CN1926159A - 互连环管反应器 - Google Patents
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Abstract
本发明描述了包括两个互连环管的反应器,其中生长的聚合物连续地在回路中从第一环管通过第一管线流向第二环管,和通过第二管线返回第一环管。本发明还公开了一种于两个互连环管反应器中聚合烯烃的方法。
Description
本发明涉及双环反应器(double loop reactor)中的乙烯聚合领域。
高分子量聚烯烃如聚乙烯通常较相应低分子量聚烯烃具有改善的机械性能。然而,高分子量聚烯烃难于加工且制备成本高。具有宽或双峰分子量分布(MWD)的聚烯烃是理想的,因为其组合了高分子量组分带来的有利的机械性能以及低分子量组分带来的改善的加工性能。
对于很多高密度聚乙烯(HDPE)应用而言,聚乙烯具有增强的韧性、强度和抗环境应力裂化(ESCR)是很重要的。高分子量的聚乙烯更易于具有这些增强的性能。然而,随聚合物分子量的增加,树脂的可加工性就会下降。通过提供具有宽或双峰MWD的聚合物,在可加工性,特别是挤压性能得以改善的同时保有高分子量树脂特性的理想性能。
一些制备具有双峰或宽分子量分布的树脂的方法有:溶体混合、串联结构反应器或带有双位催化剂体系的单反应器。
用于制备聚烯烃的铬催化剂趋向扩大分子量分布,且在某些情况下能够得到双峰分子量分布,但通常这些树脂的低分子部分含有大量的共聚单体。尽管宽分子量分布提供了可接受的加工性能,双峰分子量分布可提供更优良的性能。在某些情况下,后者甚至可调节高分子量和低分子量部分的份量从而调节机械性能。
已知使用两个串联反应器由Ziegler Natta催化剂可制得双峰聚乙烯。典型地,在第一反应器中,由氢气和乙烯在Ziegler Natta催化剂存在下反应形成低分子量均聚物。该方法中必需使用过量的氢,由此需在产物通入第二反应器之前从第一反应器中除去所有的氢气。在第二反应器中,得到乙烯和己烯的共聚物从而制得高分子量的聚乙烯。本领域还公开了相反结构(reverse configuration)。
金属茂催化剂也已知用于制备聚烯烃。例如,EP-A-0619325描述了制备具有多峰或至少双峰分子量分布的聚烯烃如聚乙烯的方法。在该方法中,使用包括至少两种金属茂组分的催化剂体系。金属茂组分可选自,例如双(环戊二烯基)二氯化锆和亚乙基-双(茚基)二氯化锆。通过在相同反应器中使用两种不同的金属茂催化剂组分,得到至少双峰的分子量分布。
某些如管材的应用需要聚乙烯树脂具有裂纹缓慢扩展(slow crackgrowth)的高耐受力以及快速裂纹扩展产生的冲击韧性(rapid crackpropagation yielding toughness)的耐受力。EP-A-0571987公开了例如使用多级聚合制备乙烯聚合物组合物的方法。作为主要组分的催化剂包括,过渡金属化合物,能够与过渡金属化合物反应形成离子络合物的化合物和有机铝化合物。
或者,宽或多峰分子量分布可通过如EP-A-0735090中所述的物理共混两种或多种树脂而获得,该文献中公开的聚乙烯树脂组合物由三种聚乙烯组分通过物理共混制得。
在另一种方法中,使用Ziegler-Natta催化剂体系在两个或多个互连聚合区内进行α-烯烃的气相催化聚合,其特征在于第二聚合区内引入的气体与第一聚合区内的气体组分不同:即多区循环反应器工艺。它由两个互连的聚合区组成:
1.“升液管”或快速流化区,其中气体速度大于转移速度;
2.“降液管”,其中聚合颗粒在重力作用下流下。
将单体和催化剂体系在聚合条件下加料入“升液管”。生长的聚合物(growing polymer)于快速流化条件下向上流动,然后离开“升液管”并进入“降液管”,其中聚合颗粒在重力作用下向下流动。然后颗粒离开“降液管”,并再次引入到“升液管”中。于是在两个聚合区内建立了循环。
该方法进一步需要:
1.完全或部分地阻止“升液管”中存在的气体混合物进入“降液管”;
2.引入到“降液管”中的气体和/或液体混合物不同于“升液管”中存在的气体混合物;
多区循环反应器工艺例如在WO-A-97/04015和WO-A-00/02929中所述。其主要应用Ziegler-Natta催化剂体系,并受限于难于完全除去“升液管”中存在的气体混合物并难于阻止其进入“降液管”缺陷。且该工艺难于控制两区中的气体组成。由此需要一个不存在上述缺陷的聚合体系。
本发明的一个目的在于提供一种制备非常均质聚合物的聚合工艺。
本发明的另一目的在于提供一种制备具有宽或多峰分子量分布的聚合物的聚合工艺。
本发明相应地公开了一种用于聚合烯烃的双环反应器,其包括:
a)双环反应器(1)和(11);
b)将生长的聚合物从第一环管反应器转移至第二环管反应器的连接装置(4);
c)将生长的聚合物从第二环管反应器返回至第一环管反应器的连接装置(14)。
本发明还公开了由两个互相连接的环管组成的聚合技术,其中生成的聚合物在回路中(in circuit)连续地从第一环管流向第二环管和返回第一环管。
聚合物环绕两环管流动优选平均不超过三次,更优选不超过两次。
在双环反应器正常操作条件下,单体、稀释剂、氢气和共聚单体在泵下游注入第一环管中,生长的聚合物以约8m/sec的速度环绕环管循环流动,相当于每30秒循环一次100m3的反应器。单体溶于稀释剂中,颗粒聚合物悬浮于液体中。在第一环管平均驻留时间的40分钟到1小时后,相当于环绕环管约100转后,颗粒聚合物转移至第二环管中。
转移通常难于进行,因为需要单独控制每一环管中的聚合混合物,从而从第一反应器存在的蒸汽中除去任何第二环管中不理想的组分。文献中公开了一些转移操作方法。例如,US-2001/0018499中描述了一种通过在将悬浮液送入第二反应器之前降低其压力而除去大部分第一反应器中的氢的方法。US-A-5,639,834描述了一种方法,其中第一反应器中形成的富含共聚单体的悬浮液通过沉降柱(settling leg)从该反应器中移除,浓缩的悬浮液送入第二反应器,其中共聚单体量减少。US-A-4,692,501描述了一种方法,其中第一反应器形成的悬浮液在送入第二反应器之前于交换区用逆流液体洗涤。US-A-2001/0018500描述了一种连续聚合方法,其中聚乙烯颗粒的悬浮液从第一反应器中移除,送入旋液分离器,在其中将其分离成的浓缩悬浮液送入第二反应器,分离成的含有稀释剂的液体部分循环回第一聚合区。
第二反应器中的操作条件通常与第一反应器不同,因为其需要制备具有宽分子量分布的聚烯烃。第二反应器的驻留时间短于第一反应器,典型地短少50%,压力通常较第一反应器低1bar以促进转移。
双环反应器可以直接模式(direct mode)进行操作,其中于第一反应器中制得高分子量组分的聚合物,并于第二反应器中制得低分子量组分,或以相反模式(reverse mode)进行。
最终聚合物优选通过沉降柱移出,可增加其固含量。
这些操作条件是本领域已知的。本发明进一步公开了将生长的聚合物从第二环管转移回第一环管中,于是生长的聚合物连续地从一个环管转移至另一个环管。
根据本发明的一个优选实施方式,从第一环管转移至第二环管并回到第一环管是通过沉降柱进行操作。
图1表示了根据本发明的互连环管反应器。单体、任选的共聚单体、氢气和稀释剂加料入在泵(2)下游的第一环管(1)中。生长的聚合物使用沉降柱(3)通过线路(4)转移至第二环管,将其供应到在泵(12)的上游处的第二环管(11)中。循环回第一环管的一部分生长聚合物在第二反应器泵下游处在沉降柱中收集,然后通过线路(14)加入在泵的上游处的第一反应器。该装置具有在第二反应器脱离点和第一反应器进入点之间的正压差,由此易于从第二环管向第一环管的转移。最终聚合物使用沉降柱(13)通过线路(15)从第二环管中取出。
根据本发明的另一个实施方式示于图2,脱离第一环管的物质通过传送线路24送入旋液分离器(25)。所有或部分聚合物颗粒悬浮液通过传送线26被送入第二环管,如果有任何残余物,可通过传送线27返回第一环管或取出。在第二环管驻留后,聚合物颗粒于沉降柱13中浓缩,然后通过传送线28返回第一环管或通过线29取出。
选择易于从一个环管向另一个环管转移的新聚合工艺的几何结构和操作条件。更特别地,必须选择各反应器的压力以使得接受部分的压力总是低于发送部分的压力。这将通过图1公开的结构达到,其利用了以下事实:泵下游的压力比泵上游的压力高约1bar。
或者,可使用离心泵以推动聚合物颗粒通过转移管线,脱离压差限制。
在另一个实施方式中,从第二反应器中排出的聚合物浆料于低压在搅拌器中脱气以除去所有痕量的氢气,并借助于多级离心泵注入第一反应器(图3)。
根据本发明的另一个实施方式中,从反应器中排出的浆料被送入闪蒸罐并完全脱除气体。气体返回循环部分。一部分聚合物被送入挤出机,一部分聚合物被异丁烷润湿并泵送回第一反应器(图4)。
可用于本发明聚合反应的催化剂体系没有特别限制,但优选选择对氢气和共聚单体均能表现良好响应的催化剂体系,因为该反应需要两个聚合区各自独立地操作。优选的催化剂体系包括金属茂组分,更优选如下通式的双茚基组分,
R”(Ind)2MQ2
其中R”是结构桥,Ind是取代或未取代的茚基或四氢茚基,M是周期表IV族金属,Q是具有1-20个碳原子的烃基或卤素,
或如下通式的环戊二烯基-芴基组分,
R”(Cp-Flu)MQ2
其中Cp是取代的或未取代的环戊二烯基,Flu是取代的或未取代的芴基。
用于本发明的催化剂体系除上述催化剂组分外,还包括一种或多种具有离子化作用和能够活化金属茂催化剂组分的活性剂。典型地,活化剂包括本领域公知的含铝或含硼化合物。
该方法当使用金属茂催化剂体系时特别有利,因为它们难以混合:不断地从一个环管向另一个环管转移物质增加了聚合物的均一性。均一性在聚合组合物的水平上增加,且在各颗粒内均一性在聚合物中高分子量和低分子量的百分比水平上增加。此外,由于金属茂消耗氢,因此在向第二环管转移前,无需除去脱离第一环管的聚合物中残余的氢。金属茂催化剂体系对氢和共聚单体均能产生优良的响应。
优选的聚合物是聚乙烯。
图列
图1表示根据本发明的一个实施方式,其中聚合物通过压差从一个环管反应器向另一个环管反应器转移。
图2表示根据本发明的一个实施方式,其中聚合物通过旋液分离器从一个环管反应器向另一个环管反应器转移。
图3表示根据本发明的一个实施方式,其中聚合物通过Moineau型泵从第二环管反应器向第一环管反应器转移。从第二反应器排出的聚合物浆料在低压在搅拌器中脱气以去除所有痕量氢,并借助多级离心泵注入第一反应器。
图4表示根据本发明的另一个实施方式,其中聚合物通过Moineau型泵从第二环管反应器向第一环管反应器转移。从反应器中排出的浆料送入闪蒸罐并完全脱除气体。部分聚合物送入挤出机,其它部分聚合物用异丁烷润湿并泵送回第一反应器。
实施例
在根据本发明的一个特别的操作实施例中,根据图1所示的结构,泵(2)下游处第一环管中的压力为约41bars。大约在第一环管中部约40.5bars压力处从第一环管取出聚合物。第二环管总是保持在比第一环管压力稍低的总压下,此处指泵(12)下游约40.5bars的压力。从第一环管取出的聚合物注入泵(12)上游约39.5bars压力处的第二环管中。在泵(12)下游约40.5bars压力处从第二环管取出聚合物,注入泵(2)上游约40bars压力处的第一环管中。该结构易于聚合物在两个反应器间的流动,但也可使用其它任何聚合物在两个环管间循环流动的方法。
根据本发明制得的聚合物非常均质,因为它们在各反应器中从一个到另一个地逐步生长,而先前的双环体系制得的聚合物是第一反应器继而第二反应器条件的叠加结果。
Claims (8)
1.一种用于聚合烯烃的双环反应器,其包括:
d)双环反应器(1)和(11);
e)将生长的聚合物从第一环管反应器转移至第二环管反应器的连接装置(4);
f)将生长的聚合物从第二环管反应器返回至第一环管反应器的连接装置(14)。
2.一种于两个互连环管反应器(1)和(11)中聚合烯烃的方法,其中生长的聚合物在回路中连续地从第一环管反应器通过管线(4)流向第二环管反应器,和通过管线(14)返回第一环管反应器。
3.权利要求2的方法,其中生长的聚合物通过沉降柱(3)从第一环管反应器转移至第二环管反应器,和/或从第二环管反应器转移至第一环管反应器。
4.权利要求2的方法,其中生长的聚合物通过压差从第一环管反应器转移至第二环管反应器,和/或从第二环管反应器转移至第一环管反应器。
5.权利要求3的方法,其中压差是由各反应器中循环泵的上游和下游压力的差异而产生的。
6.权利要求2的方法,其中生长的聚合物通过旋液分离器(25)从第一环管反应器转移至第二环管反应器,和/或从第二环管反应器转移至第一环管反应器。
7.权利要求2的方法,其中生长的聚合物通过Moineau型泵从第一环管反应器转移至第二环管反应器,和/或从第二环管反应器转移至第一环管反应器。
8.权利要求2-7任一项的方法,其中催化剂体系基于金属茂催化剂组分。
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US9556283B2 (en) | 2010-05-21 | 2017-01-31 | Chevron Phillips Chemical Company, Lp | Polyethylene production with multiple polymerization reactors |
US9180405B2 (en) * | 2010-10-15 | 2015-11-10 | Chevron Phillips Chemical Company Lp | Ethylene recovery by absorption |
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DE602005000008D1 (de) | 2006-06-22 |
KR101174524B1 (ko) | 2012-08-16 |
ES2264120T3 (es) | 2006-12-16 |
EA010065B1 (ru) | 2008-06-30 |
JP5006052B2 (ja) | 2012-08-22 |
US20080242808A1 (en) | 2008-10-02 |
DE602005000008T2 (de) | 2006-11-23 |
EA200601485A1 (ru) | 2007-02-27 |
EP1564223A1 (en) | 2005-08-17 |
PT1603955E (pt) | 2007-07-23 |
CN100471876C (zh) | 2009-03-25 |
JP2007522307A (ja) | 2007-08-09 |
EP1603955A1 (en) | 2005-12-14 |
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ATE326485T1 (de) | 2006-06-15 |
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