，而且在实践中，通常是由现场可利用的工业冷却水的温度来决定。如果需要，可以采用冷冻的方法，但是这增加了生产费用。因此，在工业化的实践中，利用冷却的循环气作为从烯烃的气相流化床聚合反应中除去聚合反应热的唯一方法有限制得到最大生产率的缺点。
现有技术建议了许多从气相流化床聚合反应过程中除去聚合反应热的方法。
GB1415442号涉及了在搅动床或流化床反应器中氯乙烯的气相聚合方法。聚合反应是在至少一种沸点低于氯乙烯的沸点的气态稀释剂存在下进行的。该文献的例1描述了通过将液态的氯乙烯间歇地加入流化的聚氯乙烯物料中来控制聚合反应温度的方法。在床中液态的氯乙烯立即蒸发，因而除去聚合反应热。
US3625932号描述了氯乙烯的聚合方法，其中通过在反应器的底部引入气态氯乙烯单体，使多段流化床反应器内的聚氯乙烯颗粒床保持流化态。通过将液态的氯乙烯单体喷入在塔板下面的上行气流，在该塔板上床是流化的，除去其中的聚合反应热，为每个床提供冷却。
FR2215802号涉及一止逆阀型的喷咀，它适宜用于将各种液体喷入流化床，例如，在
未饱和单体的气相流化床聚合反应中。该液体用来冷却床，它可以是被聚合的单体，或者如果乙烯是被聚合的单体，那么它可以是液态的饱合烃。该文献所描述的喷咀是对氯乙烯的流化床聚合反应来说的。
GB1398965号描述了(乙)烯化不饱合单体尤其是氯乙烯的流化床聚合反应，其中利用位于反应器中流化物料的0-75％之间的高度的一个或几个喷咀，将液态单体喷入床来实现聚合反应的热量控制。
US4390669号涉及在搅动床反应器、流化床反应器、搅动流化床反应器或管式反应器中进行的多段气相法的烯烃的均聚或共聚反应。在该方法中，从第-聚合反应区得到的聚合物在易挥发液态烃的中间区内悬浮，这样得到的悬浮物加入第二聚合区，在此液态烃蒸发。在例1-5中，来自第二聚合区的气体通过-冷却器(换热器)输送，其中一些液态烃冷凝(和共聚单体，如果采用的话)。挥发的液体冷凝物以液态部分地送往聚合反应器，在此它进行蒸发，通过它的蒸发潜热用来除去聚合反应热。该文献并没有具体说明如何将液体引入聚合反应。
EP89691涉及一种用于流体单体聚合反应的连续气相流化床法中提高时空产率的方法，该方法包括将部分或全部的未反应流体进行冷却，生成气体和携带露点以下液体的两相混合物，和将上述的两相混合物再引入反应器。这种技术称为“冷凝模式”操作。EP89691号说明书描述了循环气流可以冷却到露点以下程度的主要限制，是要求气体与液体足以保持在两相流体混合物中的液相呈携带或悬浮状态这样的水平，直副液体蒸发为止，并且该文献还描述了气相中液体量应不超过20％(wt)，优选应不超过10％(wt)，条件是两相循于环物流的速度总是高到足以保持液相悬浮在气相中，且支持反应器中的流化床。EP89691号还公开了在将产生两相物流的条件下，在反应器内的喷射点处，独立地喷射气体和液体可以生成两相流体物流，但是由于在冷却后增加和不必须的负荷与分离气体和液的费用，使这种方式的操作似乎没有多少优点。
EP173261具体涉及了引入流化床反应器的流体分布的改进，并具体提供了如EP89691号(上述)所描述的“冷凝模式”的操作。更具体地说，EP173261号说明了由于在底头(bottom head)中的液体液泛或起沫，在循环物流中的液体较低量时，工业反应器的经验现象，利用竖管/圆锥帽型(如EP89691号附图中所描述的)反应器的入口到底部(在分布板或栅板下面)的操作是不满意的“冷凝模式”操作。
现在已经发现，通过将循环气流冷却到足以生成液体和气体的温度，和从气体中分离液体，然后将该液体直接地加入流化床，通过液体蒸发冷却床，再引入流化床聚合反应器的液体的总量可以增加，从而增强了冷却效果，使生产率达到更高的水平。
这样，按照本发明，就提供了用于烯烃单体聚合的连续气相流化床方法，该烯烃单体选自(a)乙烯、(b)丙烯、(c)乙烯与丙烯的混合物和(d)a、b或c与一种或一种以上其它α-烯烃的混合物，该聚合反应是在-流化床反应器中进行，在反应条件下，在聚合催化剂存在下，至少包括一些乙烯和/或丙烯的循环气流连续地通过上述反应器中的流化床，从上述反应器中至少部分排出上述的气流，并冷却到液体凝出的温度，从气流中至少部分分离冷凝的液体，并将至少部分分离的液体在通过流化床的气流的温度基本上达到了从反应器排出的气流的温度的那一点处或那一点处的上面直接引入流化床。
从反应器排出的循环气流(下文称“未反应流体”)包括未反应的气态单体、和任选的不活泼烃类、反应活化剂或缓和剂以及携带的催化剂和聚合物颗粒。
加入反应器的循环气流还包括足以代替在反应器中已经聚合的那些单体的补充单体。
本发明的方法适用于在气相中通过一种或几种烯烃，其中至少一种是乙烯或丙烯的聚合反应来制备聚烯烃。在本发明方法中所使用的(α-烯烃优选有3-8个碳原子的那些。但是少量含8个以上碳原子的α-烯烃，如9-18个碳原子的α-烯烃，如果需要也可以采用。这样就能生产乙烯或丙烯的均聚物或乙烯或丙烯与-个或几个C3-C3α-烯烃的共聚物。α-烯烃优选丁-1-烯、戊-1-烯、己-1-烯、4-甲基戊-1-烯，辛-1-烯和丁二烯。可以与主要的乙烯或丙烯单体聚合，或用作C3-C8单体的部分替代物的较高烯烃的例子是癸-1-烯和亚乙基降冰片。
当本发明的方法用于乙烯或丙烯与α-烯烃聚合时，乙烯或丙烯是以共聚物的主要组分存在，优选以至少总单体的70％量存在。
本发明的方法可以用来制备各种样的聚合物产品，例如主要是乙烯与丁烯、4-甲基戊-1-烯或己烯的共聚物的线型低密度聚乙烯(LLDPE)和高密度聚乙烯(HDPE)，例如它可以是乙烯与少部分的高α-烯烃如丁烯、戊-1-烯、己-1-烯或4-甲基戊-1-烯的均聚乙烯或共聚物。
循环气流中冷凝出的液体，可以是可冷凝的单体，例如生产LLDPE用作共聚单体的丁烯、己烯、辛烯，或可以是不活泼的可冷凝液体，例如丁烷、戊烷和己烷。
重要的是，在所采用的聚合反应条件下，液体在床内应该蒸发，因此得到所要求的冷却效果，以基本上避免在床内积聚液体。加入床的液体95％(wt)，优选至少98％(wt)，而更优选基本上全部都蒸发是适宜的。在液态共聚单体的情况下，一些共聚单体在床中聚合，而这种聚合反应可以是液相和气相的。众所周知，在传统的气相聚合或共聚过程中，小比率的单体(和共聚单体，如果使用的话)在产品聚合物中倾向于保持缔合(吸收或溶解)，直到该聚合物进行随后的脱气为止。这种缔合的量，或吸收或溶解单体/共聚单体甚至较高的量，如果这些量对床的流化特性的确没有不利影响的话，就是可以容许的。
本发明的方法特别适用于在0.5和6MPa的压力下，在30℃和130℃之间的温度进行烯烃的聚合反应。例如LLDPE的生产温度适宜在80-90℃范围，而HDPE的生产温度一般为85-105℃，这取决于所使用的催化剂的活性。
聚合反应可以在齐格勒-纳塔型(Ziegler-Natta type)催化剂体系存在下进行，固体催化剂的组成主要包括一种过渡金属的化合物和包含一种金属(即一种有机金属化合物，例如烷基铝化合物)的有机化合物的一种助催化剂。高活性的催化剂体系多年来都是已知的，并且在较短的时间内能够生产大量的聚合物，因此能够避免从聚合物中除去催化剂残留物的步骤。这些高活性的催化剂体系通常包括一种基本上由过渡金属、镁和卤原子组成的固体催化剂。也可以利用主要由通过热处理活化的铬氧化物和与以耐高温氧化物为主的颗粒状载体相结合组成的高活性催化剂体系。本发明的方法也可适宜使用载在二氧化硅载体上的金属茂催化剂和齐格勒催化剂。
本发明的方法的优点是利用高活性的催化剂，例如金属茂催化剂，提高了冷却效果，对聚合过程是特别有利的。
在用如上述的催化剂4进行聚合反应期间，适宜采用预先制备的预聚物粉末状的催化剂。预聚合反应可以任何适宜的方法进行，例如利用间歇法、半连续法或连续法在液态烃稀释剂中或在气相中进行聚合反应。
本发明的方法优选是将基本上全部的循环气流冷却并分离，然后将基本上全部的分离液体引入流化床的这样的一种方法。
在本发明的另一优选方案中，将循环气流分成第一气流和第二气流。第一气流通过在流化棚板下面喷射的一般方法直接通到反应器，而第二气流冷却后，该物流分离成一气流和液体物流。该气流返回到第一物流中，并在床的下面再引入反应器中，例如如果采用棚板的话，就在流化棚板下面引入反应器中。按照本发明分离出的液体引入流化床。
利用一台或几台换热器使循环气流适当地冷却到气流中的液体冷凝的温度。适用的换热器是本技术领域内公知的。
离开反应器顶部的气流可能携带大量的催化剂和聚合物颗粒，如果要求的话，用一旋风分离器可以将它们从循环气流中除去。小比率的这些颗粒或细颗粒可能保持携带在循环气流中，在冷却和从气流中分离液体后，如果需要该细颗粒可以与分离的液流一起再引入流化床。
循环气流中还包含用来将催化剂、反应活化剂或缓和剂喷入反应器的不活泼的烃类。
补充单体例如乙烯用来代替为聚合反应所消耗的单体，可以在任何适宜的位置加入循环气流。
可冷凝的单体例如丁烯、己烯、4-甲基戊-1-烯和辛烯例如可以用作生产LLDPE的共聚单体，或不活泼的可冷凝的液体，如戊烷、异戊烷、丁烷和己烷可以液体方式引入。
例如，不活泼的可冷凝液体如戊烷可以在换热器和分离器之间喷入循环气流。为制备LLDPE，如果需要，共聚单体如丁烯在通到换热器前，可以先喷入循环气流。
用于分离液体的适宜装置例如是旋风分离器、使气流减速以实现分离的大容器(分离罐)、除雾器型的气-液分离器和液体洗涤器，例如文丘里洗涤器。这些分离器在本技术领域内是公知的。
在本发明的方法中，利用除雾器型的气-液分离器特别有利。
在气-液分离器前，在循环气流中优选使用旋风分离器。这能够以离开反应器的气流中除去大部分的细颗粒，从而有利除雾器型分离器的使用和减少分离器液泛的可能性，因此能更有效地操作。
利用除雾器型分离器的另一优点是该分离器内的压力降比其它类型的分离器低，从而提高了整个过程的效率。
在本发明的方法中使用的特别适宜的除雾器型分离器是称为“Peerless”(DPV P8X型)的商购立式气体分离器。这种类型的分离器使液滴聚结在设置的叶片上，以从气流中分离液体。为收集液体在分离器的底部设置-大的液体收集器。该液体收集器能够贮存液体，因此提供了从分离器排放液体的控制。这种类型的分离器很有效，并且能基本上100％地从气流中分离冷凝的液体。
如果需要，在分离器的液体收集器中可以设置过滤网或其它的适宜装置，以收集存在于分离液体中残留的细颗粒。
分离的液体加入反应器的循环气流，基本上是在达到了从反应器排出的循环气流的温度的那点或那点上面处适宜地引入流化床。分离的液体可以在流化床的这个区域的许多点处引入，而这些点可以是在这个区域的不同高度处。引入液体的一个点或多个点是设置成液体的局部浓度对床的流化或产物的量没有不利的影响，并能够使液体从各个点容易分散和在床中容易蒸发，除去来自放热反应的聚合热。按这样的方法，为冷却目的引入液体的量.可以非常接近能够容许的最大负荷，而不干扰床的流化特性，因而为实现提高反应器的生产率的水平提供了机会。
如果需要，液体可以在床内的不同高度处引入流化床。这一技术可以使改进控制共聚单体的结合容易。进入流化床的液体的控制测量对床的温度的分布情况提供有利的附加控制，在液体含共聚单体的情况下，对共聚单体并入共聚物提供了有利的控制。
液体优选引入流化床的下部区域，在此，循环气流基本上达到了从反应器排出的气流温度。用于烯烃气相流化床聚合的工业方法通常是在基本上等温、稳态条件下操作。但是，虽然流化床的至少大部分是维持在所要求的基本上等温聚合温度下，但是在引入冷的循环气流进入床的点的直接上面的床的区域中通常都有温度梯度。存在温度梯度的这个区域的温度下限是进入的冷循环气流的温度，而上限基上是等温床的温度。在采用流化栅板的这种类型的工业反应器中，在栅板以上的15-30cm(6-12英寸)的床层中通常存在温度梯度。
为了获得分离液体冷却的最大的利益，重要的是液体是在存在这种温度梯度的区域的上面，即在床基本上达到了离开反应器的气流的温度的那部分引入床。
液体引入流化床的一点或多点处大约在流化棚板以上50-70cm处。
实际上，本发明的方法，在聚合反应期间，例如利用设置在反应器内或反应器壁上的热电偶，首先测量流化床内温度分布图来进行。然后，排列引入液体的一点(多点)，以保证液体进入床的区域的循环气流基本上达到了从反应器排出的气流的温度。
图1表示适用于烯烃气相聚合的典型的流化床反应器内的温度分布图。
温度分布图(图1A)示出了在流化床中以23.7公吨/时的速率制备HDPE。利用设置在反应器壁上(相应流化床内的不同位置(1-5))的热电偶测量温度。流化床反应器中的位置1-5示如图1B。
在温度分布图和图形上表明了流化棚板(A)的水平面和流化床(B)的顶部。上述所称的温度梯度可能是所看到的位置1-3之间的区域。在该区域中，基本上达到了离开反应器的未反应流体温度的循环气流的温度，如位置3-5之间的区域所示。按照本发明方法引入流化床的分离液体，正是进入这个区域。
液体优选在这个区域的下部，即刚好在图1A温度分布图位置3的上面引入流化床。
通过增加引入流化床的流体量，来达到较高的生产率，这是由于提高了冷却容量。与其它的气相流化床聚合方法相比，可以提高时空产率。
本发明方法的其它优点是，通过将液体独立地引入流化床，可以采用精确的计量装置调节输送到床的液体。这种技术使冷却的改进控制变得容易，且以这种方式对输送到床的任何液态共聚单体提供改进的控制。这样，本发明的方法可以以不依赖于任何必须保持在循环气流中携带液体的这种方式操作。因此，加入床的液体量可以在比迄今为止宽得多的限度范围内改变。可以利用改进控制加入床的共聚单体或不活泼烃的速率，以控制生成的聚合物密度和生成这种聚合物的时空产率。
重要的是，要保证流化床内的温度维持在低于组成床的聚烯烃的烧结温度。
来自分离器的气流循环到床，通常进入反应器的底部。如果采用流化栅板，这种气流通常循环到栅板下面的区域，而该栅板使到流化床的气流易于均布。优选使用流化棚板。适用于本发明方法的流化栅板可以是通常设计的那些，例如经过其表面基本上均匀分布的许多孔的钻孔的平的或盘形板。例如孔径大约为5mm。
在流化床中，本发明方法必须用大于或等于床流化所要求的气速操作。最小的气速一般为约6cm/秒，但是本发明的方法优选使用40-100，更优选50-70cm/秒的气速进行。
在本发明的方法中，如果需要，催化剂或预聚物可以与分离液体物流直接引入流化床。这种技术可以导致改进床中催化剂或预聚物的分散。
在本发明的方法中，如果需要，液体或可溶的液态衍生物如活化剂、助催化剂等可以与冷凝液体一起引入床。
在采用本发明的方法生产己烯均聚物或共聚物的情况下，补充的乙烯，例如为替代在聚合期间消耗的乙烯，在分离气流再引入床(例如在流化棚板下面，如果采用栅板)前，可以便利地引入分离气流。由于补充的乙烯是加入分离气流而不是如入分离前的循环气流，因此从分离器回收的液体量增加了，而且也提高了生产率。
分离液流在引入流化床前，先进行附加的冷却(例如利用致冷技术)。与只通过液体蒸发(蒸发潜热)提供冷却效果相比，这将对床提供更好的冷却效果，从而进一步潜在地提高过程的生产率。通过使用适宜的冷却装置，例如位于分离器和反应器之间的简单的换热器或冷冻机可以实现分离液流的冷却。本发明这个特殊方案的另一优点是，通过在引入流化床前进行液体的冷却，包含在液流中的催化剂或预聚物在引入床前产生聚合的任何倾向都将减少。
通过适宜排列的喷射装置可以将液体引入流化床。可以使用单个的喷射装置，或设置在流化床内的一组喷射装置。
优选的排列方式是在流化床的液体引入区域内以基本等间隔的距离设置一组喷射装置。所使用的喷射装置的数量为，在每个喷射装置为液体提供充分渗透和分散，以实现经过床的液体的良好分散所需要的数量。优选喷射装置的数量为4。
如果需要，通过适当设置在反应器内的普通导管，喷射装置的每一个都可输送分离液体。例如这可以利用向上通过反应器中心的导管来实现。
喷射装置优选设置成使它们基本垂直伸入流化床，但是它们也可设置成基本上沿水平方向从反应器壁伸出。
液体引入床的速率主要取决于床所要求的冷却程度，而这又决定于床所要求的生产率。用于烯烃聚合的工业流化床聚合方法可获得的生产率，尤其取决于所采用的催化剂的活性，和这类催化剂的动力学特性。这样，例如当所采用的催化剂有很高的活性和要求高的生产率时，加入液体的速率将是高的。例如，加入液体的速率一般为0.3-4.9m3液体/m3床物料/时，或甚至更高。对“超活性”型的传统的齐格勒催化剂(即以过渡金属、镁卤化物为主的那些催化剂和有机金属助催化剂)，例如加入液体的速率为0.5-1.5m3液体/m3床材料/时。
在本发明的方法中，可以引入床的液体与总气体的重量比例如可以为1∶100-2∶1，优选为5∶100-85∶100，更优选为6∶100-25∶100。所谓总气体的意思是返回反应器到流化床的气体和维持喷射装置的操作所使用的任何气体例如雾化气体。
通过以这种方式将液体喷入流化床，液体中的任何催化剂都可以受益于液体穿过周围每个喷射装置而得到的局部冷却效果，这可以避免热点和因而引起的烧结。
提供从这类装置进入床的液体渗透和分散，可以利用任何其它适宜的喷射装置，充分实现了经过床的液体的良好分散。
优选的喷射装置是一个喷咀或一组喷咀，包括气一致雾化喷咀，其中利用气体参与液体的喷射，或液体喷雾型喷咀(Liquid-onlyspray-type)。
根据本发明的另一方面，提供了在流化床反应器中烯烃单体聚合的连续气相流化床方法，烯烃单体选自(a)乙烯、(b)丙烯、(c)乙烯与丙烯的混合物和(d)a、b或c与一种或几种其它α-烯烃的混合物，在反应条件下，在聚合催化剂存在下，使包括至少一些乙烯和/或丙烯的循环气流连续地通过上述反应器中的流化床，从上述反应器中至少排出部分的上述气流，冷却到液体冷凝出的温度，从上述气流中至少分离出部分冷凝液体，和用一个或几个液体喷雾型喷咀或气一致雾化喷咀，将液体直接引入流化床。流化床优选支撑在流化栅板上。
喷射装置适宜的是喷咀，它通过反应器壁伸进床内(或者通过支撑床的栅板伸进床内)，并且喷射装置带有一个或几个喷射出口，将液体输送到床。
在本发明的方法中，实现床中液体的良好分散和渗透十分重要。实现良好渗透和分散的重要因素是进入床的液体动量和方向、床单位截面积上引入液体的点的数目和引入液体的点的空间布置。
本发明的另一方面提供了在流化床反应器中烯烃单体的聚合方法，优选的烯烃单体选自(a)乙烯、(b)丙烯、(c)乙烯与丙烯的混合物和(d)a、b或c与一种或几种其它α-烯烃的混合物，在反应条件下，在聚合催化剂存在下，使包括单体，优选至少包括乙烯和/或丙烯的循环气流连续地通过上述反应器中的流化床，从上述反应器至少排出部分上述气流，将其冷却到液体冷凝出的温度，从上述气流中至少分离部分冷凝液体，在通过流化床的气体温度基本上达到了从反应器排出的气流温度的那一点或那一点上面将至少部分的分离液体直接引入流化床，上述的液体用一个或几个液体喷雾型喷咀从一个或几个喷射出口喷射，或用一个或几个气一致雾化喷咀从一个或几个喷射口喷射引入上述反应器，各个喷射的水平动量通量，在液体喷雾型喷咀喷射的情况下，至少为100×103kgs-1m-2×ms-1和在气体/液体喷射的情况下，为200kgs-1m-2×ms-1，其中水平动量通量定义为液体出现的喷射出口每单位截面积(平方米)在水平方向上的液体的质量流率(kg/秒)乘以喷咀流速(米/秒)的水平分量。
液体喷雾或液体/气体雾化喷咀的动量通量都优选为至少250×103，而更优选至少为300k×103kgs-1m-2×ms-1。特别优选使用的水平动量通量为300×103-500×103kgs-1m-2×ms-1。在液体喷雾喷射从喷射出口出现的情况下，除水平以外的方向的喷射速度的水平分量是从cosQ°×实际的喷射速度来计算，其中Q°是喷咀与水平方向的夹角。
一种或几种液体或液体/气体喷射进入床的运动方向优选基本上水平的方向。在一个或几个喷射出口沿除水平方向以外的方向喷射输送液体或液体/气体喷射的情况下，优选与水平成不大于45°角的方向，更优选与水平成不大于20°角的方向。
一个或几个喷咀每个都适宜设置一个或几个喷射出口。在获得床内液体良好的分布方面，喷咀的数目、喷射出口的数目和布置都是重要的因素。如果采用一组喷咀，它们优选互相垂直地，水平间隔和基本上等距离地设置。在此情况下，它们也可优选相互间隔等距离和与垂直流化床的壁等距离。床的水平截面积的每10m2上喷咀的数目优选为1-4个，更优选为2-3个。计算不为整数时，优选取其整数。每个喷咀中喷射出口的数目优选为1-40个，更优选为3-16个。在喷咀有一个以上的喷射出口的情况下，喷射出口围绕喷咀相互等距离圆周地排列。
如上所述，液体的喷射可单独由液体组成，或可包括液体/气体的混合物。这种气体可以只是携带液体，或采用来雾化液体，或为推动液体提供-原动力。
适用于本发明方法的气一致雾化喷咀包括(a)至少一个压缩液体的入口，(b)至少一个雾化气的入口，(c)一个混合室，混合上述的液体和气体，和(d)至少一个排放上述混合物的出口。
适宜的雾化气可以是惰性气体例如氮气，但是优选为补充的乙烯气。
每个喷咀设置一组适宜构型的喷射出口。例如出口包括圆形孔、缝隙、椭圆形孔或其它适宜的构型。每个喷咀可以包括不同构型的一组喷射出口。
喷射出口的尺寸优选成通过喷射出口没有多少压力降。
喷射出口优选围绕每个喷咀的周围对称地排列，但也可非对称地排列。
供给每个喷咀的雾化气要保持足以将液体打碎成小液滴和阻止来自流化床的颗粒的进入，或阻止颗粒堵塞喷咀出口的压力。
混合室的有关尺寸设计成以保证最佳的雾化。混合(雾化)室的体积与通过该室的液体的体积的关系表示为：混合室的体积(cm3)/液体的流率(cm3/秒)优选为5×10-3-5×10-1秒。
液体的速度优选保持足以保证任阿颗粒例如细粒从液流分出的速度。
供给每个喷咀的雾化气与液体的重量比通常为5∶95-25∶75。
图2表示适用于本发明方法的一个喷咀。在图中，该喷咀包括包含上区8和下区9的壳体7。上区设置有排列在它的周围的许多出口10和在其中的混合室11。下区设置中心定位管12，管12的口进入混合室，出口管13围绕内管定位。通过适当排列的孔14，管13与混合室相通。加压的液体通过管13供给喷咀，而雾化气供给管12。喷咀9的下区通过一般的装置与加压液体和雾化气的供应装置相连接。在室11中与气体混合后，液体以喷雾状经出口10从喷咀排出。
气-致雾化喷咀是优选的，它的出口包括一系列的围绕喷咀周围排列的基本水平的缝隙。喷咀还可包括垂直取向，或定位的孔，保证通过加压的气-液混合物除去粘附在喷咀顶部的任何颗粒。
缝隙的尺寸一般与约6.5mm的直径的孔相当的大小，例如尺寸为0.75mm×3.5mm。
供选择地，喷射装置可包括液体喷雾型喷咀或多个这种类型的喷咀。
适宜本发明方法使用的液体喷雾型喷咀至少包括一个加压液体的入口，和至少一个上述加压液体的出口，在喷咀内维持足够的液体压力，以保证从出口出现的液体具有所要求的动量通量。
如果需要，可以调节这类喷咀的压力降，例如，通过使用节流装置例如阀门来调节。
出口可以为气-致雾化喷咀上述规定的相似构型。在液体喷雾喷咀中出口的优选构型是圆形孔。该孔的直径优选为0.5-5mm，更优选0.5-2.5mm 。
液滴的大小受许多因素影响，具体讲，在气致雾化喷咀中，受供给喷咀的液体与雾化气的比率和雾化室的大小及构型的影响。对气-致雾化喷咀来说，所希望的液滴大小为约50-约1000微米。在液体喷雾喷咀的情况下，液滴的大小主要受喷咀中的压力降和出口的尺寸及构型的影响。对液体喷雾喷咀来说，所要求的液滴大小为约2000-约4000微米。例如，通过固体颗粒形成床的移动和液体喷射的分裂作用，可以产生这些液滴。
在任何类型喷咀中的压力降必须足以阻止来自流化床的颗粒的进入。在气-致雾化喷咀中，压力降适宜为2-7，优选3-5巴，在液体喷雾喷咀中，压力降适宜为2-7，优选4-5巴。
万一向任何类型的喷咀供给液体和/或雾化气出现故障，设置一适宜的装置提供事故吹洗气，以防止喷咀被来自流化床的颗粒进入堵塞。适宜的清洗气是氮气。
重要的是，气一致雾化喷咀或液体喷雾喷咀的出口的尺寸要足以允许存在于分离液流中任何细粒通过。
在任何类型的喷咀中，在每个喷咀内出口设置在不同的水平面上。例如出口可以排列成一系列的行。
图2所描述的喷咀类型中，在每个喷咀上的许多出口优选在4和40之间，例如20和40，更优选在4-16之间，每个喷咀的直径优选为4-30cm，例如10-30cm，更优选约7-12cm。
其它类型的喷咀例如超声喷咀也适合在本发明的方法中使用。
利用本发明的方法开始引入液体前，气相流化床聚合反应按传统的方法起动，例如用粒状的聚合物颗粒填充床，然后气流开始通过床。
适当的时候，将液体引入床，如使用上述的喷射装置。在起动期间，供给气一致雾化喷咀的雾化气，或供给液体喷雾喷咀的吹洗气流必须保持足以阻止颗粒进入喷咀出口的速度。
本发明的方法参考附图作进一步说明。
图3-5图示地示出了本发明的方法。
图3描述了主要由反应器体15和位于反应器底部的流化栅板16组成的气相流化床反应器，反应器体15通常为直立圆筒形体。反应器体包括流化床17和减速区18，与流化床的截面比，减速区18的截面一般都有增大。
离开流化床反应器顶部的气态反应混合物构成循环气流，并经管19通到旋风分离器20，分离大部分细粒。除去细粒后可以适当地返回流化床。离开旋风分离器的循环气流通到第一换热器21和压缩机22。目前第二换热器23是除去循环气流通过压缩机22后的压缩热。
换热器或多个换热器或设置在压缩机22的上游或下游。
在冷却和压缩到生成冷凝物的温度后，得到的气一液混合物通到分离器24，分离出液体。
离开分离器的气体经管25循环到反应器15的底部。该气体经流化栅板16通到床，从而保证床的流化状态。
来自分离器24的分离液体经管25通到反应器15。如果需要，泵26可以适宜地位于管25′。
催化剂或预聚物经管27进入分离的液流加到反应器。
产品聚合物颗粒经管28从反应器适当地排出。
图3示出的排列方案特别适用于改进利用流化床工艺的现有气相聚合反应器。
图4描述了进行本发明方法的另一布置方案。在该方案中，在循环气流被分离器241分离之后，压缩机22位于管25上。这一排列的优点是减少了压缩机压缩气体的置，因而可以降低压缩机的尺寸，达到最佳化的工艺过程和生产费用。
图5描述了进行本发明方法的又一方案，在分离器24后，压缩机22仍设置在管25、但在第二换热器23前，第二换热器23位于分离气流管上而不是在分离器前。同样，这种方案也达到工艺过程的最佳化。
本发明的方法参考下面的实例作进一步说明。
实例1-11
在本发明的条件下(实例1-5、9和10)在气相流化床反应器中用计算机模拟烯烃的聚合反应得到这些实例，为比较起见，在一般的条件下，在循环物流中不分离液体(实例6-8和11)。
实例1-8表示利用一般的齐格勒催化剂的乙烯与几种α-烯烃变体的共聚合，实例9-11表示使用传统的以二氧化硅为载体的载持铬氧化物的催化剂的乙烯的均聚反应。
利用精确度为±15％的热平衡计算机程序计算时空产率和反应器的入口温度。使用情确度为±10％的一般的软件程序计算聚合体系的露点温度和循环液体的速率。
实例1、3、4和10最接近表示进行本发明方法的有代表性的工艺条件。
表1和2列出了结果，并清楚地示出了利用本发明方法可得到提高的时空产率。
表1和2中的“循环物流中的液体％”表示以通过喷射装置的循环液体的总重量除以气体(循环气加雾化气)的总重量。
实例12-15
利用试验装备测4试利用上述的喷射装置引入流化床的液体。试验装备的布置示于图6。试验装备包括铝制的流化反应器50，该反应器有减速区56，含聚乙烯粉末床51(高密度或线型低密度聚乙烯)，它是在工业规模气相流化床装置中，由乙烯的气相流化床聚合预先制备的。将干燥的氮气流连续地通过管52和预热器53，进入反应器50的下部室54因而通过棚板使床51流化。氮气由工业液氮供应罐供给，利用阀57和69控制供给流化的氮气置和系统中的气压，使用一般的汽轮计(未示出)测定体积流量。预热器装置有一可调的公称热容量为72kw，将氮气加热到所要求的温度。用泵60和管61将挥发性的液态烃58(1-己烷或正-戊烷)从冷却器/除雾器罐59引入流化床51。挥发性的液态烃通过穿入床的喷咀/喷射出口装置进入床。测试各种喷咀/喷射出口装置，一些为液体喷雾型，而另一些是气体雾化型的。对后面的类型，通过63引入雾化气(例如这种类型的喷咀，参见附图2)。挥发性液态烃通过喷咀/喷射出口装置62进入流化床后在床中蒸发，这样通过吸收蒸发潜热产生冷却。从床的顶部出现的氮气流化气和伴随的挥发性液态烃进入减速区56，气流中携带的大量聚乙烯粉末回落入床。然后气体通入管64、过滤器装置65和通过止逆阀66进入冷却器/除雾器罐59。冷却器/除雾器罐59包含两台换热器67、68。换热器67由通过这里的冷却水冷却，而68由致冷的乙二醇/水抗冻液冷却。气体通过换热器67、68受冷却，产生的液态烃(己烷或戊烷)冷凝出来。冷凝的烃收集在罐59的底部，从那里循环回到床。这样，基本上无烃的氮气通过反压调节阀69进入大气。利用商业上购得的X-射线图象设备，它包括X-射线源70、图象增强仪71和CCD(电荷偶合装置)电视摄象机72监测床中液态烃的蒸发和流化，该电视摄象机的输出信号连续地记录在一磁带录象机上(未示出)。X-射线源、图象增强仪和电视摄象机安装在一可移动的台架上73上，以能够随意地改变床的观察区域。
本发明的方法在现有的工艺基础上在气相流化床的聚合工艺的生产率方面提供了相当大的改进。本发明的方法可以在新装置上采用，也可在现有装置上采用，都得到了显著提高生产率和加入床的液体的良好控制。在新装置的设备情况下，通过使用较小的反应器、压缩机和必须达到比得上传统装置的生产率的其它辅助设备，可以达到显著地降低投资费用。在现存装置的情况下，本发明的这种装置的改进提供显著地提高生产率和改进了过程的控制。
试验结果示于表3，其中实例12、14和15是按照本发明的方法，而实例13是用于比较的方法。实例12和比较例13描述了使用相同的喷咀，但在比较例中，是通过在45°时运行的床模拟将液体加入气相流化床聚合的“冷区”，与实例12中采用的98℃温度相比较。在这些情况下，聚合物结块被喷咀周围形成的液烃所湿润。实例12、14和比较例13采用气致雾化喷咀，而实例15是采用液体喷雾喷咀。实例12、14和15都产生了液态烃的良好渗透和分散，液体的渗透仅到反应器壁时才停止。在比较例12中，液体的渗透被聚合物/液烃形成的结块所抑制。
                      表1
          实例     1     2     3     4     5     6
          产品    C2/C4共聚物   C2/C4共聚物   C2/C6共聚物   C2/C6共聚物   C2/C4共聚物   C2/C4共聚物
反应器压力(巴)反应器温度(℃)工艺气(％mol)乙烯乙烷氢气氮气丁烯戊烷己烯4-MPl其它如低聚物气速(cm/sec)床高(m)时空产率(Kg/m3h)反应器入口温度(℃)露点温度(℃)循环物流中的液体％     249337.514.826.29.30.210.41.66014.514046.520.914.1     269342.318.529.668.2101.46014.519336.278.921.5     248229.115.94.939.117.72.36014.510553.467.711     248231.214.2103515.33.36014.511648.869.511.3     267655.83.111.15.718.65.40.36014.519344.861.621.3     249328.525.219.924.38.141.966014.57449.946.10
                    表2
        实例     7     8     9     10     11
        产品    C2/C4共聚物    C2/C4共聚物     C2均聚物     C2均聚物     C2均聚物
反应器压力(巴)反应器温度(℃))工艺气；(％mol)乙烯乙烷氢气氮气丁烯戊烷己烯4-MPl其它如低聚物气速(cm/sec)床高(m)时空产率(Kg/m3h)反应器入口温度(℃)露点温度(℃)循环物流中的液体96     247436.77.48.424.319.33.96014.55550.138.20     247637.59.77.531.912.151.256014.55549.723.50     2410329.116.412.524.413.34.36014.519336.462.321     2410329.11712.525.611.24.66014.517836.156.315.7      201033517.51528.14.46014.57557-44.50
                表3
    实例     12       13      14     15
    喷咀类型   气体雾化   气体雾化   气体雾化   液体喷雾
    出口类型 4个水平缝隙   4个水平缝隙 4个水平缝隙  2个孔径为1.75mm的孔
栅板之上的位置(cm)     52      52     10     52
流化气速(cm/s)     45      42     52     38
     床温℃     98      45     78     97
    压(MPa)     1.01      0.97     0.78     0.75
    床物料 HDPE BP级6070   HDPE BP级6070    LLDPE BP级0209  HDPE BP级6070
    床加料(kg)     60      58.5     61.2     58.0
    液体     己烯      己烯  正-戊烷     己烯
    液体流量(M3/h)     1.65      1.48     1.78     0.69
   液体对喷咀的压力(MPa)     0.33      0.32     0.38     0.54
N2雾化气压力(MPa)    0.42      0.40     0.45     无
     雾化气：液体(mass％)     5.4      5.3     5.6     无
   M3液体每M3床每小时     11.38      10.61     12.80     4.95
液体水平渗透(cm) 大于21     小于15     大于21 大于21
    ％冷凝液体液体(％总液体/总气体)     105.5       94.6     121.2     46.6

Claims (34)

1.一种在流化床反应器中进行烯烃单体聚合的连续气相流化床方法，所述的烯烃单体选自(a)乙烯、(b)丙烯、(c)乙烯与丙烯的混合物和(d)a、b或c与一种或一种以上其它的α-烯烃的混合物，在反应条件下，在聚合催化剂存在下，将至少包括一些乙烯和/或丙烯的气流，连续循环地通过在上述反应器中的流化床，从上述反应器中至少排出部分的上述气流，将其冷却到液体冷凝出的温度，从气流中至少分离部分的冷凝液体，和将至少部分的该分离液体，在通过流化床的气流基本上达到了从反应器排出的气流温度的那一点处或那一点处的上面，直接引入流化床。
2.一种在流化床反应器中进行烯烃单体聚合的连续气相流化床方法，所述的烯烃单体选自(a)乙烯、(b)丙烯、(c)乙烯与丙烯的混合物和(d)a、b或c与一种或一种以上其它的α-烯烃的混合物，在反应条件下，在聚合催化剂存在下，将至少包括一些乙烯和/或丙烯的气流，连续循环地通过在上述反应器中的流化床，从上述反应器中至少排出部分的上述气流，将其冷却到液体冷凝出的温度，从气流中至少分离部分的冷凝液体，和将该液体通过一个或几个液体喷雾喷咀，或气致雾化喷咀，直接引入流化床。
3.按权利要求1或2的方法，其中流化床是支撑在栅板上。
4.按权利要求1或2的方法，其中一种或一种以上的其它α-烯烃具有4-8个碳原子。
5.按权利要求1或2的方法，其中乙烯或丙烯的量至少为单体总量为70％。
6.按权利要求1或2的方法，其中循环气流的全部基本上都冷却，并分离成液体和气体，分离的液体的全部都基本上引入反应器。
7.按权利要求1或2的方法，其中液体在上述床内的许多位置直接引入流化床。
8.按权利要求1或2的方法，其中流化床的气速为50-70cm/秒。
9.按权利要求1或2的方法，其中的催化剂是金属茂。
10.按权利要求9的方法，其中的金属茂是以二氧化硅为载体的。
11.按权利要求1或2的方法，其中催化剂或预聚物是在冷凝液中引入流化床。
12.按权利要求1或2的方法，其中分离液流在引入流化床前，通过冷冻作用冷却。
13.按权利要求1或2的方法，其中补充的乙烯在再引入反应器前，先引入分离的循环气流。
14.按权利要求1或2的方法，其中液体引入流化床的速率为0.3-4.9m3液体/m3床物料/时。
15.按权利要求1或2的方法，其中引入床的液体与总气体的重量比为5∶100-85∶100。
16.按权利要求2的方法，其中每个喷咀在流化床中基本上直立地排列。
17.按权利要求2的方法，其中气致雾化喷咀包括：
(a)至少一个加压液体入口，
(b)至少一个雾化气入口，
(c)混合上述加压液体和上述雾化气的混合室，和
(d)至少一个排放上述气体和液体的混合物的出口。
18.按权利要求17的方法，其中雾化气是补充的乙烯气。
19.按权利要求17的方法，其中喷咀设置许多个出口。
20.按权利要求19的方法，其中基本上所有出口都是缝隙构型。
21.按权利要求17-20的任一项的方法，其中混合雾化室的体积与通过该室的液体的体积的关系表示为：混合室体积(cm3)/液体流率(cm3/秒)是5×10-3-5×10-1秒。
22.按权利要求2的方法，其中雾化气与加压液体的重量比为5∶95-25∶75。
23.按权利要求16-20的任一项的方法，其中上述喷咀出口处的液滴大小为50-4000微米。
24.按权利要求16-20的任一项的方法，其中气致雾化喷咀中的压力降为3-5巴，而在液体喷雾喷咀中的压力降为4-5巴。
25.按权利要求16-20的任一项的方法，其中喷咀带有经该喷咀提供事故吹洗气的装置。
26.按权利要求2的方法，其中所述液体是用一个或几个液体喷雾喷咀，或一个或几个气致雾化喷咀，从一个或几个喷射出口引入上述反应器，每个喷射出口的水平动量通量，对液体喷雾喷射至少为100×103Kg s-1 m-2×ms-1，对气致雾化喷射至少为200×103kg s-1 m-2×ms-3，其中水平动量通量的定义为液体出现的喷射出口的每单位截面积(m2)在水平方向的液体的质量流率(kg/秒)乘以喷射速度的水平分量(m/秒)。
27.按权利要求26的方法，其中液体喷雾射或气致雾化喷射的水平动量通量为250×103kg s-1 m-2×ms-1。
28.按权利要求26的方法，其中一个或几个液体喷雾喷咀或气致雾化喷嘴的喷射基本上成水平方向导入床中。
29.按权利要求26的方法，其中一个或几个液体喷雾喷咀或气致雾化喷咀的喷射，都是从一个或几个喷咀所带的多个喷射口喷出。
30.按权利要求2的方法，其中采用一组相互间等距离，且与流化床反应器垂直器壁等距离的喷咀。
31.按权利要求2的方法，其中床内每10m2的水平截面积上喷咀数目为1-4个。
32.按权利要求29的方法，其中每个喷咀喷射口的数目为3-16个。
33.按权利要求2的方法，其中每个喷咀有围绕喷咀的周围布置的许多喷射口。
34.按权利要求29或33的方法，其中喷射口基本上是缝隙形状。
CN94192172A 1993-05-20 1994-05-19 聚合方法 Expired - Lifetime CN1077111C (zh)

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