CN1516616A - 本体聚合反应器和聚合方法 - Google Patents

本体聚合反应器和聚合方法 Download PDF

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CN1516616A
CN1516616A CNA028119126A CN02811912A CN1516616A CN 1516616 A CN1516616 A CN 1516616A CN A028119126 A CNA028119126 A CN A028119126A CN 02811912 A CN02811912 A CN 02811912A CN 1516616 A CN1516616 A CN 1516616A
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heat exchanger
polymer reactor
exchanger plates
coolant
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CN1319638C (zh
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G·B·伊顿
P·特雷纳
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Heavy chemical Holding Co.
M Bauer Special Chemicals Co.,Ltd.
Sovereign Insurance Co.,Ltd.
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Abstract

一种具有至少四个侧壁面(81、82、83、84)和一个底壁面(85)以形成贮藏室(87)、并具有至少一个与冷却剂源流体连通的换热板(66)的聚合反应器(40)，其中所述至少一个换热板(66)中的每个被安装在盖子上。本发明的聚合反应器在每次反应器操作期内可制备大量的聚合物。优选地，聚合物在所述聚合反应器中通过本体聚合形成。还公开了制备聚合物的方法。

Description

本体聚合反应器和聚合方法
相关申请
该申请请求保护美国未决专利申请(序列号为60/297,931，申请日为2001年6月13日)的保护内容。
技术领域
本发明涉及用于进行单体聚合的反应器，及特别是用于α烯烃单体聚合的本体聚合反应器。
背景技术
通过不同的单体形成聚合物是公知的技术。在本领域中还公知的是所述单体在其中形成聚合物的聚合反应器自身具有某种限制从而不能有效地制备聚合物。一个主要的自身缺陷是需要移走所述聚合反应器内部产生的热量，所述热量是由于在聚合物的制备过程中单体与催化剂之间的化学反应产生。为了解决这一问题，人们设计在所述聚合反应器内装入冷却系统以试图移走聚合反应器内产生的热量。此外，还可在所述聚合反应器内的聚合反应混合物中加入冷却添加剂。
然而，这两种现有的改进技术具有各自的缺点。例如，在所述聚合反应器外部使用冷却系统不能高效和有效地移走聚合反应器内产生的热量，尤其是不能移走所述聚合反应器中心大部分区域的热量。因此，所述聚合反应器的尺寸一定要小及在每一反应器操作期内只能产生有限数量的聚合物。此外，对于向聚合反应物中加入冷却添加剂的方法来说，这些冷却添加剂对所制备聚合物的质量可能有不利的影响并相应地增加了制备聚合物相关的成本。
在其他现有的改进技术中，如在美国专利5449732、5504131和5504132中所讨论的，所述聚合反应器是结晶体的、烃不溶的有机聚合反应盒，所述盒基本上能阻止氧气和水通过，即是塑料袋。使用这些塑料袋使得聚合反应在没有冷却系统或添加冷却剂的条件下进行。然而，由于塑料袋没有装配任何有助于移走聚合反应热量的设备，在每个塑料袋里只能包括少量的聚合物原料，例如单体和催化剂。因而在每一个这种类型的聚合反应器中只能形成少量的聚合物。此外，所述塑料袋不易同所述聚合物分离，因而不可重复使用。
因此，在本发明的改进方案提出之前，尚没有制备所述聚合物的聚合反应器或方法能达到如下效果：从所述聚合反应器中有效地移走热量；在每个聚合反应器中制备大量的聚合物；不需要加入冷却添加剂；聚合反应器可以重复使用。因此，本发明的技术找到了这样一种制备聚合物的聚合反应器和方法，所述反应器和方法能达到如下效果：从所述聚合反应器中有效移走热量；可以在每一聚合反应器中制备大量的聚合物；不需要加入冷却添加剂；聚合反应器可以重复使用。
发明概述
根据本发明，前述优点可以通过本发明用于烯烃聚合的聚合反应器达到，所述反应器包括：一个具有至少三个侧壁面和一个底壁面从而形成贮藏室的贮槽；至少一个与冷却剂源流体连通的换热板；及一个具有顶壁面和内壁面的盖子，其中至少一个换热板沿着所述内壁面放置。
所述聚合反应器的另一个特征是所述聚合反应器可包括四个侧壁面。所述聚合反应器的另一个特征是所述四个侧壁面中的每一个可呈具有一长度和一高度的正方形。所述聚合反应器的另一个特征是所述四个侧壁面中的两个可以是长度至少为2英尺及高度至少为2英尺，其他两个侧壁面的长度至少为3英尺及高度至少为2英尺。所述聚合反应器的另一个特征是所述盖子可以是具有一长度和一宽度的呈矩形的形状，其中长度至少为3英尺及宽度至少为2英尺。所述聚合反应器的另一个特征是所述盖子可以包括至少两个换热板。所述聚合反应器的另一个特征是所述至少两个换热板中的每个板之间的相互距离至少为3英寸。所述聚合反应器的另一个特征是所述聚合反应器还包括至少一个与冷却剂源流体连通的冷却剂入口集管，及至少一个与冷却剂源流体连通的冷却剂出口集管。所述聚合反应器的另一个特征是聚合反应器还包括至少一个冷却剂入口管道和至少一个冷却剂出口管道，所述入口管道与至少一个冷却剂入口集管和至少一个换热板中的每个都流体连通，所述出口管道与至少一个冷却剂出口集管和至少一个换热板中的每个都流体连通。所述聚合反应器的另一个特征是所述盖子可包括沿着内壁面放置的吊板架组件，从而将至少一个换热板中的每个附着在所述盖子的内壁面上。所述聚合反应器的另一个特征是所述至少一个换热板中的每一个可以与冷却剂入口管道和冷却剂出口管道流体连通。所述聚合反应器的另一个特征是所述冷却剂入口管道中的每一个可以与冷却剂入口集管流体连通，及所述冷却剂出口管道中的每一个与冷却剂出口集管流体连通。所述聚合反应器的另一个特征是所述冷却剂入口集管和所述冷却剂出口集管与所述冷却剂源流体连通。所述聚合反应器的另一个特征是所述贮槽包括具有一定长度和宽度的四个壁，所述长度至少为4英尺，所述宽度至少为2英尺。所述聚合反应器的另一个特征是所述盖子的内壁面包括至少6个换热板。所述聚合反应器的另一个特征是所述至少一个换热板中的每一个可包含一种可除去的膜。
根据本发明，前述优点可以通过本发明用于烯烃聚合的聚合反应器达到，所述反应器包括：一个具有至少三个侧壁面和一个底壁面从而形成贮藏室的贮槽；一个换热器，所述换热器具有一个热交换组件，冷却剂入口集管与冷却剂源流体连通，至少一个冷却剂入口管道与至少一个换热板流体连通，至少一个冷却剂出口管道与至少一个换热板中的每一个和冷却剂出口集管流体连通，所述冷却剂出口集管与所述冷却剂源流体连通；及一个具有顶壁面和内壁面的盖子，其中至少一个换热板沿着内壁面放置。
所述聚合反应器的另一个特征是所述聚合反应器包括四个侧壁面，所述四个侧壁面中的两个是长度至少为2英尺和高度至少为2英尺，所述四个壁面中的另外两个是长度至少为3英尺和高度至少为2英尺，及所述盖子可以是具有一长度和一宽度的呈矩形的形状，其中长度至少为3英尺及宽度至少为2英尺。
根据本发明，上述优点也可以通过本发明包括下述步骤的聚合方法达到：将至少一种单体和至少一种催化剂在贮槽中结合以形成聚合反应混合物，所述贮槽具有至少三个侧壁和一个底壁以形成贮藏室；将至少一个换热板插入所述贮藏室从而与所述聚合反应混合物相接触，所述换热板具有与冷却剂源流体连通的交换室；经过足够的时间所述至少一种单体的大部分形成聚合物之后从所述反应混合物中移走至少一个换热板。
所述聚合方法的另一个特征是所述方法还包括如下步骤，在将所述至少一个换热板插入所述贮藏室之前，还在所述至少一个换热板中的每一个上面安置一种可除去的膜。
所述制备聚合物的聚合反应器和方法具有如下优点：能够有效地从所述聚合反应器中移走热量；在每个聚合反应器中允许形成大量的聚合物；不需要加入冷却添加剂；及聚合反应器可以重复使用。
附图的简要说明
图1是本发明所述聚合反应器的一个具体技术方案的侧视图。
图2是图1所示聚合反应器的换热器的透视图。
图3是图1所示聚合反应器的透视图。
虽然已经结合优选的技术方案对本发明做出了描述，应该理解到本发明并不局限于该技术方案。相反，在本发明的精神和主题范围内所做的替换、修改及相当技术方案都落在所附权利要求书保护范围内。
发明详述
广义地说，本发明的聚合反应器包括一个贮槽和一个具有换热器的盖子。当所述盖子被放置于贮槽之上时，所述换热器因位于贮槽的内部便可冷却贮槽内的物质，即移走贮槽内物质产生的热量。
现在参照图1-3，在本发明一个具体的技术方案中，聚合反应器40包括贮槽80和盖子70。盖子70包括换热器60。贮槽80包括至少三个壁面和一个底面以形成一个室。如图1-3所示，贮槽优选地包括四个侧壁面81、82、83、84和底壁面85以形成贮藏室87。但是应该理解还可以包括作为贮槽80的部分的附加壁面，因而可以允许贮槽80具有任何期望的形状，优选地贮槽80包括四个壁面，因而具有长方体形(图1-3)或立方体形。
贮槽80优选地包括至少一个滑道88。如图1和3所示，贮槽80包括两个滑道88。滑道88允许叉车或其它升降设备与贮槽80相啮合，从而可使所述贮槽被移动至任何期望的位置，也就是说被置于靠近单体源的地方，所述单体将被装入或输入贮槽80中。
如图1和3所示，贮槽80包括长度92、高度91和宽度93。长度92、高度91和宽度93可以是使用聚合反应器40的技术人员期望的任何距离。然而应该理解，一般来说，若长度92增加则换热板66的数量也增加，及随着长度91和宽度93的增加则换热板66的尺寸也增加。在一个具体的技术方案中，长度92、高度91和宽度93相等且每个值至少为2英尺。在该技术方案中，聚合反应器40是立方体形。在一个优选的技术方案中，长度92至少为3英尺，高度91至少为2英尺及宽度93至少为3英尺。在该优选的技术方案中，聚合反应器40是长方体形。
贮槽80可以由本领域普通技术人员已知的任何材料制成。优选地，贮槽80由不锈钢制成。
现在参照图1-3，盖子70包括顶壁面73和侧壁面72、74、75、76。所述盖子还可包括凸缘71以提供附加的强度。盖子70保护换热器60免受周围环境的破坏及防止杂物掉到换热器60上并落入贮槽80。盖子70还可包括一个供换热器60附着其上的内壁面77。盖子70可以由本领域普通技术人员已知的任何材料制成。优选地，盖子70由不锈钢制成。
换热器60优选地包括吊板架装置61、冷却剂入口集管62、冷却剂出口集管63、至少一个冷却剂入口管道64，至少一个冷却剂出口管道65，及至少一个具有交换室69的换热板66。吊板架组件61优选地包括支架59以使每个换热器66附着在盖子70上。
冷却剂入口集管62与至少一个冷却剂入口管道64流体连通，所述管道64与换热板66流体连通。同样地，冷却剂出口集管63与至少一个冷却剂出口管道65流体连通，所述管道65与换热板66流体连通。在一个具有一个换热板66的具体技术方案中，冷却剂入口管道64和冷却剂出口管道65中的每一个分别与冷却剂入口集管62和冷却剂出口集管63流体连通。在其他如图1-3所示具有多个换热板66的技术方案中，每个换热板66包括至少一个冷却剂入口管道64和至少一个冷却剂出口管道65，它们分别与冷却剂入口集管62和冷却剂出口集管63流体连通。因此，冷却剂可以从冷却剂源流出，通过冷却剂入口集管62，通过至少一个冷却剂入口管道64中的每个进入至少一个换热板66中每个的交换室69，从所述交换室69通过冷却剂出口管道65，通过冷却剂出口集管63然后流回冷却剂源。通过这样操作，热量从所述聚合反应混合物被移走，即所述聚合反应混合物被冷却。
象上面所讨论的，冷却剂入口集管62和冷却剂出口集管63与冷却剂源流体连通。对于本领域普通技术人员来说，可以使用的冷却剂源包括但是不限于使用下述冷却剂的致冷装置，所述冷却剂为水、水-乙二醇混合物、水-乙醇混合物、可溶性天然盐如氯化钠和氯化钙，以及铵。在该装置中，冷却剂可以从所述冷却剂源循环，通过管道例如硬管或软管(图中未示出)进入冷却剂入口集管62。然后冷却剂可进入冷却剂入口管道64并进入每个换热板66的交换室69。
然后冷却剂从各个换热板66的每个交换室69排出通过冷却剂出口管道65并进入冷却剂出口集管63。然后冷却剂从冷却剂出口集管63通过一个管道如硬管或软管(图中未示出)被送回冷却剂源再次装填，也就是说冷却并通过换热器60再循环。
现在参照图1-2，每个换热板66由前壁面51、后壁面52和至少一个侧壁面53形成的室69构成。换热板66还包括长度67、宽度68和厚度55。换热板66可以是任何形状并由任何期望或需要的材料制成以提供足够的面积来冷却贮槽80中的聚合反应混合物。优选地，换热板66由铝组成。如图1-3所示，每个换热板66包括四个侧壁面53，然而应该理解到换热板66可以是圆形。在具有多于一个换热板66的技术方案中，各个换热板66之间的距离为长度56。
在一个优选的技术方案中，每个换热板66包括一可除去的膜例如塑料护层，从而防止在贮槽80中形成的聚合物在聚合作用期间粘着在每个换热板66上。适宜的可除去的膜包括塑料片、塑料护层、一种与聚合反应混合物不会发生聚合反应的喷射的不粘性物质，例如因为所述喷射的不溶性物质的熔点高于所述聚合反应混合物的温度。
在聚合反应器40的每个技术方案中存在的换热板66的数量由贮槽80的大小决定。在如图1-3所示的具体技术方案中，贮槽80包括长度92为8英尺3英寸，高度91为4英尺1英寸及宽度93为4英尺3英寸，及每个换热板66包括长度67为4英尺，宽度68为4英尺及厚度55为约7/8英寸。17个换热板66沿着吊板架组件61设置，每个换热板之间的间距56为约 英寸。应该理解到前述所有尺寸都可以随着期望或需要值而变化以对所述聚合反应混合物进行足够的冷却及使聚合物官能度最佳化。
本发明的聚合反应器40可用于将单体聚合成聚合物，具体而言，将α-烯烃单体聚合成聚α烯烃。如上所述，本领域技术人员已知很多种聚合方法、反应物如单体、催化剂、共同催化剂。此外，对本领域技术人员而言，本体聚合方法也是已知的。但是，没有在上述聚合反应器40中进行过这些已知的聚合方法。
在本发明聚合方法的一个具体技术方案中，至少一种单体和至少一种聚合物在贮槽80中被结合以形成一种聚合反应混合物。然后具有至少一个换热板66的盖子70被放置在贮槽80的顶部以保护聚合反应混合物免受环境的破坏。在放置盖子70的过程中，所述至少一个换热板66中的每个被插入贮槽80，并因而插入所述聚合反应混合物中。优选地，在至少一个换热板66中的每个被插入所述聚合反应混合物的过程中盖子70沿着箭头99的方向下降。冷却剂然后从所述冷却剂源流出，先流入所述至少一个换热板66中每个的各个换热室69再从其中流出。在冷却剂通过每个换热板66循环的过程中，所述聚合反应混合物被冷却。允许每个换热板66与所述聚合反应混合物接触足够长的时间以使得大部分所述单体被聚合为聚合物。盖子70然后沿着箭头98的方向被移走，从而将所述至少一个换热板66中的每一个都从反应混合物中移走。
应该理解，本发明并不局限于上面所描述的结构、操作、具体材料或技术方案的具体细节，对于本领域技术人员来说，显而易见的修改或等同物同样落在本发明的保护范围之内。例如，每个换热板可以包括一个以上冷却剂入口管道和一个以上冷却剂出口管道。本领域普通技术人员可以容易地决定所述聚合反应器的尺寸和形状。此外，还可附加检测仪表作为所述聚合反应器的部件，例如在聚合反应期间控制温度。此外，所述换热板的形状可以是与所述贮槽形状相匹配的任何期望的或需要的形状，例如圆形、长方形、三角形、梯形等。相应地，本发明的保护范围仅由所附权利要求书限定。

Claims (20)

1.一种用于烯烃聚合反应的聚合反应器，包括：
一个具有至少三个侧壁面和一个底壁面的贮槽，所述三个侧壁面和一个底壁面形成一个贮藏室；
至少一个与冷却剂源流体连通的换热板；及
一个具有顶壁面和内壁面的盖子，其中至少一个换热板沿着内壁面放置。
2.权利要求1的聚合反应器，其中所述聚合反应器包括四个侧壁面。
3.权利要求2的聚合反应器，其中所述四个侧壁面中的每一个都是具有一长度和一高度的正方形。
4.权利要求2的聚合反应器，其中所述四个侧壁面中的两个具有至少两英尺的长度和至少两英尺的高度；及
所述四个侧壁面中的另外两个具有至少三英尺的长度和至少两英尺的高度。
5.权利要求4的聚合反应器，其中所述盖子是具有一长度和一宽度的长方形，所述长度至少为三英尺及所述宽度至少为两英尺。
6.权利要求1的聚合反应器，其中所述盖子包括至少两个换热板。
7.权利要求6的聚合反应器，其中所述至少两个换热板中的每个按彼此具有至少3英寸的间距放置。
8.权利要求1的聚合反应器，还包括至少一个与所述冷却剂源流体连通的冷却剂入口集管及至少一个与所述冷却剂源流体连通的冷却剂出口集管。
9.权利要求8的聚合反应器，还包括至少一个与所述至少一个冷却剂入口集管和所述至少一个换热板中的每个都流体连通的冷却剂入口管道，及至少一个与所述至少一个冷却剂出口集管和所述至少一个换热板中的每个都流体连通的冷却剂出口管道。
10.权利要求1的聚合反应器，其中所述盖子包括一个沿着所述内壁面放置的吊板架组件，用于将所述至少一个换热板中的每个附着在所述盖子的内壁面上。
11.权利要求1的聚合反应器，其中所述至少一个换热板中的每个与冷却剂入口管道和冷却剂出口管道流体连通。
12.权利要求11的聚合反应器，其中所述冷却剂入口管道中的每个与冷却剂入口集管流体连通，所述冷却剂出口管道中的每个与冷却剂出口集管流体连通。
13.权利要求12的聚合反应器，其中所述冷却剂入口集管和冷却剂出口集管与所述冷却剂源流体连通。
14.权利要求1的聚合反应器，其中所述贮槽包括长度至少为4英尺及宽度至少为2英尺的四个壁。
15.权利要求1的聚合反应器，其中所述盖子的内壁面包括至少6个换热板。
16.权利要求1的聚合反应器，其中所述至少一个换热板中的每个包括可除去的膜。
17.一种用于烯烃聚合反应的聚合反应器，包括：
一个具有至少三个侧壁面和一个底壁面的贮槽，所述三个侧壁面和一个底壁面形成一个贮藏室；
一个换热器，所述换热器具有热交换组件，冷却剂入口集管与冷却剂源流体连通，至少一个冷却剂入口管道与至少一个换热板流体连通，至少一个冷却剂出口管道与所述至少一个换热板中的每个以及冷却剂出口集管流体连通，所述冷却剂出口集管与冷却剂源流体连通；及
一个具有顶壁面和内壁面的盖子，其中至少一个换热板沿着内壁面放置。
18.权利要求17的聚合反应器，其中
所述聚合反应器包括四个侧壁面，
所述四个侧壁面中的两个具有至少两英尺的长度和至少两英尺的高度，
所述四个侧壁面中的另外两个具有至少三英尺的长度和至少两英尺的高度，及
所述盖子是具有一长度和一宽度的长方形，所述长度至少为三英尺及所述宽度至少为两英尺。
19.一种聚合方法，包括以下步骤：
将至少一种单体和至少一种催化剂在贮槽中相结合以形成一种聚合反应混合物，所述贮槽具有至少三个侧壁面和一个底壁面以形成贮藏室；
将至少一个具有与冷却剂源流体连通的交换室的换热板插入所述贮藏室，从而与所述聚合反应混合物相接触；及
在经过足够长的时间使所述至少一种单体的大部分形成聚合物之后，从所述反应混合物中移走所述至少一个换热板。
20.权利要求19的聚合方法，还包括如下步骤：在将至少一个换热板插入所述贮藏室之前，在所述至少一个换热板中的每个上面安置可除去的膜。
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US8110150B2 (en) 2012-02-07
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