CN101370578B - 用于乳液聚合的环流反应器 - Google Patents

用于乳液聚合的环流反应器 Download PDF

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CN101370578B
CN101370578B CN2007800030503A CN200780003050A CN101370578B CN 101370578 B CN101370578 B CN 101370578B CN 2007800030503 A CN2007800030503 A CN 2007800030503A CN 200780003050 A CN200780003050 A CN 200780003050A CN 101370578 B CN101370578 B CN 101370578B
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D·C·亚当斯
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/2435—Loop-type reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
    • B08B9/027—Cleaning the internal surfaces; Removal of blockages
    • B08B9/032—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing
    • B08B9/0321—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing using pressurised, pulsating or purging fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
    • B08B9/027—Cleaning the internal surfaces; Removal of blockages
    • B08B9/04—Cleaning the internal surfaces; Removal of blockages using cleaning devices introduced into and moved along the pipes
    • B08B9/053—Cleaning the internal surfaces; Removal of blockages using cleaning devices introduced into and moved along the pipes moved along the pipes by a fluid, e.g. by fluid pressure or by suction
    • B08B9/055—Cleaning the internal surfaces; Removal of blockages using cleaning devices introduced into and moved along the pipes moved along the pipes by a fluid, e.g. by fluid pressure or by suction the cleaning devices conforming to, or being conformable to, substantially the same cross-section of the pipes, e.g. pigs or moles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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Abstract

一种聚合反应器，包含一个或多个具有一个或多个原材料入口、一个或多个出口和使反应器进料在循环回路内循环的循环泵的循环回路。绕过循环泵的旁通管将泵上游的回路点与泵下游的点相连，这两个点均配备三通阀。

Description

用于乳液聚合的环流反应器
本发明涉及包含一个或多个带有一个或多个原材料入口、一个或多个出口和使反应器进料在循环回路内循环的循环泵的循环回路的聚合反应器。
WO 00/07177公开了用于乳液聚合的环流反应器。该环流反应器包含循环泵和将泵出口连接到其入口上的管式循环回路。将水、单体和稳定剂连续送入回路并循环并连续取出聚合物乳液。该反应器特别适用于制造例如用在漆料或粘合剂中的衍生自乙烯基和/或丙烯酸单体的聚合物。
使用管式反应器的聚合法中遇到的问题是在反应器内壁上形成来自反应产物的沉积物。这些沉积物导致需要提高循环泵的输送压力并损害从反应介质向例如反应管周围的护套中的冷却剂的传热，由此造成更高且通常有害的反应器温度或必须具有提高的冷却剂循环速率、较低的冷却剂温度或降低的生产率。结垢也降低了反应器容积，提高再循环速率和乳液上的剪切。这改变了可能已对洁净反应器优化的工艺条件。在任何情况下，产物性质会改变，消除了对连续反应器所期望的生产一致性优点。在WO00/07177中，使用清管器清洁反应管内部。清管器的直径大致为反应管的内径。清管器从清管器基站(pig station)发出，并被聚合乳液推过回路。由于不允许清管器通过循环泵，所以提供旁通管以使清管器从该泵周围绕过。
为了清洁不能用清管器清洁的部件，例如循环泵，定期用清洁溶剂冲洗反应器。为此，必须首先排空整个反应器。尽管溶剂清洁仅用于清洁回路的不能用清管器清洁的区段，但整个回路都被清洁溶剂填充。在清洁后，除去溶剂并需要将整个反应器重新装料。该程序造成生产时间的大量损失和高的经济和环境成本。
本发明的目的是提供可以使用较少清洁溶剂更有效清洁的环流反应器。
通过提供根据第一段的具有绕过循环泵的旁通管的聚合反应器，实现了本发明的目的，该旁通管将上游回路点与下游回路点相连，这两个点均配备三通阀，从而形成包含泵、清洁溶剂入口和清洁溶剂出口的短回路。这样有可能使泵区段短路，从而封闭主盘管。可以使清洁溶剂在隔离的泵区段中循环泵送以清洁该泵。由于现在只用溶剂清洁短路的泵区段而非整个回路，所用清洁溶剂的量可以显著降低90％以上。此外，不再需要排空主盘管。
为了有助于要清洁的区段中的聚合物残留物的增溶，可以为该区段和/或旁通管配备与加热介质源，例如加热的水相连的护套以加热溶剂。
溶剂可以例如在其从设备中泵出之前再循环大约15至45分钟。任选地，再填充该线路以二次洗涤，或在清洁周期中将小溶剂流连续泵入该线路，以使用过的溶剂溢出到储器或类似物中。
适用在本聚合法中的一些典型单体包括，例如，丙烯酸丁酯、甲基丙烯酸甲酯、苯乙烯、乙酸乙烯酯、Veova
Figure S2007800030503D00021
9、Veova
Figure S2007800030503D00022
10(各自ex Shell)、丙烯酸乙酯、丙烯酸2-乙基己酯、乙烯、和氯乙烯。通过自由基引发加成反应以产生悬浮在聚合物不溶的介质，通常是水中的直径通常为50至3000纳米的高分子量聚合物粒子的分散体。常见的自由基生成剂包括过氧二硫酸的钠、钾和铵盐，例如过氧二硫酸铵。或者，可以使用氧化还原耦。这些由氧化剂和还原剂构成。常用的氧化剂是过氧二硫酸的盐和过氧化氢叔丁基和过氧化氢本身。还原剂是亚硫酸钠、偏亚硫酸氢钠、甲醛次硫酸钠和连二硫酸钠。
单体的聚合可以在水悬浮液中进行，在该情况下，原材料优选通过单独的进料流提供。这些流体以分开的小股流体引入新鲜单体和称作水相的稳定剂的水溶液，或例如，单体与水的预乳液及水溶液。在反应开始时，向反应器中装入在溶液槽中制成的水相。其它填料也是可以的，特别是来自之前的操作的最终乳液聚合物(具有相同或不同组成)，任选稀释至任何浓度。
借助在线循环泵提供反应器中的搅拌。在进料流开始流动后不久，单体开始反应并生热。通过冷却装置，通常通过冷却流体(例如水)经过冷却护套受控循环使温度稳定。产物流入冷却槽，在此残留单体转化成聚合物。
在冷却后，在过滤器中过滤乳液聚合物以除去任何过大粒子或砂砾材料并转移到产物储槽中。
任选地，聚合法可以在压力下，例如在10至150巴的压力下进行。或者，可以在环境压力下进行聚合。
合适的循环泵是例如容积式泵或离心泵。
通过附图进一步例示本发明，其在图1中显示了环流反应器的泵区段1，其具有两个连接到管式盘绕回路(未显示)的外端4、5上的外端2、3。泵区段1包含单体入口6、水相入口7、和最终产物出口8。循环泵9充当使反应器进料在循环回路内循环的驱动装置。绕过循环泵9的旁通管10将泵9上游的回路点11与泵9下游的点12相连。这两个点11、12均配备三通阀13、14。第二旁通管15包括清管器基站16以存放一个或多个闲置的清管器。清管器基站16可以使用阀隔离。在阀19下游，旁通管15形成U-转弯，回线隐藏在该图的侧视图中。第二旁通管15刚好在阀14上游返回主管路。U-转弯的下游是出口8。排放管20将清管器基站16连到出口管8上。排放管20用于在清管器从盘管中返回之后将其带向清管器基站16中的安放位置。就在与排放管20的接点上游，出口管8配有阀21。排放管20配有阀22。
为了清洁循环泵9，使用阀13、14封闭主盘管并打开旁通管10。在通过启动阀13和14而围住的隔离区段内所含的聚合物乳液经由阀23和位于循环泵9和三通阀13之间的管道下方的排料管24排出。
打开阀18和22并关闭阀21。或者，阀21保持打开，阀18和22保持关闭。这两个阀选项各自都提供了溶剂的排出路径。溶剂可以从排放管20上移到出口管8或更简单地经由阀21垂直上移到管道8。在阀21上方，具有管接头25，在该接头25之后紧接着一个三通阀(未显示)，其用于将溶剂转移到小内径管并引向废溶剂储器。将高温沸腾溶剂从溶剂供应管26经由循环泵9泵入清洁线路。该线路内捕集的空气经由阀14附近的旁通管10上的小阀27放出。然后使循环泵9运行以提供溶剂循环。这种循环有助于任何聚合物沉积物的增溶。管道上的护套28用热水加热，这使溶剂温度升高并且也有助于增溶。在通常15至45分钟的时间后，将溶液经由阀23从设备中泵出。任选地，再填充该线路以二次洗涤或在清洁周期中将小溶剂流连续泵入该线路，以使其溢出到储器或类似物中。当已经排空所有溶液时，向该线路填充水相，阀13、14、18和22和/或21回复到其初始位置，此后可以重新开始生产。

Claims (6)

1.一种聚合反应器，包含一个或多个带有一个或多个原材料入口、一个或多个出口和使反应器进料在循环回路内循环的循环泵的循环回路，其特征在于绕过循环泵的旁通管将上游回路点与下游回路点相连，这两个点均配备三通阀，从而形成包含该泵和清洁溶剂入口和清洁溶剂排放出口的短回路区段。
2.根据权利要求1的反应器，其特征在于至少一部分该短回路区段和/或旁通管配有与加热介质源相连的护套。
3.一种用于清洁包括使反应器进料在循环回路内循环的循环泵的环流反应器的区段的方法，其特征在于用将该待清洁的区段与旁通管相连的三通阀将该待清洁的区段与循环回路隔离以经由泵形成短路回路区段，且特征在于经由短路回路区段中的清洁溶剂入口引入清洁溶剂并再循环通过该短路回路区段一次或多次，随后经由溶剂排出口排出。
4.根据权利要求3的方法，其特征在于随后启动这两个三通阀以封闭旁通管并将该短路回路区段用泵与循环回路的另一部分相连。
5.根据权利要求3或4的方法，其特征在于至少一部分旁通管和/或该短路回路区段用流经围绕管道的护套的加热介质加热。
6.根据权利要求3的方法，其特征在于在溶剂进料再循环过程中，将小溶剂流连续泵入该短路回路区段和旁通管中，同时在相同比率下用过的溶剂经出口连续溢出到容器中。
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